JP2011129901A - Method of manufacturing semiconductor light emitting device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a simple method of manufacturing an appropriate semiconductor light emitting device by using a robust sealing material for a semiconductor light emitting device having excellent optical transparency, high-temperature resistance, ultraviolet resistance, and a high refractive index, and also having various elasticity characteristics, and a package material. <P>SOLUTION: This method of manufacturing a semiconductor light emitting device having a process of sealing a semiconductor light emitting element includes a process of irradiating a specific ultraviolet curable resin (A) with an ultraviolet ray in an environment of 50-100°C during the process of sealing the semiconductor light emitting element. Alternatively, the method of manufacturing a semiconductor light emitting device having a process of manufacturing a package for mounting a semiconductor light emitting element thereon by using a resin material includes a process of irradiating the specific ultraviolet curable resin (A) with an ultraviolet ray in an environment of 50-100°C during a process of manufacturing the package using the resin material. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a method for manufacturing a semiconductor light emitting device using an ultraviolet curable resin as an encapsulating material or a packaging material. More specifically, the present invention includes a step of sealing a semiconductor light emitting device by curing an ultraviolet curable resin using ultraviolet rays and appropriate heat in combination, or manufacturing a package on which the semiconductor light emitting device is mounted. The present invention relates to a method for manufacturing a semiconductor light emitting device having high heat resistance and high light resistance.

  In recent years, light-emitting diodes (LEDs) have been used in various fields. Among these, high-intensity light-emitting diodes (HBLEDs) have extremely high energy efficiency and are particularly suitable for lighting applications. In general, a light-emitting diode device (hereinafter sometimes referred to as “semiconductor light-emitting device”) is usually an LED chip (hereinafter also referred to as “semiconductor light-emitting element”) assembled on a substrate, and further. It consists of the material (sealing material) which seals it, and the sealing material often also plays the role of a lens. Necessary conditions for materials used as a sealing material for semiconductor light-emitting elements include optical transparency, high temperature resistance, UV resistance, high refractive index, and various mechanical properties. Various materials are used. The level of the above requirements has become higher and higher with the recent development of HBLEDs.

LED devices face high temperatures during device assembly (soldering up to about 260 ° C.) and during actual device operation (typically around 50 ° C. to 100 ° C. for tens of thousands of hours), so semiconductors The sealing material of the light emitting element is required to be optically transparent (transmittance of 90% or more) and the like, and further to withstand high temperatures for a long time without degrading mechanical and optical functions. The
Conventionally, an epoxy resin has been frequently used as a transparent resin for sealing a semiconductor light emitting device (Patent Documents 1 and 2). PMMA (polymethyl methacrylate), polycarbonate, optical nylon, and the like are also used. However, there has been a problem in that the optical properties of such conventional organic resins deteriorate over time during use. In particular, there is a problem that yellowing or other coloring occurs due to deterioration due to heat or irradiation with short wavelength light for a long time. When such deterioration proceeds, moisture may enter from the sealing material layer, which may lead to performance deterioration of the semiconductor light emitting device. Mechanical degradation of the encapsulant also causes cracking, shrinking or delamination of the substrate. Therefore, it is desirable that the sealing material be a material system that is a soft elastomer and also has a plastic-like hardness. That is, the sealing material is required to have the following properties at the same time. (I) It is hard enough to be used as a mechanical support for members constituting the semiconductor light emitting device. (Ii) To the extent that damage to the semiconductor light emitting elements or wires can be prevented during assembly of the device. In addition, when the temperature rises and falls, it is soft enough to soften the internal strain so that peeling or cracking does not occur due to the difference in expansion and contraction of each material having a different thermal expansion coefficient used as a member. Be supple.

On the other hand, Patent Document 3 discloses an ultraviolet curable silicone composition suitable as a protective material for a light-emitting diode element, a lens material, etc., which should give a cured product having excellent transparency and little discoloration over time.
However, the ultraviolet curable silicone composition has the following problems. That is, depending on the shape of the package constituting the semiconductor light-emitting device, there are places where it is difficult for ultraviolet rays to hit, and thus there is a problem that uneven curing occurs. In addition, when a phosphor that easily absorbs ultraviolet rays is used, there is a problem that uneven curing occurs due to the presence or absence of the phosphor. Due to such unevenness of curing, a difference in stress occurs inside the sealing material, and there is also a problem that the ultraviolet curable silicone composition is easily peeled from the package. Further, Patent Document 3 has no description regarding light resistance, and it is difficult to say that it can be used for a high-power and high-brightness semiconductor light-emitting element.

US Patent Publication No. 2004/0063840 International Publication WO2005 / 085303 Pamphlet JP 2007-214543 A

  As described above, a sealing material for a robust semiconductor light-emitting device having excellent optical transparency, high temperature resistance, ultraviolet resistance, high refractive index, and various elastic characteristics, and such a sealing material. There is a need for a simple method of using and manufacturing a suitable semiconductor light emitting device. The present invention aims to achieve this.

As a result of intensive studies, the present inventors have made simple use of a specific ultraviolet curable resin having excellent light transmission, light resistance, heat resistance, wet heat resistance, and ultraviolet resistance in the wavelength range of ultraviolet light to visible light. It has been found that the method can produce a semiconductor light emitting device that does not crack and peel even when used for a long time.
In addition, the method for manufacturing a semiconductor light emitting device of the present invention has also found that the curing rate of the ultraviolet curable resin is increased, and phosphors of different types can be prevented from being separated during curing due to a difference in specific gravity or shape. It was.

Furthermore, it has been found that the above-described method using an ultraviolet curable resin can be applied to a package material for mounting a semiconductor light emitting element in a semiconductor light emitting device.
That is, this invention has the summary characterized by the following.
[1] A method of manufacturing a semiconductor light emitting device including a step of sealing a semiconductor light emitting element, wherein the semiconductor light emitting element is sealed,
(A) A step of irradiating ultraviolet curable resin with ultraviolet rays in an environment of 50 ° C. or higher and 100 ° C. or lower, wherein 15% or more of the weight of the ultraviolet curable resin is silicon and oxygen adjacent to silicon. A method for manufacturing a semiconductor light emitting device.

[2] A method of manufacturing a semiconductor light-emitting device including a step of manufacturing a package mounting a semiconductor light-emitting element using a resin material, wherein the package is manufactured using a resin material,
(A) It has a step of irradiating ultraviolet resin in an environment of 50 ° C. or more and 100 ° C. or less, and 15% or more of the weight of the ultraviolet curable resin is silicon and oxygen adjacent to silicon. A method for manufacturing a semiconductor light emitting device.

[3] The method for manufacturing a semiconductor light-emitting device according to [1] or [2], further including a step (B) of heating without ultraviolet irradiation after the step (A).
[4] The method for manufacturing a semiconductor light-emitting device according to [3], wherein the heating condition in the step (B) is 120 ° C. or more and 5 minutes or more.
[5] When the ultraviolet curable resin is irradiated with ultraviolet rays at a peak wavelength of 360 nm and an energy amount of 300 mJ / m ² in an environment of 60 ° C. to form a cured film having a thickness of 2 mm, the following physical properties are obtained: [1] to [4] The method for producing a semiconductor light emitting device according to any one of [1] to [4].

<Physical property 1>
The YI value of the cured film after storing the cured film in the atmosphere at 150 ° C. for 500 hours is 20.00 or less <Physical property 2>
The cured film has a YI value of 20.00 or less after being irradiated with light having a wavelength of 350 nm or more at room temperature in the atmosphere at an intensity of 2100 mW / cm ² for 20 hours. The semiconductors according to [1] and [3] to [5] above, wherein the resin contains a phosphor containing at least one of a silicate, nitride, oxynitride, and garnet oxide substance. Manufacturing method of light-emitting device.

  [7] The method for manufacturing a semiconductor light emitting device according to any one of [1] to [6], wherein an emission peak wavelength of the semiconductor light emitting element is 350 nm or more and 500 nm or less.

  According to the present invention, a semiconductor light emitting device having an excellent function as a sealing material for a semiconductor light emitting element or a package for mounting a semiconductor light emitting element using an ultraviolet curable resin having adhesiveness, transparency, wet heat resistance and ultraviolet resistance Can be manufactured.

It is a graph which shows the brightness | luminance maintenance factor of the semiconductor light-emitting device (LED) manufactured by this invention. It is a graph which shows the brightness | luminance maintenance factor of the semiconductor light-emitting device (LED) manufactured by this invention. It is a graph which shows the brightness | luminance maintenance factor of the semiconductor light-emitting device (LED) manufactured by this invention. It is a graph which shows the brightness | luminance maintenance factor of the semiconductor light-emitting device (LED) manufactured by this invention. It is a graph which shows the brightness | luminance maintenance factor of the semiconductor light-emitting device (LED) manufactured by this invention. It is a graph which shows the result of having measured the reflectance of the self-supporting film | membrane obtained by this invention. 1 is a schematic cross-sectional view showing a first embodiment. FIG. 6 is a schematic cross-sectional view showing a second embodiment. FIG. 6 is a schematic cross-sectional view showing a third embodiment.

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.
The present invention is a method for manufacturing a semiconductor light emitting device, and can be roughly divided into the following two.
(I) A method of manufacturing a semiconductor light emitting device that uses an ultraviolet curable resin when sealing the semiconductor light emitting element (hereinafter sometimes referred to as “the manufacturing method of the first aspect of the present invention”).
(Ii) Manufacturing method of a semiconductor light emitting device manufactured using an ultraviolet curable resin as a part of a member for manufacturing a package on which the semiconductor light emitting element is mounted (hereinafter referred to as “the manufacturing method of the second invention”). May be called.)
The first and second production methods of the present invention (hereinafter sometimes collectively referred to as “the production method of the present invention”) have the following step (A) as a common technical feature: Preferably, the method includes the following step (B) after the step (A).
(A) A step of irradiating a specific ultraviolet curable resin with ultraviolet light in an environment of 50 ° C. or higher and 100 ° C. or lower (B) A step of heating without irradiating with ultraviolet rays. Steps (A) and (B) will be described in detail, and each embodiment of the first and second production methods of the present invention will be exemplified in Chapter [2].

[1] Curing method of ultraviolet curable resin [1-1] (A) Ultraviolet irradiation process As described above, the production method of the present invention uses a specific ultraviolet curable resin as a resin for a semiconductor light-emitting device, and in that case It is characterized by irradiating with ultraviolet rays while heating. As a result, the ultraviolet curable resin is moderately cured quickly by using heat energy together, and finally has excellent light transmittance, light resistance, heat resistance, wet heat resistance in the wavelength range of ultraviolet light to visible light, and A cured product having ultraviolet resistance can be obtained appropriately and economically.
In the present invention, the term “curing” means that the hardness of the ultraviolet curable resin or the composition containing the ultraviolet curable resin (ultraviolet curable resin composition) is usually 10 or more with a JIS Type A hardness meter. .

[1-1-1] Ultraviolet Irradiation Conditions As the ultraviolet irradiation light source in the present invention, a light source that emits light at 450 nm or less, such as a high-pressure mercury lamp, a xenon lamp, a xenon mercury lamp, or a black light, can be used. In particular, it is preferable to use an apparatus that emits light including light having a peak wavelength of 380 nm or less. Irradiation energy amount is usually 30 mJ / ^{m 2} or more, preferably 50 mJ / ^{m 2} or more, more preferably 100 mJ / ^{m 2} or more, usually 10000 mJ / ^{m 2} or less, preferably 5000 mJ / ^{m 2} or less, more preferably 4000mJ / M ² or less. If the amount of irradiation energy is too large, a trace amount of impurities may begin to color gradually, and if it is too small, the curing reaction may not proceed sufficiently. The irradiation time is usually 0.1 seconds or longer, preferably 0.5 seconds or longer, more preferably 1 second or longer, and usually 3 hours or shorter, preferably 30 minutes or shorter. If the irradiation time is too short, curing may not be performed uniformly. If it is too long, the productivity is inferior, which is economically disadvantageous.

[1-1-2] Heating condition The step (A) of the present invention is characterized in that the above-described ultraviolet irradiation is performed in an environment of 50 ° C. or more and 100 ° C. or less. It is preferable to cure the ultraviolet curable resin while heating appropriately for the following reason. First, the curing rate can be accelerated. When an ultraviolet curable resin is used as a sealing material containing a plurality of different types of phosphors as will be described later, different types of phosphors are cured by differences in specific gravity and shape by increasing the curing speed by heating. It is possible to prevent separation inside. Second, depending on the shape of the package that constitutes the semiconductor light emitting device, there are places where it is difficult for ultraviolet rays to hit, but there is a problem that uneven curing occurs, but such uneven curing can be reduced. In addition, when a phosphor or white filler that easily absorbs ultraviolet rays is included to form a sealing material or package, curing unevenness may occur depending on the presence or absence of the phosphor or white filler. Trees can be reduced. Third, since the environment of 50 ° C. or more and 100 ° C. or less is also the temperature applied to the sealing material and the package material when the semiconductor light emitting device is actually used, the temperature during curing and the temperature during actual use are By making the same, the method of applying internal stress during use is reduced, and problems such as peeling are less likely to occur. Therefore, the heating temperature is usually 50 ° C. or higher, preferably 55 ° C. or higher. Moreover, as an upper limit, it is 100 degrees C or less normally, Preferably it is 80 degrees C or less. If the heating temperature is too low, the effect of accelerating curing is lost, and it is difficult to suppress the generation of internal stress during use. On the other hand, if the heating temperature is too high, the generation of internal stress at the time of use is increased, which is economically undesirable as equipment.

[1-1-3] Ultraviolet curable resin Examples of the ultraviolet curable resin used in the present invention include various types. Among these, a so-called silicone resin having a siloxane skeleton is preferable, and an ultraviolet curable resin in which 15% or more of the weight of the resin is silicon and oxygen adjacent to silicon is particularly preferable. The proportion of silicon and oxygen adjacent to silicon is preferably 20% or more, more preferably 30% or more. The upper limit of the ratio of silicon and oxygen adjacent to silicon is not particularly limited, but is usually 70% or less. If the amount of silicon and oxygen adjacent to silicon is too small, the durability of the cured product, such as heat resistance and light resistance, may be lowered.

In addition, functional groups usually accompanied by organic groups are often bonded to silicon. The organic group is not particularly limited, but a hydrocarbon group, particularly a methyl group, an ethyl group, a propyl group, an isopropyl group, a phenyl group, etc. are preferably used. Some or all of the protons of these hydrocarbon groups may be halogenated, and for example, a trifluoropropyl group is preferably used.
Of these, a methyl group and a phenyl group are preferred mainly from the viewpoint of excellent heat resistance and light resistance and industrial availability, and a methyl group mainly is preferred in applications where light resistance is particularly important. Moreover, when coloring of electrode silver plating, electrode migration, hydrolysis of phosphors, and the like are problems, it can be mainly composed of phenyl groups and have low gas permeability. Even when a high refractive index is desired for improving light extraction from the light emitting element, a high refractive index can be achieved by introducing a phenyl group. When it is necessary to adjust the melting point, softening point, elastic modulus, etc. of the ultraviolet curable resin before or after curing, a branched or unbranched monovalent alkyl group having 3 to 10 carbon atoms, cyclic, A monovalent cycloalkyl group having 6 to 10 carbon atoms including a cyclic structure can be used.

Moreover, an acrylic group, a methacryl group, a vinyl group, an epoxy group, an oxetane group, etc. are used suitably as a functional group which ensures ultraviolet curable property. Among them, an acryloxypropyl group or a methacryloxypropyl group is preferable because of its high reaction activity, economical reasons, and the variety of available raw materials.
The amount of functional groups introduced to ensure the ultraviolet curability is usually 85% or less, preferably 60% or less, based on the number of functional groups other than Si—O—Si on all silicon atoms in the composition before curing. More preferably, it is 30% or less. Moreover, it is 0.1% or more normally, Preferably it is 1% or more. When the introduction amount of the reactive group is too large, there is a problem that the degree of cure shrinkage at the time of curing becomes very high, and the heat resistance and UV resistance of the cured product are lowered. Moreover, when there are too few introduction amounts of a reactive group, a cure rate and the hardness of hardened | cured material may become unnecessarily low. Moreover, it is preferable to have such an organic group appropriately because gas barrier properties when used as a sealing material or a package material are increased.

  Furthermore, it is also preferable to introduce a hydrosilyl group or a condensable functional group instead of an organic group for the purpose of imparting adhesiveness. The amount of the hydrosilyl group or condensable functional group introduced is usually 80% or less, preferably 50% or less, based on the number of functional groups on silicon other than Si—O—Si bonds on silicon atoms in the cured product. The lower limit is not particularly defined, but the amount when introduced is usually 0.1% or more, preferably 1% or more. Examples of the condensable functional group in this case include alkoxy groups such as silanol group, methoxy group, and ethoxy group, acetoxy group, enoxy group, oxime (ketoxime) group, amino group, and thiol group.

Of the silicone resins described above, examples of acrylic / methacrylic compounds that are preferably used in the present invention are shown below.
(Example 1 of acrylic / methacrylic silicone resin suitably used in the present invention)

(Example 2 of acrylic / methacrylic silicone resin suitably used in the present invention)

  As an example of a method for producing an ultraviolet curable resin used in the present invention, a silicone-based ultraviolet curable resin in which an acrylic group, a methacryl group, a vinyl group, an epoxy group, an oxetane group or the like is introduced as a functional group that ensures ultraviolet curable A method for synthesizing the resin (polyorganosiloxane) is shown below. Needless to say, the ultraviolet curable resin used in the present invention is not limited to the following production method.

  Examples of the silicone-based ultraviolet curable resin include hydrolysis and polymerization reactions such as 3-acryloxypropyltrimethoxysilane and vinyltrichlorosilane, 1,3,5,7-tetramethyl-1,3,5,7-tetra Using ring-opening polymerization reaction of vinylcyclotetrasiloxane (1,3,5,7-Tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane), coupling reaction of acrylic acid to polydimethylsiloxane at both terminal hydroxyl groups, etc. A synthesis method is preferably used.

In addition, it is also preferable for economical reasons to use a commercially available oligomer or polymer having an ultraviolet curable functional group, or a blend thereof as it is. Examples of preferable commercial products include the following.
Examples of acrylic / methacrylic compounds include methacrylic modified silicones (X-22-164, X-22-164AS, X-22-164A, X-22-164B, X-22-164C, X, manufactured by Shin-Etsu Chemical Co., Ltd.) -22-164E), side chain type acrylic modified silicone (X-22-2457, X-22-2459), side chain both ends acrylic modified silicone (X-22-2458), both ends acrylic polyether modified silicone (X -2-1602), side chain type acrylic phenyl silicone (X-22-2477), single-end acrylic modified silicone (X-22-1615, X-22-1618), single-end methacryl-modified silicone (X-22-174DX) , X-22-2426, X-22-2475), methyl / methacrylic / methoxy-based silicone oil (X-40-2655A), methyl / acrylic / methoxy silicone oligomer (X-40-9271), side chain type methacryl-modified silicone (RMS-044, RMS-044, RMS-033, RMS-manufactured by Gelest) 083, RTT-1011), side chain acrylic modified silicone (UMS-182, UMS-992, UCS-052, UTT-1012), Daicel Cytec silicone acrylate (EBECRYL1360, EBECRYL350).

Examples of vinyl compounds include DMS series, PDV series, FMV series, VDT series, VQM series, VMS series, VTT series and MTV series manufactured by Gelest, ME-91 manufactured by Momentive Performance Materials, and vinyl-containing silanes. Examples of the coupling agent include vinylphenylmethylmethoxysilane, vinylmethyldiethoxysilane, and vinyltriethoxysilane.

  Examples of the epoxy compounds include epoxy-modified silicones (X-22-163, KF-105, X-22-163A, X-22-163B, X-22-163C, X-22-169AS manufactured by Shin-Etsu Chemical Co., Ltd.). X-22-169B, one-end epoxy-modified silicone (X-22-173DX), side-chain both-end epoxy-modified silicone (X-22-9002), side-chain epoxy-modified silicone (X-22-343, KF) -101, KF-1001, X-22-2000, X-22-2046, KF-102, X-22-4741, KF-1002), epoxy / methoxy / ethoxy silicone oligomer (X-41-1053), Methyl / epoxy / methoxy silicone oligomer (X-41-1056), glycidoxypropyltrimethoxysilane In addition, various organic compounds including substances having the same functional group can be added to these, and specifically, acryloxy group, methacryloxy group, vinyl group, epoxy group at both ends can be added. From the viewpoint of heat resistance and light resistance, an additive such as polyethylene glycol, polypropylene glycol, etc. is preferable as an additive, and when added, a composition that does not become cloudy including before and after curing is preferable.

  In the present invention, an ultraviolet curable resin composition can be obtained by adding an additive to the ultraviolet curable resin within a range not inhibiting the curing reaction. For example, in order to control the mechanical properties of the cured product, it is very preferable to add a polyfunctional alkoxycarbosilane. The addition amount of the alkoxycarbosilane is usually 0.1% by weight, preferably 0.2% by weight or more, and usually 50% by weight or less, preferably 20% by weight or less based on the whole ultraviolet curable resin composition. . If the amount added is too small, the effect of improving physical properties is hardly recognized. Moreover, when there is too much addition amount, the shrinkage | contraction at the time of hardening will become large, and it will cause heat resistance and UV tolerance to fall.

  When the viscosity of the ultraviolet curable resin or the ultraviolet curable resin composition is high, for example, an organic solvent typified by toluene is also preferably used. The addition of a hydrophobic organic solvent such as toluene or heptane is often preferable in terms of controlling the physical properties of the resulting resin. However, the amount added is usually preferably 50% by weight or less of the total weight. If the amount added is too large, the shrinkage at the time of curing becomes extremely large, and the heat resistance and UV resistance may be lowered by the residual solvent.

For the purpose of efficiently proceeding the ultraviolet curing reaction, it is preferable to add a small amount of an organic compound called an initiator to the ultraviolet curable resin composition. For example, when the ultraviolet curable resin has an acrylic or methacrylic functional group, cationic polymerization or anionic polymerization is possible, but it is preferable to cure by a light or heat radical reaction with a small amount of initiator. . The same applies to the case of containing a vinyl group. Further, when the ultraviolet curable resin has an epoxy group or an oxetane group, it can be photocured by the presence of an acid generator. When utilizing a reaction between a vinyl group and a thiol group as a functional group of an ultraviolet curable resin, a radical reaction mechanism similar to an acrylic or methacrylic group can be used. It is also preferable to use vinyl ether cationic polymerization. Furthermore, it is also preferable to use a photosensitizer together as necessary.

Various initiators can be selected and used using the above-described curing reaction mechanism. For example, organic oxides typified by benzoyl peroxide, azo compounds typified by AIBN, photo radical polymerization initiators typified by acetophenone series, benzoin ether series, benzophenone series, and thioxanthone series shown below, sulfonium salts And a cationic photopolymerization initiator typified by iodonium salt, an anionic polymerization initiator typified by alkyllithium, and a cationic polymerization initiator typified by aluminum trichloride. Among them, the radical photopolymerization initiator is more stable than azo compounds and can be used industrially safely. Furthermore, unlike a sulfonium salt or the like, it is preferable because peripheral materials used are not corroded. Furthermore, since various radical photopolymerization initiators are already used in the industry, it is possible to select an optimum one from a wide range of options according to conditions.

  Although depending on the type of initiator, the type of polymerizable functional group, and the like, the ultraviolet curing treatment is usually carried out in the atmosphere or in an atmosphere in which the oxygen concentration is lower than in the atmosphere. In particular, when polymerizing acrylate-based functional groups, it is preferable that the oxygen concentration is as low as possible. When curing in an open system in which a structure close to sealing is not physically removed, the oxygen concentration is 10% by volume or less. It is preferable.

Also, if necessary, known solvents, adhesion promoters (for example, epoxy-containing materials), other silicon compounds and organic compounds for improving physical properties, filler-like substances (for example, silica gel or nano-sized materials) Any one or more of carbon and the like may be added to the ultraviolet curable resin composition.
Especially when used for packaging materials, substrate coating materials, coating materials, etc., known white fillers, such as titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, aluminum nitride, etc., together with fumed silica etc. The addition to the resin is preferably performed. Some of these fillers absorb a part of ultraviolet light and have a high light hiding property. Therefore, when added at a high concentration, the ultraviolet ray may not reach the deep part of the composition, resulting in poor deep curing. In that case, in addition to the use of an initiator that works with light closer to the visible light range, combined use with a photosensitizer, etc., stable molding by controlling the film thickness, such as selecting a molding method by thin film coating such as screen coating Is possible. In the present invention, it is possible to mold even more complicated shapes by using both ultraviolet curing and heat curing.
When the ultraviolet curable resin used in the present invention is irradiated with ultraviolet rays at a peak wavelength of 360 nm and an energy amount of 300 mJ / m ² in an environment of 60 ° C. to form a cured film having a thickness of 2 mm, the following ultraviolet curable resin is used. It is preferable to have at least one of physical property 1 and physical property 2.

<Physical property 1>
The YI value of the cured film after storing the cured film in the atmosphere at 150 ° C. for 500 hours is 20.00 or less. The YI value is preferably 10.00 or less, more preferably 5.00. It is as follows. If the YI value is too large, it is colored yellow or brown, and when used as a sealing material for a semiconductor light emitting device, the light extraction efficiency decreases.
Moreover, it is more preferable that the YI value of the cured film after storing the cured film in the atmosphere at 200 ° C. for 500 hours is 20.00 or less, preferably 10.00 or less, and more preferably Is 5.00 or less.
<Physical property 2>
The cured film has a YI value of 20.00 or less after irradiation with light having a wavelength of 350 nm or more at room temperature in the atmosphere at an intensity of 2100 mW / cm ² for 20 hours. The YI value is preferably 10.00 or less. When the YI value is too large, it is colored yellow or brown, and when used as a sealing material or package material for a semiconductor light emitting device, it changes color due to strong ultraviolet irradiation, and the light extraction efficiency of the semiconductor light emitting device as a whole is increased. descend.

The physical property 1 and the physical property 2 are properties of the material, and the correlation between this property and the presence or absence and degree of coloring after the light resistance test and heat resistance test is not necessarily clear. However, in UV-curable resins, the content of elements other than oxygen, silicon, oxygen, and hydrogen in the molecule, such as nitrogen, is reduced as much as possible, and the carbon content is also required except for functional groups necessary for curing. It is important not to make more.
Furthermore, light resistance and heat resistance can be improved by not containing organic impurities and acid / alkaline impurities as much as possible. Moreover, it is also preferable to remove and purify coloring impurities using an adsorbent such as activated carbon or activated clay during the production of the ultraviolet curable resin.

[1-2] (B) Heating step In the production method of the present invention, it is preferable to perform the heat treatment in a state where intentional ultraviolet irradiation is not performed after the step (A). The heating temperature is usually 120 ° C. or higher, preferably 130 ° C. or higher, more preferably 150 ° C. or higher, and usually 400 ° C. or lower, preferably 200 ° C. or lower. The heating time is usually 5 minutes or longer, preferably 10 minutes or longer, more preferably 20 minutes or longer, and usually 24 hours or shorter, preferably 10 hours or shorter. If the heating temperature is too low, curing by heat treatment may not proceed well, and if it is too high, decomposition of the material will begin to proceed. If the heating time is too short, uniform thermosetting does not proceed, and if it is too long, it is economically disadvantageous.

  The heat treatment in this step may be performed in a low oxygen concentration atmosphere, but is preferably performed in the air from the standpoint of apparatus simplicity. When the UV curing mechanism proceeds via radicals, it is preferable to perform heat treatment in the presence of oxygen after UV irradiation to reduce the coloration derived from radicals. In the case where there are functional groups (hydrosilyl group and vinyl group) used for conversion, the hardness can be further increased by a thermal reaction.

  It is also preferable to adjust the amount of the UV curable functional group so that the entire resin is lightly hardened in the step (A) and to complete the curing in the step (B). In this case, “lightly solidifies” means that the UV curable resin composition is cured to such an extent that solids other than the UV curable resin such as filler and phosphor existing in the UV curable resin composition do not substantially move. It means to do. When the ultraviolet curable resin contains an adhesion-imparting agent such as a silane coupling agent, or is a polyorganosiloxane having a hydrosilyl group, silanol or hydrolyzable silyl group, (A) the cured product is a thermal adhesive group. (A) Create a semi-cured film-like cured product that is lightly hardened in step (A), and heat-press the metal substrate for heat dissipation or wiring substrate in step (B) to the substrate. An ultraviolet curable resin layer can be adhered.

[2] Embodiment of Semiconductor Light-Emitting Device A cured product obtained by the above-described method of curing an ultraviolet curable resin is an optically transparent, thermally stable and mechanically strong material, and is often an elastomer matrix ( matrix). These heat resistance and light resistance, and adhesion to various materials (silver, aluminum, amide resin, other silicone resins, etc.) are compared with the cured products of conventional ultraviolet curable resins, especially ultraviolet curable silicone resins. Compared with the sealing material and the package material, it is suitable for the resin material for the semiconductor light emitting device including the die bond material and the underfill material.

Hereinafter, the semiconductor light-emitting device provided with the said hardened | cured material is demonstrated using embodiment. In each of the following embodiments, the semiconductor light emitting device of the present invention may be abbreviated as “light emitting device” as appropriate.
Further, the cured product is referred to as a light emitting device member. Further, in which part the light emitting device member 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 the semiconductor light-emitting device including at least the light-emitting device member are not limited to these embodiments.

[2-1] Embodiment 1
In the light emitting device 1A of the present embodiment, as shown in FIG. 7, the light emitting element 2 is surface-mounted on an insulating substrate 16 on which a printed wiring 17 is provided. 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 through the 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. 7 and a p-type semiconductor layer (not shown) formed on the upper surface side. Therefore, the upper part of FIG.

  A frame-shaped frame member 18 surrounding the light emitting element 2 is fixed on the insulating substrate 16. The frame member 18 and the insulating substrate 16 may be configured as a package in which these are integrated. A sealing portion 19 that seals and protects the light emitting element 2 is provided inside the frame member 18. The sealing portion 19 is formed by the light emitting device member according to the present invention, and can be formed by potting the ultraviolet curable resin according to the present invention. The sealing part 19 may contain a phosphor for the purpose of functioning as a wavelength conversion member of the light emitting element 2.

Therefore, since the light emitting device 1A of the present embodiment includes the light emitting element 2 and the sealing portion 19 using the light emitting device member, the light durability and the heat durability of the light emitting device 1A are improved. Can do. In addition, since cracks and peeling do not easily occur in the sealing portion 19, it is possible to increase the light transmittance of the light emitting element 2 in the sealing portion 3A.
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 19 can be made to have high light transmittance with respect to the light emitting element 2 without cloudiness or turbidity, the light color uniformity is excellent, and there is almost no light color variation between the light emitting devices 1A. The light extraction efficiency of the light emitting element 2 to the outside can be increased compared to 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.

Furthermore, in this embodiment, as shown in FIG. 7, the optical member 3A covers the front surface of the light emitting element 2, and the sealing portion 19 is formed on the optical member 3A with a material different from that of the optical member 3A. Is formed. The optical member 3A is used in the following applications, for example.
i) A transparent thin film that functions as a light extraction film and a sealing film on the surface of the light emitting element 2 ii) A phosphor-containing thin film optical member 3A that functions as a wavelength converting member of the light emitting element 2 is, for example, a chip of the light emitting element 2 It can be formed by applying the above-described ultraviolet curable resin by spin coating or the like at the time of formation. The optical member 3A is used as necessary, and the light emitting device of the present invention may naturally be an embodiment that does not have this.

[2-2] Embodiment 2
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the first embodiment. As shown in FIG. 8, an optical member 33 previously formed into a lens shape is disposed on the upper surface of the sealing portion 19. There is a feature in that. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 1, and description is abbreviate | omitted.

The optical member 33 is used for the following applications, for example.
i) Lid that shields the light emitting device 1B from external oxygen and moisture ii) A phosphor-containing optical member that functions as a wavelength converting member of the light emitting element 2 That is, in i), the light emitting element 2 and the sealing portion 19 The upper surface side is shielded from oxygen and moisture in the outside by an optical member 33 as a transparent lid made of, for example, glass or highly airtight resin.

The optical member 33 and the sealing portion 19 may be in direct contact or may have a gap, but a semiconductor light emitting device with high light extraction efficiency and high luminance can be obtained when there is no gap. When it has a space | gap, it is preferable to set it as vacuum sealing or inert gas enclosure.
In such an embodiment, since the optical member 33 suppresses the entry of external factors such as moisture and oxygen, which accelerate the deterioration of the phosphor and the sealing resin, and volatilization of the sealing resin decomposition gas due to heat and light. There is an advantage that the luminance reduction and shrinkage peeling of the sealing portion due to the can be reduced.

  In ii), the optical member 33 is excited by the light from the light emitting element 2 and emits light of a desired wavelength. In the case where the sealing part 19 is formed of an optical member that does not contain a phosphor, impurities due to heat generation or phosphor deterioration due to excitation of the phosphor than in the embodiment in which the phosphor is directly contained in the sealing part 19 It is preferable in that it is not damaged due to elution of selenium.

Thus, in the light emitting device 1B of the present embodiment, the optical member 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. When the lens effect is not expected and only one or more of the above i) or ii) is expected, the optical member is not in a lens shape but may have a plate shape with a flat surface (upper surface). Good. Further, when the light extraction effect is expected, the surface (upper surface) may be formed to have an uneven shape instead of the lens shape.
In addition, various embodiments of the light emitting device of the present invention can be applied. For example, the light emitting device can be applied as it is to those described in paragraphs [0395] to [0512] of Japanese Patent Laid-Open No. 2006-294821. It can also be applied to a light emitting device whose design has been changed.

[2-3] Embodiment 3
As shown in FIG. 9, the basic configuration of the lighting device 1 </ b> C of the present embodiment includes a casing 101 having a window portion, a reflector portion 102, a light source portion 103, and a heat sink 104. The light source unit 103 includes a light emitting unit 105 on a wiring board, and the semiconductor light emitting device according to the first or second embodiment is in a COB (Chip on Board) format in which a semiconductor light emitting element is directly mounted on the wiring board 106. Any of the implemented formats can be used. When the light source unit 103 is in the COB format, the light emitting element may be sealed without using a frame material by a sealing resin formed in a dome shape or a flat plate shape. One or a plurality of semiconductor light emitting elements mounted on the wiring substrate 106 may be used. Similarly, one or a plurality of semiconductor light emitting elements mounted inside the semiconductor light emitting device of the first or second embodiment may be used. good. The reflector unit 102 and the heat sink 104 may be integrated with the housing 101 or may be separate, and can be used as necessary. From the viewpoint of heat dissipation, it is preferable that the light source unit 103, the casing 101, and the heat sink 104 are in contact with each other with a single structure or a high thermal conductive sheet or grease. The window 107 can be made of a known transparent resin, optical glass, or the like, and may be flat or curved.

  In the case where a white LED is provided by providing a phosphor portion, the phosphor portion may be provided in the light source portion 103 or the window portion 107. However, when the phosphor portion is provided in the window portion 107, the phosphor is disposed at a position away from the light emitting element. There is an advantage that it is possible to suppress the deterioration of the phosphor that is easily deteriorated by heat and light, and to obtain white light that is uniform and has high luminance over a long period of time. The phosphor part is a mixture of a phosphor and a binder resin, and converts excitation light from the semiconductor light emitting element 1 into fluorescence. The phosphor contained in the phosphor part is appropriately selected according to the wavelength of the excitation light of the semiconductor light emitting device. In the case of a light emitting device that emits white light, in the case of a semiconductor light emitting element that emits blue excitation light, white light can be generated by including green and red phosphors in the phosphor portion. In the case of a semiconductor light emitting device that emits purple excitation light, there are cases where blue and yellow phosphors are included in the phosphor layer, and blue, green, and red phosphors are included in the phosphor layer. It is done.

When the phosphor layer is provided on the window 107, the phosphor layer can be manufactured on a transparent window material (not shown) by a method such as screen printing, die coating, or spray coating. In such a case, since the semiconductor light emitting element and the phosphor layer are arranged at a distance, it is possible to prevent the phosphor layer from being deteriorated by the energy of light from the semiconductor light emitting element, and to emit light. The output of the device can also be improved. The distance between the semiconductor light emitting element and the phosphor layer of the window 107 is preferably 5 to 50 mm. The phosphor layer in FIG. 9 has a multi-layer structure in which each phosphor color to be used is separately applied, or a pattern such as a stripe shape or a dot shape, in order to reduce self-resorption of fluorescence and reabsorption between RGB phosphors. Or may be formed.
The shape of each part of the illuminating device 1C is not limited to that shown in the drawing, and may include a curved surface part or an attached device such as a light control device or a circuit protection device if necessary.

[2-4] Application to semiconductor light emitting device members
In the light emitting device (semiconductor light emitting device) of each of the first to third embodiments described above, the position to which the light emitting device optical member according to the present invention (hereinafter simply referred to as “optical member”) is not particularly limited. In each of the above-described embodiments, the example in which the optical member according to the present invention is applied as the member that forms the sealing portion 19 is shown. However, in addition to this, for example, the above-described optical member 3A (FIG. 7), optical member 33 (FIG. 8), the frame member 18 (FIGS. 7 and 8), the package (FIG. 7 and 8) in which the frame member 18 and the insulating substrate 16 are integrated, and the like can be suitably used. In addition, in the lighting device 1C of the third embodiment, the housing 101, the reflector unit 102, the light source unit 103, the light emitting devices 1A and 1B of the surface mounted embodiment 1 and the second embodiment are used as the respective members. The light emitting unit 105, the wiring board 106, and the window unit 107 can be used for each member. Since the ultraviolet curable resin according to the present invention has a faster curing speed than the addition type or condensation type curable resin, the printed part edge does not sag before being cured. Therefore, when used as the binder component of the phosphor layer described above, the screen is used. When pattern printing is performed by printing or the like, a high-definition pattern can be formed with good reproducibility. Since the obtained phosphor layer is not colored by light or heat, it can maintain high luminance and can be used particularly suitably. By using the optical member according to the present invention as these members, various excellent sealing properties, transparency, light resistance, heat resistance, film-forming properties, cracks associated with long-term use, suppression of peeling, etc. An effect can be obtained.

In addition, since the ultraviolet curable resin according to the present invention has good adhesion, it can be used as an adhesive for a semiconductor light emitting device in addition to the optical member as described above. Specifically, for example, when bonding a semiconductor element and a package, when bonding a semiconductor element and a submount, when bonding package components, when bonding a semiconductor light emitting device and an external optical member, etc. The ultraviolet curable resin according to the present invention can be used by coating, printing, potting and the like. Since the ultraviolet curable resin according to the present invention is particularly excellent in light resistance and heat resistance, when used as an adhesive for a high-power semiconductor light-emitting device that is exposed to high temperature or ultraviolet light for a long time, it has a long-term use and high reliability. A semiconductor light emitting device having the same can be provided.

The light-emitting device according to the present invention is 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. be able to.
[3] Embodiment of Manufacturing Method The semiconductor light emitting device represented by the above embodiment can be manufactured by using the manufacturing method of the semiconductor light emitting device of the present invention.
Hereinafter, the embodiment in the case of using for a sealing material and a package material is illustrated.

[3-1] Embodiment as Sealing Material The method for manufacturing a semiconductor light emitting device according to the first aspect of the present invention includes a step of sealing a semiconductor light emitting element. In this step, the step (A) described above is included. And preferably has step (B).
Hereinafter, the step of sealing the semiconductor light emitting element will be described in detail with an example of the embodiment. In the present invention, it goes without saying that the step of sealing the semiconductor light emitting element is not limited to this embodiment.

  The step of sealing the semiconductor light emitting element mainly includes a step of adjusting the ultraviolet curable resin, a step of applying the ultraviolet curable resin to a predetermined position, the step (A), and the step (B). Hereinafter, the step of adjusting the ultraviolet curable resin (hereinafter sometimes referred to as “adjusting step”) and the step of applying the ultraviolet curable resin at a predetermined position (hereinafter referred to as “application step”). ) Will be described in detail.

[3-1-1] Adjustment process In the present invention, the adjustment process refers to a process of producing the ultraviolet curable resin composition by producing the aforementioned ultraviolet curable resin and appropriately mixing predetermined additives.
In particular, in the production method of the first aspect of the present invention, the ultraviolet curable resin can be used as, for example, a wavelength conversion member by dispersing a phosphor. The phosphor may be used alone, but may be used in combination with two or more types of phosphors at an arbitrary ratio to produce, for example, a “white LED” light-emitting device. As described above, in the production method of the present invention, the curing rate is increased by heating in the step (A), so that different types of phosphors can be prevented from being separated during curing due to a difference in specific gravity or shape. For this reason, it has great technical significance from the viewpoint of dispersion of the phosphor.

The composition of the phosphor is not particularly limited as long as it is a substance that emits light when excited by the emission wavelength of the semiconductor light emitting device. For example, a phosphor combined with an active element or a coactivator may be used. As the host crystal, metal oxides typified by Y ₂ O ₃ , YVO ₄ , Zn ₂ SiO ₄ , Y ₃ Al ₅ O ₁₂ , Sr ₂ SiO _4, etc., metals typified by Sr ₂ Si ₅ N _8, etc. Nitride, phosphates typified by Ca ₅ (PO ₄ ) ₃ Cl, etc., sulfides typified by ZnS, SrS, CaS, etc., acids typified by Y ₂ O ₂ S, La ₂ O ₂ S, etc. Examples thereof include sulfides. Specific examples of preferred crystal matrixes are shown in the following table.

As the activator element or coactivator element, ions of rare earth metals such as Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, Ag, Cu, Au, Al, Mn And ions of metals such as Sb.
The matrix crystal and the activator or coactivator are not particularly limited in element composition, and can be partially replaced with elements of the same family, and the obtained phosphor absorbs light in the near ultraviolet to visible region. Any material that 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, as described above, phosphors that differ only in part of the structure are omitted as appropriate.

<Orange to red phosphor>
The emission peak wavelength of the orange or red phosphor used in the present invention is usually 570 nm or more, preferably 580 nm or more, more preferably 585 nm or more, and usually 780 nm or less, preferably 700 nm or less, more preferably 680 nm or less. It is preferable that it exists in.
The phosphors that can be used as such orange or red phosphors are shown in the following table.

Among these, as the red phosphor, (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, (Ca, Sr, Ba) Si (N, O) ₂ : Eu, (Ca, Sr , Ba) AlSi (N, O) ₃ : Eu, (Sr, Ba) ₃ SiO ₅ : Eu, (Ca, Sr) S: Eu, (La, Y) ₂ O ₂ S: Eu, Eu (dibenzoylmethane) ) ₃ · 1,10-phenanthroline complexes of β- diketone Eu complex, a carboxylic acid Eu _complex, K 2 _SiF 6: Mn is _{preferred, (Ca, Sr, Ba)} 2 Si 5 (N, O) 8: Eu, (Sr, Ca) AlSi (N, O): Eu, (La, Y) ₂ O ₂ S: Eu, K ₂ SiF ₆ : Mn are more preferable.
As the orange phosphor, (Sr, Ba) ₃ SiO ₅ : Eu, (Sr, Ba) ₂ SiO ₄ : Eu, (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, ( Ca, Sr, Ba) AlSi (N, O) ₃ : Ce is preferred.

<Blue phosphor>
When using blue fluorescent substance, the said blue fluorescent substance can use arbitrary things, unless the effect of this invention is impaired remarkably. At this time, the emission peak wavelength of the blue phosphor is usually 420 nm or more, preferably 430 nm or more, more preferably 440 nm or more, and usually 490 nm or less, preferably 480 nm or less, more preferably 470 nm or less, and further preferably 460 nm or less. It is preferable to be in the wavelength range.
The following table shows phosphors that can be used as such blue phosphors.

Among these, as the blue phosphor, (Ca, Sr, Ba) MgAl ₁₀ O ₁₇ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu, (Ba , Ca, Mg, Sr) ₂ SiO ₄ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu, (Ba, Ca, Sr) ₃ MgSi ₂ O ₈ : Eu is preferred, (Ba, Sr) MgAl ₁₀ O ₁₇ : Eu, (Ca, Sr, Ba) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu, Ba ₃ MgSi ₂ O ₈ : Eu is more preferred, Sr ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu
BaMgAl ₁₀ O ₁₇ : Eu is particularly preferable.

<Green phosphor>
When the green phosphor is used, any green phosphor can be used as long as the effect of the present invention is not significantly impaired. At this time, the emission peak wavelength of the green phosphor is usually larger than 500 nm, preferably 510 nm or more, more preferably 515 nm or more, and usually 550 nm or less, especially 542 nm or less, and further preferably 535 nm or less. If this emission peak wavelength is too short, it tends to be bluish, while if it is too long, it tends to be yellowish, and the characteristics as green light may deteriorate.

  The phosphors that can be used as such green phosphors are shown in the table below.

Among these, as the green phosphor, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, CaSc ₂ O ₄ : Ce, Ca ₃ (Sc, Mg) ₂ Si ₃ O ₁₂ : Ce, (Sr, Ba) ₂ SiO ₄ : Eu, (Si, Al) ₆ (O, N) ₈ : Eu (β-sialon), (Ba, Sr) ₃ Si ₆ O ₁₂ : N ₂ : Eu, SrGa ₂ S ₄ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, Mn is preferred.

When the obtained light-emitting device is used for a lighting device, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, CaSc ₂ O ₄ : CeCa ₃ (Sc, Mg) ₂ Si ₃ O ₁₂ : Ce, (Sr, Ba ) ₂ SiO ₄ : Eu, (Si, Al) ₆ (O, N) ₈ : Eu (β-sialon), (Ba, Sr) ₃ Si ₆ O ₁₂ : N ₂ : Eu are preferable.
When the obtained light emitting device is used for an image display device, (Sr, Ba) ₂ SiO ₄ : Eu, (Si, Al) ₆ (O, N) ₈ : Eu (β-sialon), (Ba, _{sr) 3 Si 6 O 12:} N 2: Eu, SrGa 2 S 4: Eu, BaMgAl 10 O 17: Eu, Mn are preferable.

<Yellow phosphor>
When a yellow phosphor is used, any yellow phosphor can be used as long as the effects of the present invention are not significantly impaired. At this time, the emission peak wavelength of the yellow phosphor is usually in the wavelength range of 530 nm or more, preferably 540 nm or more, more preferably 550 nm or more, and usually 620 nm or less, preferably 600 nm or less, more preferably 580 nm or less. Is preferred.
The phosphors that can be used as such yellow phosphors are shown in the table below.

More in even, as the yellow _{phosphor, Y 3 Al 5 O 12:} Ce, (Y, Gd) 3 Al 5 O 12: Ce, (Sr, Ca, Ba, Mg) 2 SiO 4: Eu, (Ca, One or two or more yellow phosphors selected from the group consisting of Sr) Si ₂ N ₂ O ₂ : Eu and α-sialon phosphors are preferred.
One phosphor can be used alone or in any composition and ratio with two or more types of phosphors.

The weight median diameter of these phosphor particles is not particularly limited, but is usually 100 nm or more,
The thickness is preferably 2 μm or more, more preferably 5 μm or more, and usually 100 μm or less, preferably 50 μm or less, more preferably 20 μm or less. When the weight median diameter is too small, the luminance is lowered and the phosphor particles tend to aggregate. On the other hand, if the weight median diameter is too large, there is a tendency for coating unevenness and blockage of the dispenser to occur.

The shape of the phosphor particles has an adverse effect on the semiconductor light emitting device member, for example, a phosphor formation liquid (a liquid obtained by adding a phosphor to the liquid forming the semiconductor light emitting device member of the present invention) As long as it does not adversely affect the fluidity of the liquid, there is no particular limitation.
In the present invention, the method for adding the phosphor is not particularly limited. If the phosphor is in a well dispersed state, it is sufficient to post-mix the phosphor into the UV curable resin composition. When the phosphor has a tendency to aggregate, for example, if it is a silicone-based ultraviolet curable resin composition, it can be mixed in advance with the raw material before hydrosilylation.
Furthermore, inorganic particles can be added to suppress aggregation and sedimentation of phosphors and the like, and as the inorganic particles, for example, metal oxide particles, preferably fumed silica can be used. it can.

In addition, it is also very preferable to put particles with relatively little ultraviolet absorption in the sealing resin composition together with the phosphor in order to make the ultraviolet rays for curing reach the deep part. Examples of such particles include silica particles and glass beads. Of these, natural quartz powder and artificial quartz powder are preferable from the viewpoint that absorption of ultraviolet rays is small and the refractive index is relatively high at 1.46, so that light extraction efficiency can be increased. The particle size of the particles in this case is usually 5 μm or more, preferably 30 μm or more, more preferably 60 μm or more, and usually 500 μm or less, preferably 200 μm or less, more preferably 100 μm or less. The amount of these particles added is usually 0.1% by weight or more, preferably 1% by weight or more, based on the total weight of the UV curable resin composition including the UV curable resin and the phosphor. The amount is preferably 5% by weight or more, usually 70% by weight or less, preferably 50% by weight or less, more preferably 30% by weight or less, and particularly preferably 15% by weight or less. When the added amount of the particles is too small, the effect of increasing the reach of ultraviolet rays is not expressed. If the amount of the particles added is too large, the excited light emission from the semiconductor light emitting device during use is not preferable.

  In addition, when an acrylate-based functional group is used as a functional group that guarantees UV curability, an acidic functional group is obtained when only a small part of the functional group is hydrolyzed, and the phosphor is separated from carbon dioxide and moisture in the atmosphere. It is preferable because it captures the basic degradation product of the surface layer produced by the reaction, suppresses the degradation of the sealing layer itself, and also extends the lifetime of the phosphor.

[3-1-2] Application Step In the present invention, the application step refers to a step of applying the aforementioned ultraviolet curable resin (including the aforementioned ultraviolet curable resin composition) on the semiconductor light emitting device.
A semiconductor light emitting device suitable for use in the present invention preferably has an emission peak wavelength of 350 nm or more and 500 nm or less. Thereby, white LED device can be manufactured combining an ultraviolet curable resin with the said fluorescent substance. A preferable range for the peak wavelength of the semiconductor light emitting device is 360 nm to 430 nm, or 440 nm to 480 nm. The former is a semiconductor light emitting device that emits violet light from ultraviolet, and the latter is a semiconductor light emitting device that emits blue light. Among these, a semiconductor light emitting device emitting ultraviolet to near ultraviolet light is preferable in that various color temperatures can be realized by combining with a phosphor and a light source having high color rendering properties can be obtained. Further, from the viewpoint of safety, a semiconductor light emitting element that emits violet light from near ultraviolet light having a peak wavelength of 380 nm to 430 nm and a semiconductor light emitting element that emits blue light having a peak wavelength of 440 nm to 480 nm are preferable.

If the peak wavelength of the semiconductor light emitting element is too short, the energy of light increases, which may promote photodegradation of the sealing material and other peripheral materials of the semiconductor light emitting device. Moreover, if the peak wavelength of the semiconductor light emitting device is too long, it is difficult to realize a white LED device by combining with a phosphor.
For the application of the ultraviolet curable resin, various coating methods such as potting, spin coating, and printing can be selected depending on the type and shape of the object to be coated.

Further, when the ultraviolet curable resin of the present invention is used as a sealing material, the structure of the sealing layer is a two-layer structure, (i) a system in which the lower layer is cured by ultraviolet irradiation and the upper layer is cured by thermosetting, Conversely, (ii) a system in which the lower layer is cured by thermal curing and the upper layer is cured by ultraviolet irradiation is also suitable.
(I) As a system for curing the lower layer by ultraviolet irradiation and curing the upper layer by heat curing, for example, after using an ultraviolet curable resin not containing a phosphor in the lower layer and quickly and economically curing by ultraviolet irradiation And a system using a thermosetting phosphor paste (thermosetting resin containing a phosphor) as an upper layer. Accordingly, the phosphor can be kept away from the semiconductor light emitting element, and deterioration of the phosphor due to the semiconductor light emitting element can be prevented.

  (Ii) As a system for curing the lower layer by thermal curing and curing the upper layer by ultraviolet irradiation, for example, after curing a thermosetting phosphor paste, an ultraviolet curable resin not containing a phosphor is applied to the upper layer. And a curing system. Thereby, the upper layer can secure the role of the lens for the semiconductor light emitting device and the lid for the gas barrier, and the upper layer can be cured quickly and economically.

In this case, the ratio between the average thicknesses of the lower layer and the upper layer is usually 1/10 or more, preferably 3/7, and usually 10/1 or less, preferably 7/3.
Further, the above systems (i) and (ii) can be combined. For example, a rapid curing process can be expected by using an ultraviolet curable resin for both the upper layer and the lower layer. Furthermore, for example, a system having a multilayer structure of three or more layers can be appropriately designed.

[3-2] Embodiment as Package Material The method for manufacturing a semiconductor light emitting device according to the second aspect of the present invention includes a step of manufacturing a package on which a semiconductor light emitting element is mounted. Preferably, it has (B) process.
Hereinafter, the process of manufacturing the package will be described in detail. In the present invention, it goes without saying that the process of manufacturing the package is not limited to this embodiment.

  As a process of manufacturing a package mounting a semiconductor light emitting element, a process of mainly preparing an ultraviolet curable resin, a process of putting an ultraviolet curable resin into a mold of the package, the process (A), the process (B), and curing A step of removing the object from the mold. Hereinafter, a step of preparing an ultraviolet curable resin (hereinafter sometimes referred to as “preparation step”) and a step of placing the ultraviolet curable resin in a package mold (hereinafter referred to as “molding step”). ) The step of taking out the cured product from the mold (takeout step) will be described in detail.

[3-2-1] Preparation Step In the present invention, the preparation step refers to a step of producing the above-described ultraviolet curable resin and appropriately mixing predetermined additives to obtain an ultraviolet curable resin composition.
In particular, in the production method of the second aspect of the present invention, the ultraviolet curable resin can be used as a packaging material, for example, by dispersing white inorganic oxide particles. The white inorganic oxide particles are effective for increasing the reflectance inside the package and realizing light extraction of the semiconductor light emitting device.

  As described above, in the manufacturing method of the present invention, the curing in the step (A) can reduce unevenness in curing due to the shape of the package and the ultraviolet absorption of the inorganic oxide particles. It has great technical significance.

[3-2-2] Mold Placement Step In the present invention, the mold placement step refers to a step of placing the aforementioned ultraviolet curable resin (including the aforementioned ultraviolet curable resin composition) into a package mold. Here, before putting the ultraviolet curable resin, a metal lead frame on which a semiconductor light emitting element is mounted or a metal lead frame on which a semiconductor light emitting element is not mounted can be prepared and previously set in a mold. For the mold, a material such as quartz that transmits ultraviolet rays can be used.

[3-2-3] Extraction step In the present invention, the extraction step refers to a step of removing the cured product cured in step (A) from the mold. The extraction step is usually performed after the step (A), but when there is a step (B), it is carried out before or after the step (B). From the viewpoint of suppressing breakage during removal, the removal step is preferably performed after step (B).

The present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples without departing from the gist of the present invention.
[1] Ultraviolet irradiation resistance test and heat resistance test The following ultraviolet radiation resistance test is conducted for the purpose of examining the applicability to the semiconductor light emitting device of the present invention from the viewpoint of the basic physical properties of the cured product of the ultraviolet curable composition. And a heat resistance test was carried out.

[Example 1]
Example: In a small bottle equipped with a rotor, 0.015 g of photoradical initiator Luna200 made by DKSH Japan was mixed and dissolved in 3 g of side chain type acrylic phenyl-containing silicone (X-22-2477) made by Shin-Etsu Chemical Co., Ltd. 1 UV curable resin composition was obtained. This ultraviolet curable resin composition was placed in a Teflon (registered trademark) petri dish having a diameter of 5 cm so as to have a thickness of 2 mm, and 300 mJ using an ECS-151U (1500 W high-pressure mercury lamp) manufactured by Eye Graphics Co., Ltd. in a nitrogen atmosphere. Curing was performed by irradiation with ultraviolet rays (irradiation time: 20 seconds) at an energy of / cm ² at 60 ° C. The total proportion of silicon and oxygen adjacent to silicon in the cured resin was calculated to be about 46% by weight.
The cured film (referred to as “self-supporting film”, hereinafter the same) was subjected to the following ultraviolet irradiation test and heat resistance test.

<Ultraviolet irradiation test>
When light (2100 mW / cm ² ) from an ultraviolet curing device Aicure ANUP5204 manufactured by Matsushita Electric Works and Vision Co., Ltd. was cut at a room temperature in the atmosphere using an optical filter manufactured by Asahi Spectroscopic Co., Ltd., 20 nm was irradiated. The YI value of the film after time irradiation was 2.34. The YI value was measured using COH-300A manufactured by Nippon Denshoku Industries Co., Ltd.

<Heat resistance test>
Further, the YI value of the self-supporting film after being held in the atmosphere at 150 ° C. for 500 hours was 1.93. Furthermore, when the YI value of the free-standing film after being held at 200 ° C. for 500 hours was measured, it was 74.09.

[Example 2]
The same as Example 1 except that 3 g of both-end type methacryl-modified dimethyl silicone (X-22-164) manufactured by Shin-Etsu Chemical Co., Ltd. was used instead of the side chain type acrylic phenyl-containing silicone (X-22-2477) of Example 1. Thus, a liquid was prepared to obtain an ultraviolet curable resin composition of Example 2. This ultraviolet curable resin composition was placed in a Teflon (registered trademark) petri dish having a diameter of 5 cm so as to have a thickness of 2 mm, and irradiated with ultraviolet rays (irradiation time: 20 seconds) with an energy of 300 mJ / cm ² at 60 ° C. in a nitrogen atmosphere. And then cured. The total proportion of silicon and oxygen adjacent to silicon in the cured resin was calculated to be about 18% by weight.
About the self-supporting film after curing, the heat resistance test was performed in the same manner as in Example 1. As a result, the YI values at 150 ° C. and 200 ° C. were 3.81 and 140.99, respectively.

[Example 3]
Instead of the side chain type acrylic phenyl-containing silicone (X-22-2477) of Example 1, 3.5 g of both-end type methacryl-modified dimethyl silicone (X-22-164A) manufactured by Shin-Etsu Chemical Co., Ltd. was used, and a photo radical initiator was used. A liquid was prepared in the same manner as in Example 1 except that 0.0175 g of ESACURE KTO46 was used instead of Luna200, and an ultraviolet curable resin composition of Example 3 was obtained. This ultraviolet curable resin composition was placed in a Teflon (registered trademark) petri dish having a diameter of 5 cm so as to have a thickness of 2 mm, and irradiated with ultraviolet rays (irradiation time: 20 seconds) with an energy of 300 mJ / cm ² at 60 ° C. in a nitrogen atmosphere. And then cured. The total proportion of silicon and oxygen adjacent to silicon in the cured resin was calculated to be about 50% by weight.

For the self-supporting film after curing, an ultraviolet irradiation test was performed in the same manner as in Example 1. As a result, the YI value was 1.93.
Moreover, the heat resistance test similar to Example 1 was implemented. As a result, the YI values at 150 ° C. and 200 ° C. were 1.46 and 48.47, respectively.

[Example 4]
Instead of using 3.5 g of both-end type methacryl-modified dimethyl silicone (X-22-164C) manufactured by Shin-Etsu Chemical Co., Ltd. instead of the both-end type methacryl-modified dimethyl silicone (X-22-164A) manufactured by Shin-Etsu Chemical Co., Ltd. in Example 3. Prepared a liquid in the same manner as in Example 3 to obtain an ultraviolet curable resin composition of Example 4. This ultraviolet curable resin composition was placed in a Teflon (registered trademark) petri dish having a diameter of 5 cm so as to have a thickness of 2 mm, and irradiated with ultraviolet rays (irradiation time: 20 seconds) with an energy of 300 mJ / cm ² at 60 ° C. in a nitrogen atmosphere. And then cured. The total proportion of silicon and oxygen adjacent to silicon in the cured resin was calculated to be about 56% by weight.

For the self-supporting film after curing, an ultraviolet irradiation test was performed in the same manner as in Example 1. As a result, the YI value was 2.01.
Moreover, the heat resistance test similar to Example 1 was implemented. As a result, the YI values at 150 ° C. and 200 ° C. were 1.71 and 10.26, respectively.

[Example 5]
Except for using 3.5 g of both-end type methacryl-modified dimethyl silicone (X-22-164B) manufactured by Shin-Etsu Chemical Co., Ltd. instead of the both-end type methacryl-modified dimethyl silicone (X-22-164A) manufactured by Shin-Etsu Chemical Co., Ltd. in Example 3. Prepared a liquid in the same manner as in Example 3 to obtain an ultraviolet curable resin composition of Example 5. This ultraviolet curable resin composition was placed in a Teflon (registered trademark) petri dish having a diameter of 5 cm so as to have a thickness of 2 mm, and irradiated with ultraviolet rays (irradiation time: 20 seconds) with an energy of 300 mJ / cm ² at 60 ° C. in a nitrogen atmosphere. And then cured. The total proportion of silicon and oxygen adjacent to silicon in the cured resin was calculated to be about 54% by weight.

For the self-supporting film after curing, an ultraviolet irradiation test was performed in the same manner as in Example 1. As a result, the YI value was 2.43.
Moreover, the heat resistance test similar to Example 1 was implemented. As a result, the YI values at 150 ° C. and 200 ° C. were 2.29 and 17.56, respectively.

[Example 6]
Implemented except that 3 g of both-end type methacryl-modified dimethyl silicone (X-22-164E) manufactured by Shin-Etsu Chemical Co., Ltd. was used instead of the side chain type acrylic phenyl-containing silicone (X-22-2477) manufactured by Shin-Etsu Chemical Co., Ltd. of Example 1. A liquid was prepared in the same manner as in Example 1 to obtain an ultraviolet curable resin composition of Example 6. This ultraviolet curable resin composition was placed in a Teflon (registered trademark) petri dish having a diameter of 5 cm so as to have a thickness of 2 mm, and irradiated with ultraviolet rays (irradiation time: 20 seconds) with an energy of 300 mJ / cm ² at 60 ° C. in a nitrogen atmosphere. And then cured. The total proportion of silicon and oxygen adjacent to silicon in the cured resin was calculated to be about 57% by weight.
About the self-supporting film after curing, the heat resistance test was performed in the same manner as in Example 1. As a result, the YI values at 150 ° C. and 200 ° C. were 1.51 and 3.67, respectively.

[Example 7]
In place of the side chain type acrylic phenyl-containing silicone (X-22-2477) manufactured by Shin-Etsu Chemical Co., Ltd. in Example 1, 2.5 g of side chain type methacryloxypropyl modified dimethyl silicone (UMS-182) manufactured by Gilest Co., Ltd. was used. A liquid was prepared in the same manner as in Example 1 except that 0.0125 g was used, and an ultraviolet curable resin composition of Example 7 was obtained. This ultraviolet curable resin composition was placed in a Teflon (registered trademark) petri dish having a diameter of 5 cm so as to have a thickness of 2 mm, and irradiated with ultraviolet rays (irradiation time: 20 seconds) with an energy of 300 mJ / cm ² at 60 ° C. in a nitrogen atmosphere. And then cured. The total proportion of silicon and oxygen adjacent to silicon in the cured resin was calculated to be about 45% by weight.

  About the self-supporting film after curing, the heat resistance test was performed in the same manner as in Example 1. As a result, the YI values at 150 ° C. and 200 ° C. were 3.85 and 108.54, respectively.

[Example 8]
In addition to 2.5 g of side chain methacryloxypropyl-modified dimethylsilicone (UMS-182) manufactured by Dilest as a substrate of Example 7, 0.5 g of Poly (propylene glycol) dimethacrylate manufactured by Aldrich was used, and Luna200 was added in an amount of 0. Example 7 except that 015 g was used
A liquid was prepared in the same manner as described above to obtain an ultraviolet curable resin composition of Example 8. This ultraviolet curable resin composition was placed in a Teflon (registered trademark) petri dish having a diameter of 5 cm so as to have a thickness of 2 mm, and irradiated with ultraviolet rays (irradiation time: 20 seconds) with an energy of 300 mJ / cm ² at 60 ° C. in a nitrogen atmosphere. And then cured. The total proportion of silicon and oxygen adjacent to silicon in the cured resin was calculated to be about 37% by weight.

  About the self-supporting film after curing, the heat resistance test was performed in the same manner as in Example 1. As a result, the YI values at 150 ° C. and 200 ° C. were 9.93 and 155.79, respectively.

[Example 9]
Low-boiling components such as low molecular weight cyclic siloxane groups were cut by vacuum distillation, and 3 g of both-end vinyl group-modified dimethyl silicone (DMS-V22) manufactured by Gilest and side chain mercapto-modified dimethyl silicone (KF-2001) manufactured by Shin-Etsu Chemical Co., Ltd. ) 1.28 g, 0.0021 g of a photoradical initiator Luna200 manufactured by DKSH Japan was mixed and dissolved to obtain an ultraviolet curable resin composition of Example 9. This ultraviolet curable resin composition was placed in a Teflon (registered trademark) petri dish having a diameter of 5 cm so as to have a thickness of 2 mm, and irradiated with ultraviolet rays (irradiation time: 20 seconds) with an energy of 300 mJ / cm ² at 60 ° C. in a nitrogen atmosphere. And then cured. The total proportion of silicon and oxygen adjacent to silicon in the cured resin was calculated to be about 58% by weight.

  For the self-supporting film after curing, an ultraviolet irradiation resistance test was conducted in the same manner as in Example 1. However, the ultraviolet irradiation time was 5 hours. As a result, the YI value was 45.37.

[Example 10]
Momentive Performance Materials Japan Godo Kaisha Terminal Silanol Dimethyl Silicone Oil YF-3800 15g, Shinetsu Chemical Co., Ltd. Methacryloxypropyltrimethoxysilane 1.66g, Wako Pure Chemical Industries, Ltd. tin octanoate 0 0.0133 g was stirred in a 100 mL eggplant flask equipped with a rotor and a Dimroth condenser at room temperature for 15 minutes and at 80 ° C. for 30 minutes. Thereafter, the temperature of the reaction solution was raised to 100 ° C. to completely dissolve the catalyst, and initial hydrolysis was performed while stirring at 500 rpm for 30 minutes at 100 ° C. under total reflux. Thereafter, methanol, water, and low boiling silicon components slightly remaining for 10 minutes at room temperature and 1 kPa were distilled off using a rotary evaporator. An ultraviolet curable resin composition of Example 10 was obtained by mixing and dissolving 0.54 g of a photoradical initiator Luna100 manufactured by DKSH Japan in 10.8 g of the obtained liquid. This ultraviolet curable resin composition was placed in a Teflon (registered trademark) petri dish having a diameter of 5 cm so as to have a thickness of 2 mm, and irradiated with ultraviolet rays (irradiation time: 20 seconds) with an energy of 300 mJ / cm ² at 60 ° C. in a nitrogen atmosphere. And then cured. The total proportion of silicon and oxygen adjacent to silicon in the cured resin was calculated to be about 55% by weight.

[Comparative Example 1]
A liquid was prepared in the same manner as in Example 6 except that the side chain type methacryloxypropyl-modified dimethyl silicone (UMS-182) manufactured by Gilest in Example 7 was changed to 6 g scale and 0.03 g of the photoradical initiator Luna200 was used. The UV curable resin composition of Comparative Example 1 was prepared. This ultraviolet curable resin composition was subjected to ultraviolet rays (irradiation time 20 seconds) with an energy of 300 mJ / cm ² using ECS-151U (1500 W high-pressure mercury lamp) manufactured by Eye Graphics Co., Ltd. in a nitrogen atmosphere at 15 ° C. and 30 ° C. It was cured by irradiation at 0 ° C. Table 6 shows the hardness of the cured product. As a result, it was found that it is preferable to perform heating simultaneously with ultraviolet irradiation in order to cure quickly and with a high degree of crosslinking at an energy of about 300 mJ / cm ² .

[Comparative Example 2]
100 parts by weight of A and B liquids of thermosetting transparent sealing resin SCR-1011 for photo devices manufactured by Shin-Etsu Chemical Co., Ltd. were mixed, and this liquid was 2 m thick in a Teflon (registered trademark) petri dish with a diameter of 5 cm.
m, and cured by heating at 70 ° C. for 1 hour and 150 ° C. for 5 hours.

For the self-supporting film after curing, an ultraviolet irradiation test was performed in the same manner as in Example 1. As a result, the YI value was 74.25.
Moreover, the heat resistance test similar to Example 1 was implemented. As a result, the YI value at 150 ° C. was 45.37. From this result, compared with the manufacturing method of LED using the conventional thermosetting Shin-Etsu Chemical Co., Ltd. transparent sealing resin SCR-1011 for photo devices, the manufacturing method of the present invention has a very fast curing time, It was found that the durability in terms of durability was extremely excellent.

[Comparative Example 3]
A liquid was prepared in the same manner as in Example 1 except that the side chain type acrylic phenyl-containing silicone (X-22-2477) manufactured by Shin-Etsu Chemical Co., Ltd. in Example 1 was changed to urethane acrylate UXF-3204A manufactured by Nippon Kayaku Co., Ltd. Then, an ultraviolet curable resin composition of Comparative Example 3 was obtained. This ultraviolet curable resin composition was placed in a Teflon (registered trademark) petri dish having a diameter of 5 cm so as to have a thickness of 2 mm, and irradiated with ultraviolet rays (irradiation time: 20 seconds) with an energy of 300 mJ / cm ² at 60 ° C. in a nitrogen atmosphere. And then cured. The total proportion of silicon and oxygen adjacent to silicon in the cured resin was calculated to be about 0% by weight.

The cured self-supporting film was subjected to an ultraviolet-resistant irradiation test in the same manner as in Example 1. However, the irradiation was interrupted because the self-supporting film changed drastically after several minutes. Moreover, the heat resistance test similar to Example 1 was implemented. As a result, the YI value at 150 ° C. and 200 ° C. was 40.20, respectively.
From this result, the manufacturing method of the present invention has no coloring problem and is extremely excellent in durability as compared with a manufacturing method of LED using silicon and an ultraviolet curable resin having a low oxygen content adjacent to silicon. It turned out that there was an effect.

[2] Hygroscopic reflow test and heat cycle test The following hygroscopic reflow test and heat cycle test were conducted for the purpose of examining the durability of the LED package for applicability to the semiconductor light emitting device of the present invention.

[Example 11]
Example 6 except that the both-end type methacryl-modified dimethyl silicone (X-22-164E) manufactured by Shin-Etsu Chemical Co., Ltd. in Example 6 was changed to 7 g scale and 0.035 g of ESACURE KTO46 was used instead of the photoradical initiator Luna200. A liquid was prepared in the same manner as described above to obtain an ultraviolet curable resin composition of Example 11. The total proportion of silicon and oxygen adjacent to silicon in this ultraviolet curable resin composition was calculated to be about 57% by weight.

<Hygroscopic reflow test>
The liquid prepared in Example 11 was applied to each of 10 LED packages on the silver surface, LED package on the ceramic (alumina) surface, and LED package on the polyphthalamide surface, and 300 mJ / cm ² in a nitrogen atmosphere. The resin was cured by irradiation with ultraviolet light (irradiation time: 20 seconds) at the energy of. The obtained LED package was absorbed at 85 ° C./85% RH for 20 hours and then heated at 260 ° C. for 1 minute to confirm the number of LED packages from which the resin was peeled off from the package surface.

After the moisture absorption operation and after heating at 260 ° C., no peeling was confirmed from any of the packages on the silver surface, ceramic surface, and polyphthalamide surface.
Further, 13 parts by weight of a thixotropic agent (AEROSIL RX-200 manufactured by Evonik) was added to 100 parts by weight of the liquid prepared in Example 11, and the LED surface having a silver surface, a ceramic surface, and a polyphthalamide surface in the same manner as described above. When the peeling test from the package was performed, no peeling occurred after moisture absorption from any of the packages. After heating at 260 ° C., minute peeling was confirmed only from two of the 10 ceramic surface packages. No peeling was confirmed.

<Heat cycle test>
The solution prepared in Example 11 was applied to each of 10 LED packages on the silver surface, LED device package on the ceramic (alumina) surface, and 10 LED packages on the polyphthalamide surface, and 300 mJ / cm in a nitrogen atmosphere. Curing was performed by irradiating with ultraviolet energy of ² (irradiation time 20 seconds). When the obtained LED package was subjected to heating / cooling cycles of (120 ° C., 10 minutes) and (−50 ° C., 10 minutes) for 500 cycles, no peeling was confirmed in any of the LED packages on the surface. .

[3] Semiconductor Light-Emitting Device (LED) Test With regard to the applicability of the present invention to the semiconductor light-emitting device, the following test was conducted for the purpose of examining the performance of the semiconductor light-emitting device (LED) itself.

[Example 12]
The ultraviolet curable composition of Example 11 was potted on a silver surface package on which a near ultraviolet LED having a peak wavelength at 405 nm was mounted, and was irradiated with ultraviolet rays with an energy of 300 mJ / cm ² at 60 ° C. in a nitrogen atmosphere (irradiation time 20 Second) was cured to produce a semiconductor light emitting device (LED).
The luminance maintenance rate of the LED was measured over time under each environmental condition of 25 ° C./55% RH and 60 ° C./90% RH. The measurement results are shown in FIG.

[Example 13]
Example 1 except that the side chain type acrylic phenyl-containing silicone (X-22-2477) manufactured by Shin-Etsu Chemical Co., Ltd. of Example 1 was changed to 7 g scale and 0.035 g of ESACURE KTO46 was used instead of the photoradical initiator Luna200. In the same manner as in Example 1, an ultraviolet curable resin composition of Example 13 was obtained. The total proportion of silicon and oxygen adjacent to silicon in this ultraviolet curable resin composition was calculated to be about 46% by weight.

  An LED was produced in the same manner as in Example 12 using this ultraviolet curable resin composition. The luminance maintenance rate of the LED was measured over time under an environmental condition of 25 ° C./55% RH. The measurement results are shown in FIG.

[Example 14]
The red phosphor Ca _0.87 Eu _0.008 Al _0.88 Si _1.12 O _0.12 N _2.88 manufactured by Mitsubishi Chemical Corporation, green phosphor (Ba) , Sr, Eu) ₂ SiO ₄ , blue phosphor Ba _0.7 Eu _0.3 MgAl ₁₀ O ₁₇ , and AEROSIL RX-200 manufactured by Evonik as a thixotropic agent were mixed to form a paste, and the ultraviolet curability of Example 14 was used. A resin composition was obtained.

An LED was produced in the same manner as in Example 12 using this ultraviolet curable resin composition. The luminance maintenance rate of the LED was measured over time under each environmental condition of 25 ° C./55% RH and 60 ° C./90% RH. The measurement results are shown in FIG.
[Example 15]
The red phosphor Ca _0.87 Eu _0.008 Al _0.88 Si _1.12 O _0.12 N _2.88 manufactured by Mitsubishi Chemical Corporation, green phosphor (Ba) , Sr, Eu) ₂ SiO ₄ , blue phosphor Ba _0.7 Eu _0.3 MgAl ₁₀ O ₁₇ , and AEROSIL RX-200 manufactured by Evonik as a thixotropic agent are mixed to form a paste, and the ultraviolet curing property of Example 15 is used. A resin composition was obtained.

  An LED was produced in the same manner as in Example 12 using this ultraviolet curable resin composition. The luminance maintenance rate of the LED was measured over time under an environmental condition of 25 ° C./55% RH. The measurement results are shown in FIG.

[Example 16]
Momentive Performance Materials Japan G.K., both ends silanol dimethyl silicone oil XC96-723 385g, methyltrimethoxysilane 10.28g, and zirconium tetraacetylacetonate powder 0.791g as a catalyst, stirring blade Were weighed in a 500 ml three-necked Kolben equipped with a fractionating tube, a Dimroth condenser and a Liebig condenser, and stirred at room temperature for 15 minutes until the coarse particles of the catalyst were dissolved. Thereafter, the temperature of the reaction solution was raised to 100 ° C. to completely dissolve the catalyst, and initial hydrolysis was performed while stirring at 500 rpm for 30 minutes at 100 ° C. under total reflux.

Subsequently, the distillate was connected to the Liebig condenser side, nitrogen was blown into the liquid with SV20, and methanol, water, and low-boiling silicon components of by-products were distilled off with nitrogen accompanying at 100 ° C. and 500 rpm for 1 hour. Stir. The polymerization reaction was continued for 5.5 hours while the temperature was further raised and maintained at 130 ° C. while blowing nitrogen into the liquid with SV20 to obtain a reaction liquid having a viscosity of 389 mPa · s. Here, “SV” is an abbreviation for “Space Velocity” and refers to the volume of blown volume per unit time. Therefore, SV20 refers to blowing N ₂ in a volume 20 times that of the reaction solution in one hour.

  After stopping the blowing of nitrogen and cooling the reaction solution to room temperature, the reaction solution was transferred to an eggplant-shaped flask, and methanol and moisture remaining in a minute amount at 120 ° C. and 1 kPa on an oil bath using a rotary evaporator, The low boiling silicon component was distilled off to obtain a liquid having a viscosity of 584 mPa · s. This resin composition is referred to as the resin composition of Reference Example 1. The ratio of silicon and oxygen adjacent to silicon in the resin composition of Reference Example 1 was calculated to be about 59% by weight.

In the resin composition of Reference Example 1, Ca _0.87 Eu _0.008 Al _0.88 Si _1.12 O _0.12 N _2.88 manufactured by Mitsubishi Chemical Corporation, green phosphor (Ba, Sr, Eu) ₂ SiO ₄ , blue phosphor Ba _0.7 Eu _0.3 MgAl ₁₀ O ₁₇ , and AEROSIL RX-200 manufactured by Evonik as a thixotropic agent were mixed to obtain a resin composition of Reference Example 2.
The ultraviolet curable resin composition prepared in Example 6 was potted on a silver surface package on which a near ultraviolet LED having a peak wavelength at 405 nm was mounted, and irradiated with ultraviolet rays with energy of 300 mJ / cm ² at 60 ° C. in a nitrogen atmosphere ( Curing was carried out for 20 seconds). On top of this, the resin composition of Reference Example 2 was applied and subjected to a heat treatment at 150 ° C. for 3 hours to produce a semiconductor light emitting device (LED).

The luminance maintenance rate of the LED was measured over time under each environmental condition of 25 ° C./55% RH and 60 ° C./90% RH. The measurement results are shown in FIG.
[4] Package Test The following test was conducted for the purpose of examining the applicability to the package for a semiconductor light emitting device in the present invention.
<Preparation of high reflectance white resin composition according to the present invention>

[Example 17]
2.6 g of OE-6351A manufactured by Toray Dow Co., 2.6 g of OE-6351B, 2.6 g of both-end type methacryl-modified dimethyl silicone (X-22-164AS) manufactured by Shin-Etsu Chemical Co., Ltd., photoradical manufactured by DKSH Japan An ultraviolet curable white resin composition of Example 17 was obtained by mixing 0.16 g of the initiator Luna100, 1.5 g of AEROSIL RX-200 manufactured by Evonik, and 10 g of aluminum oxide CR-1 manufactured by Baikowski Japan. . This ultraviolet curable white resin composition was placed in a Teflon (registered trademark) petri dish having a diameter of 5 cm so as to have a thickness of 2 mm, and irradiated with ultraviolet rays with an energy of 2100 mJ / cm ² at 60 ° C. in a nitrogen atmosphere (irradiation time 140 seconds). And cured by ultraviolet light, and then heat-treated at 150 ° C. for 1 hour in the air to prepare a fully cured self-supporting film. The total proportion of silicon and oxygen adjacent to silicon in the cured resin net excluding aluminum oxide and AEROSIL RX-200 was calculated to be about 53% by weight.

[Example 18]
2.4 g of OE-6351A manufactured by Toray Dow Co., 2.4 g of OE-6351B, 2.4 g of both-end type methacryl-modified dimethyl silicone (X-22-164AS) manufactured by Shin-Etsu Chemical Co., Ltd., 0 of X-22-164E 8 g, 0.16 g of photoradical initiator Luna100 manufactured by DKSH Japan, 1.5 g of AEROSIL RX-200 manufactured by Evonik, and 10 g of aluminum oxide CR-1 manufactured by Baikowski Japan were mixed together. An ultraviolet curable white resin composition was obtained. This ultraviolet curable white resin composition was completely cured by the same method as in Example 17 to prepare a self-supporting film. The total proportion of silicon and oxygen adjacent to silicon in the cured resin net excluding aluminum oxide and AEROSIL RX-200 was calculated to be about 54% by weight.

<Reflectance of cured product of UV curable white resin composition>
The result of measuring the reflectance of the self-supporting films obtained in Examples 17 and 18 is shown in FIG.
All showed very high reflectance with respect to light between 360 nm which is an ultraviolet region and 740 nm which is a near infrared region.
Further, the self-supporting films obtained in Examples 17 and 18 were subjected to the above-described ultraviolet resistance irradiation test (ultraviolet irradiation time was 5 hours) and the heat resistance test at 200 ° C., and then the reflectance was measured.

  As a result, almost no reduction was observed in the reflectance of any free-standing film in the region from 360 nm to 740 nm.

  The method for producing a semiconductor light emitting device of the present invention can quickly and easily produce a semiconductor light emitting device having excellent wet heat resistance and ultraviolet light resistance, particularly a white semiconductor light emitting device. In particular, it is useful in pastes containing phosphors, and has high industrial applicability in the field of sealing materials for semiconductor light emitting devices. In addition, it is also useful in a highly reflective ultraviolet curable resin composition mixed with a white filler, and has high industrial applicability in the fields of semiconductor light emitting device package materials and substrate paints.

1A, 1B Light emitting device 1C Lighting device 2 Light emitting element 3A Optical member 15 Conductive wire 16 Insulating substrate 17 Printed wiring 18 Frame member 19 Sealing portion 21 Light emitting layer portion 33 Optical member 101 Case 102 Reflector portion 103 Light source portion 104 Heat sink 105 Light emission Part 106 Wiring board 107 Window part

Claims (7)

A method for manufacturing a semiconductor light emitting device including a step of sealing a semiconductor light emitting element,
During the step of sealing the semiconductor light emitting element,
(A) a step of irradiating the ultraviolet curable resin with ultraviolet light in an environment of 50 ° C. or higher and 100 ° C. or lower;
15. A method of manufacturing a semiconductor light emitting device, wherein 15% or more of the weight of the ultraviolet curable resin is silicon and oxygen adjacent to silicon. A method of manufacturing a semiconductor light emitting device including a step of manufacturing a package mounting a semiconductor light emitting element using a resin material,
During the process of manufacturing the package using a resin material,
(A) a step of irradiating the ultraviolet curable resin with ultraviolet light in an environment of 50 ° C. or higher and 100 ° C. or lower;
15. A method of manufacturing a semiconductor light emitting device, wherein 15% or more of the weight of the ultraviolet curable resin is silicon and oxygen adjacent to silicon. After the step (A),
(B) The manufacturing method of the semiconductor light-emitting device according to claim 1, further comprising a step of heating without ultraviolet irradiation.   The method for manufacturing a semiconductor light emitting device according to claim 3, wherein the heating condition in the step (B) is 120 ° C. or more and 5 minutes or more. When the ultraviolet curable resin is irradiated with ultraviolet rays at a peak wavelength of 360 nm and an energy amount of 300 mJ / m ² in an environment of 60 ° C. to form a cured film having a thickness of 2 mm, the following physical properties 1 and physical properties are as follows: 5. The method for manufacturing a semiconductor light-emitting device according to claim 1, wherein the semiconductor light-emitting device has at least one of two.
<Physical property 1>
The YI value of the cured film after storing the cured film in the atmosphere at 150 ° C. for 500 hours is 20.00 or less <Property 2>
The cured film has a YI value of 20.00 or less after irradiation with light having a wavelength of 350 nm or more at room temperature in the atmosphere at an intensity of 2100 mW / cm ² for 20 hours.   6. The method according to claim 1, further comprising a step of causing the ultraviolet curable resin to contain a phosphor containing at least one of a silicate-based, nitride-based, oxynitride-based, and oxide-based material. A method for manufacturing a semiconductor light-emitting device according to claim 1. 2. The emission peak wavelength of the semiconductor light emitting device is 350 nm or more and 500 nm or less.
7. A method for manufacturing a semiconductor light emitting device according to any one of items 1 to 6.

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