JP4835199B2 - SEMICONDUCTOR LIGHT EMITTING DEVICE MEMBER, ITS MANUFACTURING METHOD, AND SEMICONDUCTOR LIGHT EMITTING DEVICE USING THE SAME - Google Patents

Description

  The present invention relates to a novel semiconductor light-emitting device member, a method for manufacturing the same, and a semiconductor light-emitting device using the same. Specifically, the present invention relates to a semiconductor light-emitting device member having high durability against ultraviolet rays and heat and excellent in transparency, a method for producing the same, and a semiconductor light-emitting device using the same.

  In a semiconductor light emitting device such as a light emitting diode (hereinafter abbreviated as “LED” where appropriate) and a semiconductor laser, the semiconductor light emitting element is sealed with a member such as a transparent resin (a member for a semiconductor light emitting device). Is common.

  For example, an epoxy resin is used as the semiconductor light emitting device member. Moreover, what converts the light emission wavelength from a semiconductor light-emitting element by including pigments, such as fluorescent substance, in this sealing resin is known.

  However, since epoxy resin is highly hygroscopic, there are problems such as cracks caused by heat from the semiconductor light-emitting element that occurs when the semiconductor light-emitting device is used for a long time, and deterioration of the phosphor and light-emitting element due to the ingress of moisture. was there.

  In recent years, the epoxy resin deteriorates and becomes colored as the emission wavelength is shortened and the output is increased, so that there is a problem that the luminance of the semiconductor light emitting device is remarkably lowered during long-time lighting.

  In response to these problems, silicone resins having excellent heat resistance and ultraviolet light resistance have been used as substitutes for epoxy resins. However, since the silicone resin is soft, it is easily damaged, and adhesion, transparency and weather resistance are still insufficient. In contrast, inorganic sealing materials and semiconductor light-emitting devices using the same have been proposed as materials excellent in heat resistance and ultraviolet light resistance (see, for example, Patent Documents 1 to 5).

Japanese Patent No. 3275308 JP 2003-197976 A JP 2004-231947 A JP 2002-33517 A Japanese Patent Laid-Open No. 2002-203989

However, inorganic materials such as molten glass have not been industrially realized because the handling temperature is as high as 350 ° C. or more and damages the light emitting element.
Moreover, in the glass manufactured by the sol-gel method, there is a problem of generation of cracks due to curing shrinkage and separation when molding as a member for a semiconductor light emitting device, and a stable film in a thick film state for a long time has not yet been obtained. It was.

  For example, Patent Document 1 and Patent Document 2 describe a technique for forming a glass material using tetrafunctional alkoxysilane. However, regarding the inorganic material obtained by the techniques described in Patent Document 1 and Patent Document 2, a tetrafunctional alkoxysilane hydrolyzate is applied to the semiconductor light emitting device, and the performance of the semiconductor light emitting device is not impaired at about 150 ° C. When cured at a mild curing temperature of about several hours, the resulting glass material was usually an incomplete glass body containing more than a dozen weight percent of silanol. Therefore, from the techniques described in Patent Document 1 and Patent Document 2, it has not been possible to obtain a glass body that is composed solely of siloxane bonds as in the case of melting glass.

  Unlike general organic resins, the inorganic materials used in Patent Document 1 and Patent Document 2 have a large number of cross-linking points, so that the structure is highly constrained and the reactive ends cannot be isolated and condensed. This is probably because of this. Such a glass body is not dense, and the surface thereof is very hydrophilic like silica gel, and therefore does not have sufficient sealing ability.

  In general, by heating at 250 ° C. or higher, such a hard-to-react silanol starts to decrease slightly, and if it is baked at a high temperature of usually 350 ° C. or higher, preferably 400 ° C. or higher, the amount of silanol is actively reduced. Can be made. However, even if it is attempted to remove silanol from the inorganic materials described in Patent Document 1 and Patent Document 2 using this, the heat-resistant temperature of the semiconductor light-emitting device is usually 260 ° C. or less, which is difficult to realize.

  Furthermore, since tetrafunctional alkoxysilane has a large amount of components that are desorbed during dehydration and dealcoholization condensation, the shrinkage rate during curing is essentially large. Moreover, since the tetrafunctional alkoxysilane has a high degree of cross-linking, curing begins from the surface portion where a part of the diluted solvent evaporates in the drying step, and after forming a hard gel body containing the solvent, the internal solvent The amount of shrinkage accompanying solvent evaporation also increases. For this reason, in the inorganic materials described in Patent Document 1 and Patent Document 2, as a result, a large internal stress is generated due to shrinkage, and cracks frequently occur. Therefore, it has been difficult to obtain a large bulk body or thick film useful as a member for a semiconductor light emitting device using only tetrafunctional alkoxysilane as a raw material.

  Further, for example, Patent Document 3 describes a technique for producing a three-dimensional phosphor layer with high dimensional accuracy by using a silane compound containing various organic groups as a raw material by a sol-gel method. However, Patent Document 3 does not have a detailed description of the degree of crosslinking and the presence of a cyclic substance, and in order to obtain the inorganic material described in Patent Document 3, a high concentration of phosphor particles is essential, Since this works as an aggregate and maintains a three-dimensional shape, when the inorganic material does not contain a phosphor, a transparent and crack-free thick glass-like coating material cannot be obtained.

  Furthermore, in the technique described in Patent Document 3, acetic acid is used as a catalyst. However, since acetic acid is not removed from the obtained inorganic material, acetic acid has an adverse effect on the semiconductor light emitting device. In addition, when the inorganic material described in Patent Document 3 is formed, a high temperature of 400 ° C. is required for curing, so that it is substantially impossible to heat the semiconductor light emitting device together with the structure due to excessive condensation at a high temperature. As a result, distortion is accumulated and cracks are not suppressed.

  Also, for example, Patent Document 4 describes a technique for obtaining a member for a semiconductor light emitting device by applying an inorganic coating agent obtained by mixing an inorganic light scattering agent to an inorganic sol having a skeleton of silica or siloxane. . However, an inorganic light scattering agent is indispensable for the inorganic material described in Patent Document 4, and furthermore, Patent Document 4 does not have a detailed description of raw materials and production methods, and it is impossible to accurately reproduce the technology. .

  Furthermore, for example, Patent Document 5 describes a technique for obtaining a semiconductor light emitting device member by applying sol-gel glass. However, similarly to Patent Document 3, a phosphor is essential to obtain the inorganic material described in Patent Document 5. Moreover, although this fluorescent substance functions as an aggregate and the obtained inorganic material is a thick film, the film thickness does not exceed 100 μm. Furthermore, Patent Document 5 does not describe the raw materials and the production method, and it is difficult to stably reproduce the technique using a general alkoxysilane.

  From the above background, the curing conditions are mild and excellent in transparency, light resistance and heat resistance, and it is possible to seal the semiconductor light emitting device and retain the phosphor without cracking or peeling even after long-term use. A member for a semiconductor light emitting device has been demanded.

  The present invention has been made in view of the above-described problems. That is, the object of the present invention is a novel, which is excellent in transparency, light resistance, heat resistance, can seal a semiconductor light emitting device and retain a phosphor without cracking or peeling even after long-term use. Another object is to provide a member for a semiconductor light emitting device.

As a result of intensive studies to achieve the above object, the present inventors have obtained a solid Si-nuclear magnetic resonance (hereinafter referred to as “NMR” as appropriate) spectrum through a predetermined production process. and, along with containing D ⁿ compound and D ² cyclics specific range, polymer silicon content is a specific value or more, are possible thicken upon the semiconductor light-emitting device member, the thickness The inventors have found that the occurrence of cracks in the film portion is suppressed and that the film portion is excellent in adhesion, heat resistance and transparency, and the present invention has been completed.

That is, the gist of the present invention is a step of drying a polycondensate obtained by hydrolysis and polycondensation of a compound represented by at least one of the following formula (1) and the following formula (2) and / or an oligomer thereof. [1] In a solid Si-nuclear magnetic resonance spectrum, the molar ratio of silicon corresponding to the D ⁿ compound is 30% or more in the solid Si-nuclear magnetic resonance spectrum, and [2] solid In the Si-nuclear magnetic resonance spectrum, the total molar ratio of silicon corresponding to the trimer and tetramer D ² cyclic product to the total silicon is 0.1% or more and 15% or less, and [3] silicon content rate is characterized and this is 20 wt% or more, consists in member for a semiconductor light-emitting device (claim 1).

（式（１）中、Ｍは、ケイ素を表わし、Ｘは、加水分解性基を表わし、Ｙ¹は、１価の有機基を表わし、ｍは、Ｍの価数を表わす１以上の整数を表わし、ｎは、Ｘ基の数を表わす１以上の整数を表わす。但し、ｍ≧ｎである。）

(In formula (1), M represents a silicon, X represents a hydrolyzable group, Y ¹ represents a monovalent organic group, m is an integer of 1 or more representing the valence of M N represents an integer of 1 or more representing the number of X groups, provided that m ≧ n.

（式（２）中、Ｍは、ケイ素を表わし、Ｘは、加水分解性基を表わし、Ｙ¹は、１価の有機基を表わし、Ｙ²は、ｕ価の有機基を表わし、ｓは、Ｍの価数を表わす２以上の整数を表わし、ｔは、１以上、ｓ−１以下の整数を表わし、ｕは、２以上の整数を表わす。）

(In the formula (2), M represents a silicon, X represents a hydrolyzable group, Y ¹ represents a monovalent organic group, Y ² is represents a u-valent organic group, s Represents an integer of 2 or more representing the valence of M, t represents an integer of 1 or more and s-1 or less, and u represents an integer of 2 or more.)

At this time, it is preferable that the light transmittance in the light emission wavelength of the semiconductor light-emitting device with a film thickness of 0.5 mm is 80% or more.
Moreover, it is preferable that said member for semiconductor light-emitting devices further contains an inorganic oxide particle (Claim 3).

Another gist of the present invention is as follows: [1] In a solid Si-nuclear magnetic resonance spectrum, the molar ratio of silicon corresponding to the D ⁿ compound to the total silicon is 30% or more, and [2] solid Si-nuclear magnetic resonance. In the spectrum, the total molar ratio of silicon corresponding to the trimer and tetramer D ² cyclic product with respect to the total silicon is 0.1% or more and 15% or less, and [3] the silicon content is 20% by weight. A method for producing a semiconductor light-emitting device member as described above, which is obtained by hydrolysis / polycondensation of a compound represented by at least one of the above formula (1) and the above formula (2) and / or an oligomer thereof. It has the process of drying a polycondensate, and exists in the manufacturing method of the member for semiconductor light-emitting devices (Claim 4).

At this time, the hydrolysis rate is preferably 80% or more and 500% or less (Claim 5).
In the above manufacturing method, hydrolysis decomposition and polycondensation carries out in the presence of a solvent, drying the polycondensate obtained is, hydrolysis and fold before drying at a temperature below the boiling point of the solvent It is preferable to have a first drying step for condensing the condensate and a second drying step for drying at a temperature equal to or higher than the boiling point of the solvent.
Furthermore, in the above production method, it is also preferable that the hydrolysis and polycondensation are carried out in the presence of an organometallic compound catalyst (claim 7).

  Still another subject matter of the present invention lies in a semiconductor light emitting device comprising at least the above-mentioned member for a semiconductor light emitting device (claim 8).

  The member for a semiconductor light emitting device of the present invention can be coated with a thick film as compared with a conventional member for an inorganic semiconductor light emitting device, and the semiconductor light emitting device can be easily sealed simply by coating and drying on the semiconductor light emitting device. It can stop and hold | maintain a fluorescent substance. Moreover, it is excellent in transparency, light resistance, and heat resistance, and does not cause cracking or peeling even after long-term use.

  Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made without departing from the scope of the invention.

[I. Semiconductor light emitting device member]
The semiconductor light emitting device member of the present invention is manufactured through a predetermined manufacturing process, and further has the following features [1] to [3].
[1] In the solid Si-nuclear magnetic resonance spectrum, the molar ratio of silicon corresponding to the D ⁿ compound to all silicon is 30% or more.
[2] In the solid Si-nuclear magnetic resonance spectrum, the total molar ratio of silicon corresponding to the trimer and tetramer D ² cyclic product to the total silicon is 0.1% or more and 15% or less.
[3] The silicon content is 20% by weight or more.
Hereinafter, these features [1] to [3] will be described first.

[I-1. Feature [1]]
In the member for a semiconductor light-emitting device of the present invention, in the solid Si-NMR spectrum, the molar ratio of silicon derived from the D ⁿ compound to the total silicon is 30% or more.

A compound containing silicon as a main component is represented by the SiO ₂ .nH ₂ O formula, but structurally, oxygen atoms O are bonded to each vertex of a tetrahedron of silicon atoms Si, and these oxygens It has a structure in which silicon atom Si is further bonded to atom O and spreads in a net shape. The schematic diagram shown below represents the Si—O net structure while ignoring the tetrahedral structure, and in the repeating unit of Si—O—Si—O—, Some parts are substituted with other members (for example, —H, —CH _3, etc.). When attention is paid to one silicon atom Si, as shown in (A) of the schematic diagram, four —OSi are silicon atoms having Si (Q ^4), a silicon atom Si (Q ³⁾ having three -OSi as shown in the schematic diagram (B) or the like is present. Then, in the solid-state Si-NMR measurement, peaks based on each silicon atom Si above is sequentially referred to Q ⁴ peak, Q ³ peak, and ....

These silicon atoms having four bonded oxygen atoms are generally referred to as Q sites. In the present specification, Q ^{0 to} Q ⁴ peaks derived from the Q site are referred to as a Q ⁿ peak group. The Q ⁿ peak group of the silica film containing no organic substituent is usually observed as a multimodal peak continuous in the region of chemical shift of −80 to −130 ppm.

In contrast, silicon atoms to which three oxygen atoms are bonded and other atoms (usually carbon) are bonded together are generally referred to as T sites. The peak derived from the T site is observed as each peak of T ^{0 to} T ³ as in the case of the Q site. In this specification, each peak derived from the T site is referred to as a T ⁿ peak group. The T ⁿ peak group is generally observed as a multimodal peak continuous in the region on the higher magnetic field side (usually −80 to −40 ppm) than the Q ⁿ peak group.

Furthermore, together with the oxygen atom is bonded two, the other (usually carbon) atoms are two bonded to are silicon atoms (i.e., silicon corresponding to D ⁿ compounds) are generally collectively referred to as D sites The Similarly to the peak group derived from the Q site and the T site, the peak derived from the D site is also observed as each peak of D ^{0 to} D ⁿ (D ⁿ peak group), which is further than the peak group of Q ⁿ and T ^n. It is observed as a multimodal peak in the region on the high magnetic field side (usually the region with a chemical shift of −3 to −40 ppm).

Similarly, a silicon atom bonded with one oxygen atom and three other atoms (usually carbon atoms) is generally referred to as an M site, and is the region on the highest magnetic field side. It is observed as a multimodal peak at (usually chemical shift 0 to -3 ppm).
The ratio of the area of each peak group of M ⁿ , D ⁿ , T ⁿ , and Q ⁿ is equal to the molar ratio of silicon atoms in the environment corresponding to each peak group. if the molar amount of silicon atoms corresponding, Q ⁿ peak group, M ⁿ peak group, the total area of the D ⁿ peak group and T ⁿ peak group usually the molar amount of all silicon directly bonded to carbon atoms corresponding to these Will do.

Now, a semiconductor light-emitting device member of the present invention, in a solid-state Si-NMR spectrum, "for total silicon molar ratio of silicon corresponding to D ⁿ compound" is generally 30% or more, preferably 40% or more, more preferably Is 50% or more, usually 97% or less, preferably 95% or less, more preferably 93% or less. Here, the “molar ratio of silicon derived from the D ⁿ compound to the total silicon” is represented by “ratio of the area of the D ⁿ peak group to the total peak area of silicon” measured by a solid Si-NMR spectrum. Is. If this molar ratio is smaller than the above range, the semiconductor light emitting device member of the present invention may be difficult to exhibit flexibility. Further, if it is larger than the above range, the crosslinking density is lowered, the mechanical strength of the semiconductor light-emitting device member of the present invention is insufficient, and the sealing performance such as volatilization of the included ring and oxygen / water vapor is reduced. There is a risk of getting up.

  In addition, the value of the chemical shift of the member for semiconductor light-emitting devices can be calculated based on the result of performing solid Si-NMR measurement using the method described later in the description of the examples. In addition, analysis (peak separation) of measurement data is performed by a method of dividing and extracting each peak by, for example, waveform separation analysis using a Gaussian function or a Lorentz function.

[I-2. Feature [2]]
In the member for a semiconductor light emitting device of the present invention, in the solid Si-NMR spectrum, the total molar ratio of silicon corresponding to the trimer and tetramer D ² cyclic product with respect to the total silicon is 0.1% or more and 15%. It is as follows.

Here, “D ² ” means that the silicon of the bifunctional silane showing the D ⁿ peak group in the above-mentioned solid Si-NMR spectrum is polymerized linearly by siloxane crosslinking (that is, -OSi has two bonds Represents silicon). The D ² cyclic product is a cyclic polymer of a bifunctional silane, and unlike a linear polymer, has no reactive terminal and has properties such as a low polarity silicone oil. Solid Si-NMR usually in the spectrum, 3-membered ring and is D ² peaks of 4-membered rings are each clearly separated and D ² peaks linear, with greater than or equal to 5-membered ring with D ² peak linear Separation is difficult. In the present invention, it is preferable that there are few cyclic bodies having a degree of polymerization of usually 10-membered rings or less having volatility. Among these, it is particularly preferable that the content of 3-membered and 4-membered rings having a low boiling point and high volatility is small.

Specifically, the member for a semiconductor light-emitting device of the present invention has, in the solid Si-NMR spectrum, “the total molar ratio of silicon corresponding to the trimer and tetramer D ² cyclic product to the total silicon” Usually, it is 0.1% or more, preferably 1% or more, and usually 15% or less, preferably 10% or less. Here, “the total molar ratio of silicon corresponding to the trimer and tetramer D ² cyclic product with respect to the total silicon” is “3 amounts with respect to the total peak area of silicon” measured by solid-state Si-NMR spectrum. the ratio of the sum of the peak areas of the D ² cyclics a peak area and tetramer of D ² cyclics a body (i.e., total peak area derived from D ² cyclics a trimer or tetramer) Is represented. If this molar ratio, which represents the ratio of silicon derived from the D ² cyclic product, is smaller than the above range, the D ⁿ compound cannot be substantially used as a raw material, making it difficult to obtain a highly flexible glass body. Further, when the molar ratio is larger than the above range, the frequency of occurrence of cracks and chipping due to thermal shock is increased particularly in applications that require high heat resistance, and partial annular emission occurs. In addition, in the silicone resin having a similar structure, the content of the D ² ring body of 10-mer or less is reduced to several percent or less because of the possibility of volatilization, but the member for semiconductor light-emitting device of the present invention Has a high crosslink density, and the D ² cyclic product is less likely to volatilize, and therefore has a higher allowable content than a silicone resin.

[I-3. Feature [3]]
The semiconductor light emitting device member of the present invention must have a silicon content of 20% by weight or more. A basic skeleton of a conventional member for a semiconductor light emitting device is an organic resin such as an epoxy resin having a carbon-carbon and carbon-oxygen bond as a basic skeleton. On the other hand, the basic skeleton of the semiconductor light emitting device member of the present invention is the same inorganic siloxane bond as glass (silicate glass). As is apparent from the chemical bond comparison table shown in Table 1 below, this siloxane bond has the following characteristics excellent as a member for a semiconductor light emitting device.

(I) Light resistance is good because the bond energy is large and thermal decomposition and photolysis are difficult.
(II) It is slightly polarized electrically.
(III) The degree of freedom of the chain structure is large, a structure with high flexibility is possible, and the chain structure can freely rotate around the center of the siloxane chain.
(IV) The degree of oxidation is large and no further oxidation occurs.
(V) Rich in electrical insulation.

  Because of these characteristics, a silicone-based semiconductor light-emitting device member formed of a skeleton in which siloxane bonds are three-dimensionally bonded with a high degree of crosslinking is different from a conventional resin-based semiconductor light-emitting device member such as an epoxy resin. Alternatively, it can be understood that the protective film is close to minerals such as rocks and is rich in heat resistance and light resistance. In particular, a silicone-based semiconductor light-emitting device member having a methyl group as a substituent does not absorb in the ultraviolet region, so that photolysis hardly occurs and light resistance is excellent.

As described above, the silicon content of the semiconductor light emitting device member of the present invention is 20% by weight or more, preferably 25% by weight or more, and more preferably 30% by weight or more. On the other hand, the upper limit is usually in the range of 47% by weight or less because the silicon content of the glass composed solely of SiO ₂ is 47% by weight.

  The silicon content of the semiconductor light emitting device member is analyzed by, for example, inductively coupled plasma spectrometry (hereinafter, abbreviated as “ICP” as appropriate) using the method described later in the description of the examples. It can be calculated based on the result.

[I-4. Reasons why the effects of the present invention can be obtained by the above features [1] to [3]
The member for a semiconductor light emitting device of the present invention has the above-mentioned features [1] to [3], so that it is hardened without cracking even in the thick film portion, and adheres to the case. And a cured product having excellent durability against light and heat after curing. The reason for this is not clear, but is presumed as follows.

Conventionally, as a method for obtaining a semiconductor light emitting device member made of inorganic glass, a melting method in which low melting point glass is melted and sealed, and a liquid obtained by hydrolyzing and polycondensing alkoxysilane or the like at a relatively low temperature are applied. There is a sol-gel method for drying and curing. Of these members, only the ^Qn peak is mainly observed for the member obtained from the melting method, but it requires a high temperature of at least 350 ° C. for melting and is not a practical method because it causes thermal degradation of the semiconductor light emitting device.

On the other hand, the hydrolysis / polycondensation product obtained from the tetrafunctional silane compound in the sol-gel method becomes a completely inorganic glass and is extremely excellent in heat resistance and weather resistance, but the curing reaction is silanol condensation (dehydration / dehydration). Since the crosslinking proceeds due to the (alcohol) reaction, the dehydration occurs, resulting in weight reduction and volume shrinkage. Therefore, ^{if the} raw material is composed only of tetrafunctional silane having a Q ⁿ peak, the degree of curing shrinkage becomes too large, cracks are likely to occur in the coating, and it becomes impossible to increase the thickness. In such a system, attempts are made to increase the film thickness by adding inorganic particles as an aggregate or by overcoating, but generally the limit film thickness is about 10 μm. When sol-gel glass is used as a member for a semiconductor light-emitting device, there is a problem that a film thickness of 500 to 1000 μm must be secured because it is necessary to mold on a wiring portion having a complicated shape. Further, as described above, in order to sufficiently reduce the residual silanol and obtain a completely inorganic glass, heating at a high temperature of 400 ° C. or more is required, which is not realistic because the semiconductor device is thermally deteriorated.

In contrast, in the semiconductor light emitting device member of the present invention, a bifunctional silane having a D ⁿ peak is introduced as described in the feature [1] in order to adjust the crosslinking density and to make the film flexible. To do. Further, a trifunctional silane having a T ⁿ peak and / or a monofunctional silane having an M ⁿ peak is introduced as appropriate. By simultaneously performing hydrolysis and polycondensation of these, the volume reduction due to dehydration condensation and the crosslinking density are appropriately reduced within a range that does not hinder the function, and the hydrolysis / condensation step and the drying step are controlled. It becomes possible to obtain a transparent glass film-like member having a film thickness of 1000 μm. Therefore, in the present invention, the presence of a D ⁿ peak observed at −80 ppm or more is essential, and the proportion of silicon derived from the corresponding D ⁿ compound is also within the range described in the feature [1]. It is necessary to do. Further, it is preferable that a T ⁿ peak and / or an M ⁿ peak are also present as appropriate. Furthermore, a Q ⁿ peak may also be included. However, even if the Q ⁿ peak is included, it is usually a small amount, and the Q ⁿ peak is not essential.

Next, the feature [2] will be described.
In order to form a glass body that is highly flexible and hardly cracks, all raw materials are used in the case of adjusting the degree of crosslinking by simultaneously hydrolyzing bifunctional or trifunctional coupling agents and introducing organic groups. Is uniformly polymerized to form a network, it becomes a glass body that is uniform and highly heat resistant in a microscopic environment. However, in many cases, the polymerization reaction becomes heterogeneous according to the reactivity of the raw material, and the coupling agent with high reactivity is polymerized first, and the coupling agent with low reactivity is polymerized with a delay. Therefore, when the raw material contains a bifunctional silane coupling agent that gives a D ⁿ peak, depending on the reaction conditions, a D ² cyclic product that is not contained in the network of the glass body is generated and the resulting semiconductor is obtained. The light-emitting device member has a solid-liquid two-phase structure including a liquid, and may greatly affect heat resistance and physical properties of the coating.

Further, when these D ² ring products are contained in a state where the glass body has a high degree of cross-linking and has a high affinity to the system and does not shine, it is useful for flexibility development, crack prevention, internal stress relaxation and the like. is there. However, if the degree of cross-linking is relaxed to increase flexibility without relying on plasticizer components, the D ² ring material tends to volatilize, reducing the yield of silicon raw material before and after curing, and in a sealed environment during actual use. There is a possibility that the influence of silica deposition on the electrical contact portions such as coexisting micro relays and micro switches may occur.

In addition, depending on the method of use, the low molecular weight D ² may be produced by local heating, such as when laser processing is performed on a member for a semiconductor light emitting device, or when it is used for an application requiring particularly high heat resistance, such as a high output semiconductor light emitting device with ultra-brightness. There is a risk that the annular body volatilizes rapidly and the semiconductor light emitting device member expands and breaks, or cracks and chipping occur.
From these facts, it is useful for the semiconductor light emitting device member of the present invention to have a reduced concentration of the D ² ring. Therefore, as described in the feature [2], it is necessary to make the total ratio of silicon corresponding to the trimer and tetramer D ² cyclic products fall within a predetermined range.

In addition, the composition of the member for a semiconductor light emitting device of the present invention is limited to the case where the crosslinking in the system is mainly formed of inorganic components including silica. That is, in a member for a semiconductor light emitting device in which a small amount of Si component is contained in a large amount of organic component,
[1] In the solid Si-NMR spectrum, the molar ratio of silicon corresponding to the D ⁿ compound to the total silicon is 30% or more, and
[2] In the solid Si-NMR spectrum, even if the total molar ratio of silicon corresponding to the trimer and tetramer D ² cyclic product with respect to the total silicon is 0.1% or more and 15% or less, Good heat and light resistance and coating performance specified in the present invention cannot be obtained. Therefore, the silicon content is required to be not less than a predetermined value (20% by weight) as in the above feature [3]. The semiconductor light emitting device member having a silicon content of 20% by weight or more according to the provisions of the present invention contains 43% by weight or more of SiO ₂ in terms of silica (SiO ₂ ).

[I-5. Light transmittance]
The member for a semiconductor light-emitting device of the present invention preferably has a light transmittance of 80% or more, particularly 85% or more, and more preferably 90% or more at a light emission wavelength of a semiconductor light-emitting device having a film thickness of 0.5 mm. The light-emitting efficiency of semiconductor light-emitting devices has been enhanced by various technologies. However, if the transparency of a translucent member for sealing a chip or holding a phosphor is low, a semiconductor light-emitting device using the same Since the luminance is reduced, it is difficult to obtain a semiconductor light emitting device product with high luminance.

  Here, the “emission wavelength of the semiconductor light-emitting device” is a value that varies depending on the type of the semiconductor light-emitting device, but is generally 300 nm or more, preferably 350 nm or more, and usually 900 nm or less, preferably 500 nm. It refers to the following range of wavelengths. When the light transmittance at a wavelength in this range is low, the semiconductor light emitting device member absorbs light, the light extraction efficiency is lowered, and a high-luminance device cannot be obtained. Furthermore, the energy corresponding to the decrease in the light extraction efficiency is changed to heat, which causes thermal deterioration of the device, which is not preferable.

  In the near ultraviolet to blue region (300 nm to 500 nm), the sealing member easily deteriorates. Therefore, the semiconductor light emitting device member of the present invention having excellent durability is applied to a semiconductor light emitting device having an emission wavelength in this region. If used, the effect is increased, which is preferable.

  The light transmittance of the member for a semiconductor light emitting device is measured with an ultraviolet spectrophotometer using a sample of a single cured film having a smooth surface molded to a thickness of 0.5 mm, for example, by the method described in the examples. can do.

  However, the shape of the semiconductor device is various, and the majority is used in a thick film state exceeding 0.1 mm. However, a thin phosphor layer (for example, nanofluorescence) is located at a position away from the LED chip (light emitting element). There are also applications using thin films, such as when providing a layer having a thickness of several μm containing body particles or fluorescent ions), or when providing a high refractive light extraction film on a thin film directly above the LED chip. In such a case, it is preferable to show a transmittance of 80% or more at this film thickness. Even in such a thin-film application mode, the semiconductor light emitting device member of the present invention exhibits excellent light resistance and heat resistance, has excellent sealing performance, and can be stably formed without cracks.

[I-6. Others]
In addition to the above characteristics, the member for semiconductor light emitting device of the present invention preferably has the characteristics described below as appropriate.
[I] Characteristics related to peak half-value width:
Conventionally, as a method of thickening a bifunctional or trifunctional raw material as a main component, for example, a technique of a hard coat film such as glasses is known, but the film thickness is several μm or less. Since these hard coat films are thin, solvent volatilization is easy and uniform curing is possible, and differences in adhesion to the base material and linear expansion coefficient have been the main cause of cracks. On the other hand, in the member for semiconductor light emitting device of the present invention, since the film thickness is as large as the paint, the film itself has a certain strength, and a slight difference in linear expansion coefficient can be absorbed. Due to volume reduction, generation of internal stress different from the case of a thin film becomes a new problem.

In other words, when molding into a deep container with a small opening area such as an LED cup, if heat curing is performed in a state where drying at the deep part of the film is insufficient, solvent volatilization occurs after cross-linking and the volume is reduced, resulting in large cracks. And foaming occurs. Usually, such a film is subjected to a large internal stress, and when a solid Si-NMR spectrum of this film is measured, a D ⁿ peak group to be detected, a M ⁿ peak group to be detected as appropriate, and a T ⁿ peak are appropriately detected. group and Q ⁿ peak group results in distribution of the siloxane bond angle than when the internal stress is small, respectively, a more broad peak. This fact means that the bond angle represented by two -OSi with respect to Si has a large strain. That is, even in a film made of the same raw material, the narrower the half-value width of these peaks, the less likely cracking occurs and the higher the quality film.

It should be noted that the phenomenon that the full width at half maximum increases according to the strain is observed more sharply as the degree of restraint of the molecular motion of the Si atoms increases, and the ease of appearing becomes M ⁿ <D ⁿ <T ⁿ <Q ^n. .

Therefore, in the present invention, the half-value width of the peak observed in solid-state Si-NMR, in particular, the half-value width of the D ⁿ peak group is the half-value width of a member for a semiconductor light-emitting device known so far by the sol-gel method. It is preferably smaller (narrower) than the range.

When arranged for each chemical shift, in the present invention, the half width of the T ⁿ peak group observed at a peak top position of −80 ppm or more and less than −40 ppm is usually 5.0 ppm or less, particularly 4.0 ppm or less, A range of 0.3 ppm or more, particularly 0.4 ppm or more is preferable.

Similarly, the full width at half maximum of the D ⁿ peak group observed at a peak top position of −40 ppm or more and less than −3 ppm is generally smaller than that of the T ⁿ peak group due to small molecular motion constraints, and is usually 3.0 ppm. In the following, it is preferably 2.0 ppm or less and usually in the range of 0.3 ppm or more.
In addition, since the ^Mn peak group in which the peak top position is observed at −3 ppm or more and 0 ppm or less is usually the terminal of the siloxane chain, the constraint of molecular motion is very small, and the fluctuation range of the half width due to the magnitude of strain is small. Is very narrow.

  If the half width of the peak observed in the above chemical shift region is larger than the above range, the molecular motion is constrained and the strain becomes large, and cracks are likely to occur, which may result in a member having poor heat resistance and weather resistance. There is. For example, in the case where a large amount of tetrafunctional silane is used, or in the state where rapid drying is performed in the drying process and a large internal stress is stored, the full width at half maximum is larger than the above range.

  In addition, when the half width of the peak is smaller than the above range, Si atoms in the environment are not involved in the siloxane crosslinking, and the trifunctional silane remains in an uncrosslinked state and is formed mainly of siloxane bonds. There is a risk of becoming a member that is inferior in heat resistance and weather resistance to a substance.

[Ii] Characteristics related to silanol content:
The member for a semiconductor light emitting device of the present invention has a silanol content of usually 0.1% by weight or more, especially 0.3% by weight or more, and usually 10% by weight or less, especially 8% by weight or less, and further 5% by weight. The following range is preferable.

  Usually, a glass body obtained by a sol-gel method using alkoxysilane as a raw material does not completely polymerize and become an oxide under mild curing conditions at 150 ° C. for about 3 hours, and a certain amount of silanol remains. A glass body obtained only from tetraalkoxysilane has high hardness and high light resistance, but has a high degree of cross-linking so that the degree of freedom of molecular chains is small, and complete condensation does not occur, so the amount of residual silanol is large. Further, when the hydrolysis / condensation liquid is dry-cured, the viscosity increases quickly due to the large number of cross-linking points, and the drying and curing proceed simultaneously, resulting in a bulk body having a large distortion. When such a member is used as a member for a semiconductor light emitting device, new internal stress is generated due to condensation of residual silanol during long-term use, and problems such as cracks, peeling, and disconnection are likely to occur. In addition, the fracture surface of the member has more silanol and less moisture permeability, but it has high surface hygroscopicity and tends to invade moisture. Although it is possible to reduce the silanol content by high-temperature baking at 400 ° C. or higher, the heat resistance of semiconductor light-emitting devices is almost 260 ° C. or lower, which is not realistic.

  On the other hand, the semiconductor light-emitting device member of the present invention has excellent performance with low silanol content, little change with time, excellent long-term performance stability, and low moisture absorption and moisture permeability. However, since a member containing no silanol is inferior in adhesion to a semiconductor light emitting device, the optimum range of silanol content exists as described above in the present invention.

Moreover, when the member for semiconductor light-emitting devices of the present invention contains an appropriate amount of silanol, the silanol hydrogen bonds to the polar portion present on the device surface, thereby exhibiting adhesion. Examples of the polar part include a hydroxyl group and a metalloxane-bonded oxygen.
Furthermore, the semiconductor light-emitting device member of the present invention forms a covalent bond by dehydration condensation with the hydroxyl group on the device surface by heating in the presence of an appropriate catalyst, and exhibits stronger adhesion. Can do.
On the other hand, if there is too much silanol, the inside of the system will thicken and it will be difficult to apply, or it will become highly active and solidify before the light boiling component volatilizes by heating, resulting in increased foaming and internal stress. This may cause cracks and the like.

  The silanol content of the semiconductor light-emitting device member is determined by, for example, performing solid Si-NMR spectrum measurement using the method described later in the description of the examples, and from the ratio of the peak area derived from silanol to the total peak area, It can be calculated by obtaining the ratio (%) of silicon atoms that are silanols in the interior and comparing it with the separately analyzed silicon content.

[Iii] Other:
The semiconductor light-emitting device member of the present invention can be applied in a thick film shape, is excellent in transparency, and has excellent sealing properties, heat resistance, ultraviolet resistance, etc. Can be applied. In particular, in a semiconductor light emitting device having an emission wavelength in a blue to ultraviolet region, it can be used as a useful member with little deterioration.

[II. Manufacturing method of semiconductor light emitting device member]
A method for producing a member for a semiconductor light emitting device of the present invention (this is appropriately referred to as “a method for producing a member for a semiconductor light emitting device of the present invention”) is represented by the following general formula (1) or general formula (2). It has the process of hydrolyzing and polycondensing a compound and / or oligomer thereof and drying the polycondensate. Hereinafter, this manufacturing method will be described in detail.

[II-1. material]
As a raw material, a compound represented by the following general formula (1) (hereinafter referred to as “compound (1)” as appropriate) and / or an oligomer thereof are used.

  In general formula (1), M is at least one element selected from the group consisting of silicon, aluminum, zirconium, and titanium. Of these, silicon is preferable.

In general formula (1), m represents the valence of M, and is an integer of 1 or more and 4 or less. “M +” represents that it is a positive valence.
n represents the number of X groups and is an integer of 1 or more and 4 or less. However, m ≧ n.

  In the general formula (1), X is a hydrolyzable group that is hydrolyzed with water in solution or moisture in the air to produce a hydroxyl group rich in reactivity, and any conventionally known one is arbitrarily used. can do. For example, C1-C5 lower alkoxy group, acetoxy group, butanoxime group, chloro group and the like can be mentioned. Here, Ci (i is a natural number) represents that the number of carbon atoms is i. Moreover, these hydrolysable groups may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  Especially, since the component liberated after reaction is neutral, a C1-C5 lower alkoxy group is preferable. In particular, a methoxy group or an ethoxy group is preferable because it is highly reactive and a free solvent is light boiling.

  Furthermore, when X is an acetoxy group or a chloro group in the general formula (1), acetic acid and hydrochloric acid are liberated after the hydrolysis reaction, so that it is used as a member for a semiconductor light emitting device that requires insulation. It is preferable to add a step of removing the acid component.

In the general formula (1), Y ¹ can be arbitrarily selected from any known monovalent organic groups of so-called silane coupling agents. Among them, the organic group particularly useful as Y ¹ in the general formula (1) in the present invention is selected from the following group represented by Y ⁰ (useful organic group group).

<Useful organic group Y ⁰ >
Y ⁰ is a monovalent or higher valent organic group derived from an aliphatic compound, alicyclic compound, aromatic compound, or aliphatic aromatic compound.
The carbon number of the organic group belonging to the group Y ⁰ is usually 1 or more, and usually 1000 or less, preferably 500 or less, more preferably 100 or less, and further preferably 50 or less.

Furthermore, at least a part of the hydrogen atoms of the organic group belonging to the group Y ⁰ may be substituted with a substituent such as an atom and / or an organic functional group exemplified below. At this time, a plurality of hydrogen atoms of the organic group belonging to the group Y ⁰ may be substituted with the following substituents. In this case, one or more selected from the substituents shown below It may be replaced by a combination.

Examples of substituents that can be substituted with hydrogen atoms of organic groups belonging to group Y ⁰ include atoms such as F, Cl, Br, I, etc .; vinyl groups, methacryloxy groups, acryloxy groups, styryl groups, mercapto groups, epoxy groups, Examples thereof include an organic functional group such as an epoxycyclohexyl group, a glycidoxy group, an amino group, a cyano group, a nitro group, a sulfonic acid group, a carboxy group, a hydroxy group, an acyl group, an alkoxy group, an imino group, and a phenyl group.

In all of the above cases, among the substituents that can be substituted for the hydrogen atoms of the organic group belonging to the group Y ⁰ , for the organic functional group, at least a part of the hydrogen atoms of the organic functional group is F, It may be substituted with a halogen atom such as Cl, Br, or I.

However, among those exemplified as substituents capable of substituting for hydrogen of the organic group belonging to group Y ⁰ , the organic functional group is an example that can be easily introduced, and various other physicochemical functions depending on the purpose of use. Organic functional groups having properties may be introduced.
In addition, the organic group belonging to the group Y ⁰ may have various atoms or atomic groups such as O, N, or S as a linking group therein.

In general formula (1), Y ¹ can be selected from various groups depending on the purpose from the organic groups belonging to the useful organic group Y ⁰ described above, but from the viewpoint of excellent ultraviolet resistance and heat resistance, it is a methyl group. It is preferable to use as a main component. In addition, other organic groups are appropriately selected for the purpose of improving the affinity and adhesion with other materials constituting the semiconductor light emitting device and changing the refractive index of the semiconductor light emitting device member. May be.

  Specific examples of the compound (1) described above include, for example, compounds in which M is silicon, such as dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, vinyltrimethoxysilane, and vinyltriethoxy. Silane, vinyltriacetoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane γ-chloropropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetra Ethoxysilane, tetrapropoxysilane, tetrabutoxysilane, dimethyldichlorosilane, diphenyldichlorosilane, methylphenyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, methyltrichlorosilane, γ-acinopropyltriethoxysilane, 4-amino Butyltriethoxysilane, p-aminophenyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimeth Xysilane, aminoethylaminomethylphenethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane, 4-aminobutyltriethoxysilane, N- (6-aminohexyl) aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltrichlorosilane, (p-chloromethyl) phenyltrimethoxysilane, 4-chlorophenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, styrylethyltrimethoxy Silane, 3-mercaptopropyl trimethoxysilane, vinyl trichlorosilane, vinyltris (2-methoxyethoxy) silane, etc. trifluoropropyl trimethoxysilane.

  Examples of the compound (1) in which M is aluminum include aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum tri-t-butoxide, aluminum triethoxide, and the like.

  Examples of the compound (1) in which M is zirconium include, for example, zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetra n-propoxide, zirconium tetra i-propoxide, zirconium tetra n-butoxide, Zirconium tetra i-butoxide, zirconium tetra t-butoxide, zirconium dimethacrylate dibutoxide and the like can be mentioned.

  Moreover, as a compound whose M is titanium among compounds (1), for example, titanium tetraisopropoxide, titanium tetra n-butoxide, titanium tetra i-butoxide, titanium methacrylate triisopropoxide, titanium tetramethoxypropoxide , Titanium tetra n-propoxide, titanium tetraethoxide and the like.

  However, the compounds specifically exemplified in these are some of the commercially available coupling agents that are readily available. It can be shown by a list of coupling agents and related products. Of course, the coupling agent that can be used in the present invention is not limited by these examples.

In addition, a compound represented by the following general formula (2) (hereinafter appropriately referred to as “compound (2)”) can also be used in the same manner as the compound (1).

In the general formula (2), M, X and Y ¹ each independently represent the same as in the general formula (1). In particular, as Y ¹ , various groups can be selected according to the purpose from the organic groups belonging to the useful organic group group Y ⁰ as in the case of the general formula (1), but they are excellent in ultraviolet resistance and heat resistance. From the point of view, it is preferable to mainly use a methyl group.
Moreover, in General formula (2), s represents the valence of M and is an integer of 2-4. “S +” indicates that it is a positive integer.
Further, in the general formula (2), Y ² represents a u-valent organic group. Here, u represents an integer of 2 or more. Therefore, in the general formula (2), Y ² may be arbitrarily selected from divalent or higher ones among known organic groups of so-called silane coupling agents.
In the general formula (2), t represents an integer of 1 or more and s−1 or less. However, t ≦ s.

  Examples of the compound (2) include those in which a plurality of hydrolyzable silyl groups are bonded as side chains to various organic polymers and oligomers, and those in which a hydrolyzable silyl group is bonded to a plurality of terminals of the molecule. Etc.

Specific examples of the compound (2) and product names thereof are listed below.
・ Bis (triethoxysilylpropyl) tetrasulfide (manufactured by Shin-Etsu Chemical, KBE-846)
2-diethoxymethylethylsilyldimethyl-2-furanylsilane (manufactured by Shin-Etsu Chemical, LS-7740)
N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine (manufactured by Chisso, Silaace XS1003)
N-glycidyl-N, N-bis [3- (methyldimethoxysilyl) propyl] amine (Toshiba Silicone, TSL8227)
N-glycidyl-N, N-bis [3- (trimethoxysilyl) propyl] amine (Toshiba Silicone, TSL8228)
N, N-bis [(methyldimethoxysilyl) propyl] amine (Toshiba Silicone, TSL8206)
N, N-bis [3- (methyldimethoxysilyl) propyl] ethylenediamine (Toshiba Silicone, TSL8212)
N, N-bis [(methyldimethoxysilyl) propyl] methacrylamide (Toshiba Silicone, TSL8213)
N, N-bis [3- (trimethoxysilyl) propyl] amine (Toshiba Silicone, TSL8208)
N, N-bis [3- (trimethoxysilyl) propyl] ethylenediamine (Toshiba Silicone, TSL8214)
N, N-bis [3- (trimethoxysilyl) propyl] methacrylamide (Toshiba Silicone, TSL8215)
N, N ′, N ″ -tris [3- (trimethoxysilyl) propyl] isocyanurate (manufactured by Hydras Chemical, 12267-1)
・ 1,4-Bishydroxydimethylsilylbenzene (manufactured by Shin-Etsu Chemical Co., Ltd., LS-7325)

As a raw material, you may use only 1 type among these compounds (1) and a compound (2), However, You may mix 2 or more types by arbitrary combinations and compositions. Moreover, you may use the oligomer of these compounds (1) and a compound (2) as a raw material. Here, when the compound (2) and / or the oligomer thereof is used as a main raw material, the main chain structure in the system becomes an organic bond main body and may be inferior in durability. For this reason, it is desirable to use the minimum amount of the compound (2) for providing functions such as adhesion, refractive index adjustment, reactivity control, and inorganic particle dispersibility. When compound (1) and / or its oligomer (component derived from compound (1)) and compound (2) and / or its oligomer (component derived from compound (2)) are used at the same time, the compound ( 2) It is desirable that the amount of the derived component used is usually 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less. However, in the present invention, it is necessary to use at least one compound (1) or compound (2) containing silicon as M and having at least one organic group Y ¹ or organic group Y ² as a raw material. Moreover, since it is preferable that a crosslinking becomes a siloxane bond main body, when using a compound (1) and a compound (2) together, it is preferable that a compound (1) becomes a main body.

[II-2. Hydrolysis / polycondensation process]
In the present invention, first, at least one of the above-mentioned compound (1) and compound (2) and / or their oligomer is subjected to hydrolysis / polycondensation reaction (hydrolysis / polycondensation step). This hydrolysis / polycondensation reaction can be carried out by a known method. Hereinafter, when referring to the compound (1), the compound (2) and the oligomer thereof without distinction, they are referred to as “raw material compounds”.

  The theoretical amount of water used for conducting the hydrolysis / polycondensation reaction of the raw material compound is a 1/2 molar ratio of the total amount of hydrolyzable groups in the system based on the reaction formula shown in the following formula (3). .

なお、上記式（３）は、一般式（１），（２）のＭがケイ素である場合を例として表わしている。また、「≡Ｓｉ」及び「Ｓｉ≡」は、ケイ素原子の有する４つの結合手のうち３つを省略して表わしたものである。

In addition, the said Formula (3) represents as an example the case where M of General formula (1), (2) is a silicon | silicone. “≡Si” and “Si≡” are represented by omitting three of the four bonds of the silicon atom.

  In this specification, the theoretical amount of water required for the hydrolysis, that is, the amount of water corresponding to 1/2 molar ratio of the total amount of hydrolyzable groups is used as a reference (hydrolysis rate 100%). The amount of water used is expressed as a percentage of this reference amount, ie “hydrolysis rate”.

  In the present invention, the amount of water used for carrying out the hydrolysis / polycondensation reaction is usually 80% or more, preferably 100% or more, when expressed by the above hydrolysis rate. When the hydrolysis rate is less than this range, the hydrolysis and polymerization are insufficient, so that the raw material may volatilize during curing or the strength of the cured product may be insufficient. On the other hand, if the hydrolysis rate exceeds 200%, free water always remains in the curing system, causing deterioration of the chip and phosphor due to moisture, or the cup part absorbs water, and foaming during curing. It may cause cracks and peeling. However, what is important in the hydrolysis reaction is that hydrolysis and polycondensation are performed with water of around 100% or more (for example, 80% or more). If a step of removing free water is added before coating, 200% is obtained. It is possible to apply a hydrolysis rate exceeding. In this case, if too much water is used, the amount of water to be removed and the amount of solvent used as a compatibilizer increase, the concentration process becomes complicated, and polycondensation proceeds so much that the coating performance of the member decreases. Therefore, the upper limit of the hydrolysis rate is usually 500% or less, particularly 300% or less, preferably 200% or less.

  When the raw material compound is hydrolyzed / condensed, a known catalyst or the like may be allowed to coexist to promote hydrolysis / condensation polymerization. In this case, as a catalyst to be used, an organic acid such as acetic acid, propionic acid or butyric acid, an inorganic acid such as nitric acid, hydrochloric acid, phosphoric acid or sulfuric acid, or an organometallic compound catalyst can be used. Of these, in the case of a member used in a portion in direct contact with the semiconductor light emitting device, an organometallic compound catalyst that has little influence on the insulating properties is preferable.

  The hydrolysis / polycondensation product of the raw material compound is preferably liquid. However, even a solid hydrolysis / polycondensate can be used as long as it becomes liquid by using a solvent.

  When the inside of the system is separated and becomes non-uniform during the hydrolysis / polycondensation reaction, a solvent may be used. As the solvent, for example, C1-C3 lower alcohols, dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, methyl ethyl ketone, and other solvents that can be uniformly mixed with water can be arbitrarily used. Of these, those which do not exhibit strong acidity or basicity are preferred because they do not adversely affect hydrolysis and polycondensation. The solvent may be used alone or in combination of two or more. Furthermore, the said solvent and hydrophobic solvent can also be used together. The amount of solvent used can be freely selected. However, since the solvent is often removed when applied to a semiconductor light emitting device, it is preferably set to the minimum necessary amount. In order to facilitate the removal of the solvent, it is preferable to select a solvent having a boiling point of 100 ° C. or lower, more preferably 80 ° C. or lower. In addition, even if it does not add a solvent from the exterior, since solvents, such as alcohol, are produced | generated by a hydrolysis reaction, even if it is heterogeneous at the beginning of reaction, it may become uniform during reaction.

  When the hydrolysis / polycondensation reaction of the raw material compound is carried out at normal pressure, it is usually 15 ° C or higher, preferably 20 ° C or higher, more preferably 40 ° C or higher, and usually 140 ° C or lower, preferably 135 ° C or lower. More preferably, it is performed in a range of 130 ° C. or lower. Although it is possible to carry out at a higher temperature by maintaining the liquid phase under pressure, it is preferable not to exceed 150 ° C.

  Although the hydrolysis / polycondensation reaction time varies depending on the reaction temperature, it is usually 0.1 hour or longer, preferably 1 hour or longer, more preferably 3 hours or longer, and usually 100 hours or shorter, preferably 20 hours or shorter, more preferably It is carried out in the range of 15 hours or less.

  Under the above hydrolysis / polycondensation conditions, if the time is shortened or the temperature is too low, the hydrolysis / polymerization is insufficient, and the raw material may volatilize during curing or the strength of the cured product may be insufficient. is there. In addition, if the time is too long or the temperature is too high, the molecular weight of the polymer increases and the amount of silanol in the system decreases, resulting in poor adhesion at the time of application or curing too early, resulting in a poor cured structure. It becomes uniform and tends to cause cracks. Based on the above tendency, it is desirable to appropriately select conditions according to desired physical property values.

  After the hydrolysis / polycondensation reaction is completed, the obtained hydrolysis / polycondensation product is stored at room temperature or lower until the time of use. When used as a shaped member, it should be used within 60 days, preferably within 30 days, more preferably within 15 days at room temperature storage after the completion of the hydrolysis and polycondensation reaction by heating. Is preferred. This period can be extended by low-temperature storage in a range that does not freeze as required.

[II-3. Drying process]
The member for a semiconductor light emitting device of the present invention can be obtained by drying the hydrolysis / polycondensation product obtained by the hydrolysis / polycondensation reaction described above (drying step). As described above, the hydrolyzed / polycondensed product is usually in a liquid state, but is dried in a state where the hydrolyzed / polycondensed product is placed in a mold having a desired shape, thereby having the desired shape. The member for use can be formed. Further, by drying the hydrolyzate / polycondensate applied to the target site, the member for a semiconductor light emitting device of the present invention can be formed directly on the target site. This liquid hydrolysis / polycondensate is referred to as “hydrolysis / polycondensation liquid” or “member-forming liquid for semiconductor light emitting devices” as appropriate in this specification.

In the present invention, the hydrolysis / polycondensation reaction described above is carried out in the presence of a solvent, and this drying step is performed by substantially removing the solvent at a temperature below the boiling point of the solvent, preferably at a temperature below the boiling point. It is preferable to carry out by dividing into a drying process of 1 and a second drying process of drying at a temperature not lower than the boiling point of the solvent. Here, it referred to "solvent", is produced by the hydrolysis and polycondensation reaction of M m ⁺ X _n Y ¹ _mn and _{^{(M s + X t Y 1}} st-1) described above starting compounds represented by _u Y ² Or a solvent represented by XH or the like. Further, “drying” in the present specification refers to a step in which the hydrolysis / polycondensation product of the raw material compound loses the solvent and is further polymerized and cured to form a metalloxane bond.

  In the first drying step, the solvent contained is substantially reduced at a temperature below the boiling point of the solvent, preferably at a temperature below the boiling point, without actively proceeding with further polymerization of the hydrolysis / polycondensate of the raw material compound. To be removed. That is, the product obtained in this step is a product obtained by condensing the hydrolyzed / polycondensed product before drying into a viscous liquid or a soft film by hydrogen bonding. When the first drying is performed at a temperature equal to or higher than the boiling point of the solvent, the resulting film is foamed by the vapor of the solvent, making it difficult to obtain a uniform film having no defects. This first drying step may be performed in a single step when the evaporation efficiency of the solvent is good, such as when it is a thin-film member, but a plurality of cases when the evaporation efficiency is poor such as when molded on a cup. The temperature may be increased in steps of In the case of a shape with extremely poor evaporation efficiency, it may be dried and concentrated in advance in another efficient container, and then applied in a state where the fluidity remains, and further dried. When the evaporation efficiency is poor, it is preferable to devise a method in which the whole member is uniformly dried without taking a means of concentrating only the surface of the member, such as ventilation drying with a large amount of air.

  In the second drying step, the hydrolysis / polycondensate is heated at a temperature equal to or higher than the boiling point of the solvent in a state where the solvent of the hydrolysis / polycondensation product is substantially eliminated by the first drying step, By forming a metalloxane bond, a stable cured product is obtained. If a large amount of solvent remains in this step, the volume is reduced due to evaporation of the solvent while the crosslinking reaction proceeds, so that a large internal stress is generated, causing peeling and cracking due to shrinkage. Since the metalloxane bond is usually formed efficiently at 100 ° C. or higher, the second drying step is preferably performed at 100 ° C. or higher, more preferably 120 ° C. or higher. However, when it is heated together with the semiconductor light emitting device, it is usually preferable to carry out the drying at a temperature not higher than the heat resistance temperature of the device component, preferably 200 ° C. or lower. The curing time in the second drying step is not generally determined by the catalyst concentration, the thickness of the member, etc., but is usually 0.1 hour or longer, preferably 0.5 hour or longer, more preferably 1 hour or longer, and usually 10 It is carried out for a period of time or less, preferably 5 hours or less, more preferably 3 hours or less.

  Thus, by clearly separating the solvent removal step (first drying step) and the curing step (second drying step), the semiconductor light emitting device having the physical properties of the present invention and excellent in light resistance and heat resistance. The member can be obtained without cracking or peeling.

  In addition, as long as the above-mentioned 1st drying process and 2nd drying process are implement | achieved substantially, the temperature rising conditions in each process are not restrict | limited in particular. That is, it may be held at a constant temperature during each drying step, or the temperature may be changed continuously or intermittently. In addition, each drying step may be further divided into a plurality of times. Furthermore, even when the temperature temporarily becomes higher than the boiling point of the solvent during the first drying step, or when there is a period during which the temperature becomes lower than the boiling point of the solvent during the second drying step, In particular, so long as the solvent removal step (first drying step) and the curing step (second drying step) as described above are achieved independently, they are included in the scope of the present invention.

[II-4. Reduction of D ² ring]
In the method for producing a member for a semiconductor light-emitting device of the present invention, in addition to the hydrolysis / polycondensation step and the drying step, usually the D ² cyclic product is reduced. In addition, the reduction of the D ² cyclic product may be performed by providing another step before and after the hydrolysis / polycondensation step and the drying step, as appropriate, during the hydrolysis / polycondensation step and the drying step. You may make it reduce by performing some operation.

In addition, the reduction of D ² cyclics, it is possible to use any method if it is possible to reduce the semiconductor light-emitting while satisfying the physical properties of the device member D ² ring of the present invention described above. Two or more methods may be combined.

As a preferable method, for example,
1) A method of diluting with a siloxane polymer not containing a D ² cyclic product,
2) A method by controlling the hydrolysis reaction,
3) A method of removing after the hydrolysis reaction,
Various methods are mentioned. Above all, the above methods 1) and 2) are easy to implement and have a great effect. Further, the method 3) is applicable system is limited, can be very low D ² cyclic concentration.

Hereinafter, each method will be described.
1) Method of diluting with a siloxane polymer not containing D ² ring:
There is no limitation on the siloxane polymer containing no D ² ring, and any one can be used as long as the effects of the present invention are not significantly impaired. Examples of useful ones include nano-sized silica particles and silsesoxane compounds. And other cage-type polymers and polyhedral clusters; oligomers of Si atom pentamers or more derived from monofunctional and / or trifunctional and / or tetrafunctional silane coupling agents; and the like. Siloxane polymers containing no D ² cyclics may be used alone, or as a combination of two or more kinds in any combination and in any ratio.

  Further, at the time of dilution, these siloxane polymers are uniformly dispersed or compatible with the hydrolyzed solution of the semiconductor light emitting device member to be introduced. Furthermore, in order not to impair the transparency of the obtained semiconductor light emitting device member, if the particle size or molecular size of the siloxane polymer is small, the diameter is not more than the emission wavelength of the semiconductor light emitting device member. If the particle diameter is large, it is desirable that the refractive index is close to that of the semiconductor light emitting device member.

2) Method by controlling hydrolysis reaction:
In the case of reducing the D ² cyclic product by controlling the hydrolysis reaction, for example, the type of catalyst is preferably not an acid but an organometallic compound catalyst. An acidic catalyst is a cyclic product that easily promotes heterogeneous reaction in the system and has poor compatibility with the system when a plurality of silane coupling agents including a bifunctional silane coupling agent are simultaneously hydrolyzed. And in the extreme case, the hydrolyzed solution may be separated.

Therefore, when these acid catalysts are used, it is preferable to devise the order of introduction and the amount of the catalyst when used alone, or consideration is given to using a combined system with an organometallic compound catalyst. It is desirable. Furthermore, it is also effective to manipulate the hydrolysis order and mixing timing of each silane coupling agent according to the reactivity of a plurality of silane coupling agents to be used, or to divide and mix part of the raw materials. It is also effective to make the organic group of the silane coupling agent, which is a D ⁿ compound, bulky so that it is difficult to make a low molecular weight cyclic product.

3) Method of removing after hydrolysis reaction In the method of removal after hydrolysis reaction, for example, a small amount of high-boiling solvent is mixed with the hydrolyzed solution, and low molecular weight cyclics are distilled off together with the high-boiling solvent by distillation under reduced pressure. In addition, a method of diluting again with a high boiling solvent or the like as necessary is included. In addition, the high boiling point solvent here refers to the solvent which has a boiling point exceeding the boiling point of a cyclic | annular thing. If the system is stable even if the solvent is removed, the low-boiling ring can be directly distilled off together with the low-boiling solvent without mixing the high-boiling solvent.

[II-5. Others]
After the above-described drying step, various post-treatments may be performed on the obtained semiconductor light-emitting device member as necessary. Examples of the post-treatment include surface treatment for improving adhesion to the mold part, production of an antireflection film, production of a fine uneven surface for improving light extraction efficiency, and the like.

[III. Applications of semiconductor light emitting device components]
The use of the member for a semiconductor light-emitting device of the present invention is not particularly limited, and can be used for various uses represented by a member (sealing agent) for sealing a semiconductor light-emitting element or the like. Especially, it becomes possible to use suitably by a specific use by using together the below-mentioned fluorescent substance particle and / or inorganic oxide particle. Hereinafter, the combined use of these phosphor particles and inorganic oxide particles will be described.

[III-1. (Use of phosphor together)
The member for a semiconductor light emitting device of the present invention is, for example, a phosphor dispersed in a member for a semiconductor light emitting device and molded into a cup of a semiconductor light emitting device or applied in a thin layer on a suitable transparent support. Therefore, it can be used as a wavelength conversion member. In addition, fluorescent substance may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

[Phosphor]
There is no particular limitation on the composition of the phosphor, Y ₂ O _3, Zn ₂ metal oxide represented by SiO ₄ and the like is a crystalline matrix, Ca ₅ (PO _{4) 3} phosphate typified by Cl, etc. And sulfides represented by ZnS, SrS, CaS, etc., ions of rare earth metals such as Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, Ag, Cu, Au A combination of metal ions such as Al, Mn, and Sb as an activator or a coactivator is preferable.

Preferred examples of the crystal matrix include sulfides such as (Zn, Cd) S, SrGa ₂ S ₄ , SrS and ZnS, oxysulfides such as Y ₂ O ₂ S, and (Y, Gd) ₃ Al ₅ O. ₁₂ , YAlO ₃ , BaMgAl ₁₀ O ₁₇ , (Ba, Sr) (Mg, Mn) Al ₁₀ O ₁₇ , (Ba, Sr, Ca) (Mg, Zn, Mn) Al ₁₀ O ₁₇ , BaAl ₁₂ O ₁₉ , CeMgAl ₁₁ O ₁₉ , (Ba, Sr, Mg) O.Al ₂ O ₃ , BaAl ₂ Si ₂ O ₈ , SrAl ₂ O ₄ , Sr ₄ Al ₁₄ O ₂₅ , aluminate such as Y ₃ Al ₅ O ₁₂ , Y Silicates such as ₂ SiO ₅ and Zn ₂ SiO ₄ , oxides such as SnO ₂ and Y ₂ O ₃ , boric acid circles such as GdMgB ₅ O ₁₀ and (Y, Gd) BO ₃ , Ca ₁₀ (PO ₄ ) ₆ ( F, Cl) ₂ , (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl _{2 and} other halophosphates, Sr ₂ P ₂ Examples thereof include phosphates such as O ₇ and (La, Ce) PO ₄ .

  However, the above-mentioned crystal matrix and activator or coactivator are not particularly limited in elemental composition, and can be partially replaced with elements of the same family, and the obtained phosphor is light in the near ultraviolet to visible region. Any material that absorbs and emits visible light can be used.

Specifically, the following phosphors can be used, but these are merely examples, and phosphors that can be used in the present invention are not limited to these. In the following examples, phosphors that differ only in part of the structure are omitted as appropriate. For example, “Y ₂ SiO ₅ : Ce ³⁺ ”, “Y ₂ SiO ₅ : Tb ³⁺ ” and “Y ₂ SiO ₅ : Ce ³⁺ , Tb ³⁺ ” are changed to “Y ₂ SiO ₅ : Ce ³⁺ , Tb”. ³⁺ ”,“ La ₂ O ₂ S: Eu ”,“ Y ₂ O ₂ S: Eu ”and“ (La, Y) ₂ O ₂ S: Eu ”are changed to“ (La, Y) ₂ O ₂ S: “Eu” collectively. Omitted parts are separated by commas (,).

・ Red phosphor:
Illustrating the specific wavelength range of the fluorescence emitted by the phosphor emitting red fluorescence (hereinafter referred to as “red phosphor” as appropriate), the peak wavelength is usually 570 nm or more, preferably 580 nm or more, and usually 700 nm or less. Preferably, it is 680 nm or less.

Examples of such a red phosphor include europium activation represented by (Mg, Ca, Sr, Ba) ₂ Si ₅ N ₈ : Eu that is composed of fractured particles having a red fracture surface and emits light in the red region. An alkaline earth silicon nitride-based phosphor, composed of growing particles having a substantially spherical shape as a regular crystal growth shape, emits light in the red region (Y, La, Gd, Lu) ₂ O ₂ S: Eu Examples thereof include europium-activated rare earth oxychalcogenide phosphors.

  Furthermore, the oxynitride and / or acid containing at least one element selected from the group consisting of Ti, Zr, Hf, Nb, Ta, W, and Mo described in JP-A-2004-300247 A phosphor containing a sulfide and containing an oxynitride having an alpha sialon structure in which a part or all of the Al element is substituted with a Ga element can also be used in this embodiment. These are phosphors containing oxynitride and / or oxysulfide.

In addition, examples of red phosphors include Eu-activated oxysulfide phosphors such as (La, Y) ₂ O ₂ S: Eu, Y (V, P) O ₄ : Eu, Y ₂ O ₃ : Eu, and the like. Eu-activated oxide phosphors of (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, Mn, (Ba, Mg) ₂ SiO ₄ : Eu, Mn-activated silicate phosphors such as Eu, Mn, Eu-activated sulfide phosphors such as (Ca, Sr) S: Eu, Eu-activated aluminate phosphors such as YAlO ₃ : Eu, LiY ₉ (SiO ₄ ) ₆ O ₂ : Eu, Ca ₂ Y ₈ ( SiO ₄ ) ₆ O ₂ : Eu, (Sr, Ba, Ca) ₃ SiO ₅ : Eu, Sr ₂ BaSiO ₅ : Eu-activated silicate phosphor such as Eu, (Y, Gd) ₃ Al ₅ O ₁₂ : Ce _{, (Tb, Gd) 3 Al} 5 O 12: Ce -activated aluminate phosphor such as Ce, (Ca, Sr, Ba ) 2 Si 5 N 8: Eu, ( g, Ca, Sr, Ba) SiN 2: Eu, (Mg, Ca, Sr, Ba) AlSiN 3: Eu -activated nitride phosphor such as Eu, (Mg, Ca, Sr , Ba) AlSiN 3: Ce , etc. Ce-activated nitride phosphor, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, Mn-activated halophosphate phosphor such as Eu, Mn, (Ba ₃ Mg) Si _{2 O 8: Eu, Mn, (} Ba, Sr, Ca, Mg) 3 (Zn, Mg) Si 2 O 8: Eu, Eu such as Mn, Mn-activated silicate phosphor, 3.5MgO · 0.5MgF ₂ GeO ₂ : Mn-activated germanate phosphor such as Mn, Eu-activated oxynitride phosphor such as Eu-activated α sialon, (Gd, Y, Lu, La) ₂ O ₃ : Eu, Bi, etc. eu, Bi-activated oxide phosphor, (Gd, Y, Lu, La) 2 O 2 S: Eu, Eu Bi, etc., with Bi Oxysulfide phosphor, (Gd, Y, Lu, La) VO 4: Eu, Eu Bi, etc., Bi-activated vanadate phosphor, SrY ₂ S _4: Eu, such as Ce Eu, Ce-activated sulfide Phosphor, Ca-activated sulfide phosphor such as CaLa ₂ S ₄ : Ce, (Ba, Sr, Ca) MgP ₂ O ₇ : Eu, Mn, (Sr, Ca, Ba, Mg, Zn) ₂ P ₂ O ₇ : Eu, Mn activated phosphate phosphor such as Eu, Mn, (Y, Lu) ₂ WO ₆ : Eu, Mo activated tungstate phosphor such as Eu, Mo, (Ba, Sr, Ca) ) _X Si _{y Nz} : Eu, Ce activated nitride phosphor such as Eu, Ce (where x, y, z are integers of 1 or more), (Ca, Sr, Ba, Mg) ₁₀ (PO _{4 ) 6 (F, Cl, Br} , OH): Eu, Eu such as Mn, Mn-activated halophosphate phosphor, ((Y, Lu, Gd , Tb) 1-x S It is also possible to use _{x Ce y) 2 (Ca,} Mg) 1-r (Mg, Zn) 2 + r Si zq Ge q O 12 + δ Ce -activated silicate phosphor such like.

  Examples of the red phosphor include β-diketonates, β-diketones, aromatic carboxylic acids, red organic phosphors composed of rare earth element ion complexes having an anion such as Bronsted acid as ligands, and perylene pigments (for example, Dibenzo {[f, f ′]-4,4 ′, 7,7′-tetraphenyl} diindeno [1,2,3-cd: 1 ′, 2 ′, 3′-lm] perylene), anthraquinone pigment, Lake pigments, azo pigments, quinacridone pigments, anthracene pigments, isoindoline pigments, isoindolinone pigments, phthalocyanine pigments, triphenylmethane basic dyes, indanthrone pigments, indophenol pigments, It is also possible to use a cyanine pigment or a dioxazine pigment.

Among the red phosphors, those having a peak wavelength in the range of 580 nm or more, preferably 590 nm or more, and 620 nm or less, preferably 610 nm or less can be suitably used as the orange phosphor. Examples of such orange phosphors include (Sr, Ba) ₃ SiO ₅ : Eu, (Sr, Mg) ₃ (PO ₄ ) ₂ : Sn ²⁺ , SrCaAlSiN ₃ : Eu, and the like.

・ Green phosphor:
When a specific wavelength range of fluorescence emitted by a phosphor emitting green fluorescence (hereinafter referred to as “green phosphor” as appropriate) is exemplified, the peak wavelength is usually 490 nm or more, preferably 500 nm or more, and usually 570 nm or less. Preferably, it is 550 nm or less.

As such a green phosphor, for example, a europium activated alkali represented by (Mg, Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu that is composed of fractured particles having a fracture surface and emits light in the green region. Europium-activated alkaline earth silicate composed of an earth silicon oxynitride phosphor, broken particles having a fracture surface, and emitting green light (Ba, Ca, Sr, Mg) ₂ SiO ₄ : Eu System phosphors and the like.

In addition, as the green phosphor, Eu-activated aluminate phosphors such as Sr ₄ Al ₁₄ O ₂₅ : Eu, (Ba, Sr, Ca) Al ₂ O ₄ : Eu, (Sr, Ba) Al _{2 Si 2 O 8: Eu, (} Ba, Mg) 2 SiO 4: Eu, (Ba, Sr, Ca, Mg) 2 SiO 4: Eu, (Ba, Sr, Ca) 2 (Mg, Zn) Si 2 O 7 : Eu-activated silicate phosphor such as Eu, Y ₂ SiO ₅ : Ce, Tb-activated silicate phosphor such as Ce and Tb, Sr ₂ P ₂ O ₇ —Sr ₂ B ₂ O ₅ : Eu such as Eu Activated borate phosphor, Sr ₂ Si ₃ O ₈ -2SrCl ₂ : Eu activated halosilicate phosphor such as Eu, Zn ₂ SiO ₄ : Mn activated silicate phosphor such as Mn, CeMgAl ₁₁ O _{19: Tb, Y 3 Al 5} O 12: Tb -activated aluminate phosphors such as _{Tb, Ca 2 Y 8 (SiO} 4) 6 O 2 _{Tb, La 3 Ga 5 SiO 14} : Tb -activated silicate phosphors such as Tb, (Sr, Ba, Ca ) Ga 2 S 4: Eu, Tb, and Sm, such as Eu, Tb, Sm-activated thiogallate phosphor, Ce-activated aluminate phosphor such as Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Y, Ga, Tb, La, Sm, Pr, Lu) ₃ (Al, Ga) ₅ O ₁₂ : Ce, Ca-activated silicate phosphor such as Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, Ca ₃ (Sc, Mg, Na, Li) ₂ Si ₃ O ₁₂ : Ce, Ce-activated such as CaSc ₂ O ₄ : Ce Eu-activated oxynitride fluorescence such as oxide phosphor, SrSi ₂ O ₂ N ₂ : Eu, (Sr, Ba, Ca) Si ₂ O ₂ N ₂ : Eu, Eu-activated β sialon, Eu-activated α-sialon _{body, BaMgAl 10 O 17: Eu,} Eu such as Mn, Mn-activated aluminate phosphor, SrAl ₂ O _4: Eu Eu-activated aluminate phosphor, (La, Gd, Y) 2 O 2 S: Tb Tsukekatsusan sulfide phosphor such as Tb, LaPO _4: Ce, and Tb, etc. Ce, Tb-activated phosphate Phosphor, ZnS: Cu, Al, ZnS: Sulfide phosphor such as Cu, Au, Al, (Y, Ga, Lu, Sc, La) BO ₃ : Ce, Tb, Na ₂ Gd ₂ B ₂ O ₇ : Ce, Tb, (Ba, Sr) ₂ (Ca, Mg, Zn) B ₂ O ₆ : Ce, Tb-activated borate phosphor such as K, Ce, Tb, Ca ₈ Mg (SiO ₄ ) ₄ Cl ₂ : Eu, Mn-activated halosilicate phosphors such as Eu and Mn, (Sr, Ca, Ba) (Al, Ga, In) ₂ S ₄ : Eu-activated thioaluminate phosphors and thiogallate phosphors such as Eu, _{(Ca, Sr) 8 (Mg} , Zn) (SiO 4) 4 Cl 2: Eu, Eu such as Mn, Mn-activated halo silicate phosphor It is also possible to use such.

  Examples of green phosphors include pyridine-phthalimide condensed derivatives, benzoxazinone-based, quinazolinone-based, coumarin-based, quinophthalone-based, naltalimide-based fluorescent dyes, terbium complexes having hexyl salicylate as a ligand, etc. It is also possible to use organic phosphors.

・ Blue phosphor:
When a specific wavelength range of fluorescence emitted by a phosphor emitting blue fluorescence (hereinafter referred to as “blue phosphor” as appropriate) is exemplified, the peak wavelength is usually 420 nm or more, preferably 440 nm or more, and usually 480 nm or less. Preferably, it is 470 nm or less.

As such a blue phosphor, a europium-activated barium magnesium aluminate system represented by BaMgAl ₁₀ O ₁₇ : Eu composed of growing particles having a substantially hexagonal shape as a regular crystal growth shape and emitting light in a blue region. Europium activated halo represented by (Ca, Sr, Ba) ₅ (PO ₄ ) ₃ Cl: Eu, which is composed of phosphors and growing particles having a substantially spherical shape as a regular crystal growth shape, and emits light in the blue region. Calcium phosphate-based phosphor, composed of growing particles having an approximately cubic shape as a regular crystal growth shape, emits light in the blue region, and is activated by europium represented by (Ca, Sr, Ba) ₂ B ₅ O ₉ Cl: Eu It is composed of alkaline earth chloroborate phosphors and fractured particles having fractured surfaces, and emits light in the blue-green region (S _{, Ca, Ba) Al 2 O} 4: Eu or _{(Sr, Ca, Ba) 4} Al 14 O 25: activated alkaline earth with europium aluminate-based phosphor such as represented by Eu and the like.

In addition, as the blue phosphor, Sn-activated phosphate phosphors such as Sr ₂ P ₂ O ₇ : Sn, Sr ₄ Al ₁₄ O ₂₅ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, BaAl ₈ O ₁₃ : Eu-activated aluminate phosphors such as Eu, Ce-activated thiogallate phosphors such as SrGa ₂ S ₄ : Ce, CaGa ₂ S ₄ : Ce, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, BaMgAl ₁₀ O ₁₇ : Eu-activated aluminate phosphor such as Eu, Tb, Sm, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, Mn-activated aluminate phosphor such as Eu, Mn, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, (Ba, Sr, Ca) ₅ (PO ₄ ) ₃ (Cl, F, Br, OH): Eu activation such as Eu, Mn, Sb Halophosphate phosphor, BaAl ₂ Si ₂ O ₈ : Eu, (Sr, Ba) ₃ Eu-activated silicate phosphor such as MgSi ₂ O ₈ : Eu, Eu-activated phosphate phosphor such as Sr ₂ P ₂ O ₇ : Eu, sulfide fluorescence such as ZnS: Ag, ZnS: Ag, Al Body, Ce activated silicate phosphor such as Y ₂ SiO ₅ : Ce, tungstate phosphor such as CaWO ₄ , (Ba, Sr, Ca) BPO ₅ : Eu, Mn, (Sr, Ca) ₁₀ (PO ₄ ) ₆ · nB ₂ O ₃ : Eu, 2SrO · 0.84P ₂ O ₅ · 0.16B ₂ O ₃ : Eu, Mn-activated borate phosphate phosphor such as Eu, Sr ₂ Si ₃ O ₈ · 2SrCl ₂ : Eu-activated halosilicate phosphor such as Eu can be used.

In addition, as the blue phosphor, for example, naphthalic acid imide-based, benzoxazole-based, styryl-based, coumarin-based, pyralizone-based, triazole-based compound fluorescent dyes, thulium complexes and other organic phosphors can be used. .
In addition, fluorescent substance may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The median particle diameter of these phosphor particles is not particularly limited, but is usually 100 nm or more, preferably 2 μm or more, particularly preferably 5 μm or more, and usually 100 μm or less, preferably 50 μm or less, particularly preferably 20 μm or less. In addition, as long as the shape of the phosphor particles does not affect the formation of the semiconductor light emitting device member, for example, a phosphor part forming liquid (a liquid obtained by adding a phosphor to the above semiconductor light emitting device member forming liquid) There is no particular limitation as long as it does not affect the fluidity or the like.

  In the present invention, the method for adding phosphor particles is not particularly limited. If the dispersed state of the phosphor particles is good, it is only necessary to post-mix the phosphor particles in the above-described member forming liquid for semiconductor light emitting device. In the case where the aggregation of the phosphor particles is likely to occur, the phosphor particles are mixed in advance with a reaction solution containing the raw material compound before hydrolysis (hereinafter referred to as “pre-hydrolysis solution” as appropriate), and in the presence of the phosphor particles. When the hydrolysis / polycondensation is carried out at, the surface of the particles is partially subjected to silane coupling treatment, and the dispersed state of the phosphor particles is improved.

  Although some phosphors are hydrolyzable, the member for a semiconductor light emitting device of the present invention is potentially water as a silanol body in a liquid state before application (member forming liquid for a semiconductor light emitting device). Therefore, such phosphors can be used without being hydrolyzed. Further, when the hydrolyzed / polycondensed semiconductor light-emitting device member forming solution is used after being subjected to dehydration and dealcoholization treatment, there is also an advantage that the combined use with such a phosphor becomes easy.

  Furthermore, the member for a semiconductor light emitting device of the present invention may be a fluorescent glass in which an ionic fluorescent material or an organic / inorganic fluorescent component is dissolved and dispersed uniformly and transparently.

[III-2. Combined use of inorganic oxide particles)
Further, the member for a semiconductor light emitting device of the present invention is further subjected to inorganic oxidation for the purpose of improving optical characteristics and workability, and for obtaining any of the following effects <1> to <5>. Material particles may be included.

<1> By mixing inorganic oxide particles as a light-scattering substance in a member for a semiconductor light-emitting device and scattering the light of the semiconductor light-emitting device, the light amount of the semiconductor light-emitting element that hits the phosphor is increased and the wavelength conversion efficiency is improved. At the same time, the directivity angle of light emitted from the semiconductor light emitting device to the outside is expanded.
<2> The generation of cracks is prevented by blending inorganic oxide particles as a binder in the semiconductor light emitting device member.
<3> By adding inorganic oxide particles as a viscosity modifier to the semiconductor light emitting device member forming liquid, the viscosity of the forming liquid is increased.
<4> The shrinkage is reduced by blending the inorganic oxide particles in the semiconductor light emitting device member.
<5> By blending inorganic oxide particles with the semiconductor light emitting device member, the refractive index is adjusted to improve the light extraction efficiency.

  In this case, an appropriate amount of inorganic oxide particles may be mixed in the semiconductor light emitting device member forming liquid together with the phosphor powder according to the purpose. In this case, the effect obtained depends on the type and amount of the inorganic oxide particles to be mixed.

  For example, when the inorganic oxide particles are ultrafine silica having a particle size of about 10 nm (product name: AEROSIL # 200, manufactured by Nippon Aerosil Co., Ltd.), the thixotropic property of the member forming liquid for semiconductor light emitting devices is increased. The effect <3> is great.

  In addition, when the inorganic oxide particles are crushed silica or spherical silica having a particle size of about several μm, there is almost no increase in thixotropic property, and the function as an aggregate of a member for a semiconductor light emitting device is the center. The effects of 2> and <4> are great.

  Further, when inorganic oxide particles having a particle diameter of about 1 μm, which has a refractive index different from that of the semiconductor light emitting device member, are used, light scattering at the interface between the semiconductor light emitting device member and the inorganic oxide particles becomes large. The effect of> is great.

  In addition, when inorganic oxide particles having a particle size of 3 to 5 nm, specifically a particle diameter equal to or smaller than the emission wavelength, are used, the transparency of the semiconductor light-emitting device member is maintained while the refractive index is larger than that of the semiconductor light-emitting device member. Since the refractive index can be improved, the effect <5> is great.

  Accordingly, the type of inorganic oxide particles to be mixed may be selected according to the purpose. Moreover, the kind may be single and may combine multiple types. Moreover, in order to improve dispersibility, it may be surface-treated with a surface treatment agent such as a silane coupling agent.

  Examples of inorganic oxide particles to be used include silica, barium titanate, titanium oxide, zirconium oxide, niobium oxide, aluminum oxide, cerium oxide, yttrium oxide, etc., but other substances can be selected depending on the purpose. However, the present invention is not limited to these.

  The form of the inorganic oxide particles may be any form depending on the purpose, such as powder form, slurry form, etc., but if necessary to maintain transparency, the refractive index of the semiconductor light-emitting device member of the present invention is equivalent, It is preferable to add it as a water-based / solvent-based transparent sol to the member-forming liquid for semiconductor light-emitting devices.

[IV. Semiconductor light emitting device]
Hereinafter, a semiconductor light emitting device using the member for a semiconductor light emitting device of the present invention (semiconductor light emitting device of the present invention) will be described with reference to embodiments. In each of the following embodiments, the semiconductor light emitting device is appropriately abbreviated as “light emitting device”. Further, to which part the member for the semiconductor light emitting device of the present invention is used will be described collectively after the description of all the embodiments. However, these embodiments are merely used for convenience of explanation, and examples of light emitting devices (semiconductor light emitting devices) to which the semiconductor light emitting device member of the present invention is applied are not limited to these embodiments. Absent.

〔Basic concept〕
The semiconductor light emitting device using the member for semiconductor light emitting device of the present invention has application examples of the following A) and B), for example. The member for a semiconductor light-emitting device of the present invention shows excellent light durability and thermal durability in any application example as compared with a conventional member for a semiconductor light-emitting device, is less prone to cracking and peeling, and has a luminance of There is little decrease. Therefore, according to the semiconductor light emitting device member of the present invention, a highly reliable member can be provided over a long period of time.
A) A semiconductor light emitting device that uses the light emission color of the light emitting element as it is.
B) A phosphor part is disposed in the vicinity of the light emitting element, the phosphor and the phosphor component in the phosphor part are excited by light from the light emitting element, and light having a desired wavelength is emitted using the fluorescence. Semiconductor light emitting device.

  In the application example of A), taking advantage of the high durability, transparency and sealing agent performance of the semiconductor light-emitting device member of the present invention, a high durability sealing agent, a light extraction film, and various functional components are retained when used alone. It can be used as an agent. In particular, when the semiconductor light-emitting device member of the present invention is used as a functional component retaining agent that retains the inorganic oxide particles and the like, the semiconductor light-emitting device member of the present invention retains a transparent high refractive component, By using the semiconductor light-emitting device member of the invention in close contact with the light-emitting surface of the light-emitting element and making the refractive index close to that of the light-emitting element, reflection on the light-emitting surface of the light-emitting element is reduced, and higher light extraction efficiency Can be obtained.

  Moreover, also in the application example of B), the member for semiconductor light-emitting devices of the present invention can exhibit the same excellent performance as the application example of the above A), and retains the phosphor and the phosphor component. By doing so, a phosphor part with high durability and high light extraction efficiency can be formed. Further, when the member for semiconductor light emitting device of the present invention is held together with a transparent high refractive component in addition to the phosphor and the phosphor component, the refractive index of the member for semiconductor light emitting device of the present invention is changed to a light emitting element or phosphor. By setting the refractive index in the vicinity, the interface reflection can be reduced and higher light extraction efficiency can be obtained.

  Below, the basic concept of each embodiment to which the member for semiconductor light emitting device of the present invention is applied will be described with reference to FIGS. 49 (a) and 49 (b). FIG. 49 is an explanatory diagram of the basic concept of each embodiment. (A) corresponds to the application example of the above A), and (b) corresponds to the application example of the above B).

  The light-emitting devices (semiconductor light-emitting devices) 1A and 1B of the respective embodiments are, as shown in FIGS. 49 (a) and 49 (b), a light-emitting element 2 composed of LED chips and a book disposed near the light-emitting element 2. The semiconductor light emitting device members 3A and 3B of the invention are provided.

  However, in the embodiments (embodiments A-1 and A-2) corresponding to the application example of A) as shown in FIG. 49A, the light-emitting device 1A has a phosphor on the semiconductor light-emitting device member 3A. And does not contain phosphor components. In this case, the semiconductor light emitting device member 3 </ b> A exhibits functions such as sealing of the light emitting element 2, light extraction function, and functional component retention. In the following description, the semiconductor device member 3A containing no phosphor or phosphor component is appropriately referred to as a “transparent member”.

  On the other hand, in the embodiment (embodiments B-1 to B-40) corresponding to the application example of B) as shown in FIG. 49 (b), the light emitting device 1B has a phosphor on the semiconductor light emitting device member 3B. And phosphor components. In this case, the semiconductor device member 3B can exhibit a wavelength conversion function in addition to the various functions that the semiconductor device member 3A of FIG. 49A can exhibit. In the following description, the semiconductor device member 3B containing a phosphor or a phosphor component is appropriately referred to as a “phosphor portion”. Further, the phosphor portion may be appropriately indicated by reference numerals 33 and 34 according to the shape and function thereof.

  The light emitting element 2 is constituted by, for example, an LED chip that emits blue light or ultraviolet light, but may be an LED chip of a light emitting color other than these.

  In addition, the transparent member 3A exhibits functions such as a highly durable sealant, a light extraction film, and various function-added films of the light emitting element 2. The transparent member 3A may be used alone, but an optional additive can be contained unless the phosphor and the phosphor component are excluded unless the effects of the present invention are significantly impaired.

  On the other hand, the phosphor portion 3B can exhibit functions such as a highly durable sealant, a light extraction film, and various function-added films of the light-emitting element 2, and is excited by light from the light-emitting element 2 to have a desired wavelength. It exhibits a wavelength conversion function for emitting light. The phosphor portion 3B only needs to include at least a fluorescent material that is excited by light from the light emitting element 2 and emits light of a desired wavelength. Examples of such fluorescent materials include the various phosphors exemplified above. As a luminescent color of the phosphor portion 3B, the three primary colors of red (R), green (G), and blue (B) can be used, as well as white such as a fluorescent lamp and yellow such as a light bulb. In short, the phosphor portion 3B has a wavelength conversion function of emitting light having a desired wavelength different from the excitation light.

  In the above-described light emitting device 1A shown in FIG. 49A, the light 4 emitted from the light emitting element 2 passes through the transparent member 3A and is emitted outside the light emitting device 1A. Therefore, in the light-emitting device 1 </ b> A, the light 4 emitted from the light-emitting element 2 is used as it is in the emission color when emitted from the light-emitting element 2.

  On the other hand, in the light emitting device 1B shown in FIG. 49B, a part 4a of the light emitted from the light emitting element 2 passes through the phosphor portion 3B as it is and is emitted to the outside of the light emitting device 1B. Further, in the light emitting device 1B, the other part 4b of the light emitted from the light emitting element 2 is absorbed by the phosphor part 3B to excite the phosphor part 3B, and the phosphor particles contained in the phosphor part 3B, Light 5 having a wavelength peculiar to fluorescent components such as fluorescent ions and fluorescent dyes is emitted to the outside of the light emitting device 1B.

  Therefore, from the light emitting device 1B, the combined light 6 of the light 4a emitted from the light emitting element 2 and transmitted through the phosphor portion 3B and the light 5 emitted from the phosphor portion 3B is emitted as wavelength-converted light. Therefore, the light emission color of the light emitting device 1B as a whole is determined by the light emission color of the light emitting element 2 and the light emission color of the phosphor portion 3B. The light 4a emitted from the light emitting element 2 and transmitted through the phosphor portion 3B is not always necessary.

[A. Embodiment not using fluorescence]
[Embodiment A-1]
In the light emitting device 1A of the present embodiment, as shown in FIG. 1, the light emitting element 2 is surface-mounted on an insulating substrate 16 provided with a printed wiring 17. In the light emitting element 2, a p-type semiconductor layer (not shown) and an n-type semiconductor layer (not shown) of the light emitting layer portion 21 are electrically connected to printed wirings 17 and 17 through conductive wires 15 and 15, respectively. Has been. The conductive wires 15 and 15 have a small cross-sectional area so as not to block light emitted from the light emitting element 2.

  Here, as the light emitting element 2, an element emitting light of any wavelength from the ultraviolet to the infrared range may be used, but here, a gallium nitride LED chip is used. In addition, the light emitting element 2 has an n-type semiconductor layer (not shown) formed on the lower surface side in FIG. 1 and a p-type semiconductor layer (not shown) formed on the upper surface side, and light output from the p-type semiconductor layer side. Therefore, the upper part of FIG.

  Further, a frame-shaped frame member 18 surrounding the light emitting element 2 is fixed on the insulating substrate 16, and a sealing portion 19 for sealing and protecting the light emitting element 2 is provided inside the frame member 18. The sealing portion 19 is formed by the transparent member 3A, which is a semiconductor light emitting device member of the present invention, and can be formed by potting with the above-described semiconductor light emitting device member forming liquid.

  Since the light emitting device 1A of the present embodiment includes the light emitting element 2 and the transparent member 3A, the light durability and the heat durability of the light emitting device 1A can be improved. Moreover, since cracks and peeling do not easily occur in the sealing portion 3A, the transparency of the sealing portion 3A can be increased.

  Furthermore, light color unevenness and light color variation can be reduced as compared with the conventional case, and the light extraction efficiency can be increased. That is, since the sealing portion 3A can be made highly transparent with no cloudiness or turbidity, the light color uniformity is excellent, and there is almost no light color variation between the light emitting devices 1A. The efficiency of taking out the outside can be increased as compared with the conventional case. In addition, the weather resistance of the luminescent material can be increased, and the life of the light emitting device 1A can be extended as compared with the conventional case.

[Embodiment A-2]
As shown in FIG. 2, in the light emitting device 1 </ b> A of the present embodiment, the transparent member 3 </ b> A covers the front surface of the light emitting element 2, and the transparent member 3 </ b> A is sealed with a material different from the transparent member 3 </ b> A. Except that 19 is formed, the configuration is the same as that of the embodiment A-1. The transparent member 3A on the surface of the light emitting element 2 is a transparent thin film that functions as a light extraction film and a sealing film. For example, the above-described member forming liquid for semiconductor light emitting device is spin-coated when the chip of the light emitting element 2 is formed. It can form by apply | coating. In addition, the same code | symbol is attached | subjected to the component similar to embodiment A-1, and description is abbreviate | omitted.

Thus, the light emitting device 1A of the present embodiment also includes the light emitting element 2 and the transparent member 3A, as in the embodiment A-1, so that the light durability and the heat durability of the light emitting device 1A are improved. Since cracks and peeling do not easily occur in the sealing portion 3A, the transparency of the sealing portion 3A can be improved.
Furthermore, it is possible to obtain the same advantages as those of the embodiment A-1.

[B. Embodiment using fluorescence]
[Embodiment B-1]
As shown in FIG. 3A, the light-emitting device 1B of the present embodiment includes a light-emitting element 2 made of an LED chip and a mold part 11 formed of a translucent transparent material in a bullet shape. The mold part 11 covers the light emitting element 2, and the light emitting element 2 is electrically connected to lead terminals 12 and 13 formed of a conductive material. The lead terminals 12 and 13 are formed of a lead frame.

  The light-emitting element 2 is a gallium nitride LED chip, and an n-type semiconductor layer (not shown) is formed on the lower surface side in FIG. 3A, and a p-type semiconductor layer (not shown) is formed on the upper surface side. Since the light output is taken out from the p-type semiconductor layer side, the upper part of FIG. The rear surface of the light emitting element 2 is bonded to a mirror (cup part) 14 attached to the front end of the lead terminal 13 by die bonding. In the light-emitting element 2, conductive wires (for example, gold wires) 15 and 15 are connected to the p-type semiconductor layer and the n-type semiconductor layer by bonding, and the light-emitting element 2 and the light-emitting element 2 are connected via the conductive wires 15 and 15, respectively. The lead terminals 12 and 13 are electrically connected. The conductive wires 15 and 15 have a small cross-sectional area so as not to block the light emitted from the light emitting element 2.

  The mirror 14 has a function of reflecting light emitted from the side surface and the rear surface of the light emitting element 2 forward, and the light emitted from the LED chip and the light reflected forward by the mirror 14 function as a lens. 11 radiates forward from the mold part 11 through the front end part of the part 11. The mold part 11 covers the light emitting element 2 together with the mirror 14, the conductive wires 15 and 15, and part of the lead terminals 12 and 13, and the light emitting element 2 is deteriorated in characteristics due to reaction with moisture in the atmosphere. It is prevented. The rear end portions of the lead terminals 12 and 13 protrude from the rear surface of the mold portion 11 to the outside.

  Incidentally, as shown in FIG. 3B, in the light emitting element 2, the light emitting layer portion 21 made of a gallium nitride based semiconductor is formed on the phosphor portion 3B by using a semiconductor process, and the phosphor portion 3B. A reflective layer 23 is formed on the rear surface. Although the light emitted from the light emitting layer portion 21 is emitted in all directions, a part of the light absorbed by the phosphor portion 3B excites the phosphor portion 3B and emits light having a wavelength specific to the fluorescent component. . The light emitted from the phosphor portion 3B is reflected by the reflective layer 3 and emitted forward. Therefore, the light emitting device 1B can obtain combined light of the light emitted from the light emitting layer portion 21 and the light emitted from the phosphor portion 3B.

  Thus, the light emitting device 1B of the present embodiment includes the light emitting element 2 and the phosphor portion 3B that is excited by light from the light emitting element 2 and emits light of a desired wavelength. Here, if a phosphor having excellent translucency is used as the phosphor portion 3B, a part of the light emitted from the light emitting element 2 is emitted to the outside as it is, and other light emitted from the light emitting element 2 is used. Since the fluorescent component that becomes the emission center is excited by a part and light due to light emission specific to the fluorescent component is emitted to the outside, the light emitted from the light emitting element 2 and the light emitted from the fluorescent component of the phosphor portion 3B In addition, light color unevenness and light color variation can be reduced as compared with the conventional case, and the light extraction efficiency can be increased. That is, if a phosphor part 3B having high transparency without cloudiness or turbidity is used, the light color uniformity is excellent, and there is almost no light color variation between the light emitting devices 1B. The extraction efficiency can be increased as compared with the conventional case. In addition, the weather resistance of the light-emitting substance can be increased, and the life of the light-emitting device 1B can be extended as compared with the conventional case.

  Further, in the light emitting device 1B of the present embodiment, since the phosphor part 3B is also used as a substrate on which the light emitting element 2 is formed, the fluorescence that becomes the emission center in the phosphor part by a part of the light from the light emitting element 2 The body can be excited efficiently, and the luminance of light by light emission specific to the fluorescent component can be increased.

[Embodiment B-2]
In the light emitting device 1B of the present embodiment, as shown in FIG. 4, the light emitting element 2 is surface-mounted on an insulating substrate 16 provided with a printed wiring 17. Here, the light-emitting element 2 has the same configuration as that of the embodiment B-1, in which a light-emitting layer portion 21 made of a gallium nitride-based semiconductor is formed on the phosphor portion 3B, and a reflection layer is formed on the rear surface of the phosphor portion 3B. 23 is formed. In the light emitting element 2, the p-type semiconductor layer (not shown) and the n-type semiconductor layer (not shown) of the light emitting layer portion 21 are electrically connected to the printed wirings 17 and 17 via the conductive wires 15 and 15, respectively. It is connected.

  Further, a frame-shaped frame member 18 surrounding the light emitting element 2 is fixed on the insulating substrate 16, and a sealing portion 19 for sealing and protecting the light emitting element 2 is provided inside the frame member 18.

  Thus, also in the light emitting device 1B of the present embodiment, as in the embodiment B-1, the light emitting element 2 and the phosphor portion 3B that is excited by the light from the light emitting element 2 and emits light of a desired wavelength. Therefore, the combined light of the light from the light emitting element 2 and the light from the phosphor can be obtained. Further, similarly to the embodiment B-1, the light color unevenness and the light color variation can be reduced as compared with the conventional case, the light extraction efficiency to the outside can be increased, and the life can be extended. It becomes.

[Embodiment B-3]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-2, and does not use the frame member 18 (see FIG. 4) described in the embodiment B-2, as shown in FIG. Further, the shape of the sealing portion 19 is different. In addition, the same code | symbol is attached | subjected to the component similar to embodiment B-2, and description is abbreviate | omitted.

  The sealing portion 19 in the present embodiment includes a truncated cone-shaped sealing function portion 19 a that seals the light emitting element 2 and a lens-shaped lens function portion 19 b that functions as a lens at the front end portion of the sealing portion 19. ing.

  Therefore, in the light emitting device 1B of the present embodiment, the number of parts can be reduced compared to the embodiment B-2, and the size and weight can be reduced. Moreover, by providing the lens function part 19b functioning as a lens in a part of the sealing part 19, a light distribution with excellent directivity can be obtained.

[Embodiment B-4]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-2, and as shown in FIG. 6, a recess for housing the light emitting element 2 on one surface (the upper surface in FIG. 6) of the insulating substrate 16. The light emitting element 2 is mounted on the bottom of the recess 16a, and the sealing portion 19 is provided in the recess 16a. Here, the printed wirings 17 and 17 formed on the insulating substrate 16 extend to the bottom of the recess 16a, and are electrically connected to the light emitting layer portion 21 made of a gallium nitride based semiconductor of the light emitting element 2 via the conductive wires 15 and 15. It is connected to the. In addition, the same code | symbol is attached | subjected to the component similar to embodiment B-2, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, the sealing portion 19 is formed by filling the recess 16a formed on the upper surface of the insulating substrate 16, and therefore the frame member 18 described in the embodiment B-2. (See FIG. 5) and the sealing part 19 can be formed without using the molding die described in the embodiment B-3, and the sealing of the light emitting element 2 compared to the embodiments B-2 and B-3. There is an advantage that the stopping process can be easily performed.

[Embodiment B-5]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-4, and is characterized in that the light emitting element 2 is so-called flip-chip mounted on the insulating substrate 16 as shown in FIG. . That is, the light emitting element 2 is provided with bumps 24 and 24 made of a conductive material on the surface side of each of the p-type semiconductor layer (not shown) and the n-type semiconductor layer (not shown) of the light emitting layer portion 21. The light emitting layer portion 21 is electrically connected face down with the printed wirings 17 and 17 of the insulating substrate 16 via the bumps 24 and 24. Therefore, in the light emitting element 2 in the present embodiment, the light emitting layer portion 21 is disposed on the side closest to the insulating substrate 16, the reflective layer 23 is disposed on the side farthest from the insulating substrate 16, and the light emitting layer portion 21 and the reflective layer are reflected. The phosphor portion 3 </ b> B is interposed between the layer 23. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment B-4, and description is abbreviate | omitted.

  In the light emitting device 1B of the present embodiment, the light reflected downward (backward) in FIG. 7 by the reflective layer 23 is reflected by the inner peripheral surface of the recess 16a and radiated upward (forward) in FIG. Here, it is desirable to separately provide a reflective layer made of a material having a high reflectivity on the inner peripheral surface of the recess 16a and other than the printed wirings 17 and 17.

  Therefore, in the light emitting device 1B of the present embodiment, the conductive wires 15 and 15 as in the embodiment B-4 are not required to connect the printed wirings 17 and 17 provided on the insulating substrate 16 and the light emitting element 2. Therefore, it is possible to improve mechanical strength and reliability as compared with Embodiment B-4.

[Embodiment B-6]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-5, and is different in that the reflective layer 23 described in the embodiment B-5 is not provided as shown in FIG. In short, in the light emitting device 1B of the present embodiment, the light emitted from the light emitting layer portion 21 and the light emitted from the phosphor portion 3B pass through the sealing portion 19 and are emitted forward as they are. In addition, the same code | symbol is attached | subjected to the component similar to embodiment B-5, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, the number of parts can be reduced as compared with the embodiment B-5, and the manufacture becomes easy.

[Embodiment B-7]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-1, and as shown in FIG. It is characterized by the fact that it is integrally formed with. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment B-1, and description is abbreviate | omitted.

  In the manufacture of the light emitting device 1B of the present embodiment, the mold part 11 is formed by a method of immersing an in-process product not provided with the mold part 11 in a molding die storing the phosphor part forming liquid and drying and removing the solvent. Is forming.

  Therefore, in this embodiment, since the mold part 11 is formed integrally with the phosphor part, by using the semiconductor light-emitting device member of the present invention as described later as the phosphor part, the mold part 11 is sealed. It is possible to improve the stopping property, transparency, light resistance, heat resistance, etc., and to suppress cracks and peeling due to long-term use.

[Embodiment B-8]
The basic configuration of the light-emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-1, and as shown in FIG. It is characterized in that it is. That is, in this embodiment, instead of providing the phosphor part 3B in the light emitting element 2 as in the embodiment B-1, the phosphor part 3B having a shape along the outer periphery of the mold part 11 is provided. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment B-1, and description is abbreviate | omitted.

  The phosphor portion 3B in the present embodiment may be formed as a thin film by the solvent drying method described in the embodiment B-7, or a member obtained by molding a solid phosphor portion in a cup shape in advance is the mold portion 11. You may make it mount on.

  Therefore, in the light emitting device 1B of the present embodiment, the amount of material used in the phosphor portion is smaller than in the case where the entire mold portion 11 is formed integrally with the phosphor portion as in the light emitting device 1B of the embodiment B-7. Reduction can be achieved and cost reduction can be achieved.

[Embodiment B-9]
The basic configuration of the light-emitting device 1B of this embodiment is substantially the same as that of Embodiment B-2, and as shown in FIG. And a sealing portion 19 inside the frame member 18 is formed of a phosphor portion similar to the phosphor portion 3B described in the embodiment B-2. There is a feature in the point. In addition, the same code | symbol is attached | subjected to the component similar to embodiment B-2, and description is abbreviate | omitted.

  In this embodiment, since the sealing portion 19 is formed of the phosphor portion, the mold portion 11 is sealed by using the semiconductor light emitting device member of the present invention as described later as the phosphor portion. Property, transparency, light resistance, heat resistance, etc. can be improved, and cracks and peeling associated with long-term use can be suppressed.

[Embodiment B-10]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-2, and as shown in FIG. 12, surrounds the light emitting element 2 on the one surface (upper surface of FIG. 12) side of the insulating substrate 16. And a sealing portion 19 inside the frame member 18 is formed of a phosphor portion similar to the phosphor portion 3B described in the embodiment B-2. There is a feature in the point. In addition, the same code | symbol is attached | subjected to the component similar to embodiment B-2, and description is abbreviate | omitted.

  In this embodiment, since the sealing portion 19 is formed of the phosphor portion, the mold portion 11 is sealed by using the semiconductor light emitting device member of the present invention as described later as the phosphor portion. Property, transparency, light resistance, heat resistance, etc. can be improved, and cracks and peeling associated with long-term use can be suppressed.

  In the present embodiment, the phosphor portion 3B is formed on the rear surface of the light emitting layer portion 21 of the light emitting element 2, and the sealing portion 19 that covers the light emitting element 2 is formed of the phosphor portion. The phosphor portion is present in all directions of the light emitting layer portion 21, and there is an advantage that excitation and emission of the phosphor portion can be performed more efficiently than in the embodiment B-9.

[Embodiment B-11]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-2, and as shown in FIG. 13, the lens is formed in advance on the upper surface of the sealing portion 19 made of a translucent material. It is characterized in that the phosphor part 33 is provided. Here, the phosphor part 33 is made of the same material as the phosphor part 3B described in the embodiment B-2, and is excited by light from the light emitting element 2 to emit light of a desired wavelength. In addition, the same code | symbol is attached | subjected to the component similar to embodiment B-2, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the phosphor portion 33 has not only a wavelength conversion function but also a function as a lens, and the directivity control of light emission by the lens effect can be performed.

[Embodiment B-12]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-2. As shown in FIG. 14, the light emitting device 1B is formed in a lens shape in advance on the upper surface of the sealing portion 19 made of a translucent material. It is characterized in that the phosphor part 33 is provided. Here, the phosphor part 33 is made of the same material as the phosphor part 3B described in the embodiment B-2, and is excited by light from the light emitting element 2 to emit light of a desired wavelength. . In addition, the same code | symbol is attached | subjected to the component similar to embodiment B-2, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the phosphor portion 33 has not only a wavelength conversion function but also a function as a lens, and the directivity control of light emission by the lens effect can be performed. In the present embodiment, since the phosphor portion 3B is formed on the rear surface of the light emitting layer portion 21 of the light emitting element 2, excitation and emission of the phosphor portion are more efficiently performed than in the embodiment B-11. There is an advantage that can be done.

[Embodiment B-13]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-3, and as shown in FIG. The sealing part 19 is characterized in that it is formed of a phosphor part. Here, the sealing portion 19 is a lens-shaped sealing function portion 19a that seals the light emitting element 2 and a lens-like shape that functions as a lens at the front end portion of the sealing portion 19 as in the embodiment B-3. And a lens function unit 19b. In addition, the same code | symbol is attached | subjected to the component similar to embodiment B-3, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, not only the function of the sealing portion 19 sealing and protecting the light emitting element 2, but also the wavelength conversion function for converting the wavelength of the light from the light emitting element 2 and the directivity of light emission. It has a lens function to control. Moreover, the weather resistance of the sealing part 19 can be improved and lifetime improvement can be achieved. In the present embodiment, the phosphor portion 3B is formed on the rear surface of the light emitting layer portion 21 of the light emitting element 2, and the sealing portion 19 that covers the light emitting element 2 is formed of the phosphor portion. The phosphor portion is present in all directions of the light emitting layer portion 21, and there is an advantage that excitation and emission of the phosphor portion can be performed more efficiently than in the embodiment B-12.

[Embodiment B-14]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-3, and as shown in FIG. 16, the sealing that covers the light emitting element 2 on one surface (the upper surface of FIG. 16) side of the insulating substrate 16 There is a feature in that the sealing portion 19 is formed by the phosphor portion 3B. Here, the sealing portion 19 is a lens-shaped sealing function portion 19a that seals the light emitting element 2 and a lens-like shape that functions as a lens at the front end portion of the sealing portion 19 as in the embodiment B-3. And a lens function unit 19b. In addition, the same code | symbol is attached | subjected to the component similar to embodiment B-3, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, not only the function of the sealing portion 19 sealing and protecting the light emitting element 2, but also the wavelength conversion function for converting the wavelength of the light from the light emitting element 2 and the directivity of light emission. It has a lens function to control. Moreover, the weather resistance of the sealing part 19 can be improved and lifetime improvement can be achieved.

[Embodiment B-15]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-3. As shown in FIG. 17, a dome-shaped phosphor portion 34 that covers the light emitting element 2 on the upper surface side of the insulating substrate 16 is provided. The sealing portion 19 made of a translucent resin is formed on the outer surface side of the phosphor portion 34. Here, as in the embodiment B-3, the sealing portion 19 includes a sealing function portion 19a that seals the light emitting element 2, and a lens-shaped lens function portion 19b that functions as a lens at the front end portion of the sealing portion 19. It consists of and. In addition, the same code | symbol is attached | subjected to the component similar to embodiment B-3, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the amount of material used for the phosphor portion 34 can be reduced as compared with Embodiments B-13 and B-14. Moreover, in this embodiment, since the dome-shaped phosphor part 34 covering the light emitting element 2 is disposed, by using the semiconductor light emitting device member of the present invention as described later, the phosphor part is used from the outside. Deterioration of the light-emitting element 2 due to moisture or the like can be prevented more reliably, and the life can be extended.

[Embodiment B-16]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-3, and a dome-shaped phosphor portion 34 that covers the light emitting element 2 on the upper surface side of the insulating substrate 16 is provided as shown in FIG. The sealing portion 19 is formed on the outer surface side of the phosphor portion 34. Here, as in the embodiment B-3, the sealing portion 19 includes a sealing function portion 19a that seals the light emitting element 2, and a lens-shaped lens function portion 19b that functions as a lens at the front end portion of the sealing portion 19. It consists of and. In addition, the same code | symbol is attached | subjected to the component similar to embodiment B-3, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the amount of material used for the phosphor portion 34 can be reduced as compared with Embodiments B-13 and B-14. Moreover, in this embodiment, since the dome-shaped phosphor part 34 covering the light emitting element 2 is disposed, by using the semiconductor light emitting device member of the present invention as described later, the phosphor part is used from the outside. Deterioration of the light-emitting element 2 due to moisture or the like can be prevented more reliably, and the life can be extended. In the present embodiment, the phosphor portion 3B is formed on the rear surface of the light emitting layer portion 21 of the light emitting element 2, and the sealing portion 19 that covers the light emitting element 2 is formed of the phosphor portion. The phosphor portion is present in all directions of the light emitting layer portion 21, and there is an advantage that excitation and emission of the phosphor portion can be performed more efficiently than in the embodiment B-15.

[Embodiment B-17]
The basic configuration of the light-emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-4, and as shown in FIG. The sealing part 19 which seals the light emitting element 2 arrange | positioned is provided, and the sealing part 19 is characterized by the point formed of the fluorescent substance part. Here, the phosphor part is excited by light from the light emitting element 2 and emits light of a desired wavelength, like the phosphor part 3B described in the embodiment B-1. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment B-4, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, since the sealing portion 19 is formed of the phosphor portion, the semiconductor light emitting device member of the present invention is used as the phosphor portion to be sealed as described later. It becomes possible to improve the sealing property, transparency, light resistance, heat resistance and the like of the portion 19 and to suppress cracks and peeling due to long-term use. In the present embodiment, the phosphor portion 3B is formed on the rear surface of the light emitting layer portion 21 of the light emitting element 2, and the sealing portion 19 that covers the light emitting element 2 is formed by the phosphor portion 3B. The phosphor portion is present in all directions of the light emitting layer portion 21 and there is an advantage that the phosphor portion can be excited and emitted more efficiently than the embodiment B-15.

[Embodiment B-18]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-4, and as shown in FIG. 20, at the bottom of the recess 16a provided on one surface of the insulating substrate 16 (upper surface in FIG. 20). The sealing part 19 which seals the arrange | positioned light emitting element 2 is provided, and the sealing part 19 has the characteristics in the point formed of the fluorescent substance part 3B. Here, the phosphor portion 3B is excited by the light from the light emitting element 2 and emits light of a desired wavelength, like the phosphor portion 3B described in the embodiment B-1. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment B-4, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, since the sealing portion 19 is formed of the phosphor portion, the semiconductor light emitting device member of the present invention is used to seal the phosphor portion 3B as described later. It becomes possible to improve the sealing property, transparency, light resistance, heat resistance, and the like of the stopper 19 and to suppress cracks and peeling due to long-term use.

[Embodiment B-19]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-4, and as shown in FIG. 21, the phosphor previously molded into a lens shape on the upper surface (light extraction surface) of the sealing portion 19 It is characterized in that the portion 33 is provided. Here, the phosphor portion 33 is excited by light from the light emitting element 2 and emits light of a desired wavelength, like the phosphor portion 3B described in the embodiment B-1. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment B-4, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the phosphor portion 33 has not only a wavelength conversion function but also a function as a lens, and the directivity control of light emission by the lens effect can be performed.

[Embodiment B-20]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-4, and as shown in FIG. It is characterized in that the portion 33 is provided. Here, the phosphor portion 33 is excited by light from the light emitting element 2 and emits light of a desired wavelength, like the phosphor portion 3B described in the embodiment B-1. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment B-4, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the phosphor portion 33 has not only a wavelength conversion function but also a function as a lens, and the directivity control of light emission by the lens effect can be performed. Further, in the present embodiment, since the phosphor portion 3B is also disposed on the rear surface of the light emitting layer portion 21 of the light emitting element 2, excitation and light emission of the phosphor portion are more efficient than Embodiment B-19. There is an advantage that it is carried out automatically.

[Embodiment B-21]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-5, and as shown in FIG. The sealing part 19 which seals the arrange | positioned light emitting element 2 is provided, and the sealing part 19 has the characteristics in the point formed of the fluorescent substance part 3B. Here, as shown in FIG. 24, the sealing portion 19 has a concave portion 19 c for accommodating the light emitting element 2 in a portion corresponding to the light emitting element 2 with an outer peripheral shape corresponding to the recess 16 a. Since what was processed into the shape which it has is mounted | worn in the recess 16a of the insulated substrate 16 in which the light emitting element 2 was mounted, a sealing process can be simplified. Further, the phosphor part 3B forming the sealing part 19 is excited by light from the light emitting element 2 and emits light of a desired wavelength, like the phosphor part 3B described in the embodiment B-1. In addition, the same code | symbol is attached | subjected to the component similar to embodiment B-5, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, since the sealing portion 19 is formed of the phosphor portion, the semiconductor light emitting device member of the present invention is used to seal the phosphor portion 3B as described later. It becomes possible to improve the sealing property, transparency, light resistance, heat resistance, and the like of the stopper 19 and to suppress cracks and peeling due to long-term use. In the present embodiment, the light emitted forward from the light emitting layer portion 21 of the light emitting element 2 is once reflected by the reflective layer 23 toward the inner bottom surface of the recess 16a. If a reflection layer is provided on the inner peripheral surface, it is further reflected on the inner bottom surface and the inner peripheral surface of the recess 16a and emitted forward, so that the optical path length can be increased and the phosphor portion 3B is more efficient. There is an advantage that excitation and emission can be performed.

[Embodiment B-22]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-5, and as shown in FIG. The sealing part 19 which seals the arrange | positioned light emitting element 2 is provided, and the sealing part 19 has the characteristics in the point formed of the fluorescent substance part 3B. Here, as shown in FIG. 26, the sealing portion 19 has a recess 19 c for accommodating the light emitting element 2 in a portion corresponding to the light emitting element 2 with an outer peripheral shape corresponding to the recess 16 a. Since what was processed into the shape which it has is mounted | worn in the recess 16a of the insulated substrate 16 in which the light emitting element 2 was mounted, a sealing process can be simplified. Further, the phosphor part 3B forming the sealing part 19 is excited by light from the light emitting element 2 and emits light of a desired wavelength, like the phosphor part 3B described in the embodiment B-1. In addition, the same code | symbol is attached | subjected to the component similar to embodiment B-5, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, since the sealing portion 19 is formed of the phosphor portion 3B, by using the semiconductor light emitting device member of the present invention as described later as the phosphor portion 3B, It becomes possible to improve the sealing property, transparency, light resistance, heat resistance, etc. of the sealing part 19, and to suppress the crack and peeling accompanying long-term use.

[Embodiment B-23]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-6, and as shown in FIG. There is a feature in the point. Here, a sealing portion 19 made of a translucent material is formed around the light emitting element 2 and the phosphor portion 3B, and the phosphor portion 3B has one end surface (the lower end surface in FIG. The other end face (upper end face in FIG. 27) is exposed in close contact with the light emitting layer portion 21. In addition, the same code | symbol is attached | subjected to the component similar to embodiment B-6, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, the phosphor portion 3B whose one end face is in close contact with the light emitting layer portion 21 of the light emitting element 2 is formed in a rod shape, so The phosphor part 3B can be efficiently taken into the phosphor part 3B through the one end face of the phosphor part 3B, and the light emission of the phosphor part 3B excited by the taken-in light is efficiently transmitted to the outside through the other end face of the phosphor part 3B. Can be radiated. In this embodiment, only one phosphor portion 3B is formed in a relatively large-diameter rod shape. However, as shown in FIG. 28, the phosphor portion 3B is formed in a relatively small-diameter fiber shape. Then, a plurality of phosphor portions 3B may be arranged side by side. In addition, the cross-sectional shape of the phosphor portion 3B is not limited to a circular shape, and may be, for example, a quadrangular shape or other shapes.

[Embodiment B-24]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-23, and includes a sealing portion 19 provided in the recess 16a of the insulating substrate 16 as shown in FIG. The feature is that the portion 19 is formed by the phosphor portion 3B. Here, as shown in FIG. 30, the sealing portion 19 has a through hole 19 d for accommodating the light emitting element 2 in a portion corresponding to the light emitting element 2 with an outer peripheral shape corresponding to the recess 16 a. Since the thing processed into the shape which has this is mounted | worn in the recess 16a of the insulated substrate 16 in which the light emitting element 2 was mounted, a sealing process can be simplified. Further, the phosphor part 3B forming the sealing part 19 is excited by light from the light emitting element 2 and emits light of a desired wavelength, like the phosphor part 3B described in the embodiment B-1. In addition, the same code | symbol is attached | subjected to the component similar to embodiment B-23, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, since the sealing portion 19 is also formed by the phosphor portion 3B, it is possible to extend the life and increase the efficiency of light emission. In this embodiment, only one phosphor portion 3B is formed in a relatively large-diameter rod shape. However, as shown in FIG. 31, the phosphor portion 3B is formed in a relatively small-diameter fiber shape. Then, a plurality of phosphor portions 3B may be arranged side by side. In addition, the cross-sectional shape of the phosphor portion 3B is not limited to a circular shape, and may be, for example, a quadrangular shape or other shapes.

[Embodiment B-25]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-2, and as shown in FIG. 32, a frame member 18 disposed on one surface (upper surface in FIG. 32) of the insulating substrate 16 is provided. The light emitting layer portion 21 of the light emitting element 2 is an AlGaN-based light emitting device that emits near ultraviolet light, and phosphor powder (for example, near ultraviolet light) is used in a translucent material used as the sealing portion 19 inside the frame member 18. It is characterized in that YAG: Ce ³⁺ phosphor powder that is excited by light and emits yellow light is dispersed. In the present embodiment, the phosphor portion 3B includes a fluorophosphate glass (for example, P ₂ O ₅ · AlF ₃ · MgF · CaF ₂ · SrF ₂ · BaCl that emits blue light when excited by near ultraviolet light). ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to embodiment B-2, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 to emit light is dispersed in the sealing portion 19, so the light emitted from the light emitting element 2 and the phosphor A light output composed of the combined light of the light emitted from the portion 3B and the light emitted from the phosphor powder is obtained.

  Therefore, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the phosphor powder in the sealing portion 19 are emitted by the light emitted from the light emitting element 2. Both of them are excited and each emits a unique light emission, and the combined light is obtained. In the present embodiment, blue light is emitted from the phosphor portion 3B and yellow light is emitted from the phosphor powder, and white light different from any of the emission colors can be obtained.

In addition, in existing phosphor powders and phosphor particles in the phosphor part, materials that can emit light are limited, and a desired light color may not be obtained with only one of them, in such cases This embodiment is extremely effective. That is, when a desired light color characteristic cannot be obtained only by the phosphor part 3B, a desired powder color characteristic lacking in the phosphor part 3B is complemented and complemented. A light emitting device 1B having light color characteristics can be realized. In this embodiment, the emission color of the phosphor powder is different from the emission color of the phosphor portion 3B. However, if the emission color of the phosphor powder is aligned with the emission color of the phosphor portion 3B, the phosphor The light emission of the phosphor powder is superimposed on the light emission of the portion 3B, so that the light output can be increased and the light emission efficiency can be increased. Here, when the phosphor portion 3B and the phosphor powder have substantially the same emission color, for example, P ₂ O ₅ · SrF ₂ · BaF ₂ that emits red light as the phosphor particles of the phosphor portion 3B. : Eu ³⁺ and Y ₂ O ₂ S: Eu ³⁺ that emits red light as a phosphor powder can improve the efficiency of red light emission. Of course, the combination of the phosphor portion 3B and the phosphor powder is an example, and other combinations may be adopted.

[Embodiment B-26]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-3, and as shown in FIG. The light emitting layer portion 21 of the light emitting element 2 is AlGaN-based and emits near ultraviolet light. The phosphor powder (for example, near ultraviolet light) YAG: Ce ³⁺ phosphor powder that emits yellow light when excited by the above is dispersed, and the sealing portion 19 functions as the phosphor portion. In the present embodiment, as phosphor particles of the phosphor portion 3B, fluorophosphate glass (for example, P ₂ that emits blue light when excited by near ultraviolet light).
O ₅ · AlF ₃ · MgF · CaF ₂ · SrF ₂ · BaCl ₂ : Eu ²⁺ ). In addition,
Constituent elements similar to those in Embodiment B-3 are assigned the same reference numerals, and descriptions thereof are omitted.

  Therefore, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19 as in the case of the embodiment B-25. A light output composed of the combined light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder is obtained. That is, as in Embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the phosphor portion 3B are sealed by the light emitted from the light emitting element 2. Both of the phosphor powder in the stopper 19 are excited and each emits unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 3B. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment B-27]
The basic configuration of the light-emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-4. As shown in FIG. 34, the light-emitting element 2 is filled in the recess 16a formed on the upper surface of the insulating substrate 16. A light emitting layer portion 21 of the light emitting element 2 emits near-ultraviolet light and includes a phosphor powder (for example, a phosphor powder (for example, YAG: Ce ³⁺ phosphor powder that emits yellow light when excited by near ultraviolet light is dispersed, and the sealing portion 19 functions as the phosphor portion. Further, in the present embodiment, as the phosphor particles of phosphor part 3B, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment B-4, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19 as in the case of the embodiment B-25. A light output composed of the combined light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder is obtained. That is, as in Embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the phosphor portion 3B are sealed by the light emitted from the light emitting element 2. Both of the phosphor powder in the stopper 19 are excited and each emits unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 3B. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment B-28]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-5, and as shown in FIG. 35, the recess 16a formed on one surface (the upper surface in FIG. 35) of the insulating substrate 16 is filled. The light emitting element 2 is provided with a sealing part 19 for sealing the light emitting element 2, and the light emitting layer part 21 of the light emitting element 2 emits near-ultraviolet light in an AlGaN system. The phosphor powder (for example, YAG: Ce ³⁺ phosphor powder that emits yellow light when excited by near-ultraviolet light) is dispersed, and the sealing portion 19 functions as the phosphor portion. . Further, in the present embodiment, as the phosphor particles of phosphor part 3B, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to embodiment B-5, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19 as in the case of the embodiment B-25. A light output composed of the combined light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder is obtained. That is, as in Embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the phosphor portion 3B are sealed by the light emitted from the light emitting element 2. Both of the phosphor powder in the stopper 19 are excited and each emits unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 3B. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment B-29]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-6, and as shown in FIG. 36, the recess 16a formed on one surface (the upper surface in FIG. 36) of the insulating substrate 16 is filled. The light emitting element 2 is provided with a sealing part 19 for sealing the light emitting element 2, and the light emitting layer part 21 of the light emitting element 2 emits near-ultraviolet light in an AlGaN system. The phosphor powder (for example, YAG: Ce ³⁺ phosphor powder that emits yellow light when excited by near-ultraviolet light) is dispersed, and the sealing portion 19 functions as the phosphor portion. . Further, in the present embodiment, as the phosphor particles of phosphor part 3B, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to embodiment B-6, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19 as in the case of the embodiment B-25. A light output composed of the combined light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder is obtained. That is, as in Embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the phosphor portion 3B are sealed by the light emitted from the light emitting element 2. Both of the phosphor powder in the stopper 19 are excited and each emits unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 3B. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment B-30]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-1, and as shown in FIGS. 37 (a) and 37 (b), a bullet-shaped mold part 11 is provided, and the light emitting element 2 The light emitting layer portion 21 is an AlGaN-based material that emits near-ultraviolet light, and phosphor powder (for example, YAG: Ce that emits yellow light when excited by near-ultraviolet light in a translucent material used as the mold portion 11. ³⁺ phosphor powder) is dispersed and the mold part 11 functions as a phosphor part. Further, in the present embodiment, as the phosphor particles of phosphor part 3B, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment B-1, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 to emit light is dispersed in the mold part 11 as in the case of the embodiment B-25. A light output composed of the combined light of the emitted light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder is obtained. That is, as in the embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the mold are formed by the light emitted from the light emitting element 2. Both of the phosphor powder in the portion 11 are excited and each emits unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 3B. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment B-31]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-8. As shown in FIG. 38, the light emitting device 1B includes a bullet-shaped mold part 11 and the light emitting layer part 21 of the light emitting element 2 (FIG. 38). Is an AlGaN-based material that emits near-ultraviolet light, and phosphor powder (for example, excited by near-ultraviolet light to emit yellow light) in the translucent material used as the mold part 11. YAG: Ce ³⁺ phosphor powder) is dispersed, and the mold part 11 functions as the phosphor part. Further, in the present embodiment, as the phosphor particles of phosphor part 3B, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment B-8, and description is abbreviate | omitted.

  Thus, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 to emit light is dispersed in the mold part 11 as in the case of the embodiment B-25. A light output composed of the combined light of the emitted light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder is obtained. That is, as in the embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the mold are formed by the light emitted from the light emitting element 2. Both of the phosphor powder in the portion 11 are excited and each emits unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 3B. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment B-32]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-11, and as shown in FIG. 39, the light emitting element 2 is sealed on one surface (upper surface of FIG. 39) side of the insulating substrate 16. The light emitting layer portion 21 of the light emitting element 2 includes a sealing portion 19 and emits near-ultraviolet light in an AlGaN system. A phosphor powder (for example, near ultraviolet light) is used in a translucent material used as the sealing portion 19. YAG: Ce ³⁺ phosphor powder that emits yellow light when excited by the above is dispersed, and the sealing portion 19 functions as the phosphor portion. Further, in the present embodiment, as the phosphor particles of phosphor part 3B, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to embodiment B-11, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19 as in the case of the embodiment B-25. A light output composed of the combined light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder is obtained. That is, as in Embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the phosphor portion 3B are sealed by the light emitted from the light emitting element 2. Both of the phosphor powder in the stopper 19 are excited and each emits unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 3B. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment B-33]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-15, and as shown in FIG. 40, the light emitting element 2 is sealed on one surface (upper surface of FIG. 40) side of the insulating substrate 16. The light emitting layer portion 21 of the light emitting element 2 includes a sealing portion 19 and emits near-ultraviolet light in an AlGaN system. A phosphor powder (for example, near ultraviolet light) is used in a translucent material used as the sealing portion 19. YAG: Ce ³⁺ phosphor powder that emits yellow light when excited by the above is dispersed, and the sealing portion 19 functions as the phosphor portion. Further, in the present embodiment, as the phosphor particles of phosphor part 3B, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment B-15, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19 as in the case of the embodiment B-25. A light output composed of the combined light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder is obtained. That is, as in Embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the phosphor portion 3B are sealed by the light emitted from the light emitting element 2. Both of the phosphor powder in the stopper 19 are excited and each emits unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 3B. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment B-34]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-19, and as shown in FIG. 41, the recess 16a formed on one surface (the upper surface in FIG. 41) of the insulating substrate 16 is filled. The light emitting element 2 is provided with a sealing part 19 for sealing the light emitting element 2, and the light emitting layer part 21 of the light emitting element 2 emits near-ultraviolet light in an AlGaN system. The phosphor powder (for example, YAG: Ce ³⁺ phosphor powder that emits yellow light when excited by near-ultraviolet light) is dispersed, and the sealing portion 19 functions as the phosphor portion. . Further, in the present embodiment, as the phosphor particles of phosphor part 3B, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to embodiment B-19, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19 as in the case of the embodiment B-25. A light output composed of the combined light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder is obtained. That is, as in Embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the phosphor portion 3B are sealed by the light emitted from the light emitting element 2. Both of the phosphor powder in the stopper 19 are excited and each emits unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 3B. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment B-35]
The basic configuration of the light-emitting device 1B of the present embodiment is substantially the same as that of Embodiments B-12 and B-22, and as shown in FIG. 42, a recess formed on one surface of the insulating substrate 16 (upper surface in FIG. 42). And a light-transmitting layer portion 21 of the light-emitting element 2 that emits near-ultraviolet light and is used as the sealing portion 19. The phosphor powder (for example, YAG: Ce ³⁺ phosphor powder that emits yellow light when excited by near ultraviolet light) is dispersed in the conductive material, and the sealing portion 19 functions as the phosphor portion. There is a feature. Further, in the present embodiment, as the phosphor particles of phosphor part 3B, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment B-12 and B-22, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19 as in the case of the embodiment B-25. A light output composed of the combined light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder is obtained. That is, as in Embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the phosphor portion 3B are sealed by the light emitted from the light emitting element 2. Both of the phosphor powder in the stopper 19 are excited and each emits unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 3B. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment B-36]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-12, and includes a sealing portion 19 that seals the light emitting element 2 on the upper surface side of the insulating substrate 16, as shown in FIG. The light emitting layer portion 21 of the light emitting element 2 emits near ultraviolet light in an AlGaN system, and phosphor powder (for example, yellow light excited by near ultraviolet light in the light transmitting material used as the sealing portion 19 is used. YAG: Ce ³⁺ phosphor powder) is dispersed, and the sealing portion 19 functions as the phosphor portion. Further, in the present embodiment, as the phosphor particles of phosphor part 3B, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment B-12, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19 as in the case of the embodiment B-25. A light output composed of the combined light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder is obtained. That is, as in Embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the phosphor portion 3B are sealed by the light emitted from the light emitting element 2. Both of the phosphor powder in the stopper 19 are excited and each emits unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 3B. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment B-37]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-16, and as shown in FIG. 44, the light emitting element 2 is sealed on one surface (upper surface of FIG. 44) side of the insulating substrate 16. The light emitting layer portion 21 of the light emitting element 2 includes a sealing portion 19 and emits near-ultraviolet light in an AlGaN system. A phosphor powder (for example, near ultraviolet light) is used in a translucent material used as the sealing portion 19. YAG: Ce ³⁺ phosphor powder that emits yellow light when excited by the above is dispersed, and the sealing portion 19 functions as the phosphor portion. Further, in the present embodiment, as the phosphor particles of phosphor part 3B, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to embodiment B-16, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19 as in the case of the embodiment B-25. A light output composed of the combined light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder is obtained. That is, as in Embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the phosphor portion 3B are sealed by the light emitted from the light emitting element 2. Both of the phosphor powder in the stopper 19 are excited and each emits unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 3B. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment B-38]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-20, and as shown in FIG. 45, the recess 16a formed on one surface (the upper surface in FIG. 45) of the insulating substrate 16 is filled. The light emitting element 2 is provided with a sealing part 19 for sealing the light emitting element 2, and the light emitting layer part 21 of the light emitting element 2 emits near-ultraviolet light in an AlGaN system. The phosphor powder (for example, YAG: Ce ³⁺ phosphor powder that emits yellow light when excited by near-ultraviolet light) is dispersed, and the sealing portion 19 functions as the phosphor portion. . Further, in the present embodiment, as the phosphor particles of phosphor part 3B, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to embodiment B-20, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19 as in the case of the embodiment B-25. A light output composed of the combined light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder is obtained. That is, as in Embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the phosphor portion 3B are sealed by the light emitted from the light emitting element 2. Both of the phosphor powder in the stopper 19 are excited and each emits unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 3B. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment B-39]
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of Embodiments B-5 and B-12, and as shown in FIG. 46, a recess formed on one surface of the insulating substrate 16 (upper surface in FIG. 46). And a light-transmitting layer portion 21 of the light-emitting element 2 that emits near-ultraviolet light and is used as the sealing portion 19. The phosphor powder (for example, YAG: Ce ³⁺ phosphor powder that emits yellow light when excited by near ultraviolet light) is dispersed in the conductive material, and the sealing portion 19 functions as the phosphor portion. There is a feature. Further, in the present embodiment, as the phosphor particles of phosphor part 3B, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment B-5 and B-12, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19 as in the case of the embodiment B-25. A light output composed of the combined light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder is obtained. That is, as in Embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the phosphor portion 3B are sealed by the light emitted from the light emitting element 2. Both of the phosphor powder in the stopper 19 are excited and each emits unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 3B. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be increased.

[Embodiment B-40]
The basic configuration of the light-emitting device 1B of this embodiment is substantially the same as that of Embodiments B-20 and B-21, and as shown in FIG. 47, a recess formed on one surface of the insulating substrate 16 (upper surface in FIG. 47). And a light-transmitting layer portion 21 of the light-emitting element 2 that emits near-ultraviolet light and is used as the sealing portion 19. The phosphor powder (for example, YAG: Ce ³⁺ phosphor powder that emits yellow light when excited by near ultraviolet light) is dispersed in the conductive material, and the sealing portion 19 functions as the phosphor portion. There is a feature. Further, in the present embodiment, as the phosphor particles of phosphor part 3B, fluorophosphate salt-based glass _{(e.g., P 2 O 5 · AlF 3} · MgF · CaF 2 that emits blue light by being excited by near ultraviolet light, SrF ₂ · BaCl ₂ : Eu ²⁺ ) is used. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment B-20 and B-21, and description is abbreviate | omitted.

  Therefore, in the light emitting device 1B of the present embodiment, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19 as in the case of the embodiment B-25. A light output composed of the combined light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder is obtained. That is, as in Embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the phosphor portion 3B are sealed by the light emitted from the light emitting element 2. Both of the phosphor powder in the stopper 19 are excited and each emits unique light, and the combined light is obtained. Also in this embodiment, the emission color of the phosphor powder is made different from the emission color of the phosphor part 3B. However, if the emission color of the phosphor powder is matched to the emission color of the phosphor part 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be increased.

  Incidentally, in each of the above embodiments, the phosphor portion 3B is processed into a desired shape or formed by a sol-gel method. However, as shown in FIG. 48, the phosphor portion 3B has a diameter slightly larger than the visible wavelength. If a large number of phosphor parts 3B are formed in a large spherical shape and dispersed in a solid medium 35 made of a translucent material and used in place of the phosphor parts in the above embodiments, the fluorescence in the visible wavelength range is obtained. While maintaining the transparency of the body part, the amount of material used in the phosphor part can be reduced, and the cost can be reduced.

  In addition, the light emitting device 1B of each of the above embodiments includes only one light emitting element 2, but a plurality of light emitting elements 2 constitute one unit module, and at least a part of the module is a phosphor as a light emitting substance. Of course, the parts may be arranged close to each other. For example, in the case of a light emitting device provided with a shell-shaped mold part 11 as described in the embodiment B-1, a plurality of light emitting devices are mounted on the same printed circuit board to constitute a unit module. Also good. Further, for example, in the surface-mounted light-emitting device as described in the embodiment B-2, a plurality of light-emitting elements 2 are arranged on the same insulating substrate 16 to constitute a unit module. Good.

[Application of members for semiconductor light emitting devices]
In the light-emitting devices (semiconductor light-emitting devices) 1A and 1B of the embodiments A-1, A-2, B-1 to B-40 described above, there are no particular restrictions on the locations to which the semiconductor light-emitting device member of the present invention is applied. In each of the above embodiments, the example in which the semiconductor light emitting device member of the present invention is applied as a member for forming the transparent member 3A, the phosphor portions 3B, 33, 34, etc. has been shown. It can be suitably used as a member for forming the mold part 11, the frame member 18, the sealing part 19 and the like. By using the semiconductor light emitting device member of the present invention as these members, various effects such as the above-described excellent sealing properties, transparency, light resistance, heat resistance, suppression of cracks and peeling associated with long-term use are obtained. It becomes possible.

  Moreover, when applying the semiconductor light-emitting device member of this invention, it is preferable to modify suitably according to the location which applies this invention. For example, when the present invention is applied to the phosphor portions 3B, 33, and 34, the above-described phosphor particles or phosphor components such as phosphor ions and fluorescent dyes are mixed and used in the semiconductor light emitting device member of the present invention. That's fine. As a result, in addition to the various effects mentioned above, it is possible to obtain an effect of enhancing the retention of the phosphor.

Moreover, since the member for semiconductor light-emitting devices of the present invention is excellent in durability, a sealing material excellent in light durability (ultraviolet light durability) and heat durability even when used alone without containing a phosphor ( As an inorganic adhesive, it is possible to seal a light emitting element (LED chip or the like).
Moreover, if the inorganic oxide particles described above are mixed and used in the semiconductor light emitting device member of the present invention, in addition to the various effects listed above, the effects described above in the description of the combined use of the inorganic oxide particles can be obtained. It becomes. In particular, those adjusted to have a refractive index close to that of the light-emitting element by using inorganic oxide particles in combination act as a suitable light extraction film.

[Applications of semiconductor light-emitting devices]
The semiconductor light emitting device can be used for a light emitting device, for example. In the case where a semiconductor light emitting device is used for a light emitting device, the light emitting device may be provided with a phosphor containing layer containing a mixture of a red phosphor, a blue phosphor and a green phosphor on a light source. In this case, the red phosphor does not necessarily have to be mixed in the same layer as the blue phosphor and the green phosphor. For example, the red phosphor is placed on the layer containing the blue phosphor and the green phosphor. The layer to contain may be laminated | stacked.

  In the light emitting device, the phosphor-containing layer can be provided above the light source. The phosphor-containing layer can be provided as a contact layer between the light source and the sealing resin portion, as a coating layer outside the sealing resin portion, or as a coating layer inside the outer cap. Moreover, the form which contained the fluorescent substance in sealing resin can also be taken.

  As the sealing resin used, the member for semiconductor light emitting device of the present invention can be used. Other resins can also be used. Examples of such a resin usually include a thermoplastic resin, a thermosetting resin, and a photocurable resin. Specifically, for example, methacrylic resin such as polymethylmethacrylate; styrene resin such as polystyrene and styrene-acrylonitrile copolymer; polycarbonate resin; polyester resin; phenoxy resin; butyral resin; polyvinyl alcohol; Cellulose resins such as cellulose acetate butyrate; epoxy resins; phenol resins; silicone resins. Further, an inorganic material such as a siloxane bond formed by solidifying a solution obtained by hydrolyzing a solution containing an inorganic material such as a metal alkoxide, a ceramic precursor polymer or a metal alkoxide by a sol-gel method, or a combination thereof. An inorganic material can be used.

  Although the usage-amount of the fluorescent substance with respect to binder resin is not specifically limited, Usually, 0.01-100 weight part with respect to 100 weight part of binder resin, Preferably it is 0.1-80 weight part, Preferably it is 1-1. 60 parts by weight.

  In addition, the sealing resin contains dyes for color correction, antioxidants, processing / oxidation and heat stabilizers such as phosphorus-based processing stabilizers, light-resistant stabilizers such as UV absorbers, and silane coupling agents. Can be made.

The light source is not particularly limited as long as it emits light having a peak wavelength in the range of 350 nm to 500 nm, and specific examples include a light emitting diode (LED) or a laser diode (LD). Of these, GaN LEDs and LDs using GaN compound semiconductors are preferred. This is because GaN-based LEDs and LDs have significantly larger light emission output and external quantum efficiency than SiC-based LEDs that emit light in this region, and are extremely bright with very low power when combined with the phosphor. This is because light emission can be obtained. For example, for a current load of 20 mA, GaN LEDs and LDs usually have a light emission intensity that is 100 times or more that of SiC. GaN-based LEDs and LDs preferably have an Al _x Ga _Y N light emitting layer, a GaN light emitting layer, or an In _x Ga _Y N light emitting layer. In the GaN-based LED, since they In _X Ga _Y N having a light-emitting layer is the emission intensity is very strong in, particularly preferably, the GaN-based LD is multiquantum of In _X Ga _Y N layer and GaN layer A well structure is particularly preferable because the emission intensity is very strong.

  In the above, the value of X + Y is usually a value in the range of 0.8 to 1.2. In the GaN-based LED, those in which the light emitting layer is doped with Zn or Si or those without a dopant are preferable for adjusting the light emission characteristics.

A GaN-based LED has these light-emitting layer, p-layer, n-layer, electrode, and substrate as basic constituent elements. The light-emitting layer is made of n-type and p-type Al _x Ga _y N layers, GaN layers, or In _x. Those having a heterostructure sandwiched between Ga _Y N layers and the like have high luminous efficiency, and those having a heterostructure having a quantum well structure have higher luminous efficiency and are more preferable.

  The light emitting device emits white light, and the light emission efficiency of the device is 20 lm / W or more, preferably 22 lm / W or more, more preferably 25 lm / W or more, and particularly preferably 28 lm / W or more. The color rendering index Ra is 80 or more, preferably 85 or more, more preferably 88 or more.

  The light-emitting device can be used alone or in combination, for example, as an illumination lamp, a backlight for a liquid crystal panel, various illumination devices such as ultra-thin illumination, and an image display device.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, they are for the purpose of explaining the present invention, and are not intended to limit the present invention to these embodiments.

[I. Analysis method]
About the member for semiconductor light-emitting device of each Example and each comparative example which are mentioned later, it analyzed in the following procedures.

[I-1. Solid Si-NMR spectrum measurement]
About the member for semiconductor light-emitting devices of each Example and each comparative example, solid Si-NMR spectrum measurement and waveform separation analysis were performed on condition of the following. From the obtained waveform data, the ratio of the area of the D ⁿ peak group to the total peak area, the silicon atom corresponding to the D ⁿ compound relative to the total silicon atoms in the semiconductor light emitting device members of the examples and the comparative examples. The molar ratio (%) was determined. Similarly, from the obtained waveform data, to the total peak area, trimer and 4 than the ratio of the peak area derived from D ² cyclics a dimer, D ² ring of trimer and tetramer The total ratio (%) of the molar ratio of silicon atoms corresponding to the above was determined.

<Device conditions>
Apparatus: Chemmagnetics Infinity CMX-400 Nuclear magnetic resonance spectrometer
²⁹ Si resonance frequency: 79.436 MHz
Probe: 7.5 mmφ CP / MAS probe Measurement temperature: Room temperature Sample rotation speed: 4 kHz
Measurement method: Single pulse method
¹ H decoupling frequency: 50 kHz
²⁹ Si flip angle: 90 °
²⁹ Si 90 ° pulse width: 5.0μs
Repeat time: 600s
Integration count: 128 times Observation width: 30 kHz
Broadening factor: 20Hz

<Data processing method>
About the semiconductor light-emitting device members of Examples 1 to 3 and Comparative Examples 1 to 3 and 5, 512 points were taken as measurement data, zero-filled to 8192 points, and Fourier transformed. On the other hand, since the peak of the semiconductor light emitting device member of Comparative Example 4 made of silicone resin was very sharp, 2048 points were taken as measurement data, and zero-filled to 8192 points and Fourier transformed.

<Waveform separation analysis method>
For each peak of the spectrum after Fourier transform, optimization calculation was performed by a non-linear least square method using the center position, height, and half width of the peak shape created by Lorentz waveform and Gaussian waveform or a mixture of both as variable parameters.

  In addition, identification of a peak is AIChE Journal, 44 (5), p. Reference was made to 1141, 1998, etc.

[I-2. (Measurement of silicon content)
A single cured product of the semiconductor light emitting device member of each Example and each Comparative Example was pulverized to about 100 μm, and in a platinum crucible in air at 450 ° C. for 1 hour, then 750 ° C. for 1 hour, and 950 ° C. for 1 hour. After baking for 5 hours to remove the carbon component, add 10 times or more of sodium carbonate to a small amount of the resulting residue, heat with a burner to melt, cool this, add demineralized water, and further add hydrochloric acid. Then, the volume was adjusted to about several ppm as silicon while adjusting the pH to neutral, and ICP analysis was performed.

[I-3. (Measurement of transmittance)
An ultraviolet spectrophotometer (UV manufactured by Shimadzu Corporation) was used by using a single cured product film having a smooth surface with a thickness of about 0.5 mm, which is free from scattering due to scratches and irregularities, of the semiconductor light emitting device members of each Example and each Comparative Example. -3100), and the transmittance was measured at a wavelength of 200 nm to 800 nm.

[I-4. (Ultraviolet light resistance test)
About the member for semiconductor light-emitting devices of each Example and each comparative example, it irradiated with ultraviolet light on the following conditions using the sample of diameter 5cm produced using the Teflon (trademark) petri dish, and about 1 mm of film thickness, before and after irradiation. The state of the film was compared.

Irradiation device: Suga Test Instruments Co., Ltd. Accelerated Light Resistance Tester Metalling Weather Meter MV3000
Irradiation wavelength: 255 nm or later. Main wavelength is 300 nm to 450 nm (with emission line at 480 nm to 580 nm)
Irradiation time: 72 hours

[I-5. (Heat resistance test)
About the member for semiconductor light-emitting device of each Example and each comparative example, about 1 cm square fragment of each sample B (after-mentioned) was put into a platinum crucible, and it put into the electric furnace heated at 400 degreeC, and heated for 1 hour. Thereafter, it was taken out and cooled, and the change in weight before and after heating and the change in appearance by visual inspection were examined.

[II. Manufacture of members for semiconductor light emitting devices]
[Example 1]
9.7 g of methyltrimethoxysilane, 8.5 g of dimethyldimethoxysilane, 3.8 g of water, 14.3 g of methanol silica sol manufactured by Nissan Chemical Co. as a siloxane polymer containing no D ² ring, and 5% acetylacetone aluminum as a catalyst 3.6 g of salt methanol solution was put in a container that can be sealed, mixed, sealed, heated with a hot water bath at 50 ° C. for 8 hours while stirring with a stirrer, returned to room temperature, and the hydrolysis / polycondensation solution was added. Prepared. The hydrolysis rate of this liquid is 120%.

  This hydrolysis / polycondensation solution was divided into 4 or 5 times using a micropipette and dropped onto a GaN-based semiconductor light emitting device having a total amount of 11 μL and an emission wavelength of 405 nm. After each addition, the solution was left for a while at room temperature. When the solvent was volatilized and the next one (about 2 μL) could be added, the next was added dropwise. Then, after holding at 35 ° C. for 30 minutes and then at 50 ° C. for 1 hour for the first drying, holding at 150 ° C. for 3 hours to perform the second drying, a transparent sealing member without cracks ( Semiconductor light emitting device member: Sample A) was formed. The obtained semiconductor light emitting device was energized with 20 mA, and the luminance was measured.

  In addition, 7.4 mL of the above-mentioned hydrolysis / polycondensation liquid is placed in a Teflon (registered trademark) petri dish with a diameter of 5 cm, and kept in an explosion-proof furnace at 40 ° C. for 4 hours in a breeze. After heating for 1 hour and performing the second drying by holding at 150 ° C. for 3 hours, an independent circular transparent glass film with a thickness of about 1 mm (semiconductor light emitting device member: sample) B) was obtained. This sample B is the above-mentioned [I-4. UV light resistance test].

  In addition, by reducing the volume of the hydrolysis / polycondensation liquid to 3.7 mL and carrying out the same operation, an independent circular transparent glass film (semiconductor light emitting device member: sample C) having a thickness of about 0.5 mm is obtained. Obtained. This sample C is the above-mentioned [I-3. The transmittance was measured. The above-mentioned [I-1. Solid Si-NMR spectrum measurement] [I-2. Measurement of silicon content] was carried out using a mortar pulverized sample C.

[Example 2]
Methyltrimethoxysilane (15.1 g), dimethyldimethoxysilane (13.3 g), water (6.0 g) and 5% acetylacetone aluminum salt methanol solution (5.7 g) as a catalyst are mixed in a container that can be sealed, sealed, and stirred with a stirrer. While heating in a hot water bath at 50 ° C. for 8 hours, the temperature was returned to room temperature and a hydrolysis / polycondensation solution was prepared. The hydrolysis rate of this liquid is 120%.

To 9.0 g of the hydrolyzed / polycondensed liquid, 1.0 g of octamethylcyclotetrasiloxane, which is a D ² ring, was added and stirred at room temperature for 3 minutes until uniform.
Using the hydrolyzed / polycondensed liquid after stirring, Sample A, Sample B, and Sample C were prepared and evaluated as follows.

That is, Sample A was prepared and the luminance was measured in the same manner as in Example 1 except that the total amount of hydrolysis / polycondensation liquid dropped on the GaN-based semiconductor light-emitting device was 9 μL.
Sample B was prepared in the same manner as in Example 1 except that the amount of the hydrolysis / polycondensation liquid used was 7.9 mL, and [I-4. UV light resistance test].
Further, sample C was prepared in the same manner as in Example 1 except that the amount of the hydrolysis / polycondensation liquid used was 3.8 mL, and [I-3. The transmittance was measured. The above-mentioned [I-1. Solid Si-NMR spectrum measurement] [I-2. Measurement of silicon content] was carried out using the sample C pulverized using a freezer mill.

[Example 3]
50 g of both-end silanol dimethyl silicone oil (XC96-723) manufactured by Toshiba Silicone Co., 5 g of methyltrimethoxysilane, 11 g of a 5% aluminum acetylacetone salt methanol solution and 1.90 g of water as a catalyst, three attached with a stirring blade and a condenser The mixture was weighed in a mouth-mouthed Kolben, stirred at room temperature under atmospheric pressure for 15 minutes, and after initial hydrolysis, refluxed with stirring at about 80 ° C. for 4 hours.

  Thereafter, methanol and low boiling silicon components were distilled off until the internal temperature reached 120 ° C., and the mixture was further refluxed with stirring at 120 ° C. for 4 hours. The reaction solution was cooled to room temperature, and a hydrolysis / polycondensation solution was prepared. The hydrolysis rate of this liquid is 192% with respect to methyltrimethoxysilane. The raw material XC96-723 corresponds to a 200% hydrolyzed product.

  The hydrolysis / polycondensation liquid was divided into two portions using a micropipette and dropped onto a GaN-based semiconductor light-emitting device having a total amount of 4.5 μL and an emission wavelength of 405 nm. Next, the first drying was performed at 50 ° C. for 30 minutes, then at 130 ° C. for 1 hour, followed by holding at 150 ° C. for 3 hours to perform the second drying. As a result, a transparent elastomeric sealing member without cracks was obtained. Been formed. The obtained semiconductor light emitting device was energized with 20 mA, and the luminance was measured.

Also, 3 g of the above-mentioned hydrolyzed polycondensation liquid was placed in a Teflon (registered trademark) petri dish having a diameter of 5 cm, subjected to the first drying at 50 ° C. for 30 minutes in a breeze, and then at 130 ° C. for 1 hour. When the second drying was performed at 150 ° C. for 3 hours, an independent circular transparent elastomeric film having a thickness of about 0.5 mm was obtained.
This circular transparent elastomeric film is the above-mentioned [I-3. Measurement of transmittance] and [I-4. UV light resistance test]. In addition, the circular transparent elastomeric membrane obtained by fragmentation with scissors is the above-mentioned [I-1. Solid Si-NMR spectrum measurement] [I-2. Measurement of silicon content].

[Comparative Example 1]
30.80 g of methyl silicate (MKC silicate MS51, manufactured by Mitsubishi Chemical Corporation), 56.53 g of methanol, 6.51 g of water, and 6.16 g of 5% acetylacetone aluminum salt methanol solution as a catalyst are mixed in a sealable container. The mixture was sealed and heated with a hot water bath at 50 ° C. for 8 hours while stirring with a stirrer, and then returned to room temperature to prepare a hydrolysis / polycondensation solution. The hydrolysis rate of this liquid is 113%.

  This hydrolysis / polycondensation liquid is dropped on a GaN-based semiconductor light-emitting device having an emission wavelength of 405 nm with a micropipette, and kept at 35 ° C. for 30 minutes and then at 50 ° C. for 1 hour to perform first drying. Then, when it was kept at 150 ° C. for 3 hours and subjected to the second drying, a large number of cracks were generated, and it could not be used as a sealing member (semiconductor light emitting device member).

  Further, when 10 mL of the above-mentioned hydrolysis / polycondensation liquid was put into a 5 cm diameter Teflon (registered trademark) petri dish and dried under the same conditions as in Example 1, a glass film having a thickness of about 0.3 mm was obtained. In the middle of drying, a large number of cracks were generated and shattered, and could not be taken out as an independent circular transparent glass film.

[Comparative Example 2]
31.79 g of methyltrimethoxysilane, 28.05 g of dimethyldimethoxysilane, 15.50 g of water, and 4.67 g of 0.01 mol / l hydrochloric acid water as a catalyst are mixed in a sealable container, and sealed. Then, the mixture was heated with a hot water bath at 50 ° C. for 8 hours while stirring with a stirrer, and then returned to room temperature to prepare a hydrolysis / polycondensation liquid. The hydrolysis rate of this liquid is 120%.

  When 4 mL of this hydrolysis / polycondensation liquid was placed in a Teflon (registered trademark) petri dish having a diameter of 5 cm and dried under the same conditions as in Example 1, it became a starchy liquid and a cured product could not be obtained. Further, when the hydrolysis / polycondensation liquid that was uniformly transparent after heating at 50 ° C. was further stored at room temperature for 20 hours, it was impossible to separate into two layers and apply as a uniform liquid.

[Comparative Example 3]
To 9.0 g of the hydrolysis / polycondensation liquid of Example 2, 1.0 g of octamethylcyclotetrasiloxane, which is a D ² cyclic product, was added and stirred at room temperature for 3 minutes until uniform. Similarly, Sample A, Sample B, and Sample C were prepared and evaluated.

[Comparative Example 4]
A commercially available silicone resin (JCR6101UP manufactured by Toray Dow Corning Co., Ltd.) used as a molding agent for semiconductor light-emitting devices is dropped on a GaN-based semiconductor light-emitting device having a light emission wavelength of 405 nm with a micropipette, and each 2 at 150 ° C. When cured by heating for a time, an elastomeric sealing member (semiconductor light emitting device member: sample A) was obtained. The obtained semiconductor light emitting device was energized with 20 mA, and the luminance was measured.

  Also, after applying the above silicone resin on a Teflon (registered trademark) plate, vacuum degassing at 25 ° C. for 1 hour, curing by heating at 150 ° C. for 2 hours, and then peeling it off Elastomeric films (semiconductor light emitting device members: Sample B and Sample C) having thicknesses of about 1 mm and 0.5 mm were obtained. Sample B is the above-mentioned [I-4. UV light resistance test]. Sample C is the above-mentioned [I-3. The transmittance was measured. The above-mentioned [I-1. Solid Si-NMR spectrum measurement] [I-2. Measurement of silicon content] was carried out using the sample C pulverized using a freezer mill.

[Comparative Example 5]
A commercially available two-component curable aromatic epoxy resin used as a molding agent for semiconductor light-emitting devices is dropped onto a GaN-based semiconductor light-emitting device having an emission wavelength of 405 nm with a micropipette and heated at 120 ° C. for 4 hours. Then, when cured, it became a hard and transparent sealing member (semiconductor light emitting device member). The obtained semiconductor light emitting device was energized with 20 mA, and the luminance was measured.

  Moreover, after putting the above-mentioned epoxy resin in a 5 cm diameter Teflon (registered trademark) petri dish, performing vacuum degassing at 25 ° C. for 1 hour, and curing by heating at 120 ° C. for 4 hours, the thickness was about 1 mm and 0 mm. A 5 mm bluish circular transparent resin film (semiconductor light emitting device members: Sample B and Sample C) was obtained as an independent film. Sample B is the above-mentioned [I-4. UV light resistance test]. Sample C is the above-mentioned [I-3. The transmittance was measured. The above-mentioned [I-1. Solid Si-NMR spectrum measurement] [I-2. Measurement of silicon content] was carried out using the sample C pulverized using a freezer mill.

[III. Evaluation of members for semiconductor light emitting devices]
Above [II. About the semiconductor light-emitting device and member for semiconductor light-emitting devices of each Example and each comparative example obtained by the procedure of [Manufacture of member for semiconductor light-emitting device]. Analysis was performed according to the procedure of [Analysis method]. The results are shown in Table 2 below. In Table 2, the description in parentheses in the row of the heat resistance test represents a change in appearance.

  As shown in Table 2 below, the luminance of the semiconductor light-emitting devices obtained in each Example and each Comparative Example, except for Comparative Examples 1 and 2 where the sealing member was not formed due to the occurrence of cracks or poor curing, Compared to before the formation of the sealing member (semiconductor light emitting device member), it was improved.

In addition, as shown in Table 2 below, the members for semiconductor light emitting devices of Examples 1 to 3 that satisfy the provisions of the present invention are comparative examples 1 that do not contain a D ² ring but do not adjust the degree of crosslinking. Compared to Comparative Examples 2 and 3 including the annular body of the above, and the semiconductor light emitting device members of Comparative Examples 4 and 5 which are commercially available semiconductor light emitting device members, there is less weight loss during rapid heating, cracks, etc. Was difficult to occur, and the amount of the diffused ring contained was small. Therefore, according to the present invention, it is possible to provide a reliable member for a semiconductor light emitting device that has high heat resistance, excellent ultraviolet light resistance, and is less likely to cause contact failure even when mounted with an element having an electrical contact.

  The use of the member for a semiconductor light emitting device of the present invention is not particularly limited, and can be suitably used for various uses represented by a member (sealing agent) for sealing a semiconductor light emitting element or the like.

It is a schematic sectional drawing which shows embodiment A-1. It is a schematic sectional drawing which shows embodiment A-2. Embodiment B-1 is shown, (a) is a schematic sectional drawing, (b) is the principal part enlarged view of (a). It is a schematic sectional drawing which shows embodiment B-2. It is a schematic sectional drawing which shows embodiment B-3. It is a schematic sectional drawing which shows embodiment B-4. It is a schematic sectional drawing which shows Embodiment B-5. It is a schematic sectional drawing which shows embodiment B-6. It is a schematic sectional drawing which shows Embodiment B-7. It is a schematic sectional drawing which shows embodiment B-8. It is a schematic sectional drawing which shows embodiment B-9. It is a schematic sectional drawing which shows embodiment B-10. It is a schematic sectional drawing which shows embodiment B-11. It is a schematic sectional drawing which shows embodiment B-12. It is a schematic sectional drawing which shows embodiment B-13. It is a schematic sectional drawing which shows embodiment B-14. It is a schematic sectional drawing which shows embodiment B-15. It is a schematic sectional drawing which shows embodiment B-16. It is a schematic sectional drawing which shows embodiment B-17. It is a schematic sectional drawing which shows embodiment B-18. FIG. 20 is a schematic sectional view showing Embodiment B-19. It is a schematic sectional drawing which shows embodiment B-20. It is a schematic sectional drawing which shows embodiment B-21. It is principal part sectional drawing shown about Embodiment B-21. It is a schematic sectional drawing which shows embodiment B-22. It is principal part sectional drawing shown about Embodiment B-22. It is a schematic sectional drawing which shows embodiment B-23. It is a principal part perspective view shown about Embodiment B-23. It is a schematic sectional drawing which shows embodiment B-24. It is principal part sectional drawing shown about Embodiment B-24. It is a principal part perspective view shown about Embodiment B-24. It is a schematic sectional drawing which shows embodiment B-25. It is a schematic sectional drawing which shows embodiment B-26. It is a schematic sectional drawing which shows embodiment B-27. FIG. 29 is a schematic sectional view showing Embodiment B-28. It is a schematic sectional drawing which shows embodiment B-29. Embodiment B-30 is shown, (a) is a schematic sectional drawing, (b) is the principal part enlarged view of (a). It is a schematic sectional drawing which shows embodiment B-31. It is a schematic sectional drawing which shows embodiment B-32. It is a schematic sectional drawing which shows embodiment B-33. It is a schematic sectional drawing which shows embodiment B-34. FIG. 36 is a schematic sectional view showing Embodiment B-35. It is a schematic sectional drawing which shows embodiment B-36. FIG. 38 is a schematic sectional view showing Embodiment B-37. FIG. 39 is a schematic sectional view showing Embodiment B-38. It is a schematic sectional drawing which shows embodiment B-39. It is a schematic sectional drawing which shows embodiment B-40. It is explanatory drawing of the other structural example of the principal part of each embodiment. (A), (b) is explanatory drawing of the basic concept of each embodiment.

Explanation of symbols

1,1A, 1B Light emitting device (semiconductor light emitting device)
2 Light Emitting Element 3A Transparent Member (Semiconductor Device Member)
3B phosphor part (semiconductor device member)
4a, 4b Part of the light emitted from the light emitting element 5 Light having a wavelength peculiar to fluorescent components such as phosphor particles, fluorescent ions, fluorescent dyes contained in the phosphor part 11 Mold part 12, 13 Lead terminal 14 Mirror ( Cup part)
DESCRIPTION OF SYMBOLS 15 Conductive wire 16 Insulation board | substrate 16a Recess 17 Printed wiring 18 Frame material 19 Sealing part 19a Sealing function part 19b Lens function part 19c Recession 19d Through-hole 21 Light emitting layer part 23 Reflection layer 24 Bump 33, 34 Phosphor part 35 Solid medium

Claims (8)

For a semiconductor light emitting device obtained through a step of drying a polycondensate obtained by hydrolysis and polycondensation of a compound represented by at least one of the following formula (1) and the following formula (2) and / or an oligomer thereof: A member,
[1] In the solid Si-nuclear magnetic resonance spectrum, the molar ratio of silicon corresponding to the D ⁿ compound to the total silicon is 30% or more,
[2] In the solid Si-nuclear magnetic resonance spectrum, the total molar ratio of silicon corresponding to the trimer and tetramer D ² cyclic product to the total silicon is 0.1% or more and 15% or less,
[3] Silicon content is 20% by weight or more
It characterized the this, the semiconductor light-emitting device member.

(In the formula (1),
M represents a silicon,
X represents a hydrolyzable group,
Y ¹ represents a monovalent organic group,
m represents an integer of 1 or more that represents the valence of M;
n represents an integer of 1 or more representing the number of X groups. However, m ≧ n. )

(In the formula (2),
M represents a silicon,
X represents a hydrolyzable group,
Y ¹ represents a monovalent organic group,
Y ² represents a u-valent organic group,
s represents an integer of 2 or more that represents the valence of M;
t represents an integer of 1 or more and s-1 or less,
u represents an integer of 2 or more. ) The member for a semiconductor light-emitting device according to claim 1, wherein a light transmittance at an emission wavelength of the semiconductor light-emitting device having a thickness of 0.5 mm is 80% or more. The member for a semiconductor light-emitting device according to claim 1, further comprising inorganic oxide particles. [1] In the solid Si-nuclear magnetic resonance spectrum, the molar ratio of silicon corresponding to the D ⁿ compound to the total silicon is 30% or more,
[2] In the solid Si-nuclear magnetic resonance spectrum, the total molar ratio of silicon corresponding to the trimer and tetramer D ² cyclic product to the total silicon is 0.1% or more and 15% or less,
[3] A method for producing a semiconductor light-emitting device member having a silicon content of 20% by weight or more,
It has a step of drying a polycondensate obtained by hydrolysis / polycondensation of a compound represented by at least one of the following formula (1) and the following formula (2) and / or an oligomer thereof, A method for manufacturing a member for a semiconductor light emitting device.

(In the formula (1),
M represents a silicon,
X represents a hydrolyzable group,
Y ¹ represents a monovalent organic group,
m represents an integer of 1 or more that represents the valence of M;
n represents an integer of 1 or more representing the number of X groups. However, m ≧ n. )

(In the formula (2),
M represents a silicon,
X represents a hydrolyzable group,
Y ¹ represents a monovalent organic group,
Y ² represents a u-valent organic group,
s represents an integer of 2 or more that represents the valence of M;
t represents an integer of 1 or more and s-1 or less,
u represents an integer of 2 or more. ) The method for producing a member for a semiconductor light-emitting device according to claim 4, wherein the hydrolysis rate is 80% or more and 500% or less. While performing hydrolysis and polycondensation in the presence of a solvent,
The step of drying the resulting polycondensate includes a first drying step of concentrating the hydrolysis / polycondensate before drying at a temperature lower than the boiling point of the solvent, and a step of drying at a temperature not lower than the boiling point of the solvent. The method for producing a member for a semiconductor light emitting device according to claim 4, wherein the method comprises two drying steps. The method for producing a member for a semiconductor light-emitting device according to any one of claims 4 to 6, wherein the hydrolysis / polycondensation is performed in the presence of an organometallic compound catalyst.   A semiconductor light-emitting device comprising at least the member for a semiconductor light-emitting device according to claim 1.

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