JP5767552B2 - Semiconductor light emitting device and manufacturing method thereof - Google Patents

Description

  The present invention relates to a semiconductor light emitting device and a method for manufacturing the same.

  Semiconductor light-emitting devices are expected as next-generation light sources to replace incandescent lamps and fluorescent lamps, and technological developments such as improving luminous efficiency are being actively promoted in Japan and overseas. The range of application as the light source is also diverse, and its use is expanding not only for indoor lighting but also as a backlight for liquid crystal display devices. In particular, in recent years, with the growing awareness of energy saving, attention has been focused on semiconductor light emitting devices with low power consumption, and companies and research institutions are accelerating their technological development.

  Looking at the types of semiconductor light-emitting devices by structure, there are a shell type, a surface mount type (SMD), a chip on board (COB), and the like. FIG. 1 shows an example of a surface mount type. In this example, the semiconductor light emitting element 1 is mounted in a reflector package substrate 2 molded from ceramic or resin. The cavity (concave space) W is sealed with a resin (sealing material) 3 such as epoxy resin or silicone. The surface inside the cavity is provided with a function of a reflecting plate so that a lot of light can be extracted.

  As can be seen from the above structure, the semiconductor light-emitting device requires a structure and members that are different from those of conventional incandescent bulbs and fluorescent lamps, and is required for each application such as a backlight unit of LCD TV, lighting, and indicator lamp. Different performance is required, so development according to each is required. Even in the backlight unit, the performance required from the viewpoint of light distribution is different between the direct type and the edge type, and the development has not been made sufficiently. The same applies to the sealing material described above, and epoxy or silicone resins are currently the mainstream, but development studies and material searches for further performance improvement are required. For example, Patent Document 1 discloses a resin raw material composition for a semiconductor light emitting device using an alicyclic hydrocarbon compound.

  As a form of the sealing material, the semiconductor light-emitting device used in the backlight unit of the liquid crystal display device is cured by mixing a silicone-based resin or epoxy-based resin having no curing shrinkage with an oil-absorbing diffusing agent. Therefore, a light-emitting surface formed in a recessed shape has been proposed (Patent Documents 2 and 3). With such a concave shape, the light distribution from the semiconductor light emitting device is narrowed, and the introduction rate of the backlight unit into the light guide plate is improved. Or the thing formed so that the light emission surface may not become parallel with respect to the end surface of the light-guide plate facing a semiconductor light-emitting device is proposed. Specifically, a semiconductor light emitting device in which a cross section of a sealing material is shaped into a V shape is disclosed. (Patent Document 4).

International Publication No. 2006/051803 Pamphlet JP 2007-165803 A Japanese Patent No. 4010299 JP 2009-301725 A

By the way, although there are several development examples as described above for the sealing resin of the semiconductor light emitting device, the device configuration, the types and blends of materials particularly suitable for realizing the shape and structure, and the manufacturing suitability thereof. The research on the relationship is still not sufficiently advanced.
Therefore, the present invention pays attention to the optical characteristics of the sealing material in the semiconductor light emitting device, and adopts a molding method that has a light distribution property that realizes a narrow irradiation region that is appropriately condensed and has high manufacturing efficiency. An object of the present invention is to provide a semiconductor light emitting device and a method for manufacturing the same.

That is, the present invention provides the following means for solving the above-mentioned problems.
(1) a semiconductor comprising a reflector packaging substrate, a semiconductor light emitting element mounted on the recessed space of the Li full Rector package substrate, and a sealing material containing a polar group-containing acrylic resin sealed semi-conductor light emitting element A light emitting device,
Light-emitting surface of the sealant is recessed in a curved surface, setting the radius of curvature of the concave light exit surface, out to 1.8 times to 4.5 times the length of the diameter or short side in plan view of the optical surface It is,
The sealing material is formed as an acrylic resin by applying a sealing agent containing a polar group-containing acrylic monomer to the concave space of the reflector package substrate, curing the acrylic monomer,
A cured product of the composition liquid in which the ratio of the acrylic group or methacrylic group of the monomer constituting the acrylic resin before curing is 4 mmol / g or more and less than 6.5 mmol / g with respect to the total mass of the encapsulant containing the monomer A semiconductor light emitting device.
(2) polar group is a hydroxyl group, oligoethylene glycol group, a semiconductor light emitting device according to an isocyanuric acid derivative group (1).
(3) the surface of the electrode portion of the Li full Rector packages containing silver (1) or a semiconductor light emitting device according to any one of (2).
(4) more than 80% of the encapsulant is an organic component (1) a semiconductor light-emitting device according to any one of - (3).
(5) A acrylic resin is characterized in that it comprises more than 50 wt% resin obtained by curing the isocyanuric acid acrylate derivative (1) semiconductor light-emitting device according to any one of - (4).
(6) A ratio of acrylic group or methacrylic group is a cured product of the composition solution is less than 5.3 mmol / g or more 6.3 mmol / g (1) ~ semiconductor light emitting according to any one of (5) apparatus.
(7) The semiconductor light emitting element is mounted on the recessed space of the reflector package, the concave-shaped space so as to embed the semiconductors emitting element imparting a sealing agent containing a polar group-containing acrylic monomer, then acrylic sealant curing the system monomer Upon for shaping as a sealing material of the acrylic resin, the ratio of acrylic groups or methacrylic groups of the monomers constituting the acrylic resin before curing, the total weight of the sealant containing monomer in contrast, the cured product of the composition solution is less than 4 mmol / g or more 6.5 mmol / g, the volume shrinkage due to the curing of the sealant, the dropping surface partially lowering the, recessed drops lower surface of sealing material A method of manufacturing a semiconductor light emitting device shaped as a light exit surface.
(8) as A acrylic-based monomer, a method of manufacturing a semiconductor light emitting device according to a compound represented by the following formula 1 (7).

式（１）中のＲ^１、Ｒ^２、Ｒ^３は、それぞれ独立に、水酸基、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数６〜２４のアリールオキシ基、炭素数６〜２４のアリール基、下記式（Ｉ）で表されるアクリロイルオキシ基、又は下記式（ＩＩ）で表されるアシルオキシ基を表す。Ｌ^ａは炭素数１〜４のアルキレン基を表す。ただし、Ｒ^１、Ｒ^２、及びＲ^３の少なくとも１つはアクリロリルオキシ基である。

R ¹ , R ² and R ^{3 in} formula (1) are each independently a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, It represents an aryl group having 6 to 24 carbon atoms, an acryloyloxy group represented by the following formula (I), or an acyloxy group represented by the following formula (II). L ^a represents an alkylene group having 1 to 4 carbon atoms. Provided ^that at least one of R 1, ^{R 2,} and ^{R 3} is A Kuriroriruokishi group.

式中、Ｒ^１１は水素原子又は炭素数１〜３のアルキル基を表す。＊は結合手を表す。

In the formula , R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. * Represents a bond .

式中、Ｒ^１２は炭素数１〜１０のアルキル基又は炭素数６〜２４のアリール基を表す。＊は結合手を表す。
（９）極性基含有アクリル系モノマーを含む封止剤は、その粘度が８００ｍＰａｓ以上２０，０００ｍＰａｓ未満である（７）又は（８）に記載の半導体発光装置の製造方法。
（１０）硬化前のアクリル系モノマーについて以下の試験を行った際の揮発量が１０質量％未満である（７）〜（９）のいずれか１項に記載の半導体発光装置の製造方法。
ＴＧ／ＤＴＡにおいて５ｍｇを３℃／分の昇温速度で、８０℃６０ｍｉｎ＋１３０℃６０ｍｉｎで加熱し、そのときの重量減少を解析する。

In the formula , R ¹² represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 24 carbon atoms. * Represents a bond .
(9) sealant containing polar group-containing acrylic monomer, a method of manufacturing a semiconductor light emitting device according to the viscosity to less than 800 mPas 20,000 mPas (7) or (8).
(10) volatilization amount during the following tests were conducted for hardening before the acrylic monomer is less than 10 wt% (7) A method of manufacturing a semiconductor light emitting device according to any one of - (9).
In TG / DTA, 5 mg is heated at 80 ° C. 60 min + 130 ° C. 60 min at a rate of temperature increase of 3 ° C./min, and the weight loss at that time is analyzed .

  The present invention satisfies the required performance required for a sealing material of a semiconductor light-emitting element at a high level, has a light distribution property that realizes a narrow irradiation region appropriately focused thereon, and has high manufacturing efficiency. It is an object of the present invention to provide a semiconductor light emitting device that can employ a molding method and a method for manufacturing the same.

Device explanatory view schematically showing a semiconductor light emitting device according to a preferred embodiment of the present invention It is sectional drawing which showed an example of the semiconductor light-emitting device typically. It is the top view which showed typically the relationship between the shape of the opening part of a semiconductor light-emitting device, and each dimension.

  A semiconductor light-emitting device of the present invention includes a reflector package base material, a semiconductor light-emitting element mounted in a concave space of the reflector package base material, and a sealing material including a cured product of an acrylic resin that seals the semiconductor light-emitting element It comprises. The light exit surface of the sealing material is recessed in a curved shape, and the recessed light exit surface has a specific radius of curvature. Here, the curved surface shape only needs to be configured by a surface having substantially continuous curves, and may partially include a flat surface as long as the effects of the present invention are not impaired. For example, a substantially spherical concave surface can be mentioned. Typically, it is preferable that 50% (area ratio) or more of the light exit surface is constituted by a curved surface, and more preferably 70% or more is constituted by a curved surface. The curved surface may have a gentle curvature, and when it is necessary to strictly evaluate the surface, for example, a surface having a curvature radius of 10 times or more of the diameter of the light emitting surface or the short side is defined as a flat surface in any of the surface directions. The area ratio is calculated. The upper limit of the ratio of the curved surface is not particularly limited, but it is preferable that 100% (area ratio) is constituted by the curved surface. Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings.

[Semiconductor light emitting device]
FIG. 2 is a device explanatory view schematically showing a semiconductor light emitting device according to a preferred embodiment of the present invention. The basic device configuration is the same as the general device shown in FIG. 1, and includes a semiconductor light emitting element 1, a reflector package substrate 2, a sealing material 3, an electrode 4, a bonding wire 6, and a die bond agent 8. The light emitting device 10 is configured. However, for the convenience of illustrating the optical features described here, illustrations are omitted except for the reflector package base material 2, the sealing material 3, and the element 1. For convenience of illustration, the cross-sectional shape is slightly different from that of FIG. The upper and lower sides of the apparatus are not particularly limited, but if necessary, the light exit surface 3a side is displayed as the “upper” or “top” side, and the element 1 side is displayed as the “lower” or “bottom” side. However, the present invention should not be construed as being limited by the device in the description and the illustrated form.

The reflector package substrate 2 of the present embodiment forms a concave space W during potting before sealing, and serves as a container for receiving a resin (liquid sealing agent). On the other hand, after curing, it plays a role of protecting the semiconductor light emitting element and the bonding wire from the outside, reflecting light from the semiconductor light emitting element to increase the extraction efficiency, and also serving as a reflector for distributing the light. As a role of the container for receiving the sealing liquid, it is preferable to use a heat-resistant material that has a concave shape so that the liquid is held and can maintain the shape even during curing. In addition to protection from mechanical impact, the role of protection is to protect from sulfide gas such as hydrogen sulfide and sulfur gas. Adhesive materials are used.
As the reflector package, one in which electrodes are integrally formed, and one in which electrodes are provided as circuit wiring by plating after the package is molded can be used. Moreover, a package corresponding to an arbitrary mounting method such as a top view or a side view can be used as a mounting method.

As the shape of the package, any shape such as a cylinder, an elliptical column, a cube, a rectangular parallelepiped, a shape between a rectangular parallelepiped and an elliptical column, or a combination thereof can be adopted. In addition, it is possible to prepare a weir with a material called a dam material in a flat reflecting portion in advance and use the inside as a recess (cavity), but from the viewpoint of light distribution, a reflector package having a recess (cavity) in advance. It is preferable to use it. The reflectors w1, w2, and w3 preferably have a function of reflecting light totally reflected at the sealing material / air interface in addition to a function of directly reflecting light from the semiconductor light emitting element. In particular, in the present embodiment (FIG. 2), it is preferable that the light confined inside the sealing material by total reflection can be appropriately reflected and extracted outside in order to orient the light sharply. The shape of the inner wall portion can be selected at any angle with respect to the bottom portion, but for the purpose of extracting light by reflection or for the purpose of making the sealing material shape appropriately concave, the area becomes smaller toward the bottom. Such a mortar shape is preferable. As the shape of the bottom of the concave portion, any shape such as a flat shape or a concave shape can be selected.
As the material of the reflector package base material, the heat resistance, adhesion to the sealing material, reflectance, electrical insulation, and heat resistance are the viewpoint of maintaining the shape during curing and the viewpoint of maintaining the reflectance during use. Therefore, it is preferable that an appropriate material is selected. Specifically, it is preferable to select a material in which a white pigment such as titanium oxide is mixed with a ceramic such as alumina or a resin such as polyphthalamide. As the shape of the reflector package, a mortar shape is preferably selected so as to reflect the trapped light so as to obtain an appropriate light distribution. Moreover, the reflection part contained in a reflector package can also have an electrode, and it is preferable to have silver with a high reflectance on the surface. As a molding method of the package, insert molding, injection molding, extrusion molding, transfer molding, or the like performed by previously setting the electrode in a mold can be used.

  The semiconductor light emitting device 10 of the present embodiment has a light exit surface 3a that is gently mortar-shaped and recessed in a curved shape as the outer surface of the sealing material. A spherical shape smoothly curved like the concave lens can be suitably created by molding a specific acrylic resin by potting. Although the manufacturing method will be described in detail later, the surface tension of the side surfaces (reflectors) w1 and w2 of the concave space W acts appropriately, and the resin height of the portion is maintained at or near the virtual plane 3b. On the other hand, as it goes to the center, a concave surface is formed in a state of being shallow due to volume shrinkage. The shape of the sealing material 3 which is cured in this state and has a surface like a saucer is fixed, and the curved light exit surface 3a is formed.

  The light exit surface 3a that is recessed in the curved surface realizes a specific light distribution property in combination with the refractive index of light of the sealing material. It is practical that the refractive index of the sealing material is 1.45 or more and less than 1.7 at room temperature (about 28 ° C.). On the other hand, when the external space is air, the light emitted from the semiconductor light emitting element that is the light source is refracted by the light exit surface 3a that is the interface between them. This situation is schematically shown in the optical paths p1, p2, and p3. The optical path p1 is light that travels perpendicularly to the virtual light exit plane from the element installed at the center. In this portion, the light travels linearly without being refracted on the light exit surface 3a. On the other hand, the light path p2 travels obliquely at a low angle with respect to the light exit surface 3a. Therefore, the light is refracted at this portion, and in this embodiment, the light travels outward to the right of the device. On the other hand, since the light (optical path p3) emitted further outward reaches the light exit surface at a lower angle, it does not radiate to the outside but travels by being totally reflected by the light exit surface 3a. Thereafter, the light reflected by the reflector (side surface) w2 travels substantially perpendicular to the virtual light emission plane and is distributed. Such light reflection and propagation forms are the same on the left side of FIG. 2, and light with a narrower light distribution is emitted over the entire opening of the light emitting element.

  On the other hand, in the device (comparative example) in which the virtual light emission plane 3b is the light emission surface, when light travels along the optical path p3 in FIG. 2, light is refracted to the right outside of the device as in the case of p2. Radiated. That is how much light is diverged, and when the light guide plate is in front, it becomes inefficient light irradiation. The loss becomes significant in the case of a backlight unit of a liquid crystal display device, for example, and not only the diverging light is wasted but also the image display may be adversely affected by buffering inside the device.

  According to the semiconductor light emitting device 10 of the present embodiment, such divergence of light is effectively suppressed, and light can be supplied to the object in a state of being appropriately condensed and distributed. In general, in the case of performing such light collection, it is conceivable to provide a convex lens above the sealing material. A device having a simple structure is preferable. Further, as will be described later, the advantage of the device of the present embodiment is that the sealing material having a special shape as described above can be shaped by a simple manufacturing method called potting, and the molding method using a mold or the like can be used. In comparison, it has a great advantage in terms of production efficiency. In particular, backlight units for liquid crystal display devices have recently been apt to be reduced in size in response to support for portable devices, and the potting method has greatly improved manufacturing efficiency compared to mold using micro molds. It is possible to realize.

<Curvature radius>
In the present invention, the diameter or the length of the short side of the light emitting surface of the sealing material is set to 1.8 times to 4.5 times the length of the short side, and is 2.0 times to 3.7 times. Is more preferable, and 2.2 to 2.5 times is more preferable. By making this curvature radius below the upper limit, the light distribution can be made narrower. On the other hand, the occurrence of cracks can be suppressed by setting the value to the above lower limit or more.

  In the present invention, the radius of curvature of the light exit surface of the sealing material represents the degree of depression. Examples of the analysis method include a method of measuring the shape of the sealing material with a laser microscope using a confocal optical system and geometrically calculating the shape. Specifically, the approximate curvature radius of the shape of the sealing material can be obtained by displaying the surface shape of the central portion of the sealing material obtained by the analysis with a line and drawing a circle that fits the surface. At this time, if it is a spherical recess, the center of the recess is determined, the radius of curvature is determined at regular intervals in the 360 ° plane direction, and the average value can be adopted. Alternatively, in the case of a cylindrical recess, the radius of curvature of the leading curve or an arc parallel to the leading curve may be obtained. At this time, you may obtain | require several points in a bus-line direction as the average value. In relation to the planar shape of the light emitting surface of the device, if it is circular (FIG. 3 (a)), its diameter D is measured, while the radius of curvature of the spherical recess is measured as described above. Then, the ratio may be obtained. In the case of an elliptical light exit surface (FIG. 3B), the length Ls of the short side is measured, the radius of curvature of the arc corresponding to the short side Ls is measured, and the ratio can be obtained. The short side indicates the shortest line segment among the straight lines passing through the center of the reflector package and passing through the two outer edges of the package.

  Note that the above is a technique that can be analyzed when the sealing material is sufficiently recessed, and if it is flat, convex, or uneven, an analysis technique according to that may be adopted as appropriate. If the ratio of the radius of curvature and the package diameter or the length of the short side obtained by the above method exceeds 10, it can be determined that it is sufficiently flat. As a measuring instrument for analysis, for example, a shape measurement microscope VK-9500 (trade name) manufactured by Keyence Corporation can be used.

  Here, the potting will be described. Potting represents an operation of discharging the sealing liquid into a cavity (concave space) of the reflector package base material to fill the interior. The curing process can be performed by placing a reflector package filled with sealing liquid after potting (a package containing a reflector package substrate, as well as a device, bonding wires, and electrodes) in a general heating device such as an oven. Requires only a very simple configuration with only a dispenser and a heating device. In addition, since a mold and a mask are not required, it is possible to deal with a change in the shape of the device quickly and inexpensively, which can be said to be a highly versatile sealing method. Furthermore, in mold molding methods such as compression mold molding and transfer mold molding, there are problems such as poor mold releasability, high disposal rate of sealing liquid, and restriction of viscosity. there is no problem.

  On the other hand, compared to the molding method, potting has a low controllability of the sealing shape, and thus it is difficult to impart light distribution. In particular, when the light distribution is narrowed, a technique in which a convex lens is integrally formed on the upper part of the light emitting element is generally employed as generally seen in a bullet-type LED. Since bullet-type LEDs are extremely poor in heat dissipation, surface mount types are often used, but in this case as well, there is a method in which a convex lens is formed integrally with a mold or placed on a potted package. Often taken. Thus, when trying to mold the convex lens only by potting, the sealing liquid of the convex portion hangs down during the curing and becomes flat, which cannot be achieved. Therefore, a method for providing light distribution only by potting is required.

  Examples of the sealing liquid discharging method include a screw type mechanical dispensing method, an air pulse type dispensing method, a non-contact jet dispensing method, and the like. As the dispenser which is a potting device, specifically, for example, devices provided by Musashi Engineering Co., Sanei Tech Co., etc. are used.

  When creating a dent using the curing shrinkage of the resin by potting in the above embodiment, the radius of curvature of the concave surface can be adjusted by appropriately adjusting each condition. For example, it can be performed by adjusting the amount of the liquid sealing agent to be filled with respect to the height of the upper surface of the element (the virtual plane 3b). For example, if the sealing agent has a higher viscosity, the difference in height of the upper surface of the sealing material becomes larger when the filling amount is reduced and the liquid level is lowered, and the radius of curvature of the light emitting surface 3a of the sealing material is It tends to be smaller. However, there is a limit to the method of reducing the radius of curvature by reducing the filling amount, and if the filling amount is reduced too much, bonding wires and semiconductor light emitting elements may be exposed from the encapsulant, so the filling amount is adjusted to an appropriate amount. There is a need to.

[Acrylic resin]
It is preferable that the sealing material of the present invention is formed by applying the polar group-containing acrylic monomer to the concave space of the reflector package base material and curing the acrylic monomer. By containing a polar group, volatilization at the time of curing can be suppressed even if the monomer is a relatively low molecule, and thus the above-described appropriate concave shape can be formed. In addition, when this monomer volatilizes during hardening, the target dent shape cannot be formed with good reproducibility. In the present specification, the polar group refers to an electrically polarized functional group, and specifically includes a functional group containing elements such as oxygen, nitrogen, and sulfur having high electronegativity.

  Specific examples of polar groups include hydroxyl groups, oligoethylene glycol groups, isocyanuric acid derivative groups, carboxyl groups, aldehyde groups, ether groups, thiol groups, sulfo groups (sulfonic acid groups), sulfinic acid groups, sulfenic acid groups, and thioether groups. , Disulfide groups, phosphate groups, amino groups, imino groups, cyano groups, guadinino groups, acetal groups, isocyanate groups, isothiocyanate groups, aliphatic heterocyclic compound derivative groups such as oxetane, and heterocycles such as furan and benzofuran. It is preferable to include a ring compound derivative group, and from the viewpoint of suppressing side reactions, a hydroxyl group, an oligoethylene glycol group, an isocyanuric acid derivative group (preferably the following formula (A)), and particularly preferably a hydroxyl group is preferably selected. The

・ R ^a1 , R ^a2 , R ^a3
R ^a1 , R ^a2 and R ^{a3 in} formula (A) are each independently a bond, a hydrogen atom, a group containing a hydroxyl group, a group containing an alkoxy group having 1 to 10 carbon atoms, or 6 to 24 carbon atoms. Or a group containing an acyloxy group represented by the following formula (II). However, at least one of R ^a1 , R ^a2 , and R ^a3 is a bond. In addition, at least 0.5 average of R ^a1 , R ^a2 and R ^a3 per unit represented by the formula (A) is a group containing a hydroxyl group. In addition, Formula (II) is synonymous with following formula (1). Here, the group containing... Means a substituent containing the substituent in addition to the substituent. For example, the group containing a hydroxyl group may be a hydroxyalkyl group, a hydroxyaryl group, or the like, or a hydroxyl group (hydroxy group) itself.

  It is preferable that 80% or more of the sealing material is an organic component. Further, 95% or more of the acrylic resin obtained by curing the acrylic monomer is preferably an organic component, and more preferably 97 to 100% is an organic component. Since there are many organic components, the low gas barrier property derived from inorganic components, such as silicone and sol-gel-formed silica, can be reduced. In addition, since the gas barrier property is high, it is possible to prevent the gas such as hydrogen sulfide from sulfiding silver from entering, and thus it is possible to suppress a decrease in the reflectance of the reflector due to silver sulfidation.

  The ratio of the acrylic group or methacryl group of the acrylic monomer before curing is preferably 4 mmol / g or more and less than 6.5 mmol / g with respect to the total mass of the sealant, and is 5.4 mmol / g or more. More preferably, it is less than 6.3 mmol / g. Since the volume shrinkage before and after curing can be increased as the ratio is increased, the shape of the sealing material can be appropriately recessed according to the package shape. Further, if the ratio is too large, there is a problem that the cured sealing material cracks due to curing shrinkage, or the residual stress becomes large and cracks are caused by a subsequent impact. Examples of a method for adjusting the ratio to an appropriate range include a method in which monomers having a molecular weight of about 300 to 500 and containing two acrylic groups or methacryl groups per molecule are used alone or in combination. In addition, a monomer having a large molecular weight can be employed according to the number of acrylic groups or methacrylic groups. By adopting a monomer having a polar group in this range, it is possible to form an appropriate dent shape due to curing shrinkage while suppressing volatilization.

  The acrylic monomer before curing is preferably low in volatility. This is because, as described above, if the monomer component volatilizes during the curing, the desired dent shape cannot be formed with good reproducibility. In addition, since the amount of the sealing liquid is generally very small, such as less than several tens of mg per device, even if the curing temperature is lower than the boiling point of the monomer, the effect of the component that volatilizes a little is large. The volatilization amount of the next test can be adopted as the evaluation standard for volatility. As a test, 5 mg of the acrylic monomer is heated at 80 ° C. 60 min + 130 ° C. 60 min at a temperature increase rate of 3 ° C./min in TG / DTA, and the weight loss at that time is analyzed. At that time, the volatilization amount when the total amount of the acrylic monomer is 100% by mass is preferably less than 10% by mass. Moreover, although there is no limit as non-volatility, since a thing with low volatility tends to become a solid at normal temperature and normal pressure, it is necessary to melt | dissolve in a liquid component in that case.

  In the present invention, the sealing material is preferably formed by applying the acrylic resin to the concave space of the reflector package base material and curing the acrylic resin. The acrylic resin preferably has an isocyanuric acid acrylate derivative polymer, preferably 50% by mass or more (compared to the total amount of the resin), more preferably 80% or more. At this time, the isocyanuric acid acrylate derivative refers to the compound represented by Formula 1. As an analysis method, LC-MS, GC-MS, IR, NMR, etc. of decomposition products can be used in combination. By including an isocyanuric acid acrylate derivative polymer in this range, when used as a sealing material, high performance can be imparted in all of transparency, heat-resistant coloring property, and crack resistance, and it is preferable because of excellent potting properties. .

The acrylic resin preferably has a volume shrinkage of 10% or more and less than 20% before and after curing, and more preferably 12% or more and less than 18%. By setting it as such a volumetric shrinkage rate, the optically favorable concave light-emitting surface 3a can be formed in the cured sealing material, which is preferable.
The viscosity of the acrylic resin before curing is preferably 800 mPas or more and less than 20,000 mPas, and more preferably 1,000 mPas or more and less than 10,000 mPas. By setting it as such a viscosity area | region, the outstanding potting aptitude is exhibited and it is preferable at the point from which the sealing material of the target concave light emission surface is obtained.

[Specific isocyanurate compounds]
About the sealing agent which forms the sealing material of the semiconductor light-emitting device of this invention, the specific acrylate compound which has an isocyanurate structure (henceforth a specific isocyanurate compound) is contained by specific density | concentration, and if necessary, more than one Are preferably contained at a specific mixing ratio. Hereinafter, preferred embodiments of the present invention will be described in more detail.

[Compound represented by Formula (1)]
In the present invention, it is preferable to use a specific isocyanurate compound represented by the following formula (1).

・Ｒ^１、Ｒ^２、Ｒ^３
式（１）中のＲ^１、Ｒ^２、Ｒ^３は、それぞれ独立に、水酸基、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数６〜２４のアリールオキシ基、炭素数６〜２４のアリール基、下記式（Ｉ）で表されるアクリロイルオキシ基、又は下記式（ＩＩ）で表されるアシルオキシ基を表す。Ｌ^ａは炭素数１〜４のアルキレン基を表す。ただし、Ｒ^１、Ｒ^２、及びＲ^３の少なくとも１つは前記アクリロイルオキシ基である。

・ R ¹ , R ² , R ³
R ¹ , R ² and R ^{3 in} formula (1) are each independently a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, It represents an aryl group having 6 to 24 carbon atoms, an acryloyloxy group represented by the following formula (I), or an acyloxy group represented by the following formula (II). L ^a represents an alkylene group having 1 to 4 carbon atoms. However, at least one of R ¹ , R ² , and R ³ is the acryloyloxy group.

式中、Ｒ^１１は水素原子又は炭素数１〜３のアルキル基を表す。＊は結合手を表す。

In the formula, R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. * Represents a bond.

式中、Ｒ^１２は炭素数１〜１０のアルキル基又は炭素数６〜２４のアリール基を表す。＊は結合手を表す。

In the formula, R ¹² represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 24 carbon atoms. * Represents a bond.

In R ¹ , R ² , R ³ , and R ¹² , examples of the alkyl group having 1 to 10 carbon atoms include a straight chain alkyl group, a branched alkyl group, and a cyclic alkyl group. A linear alkyl group, a branched alkyl group having 6 to 10 carbon atoms, and a cyclic alkyl group having 6 to 10 carbon atoms are preferable.
As the acyloxy group represented by the formula (II), when R ¹² is an alkyl group, a linear alkyl group, a branched alkyl group, and a cyclic alkyl group can be mentioned. A linear alkyl group, a branched alkyl group having 6 to 10 carbon atoms, and a cyclic alkyl group having 6 to 10 carbon atoms are preferable.
When R ¹² in the formula (II) is an aryl group, the aryl group may be monocyclic or multicyclic, and among them, a phenyl group is preferable.
The alkyl group and aryl group may be further accompanied by a substituent, and examples thereof include the substituent T described later.

L ^a is is an alkylene group having 1 to 4 carbon atoms, among them ethylene group or an isopropylene group _{(N-CH 2 -CH (CH} 3) -R orientation: R is ^R 1, ^{R 2,} or ^R 3) Are preferable, and an ethylene group is more preferable.

[Component composition of sealant]
In the sealing agent of this invention, it is preferable that the density | concentration of the compound represented by the said Formula (1) is more than 80 mass% with respect to the organic component whole quantity of a sealing agent, and it is 90 mass% or more. Is more preferably 95% by mass or more. There is no particular upper limit, and it is particularly preferably about 100% by mass when excluding the polymerization initiator. Here, substantially, the residual solvent such as toluene may be mixed at a rate of about 0 to 10% by mass, and such inevitable contaminants are included within a range that does not impair the effects of the present invention. It allows existence. Alternatively, when it is necessary to lower the viscosity of the sealant, a necessary amount of additive may be added. In addition to the essential components, the sealant may contain an optional component such as a polymerization inhibitor described below as required, but is preferably used without a solvent. Thus, since it has sufficient fluidity | liquidity and suitable viscosity, it is excellent in the moldability of the sealing agent of a semiconductor light-emitting element, without solvent. In particular, it can effectively cope with molding by potting, and contributes to a significant improvement in production efficiency as compared with molding. In addition, although the organic component of sealing agent refers to the component which consists of a compound containing a carbon atom, even if it contains a carbon atom, the meaning which does not contain fluorescent substance. In addition, strictly speaking, it is meant to exclude trace components such as water and inorganic salts.

The clay of the sealant is not particularly limited, but is 0.1 to 100 Pa. From the viewpoint of potting property and phosphor stable dispersibility. s is preferable, and 0.5 to 20 Pa.s. s is more preferable, and 1.0 to 10 Pa.s. s is more preferable. In the present invention, the viscosity is a value measured by the following method unless otherwise specified.
(Measurement method of viscosity)
In the present invention, unless otherwise specified, it is based on the method employed in the examples described later.

  It is preferable that the sealing agent has a polymerization initiator. The polymerization initiator is not particularly limited as long as it is usually applied to this type of polymerizable compound, and specific examples thereof will be described later. The amount of the polymerization initiator is not particularly limited, but is preferably 0.1% by mass or more and 5 or less, and more preferably 0.5% by mass or more and 2.0 or less. By setting it to the above lower limit or more, the polymerization reaction can be favorably started. On the other hand, by setting it to the upper limit value or less, it is preferable because the excellent effect of the sealant due to the application of the specific isocyanurate compound can be sufficiently obtained.

(Isocyanurate compound [A])
The specific isocyanurate compound represented by the formula (1) is preferably one represented by the following formula (1-1), (1-2), or (1-3). In this specification, the isocyanurate compound [A] is referred to as a general term for the compounds represented by the formula (1-1), (1-2), or (1-3).

・ R ⁴ , R ⁵ , R ⁶ , R ⁷
In the formula, R ⁴ , R ⁵ , and R ⁶ are each independently hydrogen or a methyl group. R ⁷ is at least one of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, and an acyloxy group represented by the formula (II). L ^a is as defined for formula (1).
La is synonymous with Formula (1).

The isocyanurate compound [A] is preferably contained in a specific ratio with respect to the compounds of the above formulas. When the isocyanurate compound [A] is 100% by mass, the compound represented by the formula (1-1) is preferably 0% by mass to 35% by mass, and 0% by mass to 25% by mass. More preferably, it is particularly preferably 0% by mass or more and 10% by mass or less.
The compound represented by the formula (1-2) is preferably 65% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, and 80% by mass or more and 100% by mass or less. It is particularly preferred.
The compound represented by the formula (1-3) is preferably 0% by mass to 25% by mass, more preferably 0% by mass to 15% by mass, and 0% by mass to 10% by mass. It is particularly preferred.

  By containing the isocyanurate compound [A] at the above-mentioned ratios, transparency, heat resistance coloring property, heat shock resistance and gas barrier property can be satisfied at a higher level.

  In this invention, it is preferable that the said specific isocyanurate compound contains 1 mass% or more and less than 50 mass% of compounds represented by following formula (1-4). In this specification, the compound represented by the formula (1-4) is referred to as an isocyanurate compound [B].

* R < ⁴ >, R < ⁵ >, R < ¹² > is synonymous with Formula (1-1) and Formula (II). L ^a is as defined for formula (1).

  The addition amount of the isocyanurate compound [B] is not particularly limited, but it is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, and more preferably 5 to 30% by mass. % Or less is particularly preferable. By applying the isocyanurate compound [B] within the above range, it is possible to reduce the water absorption rate without deteriorating the thermal shock resistance (crack resistance) and heat resistance colorability of the cured product. (For example, moisture-absorbing reflow cracks generated when reflow treatment is performed in a water-absorbed state) can be reduced, and as a result, a highly reliable LED element can be provided.

  The sealant of this embodiment preferably has an acid value of 0.10 mgKOH / g or less, more preferably 0.05 mgKOH / g or less, and particularly preferably 0.02 mgKOH / g or less. . It is preferable that the heat resistance colorability is further improved by setting the amount to the upper limit or less. Although a lower limit is not specifically limited, It is practical that it is 0.001 mgKOH / g or more. Although the method for adjusting the acid value of the sealant is not particularly limited, the adsorbent such as activated carbon or silica and the isocyanurate compound of the present embodiment are mixed and left standing, and then the adsorbent is removed by filtration. The acid value of the isocyanurate compound can be reduced.

  In the present specification, when the term “compound” is added at the end or indicated by a specific name or chemical formula, it is used in the meaning including its salt and its ion in addition to the compound itself. Moreover, it is the meaning including the derivative modified with the predetermined form in the range with the desired effect. In addition, in the present specification, a substituent that does not specify substitution / non-substitution means that the group may have an arbitrary substituent. This is also synonymous for compounds that do not specify substitution / non-substitution. Preferred substituents include the following substituent T.

Examples of the substituent T include the following.
An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl A group (preferably an alkenyl group having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.), an alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms, such as ethynyl, butadiynyl, phenylethynyl, etc.), A cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), an aryl group (preferably an aryl group having 6 to 26 carbon atoms, for example, Phenyl, 1-naphthyl, 4-methoxyphenyl, -Chlorophenyl, 3-methylphenyl, etc.), heterocyclic groups (preferably heterocyclic groups having 2 to 20 carbon atoms, such as 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2 -Oxazolyl etc.), an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, such as methoxy, ethoxy, isopropyloxy, benzyloxy etc.), an aryloxy group (preferably an aryloxy group having 6 to 26 carbon atoms) , For example, phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), alkoxycarbonyl groups (preferably C2-C20 alkoxycarbonyl groups such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.) ), Amino group (preferably carbon Amino group having 0 to 20 children, such as amino, N, N-dimethylamino, N, N-diethylamino, N-ethylamino, anilino, etc.), sulfonamide group (preferably sulfonamide having 0 to 20 carbon atoms) A group such as N, N-dimethylsulfonamide, N-phenylsulfonamide, etc., an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms such as acetyloxy, benzoyloxy, etc.), a carbamoyl group (preferably A carbamoyl group having 1 to 20 carbon atoms, such as N, N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.), an acylamino group (preferably an acylamino group having 1 to 20 carbon atoms, such as acetylamino, benzoylamino, etc.) , A cyano group, or a halogen atom (eg, fluorine atom, chlorine atom, bromine atom) More preferably an alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkoxycarbonyl group, amino group, acylamino group, cyano group or halogen atom, Particularly preferred are an alkyl group, an alkenyl group, a heterocyclic group, an alkoxy group, an alkoxycarbonyl group, an amino group, an acylamino group, and a cyano group.

  The specific isocyanurate compound may be synthesized by a conventional method, and the synthesis method is not particularly limited. For information on such commercial products, reference can be made to, for example, Japanese Patent Application Laid-Open No. 2003-213159.

[Polymerization initiator]
The sealing agent of this embodiment contains a polymerization initiator.
Among these, a radical polymerization initiator is added.
Examples of thermal radical polymerization initiators that generate initiation radicals by cleavage by heat include ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1 Hydroperoxides such as 1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide and t-butyl hydroperoxide; diisobutyryl peroxide, bis-3,5,5-trimethylhexanol peroxide, lauroyl peroxide Diacyl peroxides such as oxide, benzoyl peroxide and m-toluyl benzoyl peroxide; dicumyl peroxide, 2, 5 Dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) hexane, t-butylcumyl peroxide, di-t-butyl peroxide and 2,5-dimethyl- Dialkyl peroxides such as 2,5-di (t-butylperoxy) hexene; 1,1-di (t-butylperoxy-3,5,5-trimethyl) cyclohexane, 1,1-di-t-butylperoxy Peroxyketals such as cyclohexane and 2,2-di (t-butylperoxy) butane; 1,1,3,3-tetramethylbutylperoxyneodicarbonate, α-cumylperoxyneodicarbonate, t-butylperoxyneodicarbonate , T-hexylperoxypivalate, t-butylperoxypivalate 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butyl Peroxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, 1,1,3,3-tetramethylbutylperoxy-3,5,5-trimethylhexanate, t-amylperoxy-3,5,5-trimethyl Alkyl peresters such as hexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate and dibutylperoxytrimethyladipate; di-3-methoxybutylperoxy Dicarbonate, di-2-ethylhexyl Ruperoxydicarbonate, bis (1,1-butylcyclohexaoxydicarbonate), diisopropyloxydicarbonate, t-amylperoxyisopropylcarbonate, t-butylperoxyisopropylcarbonate, t-butylperoxy-2-ethylhexylcarbonate and 1, Peroxycarbonates such as 6-bis (t-butylperoxycarboxy) hexane; 1,1-bis (t-hexylperoxy) cyclohexane and (4-t-butylcyclohexyl) peroxydicarbonate.
Specific examples of the azo compound used as an azo-based (AIBN or the like) polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2, 2'-azobis (2,4-dimethylvaleronitrile), 1,1'-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis-4-cyano Valeric acid, 2,2′-azobis- (2-amidinopropane) dihydrochloride and the like can be mentioned (see JP 2010-189471 A).

As the radical polymerization initiator, in addition to the thermal radical polymerization initiator, a radical polymerization initiator that generates an initiation radical by light, electron beam, or radiation can be used.
Examples of such radical polymerization initiators include benzoin ether, 2,2-dimethoxy-1,2-diphenylethane-1-one [IRGACURE651, manufactured by Ciba Specialty Chemicals Co., Ltd.], 1-hydroxy-cyclohexyl. -Phenyl-ketone [IRGACURE184, manufactured by Ciba Specialty Chemicals Co., Ltd., trademark], 2-hydroxy-2-methyl-1-phenyl-propan-1-one [DAROCUR1173, manufactured by Ciba Specialty Chemicals Co., Ltd., Trademarks], 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one [IRGACURE2959, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.], 2 -Hydroxy-1- [4- [4- (2-H Roxy-2-methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one [IRGACURE127, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.], 2-methyl-1- (4-methylthiophenyl) ) -2-morpholinopropan-1-one [IRGACURE907, manufactured by Ciba Specialty Chemicals, Inc.], 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 [ IRGACURE 369, manufactured by Ciba Specialty Chemicals, Inc., trademark], 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-monophorinyl) phenyl] -1-butanone [IRGACURE 379, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.] 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [DAROCUR TPO, manufactured by Ciba Specialty Chemicals, Inc.], bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide [IRGACURE819, Ciba Specialty Chemicals, Inc., Trademark], bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) Titanium [IRGACURE784, trade name, manufactured by Ciba Specialty Chemicals, Inc.], 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] [IRGACURE OXE 01, Ciba Specialty Chemicals Co., Ltd., Trademark], D Non, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) [IRGACURE OXE 02, manufactured by Ciba Specialty Chemicals Co., Ltd. , Trademark] and the like.
These radical polymerization initiators can be used singly or in combination of two or more.
Among them, a peroxide compound is preferable, and perbutyl O (t-butylperoxy-2-ethylhexanoate, manufactured by NOF Corporation) and the like can be used.
Although content of a polymerization initiator is not specifically limited, It is preferable to apply at 0.1-5 mass%.

[Polymerization inhibitor]
A polymerization inhibitor may be added to the sealant of this embodiment. Examples of the polymerization inhibitor include phenols such as hydroquinone, tert-butylhydroquinone, catechol, and hydroquinone monomethyl ether; quinones such as benzoquinone and diphenylbenzoquinone; phenothiazines; copper and the like.
The content of the polymerization inhibitor is not particularly limited, but it is preferably 0 to 20000 ppm, preferably 100 to 10000 ppm, more preferably 300 to 8000 ppm. If the addition amount of the polymerization inhibitor is too small, the polymerization occurs while generating heat abruptly at the time of sealing and curing, so that the adhesiveness with the reflector package substrate is lowered and the sealing material is applied when a thermal shock is applied. / Peeling easily occurs at the substrate interface. On the other hand, when the addition amount of the polymerization inhibitor is too large, when the sealant is cured in the air, the curing rate is remarkably reduced, resulting in poor surface curing.

[Phosphor]
In this embodiment, it is preferable to mix | blend 1-40 mass parts of fluorescent substance with respect to 100 mass parts of sealing agents, It is more preferable that they are 2 mass parts or more and 30 mass parts or less, 5 mass parts or more 20 It is particularly preferable that the amount is not more than part by mass. As the phosphor, those usually used in this type of device may be applied. For example, as a typical yellow phosphor, a general formula A ₃ B ₅₀ O ₁₂ : M (wherein component A is Y , Gd, Tb, La, Lu, Se, and Sm, the component B includes at least one element of the group consisting of Al, Ga, and In, and the component M includes Ce, It is particularly advantageous to contain phosphor particles comprising the garnet group of at least one element of the group consisting of Pr, Eu, Cr, Nd and Er. Y ₃ A ₁₅ O ₁₂ : Ce phosphor and / or (Y, Gd, Tb) ₃ (Al, Ga) as a phosphor for a light emitting diode element that emits white light with a light emitting diode chip that emits blue light. ) ₅ O ₁₂ : Ce phosphor is suitable. Other phosphors include, for example, CaGa ₂ S ₄ : Ce ³⁺ and SrGa ₂ S ₄ : Ce ³⁺ , YAlO ₃ : Ce ³⁺ , YGaO ₃ : Ce ³⁺ , Y (Al, Ga) O ₃ : Ce ³⁺ , Y ₂ Examples thereof include SiO ₅ : Ce ³⁺ (see JP 2011-144360 A). In addition to these phosphors, aluminate doped with rare earths or orthosilicates doped with rare earths are suitable for producing mixed color light. By blending 1 to 50 parts by mass of this type of phosphor with respect to 100 parts by mass of the curable composition, when an element emitting blue light is used, the emission color can be converted to white.

[Antioxidant]
It is preferable that the sealant of this embodiment contains an antioxidant as necessary. Examples of antioxidants include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, thioether antioxidants, vitamin antioxidants, lactone antioxidants, and amine antioxidants. .

  Examples of phenolic antioxidants include Irganox 1010 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), Irganox 1076 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), Irganox 1330 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Trademark), Irganox 3114 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), Irganox 3125 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), ADK STAB AO-20 (ADEKA Corporation, Trademark), ADK STAB AO-50 ( ADEKA Corporation (trademark), ADK STAB AO-60 (ADEKA Corporation), ADK STAB AO-80 (ADEKA Corporation), ADK STAB AO-30 (ADEKA Corporation), Adeka Stub AO-40 (ADEKA, Inc., trademark), BHT (produced by Takeda Pharmaceutical Co., Ltd., trademark), Cyanox 1790 (produced by Cyanamid, trademark), SumiliZerGP (produced by Sumitomo Chemical, trademark), SumiliZerGM (Sumitomo Chemical) Commercial products such as (trademark), SumiliZerGS (trademark, manufactured by Sumitomo Chemical Co., Ltd.) and SumiliZerGA-80 (trademark, manufactured by Sumitomo Chemical Co., Ltd.) can be given.

  Examples of phosphorus compounds include IRAGAFOS 168 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), IRAGAFOS 12 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), IRAGAFOS 38 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), IRAGAFOS P-EPQ (trade name, manufactured by Ciba Specialty Chemicals), IRAGAFOS 126 (trade name, manufactured by Ciba Specialty Chemicals), ADKSTAB 329K (ADEKA, trademark), ADKSTAP PEP-36 (trade name) ADEKA, trademark), ADKSTAP PEP-8 (ADEKA, trademark), ADKSTAB HP-10 (ADEKA, trademark), ADKSTAB 2112 (ADEKA, trademark), DKSTAB 260 (ADEKA Corporation, trademark), ADKSTAB 522A (ADEKA Corporation, trademark), Weston 618 (GE Corporation, trademark), Weston 619G (GE Corporation, trademark), and Weston 624 (GE Corporation, trademark) And other commercial products.

  Examples of sulfur-based antioxidants include DSTP (Yoshitomi) (trademark), DLTP (Yoshitomi) (trademark, produced by Yoshitomi Corporation), DLTOIB (trademark, produced by Yoshitomi Corporation), DMTP (Yoshitomi). ) [Trademark] made by Yoshitomi Co., Ltd., Seenox 412S [trademark made by Sipro Kasei Co., Ltd.], Cyanox 1212 (trademark made by Cyanamid Co., Ltd.) and TP-D, TPS, TPM, TPL-R [Sumitomo Chemical Co., Ltd. ), Trade name, etc.). Examples of vitamin-based antioxidants include tocopherol (trade name, manufactured by Eisai Co., Ltd.) and Irganox E201 (trade name, compound name: 2,5,7,8-tetramethyl-2 (4, manufactured by Ciba Specialty Chemicals Co., Ltd.). Commercial products such as ', 8', 12'-trimethyltridecyl) coumarone-6-ol].

  Examples of the thioether-based antioxidant include commercial products such as ADK STAB AO-412S (trademark manufactured by ADEKA Corporation) and ADK STAB AO-503 (trademark manufactured by ADEKA Corporation). As the lactone antioxidant, those described in JP-A-7-233160 and JP-A-7-247278 can be used. Moreover, HP-136 [Ciba Specialty Chemicals Co., Ltd., trademark, compound name; 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one] And other commercial products.

  Examples of amine-based antioxidants include commercially available products such as Irgastab FS042 [trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.] and GENOX EP [trade name, compound name; dialkyl-N-methylamine oxide] manufactured by Crompton Co., Ltd. Can do. These antioxidants can be used singly or in combination of two or more.

  The content of the antioxidant is usually 0.01 to 10 with respect to 100 parts by mass of the total amount with the derivative A or B from the viewpoint of suppressing the transparency of the resin material for a semiconductor light emitting device and the reduction in yellowing. It is a mass part, Preferably it is 0.01-5 mass part, More preferably, it is 0.02-2 mass part.

[Light stabilizers, etc.]
In addition to the above-described antioxidant, the sealant of this embodiment includes a lubricant, a light stabilizer, an ultraviolet absorber, a plasticizer, an antistatic agent, an inorganic filler, a colorant, and an antistatic agent as necessary. Agents, mold release agents, flame retardants, components for the purpose of improving adhesion with inorganic compounds such as titanium oxide and silicon oxide, and the like can be blended. As the lubricant, higher dicarboxylic acid metal salts, higher carboxylic acid esters, and the like can be used.

  Any known light stabilizer can be used, but a hindered amine light stabilizer is preferred. Specific examples of the hindered amine light stabilizer include ADKSTAB LA-77, LA-57, LA-52, LA-62, LA-67, LA-68, LA-63, and LA-94. LA-94, LA-82 and LA-87 (above, manufactured by ADEKA Corporation), Tinuvin 123, 144, 440 and 662, Chimassorb 2020, 119, 944 (above, manufactured by CSC), Examples include Hostavin N30 (manufactured by Hoechst), Cyasorb UV-3346, UV-3526 (manufactured by Cytec), Uval 299 (GLC), and SanduvorPR-31 (Clariant). These light stabilizers can be used singly or in combination of two or more.

The usage-amount of a light stabilizer is 0.005-5 mass parts normally with respect to 100 mass parts of total amounts with the said derivative A or B, Preferably it is 0.02-2 mass parts.
Examples of the component for improving the adhesion with inorganic compounds such as titanium oxide and silicon oxide include silane coupling agents containing a methacryloxy group or an acryloxy group of the silane compound. This may be contained in the raw material composition and polymerized and molded.

(Sealing method)
As a sealing method of the sealing agent, a method usually used for sealing a semiconductor light emitting element or a method similar to a general thermosetting resin molding can be used. Examples thereof include potting (dispensing), printing, coating, injection molding, compression molding, transfer molding, and insert molding. Potting represents an operation of discharging the sealing agent into a cavity (concave space) of the package to fill the interior. In addition, printing represents an operation of disposing a sealant at a target site using a mask, and a so-called vacuum printing method in which the surrounding pressure is reduced according to the purpose can be employed. Various types of coating methods can be used for coating. For example, a method of preparing a weir called a dam material for holding a sealing agent in advance and coating the sealing agent on the inside thereof can also be used. Moreover, in various mold shaping | molding, the method of filling the sealing agent inside a mold and thermosetting as it is is mentioned. Further, curing after sealing can be performed by heat curing, UV curing, or a combination thereof.
The semiconductor light-emitting device in preferable embodiment of this invention comprises the sealing material produced by sealing with said liquid sealing agent and hardening | curing it. As a sealing method of the sealing agent, a sealing method called potting is preferable. Further, curing after sealing can be performed by heat curing, UV curing, or a combination thereof.

  Here, the potting will be described. Potting represents an operation of filling the interior of the reflector package substrate by discharging the liquid sealing agent into the cavity (concave space) W (FIG. 1). The curing process can be performed by placing a reflector package filled with sealing liquid after potting (a package containing a reflector package substrate, as well as a device, bonding wires, and electrodes) in a general heating device such as an oven. Requires only a very simple configuration with only a dispenser and a heating device. In addition, since a mold and a mask are not required, it is possible to deal with a change in the shape of the device quickly and inexpensively, which can be said to be a highly versatile sealing method. Furthermore, in mold molding methods such as compression mold molding and transfer mold molding, there are problems such as poor mold releasability, high disposal rate of sealing liquid, and restriction of viscosity. there is no problem.

  Further, when touching the characteristics of the preferred embodiment of the present invention, since the above acrylate compound is used as a sealing agent, the sealing agent is filled into a cavity (concave space) by potting, and this is polymerized and cured. A concave light-emitting surface having a light effect is formed. This is mainly based on volume shrinkage in the curing of the resin, and is preferable because a suitable concave light-emitting surface is formed by selecting the above acrylic resin.

  Examples of the liquid discharging method include a screw-type mechanical dispensing method, an air pulse type dispensing method, a non-contact jet dispensing method, and the like. As the dispenser which is a potting device, specifically, for example, devices provided by Musashi Engineering Co., Sanei Tech Co., etc. are used.

(Semiconductor light emitting device)
As the semiconductor light emitting element, a blue light emitting LED chip made of a gallium nitride (GaN) based semiconductor, an ultraviolet light emitting LED chip, a laser diode, or the like is used. In addition, for example, a substrate in which a nitride semiconductor such as InN, AlN, InGaN, AlGaN, InGaAlN or the like is formed as a light emitting layer on a substrate by MOCVD or the like can be used. Either a semiconductor light-emitting element that is mounted face-up or a semiconductor light-emitting element that is flip-chip mounted can be used. The semiconductor light emitting device is an example of a semiconductor light emitting device having an n-side electrode and a p-side electrode on the same plane, but a semiconductor light-emitting device having an n-side electrode on one surface and a p-side electrode on the opposite surface is also used. be able to.

(package)
As the package, a package in which electrodes are integrally formed, and a package in which electrodes are provided as circuit wiring by plating after the package is molded can be used. As the shape of the package, any shape such as a cylinder, an elliptical column, a cube, a rectangular parallelepiped, a shape between a rectangular parallelepiped and an elliptical column, or a combination thereof can be adopted. As the shape of the inner wall portion, an arbitrary angle can be selected with respect to the bottom portion, and a box shape that is perpendicular to the bottom surface or a mortar shape that is obtuse can be selected. As the shape of the bottom of the concave portion, any shape such as a flat shape or a concave shape can be selected. Moreover, a package corresponding to an arbitrary mounting method such as a top view or a side view can be used as a mounting method.
As a material constituting the package, an electrically insulating material excellent in light resistance and heat resistance is suitably used. For example, a thermoplastic resin such as polyphthalamide, a thermosetting resin such as an epoxy resin, a glass epoxy, Ceramics or the like can be used. Moreover, in order to reflect the light from a semiconductor light emitting element efficiently, white pigments, such as a titanium oxide, can be mixed with these resins. As a method for molding the package, insert molding, injection molding, extrusion molding, transfer molding, or the like performed by previously setting the electrode in a mold can be used.

(electrode)
The electrode is electrically connected to the semiconductor light emitting element, and may be, for example, a plate-like electrode inserted into a package or a conductive pattern formed on a substrate such as glass epoxy or ceramic. As the material of the electrode, there can be used silver or an alloy containing silver, or a material in which silver or an alloy containing silver is plated on a part of an electrode containing copper or iron as a main component.

(Phosphor)
The sealing member may contain a fluorescent material, a light diffusing material, and the like. The fluorescent material may be any material that converts the wavelength by absorbing light from the semiconductor light-emitting element and emitting fluorescence, such as a nitride-based phosphor mainly activated by a lanthanoid-based element such as Eu or Ce, or Oxynitride phosphors, lanthanoids such as Eu, alkaline earth halogen apatite phosphors activated mainly by transition metal elements such as Mn, alkaline earth metal borate halogen phosphors, alkaline earth metals Lanthanoid elements such as aluminate phosphor, alkaline earth silicate phosphor, alkaline earth sulfide phosphor, alkaline earth thiogallate phosphor, alkaline earth silicon nitride phosphor, germanate phosphor, Ce Selected from rare earth aluminate phosphors, rare earth silicate phosphors, or organic and organic complexes mainly activated by lanthanoid elements such as Eu. It is preferably be at least 1 or more. More preferably, (Y, Gd) ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Ca, Sr, Ba) ₂ SiO ₄ : Eu, (Ca, Sr) ₂ Si ₅ N ₈ : Eu, CaAlSiN ₃ : Eu or the like is used.

(Evaluation method)
The semiconductor light emitting device can be evaluated by a conventional test method. For example, electrical characteristics, optical characteristics, temperature characteristics, thermal characteristics, lifetime, reliability, safety, and the like can be given. As a technique, for example, the technique and standard described in pages 71 to 84 of Chapter 2 of the book “LED Lighting Handbook, LED Lighting Promotion Council Edition” published by Ohm Co., Ltd. can be adopted.

(Use)
The semiconductor light-emitting device can be used for various applications that require maintenance of luminous intensity, for example, a backlight of a liquid crystal display, a mobile phone or an information terminal, an LED display, a flashlight, and indoor / outdoor lighting. Further, the acrylic sealing material used in the present invention can be used not only for light emitting elements such as LEDs and laser diodes but also for sealing light emitting elements, semiconductor light emitting elements other than semiconductor light emitting elements such as LSI and IC. it can

  Since the semiconductor light emitting device of this embodiment is excellent in light distribution, not only an edge light type backlight such as a liquid crystal display, a mobile phone or an information terminal, but also indoor and outdoor lighting where sharp light distribution is required, Encapsulation of semiconductor devices other than semiconductor light emitting devices such as light receiving devices, LSIs and ICs, as well as lighting devices for automobiles, passenger planes, railways, etc., flashlights, LED displays, and light emitting devices such as LEDs and laser diodes It can respond suitably also as a material.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is limited to a following example and is not interpreted.

Example 1
M215 (trade name: manufactured by Toagosei Co., Ltd.) mixed with 100 parts by mass of a bifunctional monomer column purified product (see formula a below) and 1 part by mass of a polymerization initiator perbutyl O (trade name: manufactured by NOF Corporation). Thus, a sealant was prepared. Regarding the polymerization inhibitor, 4-methoxyphenol (manufactured by Tokyo Kasei Kogyo Co., Ltd., hereinafter referred to as MEHQ) was prepared to be 2400 ppm in total with the amount mixed during column purification.
In the center of the reflector package substrate KD-LA9R48 (trade name: manufactured by Kyocera Corporation) on which the blue LED B2424DCI0 (trade name: manufactured by Genelites) is mounted, a recessed portion (cavity) having an opening diameter of 2640 μm and a depth of about 550 μm is formed. It was formed and the sealing agent was potted there. The amount of potting at this time was adjusted so that the center portion of the encapsulating material after curing was deepened by 170 μm from the upper end of the package substrate. This was cured in a blowing oven at 80 ° C. for 30 minutes, 130 ° C. for 30 minutes, and 150 ° C. for 5 hours to obtain a semiconductor light emitting device in which a sealing material was formed (each temperature rising rate was 3 ° C./min).

(Example 2)
The same procedure as in Example 1 was performed except that the amount was adjusted so that the depth of the sealing material was recessed by 220 μm.

(Example 3)
The same procedure as in Example 1 was performed except that the amount was adjusted so that the depth of the sealing material was recessed by 280 μm.

Example 4
The same procedure as in Example 1 was performed except that the amount was adjusted so that the depth of the sealing material was recessed by 330 μm.

(Example 5)
In addition to 70 parts by mass of the bifunctional monomer used in Example 1, 30 parts by mass of trifunctional monomer (formula b) obtained by column purification and 1 part by mass of polymerization initiator perbutyl were mixed and sealed. An agent was prepared. This was used in the same manner as in Example 1 except that the amount was adjusted so that the depth of the sealing material was recessed by 210 μm.

(Example 6)
In place of the monomer used in Example 1, 2.2 Bis [4- (Methacryloxy
Ethoxy] Phenyl] Propane (EO 2.3 mol / molecule) (hereinafter MEPP; manufactured by Shin-Nakamura Chemical Co., Ltd.) is used to adjust the amount so that the depth of the sealing material is recessed by 250 μm. Except that, the same procedure as in Example 1 was performed.

(Comparative Example 1)
The same procedure as in Example 1 was performed except that the amount was adjusted so that the depth of the sealing material was recessed by 50 μm.
(Comparative Example 2)
The same procedure as in Example 1 was performed except that the sealing material was sealed over the cavity so that the height of the sealing material was expanded by 120 μm.

(Comparative Example 3)
The same procedure as in Example 2 was performed except that 100 parts by mass of tricyclodecane dimethanol diacrylate (hereinafter A-DCP: Shin-Nakamura Chemical Co., Ltd.) and 1 part by mass of perbutyl were used as the liquid sealant. However, since the amount and shape of the sealing material after curing cannot be controlled by volatilization, the amount of potting was set to the same level as in Example 2.

(Comparative Example 4)
90 parts by mass of 1,6-hexanediol diacrylate (hereinafter HDA: Tokyo Chemical Industry Co., Ltd.) and 10 parts by mass of bis [2- (methacryloyloxy) ethyl] phosphate (P2M (Kyoeisha Chemical Co., Ltd.)) And 1 part by mass of perbutyl, except that the amount and shape of the sealing material after curing cannot be controlled by volatilization. Same level.

(Comparative Example 5)
The same procedure as in Example 1 was performed except that the sealing material was changed to Pernox epoxy-based sealing material (liquid obtained by mixing equal amounts of Pernox 562 and Percure 562, hereinafter referred to as P562). However, sealing was carried out over the cavity so that the height of the liquid after curing was expanded by 60 μm.

(Comparative example, 6, 7, 8)
The process was performed in the same manner as in Comparative Example 5 except that the amount of the sealing material was adjusted so as to be recessed to −160 μm, −220 μm, and −320 μm, respectively.

(Comparative Example 9)
The sealing was performed in the same manner as in Example 2 except that the following condensation type silicone sealing agent was used. Condensation type silicone-based encapsulant is composed of hydroxyl group polydimethylsiloxane (XF3905 manufactured by Momentive Performance Materials, viscosity 700 mm ^{2 / s)} 84.8 g and tetraethoxysilane (Tokyo Chemical Industry Co., Ltd., Tetrahethyl Orthosilicate) 15.2 g + A zirconium acetylacetonate solution (ZC-700 manufactured by Matsumoto Fine Chemical Co., Ltd.) was mixed at 1% by mass, potted on the reflector package, and cured by heating at 85 ° C. for 4 hours + 150 ° C. for 4 hours. The polymerization inhibitor MEHQ was not mixed.

<Crack evaluation>
The cured device was observed with an optical microscope to check for cracks. When there was no crack, “A”, when the end had a small crack of less than 1/5 of the package diameter, “B”, and when there was a larger crack, “C”.

<Shape analysis>
The curvature radius of the dent was obtained by measuring the shape after curing with a laser microscope and calculating geometrically. Specifically, the shape of the sealing material as viewed from the upper surface of the package was measured using a shape measurement laser microscope (Keyence VK-9500) for the sealed and cured reflector package. After measuring the entire surface of the package and connecting images, VK
The shape of the sealing material on the two lines orthogonal to each other so as to pass through the center of the package (the part where the chip is mounted) was analyzed by an analyzer. The data was output as text data, and after removing noise on Excel, a circle along the shape of the sealing material was drawn, and the radius of the circle was defined as the radius of curvature of the sealing material recess. In addition, when it was not able to match completely, it drawn so that the interface of a sealing material and a package and the center part of a sealing material may follow a circle as much as possible. In addition, when the sealing material was convex shape, it did not quantify. Further, when the radius of curvature is 10 times or more of the package diameter, it is determined that the surface is sufficiently flat and 10 is used as a numerical value.

<Light distribution evaluation>
The light distribution of the semiconductor light-emitting device was measured using a light distribution measuring device (RADIANT IMAGEING, IS-LI). After measuring the light emission distribution in space, the light distribution distribution on two lines orthogonal to each other so as to pass through the center of the chip was analyzed. The data was output as text data, and the angle at which the light emission amount was half that of the front light emission amount with the maximum light emission amount was determined as the half-value angle. The narrower the half-value angle is, the light distribution is more sharply collected, which is preferable because the introduction rate into the light guide plate can be increased. Specifically, the half-value angle is required to be less than 50 °.
The evaluation is shown separately as follows.
AA: Less than 49 ° A: 49 ° or more and less than 50 ° B: 50 ° or more and less than 51 ° C: 51 ° or more

<± 30 ° luminescence>
Further, in order to quantify the amount of light emitted in the forward direction, the light emission intensity in the direction of ± 30 ° with the front being 0 ° was integrated and determined. A larger value is preferable because the amount of light introduced into the light guide plate or the like increases.
The evaluation is shown separately.
AA: 0.65 or more A: 0.61 or more and less than 0.65 B: 0.58 or more and less than 0.61 C: Less than 0.58

<Volatility test>
A liquid obtained by removing the initiator (perbutyl oxide or ZC-700) in various sealants was prepared, and dispensed into an aluminum pan at 20 mg ± 2 mg, and at a temperature rising rate of 3 ° C./min, 80 ° C. Heat at 60 min + 130 ° C. for 60 min and analyze the weight loss at that time. When the weight loss amount was 10% by mass or more, the volatility was judged to be a problem, and “C” was described, and less than “A”.

<(Meth) krill ratio>
For each sealant, the ratio of acrylic groups and methacryl groups in the total amount was determined by calculation.

<Gas barrier properties>
Prepare a sealed can of about 25cm x 25cm x 35cm, and evenly place 5 small PFA petri dishes, each containing 0.5g of sulfur powder, and place your legs so that there is a distance of about 10cm above it. Attached net board was attached. Various packages that had been sealed and cured were arranged n = 3 at a time so that the packages looked downward from the gaps in the mesh, and in that state, the sealed cans were covered. The sealed can was placed in an oven set at 80 ° in advance and allowed to react for 48 hours. At this time, by heating the sulfur powder, a compound in which sulfur atoms are connected is released in a gaseous state. This sulfur gas causes the silver in the reflector package to sulfidize and turn black, reducing the amount of light emitted. When blackening was observed, it was “C”, and when it was not confirmed, it was “A”.

<Light distribution stability evaluation>
The light distribution stability (the degree of no change) was evaluated by measuring the light distribution of the semiconductor light emitting device subjected to the gas barrier evaluation in the same manner as the light distribution evaluation.
The evaluation is shown separately as follows.
A: Change in half-value angle before and after gas barrier property test is less than 2 ° C: Change in half-value angle before and after gas barrier property test is 2 ° or more

<Viscosity>
The average of the values obtained by measuring the viscosity 5 times every 100 seconds using a vibration viscometer, VISCOMATE MODEL VM-10A-MH (trade name: manufactured by CBC Corporation) was taken as the measured value. The measurement temperature was 25 ° C., which is room temperature.
A: 700 mPa · s or more
C: Less than 700 mPa · s

As described above, it can be seen that the sealing materials of the examples have a good concave light-emitting surface and can achieve both excellent optical characteristics and high productivity by using potting. In addition, although P2M of the comparative example 4 is an acrylate resin containing a polar group, in this case, the volatility is inappropriate and the shape of the intended light exit surface was not achieved.
Thus, according to the present invention, the light distribution that satisfies the required performance required for the sealing material of the semiconductor light emitting device at a high level and stably realizes a good and properly condensed narrow irradiation region. It is possible to adopt a molding method that has good performance and high production efficiency.

1 Optical Semiconductor Element
2 Reflector package base material 3 Sealing material 3a Light exit surface 3b Virtual plane 4 Electrode 6 Bonding wire 8 Die bond agent 10 Semiconductor light emitting device (Optical Semiconductor Device)

Claims (10)

A semiconductor light emitting device comprising a reflector package substrate, a semiconductor light emitting device mounted in a concave space of the reflector package substrate, and a sealing material containing a polar group-containing acrylic resin that seals the semiconductor light emitting device There,
The light exit surface of the sealing material is recessed in a curved shape, and the radius of curvature of the recessed light exit surface is 1.8 to 4.5 times the diameter or short side length of the light exit surface in plan view. Set ,
The sealing material is formed by applying a sealing agent containing a polar group-containing acrylic monomer to the concave space of the reflector package base material, and curing the acrylic monomer to form an acrylic resin. In the cured product of the composition liquid, the ratio of the acrylic group or methacryl group of the monomer constituting the previous acrylic resin is 4 mmol / g or more and less than 6.5 mmol / g with respect to the total mass of the encapsulant containing the monomer. A semiconductor light emitting device. The semiconductor light-emitting device according to claim 1 , wherein the polar group is a hydroxyl group, an oligoethylene glycol group, or an isocyanuric acid derivative group. The semiconductor light emitting device according to claim 1 or 2 the surface of the electrode portion of the reflector package contains silver. The semiconductor light emitting device according to any one of claims 1 to 3 or 80% of the encapsulant is an organic component. The semiconductor light emitting device according to any one of claims 1 to 4, wherein the acrylic resin is characterized in that it comprises more than 50 wt% resin obtained by curing the isocyanuric acid acrylate derivatives. The semiconductor light emitting device according to any one of the claims 1-5 the ratio of acrylic groups or methacrylic groups are cured composition solution is less than 5.3 mmol / g or more 6.3 mmol / g. A semiconductor light emitting device is mounted in the concave space of the reflector package, and a sealing agent containing a polar group-containing acrylic monomer is applied to the concave space so as to embed the semiconductor light emitting device, and then the acrylic material of the sealing agent curing the monomer Upon for shaping as a sealing material of the acrylic resin, the ratio of acrylic groups or methacrylic groups of the monomers constituting the acrylic resin before the curing, the total weight of the sealant including the monomer On the other hand, a composition liquid of 4 mmol / g or more and less than 6.5 mmol / g is used as a cured product, and the dropping surface is partially lowered by volume shrinkage due to curing of the sealing agent, and the dropping surface is sealed. A method of manufacturing a semiconductor light emitting device, which is shaped as a light exit surface having a recessed stop material. The manufacturing method of the semiconductor light-emitting device according to claim 7 , wherein a compound represented by the following formula 1 is used as the acrylic monomer.

R ¹ , R ² and R ^{3 in} formula (1) are each independently a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, It represents an aryl group having 6 to 24 carbon atoms, an acryloyloxy group represented by the following formula (I), or an acyloxy group represented by the following formula (II). L ^a represents an alkylene group having 1 to 4 carbon atoms. However, at least one of R ¹ , R ² , and R ³ is the acrylolyloxy group .

In the formula , R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. * Represents a bond .

In the formula , R ¹² represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 24 carbon atoms. * Represents a bond . Sealant comprising the polar group-containing acrylic monomer, a method of manufacturing a semiconductor light emitting device according to claim 7 or 8 whose viscosity is less than 20,000mPas than 800 mPas. The method of manufacturing a semiconductor light emitting device according to any one of claims 7-9 volatilization amount during the following tests were conducted for the acrylic monomer prior to the curing is less than 10 wt%.
In TG / DTA, 5 mg is heated at 80 ° C. 60 min + 130 ° C. 60 min at a rate of temperature increase of 3 ° C./min, and the weight loss at that time is analyzed .

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