JP2008144127A - Thermosetting resin composition for light reflection, photosemiconductor element-loading substrate using the same, photosemiconductor device, and manufacturing process for the articles - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition for light reflection having high reflectance of from visible light to near ultraviolet light after curing, excellent heat deterioration resistance and tablet moldability as well as less molding flash upon transfer molding, and to provide a photosemiconductor element-loading substrate using the resin composition, a photosemiconductor device and manufacturing processes for the articles. <P>SOLUTION: This thermosetting resin composition comprises (A) an epoxy resin, (B) a curing agent, (C) a curing accelerator, (D) an inorganic filler, (E) a white pigment, and (F) a coupling agent. When a transfer molding using the resin composition is performed under a condition in which a molding temperature is 100-200°C, molding pressure is ≤20 MPa, and a molding period of time is 60-120 seconds, a length of the molding flash is ≤5 mm, as well as the light reflectance at a wavelength of 350-800 nm after curing is ≥80%. The photosemiconductor element-loading substrate using the resin composition, the photosemiconductor device and these manufacturing processes are also disclosed. <P>COPYRIGHT: (C)2008,JPO&INPIT

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, an optical semiconductor element mounting substrate using the resin composition, light The present invention relates to a semiconductor device and a manufacturing method thereof.

An optical semiconductor device in which an optical semiconductor element such as an LED (Light Emitting Diode) and a phosphor are combined has advantages such as high energy efficiency and long life. Therefore, an outdoor display, a portable liquid crystal backlight, and an in-vehicle application. The demand is expanding. As a result, the brightness of LED devices has increased, and there has been a problem of heat resistance degradation and light resistance degradation of materials due to an increase in junction temperature due to an increase in the amount of heat generated by the element or a direct increase in light energy. Patent Document 1 discloses a substrate for mounting an optical semiconductor element that is excellent in light reflection characteristics after a heat resistance test.
JP 2006-140207 A

  However, when an optical semiconductor element mounting substrate is manufactured by transfer molding using the thermosetting light reflecting resin composition disclosed in Patent Document 1, the composition is placed in the gap between the upper mold and the lower mold of the mold. There was a problem that exudation and resin burr were likely to occur. When a burr | flash generate | occur | produces, a burr | bulb will protrude to the opening part (concave part) of an optical semiconductor element mounting area | region, and will become an obstacle at the time of mounting an optical semiconductor element. Further, even if the optical semiconductor element can be mounted, it becomes an obstacle when the optical semiconductor element and the metal wiring are electrically connected by a known method such as a bonding wire. When such a failure occurs, a step of removing burrs is essential in the manufacturing process of the substrate for mounting an optical semiconductor element, resulting in a loss of cost and manufacturing time.

  The present invention has been made in view of the above, and after curing, thermosetting which has high reflectivity from visible light to near ultraviolet light, is excellent in heat deterioration resistance and tablet moldability, and hardly generates burrs during transfer molding. An object of the present invention is to provide a resin composition for reflective light reflection, a substrate for mounting an optical semiconductor element using the resin composition, an optical semiconductor device, and a manufacturing method thereof.

  That is, the present invention is characterized by the following items (1) to (16).

  (1) Thermosetting light reflecting resin containing (A) epoxy resin, (B) curing agent, (C) curing accelerator, (D) inorganic filler, (E) white pigment and (F) coupling agent The composition has a molding temperature of 100 ° C. to 200 ° C., a molding pressure of 20 MPa or less, a burr length generated when transfer molding is performed for 60 to 120 seconds, and a wavelength of 350 nm to 350 nm after thermosetting. A thermosetting light reflecting resin composition, wherein the light reflectance at 800 nm is 80% or more.

  (2) As said (A) epoxy resin, at least (A ') epoxy resin and (B') hardening | curing agent are knead | mixed, and the viscosity in 100-150 degreeC is the range of 100-2500 mPa * s (G ) The thermosetting light reflecting resin composition as described in (1) above, wherein an oligomer is used.

  (3) The (B) curing agent capable of reacting with the epoxy group with respect to 1 equivalent of the epoxy group in the (A) epoxy resin, wherein the blending ratio of the (A) epoxy resin and the (B) curing agent is The thermosetting light-reflecting resin composition as described in (1) or (2) above, wherein the ratio is such that the active groups therein are 0.5 to 0.7 equivalents.

  (4) The thermosetting light reflecting resin as described in any one of (1) to (3) above, further comprising (H) a thickener as a nanoparticle filler having a center particle diameter of 1 nm to 1000 nm. Composition.

  (5) The (D) inorganic filler 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 according to any one of the above (1) to (4), which is at least one selected from the above.

  (6) The (E) white pigment is at least one selected from the group consisting of alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, and inorganic hollow particles. ) To (5) The thermosetting resin composition for light reflection.

  (7) The thermosetting light reflecting resin composition as described in any one of (1) to (6) above, wherein the center particle diameter of the white pigment (E) is in the range of 0.1 to 50 μm. object.

  (8) The above (1), wherein the blended amount of (D) inorganic filler and (E) white pigment is in the range of 10% by volume to 85% by volume with respect to the entire resin composition. The thermosetting light reflecting resin composition according to any one of to (7).

  (9) The resin composition for thermosetting light reflection according to any one of (1) to (8) above, wherein the resin composition is aged at 0 to 30 ° C. for 1 to 72 hours. .

  (10) Any of (1) to (9) above, wherein the components (A) to (F) are kneaded under conditions of a kneading temperature of 20 to 100 ° C. and a kneading time of 10 to 30 minutes. 2. A thermosetting light reflecting resin composition as described in 1. above.

  (11) A method for producing the thermosetting light reflecting resin composition according to any one of (1) to (10) above, wherein after kneading the components (A) to (F), 0 to A method for producing a thermosetting light reflecting resin composition, comprising a step of heat aging at 30 ° C for 1 to 72 hours.

  (12) The method for producing a thermosetting light reflecting resin composition as described in (11) above, wherein the kneading is performed under conditions of a kneading temperature of 20 to 100 ° C. and a kneading time of 10 to 30 minutes.

  (13) An optical semiconductor element mounting substrate comprising the thermosetting light reflecting resin composition according to any one of (1) to (10).

  (14) An optical semiconductor element mounting substrate in which at least one recess serving as an optical semiconductor element mounting region is formed, and at least an inner peripheral side surface of the recess is any one of the above (1) to (10). A substrate for mounting an optical semiconductor element, comprising: a thermosetting resin composition for light reflection.

  (15) A method for manufacturing an optical semiconductor element mounting substrate in which one or more recesses to be an optical semiconductor element mounting region are formed, wherein at least the recesses are any one of the above (1) to (10). A method for producing a substrate for mounting an optical semiconductor, which comprises forming the substrate by transfer molding using the thermosetting resin composition for light reflection.

  (16) An optical semiconductor element mounting substrate described in (13) or (14) or an optical semiconductor element mounting substrate manufactured by the manufacturing method described in (15), and the optical semiconductor element mounting substrate. An optical semiconductor device comprising at least an optical semiconductor element mounted on a bottom surface of a recess, and a phosphor-containing transparent sealing resin layer formed in the recess so as to cover the optical semiconductor element.

  According to the present invention, after curing, a thermosetting light reflecting resin composition having high reflectivity from visible light to near ultraviolet light, excellent in heat deterioration resistance and tablet moldability, and less likely to cause burrs during transfer molding, and It becomes possible to provide a substrate for mounting an optical semiconductor element, an optical semiconductor device, and a manufacturing method thereof using the resin composition.

  Embodiments of the present invention will be described below.

  The thermosetting light reflecting resin composition of the present invention comprises (A) an epoxy resin, (B) a curing agent, (C) a curing accelerator, (D) an inorganic filler, (E) a white pigment, and (F) a cup. It contains a ring agent.

  As said (A) epoxy resin, what is generally used by the epoxy resin molding material for electronic component sealing can be used, Although it does not specifically limit, For example, a phenol novolak type epoxy resin, an ortho cresol novolak type epoxy resin Obtained by epoxidizing a novolak resin of phenols and aldehydes such as bisphenol A, bisphenol A, bisphenol F, bisphenol S, diglycidiethers such as alkyl-substituted biphenols, polyamines such as diaminodiphenylmethane, isocyanuric acid and epichlorohydrin Glycidylamine type epoxy resins, linear aliphatic epoxy resins obtained by oxidizing olefinic bonds with peracids such as peracetic acid, and alicyclic epoxy resins, etc., either alone or in combination of two or more. GoodMoreover, it is preferable that the epoxy resin to be used is relatively uncolored, and examples of such an epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and diglycidyl isocyanate. Examples thereof include nurate and triglycidyl isocyanurate.

  Moreover, as said (A) epoxy resin, (A ') epoxy resin and (B') hardening | curing agent are further mix | blended with (C ') hardening accelerator as needed, and also the viscosity in 100-150 degreeC. It is preferable to use (G) an oligomer having a range of 100 to 2500 mPa · s. The (A ′) epoxy resin, the (B ′) curing agent, and the (C ′) curing accelerator are the (A) epoxy resin, (B) curing agent, and (C) curing accelerator in the present invention. Similar ones can be used.

  For example, the oligomer (G) can react (A ′) an epoxy resin and (B ′) a curing agent with the epoxy group with respect to 1 equivalent of the epoxy group in the (A ′) epoxy resin. B ′) It can be obtained by blending so that the active group (acid anhydride group or hydroxyl group) in the curing agent is 0.3 equivalent or less, and kneading until it becomes a clay, preferably further, clay The composition is aged at a temperature in the range of 25-60 ° C for 1-6 hours. Moreover, when mix | blending (C ') hardening accelerator, it is 0.005-0.05 weight part with respect to 100 weight part of total of (A') epoxy resin and (B ') hardening | curing agent. Blend. The (G) oligomer thus produced preferably has a viscosity at 100 to 150 ° C. in the range of 100 to 2500 mPa · s from the viewpoint of suppressing the occurrence of burrs in the resin composition of the present invention. The viscosity is more preferably in the range of 100 to 2500 mPa · s. (G) If the viscosity of the oligomer is less than 100 mPa · s, burrs are likely to occur during transfer molding, and if it exceeds 2500 mPa · s, the fluidity during molding is lowered and the moldability is poor. In addition, the oligomer (G) can be pulverized until the particle size becomes 1 mm or less, and when stored in an environment at a temperature of 0 ° C. or less, the increase in viscosity can be suppressed or stopped. As for the pulverization method, any known method such as using a ceramic mortar may be used.

  As said (B) hardening | curing agent, if it reacts with an epoxy resin, it can be used without a restriction | limiting especially, However, The thing without a coloring is preferable. Specifically, acid anhydride curing agents, isocyanuric acid derivatives, phenolic curing agents, and the like can be used. Examples of the acid anhydride curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, glutaric anhydride. Acid, dimethylglutaric anhydride, diethylglutaric anhydride, succinic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride and the like. Examples of isocyanuric acid derivatives include 1,3,5-tris (1-carboxyl Methyl) isocyanurate, 1,3,5-tris (2-carboxyethyl) isocyanurate, 1,3,5-tris (3-carboxypropyl) isocyanurate, 1,3-bis (2-carboxyethyl) isocyanurate These can be used alone or in combination of two or more And it may be. Among these curing agents, phthalic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, dimethylglutaric anhydride, anhydrous Diethyl glutaric acid and 1,3,5-tris (3-carboxypropyl) isocyanurate are preferably used. The (B) curing agent preferably has a molecular weight of about 100 to 400, and is preferably colorless or light yellow.

  The blending ratio of (A) epoxy resin (or (G) oligomer) and (B) curing agent is such that (A) 1 equivalent of epoxy group in epoxy resin can react with the epoxy group (B) The ratio is preferably such that the active group (acid anhydride group or hydroxyl group) in the curing agent is 0.5 to 0.7 equivalent, and 0.6 to 0.7 equivalent. Is more preferable. When the active group is less than 0.5 equivalent, the curing rate of the epoxy resin composition is slowed, the glass transition temperature of the resulting cured product is low, and sufficient elastic modulus may not be obtained, On the other hand, when the above active group exceeds 0.7 equivalent, the strength after curing may decrease (when (G) oligomer is used alone or (G) oligomer and (A) epoxy resin are used in combination) The equivalent number of (B) curing agent in (G) is (G) The total amount of epoxy groups contained in each of (A ′) epoxy resin and (A) epoxy resin contained in the oligomer is 1 equivalent, B ′) (B) The total number of active groups capable of reacting with the epoxy group contained in the curing agent is defined as the equivalent number).

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

  It is preferable that the content rate of the said (C) hardening accelerator is 0.01 to 8.0 weight% with respect to (A) epoxy resin, More preferably, it is 0.1 to 3.0 weight%. is there. When the content of the curing accelerator is less than 0.01% by weight, a sufficient curing accelerating effect may not be obtained. When the content exceeds 8.0% by weight, discoloration is observed in the resulting molded product. There is.

  The (D) inorganic filler is not particularly limited, and examples thereof include silica, alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, and barium carbonate. At least one selected from the group consisting of silica, alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide can be used from the viewpoint of thermal conductivity, light reflection characteristics, moldability, and flame retardancy. A mixture of two or more of aluminum hydroxide and magnesium hydroxide is preferred. In addition, the center particle diameter of the inorganic filler (D) is not particularly limited, but it is preferable to use one in the range of 1 to 100 μm so that packing with the white pigment is efficient.

  As the (E) white pigment, known pigments can be used, and are not particularly limited. For example, alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, inorganic hollow particles, and the like can be used. These may be used alone or in combination. Examples of the inorganic hollow particles include sodium silicate glass, aluminum silicate glass, borosilicate soda glass, and shirasu. (E) As for the particle size of a white pigment, it is preferable that a center particle size exists in the range of 0.1-50 micrometers. If the center particle size is less than 0.1 μm, the particles tend to aggregate and the dispersibility tends to deteriorate. If it exceeds 50 μm, the light reflection characteristics of the cured product may not be sufficiently obtained.

  Although the total compounding quantity of the said (D) inorganic filler and the said (E) white pigment is not specifically limited, It is preferable that it is the range of 10 volume%-85 volume% with respect to the whole resin composition. If this total blending amount is less than 10% by volume, the light reflection characteristics of the cured product may not be sufficiently obtained, and if it exceeds 85% by volume, the moldability of the resin composition is deteriorated, and the substrate for mounting an optical semiconductor Is difficult to manufacture.

  Although it does not specifically limit as said (F) coupling agent, For example, a silane coupling agent, a titanate coupling agent, etc. can be used, As an silane coupling agent, an epoxysilane type, an aminosilane type, for example Cationic silane, vinyl silane, acrylic silane, mercapto silane, and composites thereof can be used. (F) The type and processing conditions of the coupling agent are not particularly limited, but the blending amount of (F) coupling agent is preferably 5% by weight or less based on the resin composition.

  Moreover, you may add (H) thickener to the thermosetting light reflection resin composition of this invention for the purpose of melt viscosity adjustment. (H) Although it does not specifically limit as a thickener, For example, Reolosil CP-102 currently sold by Tokuyama Co., Ltd. can be used. The amount of (H) thickener added is preferably 0.15% by volume or less of the total volume of the resin composition. When (H) a thickener is added in an amount of more than 0.15% by volume, the fluidity at the time of melting of the resin composition is impaired and sufficient material strength may not be obtained after curing. The (H) thickener is preferably a nanoparticle filler having a center particle diameter of 1 nm to 1000 nm, and more preferably a nanoparticle filler having a center particle diameter of 10 nm to 1000 nm. . A filler having a center particle size of less than 1 nm is not preferred in terms of properties because the particles tend to aggregate and the dispersibility tends to decrease. On the other hand, if a filler larger than 1000 nm is added, burrs tend not to be reduced, which is not preferable in terms of characteristics.

  Moreover, you may add additives, such as antioxidant, a mold release agent, and an ion supplement agent, to the resin composition of this invention as needed.

  The thermosetting light-reflecting resin composition of the present invention containing the above components is desirably pressure-moldable at room temperature (0 to 30 ° C.) before thermosetting, and after thermosetting. The light reflectance at a wavelength of 350 nm to 800 nm is desirably 80% or more. The said press molding should just be able to perform shaping | molding on the conditions of about 5-50 MPa and about 1-5 second at room temperature, for example. Further, if the light reflectance is less than 80%, there is a tendency that it cannot sufficiently contribute to the improvement in luminance of the optical semiconductor device. A more preferable light reflectance is 90% or more.

  Further, the thermosetting light reflecting resin composition of the present invention can be obtained by uniformly dispersing and mixing the various components described above, and means and conditions thereof are not particularly limited. Examples include a method in which components of a predetermined blending amount are sufficiently uniformly stirred and mixed by a mixer or the like, then (melted) kneaded by a mixing roll, an extruder, a kneader, a roll, an extruder, etc., and further cooled and pulverized. . The conditions for (melting) kneading may be appropriately determined depending on the type and blending amount of the components, and are not particularly limited. It is more preferable to perform kneading (melting) for 10 to 30 minutes within the above range. When the (melting) kneading temperature is less than 15 ° C., it is difficult to (melt) kneading each component, and the dispersibility tends to decrease. When the temperature is higher than 100 ° C., the resin composition has a high temperature. There is a possibility that the molecular weight proceeds and the resin composition is cured. Further, if the (melting) kneading time is less than 5 minutes, there is a tendency that the generation of burrs cannot be effectively suppressed. If it is longer than 40 minutes, the resin composition has a higher molecular weight, and the resin The composition may be cured.

  Further, the thermosetting light reflecting resin composition of the present invention is preferably aged (aged) for the purpose of increasing the melt viscosity at the time of molding after blending and kneading the above-mentioned components. More preferably, aging at -30 ° C for 1 to 72 hours, more preferably thermal aging at 15 ° C to 30 ° C for 12 to 72 hours, and thermal aging at 25 ° C to 30 ° C for 24 to 72 hours. Is particularly preferred. When aging is performed for a short time of 1 hour or less, the generation of burrs tends not to be effectively suppressed. When aging is performed for longer than 72 hours, sufficient fluidity may not be ensured during transfer molding. In addition, when aging is performed at a temperature lower than 0 ° C., (C) the curing accelerator is inactivated, and the three-dimensional crosslinking reaction of the resin composition does not proceed sufficiently, and the viscosity at the time of melting may not increase. In the case of aging at a temperature higher than 30 ° C., the resin composition absorbs moisture, and mechanical properties such as strength and elastic modulus of the cured product tend to be deteriorated.

  Moreover, the thermosetting light reflecting resin composition of the present invention has a burr length of 5 mm or less when transfer molded under conditions of a molding temperature of 100 ° C. to 200 ° C., a molding pressure of 20 MPa or less, and 60 to 120 seconds. Is preferred. More preferably, it is 3 mm or less, Most preferably, it is 1 mm or less. If the burr length is more than 5 mm, the burr may protrude from the opening (recessed portion) of the optical semiconductor element mounting region and become an obstacle when mounting the optical semiconductor element, or the optical semiconductor element and the metal wiring may be bonded to the bonding wire. There is a possibility that it may become an obstacle in electrical connection by a known method.

  The substrate for mounting an optical semiconductor element of the present invention is formed using the thermosetting light reflecting resin composition of the present invention, and, for example, one or more recesses to be an optical semiconductor element mounting region are formed, At least the inner peripheral side surface of the recess is made of the thermosetting light reflecting resin composition of the present invention. One embodiment of a substrate for mounting an optical semiconductor element of the present invention is shown in FIG.

  Although the manufacturing method of the optical semiconductor element mounting substrate of this invention is not specifically limited, For example, the thermosetting light reflection resin composition of this invention can be shape | molded and manufactured by transfer molding. More specifically, for example, as shown in FIG. 2A, a metal wiring 105 is formed from a metal foil by a known method such as punching or etching, and then the metal wiring 105 is formed into a mold 301 having a predetermined shape. (FIG. 2 (b)), 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 temperature of 170 to 200 ° C. and a molding pressure. After thermosetting under conditions of 0.5 to 20 MPa for 60 to 120 seconds and after-curing temperature of 120 to 180 ° C. for 1 to 3 hours, the mold 301 is removed, and the cured thermosetting light reflecting resin composition. It can be manufactured by applying Ni / silver plating 104 by electroplating to a predetermined position of the optical semiconductor element mounting region (recessed portion) 200 surrounded by the reflector 103 made of (FIG. 2 (c)).

  The optical semiconductor device of the present invention is formed in the recess so as to cover the optical semiconductor element, the optical semiconductor element mounting substrate of the present invention, the optical semiconductor element mounted on the bottom surface of the recess of the optical semiconductor element mounting substrate. And a phosphor-containing transparent encapsulating resin layer. In FIG. 3, the optical semiconductor element 100 is mounted at a predetermined position on the bottom of the optical semiconductor element mounting region (recess) 200 of the optical semiconductor element mounting substrate 110 of the present invention, and the optical semiconductor element 100 and the metal wiring 105 are bonded to each other. One of the optical semiconductor devices of the present invention, which is electrically connected by a known method such as a 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. An embodiment is shown.

  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 1-11, Comparative Examples 1-8)
Each material is blended according to the blending table shown in Table 1 and Table 2, sufficiently kneaded with a mixer, then melt-kneaded under a predetermined condition with a mixing roll, subjected to heat aging as necessary, cooled and ground, and then carried out. Thermosetting light reflecting resin compositions of Examples 1 to 11 and Comparative Examples 1 to 8 were prepared. In addition, the unit of the compounding quantity of each component in a table | surface is a weight part, and a blank represents no compounding or no process. Moreover, Examples 1-5 are the methods which use specific (G) oligomer, respectively; (A) The range of 0.5-0.7 equivalent of the active group in the hardening | curing agent with respect to 1 equivalent of epoxy groups in an epoxy resin (H) A method of adding nanofiller as a thickener; a method of thermally aging the composition under predetermined conditions; and a method of adjusting melt kneading conditions (kneading time from 15 minutes to 30 minutes) were applied. Examples 6 to 11 are cases in which any two of the above methods are used in combination. The oligomers used in Examples 1, 6, 7 and 9 were prepared as follows, and had a viscosity at 100 ° C. of 1000 mPa · s.

(Oligomer production method)
Each material was blended according to the blending table shown in Table 1 (0.1 equivalent of acid anhydride group with respect to 1 equivalent of epoxy group), melt-kneaded at 25 ° C. for 10 minutes with a mixing roll, and then obtained clay The composition was heat aged at a temperature of 55 ° C. for 4 hours. Subsequently, it grind | pulverized until the particle size became 1 mm or less using the earthenware mortar of 300 mm in diameter, and preserve | saved in the environment of temperature 0 degrees C or less.

<Evaluation of Thermosetting Light Reflecting Resin Composition>
The resin compositions of each Example and each Comparative Example were evaluated by the following various characteristic tests. The results are shown in Tables 1 and 2.

(Light reflectance)
The resin composition of each example and each comparative example was formed by transfer molding under conditions of a molding die 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 to obtain a thickness of 1 A test piece of 0.0 mm was produced. Next, the light reflectance at a wavelength of 400 nm was measured with an integrating sphere type spectrophotometer V-750 type (manufactured by JASCO Corporation), and the light reflectance of each test piece was evaluated according to the following evaluation criteria.
Evaluation criteria ○: Light reflectance of 80% or more at a light wavelength of 400 nm Δ: Light reflectance of 70% or more and less than 80% at a light wavelength of 400 nm ×: Light reflectance of less than 70% at a light wavelength of 400 nm

(Bali evaluation)
The light reflecting resin compositions of Examples and Comparative Examples were cast from a pot into a mold provided with slits having a depth of 75, 50, 30, 20, 10, and 2 μm, respectively. Thereafter, the maximum value of the length of the resin burr generated by flowing in the gap between the upper mold and the lower mold of the mold was determined with calipers. A schematic diagram of the mold for measuring burrs and the resulting resin burrs is shown in FIG. In addition, the case where the maximum value of the burr length was less than 5 mm was good, and the case where it was 5 mm or more was judged as NG. The evaluation results are shown in Table 1. The evaluation criteria are as follows.
Evaluation criteria A: Burr length less than 3 mm B: Burr length less than 5 mm X: Maximum burr length is 5 mm or more

(Wire bonding property)
Using the resin compositions of the examples and comparative examples, a substrate for mounting an optical semiconductor element was manufactured according to the procedure of FIG. 2 under the same molding and curing conditions as the test piece prepared for light reflectance evaluation. Next, after mounting the semiconductor element in the optical semiconductor element mounting region (recessed portion) of the substrate, the optical semiconductor element and the wiring of the substrate are connected to a wire bonder (HW22U-H, manufactured by Kyushu Matsushita Electric Co., Ltd., trade name) and a diameter of 28 μm. Using the bonding wire, wire bonding was performed and electrical connection was made. The substrate heating temperature during wire bonding was 180 ° C. Next, the tensile strength of the gold wire bonded by wire bonding was measured using a pull tester PTR-01 (trade name, manufactured by Reska Co., Ltd.), and the wire bonding property was evaluated according to the following evaluation criteria.
Evaluation criteria A: 10 g or more ○: 4 g or more and less than 10 g Δ: Less than 4 g ×: Bonding not possible

＊１：トリグリシジルイソシアヌレート
（エポキシ当量100、日産化学社製、商品名TEPIC-S）
＊２：ヘキサヒドロ無水フタル酸（和光純薬社製）
＊３：テトラヒドロ無水フタル酸（アルドリッチ社製）
＊４：メチルヘキサヒドロ無水フタル酸（日立化成工業社製、商品名HN5500）
＊５：日本化学工業社製、商品名PX-4ET）
＊６：トリメトキシエポキシシラン（東レダウコーニング社製、商品名A-187）
＊７：脂肪酸エステル（クラリアント社製、商品名 ヘキストワックスE）
＊８：脂肪族エーテル（東洋ペトロライト社製、商品名 ユニトックス420）
＊９：溶融シリカ（電気化学工業社製、商品名FB-301）
＊１０：溶融シリカ（電気化学工業社製、商品名FB-950）
＊１１：溶融シリカ（アドマテックス社製、商品名SO-25R）
＊１２：中空粒子（住友３M社製、商品名S60-HS）
＊１３：アルミナ（アドマテックス社製、商品名AO-25R）
＊１４：ナノシリカ（トクヤマ社製、商品名 レオロシールCP-102）

* 1: Triglycidyl isocyanurate (epoxy equivalent 100, manufactured by Nissan Chemical Co., Ltd., trade name TEPIC-S)
* 2: Hexahydrophthalic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.)
* 3: Tetrahydrophthalic anhydride (manufactured by Aldrich)
* 4: Methylhexahydrophthalic anhydride (manufactured by Hitachi Chemical Co., Ltd., trade name HN5500)
* 5: Product name PX-4ET, manufactured by Nippon Chemical Industry Co., Ltd.
* 6: Trimethoxyepoxysilane (Toray Dow Corning, product name A-187)
* 7: Fatty acid ester (trade name Hoechst Wax E, manufactured by Clariant)
* 8: Aliphatic ether (Toyo Petrolite, product name Unitox 420)
* 9: Fused silica (trade name FB-301, manufactured by Denki Kagaku Kogyo Co., Ltd.)
* 10: Fused silica (trade name FB-950, manufactured by Denki Kagaku Kogyo Co., Ltd.)
* 11: Fused silica (manufactured by Admatechs, trade name SO-25R)
* 12: Hollow particles (Sumitomo 3M, trade name S60-HS)
* 13: Alumina (manufactured by Admatechs, trade name AO-25R)
* 14: Nanosilica (product name: Leoroseal CP-102, manufactured by Tokuyama Corporation)

  As shown in Tables 1 and 2, the curable light reflecting resin compositions of the examples are excellent in light reflecting properties, can suppress generation of burrs due to transfer molding, and improve wire bonding properties. Is possible. As a result, when manufacturing an optical semiconductor element mounting substrate or an optical semiconductor device using the curable light reflecting resin composition of the present invention, a step of removing burrs is not required, and productivity such as cost and manufacturing time is improved. This is very advantageous.

It is the perspective view and sectional drawing which show one Embodiment of the board | substrate for optical semiconductor element mounting of this invention. It is the schematic which shows one Embodiment of the process of manufacturing the board | substrate for optical semiconductor element mounting of this invention. It is sectional drawing which shows one Embodiment of the optical semiconductor device of this invention. It is the schematic diagram of the metal mold | die for a burr | flash measurement and resin burr | flash used in the Example.

Explanation of symbols

100 ... Optical semiconductor element (LED element)
101... Transparent sealing resin 102... Bonding wire 103... Reflector 104... Ni / Ag plating 105. Body 107... Solder bump 110... Optical semiconductor element mounting substrate 200... Optical semiconductor element mounting area (concave portion)
300... Resin injection port 301... Mold 400...
401 ...... Burr measurement mold (lower mold)
402... Resin injection port 403... Cavity 404... Slit (75 .mu.m)
405 ... Slit (50μm)
406 ... Slit (30μm)
407 ... Slit (20μm)
408 ... Slit (10μm)
409 ... Slit (2μm)
410 ... Resin burr

Claims (16)

  A thermosetting light reflecting resin composition comprising (A) an epoxy resin, (B) a curing agent, (C) a curing accelerator, (D) an inorganic filler, (E) a white pigment and (F) a coupling agent. The burr length generated when transfer molding is performed under conditions of a molding temperature of 100 ° C. to 200 ° C., a molding pressure of 20 MPa or less, and 60 to 120 seconds, and light at a wavelength of 350 nm to 800 nm after thermosetting. A thermosetting light reflecting resin composition having a reflectance of 80% or more.   (G) Oligomer having (A) epoxy resin and (B ′) curing agent kneaded as (A) epoxy resin and having a viscosity at 100 to 150 ° C. in the range of 100 to 2500 mPa · s. The thermosetting light reflecting resin composition according to claim 1, wherein the thermosetting light reflecting resin composition is used.   The activity in the (B) curing agent is such that the blending ratio of the (A) epoxy resin and the (B) curing agent can react with the epoxy group with respect to 1 equivalent of the epoxy group in the (A) epoxy resin. The thermosetting light reflecting resin composition according to claim 1 or 2, wherein the ratio is such that the group is 0.5 to 0.7 equivalents.   The thermosetting light reflecting resin composition according to any one of claims 1 to 3, further comprising a nanoparticle filler having a center particle diameter of 1 nm to 1000 nm as (H) a thickener.   The (D) inorganic filler is at least 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. It is 1 or more types, The thermosetting light reflecting resin composition in any one of Claims 1-4 characterized by the above-mentioned.   6. The (E) white pigment is at least one 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 the above.   The center particle size of the (E) white pigment is in the range of 0.1 to 50 µm, and the thermosetting light reflecting resin composition according to any one of claims 1 to 6.   The amount of (D) inorganic filler and (E) white pigment combined is in the range of 10% by volume to 85% by volume with respect to the entire resin composition. The thermosetting light reflecting resin composition according to claim 1.   The thermosetting light reflecting resin composition according to any one of claims 1 to 8, wherein the resin composition is aged at 0 to 30 ° C for 1 to 72 hours.   The thermosetting property according to any one of claims 1 to 9, wherein the components (A) to (F) are kneaded under conditions of a kneading temperature of 20 to 100 ° C and a kneading time of 10 to 30 minutes. A resin composition for light reflection.   It is a method of manufacturing the resin composition for thermosetting light reflections in any one of Claims 1-10, Comprising: After knead | mixing the said (A)-(F) component, it is 1-72 at 0-30 degreeC. A method for producing a thermosetting light reflecting resin composition, comprising a step of heat aging over time.   The method for producing a thermosetting light reflecting resin composition according to claim 11, wherein the kneading is performed under conditions of a kneading temperature of 20 to 100 ° C and a kneading time of 10 to 30 minutes.   A substrate for mounting an optical semiconductor element, comprising the thermosetting light reflecting resin composition according to claim 1.   It is 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 a thermosetting for light reflection according to any one of claims 1 to 10. A substrate for mounting an optical semiconductor element, comprising an adhesive resin composition.   It is a manufacturing method of the optical semiconductor element mounting substrate in which one or more recessed parts used as an optical semiconductor element mounting area are formed, Comprising: At least the said recessed part is the thermosetting for light reflections in any one of Claims 1-10. A method for producing a substrate for mounting an optical semiconductor, characterized in that the substrate is formed by transfer molding using a functional resin composition. The substrate for mounting an optical semiconductor element according to claim 13 or 14, or the substrate for mounting an optical semiconductor element manufactured by the manufacturing method according to claim 15,
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 at least

Images