TW201815899A - Hardened material, wavelength conversion sheet, light emitting device, sealing element, and semiconductor light emitting device - Google Patents

Abstract

The present invention provides a hardened material having both high hardness, high fracture resistance and high heat resistance. This invention is a hardened | cured material which contains a condensation type silicone resin hardened | cured material and satisfies (1) and (2). (1) In the solid ²⁹ Si-NMR spectrum of the condensation type siloxane resin hardened substance, there are peaks of silicon atoms (silicon atoms bonded to 3 oxygen atoms) belonging to the T body; (2) Heterogeneous domain ( Domain) size (by setting the wave number of X-rays as the horizontal axis, and reducing the scattered intensity of the measured scattering intensity from the measured scattering intensity as the vertical axis, the condensed silicone resin hardened product is impregnated with tetrahydrofuran to make it swell The measured value of the small-angle X-ray scattering of the sample was plotted in a graph, and the value obtained by fitting the formula (A) was 50 Å or more. (In the formula, ξ represents the size of the network sieve, Ξ represents the size of the non-uniform domain, I (q) represents the scattering intensity, q represents the wave number, and A and B represent the fitting constant.

Description

Hardened object, wavelength conversion sheet, light-emitting device, sealing element, and semiconductor light-emitting device

[0001] The present invention relates to a cured product, a wavelength conversion sheet, a light-emitting device, a sealing element, and a semiconductor light-emitting device.

[0002] In recent years, light emitting devices using a semiconductor laser (LD, Laser Diode) or a light emitting diode (LED, Light Emitting Diode) are being studied. Semiconductor lasers maintain high conversion efficiency even in high current density regions. In addition, the semiconductor laser can also reduce the size of the device by separating the light emitting portion from the excitation portion. Therefore, semiconductor lasers are expected to be used in lighting devices. With the recent advances in technology development, tritium light-emitting diodes are becoming brighter. [0003] As a transparent material used in a light-emitting device, a cured silicone resin is known. For example, Patent Document 1 describes that as a matrix material of a phosphor sheet of an LED, a cured product of a polymerizable silicone resin is used. The cured silicone resin is not only excellent in light transmittance, but also excellent in heat resistance and UV resistance. Therefore, it is suitable to use a cured silicone resin as a material for forming a material, since it is not easily deteriorated even when a light emitting device used for a long period of time is used. [Prior Art Document] [Patent Document] [0004] [Patent Document 1] Japanese Patent Laid-Open No. 2013-1792

[Problems to be Solved by the Invention] [0005] The use of a high-hardness silicone hardened material as a component forming material has an advantage that it is difficult to attach a flaw. On the other hand, high-hardness siloxane resin hardened products are prone to cracking during hardening, and have the disadvantage of being liable to reduce yield. In addition, a hardened silicone resin hardened product has a disadvantage that cracks due to thermal stress and the like are liable to occur during use. Therefore, a silicone hardened material having a high hardness is required, and it is difficult to cause cracking during hardening, and it is difficult to generate a hardened silicone resin when heated. [0006] In the following description, the “property to prevent cracking during hardening” may be referred to as “crack resistance”. In addition, "the property that cracks are hard to occur when heated" is sometimes called "heat resistance". [0007] In a light emitting device using a semiconductor laser or a UV-LED, the element may be irradiated with light having a high energy density. In addition, in a light-emitting device using a high-brightness LED, elements may be exposed to high temperatures due to heat generated during use. Therefore, high heat resistance is sought among the elements used in these light emitting devices. [0008] The present invention has been made in view of such circumstances, and an object thereof is to provide a hardened material having both high hardness, high fracture resistance, and high heat resistance. It is also an object of the present invention to provide a wavelength conversion sheet, a light-emitting device, a sealing element, and a semiconductor light-emitting device using the cured material as a forming material. [Means for Solving the Problems] [0009] In order to solve the problems described above, the present invention provides the following [1] to [13]. [1] A hardened material containing a condensation type silicone resin hardened material, which satisfies the following (1) and (2), (1) a solid ²⁹ Si-NMR in the above condensation type silicone resin hardened material The resonance spectrum has a peak of the silicon atom belonging to the T body; (here, the so-called silicon atom of the T body means a silicon atom bonded to 3 oxygen atoms) (2) The size of the non-uniform domain described below is 50 ° or more (here, the size of the non-uniform domain refers to the horizontal axis of the X-ray wave used for the measurement of small-angle X-ray scattering, and the scattering intensity measured from the small-angle X-ray scattering The scattering intensity for reducing the control scattering is defined as the vertical axis, and the measured value of small-angle X-ray scattering of a sample in which the above-mentioned condensation-type silicone resin hardened material is impregnated with tetrahydrofuran is plotted, and the graph is obtained by the following formula (A) (Fitted value) (Here, ξ represents the size of the network sieve, Ξ represents the size of the non-uniform domain, I (q) represents the scattering intensity, q represents the wave number, and A and B represent the fitting constants.) [2] The hardened product according to [1], wherein a ratio of the silicon atom of the T body to the total silicon atom contained in the condensation-type silicone resin hardened material is 50 mol% or more. [3] The hardened product according to [2], wherein the ratio of the T3 silicon atom to the total silicon atoms contained in the condensation type silicone resin hardened material is 50 mol% or more (here, the so-called T3 silicon Atom means the silicon atom of T body, all 3 oxygen atoms are bonded to other silicon atoms). [4] The cured product according to any one of [1] to [3], wherein the condensation-type silicone resin cured product includes formula (A1), formula (A1 '), formula (A2), or formula ( A3) indicates the structural unit, (In formula (A1), formula (A1 '), formula (A2), and formula (A3), R ¹ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ² represents a carbon number 1 An alkoxy group or a hydroxyl group of ˜4, and a plurality of R ¹ and R ² may be the same as or different from each other). [5] The cured product according to [4], wherein the R ¹ is a methyl group, the R ² is an alkoxy group or a hydroxyl group having 1 to 3 carbon atoms, and the plurality of R ² may be the same or different . [6] The cured product according to any one of [1] to [5], wherein the filler is dispersed in the condensation-type silicone resin cured product. [7] The cured product according to [6], wherein the filler is a wavelength conversion material. [8] The cured product according to [7], wherein the wavelength conversion material is a phosphor. [9] A wavelength conversion sheet using the hardened material according to [7] or [8] as a forming material. [10] A light-emitting device comprising a light source that emits light and a wavelength conversion sheet according to [9] that is disposed at a position where the light emitted from the light source is incident. [11] A sealing element using the hardened material according to any one of [1] to [8] as a forming material. [12] A semiconductor light-emitting device comprising a substrate, a semiconductor light-emitting element disposed on the substrate, and a sealing element that seals at least a portion of the semiconductor light-emitting element, wherein the sealing element is as described in [11] Sealing components. [13] The semiconductor light-emitting device according to [12], wherein the light-emitting wavelength of the semiconductor light-emitting element is 400 nm or less. [Effects of the Invention] [0011] According to the present invention, it is possible to provide a hardened material having both high hardness, high fracture resistance, and high heat resistance. In addition, a wavelength conversion sheet, a light-emitting device, a sealing element, and a semiconductor light-emitting device using the cured material as a forming material can be provided.

[0013] Hereinafter, embodiments of the present invention will be described. [0014] The structural unit included in the silicone resin is preferably included in the silicone resin as a repeating unit. [0015] 〈Hardened material〉 硬化 The hardened material of the present invention contains a condensation type silicone resin hardened material, which satisfies the following (1) and (2), (1) is a solid of the condensation type silicone resin hardened material²⁹ Si-nuclear magnetic resonance spectrum, there is a peak of the silicon atom belonging to the T body; (here, the so-called silicon atom of the T body means a silicon atom bonded to 3 oxygen atoms) (2) the following unevenness The size of the domain is 50 Å or more, 于 (here, the size of the non-uniform domain refers to the horizontal axis of the X-ray wave used for the measurement of small-angle X-ray scattering. Measure the scattering intensity to reduce the scattering intensity. The scattering intensity of the control scattering is determined as the vertical axis. The measured values of the small-angle X-ray scattering of the sample obtained by impregnating the condensation-type silicone resin hardened material with tetrahydrofuran and making it swell are plotted. A) The value obtained by performing the fitting). [0016](Here, ξ represents the size of the network sieve, Ξ represents a large non-uniform domain, I (q) represents the scattering intensity, q represents the wave number, and A and B represent the fitting constants. [0017] In the following description, small angle X-ray scattering may be referred to as SAXS. [0018] (Condensed Silicone Resin Hardened Material) Condensed silicone resin is used as the raw material of the condensed silicone resin hardened material included in the cured product of this embodiment. Condensed silicone resins can be used alone or in combination of two or more. The so-called condensation-type silicone resin is a resin that is polycondensed by a dealcoholization reaction or a dehydration reaction of a hydroxyl group bonded to a silicon atom and an alkoxy group or a hydroxyl group bonded to another silicon atom. [0019] The condensation-type silicone resin as a raw material of the condensation-type silicone resin hardened material included in the cured material of this embodiment includes a structural unit represented by the following formula (A3). The condensation-type silicone resin preferably further includes one selected from the group consisting of a structural unit represented by the formula (A1), a structural unit represented by the formula (A1 '), and a structural unit represented by the formula (A2). The above-mentioned structural unit preferably further includes all of the structural unit represented by the formula (A1), the structural unit represented by the formula (A1 '), and the structural unit represented by the formula (A2). [0020](In formula (A1), formula (A1 '), formula (A2), and formula (A3), R¹ Represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R² Represents an alkoxy or hydroxyl group having 1 to 4 carbon atoms, plural R¹ And R² They can be the same or different). [0021] In this specification, a structural unit including a silicon atom bonded to three oxygen atoms is referred to as a "T body". In addition, a structural unit containing a silicon atom in which all of the three oxygen atoms are bonded to other silicon atoms is referred to as a "T3 body". In addition, a structural unit containing a silicon atom in which two of the three oxygen atoms are bonded to other silicon atoms is referred to as a "T2 body". In addition, a structural unit containing a silicon atom in which one of the three oxygen atoms is bonded to another silicon atom is referred to as a "T1 body". That is, "T body" means "T1 body", "T2 body", and "T3 body". [0022] In this specification, a structural unit including a silicon atom bonded to two oxygen atoms is referred to as a "D body". A structural unit containing a silicon atom bonded to one oxygen atom is referred to as "M body". [0023] The structural unit represented by formula (A3) includes three oxygen atoms bonded to other silicon atoms and¹ Bonded silicon atoms. Since R¹ Since it is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, the structural unit represented by formula (A3) is a T3 body. [0024] The structural unit represented by formula (A2) includes two oxygen atoms bonded to other silicon atoms, two, and R¹ And R² Bonded silicon atoms. Since R² Since it is an alkoxy group or a hydroxyl group having 1 to 4 carbon atoms, the structural unit represented by the formula (A2) is a T2 body. [0025] The structural unit represented by formula (A1) includes an oxygen atom bonded to another silicon atom, and R¹ And 2 R² Bonded silicon atoms. Since R¹ An alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R² Since it is an alkoxy group or a hydroxyl group having 1 to 4 carbon atoms, the structural unit represented by the formula (A1) is a T1 body. [0026] The structural unit represented by the formula (A1 ′) includes R¹ And 2 R² Bonded silicon atoms, which are bonded to oxygen atoms, which are bonded to silicon atoms in other structural units. Since R¹ An alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R² Since it is an alkoxy group or a hydroxyl group having 1 to 4 carbon atoms, the structural unit represented by the formula (A1 ') is a T1 body. [0027] The structural unit represented by the formula (A1) and the structural unit represented by the formula (A1 ') constitute the end of the organic polysiloxane chain contained in the condensation type silicone resin hardened body. The structural unit represented by the formula (A3) constitutes a branched chain structure of an organic polysiloxane chain included in the condensation-type silicone resin cured product. That is, the structural unit represented by the formula (A3) forms a part of the network structure or the ring structure of the condensation-type silicone resin hardened material. [0028] In this specification, the silicon atom contained in the T3 body is referred to as "T3 silicon atom". The silicon atom contained in the T2 body is referred to as "T2 silicon atom". The silicon atom contained in the T1 body is referred to as "T1 silicon atom". [0029] The total content of the T1 body, the T2 body, and the T3 body is preferably 50 mol% or more with respect to the total content of the entire structural unit of the condensation type silicone resin. In other words, the total content of the T1 silicon atom, the T2 silicon atom, and the T3 silicon atom is preferably 50 mol% or more with respect to the total content of the total silicon atoms of the condensation type silicone resin. Furthermore, the total content of T1 silicon atoms, T2 silicon atoms, and T3 silicon atoms is more preferably 60 mol% or more, and more preferably 70 mol% or more, relative to the total content of all silicon atoms of the condensation type silicone resin. , And more preferably 80 mol% or more, and even more preferably 90 mol% or more. [0030] The content of the D body is preferably 30 mol% or less, more preferably 20 mol% or less, and still more preferably 10 mol% or less, relative to the total content of the entire structural unit of the condensation type silicone resin. It is still more preferably 5 mol% or less, and even more preferably 4 mol% or less. [0031] The total content of T1, T2, and T3 bodies can be determined by²⁹ The total area of signals (Signal) of all silicon atoms obtained by Si-NMR measurement is obtained by dividing by the total area of signals assigned as T1 silicon atoms, T2 silicon atoms, and T3 silicon atoms. [0032] The content of the T3 body is preferably 50 mol% or more relative to the total content of the entire structural unit of the condensation type silicone resin. In other words, the content of T3 silicon atoms is preferably 50 mol% or more relative to the total content of all silicon atoms of the condensation type silicone resin. Furthermore, the content of T3 silicon atoms is more preferably 60 mol% or more, and even more preferably 70 mol% or more, relative to the total content of all silicon atoms of the condensation type siloxane resin. [0033] T3 silicon atom content can be determined by²⁹ The total area of the signals of all silicon atoms obtained by Si-NMR measurement was determined by dividing by the area of the signal assigned as the T3 silicon atom. The content of silicon atoms other than T3 silicon atoms can also be determined in the same manner. [0034] R¹ The alkyl group having 1 to 10 carbon atoms may be a linear alkyl group, a branched alkyl group, or an alkyl group having a cyclic structure. Among these, a linear or branched alkyl group is preferred, and a linear alkyl group is more preferred. [0035] R¹ The alkyl group having 1 to 10 carbon atoms represents that one or more hydrogen atoms constituting the alkyl group may be substituted with other functional groups. Examples of the substituent of the alkyl group include an aryl group having 6 to 10 carbon atoms such as a phenyl group and a naphthyl group, and a phenyl group is preferred. [0036] as R¹ Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, and neopentyl. Unsubstituted alkyl, such as phenyl, hexyl, octyl, nonyl, decyl, arylalkyl such as phenylmethyl, phenylethyl, and phenylpropyl. Among these, a methyl group, an ethyl group, an n-propyl group, or an n-butyl group is preferable, a methyl group, an ethyl group, or an isopropyl group is more preferable, and a methyl group is even more preferable. [0037] R¹ The aryl group having 6 to 10 carbon atoms represents that one or more hydrogen atoms constituting the aryl group may be substituted with other functional groups. Examples of the substituent of the aryl group include an alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, propyl, and butyl. [0038] as R¹ Examples of the aryl group having 6 to 10 carbon atoms include unsubstituted aryl groups such as phenyl and naphthyl, and alkylaryl groups such as methylphenyl, ethylphenyl, and propylphenyl. Among these, phenyl is preferred. [0039] as R¹ Is preferably an alkyl group, more preferably a methyl group, an ethyl group, or an isopropyl group, and still more preferably a methyl group. [0040] R² The alkoxy group having 1 to 4 carbon atoms may be a linear alkoxy group, a branched alkoxy group, or an alkoxy group having a cyclic structure. Among these, a linear or branched alkoxy group is preferable, and a linear alkoxy group is more preferable. 004 [0041] as R² The alkoxy group having 1 to 4 carbon atoms, for example, is preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, or a tert-butoxy group. Is preferably methoxy, ethoxy or isopropoxy. [0042] as R² , Preferably methoxy, ethoxy, isopropoxy or hydroxyl. [0043] The condensation type silicone resin as a raw material of the condensation type silicone resin hardened material included in the hardened material of this embodiment may further include the following formula (C1), formula (C1 '), formula (C2), formula (C3) or a structural unit represented by formula (C4). [0044](In formula (C1), formula (C1 '), formula (C2), formula (C3), and formula (C4), R⁷ Represents an alkoxy or hydroxyl group having 1 to 4 carbon atoms, and a plurality of R⁷ It can be the same or different). [0045] In this specification, a structural unit including a silicon atom bonded to four oxygen atoms is referred to as a "Q body". Also, a structural unit containing a silicon atom in which one of the four oxygen atoms is bonded to another silicon atom is called a "Q1 body". The structural unit represented by formula (C1) and the structural unit represented by formula (C1 ') are "Q1 bodies". Also, a structural unit containing a silicon atom in which two of the four oxygen atoms are bonded to other silicon atoms is called a "Q2 body". The structural unit represented by formula (C2) is "Q2 body". Also, a structural unit containing a silicon atom in which three of the four oxygen atoms are bonded to other silicon atoms is called a "Q3 body". The structural unit represented by formula (C3) is "Q3 body". In addition, a structural unit containing a silicon atom in which all the four oxygen atoms are bonded to other silicon atoms is referred to as a "Q4 body". The structural unit represented by formula (C4) is "Q4 body". [0046] That is, the Q system means Q1 body, Q2 body, Q3 body, and Q4 body. [0047] The specific gravity of the condensation type silicone resin hardened material included in the hardened material of this embodiment is preferably 1.20 to 1.35. The specific gravity of the condensed silicone resin hardened body can be appropriately adjusted by controlling the content ratios of D body, T body, and Q body. [Dimensions of non-uniform domain] As a result of diligent research, the inventors found that the small-angle X-ray scattering measurement is performed on the condensation type silicone resin hardened material, and a specific parameter calculated from the measured value of the small-angle X-ray scattering , Is related to the fracture resistance and hardness of the hardened material (that is, the mechanical properties of the hardened material). That is, it was found that the hardened material having specific parameters satisfying specific requirements is excellent in hardness and fracture resistance. Moreover, it was found that the hardened | cured material whose specific parameter satisfies a specific requirement maintains intensity | strength and transparency (namely, it is excellent in heat resistance) even after exposure to high temperature. 00 [0049] Specifically, as a parameter, a hardened material system having a non-uniform domain size of 50 Å or more below is excellent in hardness, fracture resistance, and heat resistance. [0050] The size of the non-uniform domain is determined by setting the wave number of X-rays used in the measurement of small-angle X-ray scattering as the horizontal axis. As a vertical axis, a graph obtained by plotting the measured values of small-angle X-ray scattering of a sample in which a condensation-type silicone resin hardened material is impregnated with tetrahydrofuran, and the value obtained by fitting the following formula (A). [0051](Here, ξ represents the size of the network sieve, Ξ represents the size of the non-uniform domain, I (q) represents the scattering intensity, q represents the wave number, and A and B represent the fitting constants). [0052] The size of the network sieve indicated by ξ refers to a sample in which the condensation type silicone resin hardened material included in the hardened material of this embodiment is impregnated with tetrahydrofuran to expand the T3 silicon atom at the crosslinking point. The index value of the distance. [0053] The fitting constants represented by A and B are arbitrary constants used when fitting by formula (A). [0054] Formula (A) means curve fitting by the Squared Lorentz function and the Ornstein-Zernike function. The fitting parameters were obtained by the method of least squares. [0055] The range of the fit is at q = 0.022.^-1 ~ 0.13Å^-1 Range. The initial value of fitting is 1Å <ξ <50Å, 1Å <Ξ <250Å. [0056] The measurement of small-angle X-ray scattering can be performed using a small-angle X-ray scattering device equipped with a two-dimensional detector. Examples of such a device include NanoSTAR (device name, manufactured by Bruker AXS Co., Ltd.). [0057] First, a condensation type silicone resin cured product is pulverized using a freeze pulverizer. Examples of the freeze pulverizer include JFC-300 manufactured by Japan Industrial Co., Ltd. The siloxane hardened material was pulverized until the average particle diameter became 100 μm or less. [0058] Next, 90 parts by mass of tetrahydrofuran was added to 10 parts by mass of the obtained pulverized product, and left to stand for 24 hours. The swelled sample thus obtained was put into a quartz cell and subjected to small-angle X-ray analysis. [0059] X-rays, such as an X-ray generator of a rotary counter-cathode type using a Cu target, are generated at an output of 50 kV and 100 mA. The swelled sample (sample) was irradiated with the generated X-rays. [0060] For example, X-rays are irradiated through an optical system of X-rays composed of a cross-coupled Gobel mirror and three pinhole slits (the apertures of the slits are 500 μmφ, 150 μmφ, 500 μmφ from the X-ray generator side) The swelling sample. The X-rays scattered on the swelling sample were detected using a two-dimensional detector (two-dimensional Multi Wire detector, Hi-STAR). [0061] The length from the swelling sample to the detector can be, for example, 106 cm, and the size of the direct beam stopper can be, for example, 2 mmφ. The degree of vacuum in the device is, for example, 40 Pa or less. [0062] The correction of the scattering angle 2θ and the position of the direct beam is performed using, for example, individual peaks of the first (2θ = 1.513 °) and the second (2θ = 3.027 °) silver behenate. In this case, the measurable scattering angle 2θ ranges from 0.08 to 3 °. [0063] A small-angle X-ray small-angle scattering spectrum can be obtained by analyzing the obtained two-dimensional scattering image using, for example, analysis software (SAXS Ver. 4.1.29) manufactured by Bruker AXS. The small-angle X-ray scattering spectrum obtained is the wave number of X-rays on the horizontal axis (unit: Å^-1 ), The vertical axis is the measured scattering intensity. [0064] In addition, the measurement of the control scattering using a quartz cell without a swelling sample can be performed in the same manner as described above. [0065] Using the measured values obtained from individual measurements, the wave number of the X-rays used for the measurement of the small-angle X-ray scattering of the swelling sample is taken as the horizontal axis, and the measurement scattering from the measurement of the small-angle X-ray scattering of the swelling sample is taken as the horizontal axis. The scattering intensity of the intensity-reduced control scattering is defined as the vertical axis, and a chart plotting the measured values of the small-angle X-ray scattering of the swelling sample is plotted. The obtained graph was fitted with the above formula (A) to obtain the uneven domain size Ξ. [0066] For small-angle X-ray scattering, in general, the contrast of electron densities in sparse and dense matter from the shape of particles or cross-linking points is reflected in the scattering profile. For regions with high crosslink density (such as T3 silicon atom-intensive regions), scattering at normal small angle X-rays does not result in scattering by the difference in electron density at the crosslink point. However, by swelling the hardened material with a solvent, due to the network structure of the diffusion hardened material and the contrast between the solvent and the hardened material, scattering from the unevenness of the cross-linking points in the hardened material can be obtained. [0067] As a result of research by the inventors, it was found that the above-mentioned heterogeneity of the cross-linking points is related to the mechanical properties of the hardened material. When a hardened product is formed, when a crosslinking reaction occurs uniformly in space, a hardened product having a uniform distribution of crosslinking points is obtained. On the other hand, when a hardened product is formed, when a crosslinking reaction occurs due to spatial unevenness due to molecular fluctuations or the like, a hardened product with unevenly distributed crosslinking points is obtained. As a result of studies conducted by the inventors, it has been found that the hardened product in which the crosslinking reaction is more unevenly distributed than a predetermined standard is controlled in controlling the cross-linking reaction when the hardened product is formed, and has excellent hardness and fracture resistance. In addition, it was found that the "non-uniformity of the cross-linking points" can be quantitatively evaluated by the above-mentioned non-uniform domain size. [0068] FIG. 1 is a schematic diagram showing a state of polymerization as described above, showing the distribution of T3 silicon atoms contained in a silicone resin. In Fig. 1, the shades of color indicate the amount of T3 silicon atoms. The dots with thin colors indicate regions with less T3 silicon atoms, and the dots with thick colors indicate regions with more T3 silicon atoms. [0069] That is, before the condensation type silicone resin hardened product is swollen with tetrahydrofuran (FIG. 1 (a)), even if the density of T3 silicon atoms is not clear, it can be emphasized that the condensation type silicone resin The hardened product swells with tetrahydrofuran, forming a "non-uniform" state (region shown in Fig., Indicated by symbol A) with a small amount of T3 silicon atoms and a region where there are more T3 silicon atoms (indicated by symbol B in the figure). 1 (b)). [0070] For small-angle X-ray scattering, the scattering profile is obtained based on the comparison of the electron densities of areas A and B. The above-mentioned non-uniform domain size corresponds to the average distance between the center-to-center distances d between the area A1 and the area A2 schematically shown in FIG. 1 (b). In FIG. 1 (b), the center of the area A1 is represented by the symbol P1, and the center of the area A2 is represented by the symbol P2. [0071] The center of a region is located at the center of gravity of each region. That is, the center of the area A1, that is, P1 and the center of the area A2, that is, P1, respectively correspond to the centers of gravity of the areas A1 and A2. [0072] When T3 silicon atoms are uniformly distributed in the hardened material, since the T3 silicon atoms are uniformly distributed even in the swelling sample, the size of the non-uniform domain is reduced. That is, it means that the size of the non-uniform domain Ξ is a small hardened product, and the distribution of T3 silicon atoms is uniform. When the T3 silicon atoms are more unevenly distributed in the hardened material than a predetermined standard, the stress can be dispersed throughout the hardened material even if stress is applied to the hardened material. Therefore, a hardened system in which T3 silicon atoms are more unevenly distributed than a predetermined reference has high fracture resistance. As a result of studies conducted by the inventors, it was found that a hardened product having a non-uniform domain size Ξ of 50 Å or more has both high hardness and high fracture resistance. It is thought that T3 silicon atoms maintain strength in dense areas, and T3 silicon atoms relax stress in sparse areas. [0073] The condensation type silicone resin hardened material included in the hardened material of the present embodiment preferably has an uneven domain size Ξ of 50 Å to 600 Å. [0074] The size of the uneven domain is preferably 60 Ξ or more, more preferably 70 Å or more, even more preferably 80 Å or more, particularly preferably 90 Å or more, particularly still more preferably 100 Å or more, and even more preferably 110 Å or more, It is still more particularly preferably 120 Å or more, and still more preferably 130 Å or more. [0075] The uneven domain size Ξ is preferably 500 Å or less, more preferably 400 Å or less, even more preferably 300 Å or less, particularly preferably 200 Å or less, and even more preferably 150 Å or less. 007 [0076] The size of the non-uniform domain Ξ satisfies the hardened matter in this range, and it is suitable for device application because it meets high hardness (with Shore D hardness of 70 or more) and high fracture resistance. [0077] In this specification, the hardness measured by a type D hardness tester (rubber · plastic hardness tester) at a falling speed of 1 mm / sec is referred to as Shore D hardness. [0078] (Control method of non-uniform field size Ξ) 进行 A control method of the non-uniform field size Ξ will be described. The condensation type silicone resin hardened material included in the hardened material of this embodiment is preferably a silicone resin (hereinafter referred to as "silicone resin A") mixed with a main agent and an oligomer described later. The condensed silicone resin obtained as a component is a cured product obtained by heating and curing. At this time, the size of the non-uniform domain can be controlled by adjusting the type of the silicone resin A and the oligomer component of the raw material, the blending ratio, or the curing conditions during curing. It is more effective to adjust the hardening conditions during hardening to control the size of the non-uniform domain. [0079] Most of the silicone resin A is a material containing a cross-linking point (branched structure) forming a network structure. The oligomer component has a linear structure such as a T2 body and a D body structure, and is a material having fewer crosslinking points than the silicone resin A. Hereinafter, the silicone resin A and oligomer components will be described. [0080] "Silicon Resin A" Silicone Resin A contains a structural unit represented by the above formula (A3). Further, the silicone resin A preferably further includes a group selected from the group consisting of a structural unit represented by the formula (A1), a structural unit represented by the formula (A1 ′), and a structural unit represented by the formula (A2). 1 or more structural units. [0081] In the silicone resin A, the total content of the T1 body, the T2 body, and the T3 body is generally 70 mol% or more relative to the total content of the entire structural unit of the silicone resin A.矽 In the silicone resin A, the content of the T3 body is generally 60 mol% to 90 mol% relative to the total content of the entire structural unit of the silicone resin A. The weight average molecular weight of silicone resin A in terms of polystyrene is usually 1500 to 8000. [0082] In the silicone resin A, the total content of the T1 body, the T2 body, and the T3 body is preferably 80 mol% or more, and more preferably 90 mol% relative to the total content of the entire structural unit of the silicone resin A. Above, still more preferably above 95 mol%. [0083] In the silicone resin A, the content of the T3 body is preferably 65% or more and 90% or less, and more preferably 70% or more and 85% or less, relative to the total content of the entire structural unit of the silicone resin A. [0084] The polystyrene equivalent weight average molecular weight of the silicone resin A is preferably 1,500 or more and 7,000 or less, and more preferably 2,000 or more and 5,000 or less. [0085] As the silicone resin A, a commercially available silicone resin can be used. [0086] The silicone resin A preferably has a silanol group (Si-OH). In the silicone resin A, the silicon atom having a silanol group is preferably 1 to 30 mole%, more preferably 5 to 27 mole%, and even more preferably to all the silicon atoms contained in the silicone resin A. 10 to 25 mole%. In the case of the silicone resin A, if the content of the silicon atom having a silanol group is within the above-mentioned range, since the rate of progress of hardening is within an appropriate range, the structure is controlled by the hardening conditions of the silicone resin described later. The combination can effectively control the mechanical properties such as hardness and strength of the hardened material. [0087] In the silicone resin A, the silicon atom having an alkoxy group is preferably more than 0 mol% and 20 mol% or less, more preferably, all silicon atoms contained in the silicone resin A. More than 0 mole% and 10 mole% or less, more preferably 1 mole% or more and 10 mole% or less. In the silicone resin A, if the content of silicon atoms having an alkoxy group is within the above-mentioned range, the flowability of the silicone resin composition obtained by dissolving the silicone resin in a solvent becomes an appropriate range, and the silicon is improved. The operability of the oxygen resin composition. [0088] Silicone resin A can be synthesized using an organic silicon compound having a functional group capable of generating a siloxane bond as a starting material. Here, examples of the "functional group capable of generating a siloxane bond" include a halogen atom, a hydroxyl group, and an alkoxy group. Examples of the organic silicon compound corresponding to the structural unit represented by the formula (A3) include organic trihalosilane and organic trialkoxysilane. Silicone resin A can be hydrolyzed and condensed by the organic silicon compound of the starting material at a ratio corresponding to the existence ratio of each structural unit in the presence of an acid such as hydrochloric acid or a base such as sodium hydroxide. The reaction is performed to synthesize. The proportion of T3 silicon atoms contained in the siloxane resin A can be adjusted by appropriately selecting the organic silicon compound of the starting material. [0089] The content of the silicone resin A contained in the condensation-type silicone resin is preferably 60% to 100% by mass, and more preferably 70% relative to the total content of the total silicone resin contained in the condensation-type silicone resin. ~ 95 mass%. [0090] "Oligomer Components" Condensation type siloxane resin contains siloxane resin A, has a lower content than siloxane resin AT3, and has a linear structure oligomer. It is easy to produce a polymerization reaction. The area that is caused and the area that is not easily caused by the polymerization reaction. As a result, the obtained hardened material has "appropriate unevenness". [0091] [Oligomer B] As the oligomer component, for example, an oligomer containing a structural unit represented by the following formula (B1), formula (B1 '), formula (B2), or formula (B3) is mentioned. [0092](In formula (B1), formula (B1 '), formula (B2), and formula (B3), R³ Represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R⁴ Represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group or hydroxyl group having 1 to 4 carbon atoms, plural R³ And R⁴ They can be the same or different). [0093] The weight average molecular weight in terms of polystyrene of an oligomer including a structural unit represented by formula (B1), formula (B1 ′), formula (B2), or formula (B3) is preferably 1,000 to 10,000, and more It is preferably 2000 to 8000, and even more preferably 3000 to 6000. [0094] In the following description, an oligomer having a weight average molecular weight of 1,000 to 10,000 including a structural unit represented by the formula (B1), the formula (B1 ′), the formula (B2), or the formula (B3) is included. The composition is called "oligomer B". [0095] The oligomer B is preferably (a) an oligomer containing a T2 body or (b) an oligomer containing a D body, more preferably an oligomer satisfying (a) and (b), that is, (c) An oligomer comprising a T2 body and a D body. [0096] (a) T2 oligomer As (a) T2 oligomer, its structural unit represented by formula (B2), preferably R⁴ The content of the structural unit of an alkoxy group or a hydroxyl group of 1 to 4 carbons, that is, the content of the T2 body is 30 to 60 mole%, and more preferably 40 to 55 mole%. [0097] When the oligomer B is (a) an oligomer containing a T2 body, if the content of the T2 body is within the above-mentioned range, the condensation type silicone resin secures the silicone resin A and the oligomer B. It has good solubility and shows good curing reactivity during thermal curing. (B) an oligomer containing a D-form as (b) an oligomer containing a D-form, which includes one represented by formula (B1), formula (B1 '), formula (B2), or formula (B3) The siloxane resin having a structural unit is preferably a siloxane resin having an average composition formula represented by the following formula (I).(Where R⁵ Represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R⁶ Represents an alkyl group having 1 to 10 carbon atoms, an aryl group or hydrogen atom having 6 to 10 carbon atoms, n represents a real number satisfying 1 <n <2, and m represents a real number satisfying 0 <m <1). [0099] The oligomer B having an average composition formula represented by the above formula (I) includes the above-mentioned T-form and D-form. [0100] In formula (I), R⁵ Methyl is preferred, R⁶ A methyl group or a hydrogen atom is preferred. Preferably, n is a real number satisfying 1 <n ≦ 1.5, and m is a real number satisfying 0.5 ≦ m <1, more preferably n is a real number satisfying 1.1 ≦ n ≦ 1.4, and m is a real number satisfying 0.55 ≦ m ≦ 0.75. Real number. When n and m in the formula (I) fall within these ranges, the compatibility between the oligomer B and the silicone resin A becomes good. [0101] Among all the structural units included in the oligomer B, the structural unit represented by formula (B1) and the structural unit represented by formula (B1 '), 2 R⁴ One of them is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and the other is an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group. The structural unit is "D1 form". [0102] Among all the structural units included in the oligomer B, the structural unit represented by the formula (B2), R⁴ The structural unit of an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms is "D2 body". [0103] When the oligomer B is (b) an oligomer containing a D form, the total content of the D1 form and the D2 form among the total structural units included in the oligomer B is preferably 5 to 80 moles. %, More preferably 10 to 70 mole%, even more preferably 15 to 50 mole%. (C) an oligomer containing a T2 body and a D body (c) an oligomer containing a T2 body and a D body, which satisfies (a) an oligomer containing a T2 body and (b) a containing D body The oligomers are the requirements of both parties. [0105] Among all the structural units included in the oligomer B, the structural unit represented by formula (B1) and the structural unit represented by formula (B1 '), 2 R⁴ The structural unit which is an alkoxy group or a hydroxyl group having 1 to 4 carbon atoms is a T1 body. [0106] Among all the structural units included in oligomer B, the structural unit represented by formula (B2), R⁴ The structural unit having an alkoxy group or a hydroxyl group having 1 to 4 carbon atoms is a T2 body. [0107] Among all the structural units included in the oligomer B, the structural unit represented by the formula (B3) is a T3 body. [0108] When the oligomer B is (c) an oligomer containing a T2 body and a D body, among the total structural units included in the oligomer B, the total content of the T1 body, T2 body, and T3 body, The molar ratio of the content of the D body (T body: D body) is preferably 60:40 to 90:10. [0109] The oligomer B corresponds to each of the above-mentioned structural units constituting the siloxane resin, and an organic silicon compound having a functional group capable of generating a siloxane bond can be synthesized as a starting material. Here, examples of the "functional group capable of generating a siloxane bond" include a halogen atom, a hydroxyl group, and an alkoxy group. [0110] Examples of the organic silicon compound corresponding to the structural unit represented by the formula (B3) include organic trihalosilane and organic trialkoxysilane. Examples of the organic silicon compound corresponding to the structural unit represented by the formula (B2) include an organic dihalosilane and an organic dialkoxysilane. [0111] The oligomer B can be hydrolyzed and condensed by converting the organosilicon compound of the starting material at a ratio corresponding to the existence ratio of each structural unit in the presence of an acid such as hydrochloric acid or a base such as sodium hydroxide. It is made to react and synthesize | combine. By appropriately selecting the organic silicon compound of the starting material, the existence ratio of the silicon atom of the T body to the silicon atom of the D body can be adjusted. [0112] The content of the oligomer B contained in the condensation silicone resin is preferably 0.1 to 20% by mass, and more preferably 0.2 to 15% with respect to the total content of the all silicone resin contained in the condensation silicone resin. Mass%, more preferably 0.5 to 10 mass%. [0113] The content of the oligomer B contained in the condensation-type silicone resin is preferably 0.1% to 20% by mass, and more preferably, relative to the content of the silicone-type resin A contained in the condensation-type silicone resin. 1 mass% to 15 mass%, and even more preferably 5 mass% to 12 mass%. [0114] "Oligomer C" (1) As another oligomer component, for example, it may include a structural unit represented by the above formula (A1), the above formula (A1 '), the above formula (A2), or the above formula (A3) The content of the structural unit represented by the above formula (A3) is relative to the total content of the structural unit represented by the above formula (A1), the above formula (A1 '), the above formula (A2) and the above formula (A3) Silicone resin with a ratio of 0 to 30 mol% and a polystyrene equivalent weight average molecular weight of less than 1500. In the following description, such a silicone resin is referred to as "oligomer C". [0115] The ratio of the content of the oligomer C-based T3 silicon atom to the total content of the T1 silicon atom, the T2 silicon atom, and the T3 silicon atom is 0 to 30 mol%, and the weight average molecular weight in terms of polystyrene is less than 1500. Of silicone. The ratio of the content of the T3 silicon atom to the total content of the T1 silicon atom, the T2 silicon atom, and the T3 silicon atom is preferably 0 to 25 mol%. [0116] It is preferable that the oligomer C has substantially no silicon atom (hydrosilyl group) bonded to a hydrogen atom and a silicon atom bonded to an alkenyl group. When the oligomer C has a silicon atom or a hydrosilyl group bonded to an alkenyl group, the heat resistance of the hardened product of this embodiment tends to decrease. [0117] The oligomer C is preferably an oligomer having an organic polysiloxane structure represented by the following formula (2). [0118](In formula (2), R¹ And R² Represents the same meaning as before, plural R¹ And R² Can be the same or different, p² , Q² , R² , A² And b² Expressed as [a² × q² ] / [(p² + b² × q² ) + a² × q² + (r² + q² )] = Any number from 0 to 0.3). [0119] The structure of the organopolysiloxane represented by formula (2), preferably R¹ Is one or more groups selected from the group consisting of methyl, ethyl, and phenyl, R² One or more groups selected from the group consisting of methoxy, ethoxy, isopropoxy, and hydroxyl groups, more preferably R¹ Is one or more groups selected from the group consisting of methyl and ethyl, R² It is one or more types selected from the group consisting of methoxy, ethoxy, and isopropoxy. In particular, from the viewpoint of the heat resistance of the cured product of this embodiment, R is¹ It is preferably methyl. [0120] The existence ratio of each structural unit of the oligomer C having the organic polysiloxane structure represented by formula (2) can be expressed by the existence ratio of T1 silicon atom, T2 silicon atom, and T3 silicon atom. That is, T1 silicon atom: T2 silicon atom: T3 silicon atom = [r² + q² ]: [P² + b² × q² ]: [A² × q² ]. The presence ratio of each silicon atom in oligomer C can be adjusted by appropriately adjusting p² , Q² , R² , A² And b² Value to adjust. For example, a² With q² When at least one of them is 0, there is no T3 silicon atom in the oligomer C, and only a linear or cyclic molecule is included. On the other hand, r² With q² When both are zero, only T2 silicon atoms are present in the oligomer C, and only cyclic molecules are included. [0121] The structure of the organopolysiloxane represented by formula (2), where the number of T2 silicon atoms is x₂ Let the number of T3 silicon atoms be y₂ , Set the number of T1 silicon atoms to z₂ The ratio of T3 silicon atoms in the organopolysiloxane structure represented by formula (2) is expressed as [y₂ / (x₂ + y₂ + z₂ )]. [0122] [a² × q² ] / [(p² + b² × q² ) + a² × q² + (r² + q² )] Equivalent to the existence ratio of T3 silicon atoms in the organic polysiloxane structure represented by formula (2): [y₂ / (x₂ + y₂ + z₂ )]. That is, p in equation (2)² , Q² , R² , A² And b² It is appropriately adjusted so that the T3 silicon atom existence ratio falls within a range of 0 to 0.3. [0123] An oligomer C of a condensation type silicone resin which may include a raw material of a condensation type silicone resin hardened material included in the hardened material of this embodiment, has an organic polysiloxane structure represented by formula (2) Silicone resin, preferably the ratio of the content of T3 silicon atoms to the total content of T1 silicon atoms, T2 silicon atoms, and T3 silicon atoms: [y₂ / (x₂ + y₂ + z₂ )] Is an oligomer having a weight average molecular weight of less than 1500 and a polystyrene conversion of 0 to 0.3. If the ratio of T3 silicon atoms is within this range, the ratio of T2 silicon atoms is: [x₂ / (x₂ + y₂ + z₂ )] And T1 silicon atom existence ratio: [z₂ / (x₂ + y₂ + z₂ )] Is not particularly limited. As the oligomer C, [y₂ / (x₂ + y₂ + z₂ )] Is in the range of 0 to 0.25, and more preferably in the range of 0.05 to 0.2. [0124] The oligomer C has a relatively low ratio of T3 silicon atoms, has a small branched structure, and most of them include linear or cyclic molecules. The oligomer C may be one containing only cyclic molecules, but preferably one containing a large number of linear molecules. As the oligomer C, for example, the presence ratio of T1 silicon atoms is preferred: [z₂ / (x₂ + y₂ + z₂ )] Is in the range of 0 to 0.80, more preferably in the range of 0.30 to 0.80, even more preferably in the range of 0.35 to 0.75, and particularly preferably in the range of 0.35 to 0.55. [0125] The content of the oligomer C contained in the condensation-type silicone resin is preferably 0.1% to 20% by mass, and more preferably 0.2% with respect to the total content of the all-silicone resin included in the condensation-type silicone resin. Mass% to 15% by mass, and even more preferably 0.5% to 10% by mass. [0126] The content of the oligomer C contained in the condensation-type silicone resin is preferably 0.1% to 20% by mass, and more preferably the content of the siloxane-resin A contained in the condensation-type silicone resin. 0.3 mass% to 10 mass%, and even more preferably 0.5 mass% to 5 mass%. [0127] The polystyrene-equivalent weight average molecular weight of the oligomer C is less than 1,500. When the polystyrene-equivalent weight average molecular weight of the oligomer C is too large, the crack resistance of the cured product of this embodiment may be insufficient. The polystyrene-equivalent weight average molecular weight of the oligomer C measured by GPC may be less than 1,000. The number of T1 silicon atoms, T2 silicon atoms, and T3 silicon atoms in one molecule of oligomer C is a resin having an organic polysiloxane structure represented by formula (2) so as to have a desired molecular weight. Modes are appropriately adjusted. In one embodiment, the sum of the number of T1 silicon atoms and the number of T2 silicon atoms and the number of T3 silicon atoms in the oligomer C1 molecule is preferably 2 or more. [0129] The oligomer C corresponds to each of the aforementioned structural units constituting the oligomer C, and an organic silicon compound having a functional group capable of generating a siloxane bond can be synthesized as a starting material. Here, the "functional group capable of generating a siloxane bond" means the same meaning as the above. Examples of the organic silicon compound corresponding to the structural unit represented by the formula (A3) include organic trihalosilane and organic trialkoxysilane. The oligomer C can be synthesized by hydrolyzing and condensing the organosilicon compound of such a starting material at a ratio corresponding to the existence ratio of each structural unit. [0130] In the synthesis of oligomer C, as a starting material, an organic silicon compound corresponding to the structural unit represented by the above formula (A1) and an organic silicon compound corresponding to the structural unit represented by the above formula (A1 ') are mixed. . When these organosilicon compounds are polymerized by hydrolysis and condensation reaction, the organosilicon compounds are bonded to the ends of the polymerization reaction to stop the polymerization reaction. [0131] The condensation-type silicone resin that is a raw material of the condensation-type silicone resin cured material included in the cured material of this embodiment, preferably includes the silicone resin A and an oligomer component. The oligomer component is preferably oligomer B or oligomer C. The condensation type silicone resin which is the raw material of the condensation type silicone resin hardened material included in the hardened material of this embodiment, preferably includes the silicone resin A and the oligomer B, and more preferably includes the silicone resin A, and Oligomer B, and oligomer C. [0132] Examples of other oligomer components include a silicone resin containing a structural unit represented by the above formula (A1) and a structural unit represented by the above formula (A2). The silicone resin may include a D body. (Solvent) 缩 The content of the T3 body is high in the condensation type silicone resin which is the raw material of the condensation type silicone resin hardened material included in the cured material of this embodiment. Therefore, in order to improve the operability, a solvent may be added to the condensation type silicone resin. A composition containing a condensation type silicone resin and a solvent is referred to as a "silicone resin composition". [0134] The solvent is not particularly limited as long as it can dissolve the silicone resin. As the solvent, for example, two or more solvents having different boiling points (hereinafter referred to as a solvent P and a solvent Q) can be used. [0135] As the solvent P, an organic solvent having a boiling point of less than 100 ° C is preferred. Specifically, preferred are ketone solvents such as acetone and methyl ethyl ketone; alcohol solvents such as methanol, ethanol, isopropyl alcohol, and n-propyl alcohol; hexane, cyclohexane, heptane, and benzene And other hydrocarbon-based solvents; methyl acetate, ethyl acetate and other acetate-based solvents; diethyl ether, tetrahydrofuran and other ether-based solvents. [0136] Among these, as the solvent P, alcohol solvents such as methanol, ethanol, isopropyl alcohol, and n-propyl alcohol are more preferable. [0137] The solvent Q is preferably an organic solvent having a boiling point of 100 ° C or higher. Specifically, a glycol ether solvent and a glycol ester solvent are preferred. Specific examples of the glycol ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, and ethylene glycol. Monohexyl ether, ethylene glycol monoethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Alcohol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monoethylhexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl Ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol monohexyl ether, propylene glycol monoethylhexyl ether, propylene glycol monophenyl ether, propylene glycol monobenzyl ether , Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monohexyl ether, dipropylene glycol monoethylhexyl ether, dipropylene glycol monophenyl ether Dipropylene glycol monobenzyl ether. [0139] Specific examples of the glycol ester solvent include ethylene glycol monoethyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol. Alcohol monohexyl ether acetate, ethylene glycol monoethylhexyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol monobenzyl ether acetate. [0140] Among these, as the solvent Q, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and ethylene glycol monobutyl ether acetate are more preferable. [0141] (Silicon Resin Composition) 矽 A silicone resin composition is obtained by mixing a condensation-type silicone resin and a solvent as raw materials of the condensation-type silicone resin hardened material included in the cured product of this embodiment. The silicone resin composition may include a hardening catalyst, a filler, and other components described later. [0142] The viscosity of the silicone resin composition is at 25 ° C, usually 100 to 500,000 mPa ･ s, preferably 300 to 20,000 mPa ･ s, more preferably 400 to 15000 mPa ･ s, and even more preferably 500 to 10,000 mPa ･ s. When the viscosity of the silicone resin composition is within the above-mentioned range, when the wavelength conversion material is further included, the miscibility of the condensation silicone resin and the wavelength conversion material is good, and precipitation of the wavelength conversion material is suppressed. [0143] "Manufacturing Method of Silicone Resin Composition" The mixing method of the silicone resin A, oligomer B, and oligomer C is not particularly limited, and a known method used when mixing two or more kinds of polymers can be used. Either way. For example, silicone resin A, oligomer B, oligomer C, and other components, if necessary, may be dissolved in an organic solvent, and the resulting solution may be mixed. [0144] Since the silicone resin can be more uniformly mixed, and the stability of the prepared silicone resin composition can be improved, it is preferable to dissolve the silicone resin in an organic solvent with high volatility and solubility, and then The solvent is replaced by another solvent. [0145] Specifically, first, after adding siloxane resin A to a highly volatile and soluble organic solvent (for example, the “solvent P” described above), the mixture is heated to a temperature near the boiling point of the solvent P and stirred. , And the silicone resin A is dissolved in the solvent P. Secondly, after adding oligomer B, oligomer C, and other components if necessary, the oligomer B, oligomer C, and other components if necessary are dissolved in the same manner as described above. In solvent P. Secondly, after adding a solvent having a lower volatility than the solvent P (for example, the above-mentioned "solvent Q"), the solvent P can be replaced by the solvent P by heating the concentration of the solvent P to 1% or less. . In order to perform solvent substitution efficiently, heating distillation can be performed under reduced pressure. [0146] By performing solvent substitution, it is possible to remove residual solvents, water, etc. contained in each of silicone resin A, oligomer B, oligomer C, and other components. Therefore, by replacing with a solvent, the stability of the silicone resin composition can be improved. [0147] By adjusting the hardening conditions when the condensation-type silicone resin is hardened, the size of the uneven domain of the hardened material can be controlled. 0 [0148] In order to make the uneven domain size 硬化 of the hardened material 50 or more, it is preferable to set the temperature increase rate from 80 ° C to 125 ° C to 4 ° C / min or more, and more preferably 4.5 ° C / min or more. By increasing the temperature rise rate in this temperature range, due to the activation of molecular movements in the initial hardening period of the condensation-type silicone resin, condensation reactions occur simultaneously everywhere, increasing the distance between regions where the crosslinking points are dense. When the temperature increase rate from 80 ° C to 125 ° C is 1 ° C / minute or less, it is difficult to form a dense cross-linking region (domain structure) at the initial stage of curing of the condensation type silicone resin, and the uneven domain size is more likely to be larger than 50 °. small. [0149] In addition, by increasing the rate of temperature increase from 80 ° C to 125 ° C, the condensation type silicone resin that is cured when it reaches a temperature of 120 ° C or higher may be in a gel state and may have fluidity. In such a state, a larger domain is formed early because the domain formation reaction proceeds more effectively. The larger domain thus formed is immobilized in the later hardening reaction. [0150] The heating rate from 125 ° C to 180 ° C is preferably 0.1 ° C to 7 ° C / minute. By increasing the temperature in this temperature range, the size of the uneven region can be controlled. For example, if the temperature increase rate is 0.1 ° C / min, a reaction to form a region with denser cross-linking points tends to occur, so that the size of the uneven region can be set to 100 Å or more. For example, if the temperature increase rate is 5.5 ° C./minute, the hardening reaction is ended before the reaction for forming a region having a denser cross-linking point is completed, so that the size of the uneven region may be 50 Å or more and less than 100 Å. [0151] It is preferable to keep it in a temperature range of 150 ° C or more for 30 minutes or more. By sufficiently ensuring the holding time in this temperature range, the size of the uneven domain is further increased, and the fixing is performed in a state where the size of the uneven domain is large. The size of the uneven region is a large hardened product, which is stable in energy, and has high hardness, high fracture resistance, and high heat resistance. [0152] In addition, in order to control the speed of the hardening reaction, a hardening accelerator such as a phosphoric acid-based catalyst or a metal-based catalyst may be added to the silicone resin. [0153] (Hardening catalyst) As a hardening catalyst, for example, the structural unit represented by the above formula (A1), the structural unit represented by the above formula (A1 '), and the structural unit represented by the above formula (A2) is R² In the case of an alkoxy group or a hydroxyl group, in order to promote the hydrolysis and condensation reaction, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, citric acid, propionic acid, butyric acid, lactic acid, succinic acid, etc. Organic acids. [0154] As the curing catalyst, not only acidic compounds but also basic compounds can be used. Specifically, as the curing catalyst, ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and the like can be used. [0155] As a curing catalyst, an organometallic compound catalyst may also be used. Specifically, as the curing catalyst, an organometallic compound catalyst containing aluminum, zirconium, tin, titanium, or zinc can be used. [0156] Examples of the organometallic compound catalyst containing aluminum include aluminum triacetamate and aluminum triisopropoxide. [0157] Examples of the zirconium-containing organometallic compound catalyst include zirconium tetraacetylacetonate, zirconium tributoxyacetonate, zirconium dibutoxydiacetonate, zirconium tetra-n-propoxylate , Zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium acylate, zirconium tributoxide. [0158] Examples of the tin-containing organometallic compound catalyst include tetrabutyltin, monobutyltin trichloride, dibutyltin dichloride, dibutyltin oxide, tetraoctyltin, dioctyltin dichloride, and dioxane. Octyltin, tetramethyltin, dibutyltin laurate, dioctyltin laurate, bis (2-ethylhexanoate) tin, bis (neodecanoate) tin, di-n-butylbis ( Ethylhexyl maleate) tin, di-n-butylbis (2,4-pentanedione) tin, di-n-butylbutoxychlorotin, di-n-butyldiethoxytin , Di-n-butyltin dilaurate, tin dimethyl dineodecanoate. [0159] Examples of the titanium-containing organometallic compound catalyst include titanium tetraisopropoxide, titanium tetra-n-butoxide, butyl titanate dimer, tetraoctyl titanate, and titanium acetone acetone. , Octyl glycolate titanium, ethyl acetoacetate titanium. [0160] Examples of the zinc-containing organometallic compound catalyst include zinc triacetylacetonate. [0161] Among these, from the viewpoint of the transparency of the obtained cured product, a phosphate or phosphoric acid is preferable, and a phosphoric acid is more preferable. [0162] In order to add the curing catalyst to the silicone resin at a predetermined concentration, it is preferable to dilute the curing catalyst in water, an organic solvent, a silicone-based monomer, an alkoxysilane oligomer, and the like. Add silicone resin. [0163] The content of the curing catalyst can be appropriately adjusted by considering the temperature, time, and type of the curing reaction of the silicone resin. The content of the curing catalyst is preferably from 0.01 to 10 parts by mass, more preferably from 0.01 to 5 parts by mass, and particularly preferably from 0.1 to 1 part by mass based on 100 parts by mass of the condensation type silicone resin. The following. [0164] The curing catalyst may be added to the silicone resin in advance, or may be added to the silicone resin just before the curing reaction of the silicone resin is performed. [0165] (Filler) The hardened material of this embodiment can disperse the filler in a condensation type silicone resin hardened material. As the filler, a wavelength conversion material is preferred. [0166] Examples of the wavelength conversion material include phosphors and quantum dots. Examples of the phosphor include red phosphors that emit fluorescence in a wavelength range of 570 nm to 700 nm, green phosphors that emit fluorescence in a range of 490 nm to 570 nm, and blue that emits fluorescence in a range of 420 nm to 480 nm. Color phosphors, etc. [0167] "Red Phosphor" As a red phosphor, for example, it may be composed of ruptured particles having a red ruptured surface (Mg, Ca, Sr, Ba)₂ Si₅ N₈ : Eu-activated alkaline-earth silicon nitride-based phosphor represented by Eu; composed of growing particles having an almost spherical shape as a regular crystal growth shape (Y, La, Gd, Lu)₂ O₂ S: Eu-activated rare earth oxychalcogenide-based phosphors represented by Eu. [0168] As another red phosphor, it contains an oxynitride or oxysulfide containing at least one element selected from the group consisting of Ti, Zr, Hf, Nb, Ta, W, and Mo. The phosphors of both or both include phosphors containing an oxynitride having an α-silicon nitride structure in which a part or all of the Al element is replaced by a Ga element. [0169] Examples of other red phosphors include (La, Y)₂ O₂ S: Eu-activated oxysulfide phosphors such as Eu; Y (V, P) O₄ : Eu, Y₂ O₃ : Eu-activated oxide phosphors such as Eu; (Ba, Sr, Ca, Mg)₂ SiO₄ : Eu, Mn, (Ba, Mg)₂ SiO₄ : Eu, Mn-activated silicate phosphors such as Eu, Mn; (Ca, Sr) S: Eu-activated sulfide phosphors such as Eu; YAlO₃ : Eu-activated aluminate phosphors by Eu et al .; LiY₉ (SiO₄ )₆ O₂ : Eu, Ca₂ Y₈ (SiO₄ )₆ O₂ : Eu, (Sr, Ba, Ca)₃ SiO₅ : Eu, Sr₂ BaSiO₅ : Eu-activated silicate phosphors by Eu et al. (Y, Gd)₃ Al₅ O₁₂ : Ce, (Tb, Gd)₃ Al₅ O₁₂ : Ce-activated aluminate phosphors by Ce et al. (Ca, Sr, Ba)₂ Si₅ N₈ : Eu, (Mg, Ca, Sr, Ba) SiN₂ : Eu, (Mg, Ca, Sr, Ba) AlSiN₃ : Eu-activated nitride phosphors such as Eu; (Mg, Ca, Sr, Ba) AlSiN₃ : Ce-activated nitride phosphors such as Ce; (Sr, Ca, Ba, Mg)₁₀ (PO₄ )₆ Cl₂ : Eu, Mn-activated halogenated phosphate phosphors; (Ba₃ Mg) Si₂ O₈ : Eu, Mn, (Ba, Sr, Ca, Mg)₃ (Zn, Mg) Si₂ O₈ : Eu, Mn-activated silicate phosphors such as Eu, Mn; 3.5MgO ･ 0.5MgF₂ ･ GeO₂ : Mn-activated germanate phosphors such as Mn; Eu-activated oxynitride phosphors such as α-silicon nitride; (Gd, Y, Lu, La)₂ O₃ : Eu, Bi activated oxide phosphors such as Eu, Bi; (Gd, Y, Lu, La)₂ O₂ S: Eu, Bi and other Eu, Bi activated oxysulfide phosphors; (Gd, Y, Lu, La) VO₄ : Eu, Bi-activated vanadate phosphors such as Eu, Bi; SrY₂ S₄ : Eu, Ce and other Eu, Ce activated sulfide phosphors; CaLa₂ S₄ : Ce-activated sulfide phosphors such as Ce; (Ba, Sr, Ca) MgP₂ O₇ : Eu, Mn, (Sr, Ca, Ba, Mg, Zn)₂ P₂ O₇ : Eu, Mn-activated phosphate phosphors such as Eu, Mn; (Y, Lu)₂ WO₆ : Eu, Mo activated tungstate phosphors such as Eu, Mo; (Ba, Sr, Ca)_x Si_y N_z : Eu, Ce (here, x, y, and z are integers of 1 or more) and other Eu, Ce activated nitride phosphors; (Ca, Sr, Ba, Mg)₁₀ (PO₄ )₆ (F, Cl, Br, OH): Eu, Mn, etc., activated halophosphate phosphors; ((Y, Lu, Gd, Tb)_1-x Sc_x Ce_y )₂ (Ca, Mg)_1-r (Mg, Zn)_{2 + r} Si_zq Ge_q O_{12 + δ} Etc. Ce activates silicate phosphors. [0170] Examples of other red phosphors include anions having β-diketonate, β-diketone, aromatic carboxylic acid, Bronsted acid, and the like as ligands. Red organic phosphors and fluorene-based pigments (such as dibenzo {[f, f ']-4,4', 7,7'-tetraphenyl} diindeno [ 1,2,3-cd: 1 ', 2', 3'-lm] 苝), anthraquinone pigment, chelate pigment, azo pigment, quinacridone pigment, onion pigment, Isoindolline pigments, isoindolinone-based pigments, phthalocyanine-based pigments, triphenylmethane-based basic dyes, indanthrone-based pigments, indophenol-based pigments, cyan-based pigments, dioxins Azine pigment. [0171] Among red phosphors, the peak wavelength of fluorescent light emission is 580 nm or more, preferably 590 nm or more, and the peak wavelength of fluorescent light emission is 620 nm or less, preferably 610 nm or less, which is suitable as a red phosphor. Orange phosphor is used. Examples of such an orange phosphor include (Sr, Ba)₃ SiO₅ : Eu, (Sr, Mg)₃ PO₄ )₂ : Sn²⁺ , SrCaAlSiN₃ : Eu. [0172] "Yellow Phosphor" As the yellow phosphor, for example, oxide-based, nitride-based, oxynitride-based, sulfide-based, oxysulfide-based phosphors can be cited. Specifically, with RE₃ M₅ O₁₂ : Ce (herein, RE represents at least one element selected from the group consisting of Y, Tb, Gd, Lu, and Sm, and M represents at least 1 selected from the group consisting of Al, Ga, and Sc Kind of element), M² ₃ M³ ₂ M⁴ ₃ O₁₂ : Ce (Here, M² Represents a divalent metal element, M³ Represents a trivalent metal element, M⁴ A garnet-based phosphor with a garnet structure, such as a metal element of 4 valence;₂ M⁵ O₄ : Eu (here, AE represents at least one element selected from the group consisting of Ba, Sr, Ca, Mg, and Zn, M⁵ Represents at least one element selected from the group consisting of Si and Ge) orthosilicate-based phosphors such as those represented by the group; a part of oxygen atoms that are the constituent elements of these phosphors is replaced by nitrogen atoms Oxynitride phosphors; AAEAlSiN₃ : Ce (here, AE represents at least one element selected from the group consisting of Ba, Sr, Ca, Mg, and Zn) and the like having CaAlSiN₃ Ce-activated phosphors such as structured nitride-based phosphors. 017 [0173] Examples of other yellow phosphors include CaGa₂ S₄ : Eu (Ca, Sr) Ga₂ S₄ : Eu, (Ca, Sr) (Ga, Al)₂ S₄ : Sulfide-based phosphors such as Eu; Ca_x (Si, Al)₁₂ (O, N)₁₆ : Eu-activated phosphors such as oxynitride-based phosphors having a SiAlON structure such as Eu. [0174] "Green Phosphor" As the green phosphor, for example, (Mg, Ca, Sr, Ba) Si composed of ruptured particles having a ruptured surface can be cited.₂ O₂ N₂ : Eu-activated alkaline-earth silicon oxynitride phosphors expressed by Eu; composed of ruptured particles with a ruptured surface (Ba, Ca, Sr, Mg)₂ SiO₄ : Activated alkaline earth silicate-based phosphors expressed by Eu. [0175] Examples of other green phosphors include Sr₄ Al₁₄ O₂₅ : Eu, (Ba, Sr, Ca) Al₂ O₄ : Eu-activated aluminate phosphors by Eu et al .; (Sr, Ba) Al₂ Si₂ O₈ : Eu, (Ba, Mg)₂ SiO₄ : Eu, (Ba, Sr, Ca, Mg)₂ SiO₄ : Eu, (Ba, Sr, Ca)₂ (Mg, Zn) Si₂ O₇ : Eu-activated silicate phosphors by Eu et al .; Y₂ SiO₅ : Ce, Tb and other Ce, Tb activated silicate phosphors; Sr₂ P₂ O₇ -Sr₂ B₂ O₅ : Eu-activated borate phosphate phosphors; Sr₂ Si₃ O₈ -2SrCl₂ : Eu-activated halosilicate phosphors by Eu et al .; Zn₂ SiO₄ : Mn-activated silicate phosphors such as Mn; CeMgAl₁₁ O₁₉ : Tb, Y₃ Al₅ O₁₂ : Tb and other Tb activated aluminate phosphors; Ca₂ Y₈ (SiO₄ )₆ O₂ : Tb, La₃ Ga₅ SiO₁₄ : Tb and other Tb activated silicate phosphors; (Sr, Ba, Ca) Ga₂ S₄ : Eu, Tb, Sm and other Eu, Tb, Sm activated thiogallate phosphors; Y₃ (Al, Ga)₅ O₁₂ : Ce, (Y, Ga, Tb, La, Sm, Pr, Lu)₃ (Al, Ga)₅ O₁₂ : Ce-activated aluminate phosphors such as Ce; Ca₃ Sc₂ Si₃ O₁₂ : Ce, Ca₃ (Sc, Mg, Na, Li)₂ Si₃ O₁₂ : Ce-activated silicate phosphors such as Ce; CaSc₂ O₄ : Ce-activated oxide phosphors such as Ce; SrSi₂ O₂ N₂ : Eu, (Sr, Ba, Ca) Si₂ O₂ N₂ : Eu-activated oxynitride phosphors such as Eu, Eu-activated β-silicon nitride, Eu-activated α-silicon nitride; BaMgAl₁₀ O₁₇ : Eu, Mn-activated aluminate phosphors such as Eu, Mn; SrAl₂ O₄ : Eu-activated aluminate phosphors by Eu et al. (La, Gd, Y)₂ O₂ S: Tb and other Tb-activated oxysulfide phosphors; LaPO₄ : Ce, Tb activated phosphor phosphors such as Ce, Tb; ZnS: Cu, Al, ZnS: sulfide phosphors such as Cu, Au, Al; (Y, Ga, Lu, Sc, La) BO₃ : Ce, Tb, Na₂ Gd₂ B₂ O₇ : Ce, Tb, (Ba, Sr)₂ (Ca, Mg, Zn) B₂ O₆ : K, Ce, Tb and other Ce, Tb activated borate phosphors; Ca₈ Mg (SiO₄ )₄ Cl₂ : Eu, Mn and other activated halosilicate phosphors; (Sr, Ca, Ba) (Al, Ga, In)₂ S₄ : Eu-activated thioaluminate phosphors or thiogallate phosphors by Eu et al. (Ca, Sr)₈ (Mg, Zn) (SiO₄ )₄ Cl₂ : Eu, Mn and other Eu, Mn activated halosilicate phosphors. Examples of other green phosphors include a pyridine-xylylenediamine condensed derivative, a benzooxazinone-based, a quinazolinone-based, a coumarin-based, a quinoline-based, and naphthalene Formaldehyde fluorescent pigments such as naphthalic acid imide; organic phosphors such as fluorene complexes having hexyl salicylate as a ligand. [0177] "Blue Phosphor" As the blue phosphor, BaMgAl composed of growing particles having an almost hexagonal shape as a regular crystal growth shape can be cited₁₀ O₁₇ : Eu-activated barium-magnesium-aluminate-based phosphors represented by Eu; composed of growing particles having almost spherical shapes as regular crystal growth shapes (Ca, Sr, Ba)₅ (PO₄ )₃ Cl: Europium-activated calcium halophosphate-based phosphor represented by Eu; composed of growing particles having almost cubic shape as a regular crystal growth shape (Ca, Sr, Ba)₂ B₅ O₉ Cl: Eu-activated alkaline-earth chloroborate phosphors expressed by Eu; (Sr, Ca, Ba) Al composed of broken particles with a broken surface₂ O₄ : Eu or (Sr, Ca, Ba)₄ Al₁ 4O₂₅ : Eu-activated alkaline earth aluminate-based phosphors, represented by Eu. [0178] Examples of other blue phosphors include Sr₂ P₂ O₇ : Sn-activated phosphate phosphors such as Sn; Sn₄ Al₁₄ O₂₅ : Eu, BaMgAl₁₀ O₁₇ : Eu, BaAl₈ O₁₃ : Eu-activated aluminate phosphors by Eu et al .; SrGa₂ S₄ : Ce, CaGa₂ S₄ : Ce-activated thiogalatate phosphor; Ce and others; (Ba, Sr, Ca) MgAl₁₀ O₁₇ : Eu, BaMgAl₁₀ O₁₇ : Eu-activated aluminate phosphors such as Eu, Tb, Sm; (Ba, Sr, Ca) MgAl₁₀ O₁₇ : Eu, Mn-activated aluminate phosphors such as Eu, Mn; (Sr, Ca, Ba, Mg)₁₀ (PO₄ )₆ Cl₂ : Eu, (Ba, Sr, Ca)₅ (PO₄ )₃ (Cl, F, Br, OH): Eu-activated halophosphate phosphors such as Eu, Mn, Sb; BaAl₂ Si₂ O₈ : Eu, (Sr, Ba)₃ MgSi₂ O₈ : Eu-activated silicate phosphors by Eu et al .; Sr₂ P₂ O₇ : Eu-activated phosphate phosphors such as Eu; ZnS: Ag, ZnS: sulfide phosphors such as Ag, Al; Y₂ SiO₅ : Ce-activated silicate phosphors such as Ce; CaWO₄ Tungstate phosphors, etc .; (Ba, Sr, Ca) BPO₅ : Eu, Mn, (Sr, Ca)₁₀ (PO₄ )₆ ･ NB₂ O₃ : Eu, 2SrO ･ 0.84P₂ O₅ ･ 0.16B₂ O₃ : Eu, Mn-activated borate phosphate phosphor; Eu₂ Si₃ O₈ ･ 2SrCl₂ : Eu-activated halosilicate phosphors. [0179] Examples of other blue phosphors include naphthalene dimethyl imine-based compounds, benzoxazole-based compounds, styryl-based compounds, coumarin-based compounds, pyrazoline-based compounds, and triazole-based compounds. Fluorescent pigments such as compounds; organic phosphors such as europium complexes. [0180] These types of phosphors can be used alone or in combination of two or more. [0181] "Quantum Dots" As quantum dots, for example, quantum dots of the InAs system, and quantum dots of the CdE (E = S, Se, Te) system (CdS)_x Se_1-x / ZnS, etc.). [0182] The content of the wavelength conversion material is usually 20% by mass or more and 95% by mass or less, more preferably 40% by mass or more and 95% by mass or less, with respect to the total content of the condensation type silicone resin hardened material and the wavelength conversion material. It is 50% by mass or more and 95% by mass or less, and more preferably 60% by mass or more and 95% by mass or less. [0183] In addition, the cured product of this embodiment may include a silica filler. Examples of the siloxane filler include a siloxane resin filler and a siloxane rubber filler. [0184] (Other components) The hardened product of this embodiment may contain additives such as inorganic particles and a silane coupling agent in addition to the condensation-type silicone resin hardened material and filler. [0185] (Inorganic Particles) Inorganic particles are contained in the hardened material of this embodiment, and can effectively excite the wavelength conversion material by scattering light. Moreover, in the manufacturing stage of the hardened | cured material of this embodiment, precipitation of a wavelength conversion material in the composition containing a silicone resin can be suppressed. [0186] Examples of the inorganic particles include oxides of silicon, titanium, zirconia, aluminum, iron, and zinc, carbon black, barium titanate, calcium silicate, and calcium carbonate, and silicon, titanium, and zirconia are preferred. , Aluminum and other oxides. [0187] Examples of the shape of the inorganic particles include a slightly spherical shape, a plate shape, a columnar shape, a needle shape, a whisker shape, and a fibrous shape. Since a more uniform composition is obtained, a slightly spherical shape is preferred. [0188] Although the inorganic particles included in the hardened material of this embodiment may be only one type or two or more types, it is preferably two or more types of inorganic particles having different particle sizes. Specifically, the hardened material of this embodiment is more preferably composed of inorganic particles having an average particle diameter of primary particles of 100 nm to 500 nm and inorganic particles having an average particle diameter of the same primary particles of less than 100 nm. By including two or more kinds of inorganic particles having different average particle diameters of primary particles, the excitation efficiency of the wavelength conversion material due to light scattering is improved, and the precipitation of the wavelength conversion material in the composition including the silicone resin is suppressed. [0189] The average particle diameter of the primary particles of the inorganic particles can be obtained, for example, by an image imaging method of directly observing the particles with an electron microscope or the like. Specifically, first, a liquid in which inorganic particles to be measured are dispersed in an arbitrary solvent is prepared, and the obtained dispersion is dropped on a glass slide or the like and dried. An inorganic particle can be directly dispersed on the adhesive surface of the adhesive tape, so that the inorganic particle can be attached. Secondly, the particles were directly observed by a scanning electron microscope (SEM) or a transmission electron microscope (TEM), and the size of the inorganic particles was calculated from the obtained shape, and the average particle diameter of the primary particles of the inorganic particles was obtained. [0190] The content of the inorganic particles is preferably 0.01 parts by mass or more and 100 parts by mass or less, and more preferably 0.1 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the condensation-type silicone resin cured product. (Silane coupling agent) As the silane coupling agent, for example, it is preferable to have a material selected from the group consisting of vinyl, epoxy, styryl, methacryl, acryl, amine, urea, mercapto, and sulfur. Silane coupling agent based on at least one of the group consisting of physical groups and isocyanate groups. Among these, a coupling agent having an epoxy group or a mercapto group is preferred. Specific examples of the silane coupling agent include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyl Methylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane. [0193] When the composition containing a siloxane resin includes a silane coupling agent, although the silicon atom contained in the silane coupling agent is also used as²⁹ The signal of Si-NMR is detected, but in this specification, in the calculation of the signal area of a composition including a siloxane resin, it becomes a signal that also includes a silane coupling agent. [0194] The content of the silane coupling agent is preferably 0.0001 mass parts or more and 1.0 mass parts or less, and more preferably 0.001 mass parts or more and 0.1 mass parts or less, based on 100 mass parts of the total content of the silicone resin. [0195] (Other additives) The hardened product of this embodiment may contain additives other than the materials described above. Examples of the additives other than the above-mentioned materials include a dispersant, a leveling agent, and an antifoaming agent. [0196] (Hardened material) 缩 The condensation-type silicone resin hardened material included in the hardened material of this embodiment preferably includes a structural unit represented by the above formula (A3). In addition, it is more preferable that the condensed silicone resin cured product further includes a group selected from the group consisting of a structural unit represented by the formula (A1), a structural unit represented by the formula (A1 '), and a structural unit represented by the formula (A2). One or more structural units in the group. [0197] The condensation type silicone resin hardened material included in the hardened material of this embodiment may further include the above formula (C1), the above formula (C1 '), the above formula (C2), the above formula (C3), or the above formula ( C4) represents the structural unit. [0198] The content of the T3 body in the condensation type silicone resin hardened material included in the hardened material of this embodiment is preferably 50 mol% or more relative to the total content of the entire structural unit of the condensation type silicone resin hardened material. . In other words, the content of T3 silicon atoms is preferably 50 mol% or more with respect to the total content of all silicon atoms in the condensation-type silicone resin hardened material. Furthermore, the content of T3 silicon atoms is more preferably 60 mol% or more, more preferably 70 mol% or more, and still more preferably 75 mols relative to the total content of all silicon atoms in the condensation type silicone resin hardened material. Ear%. [0199] In the case of a hardened material having a non-uniform domain size of 50 Å or more, when stress is applied, the stress can be dispersed throughout the hardened material. On the other hand, for hardened products with a smaller heterogeneous domain size than 50Å, the distribution of T3 silicon atoms is uniform. Therefore, when stress is applied, the stress cannot be dispersed throughout the hardened material, and cracks easily enter. [0200] A hardened product having a non-uniform domain size of 50 ， or more has both high hardness and high fracture resistance. For example, even under continuous heating at 250 ° C, the stress due to heating can be dispersed throughout the hardened product. [0201] According to this embodiment, it is possible to provide a hardened material having both high hardness, high fracture resistance, and high heat resistance. [0202] <Wavelength Conversion Sheet> FIG. 2 is a schematic diagram showing a wavelength conversion sheet according to this embodiment. The wavelength conversion sheet 30 is formed by using a cured product including the condensation type silicone resin cured material 40 and a filler 50 which is a wavelength conversion material dispersed in the condensation type silicone resin cured material 40. Such a wavelength conversion sheet 30 is formed by forming the hardened material of the embodiment described above as a forming material to form a thin plate. [0203] The wavelength conversion sheet 30 may include a substrate on one surface. The substrate may be appropriately selected depending on the application of the wavelength conversion sheet, and examples thereof include metal substrates such as aluminum, and transparent substrates such as quartz and sapphire. [0204] The wavelength conversion sheet of this embodiment can be suitably used for wavelength conversion sheets such as LEDs, solar cells, semiconductor lasers, photodiodes, CCDs, and CMOS. In particular, the wavelength conversion sheet of this embodiment is excellent in heat resistance, and can be suitably used in a semiconductor laser light emitting portion expected to be used at a high temperature. [0205] The wavelength conversion sheet of this embodiment may include the inorganic particles described above. By containing inorganic particles in the wavelength conversion sheet, light scattering can excite the wavelength conversion material more effectively. In addition, in the manufacturing stage of the wavelength conversion sheet, it is possible to suppress the precipitation of the wavelength conversion material in the composition containing the silicone resin. (Film thickness) The thickness (film thickness) of the wavelength conversion sheet is preferably 10 μm or more because the wavelength conversion sheet can be manufactured stably. The thickness of the wavelength conversion sheet is preferably 1 mm or less, more preferably 500 μm or less, and still more preferably 200 μm or less from the viewpoint of improving the optical characteristics or heat resistance of the wavelength conversion sheet. With the thickness of the wavelength conversion sheet being 1 mm or less, the light absorption or light scattering caused by the silicone resin can be reduced. [0207] The film thickness of the wavelength conversion sheet can be determined, for example, by measuring the film thickness at a plurality of points of the wavelength conversion sheet using a micrometer and calculating the average value. For the plurality of points, for example, in a case where the shape of the wavelength conversion sheet is a quadrangle, a total of five points including one point in the center of the wavelength conversion sheet and four points in the corner of the wavelength conversion sheet are mentioned. [0208] The wavelength conversion sheet 30 may be formed on a supporting substrate. As the supporting substrate, a substrate made of a known metal, film, glass, ceramic, paper, or the like can be used. [0209] Specific examples of the material forming the supporting substrate include transparent inorganic oxide glass such as quartz glass, borosilicate glass, and sapphire; metals such as aluminum (including aluminum alloys), zinc, copper, and iron Board or foil; cellulose acetate, polyethylene terephthalate (PET), polyethylene, polyester, polyamide, polyimide, polyphenylene sulfide, polystyrene, polypropylene, poly Films of plastics such as carbonate, polyvinyl acetal, aramid, etc .; papers laminated with the above plastics; papers coated with the above plastics; papers laminated or evaporated with the above metals; plastics laminated or evaporated with the above metals film. Among these, an inorganic oxide glass or a metal plate is preferred. [0210] The thickness of the supporting substrate is preferably 30 μm or more, and more preferably 50 μm or more. When the thickness of the supporting substrate is 30 μm or more, it has sufficient strength to protect the shape of the wavelength conversion sheet. The thickness of the supporting substrate is preferably 5,000 μm or less, and more preferably 3,000 μm or less, from the viewpoint of economy. [0211] (Manufacturing Method of Wavelength Conversion Sheet) The manufacturing method of the wavelength conversion sheet of this embodiment will be described. [0212] First, a siloxane resin composition containing a wavelength conversion material in which a wavelength conversion material is dispersed in the above-mentioned siloxane resin composition (condensation type siloxane resin + solvent) is prepared. [0213] In order to improve the diffusion of the wavelength conversion material or the coating property of the silicone resin composition containing the wavelength conversion material, the silicone resin composition containing the wavelength conversion material may include additives such as inorganic particles and an auxiliary agent. [0214] After mixing these components so as to have a predetermined composition, a well-known stirring / kneading machine is used for homogeneous mixing and dispersion to obtain a silicone resin composition containing a wavelength conversion material. Examples of well-known mixing kneading kneaders include a homogenizer, a self-transition mixer, a 3-roller, a ball mill, a planetary ball mill, and a bead mill. After mixing or dispersion, if necessary, the silicone resin composition containing the wavelength conversion material may be defoamed under vacuum or reduced pressure. [0215] Next, the obtained silicone resin composition containing a wavelength conversion material is coated on a supporting substrate. The coating of the silicone resin composition containing the wavelength conversion material can be performed using a known coating device. Examples of known coating devices include a reverse roll coater, a knife coater, a slit die coater, a direct gravure coater, an offset gravure coater, a reverse roll coater, a knife coater, Kiss Coater, Natural Roller Coater, Air Knife Coater, Roller Blade Coater, Roller Roller Coater, Double Flow Coater, Bar Coater, Winding Bar Coater, Applicator , Dip coater, curtain coater, spin coater, knife coater. Among these, since the film thickness of the obtained molded body is likely to become uniform, a slit die coater or applicator is preferred. [0216] Examples of other coating methods include printing methods such as screen printing, gravure printing, and lithographic printing. Among these, screen printing is preferred from the viewpoint of simplicity. [0217] Next, the coating film formed on the support substrate is heat-hardened to obtain a wavelength conversion sheet. The coating film is heated using a natural convection oven, a ventilation oven, a vacuum oven, an inert oven, a hot plate, a hot press, an infrared heater, and the like. Among these, a blower oven is preferable from the viewpoint of productivity. [0218] Examples of heating conditions for the coating film include a method of heating at 40 ° C to 250 ° C for 5 minutes to 100 hours. The heating time is preferably 1 to 30 hours, more preferably 2 to 10 hours, and even more preferably 3 to 8 hours. With the heating time within this range, the solvent can be sufficiently removed, and at the same time, coloring during heating can be prevented. [0219] The coating film can be hardened by applying a silicone resin composition containing a wavelength conversion material on a supporting substrate and then placing it in an environment at a temperature of 250 ° C. or lower. The coating film is cured in an environment at a temperature of from ℃ to 200 ° C. In addition, when the coating film is hardened, in order to reduce the solvent or water existing in the siloxane resin composition containing the wavelength conversion material, and to control the condensation reaction rate of the siloxane resin A and the siloxane oligomer, it can be, for example, 40 The method is performed for 5 minutes to 30 minutes at 60 ° C to 60 ° C, followed by 10 minutes to 60 minutes at 60 ° C to 100 ° C, and then for 30 minutes to 5 hours at 140 ° C to 200 ° C, and the coating film is hardened stepwise. [0220] Regarding the hardening conditions of the coating film, by increasing the temperature rise rate from 80 ° C. to 125 ° C. to 4 ° C./min or more, it is possible to increase the size of the non-uniform domain of the cured product forming the wavelength conversion sheet Ξ. [0221] In addition, by increasing the temperature increase rate from 80 ° C to 125 ° C, the coating film may be in a gel state when it reaches a temperature of 120 ° C or higher, and may have fluidity. In this state, it is preferable to perform the formation reaction of the domain more effectively and form a larger domain early. [0222] The rate of temperature increase from 125 ° C to 180 ° C is preferably 0.1 ° C to 7 ° C / minute. By this temperature rise rate in the temperature range, the size of the non-uniform domain of the hardened material forming the wavelength conversion sheet can be controlled. For example, if the heating rate is 0.1 ° C./minute, since the reaction to form regions with denser cross-linking points tends to occur, the size of the non-uniform domain of the hardened product forming the wavelength conversion sheet can be set to 100 ° or more. For example, if the heating rate is 5.5 ° C / min, the curing reaction is terminated before the reaction to form a region with a denser cross-linking point is completed. Therefore, the size of the non-uniform domain of the hardened product forming the wavelength conversion sheet may be set to 50 ° or more. Under 100 满. [0223] It is preferable to keep it in a temperature range of 150 ° C or more for 30 minutes or more. By sufficiently ensuring the holding time in this temperature range, the uneven domain size of the hardened material forming the wavelength conversion sheet is further increased, and the uneven domain size is fixed to be large. [0224] Since the wavelength conversion sheet of this embodiment uses the hardened material of this embodiment as a forming material, it has both high hardness, high fracture resistance, and high heat resistance, and has become a highly reliable person. [0225] <Light-Emitting Device> FIG. 3 is a schematic diagram of the light-emitting device of this embodiment. The light emitting device 100 includes the above-mentioned wavelength conversion sheet 30 and a light source 60. [0226] As the light source 60, a known light source such as a mercury lamp or a semiconductor light emitting element can be used. In the light-emitting device of this embodiment, a light source that irradiates high-density energy such as high-brightness LEDs, semiconductor lasers, and a light source that emits high-energy ultraviolet rays with a wavelength of 400 nm or less and 300 nm or less such as UV-LEDs is suitable. The light source 60 includes a substrate 70 and a light emitting element 80 provided on one surface of the substrate 70. [0227] The wavelength conversion sheet 30 is disposed at a position where the light L1 emitted from the light source 60 is incident. [0228] In such a light emitting device 100, the light L1 emitted from the light source 60 is incident on the wavelength conversion sheet 30. In the wavelength conversion sheet 30, the filler 50 of the wavelength conversion material converts the light L1 into converted light L2 having a wavelength different from the light L1. The converted light L2 is emitted from the wavelength conversion sheet 30. [0229] FIG. 4 is a cross-sectional view showing the structure of a light-emitting device including the wavelength conversion sheet according to this embodiment. The light emitting device 1000 includes a substrate 110, a semiconductor laser element (light source) 120, a light guide 130, a wavelength conversion sheet 140, and a reflector 150. The wavelength conversion sheet 140 can use the above-mentioned constituents. [0230] The semiconductor laser element 120 is set on the substrate 110. [0231] The light guide 130 enters the laser light La emitted from the semiconductor laser element 120 inside, and guides the laser light La inside. The semiconductor laser element 120 is optically connected to one end of the light guide 130 and the wavelength conversion sheet 140 is optically connected to the other end. The light guide 130 has a hammer shape that gradually decreases in width from one end side to the other end side, and has a structure in which the laser light La emitted from the semiconductor laser element 120 is collected on the wavelength conversion sheet 140. [0232] The reflector 150 is a bowl-shaped element arranged around the wavelength conversion sheet 140, and the curved surface facing the wavelength conversion sheet 140 becomes a light reflection surface. The reflector 150 is configured to deflect the light emitted from the wavelength conversion sheet 140 toward the front of the device (the irradiation direction of the laser light La). [0233] The laser light La irradiated by the wavelength conversion sheet 140 is converted into white light Lb by the wavelength conversion material contained in the wavelength conversion sheet 140, and is output from the light emitting device 1000. [0234] Although the light emitting device 1000 includes one semiconductor laser element 120, it may include two or more. [0235] FIG. 5 is a cross-sectional view showing a modified example of the light-emitting device. In the description of FIG. 5 and the following, the same components as those described in FIG. 4 are assigned the same symbols as those in FIG. 4. [0236] The light-emitting device 1100 includes a plurality of substrates 110, a plurality of semiconductor laser elements (light sources) 120, a plurality of optical fibers 180, a light guide 130, a wavelength conversion sheet 140, a reflector 150, and a transparent substrate. Support 190. [0237] The optical fiber 180 enters the laser light La emitted from the semiconductor laser element 120 inside, and guides the laser light La inside. Semiconductor laser elements 120 are optically connected to one end of the plurality of optical fibers 180, respectively. In addition, a plurality of optical fibers 180 are bundled at the other end side, and are optically connected to the light guide 130 at the other end in a state of being bundled together. The light guide unit 130 enters the laser light La emitted from the semiconductor laser element 120 internally, and after the internal light guide laser light La is emitted toward the front of the device. The light guide 130 may have a function of collecting the laser light La emitted from the front of the device. [0238] The wavelength conversion sheet 140 is disposed in a state supported by the transparent support 190, is separated from the light guide portion 130, and is opposed to the light guide portion 130. The transparent support 190 is provided so as to cover the opening portion of the mirror 150 and is provided in front of the device. The transparent support 190 is made of a transparent material that does not deteriorate due to the heat generated during the use of the device, and is made of, for example, a glass plate. [0239] The laser light La radiated by the wavelength conversion sheet 140 is converted into white light Lb by the wavelength conversion material contained in the wavelength conversion sheet 140, and is output from the light emitting device 1100. [0240] The light emitting devices 1000 and 1100 separate the light source (semiconductor laser element 120) and the light emitting section (wavelength conversion sheet 140) as described above. This makes it easy to reduce the size of the light-emitting device or to improve the design. [0241] The light-emitting device configured as described above is highly reliable because it has a wavelength conversion sheet of this embodiment that has both high hardness, high fracture resistance, and high heat resistance. [0242] <Seal Element, Semiconductor Light-Emitting Device> FIG. 6 is a cross-sectional view of a semiconductor light-emitting device 200 according to this embodiment. The semiconductor light emitting device of this embodiment can also be used as a light source of the light emitting device of FIGS. 3 to 5. [0243] The semiconductor light emitting device 200 includes a substrate 210, a semiconductor light emitting element 220 disposed on the substrate, and a sealing element 230 that seals the semiconductor light emitting element 220. The sealing element 230 uses the above-mentioned hardened material as a forming material. The semiconductor light emitting element 220 is sealed by being covered with the substrate 210 and the sealing element 230 to isolate the outside air. [0244] As described above, the hardened material constituting the sealing element 230 has both high hardness, high fracture resistance, and high heat resistance. In addition, compared with the sealing portion made of quartz glass, the transmittance of UV light is the same, and the light extraction efficiency is improved and inexpensive. Therefore, the semiconductor light-emitting device having the sealing element 230 of this embodiment is less likely to be broken and has high reliability. [0245] In addition, since the hardened material constituting the sealing element 230 has a condensation type silicone resin hardened material as a constituent element, it is less likely to be deteriorated by UV light. Therefore, the semiconductor light emitting device 200 having the sealing element 230 and the semiconductor light emitting element 220 of the light source as the UV light source having a light emission wavelength of 400 nm or less and further 300 nm or less are not easily deteriorated and have high reliability. [0246] The semiconductor light emitting element 220 is not limited to those emitting UV light. The light emitting wavelength of the semiconductor light emitting device 220 may be in an ultraviolet region (for example, 10 to 400 nm), a visible light region (for example, more than 400 nm and less than 830 nm), or an infrared region (for example, 830 nm to 1000 nm). [0247] The sealing element configured as described above has a high reliability because the hardened material of this embodiment described above is used as a forming material. Furthermore, since the semiconductor light-emitting device configured as described above has a sealing element using the hardened material of the embodiment described above as a forming material, it is highly reliable. [0248] Although the preferred embodiments of the present invention will be described using the drawings 1 to 6, the embodiments of the present invention are not limited to these examples. The shapes, combinations, and the like of the constituent elements shown in the above examples can be variously changed according to design requirements and the like. [Examples] [0249] Although the present invention will be described more specifically with reference to the following examples, the present invention is not limited to the following examples. [0250] In this example, the obtained sample was evaluated or measured by the following method. [0251] <Crack Resistance> 1.2 1.2 g of a silicone resin composition was added to an aluminum cup with a diameter of 4 cm to harden it. The obtained hardened | cured material was visually evaluated for the presence or absence of a crack. [0252] <Strength> A test piece having a width of 10 mm, a length of 30 mm, and a thickness of 1 mm was prepared, and a load was applied at a rate of 2.0 mm / sec in the center of the test piece under the following conditions, and the load and fracture displacement of the test piece were measured. The number of trials (n number) was set to 5 and the arithmetic mean was determined to be the measurement result. [0253] The average value of the load (bending failure load, unit N) when the test piece was broken was defined as the bending strength. A test piece having a flexural strength of 20 MPa or more was determined to be good. [0254] The average value of the fracture displacement (amount of deformation at the time of failure, unit mm) at the time of fracture of the test piece was determined as the distortion at the time of fracture. A test piece having a distortion at the time of rupture of 3.0% or more was regarded as good. [0255] <Heat resistance> 加热 The condensation-type silicone resin hardened product (a disk-like shape having a diameter of 4 cm and a thickness of 500 μm) was heated in an oven at 250 ° C. Condensation-type silicone resin hardened | cured material before and after heating was evaluated for light transmittance and appearance (presence or absence of wrinkles and cracks) at a wavelength of 400 nm. [0256] <Shore Hardness> The Shore D hardness was measured under the following conditions for a condensation type silicone resin hardened product (a disk shape having a diameter of 4 cm and a thickness of 1500 μm). [0257] An automatic low-pressure loader (manufactured by Teclock Co., Ltd., model number GS-610) for a hardness tester, and a device equipped with a hardness meter (manufactured by Teclock Co., Ltd., model GS-720G, model D) was used as a measuring device. The hardness tester is a rubber and plastic hardness tester. Using this measuring device, Shore D hardness was measured at a falling rate of 1 mm / sec on a cured product of the condensation type silicone resin. The measurement was performed at 5 points, and the average value was calculated. [0258] A condensation type silicone resin cured product having a Shore D hardness of 70 or more was determined to be good. [0259] <Transmittance> Prepare a 500 μm thick condensation type silicone resin hardened product. About the obtained hardened | cured material, the transmittance with respect to the light of a wavelength of 400 nm was measured on the following conditions. Device name: JASCO V-670 UV-Vis near-infrared spectrophotometer integrating sphere unit (ISN-723 / B004861118) 瞄 Scanning speed (C): 1000nm / min Measuring wavelength: 200 ～ 800nm Data reading interval (L): 1.0nm [0260] A hardened material having a transmittance of 85% or more is considered good. [0261] <Gel Permeation Chromatography (GPC) Measurement> 测定 The sample (silicone resin) was dissolved in the eluent, and then filtered through a membrane filter having a pore size of 0.45 μm to prepare a measurement solution. With respect to the obtained prepared solution, the weight average molecular weight (Mw) in terms of standard polystyrene was measured under the following conditions. [Solids]²⁹ Si-NMR> (i) A hardened product was produced, and the peak of the silicon atom belonging to the T body was measured for the obtained hardened product under the following conditions. Specifically, the presence of the peak in the region of -80 ppm to -40 ppm as the peak of the silicon atom attributed to the T body was confirmed. [0263] <Uneven field size> (Measurement conditions) [0264] First, the silica hardened product was pulverized using a freeze pulverizer. Examples of the freeze pulverizer include JFC-300 manufactured by Japan Industrial Co., Ltd. After the siloxane hardened body was left in liquid nitrogen for 10 minutes, it was pulverized for 15 minutes. FIG. 7 is a SEM photograph of the sintered silica hardened material. [0265] Next, 90 parts by mass of tetrahydrofuran was added to 10 parts by mass of the obtained pulverized product, and left to stand for 24 hours. The obtained swelled sample was put into a quartz cell and subjected to small-angle X-ray analysis. [0266] The swelling sample (sample) was irradiated with X-rays, and the small-angle X-ray scattering of the swelling sample was measured. The length from the swelling sample to the detector can be, for example, 106 cm, and the size of the direct beam stopper can be 2 mmφ. [0267] The correction of the scattering angle 2θ and the position of the direct beam is performed using, for example, individual peaks of the first (2θ = 1.513 °) and the second (2θ = 3.027 °) silver silver behenate. The measurable scattering angle 2θ ranges from 0.08 to 3 °. [0268] A small-angle X-ray small-angle scattering spectrum can be obtained by analyzing the measurement results using analysis software (SAXS Ver. 4.1.29) manufactured by Bruker AXS. In addition, the same measurement is carried out as described above, even for a control measurement using a quartz cell without a swelling sample. [0269] Using the measured values obtained from individual measurements, the wave number of X-rays used for the measurement of the small-angle X-ray scattering of the swelling sample is taken as the horizontal axis, and the measurement scattering measured from the small-angle X-ray scattering of the swelling sample is taken as the horizontal axis. The scattering intensity of the intensity-reduced control scattering is defined as the vertical axis, and a chart plotting the measured values of the small-angle X-ray scattering of the swelling sample is plotted. The obtained graph was fitted with the above formula (A) to obtain the non-uniform domain size Ξ. The range of fitting is with q = 0.022Å^-1 ~ 0.13Å^-1 Range. The initial value of fitting is 1Å <ξ <50Å, 1Å <Ξ <250Å. [Example 1] (1) The following siloxane resin A (Mw = 3500), low molecular weight siloxane (Mw <1000), and alkoxy siloxane oligomer (modified siloxane, Mw = 3400) All are "condensed silicone resins." The alkoxysilyl oligomer is equivalent to "oligomer B" in this specification. The low-molecular-weight silica is equivalent to "oligomer C" in this specification. [0271] The total area of the peaks of the alkoxysiloxy oligomers existing in a region having a weight average molecular weight of 7500 or more, the total of the total area of the peaks is 20% or more, and The total area of the peaks is more than 30% relative to the total area of the peaks. [0272] Table 1 shows the structural units included in the silicone resin A. The structural units included in the low-molecular-weight silicon oxygen are shown in Table 2. The alkoxysilyl oligomer is a resin composed of 95% or more of the structural units shown in Table 3. [0273] (silicone resin A) [0274](Low-molecular-weight silicon oxide)(Alkoxysilyl oligomer) (0278)[0279] The existence ratio of the structural units of each of the condensation-type silicone resins shown in Tables 1 to 3 is a value calculated from the measurement results of the solution NMR measured under the following conditions. [0280] ＜¹ H-NMR measurement conditions ＞ [0281] <²⁹ Si-NMR measurement conditions ＞ [0282] By adding 789.60 g of silicone resin A, 96.00 g of propyl acetate, and 314.40 g of isopropyl alcohol into the flask set in the oil bath, the silicone resin was stirred at 80 ° C. A is dissolved in a solvent. By adding the obtained solution, 8.47 g of low-molecular-weight silicon oxide and 75.08 g of alkoxy-silica oligomer were added, and the mixture was stirred for more than 1 hour to dissolve the low-molecular-weight silicon oxide and the alkoxy-silica oligomer in a solvent . (2) To the resulting solution, 274.49 g of 2-butoxyethyl acetate and 0.22 g of 3-glycidoxypropyltrimethoxysilane (silane coupling agent) were added. [0283] The obtained mixture was set in an evaporator, the temperature of the mixture was set to 85 ° C., and the pressure reduction degree of the evaporator was set to 2.0 kPa. Then, propyl acetate and isopropyl alcohol were distilled off to the mixture. The total concentration of propyl acetate and isopropyl alcohol in the mixture is 1% by mass or less. [0284] A silicone resin composition was obtained by adding 2 parts by mass of a curing catalyst (containing 15% by mass of phosphoric acid) to 100 parts by mass of the obtained mixture, followed by sufficient stirring. [0285] The obtained siloxane resin composition was gradually heated from room temperature (25 ° C) to 80 ° C, 125 ° C, and 180 ° C, and held at 80 ° C for 30 minutes, at 125 ° C for 30 minutes, and at 180 ° C. Hold for 60 minutes to perform the step curing. Specifically, the temperature was raised from room temperature (25 ° C) to 80 ° C at 1.4 ° C / min, and the temperature was maintained at 80 ° C for 30 minutes. Next, the temperature was raised to 125 ° C at 4.5 ° C / min, and the temperature was maintained at 125 ° C for 30 minutes. Next, the temperature was raised to 180 ° C at 5.5 ° C / min, and the temperature was maintained at 180 ° C for 60 minutes. Then, it was allowed to cool from 180 ° C to 25 ° C over 100 minutes to obtain a cured product. 0 [0286] In the obtained hardened solid²⁹ Si-NMR measurement confirmed the peak of the silicon atom assigned to the T body. [0287] A SAXS profile was prepared from the results of the SAXS measurement for the obtained hardened material. The SAXS outline is shown in FIG. 8. In FIG. 8, the horizontal axis Q represents the wave number (unit: Å) of X-rays used for measurement of small-angle X-ray scattering.^-1 ). The vertical axis I indicates the scattering intensity in which the measured scattering intensity measured from the small-angle X-ray scattering of the condensed silicone resin hardened body is reduced by the control scattering. From the prepared SAXS profile, it was confirmed that the size of the uneven region Ξ was 74Å. [0288] The obtained hardened product has no cracking and good cracking resistance. For the obtained hardened product, the bending strength was 35 MPa, and the bending strain was 5%, and the strength was good. The hardness of Shore D is 73, which is good for the obtained hardened material. The transmittance of the obtained hardened product is 92%, which is good. [0289] The obtained cured product was subjected to a heat resistance test at 250 ° C for 100 hours. In the appearance of the cured product after the heat resistance test, no occurrence of wrinkles or cracks was observed. The transmittance of the cured product after the heat resistance test was 92%, and the transparency was maintained. [Example 2] (1) The thermal curing conditions of the silicone resin composition in Example 1 were the same as in Example 1 except that the temperature rising rate from 125 ° C to 180 ° C was changed to 0.1 ° C / min. The same procedure was performed to obtain a cured product. 029 [0291] in the obtained hardened solid²⁹ Si-NMR measurement confirmed the peak of the silicon atom assigned to the T body. [0292] A SAXS profile was prepared from the results of SAXS measurement for the obtained hardened material. The created SAXS outline is shown in FIG. 8. From the prepared SAXS contour, it was confirmed that the size of the uneven region 域 was 134Å. [0293] The obtained hardened product has no cracking and good cracking resistance. For the obtained hardened material, the bending strength is 28 MPa, the bending strain is 5%, and the strength is good. For the obtained hardened material, the Shore D hardness is 76, which is good. The transmittance of the obtained hardened product is 92%, which is good. [0294] The obtained cured product was subjected to a heat resistance test at 250 ° C for 100 hours. In the appearance of the cured product after the heat resistance test, no occurrence of wrinkles or cracks was observed. The transmittance of the cured product after the heat resistance test was 92%, and the transparency was maintained. [0293] [Example 3] Table 4 shows the structural units included in the following silicone resin B (Mw = 3500). The existence ratio of the structural unit of the silicone resin B shown in Table 4 is a value calculated based on the measurement results of the solution NMR described above. The silicone resin B corresponds to the "condensed silicone resin" in this specification. [0296] (silicone resin B) [0297][0298] 80 parts by mass of a silicone resin and 20 parts by mass of 2-butoxyethyl acetate were added to a flask, and the mixture was stirred to obtain a mixture. Then, 2 parts by mass of a curing catalyst (containing 15% by mass of phosphoric acid) was added to 100 parts by mass of the obtained mixture, and the mixture was sufficiently stirred to obtain a silicone resin composition. [0299] The obtained siloxane resin composition was heat-cured under the same conditions as the heat-curing conditions of the siloxane resin composition of Example 2 to obtain a cured product. [0300] In the obtained hardened solid²⁹ Si-NMR measurement confirmed the peak of the silicon atom assigned to the T body. [0301] A SAXS profile was prepared from the results of SAXS measurement for the obtained hardened material. From the prepared SAXS profile, it was confirmed that the size of the uneven domain Ξ was 213Å. 030 [0302] The obtained hardened product has no cracks and good crack resistance. For the obtained hardened product, the bending strength is 35 MPa, the bending strain is 5.0%, and the strength is good. For the obtained hardened material, the Shore D hardness is 74, which is good. The transmittance of the obtained hardened product is 92%, which is good. [0303] The obtained cured product was subjected to a heat resistance test at 250 ° C for 100 hours. In the appearance of the cured product after the heat resistance test, no occurrence of wrinkles or cracks was observed. The transmittance of the cured product after the heat resistance test was 92%, and the transparency was maintained. [Comparative Example 1] 例 80 parts by mass of silicone resin B and 20 parts by mass of 2-butoxyethyl acetate were mixed by stirring to obtain a silicone resin composition. [0305] The obtained siloxane resin composition was hardened by heating it from room temperature to 150 ° C and holding it at 150 ° C for 5 hours. Specifically, the temperature was raised from room temperature (25 ° C) to 40 ° C at 3 ° C / min, and the temperature was maintained at 40 ° C for 10 minutes. Next, the temperature was raised to 150 ° C at 4 ° C / min, and the temperature was maintained at 150 ° C for 5 hours. Then, it was allowed to cool to room temperature over 2 hours to obtain a cured product. [0306] In the obtained hardened solid²⁹ Si-NMR measurement confirmed the peak of the silicon atom assigned to the T body. [0307] A SAXS profile was prepared from the results of SAXS measurement for the obtained hardened material. The created SAXS outline is shown in FIG. 8. From the prepared SAXS profile, it was confirmed that the size of the uneven region Ξ was 36Å. [0308] The obtained hardened product was cracked, and the crack resistance was poor. The hardened product obtained is not a measurable value of flexural strength, Shore D hardness, and transmittance. [0309] From the above, it is understood that the cured product of the present invention is useful. [Industrial Applicability] 03 [0310] According to the present invention, it is possible to provide a hardened material having both high hardness, high fracture resistance, and high heat resistance. In addition, a wavelength conversion sheet, a light-emitting device, a sealing element, and a semiconductor light-emitting device using the cured material as a forming material can be provided.

[0311]

10‧‧‧ silicone resin

30‧‧‧ Wavelength Conversion Sheet

40‧‧‧polymer

50‧‧‧ filler

60‧‧‧light source

70, 110, 210‧‧‧ substrate

80‧‧‧Light-emitting element

100, 1000, 1100 ‧‧‧ light-emitting devices

120‧‧‧semiconductor laser element (light source)

130‧‧‧light guide

140‧‧‧wavelength conversion sheet

150‧‧‧mirror

160‧‧‧laser light

170‧‧‧ white light

180‧‧‧ Optical Fiber

190‧‧‧Transparent support

200‧‧‧Semiconductor light emitting device

220‧‧‧Semiconductor light emitting element

230‧‧‧sealing element

L1‧‧‧light

L2‧‧‧Converted light

[0012] FIG. 1 is a schematic diagram showing a state of a swelled sample of a hardened material of this embodiment. [Fig. 2] is a schematic diagram showing a wavelength conversion sheet in this embodiment. [Fig. 3] is a schematic diagram showing a light emitting device according to this embodiment. [Fig. 4] is a schematic diagram showing a light emitting device according to this embodiment. [Fig. 5] is a schematic diagram showing a light emitting device according to this embodiment. [Fig. 6] is a sectional view showing a semiconductor light emitting device according to this embodiment. [Fig. 7] This is a SEM photograph of a silica hardened product after being pulverized by a freeze pulverizer.图 [Fig. 8] It is a SAXS profile made for the hardened materials of Examples and Comparative Examples.

Claims (13)

A hardened material containing a condensation type silicone resin hardened material, which satisfies the following (1) and (2), (1) The solid ²⁹ Si-NMR spectrum of the condensation type silicone resin hardened material, which exists and belongs to The peak of the silicon atom of the T body; (here, the so-called silicon atom of the T body means a silicon atom bonded to 3 oxygen atoms) (2) The size of the following non-uniform domain (Domain) is 50 Å or more, (Here, the size of the non-uniform domain refers to a case where the wave number of X-rays used for the measurement of small-angle X-ray scattering is determined as the horizontal axis, and the scattering intensity measured from the small-angle X-ray scattering is reduced. The scattering intensity of the scattering is determined on the vertical axis, and a graph is obtained by plotting the measured values of small-angle X-ray scattering of a sample in which the above-mentioned condensation-type silicone resin hardened material is impregnated with tetrahydrofuran, and fitted with the following formula (A) Value) (Here, ξ represents the size of the network sieve, Ξ represents the size of the non-uniform domain, I (q) represents the scattering intensity, q represents the wave number, and A and B represent the fitting constants.) For example, the hardened product of claim 1, wherein the ratio of the silicon atom of the T body to the total silicon atom contained in the condensation-type silicone resin hardened product is 50 mol% or more. For example, the hardened product of claim 2, wherein the ratio of the T3 silicon atom to the total silicon atoms contained in the condensation-type silicone resin hardened material is 50 mol% or more. Among the silicon atoms of the T body, all three oxygen atoms are bonded to other silicon atoms). The cured product according to any one of claims 1 to 3, wherein the condensation-type silicone resin cured product includes a structural unit represented by formula (A1), formula (A1 '), formula (A2), or formula (A3), (In formula (A1), formula (A1 '), formula (A2), and formula (A3), R ¹ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ² represents a carbon number 1 An alkoxy group or a hydroxyl group of ˜4, and a plurality of R ¹ and R ² may be the same as or different from each other). For example, the hardened product of claim 4, wherein the aforementioned R ¹ is a methyl group, the aforementioned R ² is an alkoxy group or a hydroxyl group having 1 to 3 carbon atoms, and a plurality of R ² may be the same or different. The cured product according to any one of claims 1 to 5, wherein the filler is dispersed in the above-mentioned condensation-type silicone resin cured product. The cured product according to claim 6, wherein the filler is a wavelength conversion material. The cured product according to claim 7, wherein the wavelength conversion material is a phosphor. A wavelength conversion sheet comprising a hardened material as described in claim 7 or 8 as a forming material. A light-emitting device includes a light source that emits light, and a wavelength conversion sheet according to claim 9 disposed at a position where the light emitted from the light source is incident. A sealing element using a hardened material according to any one of claims 1 to 8 as a forming material. A semiconductor light-emitting device comprising a base material, a semiconductor light-emitting element arranged on the base material, and a sealing element that seals at least a part of the semiconductor light-emitting element. The sealing element is for sealing according to claim 11. element. The semiconductor light-emitting device according to claim 12, wherein the light-emitting wavelength of the semiconductor light-emitting element is 400 nm or less.