JP5233186B2 - Thermosetting light reflecting resin composition, substrate for mounting optical semiconductor element using the same, method for manufacturing the same, and optical semiconductor device - Google Patents

Description

  The present invention relates to a thermosetting light reflecting resin composition used in an optical semiconductor device in which an optical semiconductor element and a wavelength conversion means such as a phosphor are combined, and an optical semiconductor using the thermosetting light reflecting resin composition. The present invention relates to an element mounting substrate, a manufacturing method thereof, and an optical semiconductor device using the optical semiconductor element mounting substrate.

  As an optical semiconductor device using an optical semiconductor element, an SMD (Surface Mounted Device) type LED (Light Emitting Diode) configured as shown in FIG. 4 is known. In this LED, an LED element (light emitting element) 400 is usually disposed on the bottom surface of the cup-shaped part (concave part) formed on the mount substrate reflector (substrate for mounting an optical semiconductor element) 403 where the lead 404 is exposed, Further, a transparent sealing resin 402 containing a phosphor 405 is filled in the cup-like portion where the element is arranged. The reflector is used for the purpose of increasing the on-axis strength by diffusing and reflecting the light emitted from the light-emitting element to the side and distributing it in the axial direction. Patent Documents 1 to 4 disclose SMD type forming materials for LEDs in which a reflector is made of a thermoplastic resin composition.

  LEDs having such a structure are expanding their demand for outdoor displays, portable liquid crystal backlights, in-vehicle applications, etc. due to advantages such as high energy efficiency and long life. As a result, the increase in the junction temperature due to the increase in the amount of heat generated by the device, or the heat resistance degradation and light resistance degradation of the material due to the direct increase in light energy have become problems.

In response to this problem, Patent Document 5 provides an LED having excellent heat resistance and light reflection characteristics using a cured product of a resin composition containing triglycidyl isocyanurate as an epoxy resin and hexahydrophthalic anhydride as a curing agent as a reflector. Is disclosed.
JP 2005-194513 A JP 2004-277539 A JP 2004-75994 A JP 2004-128393 A JP 2006-140207 A

  However, since the melting point of hexahydrophthalic anhydride contained as a curing agent is 34 to 38 ° C., the resin composition in Patent Document 5 has problems in tablet moldability and generation of burrs.

  The present invention has been made in view of the above, and is a thermosetting light reflecting resin composition that is excellent in light reflection characteristics and tablet moldability and can reduce burrs, and an optical semiconductor element mounted using the same. An object of the present invention is to provide a manufacturing substrate, a manufacturing method thereof, and an optical semiconductor device.

  That is, the present invention is characterized by the following items (1) to (9).

(1) In a resin composition containing (A) an epoxy resin, (B) a curing agent, (C) an inorganic filler, and (D) a white pigment, the light reflectance at a wavelength of 800 nm to 350 nm after curing is 90%. The thermosetting light-reflecting resin composition as described above, which can be pressure-molded at room temperature (0 to 35 ° C.) before curing.

(2) The thermosetting light according to (1), wherein the curing agent (B) includes a compound having an isocyanuric acid skeleton, or a compound having an isocyanuric acid skeleton and an acid anhydride having a melting point of 35 ° C. or higher. Reflective resin composition.

(3) The inorganic filler (C) is selected from the group consisting of silica, alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, and barium carbonate. The thermosetting light reflecting resin composition as described in (1) or (2) above, comprising one or more selected.

(4) The above (D), wherein the white pigment (D) contains one or more selected from the group consisting of alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide and inorganic hollow particles. The thermosetting light reflecting resin composition according to any one of to (3).

(5) The thermosetting light reflecting resin composition as described in any one of (1) to (4) above, wherein the average particle diameter of the white pigment (D) is in the range of 1 to 50 μm. .

(6) The above (1), wherein the total blending amount of the (C) inorganic filler and the (D) white pigment is in the range of 10% by volume to 85% by volume with respect to the entire resin composition. ) To (5) The thermosetting resin composition for light reflection.

(7) An optical semiconductor element mounting substrate in which one or more recesses to be an optical semiconductor element mounting region are formed, and at least an inner peripheral side surface of the recess is described in any one of (1) to (6). An optical semiconductor element mounting substrate comprising the thermosetting light reflecting resin composition.

(8) A method for manufacturing a substrate for mounting an optical semiconductor element in which at least one recess serving as an optical semiconductor element mounting region is formed, wherein at least the recess is described in any one of (1) to (6) above. A method for producing a substrate for mounting an optical semiconductor, characterized by forming by transfer molding using the thermosetting light reflecting resin composition.

(9) The optical semiconductor element mounting substrate described in (7) above or the optical semiconductor element mounting substrate manufactured by the manufacturing method described in (8) above,
An optical semiconductor element mounted on the bottom of the recess of the optical semiconductor element mounting substrate;
A phosphor-containing transparent sealing resin layer formed in the recess so as to cover the optical semiconductor element;
An optical semiconductor device comprising:

  According to the present invention, a thermosetting light reflecting resin composition that is excellent in light reflection characteristics and tablet moldability and capable of reducing burrs, a substrate for mounting an optical semiconductor element using the same, a method for manufacturing the same, and light A semiconductor device can be provided.

  Embodiments of the present invention will be described below.

  As the (A) epoxy resin used in the present invention, known epoxy resins used for electronic parts can be used, and are not particularly limited. For example, phenol novolac type epoxy resins and orthocresol novolak type epoxy resins are used. Obtained by reaction of epichlorhydrin with epoxidized novolak resins of phenols and aldehydes such as bisphenol A, bisphenol F, bisphenol S, diglycidyl ethers such as alkyl-substituted bisphenol, polyamines such as diaminodiphenylmethane and isocyanuric acid There are glycidylamine type epoxy resins, linear aliphatic epoxy resins obtained by oxidizing olefinic bonds with peracids such as peracetic acid, and alicyclic epoxy resins. Kill. Among these, those having relatively little color are preferable, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, diglycidyl isocyanurate, and triglycidyl isocyanurate.

  The (B) curing agent used in the present invention can be used without particular limitation as long as it reacts with the (A) epoxy resin. For example, an acid anhydride curing agent, a compound having an isocyanuric acid skeleton (isocyanuric) Acid derivatives) and phenolic curing agents. More specifically, as the acid anhydride curing agent, for example, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, anhydrous Nadic acid, glutaric anhydride, dimethyl glutaric anhydride, diethyl glutaric anhydride, succinic anhydride, methyl hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, and isocyanuric acid derivatives include, for example, 1,3,5- Tris (1-carboxymethyl) isocyanurate, 1,3,5-tris (2-carboxyethyl) isocyanurate, 1,3,5-tris (3-carboxypropyl) isocyanurate, 1,3-bis (2- Carboxyethyl) isocyanurate, etc., and these are used alone , It may be used in combination of two or more. Among the above curing agents, phthalic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, dimethylglutaric anhydride, It is preferable to use diethyl glutaric anhydride and 1,3,5-tris (3-carboxypropyl) isocyanurate.

  The (B) curing agent preferably has a molecular weight of about 100 to 400, and is preferably colorless or light yellow. In addition, as the curing agent (B) used in the present invention, an isocyanuric acid derivative alone, an isocyanuric acid derivative and an acid anhydride, or an isocyanuric acid derivative and an acid anhydride having a melting point of 35 ° C. or higher are used. It is particularly preferred. The blending ratio of the isocyanuric acid derivative and the acid anhydride is preferably in the range of 1: 0 to 10, and is in the range of 1: 1 to 3 from the viewpoint of cost reduction and suppression of reduction in reflectance due to yellowing of the resin. preferable.

  The compounding ratio of (A) epoxy resin and (B) curing agent is such that the active group (an acid anhydride group or hydroxyl group) capable of reacting with the epoxy group in the curing agent is equivalent to 1 equivalent of epoxy group in the epoxy resin. The ratio is preferably 0.5 to 1.5 equivalents, and more preferably 0.7 to 1.2 equivalents. When the active group is less than 0.5 equivalent, the curing rate of the epoxy resin composition is slowed down, and the glass transition temperature of the resulting cured product may be low. On the other hand, when it exceeds 1.5 equivalent, Moisture resistance may be reduced.

  The inorganic filler (C) used in the present invention is not particularly limited. For example, silica, alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, At least one selected from the group consisting of barium carbonate can be used, but silica, alumina, magnesium oxide, antimony oxide, titanium oxide are used in terms of thermal conductivity, light reflection characteristics, moldability, and flame retardancy. A mixture of zirconium oxide, aluminum hydroxide and magnesium hydroxide is preferred. The average particle diameter of the inorganic filler (C) is not particularly limited, but it is preferable to use an inorganic filler in the range of 1 to 100 μm so that packing with the (D) white pigment is efficient.

  Although it does not specifically limit as (D) white pigment used by this invention, For example, an alumina, magnesium oxide, an antimony oxide, a titanium oxide, a zirconium oxide, an inorganic hollow particle etc. can be used. Examples of the inorganic hollow particles include sodium silicate glass, aluminum silicate glass, borosilicate soda glass, and shirasu. Moreover, it is preferable that the average particle diameter of (D) white pigment exists in the range of 1-50 micrometers. (D) When the average particle diameter of the white pigment is less than 1 μm, the particles tend to aggregate and the dispersibility tends to deteriorate, and when it exceeds 50 μm, the reflection characteristics tend not to be sufficiently obtained. In addition, as said (D) white pigment, it is also possible to select simultaneously the same component as the component which can be used as said (C) inorganic fillers, such as an alumina. However, even when the same components are selected, they are intended to be distinguished as independent components of (C) inorganic filler and (D) white pigment.

  The total amount of the (C) inorganic filler and the (D) white pigment is preferably in the range of 10% to 85% by volume with respect to the entire resin composition. If the blending amount is less than 10% by volume, the light reflection property of the cured product of the resin composition may be insufficient, and if it exceeds 85% by volume, the moldability of the resin composition is deteriorated, and the optical semiconductor mounting. It becomes difficult to produce the substrate.

  The resin composition of the present invention contains the above-mentioned (A) to (D) as essential components, but preferably further includes (E) a curing accelerator and (F) a coupling agent.

  The (E) curing accelerator used in the present invention is not particularly limited. For example, 1,8-diaza-bicyclo (5,4,0) undecene-7, triethylenediamine, tri-2,4, Tertiary amines such as 6-dimethylaminomethylphenol, imidazoles such as 2-ethyl-4methylimidazole and 2-methylimidazole, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetra-n-butylphosphonium-o, Phosphorus compounds such as o-diethyl phosphorodithioate, tetra-n-butylphosphonium-tetrafluoroborate, tetra-n-butylphosphonium-tetraphenylborate, quaternary ammonium salts, organometallic salts, and derivatives thereof It is done. These may be used alone or in combination. Among these curing accelerators, it is preferable to use tertiary amines, imidazoles, and phosphorus compounds.

  The content of the (E) curing accelerator is preferably 0.01 to 8.0% by weight, more preferably 0.1 to 3.0% by weight with respect to the (A) epoxy resin. is there. When the content of the curing accelerator is less than 0.01% by weight, a sufficient curing acceleration effect may not be obtained. When the content exceeds 8.0% by weight, discoloration is observed in the resulting colored product. There is.

  Although it does not specifically limit as (F) coupling agent used by this invention, For example, a silane coupling agent, a titanate coupling agent, etc. can be used, As an silane coupling agent, it is an epoxy silane type, for example. Amino silane, cationic silane, vinyl silane, acrylic silane, mercapto silane, and composites thereof can be used. The type and treatment conditions of the coupling agent are not particularly limited, but the amount of the coupling agent is preferably 5% by weight or less with respect to the entire resin composition from the viewpoint of storage stability.

  Furthermore, in addition to the above-mentioned components (A) to (F), the resin composition of the present invention may contain known additives such as antioxidants, mold release agents, and ion scavengers as necessary. Good.

  The thermosetting light reflecting resin composition of the present invention can be obtained by uniformly dispersing and mixing the various components described above, and the means and conditions thereof are not particularly limited. An example is a method in which an amount of components are sufficiently uniformly stirred and mixed by a mixer or the like, then kneaded by a mixing roll, an extruder, a kneader, a roll, an extruder, or the like, and further cooled and pulverized.

  Moreover, the thermosetting light reflecting resin composition of the present invention can be pressure-molded at room temperature (0 to 35 ° C.) before thermosetting, and has a light reflectance at a wavelength of 350 nm to 800 nm after thermosetting of 90. % Or more is desirable. The said press molding should just be performed on the conditions of about 0.5-2 MPa and about 1-5 second at room temperature, for example. Further, if the light reflectance is less than 90%, there is a tendency that it cannot sufficiently contribute to the improvement of the luminance of the optical semiconductor device.

  The substrate for mounting an optical semiconductor element of the present invention has one or more recesses to be an optical semiconductor element mounting region, and at least the inner peripheral side surface of the recess is made of the thermosetting light reflecting resin composition of the present invention. It is characterized by this. FIG. 1 shows one embodiment of a substrate for mounting an optical semiconductor element of the present invention, in which (a) is a perspective view and (b) is a side sectional view. In the optical semiconductor element mounting substrate 110 of the present invention shown in FIG. 1, the side wall of the optical semiconductor element mounting region (recessed portion) 200 is made of the thermosetting light reflecting resin composition of the present invention so as to form the bottom surface of the recessed portion. The exposed surfaces of a pair of positive and negative metal wirings 105 disposed opposite to each other with the resin composition interposed therebetween are covered with Ni / Ag plating 104.

  Although the manufacturing method of the optical semiconductor element mounting substrate of this invention is not specifically limited, For example, it is preferable to shape | mold and manufacture the thermosetting light reflection resin composition of this invention by transfer molding. FIG. 2 is a schematic diagram for explaining a method for manufacturing a substrate for mounting an optical semiconductor element according to the present invention, and (a) to (c) correspond to respective steps when a substrate is manufactured by transfer molding. More specifically, for example, as shown in FIG. 2A, the substrate for mounting an optical semiconductor element is formed with a metal wiring 105 by a known method such as punching or etching from a metal foil, and then the metal wiring. 105 is placed in a mold 301 having a predetermined shape (FIG. 2B), and the thermosetting light reflecting resin composition of the present invention is injected from the resin injection port 300 of the mold 301, and this is preferably a mold. After thermosetting at a temperature of 170 to 190 ° C., a molding pressure of 2 to 8 MPa for 60 to 120 seconds, and an after cure temperature of 120 to 180 ° C. for 1 to 3 hours, the mold 301 is removed, and the cured thermosetting It can be manufactured by applying Ni / silver plating 104 by electroplating to a predetermined position of an optical semiconductor element mounting region (recessed portion) 200 surrounded by a reflector 103 made of a reflective light reflecting resin composition ( Figure (C)).

  An optical semiconductor device using the optical semiconductor element mounting substrate of the present invention includes, for example, an optical semiconductor element mounting substrate of the present invention, an optical semiconductor element mounted on the bottom surface of the recess of the optical semiconductor element mounting substrate, And a phosphor-containing transparent sealing resin layer formed in the recess so as to cover the optical semiconductor element. FIG. 3A and FIG. 3B are side sectional views showing an embodiment of the optical semiconductor device of the present invention. More specifically, in the optical semiconductor device shown in FIG. 3, the optical semiconductor element 100 is mounted at a predetermined position on the bottom of the optical semiconductor element mounting region (concave portion) 200 of the optical semiconductor element mounting substrate 110 of the present invention. The optical semiconductor element 100 and the metal wiring 105 are electrically connected by a known method such as a bonding wire 102 or a solder bump 107, and the optical semiconductor element 100 is covered with a transparent sealing resin 101 containing a known phosphor 106. ing.

  EXAMPLES Hereinafter, although an Example explains this invention in full detail, this invention is not limited to these.

<Preparation of thermosetting light reflecting resin composition>
(Examples 1 to 3 and Comparative Examples 1 and 2)
The materials shown in Table 1 below were blended, mixed thoroughly by a mixer, melt-kneaded by a mixing roll, cooled to room temperature, pulverized, and heat-cured in Examples 1 to 3 and Comparative Examples 1 and 2. The resin composition for reflective light reflection was produced.

<Light reflectivity test>
The light reflecting resin compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were transfer molded under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds, and then post-cured at 150 ° C. for 2 hours. As a result, a test piece having a thickness of 1.0 mm was produced. Subsequently, the light reflectance in the wavelength of 350-800 nm of each produced test piece was measured with the integrating sphere type spectrophotometer V-750 type (made by JASCO Corporation). The results are shown in Table 1 below.

<Bali evaluation>
The light reflecting resin compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were poured from a pot into a mold provided with a slit having a depth of 75, 50, 30, 20, 10, and 2 μm, respectively, and the light reflection was performed. After curing in the same manner as the test piece of the property test, the length of the burrs of the obtained cured product (the resin composition cured by flowing into each slit) was measured with a caliper. The case where the burr length in each slit was all less than 2 mm was good, and the case where there was a burr of 2 mm or more was evaluated as NG. The results are shown in Table 1 below.

Note:
(1) The unit of the amount is all parts by weight.
(2) Details of each component are as follows.
TEPIC-S: Triglycidyl isocyanurate (epoxy equivalent 100, manufactured by Nissan Chemical Co., Ltd.)
HHPA: Hexahydrophthalic anhydride (manufactured by Nippon Nippon Chemical Co., Ltd., Ricacid HH, melting point 35 ° C.)
C3CIC acid: 1,3,5-tris (3-carboxypropyl) isocyanurate (manufactured by Shikoku Chemicals)
Hysilicone PX-4ET: Tetra-n-butylphosphonium-o, o-diethyl phosphorodithioate (manufactured by Nippon Chemical Industry Co., Ltd.)
FB-301: fused silica (average particle size 5.8 μm, manufactured by Denki Kagaku Kogyo Co., Ltd.)
AO-802: Alumina (average particle size of 1 μm or less, manufactured by Admatex)
Glass Bubbles S60HS: Borosilicate glass (average particle size of 20 μm or less, manufactured by Sumitomo 3M)
SH6040: Epoxysilane (Toray Dow Corning)
HW-E: Montanate ester (manufactured by Clariant)
Jutonix 420: alkyl polyether (manufactured by Toyo Petrolite)
(3) “Before / after roll temperature (° C.)” indicates each temperature at the front roll and the rear roll during kneading with two rolls.

  As shown in Table 1, the thermosetting light reflecting resin composition according to the present invention is excellent in light reflecting properties and can reduce burrs.

<Tablet molding test>
The resin composition prepared in each example and each comparative example was poured into a tablet molding die, and the tablet was pressed by pressurizing at room temperature (25 ° C.), 5 MPa, 10 MPa, and 30 MPa for 3 seconds. Molded. At the time of molding, an alumina mold composed of a die 501 as shown in FIG. 5 and an upper punch 502 and a lower punch 503 is used, and the surfaces of the die and the punch that come into contact with the resin composition 504 are made of cemented carbide. The coated one was used.

About each tablet produced as mentioned above, adhesion of the resin composition to the wrinkle surface at the time of molding, the destruction of the tablet accompanying it, and the crack of the tablet were evaluated. The evaluation results are shown in Table 2.

Note:
(1) Evaluation criteria for adhesion of the resin composition to the surface of the ridge or damage accompanying it
○: Sticking to the surface of the wrinkles cannot be confirmed by visual inspection, or there is no damage caused by it.
X: Sticking on the surface of the wrinkle is recognized visually, or damage by it is recognized.
(2) Evaluation criteria for tablet cracks
○: The tablet cannot be visually confirmed.
X: The crack of a tablet is recognized visually.

It is a figure which shows one Embodiment of the board | substrate for optical semiconductor element mounting of this invention, (a) is a perspective view, (b) is side sectional drawing.

It is the schematic explaining the manufacturing method of the board | substrate for optical semiconductor element mounting of this invention, (a)-(c) respond | corresponds to each process in the case of manufacturing a board | substrate by transfer mold molding. BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows one Embodiment of the optical semiconductor device of this invention, (a) And (b) is side sectional drawing which shows the structure of an apparatus typically, respectively. It is side surface sectional drawing which shows a general SMD type LED (optical semiconductor device). It is typical sectional drawing which shows the structure of the metal mold | die used at the time of tablet shaping | molding in an Example.

Explanation of symbols

100 ... Optical semiconductor element (LED element)
101... Transparent sealing resin 102... Bonding wire 103... Reflector (thermosetting light reflecting resin composition)
104... Ni / Ag plating 105... Metal wiring 106... Phosphor 107... Solder bump 110. ..Optical semiconductor element mounting area (concave)
300 ... Resin injection port 301 ... Mold 400 ... LED element 401 ... Bonding wire 402 ... Transparent sealing resin 403 ... Reflector 404... Lead 405... Phosphor 406... Die bond material 500... Mold 501 for tablet molding 501. ... Shimojo 504 ... Tablet (thermosetting resin composition for light reflection)
505 ... Deposits

Claims (8)

In the resin composition containing (A) an epoxy resin, (B) a curing agent, (C) an inorganic filler, and (D) a white pigment, the (B) curing agent is 1,3,5-tris (3- Carboxypropyl) isocyanurate and an acid anhydride having a melting point of 35 ° C. or higher, light reflectance at a wavelength of 800 nm to 350 nm after curing is 90% or more, and at room temperature (0 to 35 ° C.) before curing. A thermosetting light reflecting resin composition characterized by being capable of being pressure-molded.   The inorganic filler (C) is selected from the group consisting of silica, alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, barium carbonate 1 The thermosetting light-reflecting resin composition according to claim 1, comprising at least seeds. The said (D) white pigment contains 1 or more types chosen from the group which consists of an alumina, magnesium oxide, antimony oxide, a titanium oxide, a zirconium oxide, and an inorganic hollow particle, The Claim 1 or 2 characterized by the above-mentioned. Thermosetting light reflecting resin composition. The average particle diameter of said (D) white pigment exists in the range of 1-50 micrometers, The thermosetting light-reflective resin composition of any one of Claims 1-3 characterized by the above-mentioned. Wherein the inorganic filler (C) (D) the total amount of the white pigment, relative to the entire resin composition, according to claim 1-4, characterized in that in the range of 10 vol% to 85 vol% The thermosetting resin composition for light reflection according to any one of the above items. An optical semiconductor element mounting substrate recess to serve as the optical semiconductor element mounting region is formed of one or more inner peripheral side surface of at least the recess thermosetting according to any one of claims 1 to 5 A substrate for mounting an optical semiconductor element, comprising a resin composition for reflecting light. A method for manufacturing an optical semiconductor element mounting substrate recess to serve as the optical semiconductor element mounting region is formed at least one, at least the recess, thermoset as claimed in any one of claims 1 to 5 A method for producing a substrate for mounting an optical semiconductor, wherein the optical semiconductor mounting substrate is formed by transfer molding using a resin composition for light reflection. An optical semiconductor element mounting substrate according to claim 6 or an optical semiconductor element mounting substrate manufactured by the manufacturing method according to claim 7 ;
An optical semiconductor element mounted on the bottom of the recess of the optical semiconductor element mounting substrate;
A phosphor-containing transparent sealing resin layer formed in the recess so as to cover the optical semiconductor element;
An optical semiconductor device comprising:

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