JP2015023099A - Method of manufacturing semiconductor light-emitting device, method of manufacturing molded body, electron beam curable resin composition, resin frame for reflector, and reflector - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a semiconductor light-emitting device, in a case of a semiconductor light-emitting device having, on a substrate, a reflector obtained by an injection molding step of an electron beam curable resin composition containing titanium oxide and an electron beam irradiation step and an optical semiconductor element, alternatively, in a case of a molded body, that can exhibit an excellent light resistance, and that can suppress change in reflective index even when being left under a high temperature, and to provide a method of manufacturing the molded body, the electron beam curable resin composition, a resin frame for the reflector, and the reflector.SOLUTION: In a method of manufacturing a semiconductor light-emitting device, a reflector is obtained by: an injection molding step of performing injection molding of an electron beam curable resin composition containing polymethylpentene, and titanium oxide subjected to surface treatment by an aluminum compound, surface treatment by a silicon compound, and a surface treatment by a siloxane compound or a polyol compound; and an electron beam irradiation step of performing electron beam irradiation before or/and after the injection molding step.

Description

  The present invention relates to a method for manufacturing a semiconductor light emitting device, a method for manufacturing a molded body, an electron beam curable resin composition, a reflector resin frame, and a reflector.

  An LED element, which is one of semiconductor light emitting devices, is widely used as a light source for an indicator lamp or the like because it is small and has a long lifetime and is excellent in power saving. In recent years, LED elements with higher brightness have been manufactured at a relatively low cost, and therefore, use as a light source to replace fluorescent lamps and incandescent bulbs has been studied. When applying to such a light source, in order to obtain a large illuminance, a plurality of LED elements are arranged on a surface-mounted LED package, that is, a metal substrate (LED mounting substrate) such as aluminum, and each LED element. A system is often used in which a reflector (reflector) that reflects light in a predetermined direction is disposed around the.

  However, since the LED element generates heat during light emission, in such a type of LED lighting device, the reflector deteriorates due to the temperature rise during light emission of the LED element or direct light from the LED element, and the reflectance decreases. As a result, the luminance is lowered, and the life of the LED element is shortened. Therefore, the reflector is required to have heat resistance and light resistance.

In order to meet the above requirements for heat resistance and light resistance, Patent Document 1 proposes a polymer composition used for a reflector of a light emitting diode, specifically, polyphthalamide, carbon black, titanium dioxide, glass fiber, and oxidation. Disclosed is a polymer composition comprising an inhibitor. And the reflectance after heat aging is measured about the said composition, Compared with the polymer composition which does not contain carbon black, the favorable reflectance is obtained with the said composition, and it has shown that there is also little yellowing.
Patent Document 2 discloses a polymer composition containing a triazine derivative epoxy resin, alumina, and spherical silica particles. It shows that good reflectance is obtained and yellowing is small.

JP-T-2006-503160 JP 2009-149845 A WO2010 / 084845

However, the heat aging test of the polymer composition described in Patent Document 1 is an evaluation in 170 hours at a short time of 3 hours, and a good result can be obtained by changing the reflectance under a longer practical condition. Whether it is unknown.
The heat aging test of the polymer composition described in Patent Document 2 has been verified under a more practical condition of 150 hours at 150 ° C., but has a long curing molding time of 90 seconds and a post-cure 150 ° C. of 2 hours. There was a problem in mass production such as burrs.
As the polymer composition described in Patent Document 3, a resin composition and a molded body of a thermoplastic resin, a filler, and a melt viscosity reducing agent have been proposed. According to this technique, the processability is excellent and the plasticizer bleed out. It is possible to provide a molded product that is prevented. The effect of curing the plasticizer is to prevent bleeding out of the melt viscosity reducing agent, and there is no mention of light reflectivity, decrease in heat reflectivity, and light resistance. The effect of inorganic components on reflectivity is not shown.
Moreover, neither resin composition of said patent document is examined about the light resistance by irradiation of the direct light from an LED element, or the light from the outside.

  As described above, the present invention provides a semiconductor light emitting device or molding having an electron beam curable resin composition containing a titanium oxide, a reflector obtained in the electron beam irradiation step, and an optical semiconductor element on a substrate. In the case of a body, a method of manufacturing a semiconductor light emitting device that can exhibit excellent light resistance and can suppress a change in reflectance even when left at high temperature, a method of manufacturing a molded body, electron beam curing An object of the present invention is to provide a conductive resin composition, a reflector resin frame, and a reflector.

  As a result of intensive studies to achieve the above object, the present inventor has found that the object can be achieved by the following invention. That is, the present invention is as follows.

[1] A method of manufacturing a semiconductor light emitting device, comprising: an optical semiconductor element; and a reflector provided around the optical semiconductor element and reflecting light from the optical semiconductor element in a predetermined direction on a substrate,
A method for manufacturing a semiconductor light emitting device, wherein the reflector is obtained by the following method.
Using an electron beam curable resin composition comprising polymethylpentene and titanium oxide surface-treated with an aluminum compound, surface-treated with a silicon compound, and surface-treated with a siloxane compound or a polyol compound,
An injection molding process for injection molding;
An electron beam irradiation step of irradiating an electron beam before or after the injection molding step;
By getting a reflector.

[2] An electron beam curable resin composition comprising polymethylpentene and titanium oxide that has been surface-treated with an aluminum compound, surface-treated with a silicon compound, and surface-treated with a siloxane compound or a polyol compound,
An injection molding process for injection molding;
An electron beam irradiation step for performing an electron beam irradiation treatment before or after the injection molding step;
The manufacturing method of the molded object containing this.

[3] An electron beam curable resin composition comprising polymethylpentene and titanium oxide that has been surface-treated with an aluminum compound, surface-treated with a silicon compound, and surface-treated with a siloxane compound or a polyol compound.

[4] The electron beam curable resin composition according to [3], which contains glass fibers other than the titanium oxide.
[5] The electron beam curable resin composition according to [3] or [4], wherein a dispersant is blended.

[6] A reflector resin frame using a cured product of the electron beam curable resin composition according to any one of [3] to [5].
[7] The resin frame for reflectors according to [6], wherein the thickness is 0.1 to 3.0 mm.

[8] A reflector using a cured product of the electron beam curable resin composition according to any one of [3] to [5].

  According to the present invention, the substrate has the injection molding step of the electron beam curable resin composition containing the specified surface-treated titanium oxide, the reflector obtained in the electron beam irradiation step, and the optical semiconductor element. In the case of a semiconductor light emitting device or a molded body, it can exhibit excellent light resistance and can suppress a change in reflectance even when left at high temperatures.

It is a schematic sectional drawing which shows an example of the semiconductor light-emitting device of this invention. It is a schematic sectional drawing which shows an example of the semiconductor light-emitting device of this invention.

[1. Manufacturing method of semiconductor light emitting device]
A method for manufacturing a semiconductor light emitting device of the present invention will be described with reference to the semiconductor light emitting device illustrated in FIG. This is a method for manufacturing a semiconductor light-emitting device having an optical semiconductor element 10 and a reflector 12 provided around the optical semiconductor element 10 and reflecting light from the optical semiconductor element 10 in a predetermined direction on a substrate 14.

The reflector 12 is subjected to surface treatment with polymethylpentene and (1) an aluminum compound,
(2) an injection molding step of injection molding using an electron beam curable resin composition containing a titanium oxide subjected to a surface treatment with a silicon compound, and (3) a surface treatment with a siloxane compound or a polyol compound;
An electron beam irradiation step of irradiating an electron beam before or / and after the injection molding step;
It is a manufacturing method obtained by.

  Examples of the surface treatment method (1) include a method in which titanium dioxide, which is titanium oxide, and an oxide or hydroxide of aluminum are mixed and sintered at 500 to 2000 ° C. Moreover, for example, a wet method in which titanium dioxide is added to a mixture of a surface treatment agent containing alumina hydrate and a solvent, stirred, desolvated, and then heat treated at 100 to 300 ° C. can be mentioned.

  Further, for example, a surface treatment agent containing alumina hydrate and titanium oxide are mixed by a mixer or the like, and an organic solution of the surface treatment agent is sprayed and adhered to titanium oxide, and heat treatment is performed at 100 to 300 ° C. And dry method.

  The surface treatment method (2) is performed after the surface treatment (1). For example, silicon dioxide (silicon dioxide), which is a silicon compound, is used for the surface-treated titanium oxide. A surface treatment agent containing a hydrate of silica) can be subjected to surface treatment with a silicon compound by the above-described wet method, dry method, or the like.

  The surface treatment method (3) described above is performed after the surface treatment (2) above, and is applied to the titanium oxide that has been subjected to the surface treatment with the aluminum compound and the surface treatment with the silicon compound. For example, a surface treatment agent containing a polyorganosiloxane that is a siloxane compound can be used to perform a surface treatment with a siloxane compound by the above-described wet method, dry method, or the like.

In the surface treatment method of (3) above, the surface treatment with the polyol compound is a surface treatment containing, for example, a polyol compound with respect to the titanium oxide subjected to the surface treatment with the aluminum compound and the surface treatment with the silicon compound. With the agent, the surface treatment with the polyol compound can be performed by the above-described wet method, dry method, or the like.
An electron beam curable resin composition containing titanium oxide and polymethylpentene subjected to the surface treatment of (1), the surface treatment of (2), and the surface treatment of (3) is prepared.

The polymethylpentene is preferably a homopolymer of 4-methylpentene-1, but 4-methylpentene-1 and other α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1 An α-olefin having 2 to 20 carbon atoms such as octene, 1-decene, 1-dodecene, 1-tetradecene, 1-octadecene, 1-eicocene, 3-methyl-1-butene and 3-methyl-1-pentene; And a copolymer mainly composed of 4-methylpentene-1 containing 90 mol% or more of 4-methyl-1-pentene may be used.
As for the molecular weight of the homopolymer of 4-methylpentene-1, the polystyrene equivalent weight average molecular weight Mw measured by gel permeation chromatography is preferably 1,000 or more, particularly preferably 5,000 or more.

  Polymethylpentene has a refractive index of 1.46, but the titanium oxide contained in the electron beam curable resin composition is subjected to a surface treatment with an aluminum compound, a surface treatment with a silicon compound, and a surface treatment with a siloxane compound or a polyol compound. Thus, since the refractive indexes of polymethylpentene and the above titanium oxide are made very close, even when they are mixed, it is possible to suppress inhibition of optical characteristics such as transmittance and reflectance. Considering this point, for example, it is suitable for use as a reflector of a semiconductor light emitting device. The surface treatment can be measured by a known analysis method. For example, there are techniques such as XPS, RBS, SIMS, and EPMA.

Polymethylpentene has a high melting point of 232 ° C., and has a characteristic that the decomposition temperature is around 300 ° C. without being decomposed even at a processing temperature of about 280 ° C. On the other hand, since there is generally no organic peroxide or photopolymerization initiator having such characteristics, crosslinking with an organic peroxide or crosslinking with ultraviolet light is impossible.
Further, even when the polymethylpentene is irradiated with an electron beam (for example, absorbed dose: 200 kGy), since the molecular chain breaks simultaneously with the crosslinking, effective crosslinking hardly occurs with the resin alone. However, when a crosslinking agent is contained, a crosslinking reaction is effectively caused by electron beam irradiation, and thus heat resistance is obtained.

  It is formed by an electron beam curable resin composition in which titanium oxide obtained by sequentially performing the surface treatment of (1), the surface treatment of (2), and the surface treatment of (3) and polymethylpentene are combined. Molded articles (eg, reflectors) can exhibit excellent light resistance and suppress changes in reflectance even when left at high temperatures. In the case of titanium oxide not subjected to the above three-step surface treatment, the electron beam curable resin composition combined with polymethylpentene increases the dispersibility of the titanium oxide and improves the reflectance. It happens that it tends to decrease. In addition, in the case of using a titanium oxide that does not perform the above-described three-step surface treatment, the dispersibility of the titanium oxide is low and the reflectance is likely to be lowered when the type that increases the light resistance is used.

  The optical semiconductor element 10 emits radiated light (generally UV or blue light in a white light LED), for example, an active layer made of AlGaAs, AlGaInP, GaP or GaN sandwiched between n-type and p-type cladding layers. It is a semiconductor chip (light emitter) having a double heterostructure, and has a hexahedral shape with a side length of about 0.5 mm, for example. In the case of wire bonding mounting, it is connected to an electrode (connection terminal) (not shown) via a lead wire 16.

The shape of the reflector 12 conforms to the shape of the end portion (joint portion) of the lens 18 and is usually a cylindrical shape such as a square shape, a circular shape, or an oval shape, or an annular shape. In the schematic cross-sectional view of FIG. 1, the reflector 12 is a cylindrical body (annular body), and all the end faces of the reflector 12 are in contact with and fixed to the surface of the substrate 14.
In addition, in order to improve the directivity of the light from the optical semiconductor element 10, the inner surface of the reflector 12 may be expanded upward in a tapered shape (see FIG. 1).
The reflector 12 can also function as a lens holder when the end portion on the lens 18 side is processed into a shape corresponding to the shape of the lens 18.

As shown in FIG. 2, the reflector 12 is good also considering the light reflection surface side as the light reflection layer 12a which consists of an electron beam curable resin composition. In this case, the thickness of the light reflection layer 12a is preferably 500 μm or less, and more preferably 300 μm or less, from the viewpoint of reducing the thermal resistance. The member 12b on which the light reflecting layer 12a is formed can be made of a known heat resistant resin.
As described above, the lens 18 is provided on the reflector 12, but this is usually made of a resin, and various structures may be adopted and colored depending on the purpose and application.

  The space formed by the substrate 14, the reflector 12, and the lens 18 may be a transparent sealing portion, or may be a gap if necessary. This space portion is usually a transparent sealing portion filled with a light-transmitting and insulating material, and the force applied by directly contacting the lead wire 16 in wire bonding mounting and indirectly. Prevents electrical defects caused by the lead wire 16 being disconnected, cut, or short-circuited from the connection portion with the optical semiconductor element 10 and / or the connection portion with the electrode due to applied vibration, impact, etc. can do. At the same time, the optical semiconductor element 10 can be protected from moisture, dust, etc., and the reliability can be maintained over a long period of time.

  Examples of the material (transparent encapsulant composition) that imparts light-transmitting properties and insulating properties usually include silicone resins, epoxy silicone resins, epoxy resins, acrylic resins, polyimide resins, polycarbonate resins, and the like. Of these, silicone resins are preferred from the viewpoints of heat resistance, weather resistance, low shrinkage, and discoloration resistance.

  The injection molding step for injection molding the electron beam curable resin composition containing titanium oxide is preferably produced at an injection temperature of 200 to 400 ° C and a mold temperature of 20 to 200 ° C. A reflector can be produced by a molding method including an electron beam irradiation process in which an electron beam irradiation process is performed before and / or after the injection molding process. As long as the moldability is not impaired, the crosslinking reaction by electron beam irradiation is not limited to after molding, but can be performed before molding and further before and after molding.

  In the electron beam irradiation step, the acceleration voltage of the electron beam can be appropriately selected according to the resin used and the thickness of the layer. For example, in the case of a molded product having a thickness of about 1 mm, it is usually preferable to cure the uncured resin layer at an acceleration voltage of about 250 to 2000 kV. In the electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when a substrate that deteriorates due to the electron beam is used as the substrate, the transmission depth of the electron beam and the thickness of the resin layer are substantially equal. By selecting an accelerating voltage so as to be equal, irradiation of an extra electron beam to the substrate can be suppressed, and deterioration of the substrate due to excess electron beam can be minimized. Further, the absorbed dose when irradiating the electron beam is appropriately set depending on the composition of the resin composition, but the amount in which the crosslink density of the resin layer is saturated is preferably 10 to 400 kGy, and preferably 50 to 200 kGy. It is more preferable. Further, the electron beam source is not particularly limited. For example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. Can be used.

Below, an example of the manufacturing method of the semiconductor light-emitting device shown in FIG. 1 is demonstrated.
First, the electron beam curable resin composition of the present invention is molded into a reflector 12 having a predetermined shape by injection molding using a mold having a cavity space having a predetermined shape. Thereafter, the separately prepared optical semiconductor element 10, electrodes and lead wires 16 are fixed to the substrate 14 with an adhesive or a bonding member, and the reflector 12 is further fixed onto the substrate 14.
The method of fixing the reflector 12 on the substrate is preferably performed using molten solder.

After fixing the reflector and the optical semiconductor element on the substrate, a transparent sealant composition containing a silicone resin or the like is injected into the recess formed by the substrate 14 and the reflector 12 and cured by heating, drying, etc. Let it be a stop. Thereafter, the lens 18 is disposed on the transparent sealing portion to obtain the semiconductor light emitting device shown in FIG.
In addition, after mounting the lens 18 in a state where the transparent sealant composition is uncured, the composition may be cured.

[2. Method for producing molded body]
An injection molding process for injection molding using the surface-treated titanium oxide and an electron beam curable resin composition containing polymethylpentene, and an electron beam irradiation treatment before or / and after the injection molding process. And an electron beam irradiation step for applying a molded article. The electron beam curable resin composition, the injection molding process, and the electron beam irradiation process used in this method for manufacturing a molded body are the same as those described in the above method for manufacturing a semiconductor light emitting device, and are therefore omitted here. By the method for producing a molded body, various molded bodies can be molded and manufactured, and a molded body having a small thickness (for example, a reflector) can also be manufactured.

[3. Electron beam curable resin composition]
The electron beam curable resin composition of the present invention includes polymethylpentene and titanium oxide that has been surface-treated with an aluminum compound, surface-treated with a silicon compound, and surface-treated with a siloxane compound or a polyol compound.
The titanium oxide subjected to the surface treatment with polymethylpentene and the aluminum compound, the surface treatment with the silicon compound, and the surface treatment with the siloxane compound or the polyol compound of the above materials is as described in the method for manufacturing the semiconductor light emitting device. It is.

  A molded article of a resin composition that can exhibit sufficient heat resistance can be obtained by adding a crosslinking agent to the electron beam curable resin composition and irradiating it with an electron beam. Even when the polymethylpentene is irradiated with an electron beam (for example, absorbed dose: 200 kGy), the molecular chain breaks simultaneously with the crosslinking, so that effective crosslinking is unlikely to occur with the resin alone. However, by including a crosslinking treatment agent, a crosslinking reaction is effectively caused by electron beam irradiation, and a molded product having sufficient heat resistance and light resistance can be formed.

Such a crosslinking agent has a saturated or unsaturated ring structure, and at least one of atoms forming at least one ring is an allyl group, a methallyl group, an allyl group via a linking group, and Those having a structure formed by bonding to any allylic substituent of a methallyl group via a linking group are preferred. By containing the crosslinking agent having such a structure, it is possible to obtain a resin composition that exhibits good electron beam curability and has excellent heat resistance.
Examples of the saturated or unsaturated ring structure include a cyclo ring, a hetero ring, and an aromatic ring. The number of atoms forming the ring structure is preferably 3 to 12, more preferably 5 to 8, and still more preferably a 6-membered ring.

Further, the molecular weight of the crosslinking agent is preferably 1000 or less, more preferably 500 or less, and even more preferably 300 or less. When the molecular weight is 1000 or less, it is possible to prevent the dispersibility in the resin composition from being lowered and to cause an effective crosslinking reaction by electron beam irradiation.
The number of ring structures is preferably 1 to 3, more preferably 1 or 2, and further preferably 1.

The melting point of the crosslinking agent is preferably not higher than the melting point (232 ° C.) of the polymethylpentene to be used, for example, preferably not higher than 200 ° C.
Since the crosslinking agent as described above has excellent fluidity during processing, the processing temperature of the thermoplastic resin is lowered to reduce the thermal load, friction during processing is reduced, and the inorganic component filling amount is reduced. Can be increased.

  Examples of the linking group in the crosslinking agent include an ester bond, an ether bond, an alkylene group, and a (hetero) arylene group. Among the atoms forming the ring, atoms that are not bonded to the allylic substituent are in a state in which hydrogen, oxygen, nitrogen, or the like is bonded, or in a state in which various substituents are bonded.

The crosslinking agent is preferably formed by bonding at least two atoms out of atoms forming one ring of the crosslinking agent independently to an allylic substituent. When the ring structure is a 6-membered ring, at least two of the atoms forming the ring are independently bonded to an allylic substituent, and one allylic substituent is bonded to the atom. On the other hand, it is preferable that another allylic substituent is bonded to the atom at the meta position.
Furthermore, the crosslinking agent is preferably represented by the following formula (1) or (2).

（式（１）中、Ｒ¹〜Ｒ³はそれぞれ独立に、アリル基、メタリル基、エステル結合を介したアリル基、及びエステル結合を介したメタリル基のいずれかのアリル系置換基である。）

(In Formula (1), R < ¹ > -R < ³ > is an allylic substituent in any one of an allyl group, a methallyl group, an allyl group via an ester bond, and a methallyl group via an ester bond, respectively. )

（式（２）中、Ｒ¹〜Ｒ³はそれぞれ独立に、アリル基、メタリル基、エステル結合を介したアリル基、及びエステル結合を介したメタリル基のいずれかのアリル系置換基である。）

(In Formula (2), R < ¹ > -R < ³ > is an allylic substituent in any one of an allyl group, a methallyl group, an allyl group via an ester bond, and a methallyl group via an ester bond, respectively. )

Examples of the crosslinking agent represented by the above formula (1) include triallyl isocyanurate, methyl diallyl isocyanurate, diallyl monoglycidyl isocyanuric acid, monoallyl diglycidyl isocyanurate, and trimethallyl isocyanurate.
Examples of the crosslinking agent represented by the above formula (2) include orthophthalic acid diallyl ester, isophthalic acid diallyl ester, and the like.

  The crosslinking agent is blended in an amount of more than 3 parts by weight and not more than 30 parts by weight with respect to 100 parts by weight of polymethylpentene, and preferably 4 to 20 parts by weight. By blending in an amount of more than 3 parts by mass and not more than 30 parts by mass, crosslinking can be effectively advanced without bleeding out.

  In the electron beam curable resin composition, the content of the titanium oxide subjected to the surface treatment with the aluminum compound, the surface treatment with the silicon compound, and the surface treatment with the siloxane compound or the polyol compound is 100 parts by mass of polymethylpentene. It is preferable to set it as 50-500 mass parts. Product performance (for example, light reflectance of a reflector, light resistance, etc.) can be maintained satisfactorily by setting it as 50 to 500 mass parts. Moreover, even if it can process with many inorganic components, a molding state is bad, and it can prevent that product performance (for example, the light reflectivity of a reflector) falls by a boss.

  The average particle size of the surface-treated titanium oxide is preferably 0.10 to 0.50 μm in the primary particle size distribution from the viewpoint of obtaining moldability and obtaining high reflectance, and is preferably 0.10 to 0. More preferably, the thickness is 40 μm, and more preferably 0.21 to 0.25 μm. An average particle diameter can be calculated | required as mass average value D50 in the particle size distribution measurement by a laser beam diffraction method.

  Moreover, it is preferable that glass fiber is included other than the said titanium oxide. Such an electron beam curable resin composition is particularly suitable for a reflector.

  The content of the glass fiber is preferably 10 to 300 parts by mass, more preferably 30 to 200 parts by mass, and further preferably 50 to 120 parts by mass with respect to 100 parts by mass of polymethylpentene. .

  The electron beam curable resin composition of the present invention includes polymethylpentene, titanium oxide that has been surface-treated with an aluminum compound, surface-treated with a silicon compound, and surface-treated with a siloxane compound or a polyol compound, and a crosslinking agent. If necessary, glass fiber can be mixed at a predetermined ratio. As the mixing method, known means such as a two-roll or three-roll, a stirrer such as a homogenizer or a planetary mixer, or a melt kneader such as a polylab system or a lab plast mill can be applied. These may be performed at normal temperature, cooling state, heating state, normal pressure, reduced pressure state, or pressurized state.

  Various additives can be added as long as the effects of the present invention are not impaired. For example, for the purpose of improving the properties of the resin composition, various kinds of whisker, silicone powder, thermoplastic elastomer, organic synthetic rubber, fatty acid ester, glycerate ester, zinc stearate, calcium stearate and other internal mold release agents, benzophenone , Salicylic acid-based, cyanoacrylate-based, isocyanurate-based, oxalic acid anilide-based, benzoate-based, hindered amine-based, benzotriazole-based, phenol-based antioxidants, hindered amine-based, benzoate-based light stabilizers, etc. Additives can be blended.

Moreover, a dispersing agent like a silane coupling agent can be mix | blended.
Examples of the silane coupling agent include disilazane such as hexamethyldisilazane; cyclic silazane; trimethylsilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, trimethoxysilane, benzyldimethylchlorosilane, Methyltrimethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-butyltrimethoxysilane, n-hexadecyl Trimethoxysilane, n-octadecyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyl Alkylsilane compounds such as limethoxysilane and vinyltriacetoxysilane; γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane N-phenyl-3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, and N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane And aminosilane compounds such as hexyltrimethoxysilane; and the like.

  The electron beam curable resin composition of the present invention as described above can be applied to various uses as a composite material applied on a substrate and cured, or a cured product of an electron beam curable resin composition. For example, it can be applied as a heat-resistant insulating film, a heat-resistant release sheet, a heat-resistant transparent substrate, a light-reflecting sheet for solar cells, or a reflector for a light source for televisions, such as LEDs.

[4. Resin frame for reflectors]
The resin frame for a reflector of the present invention uses a cured product obtained by molding the above-described electron beam curable resin composition of the present invention. Specifically, the electron beam curable resin composition of the present invention is formed into pellets, and a resin frame having a desired shape is formed by injection molding, whereby the reflector resin frame of the present invention is manufactured. The thickness of the reflector resin frame is preferably 0.1 to 3.0 mm, more preferably 0.1 to 1.0 mm, and still more preferably 0.1 to 0.8 mm.

  In the electron beam curable resin composition of the present invention, for example, a resin frame having a smaller thickness can be produced as compared with a resin frame produced using glass fibers. Specifically, a resin frame having a thickness of 0.1 to 3.0 mm can be produced. In addition, the resin frame for reflectors of the present invention formed in this way does not generate warp due to the inclusion of fillers such as glass fibers even when the thickness is reduced. Also excellent.

  The resin frame for a reflector of the present invention can be made into a semiconductor light emitting device by placing an LED chip on this, further sealing with a known sealant, and performing die bonding to obtain a desired shape. In addition, although the resin frame for reflectors of this invention acts as a reflector, it is functioning also as a frame which supports a semiconductor light-emitting device.

[5. Reflector]
For the reflector of the present invention, a cured product obtained by curing the electron beam curable resin composition of the present invention described above is used.
The reflector may be used in combination with a semiconductor light emitting device, or may be used in combination with a semiconductor light emitting device (LED mounting substrate) made of another material.
The reflector of the present invention mainly has an action of reflecting light from the LED element of the semiconductor light emitting device toward the lens (light emitting portion). The details of the reflector are as described in the method for manufacturing the semiconductor light emitting device described above.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the material used in the present Examples 1-6 and Comparative Examples 1-7 is as follows.

(A) Resin / resin Polymethylpentene resin: TPX RT18 (Mitsui Chemicals, Inc.)

(B) Crosslinking agent The crosslinking agent is as follows.
・ Crosslinking agent TAIC (triallyl isocyanurate) manufactured by Nippon Kasei Co., Ltd.

(C) White pigment / titanium oxide (1): PF-691 (Ishihara Sangyo Co., Ltd. Rutile structure average particle size 0.21 μm, surface treatment with aluminum compound, surface treatment with silicon compound, and surface treatment with siloxane compound Titanium oxide)
Titanium oxide (2): PF-690 (Ishihara Sangyo Co., Ltd. Rutile structure average particle size 0.21 μm, surface treatment with an aluminum compound, surface treatment with a silicon compound, and surface oxidation with a polyol compound) object)
Titanium oxide (3): PF-711 (Ishihara Sangyo Co., Ltd. Rutile structure average particle size 0.25 μm, surface treatment with aluminum compound, surface treatment with silicon compound, surface treatment with polyol compound, titanium oxide )
Titanium oxide (4): CR-60 (Ishihara Sangyo Co., Ltd. Rutile structure average particle size 0.21 μm, titanium oxide surface-treated with an aluminum compound)
Titanium oxide (5): CR-60-2 (Ishihara Sangyo Co., Ltd. Rutile structure average particle size 0.21 μm, surface treatment with an aluminum compound, surface treatment with a polyol compound)
Titanium oxide (6): PF-726 (Ishihara Sangyo Co., Ltd. Rutile structure average particle size 0.21 μm, surface treatment with an aluminum compound, surface treatment with a silicon compound)
Titanium oxide (7): CR-80 (Ishihara Sangyo Co., Ltd. Rutile structure average particle size 0.25 μm, surface treatment with aluminum compound, surface treatment with silicon compound, titanium oxide)
Titanium oxide (8): CR-93 (Ishihara Sangyo Co., Ltd. Rutile structure average particle size 0.28 μm, surface treatment with aluminum compound, surface treatment with silicon compound, titanium oxide)
Titanium oxide (9): CR-95 (Ishihara Sangyo Co., Ltd. Rutile structure average particle size 0.28 μm, surface treatment with aluminum compound, surface treatment with silicon compound, surface treatment with polyol compound, titanium oxide )
-Titanium oxide (10): CR-97 (Ishihara Sangyo Co., Ltd. Rutile structure average particle size 0.25 μm, surface treatment with an aluminum compound, surface treatment with a zirconia compound)

(D) Inorganic material / glass fiber: PF70E-001 (manufactured by Nittobo Co., Ltd., fiber length: 70 μm)

(E) Additive / Silane coupling agent: KBM-3063 (manufactured by Shin-Etsu Chemical Co., Ltd.)
Mold release agent: SZ-2000 (manufactured by Sakai Chemical Co., Ltd.)
Antioxidant (1): IRGANOX 1010 (BASF Japan Ltd.)
Antioxidant (2): IRGAFOS168 (manufactured by BASF Japan Ltd.)

[Examples 1-6, Comparative Examples 1-7]
As shown in Tables 1 and 2 below, various materials were blended and kneaded to obtain a resin composition.
In addition, a resin composition mix | blends various materials and performs it using an extruder (Nippon Placon Co., Ltd. MAX30: Die diameter 3.0mm) and a pelletizer (Toyo Seiki Seisakusho MPETC1), and obtains a resin composition It was.
About these compositions, press molding to 19 (± 1) mm × 5 (± 0.1) mm × thickness 0.55 (± 0.1) mm under the conditions of 250 ° C., 30 seconds, and 20 MPa, A molded body was produced.
The compact was irradiated with an electron beam at an acceleration voltage of 800 kV and an absorbed dose of 400 kGy. The following characteristics were evaluated. The results are shown in Tables 1 and 2 below.

(Evaluation 1)
-Dispersibility The dispersibility of the pigment in the molded product was judged visually. Tables 1 and 2 show the results. “◯” indicates good dispersibility, and “×” indicates pigment aggregation.

(Evaluation 2)
-Initial reflectance The sample of the molded body was measured for light reflectance at a wavelength of 230 to 780 nm using a spectrophotometer UV-2550 (manufactured by Shimadzu Corporation) at room temperature. Tables 1 and 2 show the results at a wavelength of 450 nm.

(Evaluation 3)
-Heat resistance After leaving the sample of a molded object to stand at 150 degreeC for 24 hours, the light reflectivity in wavelength 230-780nm was measured using the spectrophotometer UV-2550 (made by Shimadzu Corporation). Tables 1 and 2 show the results at a wavelength of 450 nm.

(Evaluation 3)
-Light resistance After the sample of a molded object was left for 24 hours under ultraviolet irradiation conditions at 150 ° C, the light reflectance at a wavelength of 230 to 780 nm was measured using a spectrophotometer UV-2550 (manufactured by Shimadzu Corporation). It was measured. The ratio of the measured light reflectivity with a wavelength of 450 nm to the initial reflectivity was observed, and the appearance of the molded body was observed, and evaluated according to the following criteria.

O: Appearance of the light-resistant sample is good. Yellowing and powder bleeding are not observed.
X: The appearance of the light-resistant sample is poor. Yellowing and powder bleeding are observed.

As is clear from the results of the above Examples, the initial reflectances of the molded samples made of the resin compositions of Examples 1 to 6 were all 93.6 to 99%. After leaving at 150 ° C. for 24 hours and after leaving at 150 ° C. under ultraviolet irradiation conditions for 24 hours, there was almost no change compared to the light reflectance in the initial stage before leaving. (It was a decrease within 2% of the initial reflectivity.)
As mentioned above, according to the manufacturing method of the molded object of this invention, it can be said that a useful reflector and the reflecting material for semiconductor light-emitting devices can be manufactured.

DESCRIPTION OF SYMBOLS 10 ... Optical semiconductor element 12 ... Reflector 14 ... Board | substrate 16 ... Lead wire 18 ... Lens

Claims (8)

A method of manufacturing a semiconductor light emitting device, comprising: an optical semiconductor element; and a reflector provided around the optical semiconductor element and reflecting light from the optical semiconductor element in a predetermined direction on a substrate,
A method for manufacturing a semiconductor light emitting device, wherein the reflector is obtained by the following method.
Using an electron beam curable resin composition comprising polymethylpentene and titanium oxide surface-treated with an aluminum compound, surface-treated with a silicon compound, and surface-treated with a siloxane compound or a polyol compound,
An injection molding process for injection molding;
An electron beam irradiation step of irradiating an electron beam before or after the injection molding step;
By getting a reflector. Using an electron beam curable resin composition comprising polymethylpentene and titanium oxide surface-treated with an aluminum compound, surface-treated with a silicon compound, and surface-treated with a siloxane compound or a polyol compound,
An injection molding process for injection molding;
An electron beam irradiation step for performing an electron beam irradiation treatment before or after the injection molding step;
The manufacturing method of the molded object containing this. An electron beam curable resin composition comprising polymethylpentene and titanium oxide that has been surface-treated with an aluminum compound, surface-treated with a silicon compound, and surface-treated with a siloxane compound or a polyol compound.   The electron beam curable resin composition of Claim 3 containing glass fiber other than the said titanium oxide.   The electron beam curable resin composition according to claim 3 or 4, wherein a dispersant is blended.   The resin frame for reflectors in which the hardened | cured material of the electron beam curable resin composition of any one of Claims 3-5 was used.   The resin frame for a reflector according to claim 6, wherein the thickness is 0.1 to 3.0 mm.   The reflector in which the hardened | cured material of the electron beam curable resin composition of any one of Claims 3-5 was used.

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