JP2013211361A - Optical semiconductor device - Google Patents

Abstract

An optical semiconductor device in which the quality is not easily lowered even when used in a harsh environment, the discoloration of an electrode can be suppressed, and the adhesion between a molded body and a member in contact with the molded body can be improved. I will provide a.
An optical semiconductor device according to the present invention includes a lead frame, an optical semiconductor element mounted on the lead frame, and a molded body disposed on the lead frame. The molded body 4 is obtained by curing a white curable composition for an optical semiconductor device. The white curable composition for a semiconductor device includes an epoxy compound having an epoxy group, an acid anhydride curing agent, titanium oxide, spherical silica, and crushed silica. The spherical silica has an average particle size of 5 μm or more and 100 μm or less.
[Selection] Figure 1

Description

  The present invention relates to a white curable composition for an optical semiconductor device that is suitably used to obtain a molded body disposed on a lead frame on which an optical semiconductor element is mounted in an optical semiconductor device. Moreover, this invention relates to the molded object for optical semiconductor devices and optical semiconductor device which used this white curable composition for optical semiconductor devices.

  An optical semiconductor device such as a light emitting diode (LED) device has low power consumption and long life. Moreover, the optical semiconductor device can be used even in a harsh environment. Accordingly, optical semiconductor devices are used in a wide range of applications such as mobile phone backlights, liquid crystal television backlights, automobile lamps, lighting fixtures, and signboards.

  When an optical semiconductor element (for example, an LED), which is a light emitting element used in an optical semiconductor device, is in direct contact with the atmosphere, the light emission characteristics of the optical semiconductor element rapidly deteriorate due to moisture in the atmosphere or floating dust. For this reason, the said optical semiconductor element is normally sealed with the sealing agent. In order to fill the sealing agent, a frame-shaped molded body is disposed on a lead frame on which the optical semiconductor element is mounted. The sealing agent is filled inside the frame-shaped molded body. The molded body is sometimes called a reflector or a housing.

  As an example of a composition for forming the molded article, Patent Document 1 below discloses a curable composition containing an epoxy resin, a curing agent, a curing catalyst, an inorganic filler, and a white pigment. The light diffuse reflectance at a light wavelength of 400 nm measured after leaving the cured product obtained by curing the curable composition for 500 hours under a high temperature condition of 150 ° C. is 80% or more. Moreover, in the said curable composition, the shear mold release force at the time of transfer molding is 200 KPa or less within 10 shots.

  In the Examples of Patent Document 1, fused spherical silica is used as the inorganic filler, and hollow particles and alumina are used as the white pigment. In the example of Document 1, titanium oxide is not used.

  Patent Document 2 below discloses a curable composition containing an epoxy resin, a curing agent, a curing accelerator, an inorganic filler, and a white pigment. In Patent Document 2, a light reflection layer having a plurality of through holes formed on a wiring member by transfer molding using a curable composition is formed on the wiring member, and one opening of the through hole is closed with the wiring member. A step of obtaining a molded body in which a plurality of recesses are formed, a step of disposing an optical semiconductor element in each of the recesses, and a sealing in the recess in which the semiconductor element is disposed so as to cover the surface of the light reflecting layer. A step of supplying a stop resin, and a step of curing the sealing resin after disposing a lens covering the recess in a state of being spaced from the surface of the light reflecting layer by interposing the sealing resin. And a method of manufacturing an optical semiconductor device comprising a step of dividing the molded body into the recesses to obtain a plurality of optical semiconductor devices.

  In the examples of Patent Document 2, a curable composition containing an epoxy resin, a curing agent, a curing accelerator, two types of fused spherical silica that is an inorganic filler, and titanium oxide that is a white pigment is described. ing.

JP 2009-141327 A JP2011-009519A

  When a molded body is produced using a conventional curable composition as described in Patent Documents 1 and 2 and an optical semiconductor device provided with the molded body is obtained, the optical semiconductor device is in a harsh environment. If exposed, the quality of the optical semiconductor device tends to deteriorate. Specifically, there is a problem that the PCT (pressure cooker test) characteristics of the optical semiconductor device are low.

  Further, in the optical semiconductor device, an electrode plated with silver may be formed on the back surface of the light emitting element in order to reflect light reaching the back side of the light emitting element. In an optical semiconductor device, the electrode may be discolored by a corrosive gas such as hydrogen sulfide gas or sulfurous acid gas present in the atmosphere. When the color of the electrode changes, the reflectance decreases, which causes a problem that the brightness of the light emitted from the light emitting element decreases.

  An object of the present invention is to reduce the quality even when an optical semiconductor device provided with a molded body using a white curable composition for an optical semiconductor device is used in a harsh environment. The white curable composition for optical semiconductor devices which can suppress discoloration and can improve the adhesion between the molded body and a member in contact with the molded body, and the white curable composition for optical semiconductor devices were used. It is providing the molded object for optical semiconductor devices.

  The object of the present invention is that the quality is hardly lowered even when used in a harsh environment, and further, the discoloration of the electrode can be suppressed, and the adhesion between the molded body and the member in contact with the molded body can be improved. An optical semiconductor device is provided.

  According to a wide aspect of the present invention, there is a white curable composition for an optical semiconductor device, an epoxy compound having an epoxy group, an acid anhydride curing agent, titanium oxide, spherical silica, and crushed silica. A white curable composition for optical semiconductor devices is provided, wherein the spherical silica has an average particle size of 5 μm or more and 100 μm or less.

  Moreover, according to the wide situation of this invention, the optical semiconductor device using the white curable composition for optical semiconductor devices mentioned above is provided.

  That is, according to a wide aspect of the present invention, a lead frame, an optical semiconductor element mounted on the lead frame, and a molded body disposed on the lead frame are provided, and the molded body is an optical semiconductor device. The white curable composition for optical semiconductor devices is obtained by curing the white curable composition for optical semiconductor devices, and the white curable composition for optical semiconductor devices is a white curable composition for optical semiconductor devices. Includes an epoxy compound having an epoxy group, an acid anhydride curing agent, titanium oxide, spherical silica, and crushed silica, and the spherical silica has an average particle size of 5 μm or more and 100 μm or less. Is provided.

  In this specification, both the invention relating to the above-described white curable composition for optical semiconductor devices and the invention relating to the above-described optical semiconductor device are disclosed.

  The aspect ratio of the crushed silica is preferably 1.5 or more and 20 or less. The average particle size of the crushed silica is preferably 1 μm or more and 30 μm or less. The titanium oxide is preferably rutile type titanium oxide.

  It is preferable that the epoxy compound does not have an aromatic skeleton, and the atoms constituting the epoxy compound are only three kinds of a carbon atom, an oxygen atom, and a hydrogen atom.

  The epoxy compound preferably has an alicyclic skeleton. The epoxy compound preferably contains an epoxy compound having an alicyclic skeleton and two carbon atoms of the epoxy group being carbon atoms of the alicyclic skeleton. The epoxy compound preferably contains an epoxy compound having an alicyclic skeleton, and two carbon atoms of the epoxy group are not carbon atoms of the alicyclic skeleton. The epoxy compound has an alicyclic skeleton, and two carbon atoms of the epoxy group are carbon atoms of the alicyclic skeleton, and an alicyclic skeleton and two carbons of the epoxy group It is preferable to contain both the epoxy compound whose atom is not a carbon atom of an alicyclic skeleton.

  The white curable composition for optical semiconductor devices according to the present invention is a white curable composition for optical semiconductor devices, which is used to obtain a molded body disposed on a lead frame on which an optical semiconductor element is mounted in an optical semiconductor device. It is preferable that it is an adhesive composition. In this case, the white curable composition for optical semiconductor devices according to the present invention obtains an individual molded body by dividing the molded body before division after obtaining the molded body before division in which a plurality of molded bodies are connected. Is preferably used for this purpose.

  The white curable composition for an optical semiconductor device according to the present invention is disposed on a lead frame on which an optical semiconductor element is mounted and on the side of the optical semiconductor element in the optical semiconductor device, and is emitted from the optical semiconductor element. It is preferable that the white curable composition for optical semiconductor devices used for obtaining a molded body having a light reflecting portion that reflects the reflected light.

  The molded object for optical semiconductor devices which concerns on this invention is obtained by hardening the white curable composition for optical semiconductor devices mentioned above.

  In the optical semiconductor device according to the present invention, the molded body is disposed on a side of the optical semiconductor element, and an inner surface of the molded body is a light reflecting portion that reflects light emitted from the optical semiconductor element. It is preferable.

  The white curable composition for optical semiconductor devices according to the present invention includes an epoxy compound having an epoxy group, an acid anhydride curing agent, titanium oxide, spherical silica, and crushed silica, and the average particle of the spherical silica. Since the diameter is not less than 5 μm and not more than 100 μm, the quality of the optical semiconductor device provided with the molded body using the white curable composition for optical semiconductor devices is hardly deteriorated even when used in a harsh environment. Discoloration of the electrodes in the apparatus can be suppressed. Furthermore, the adhesiveness between the molded body and the member in contact with the molded body can be improved.

  In the optical semiconductor device according to the present invention, the molded body is obtained by curing the white curable composition for an optical semiconductor device, so that the quality is hardly deteriorated even when used in a harsh environment. Discoloration can be suppressed. Furthermore, the adhesiveness between the molded body and the member in contact with the molded body can be improved.

1A and 1B are a cross-sectional view and a perspective view schematically showing an example of an optical semiconductor device including a molded body using a white curable composition for an optical semiconductor device according to an embodiment of the present invention. It is. FIG. 2 schematically illustrates an example of a pre-division optical semiconductor device component including a pre-division molded body in which a plurality of molded bodies using a white curable composition for an optical semiconductor device according to an embodiment of the present invention are connected. It is sectional drawing shown. FIG. 3 is a cross-sectional view schematically showing an example of a pre-division optical semiconductor device including a pre-division molded body in which a plurality of molded bodies using a white curable composition for an optical semiconductor device according to an embodiment of the present invention are connected. FIG.

  Hereinafter, the present invention will be described in detail.

(White curable composition for optical semiconductor devices)
The white curable composition for optical semiconductor devices according to the present invention is a white curable composition for optical semiconductor devices. The white curable composition for optical semiconductor devices according to the present invention includes an epoxy compound (A) having an epoxy group, a curing agent (B), titanium oxide (C), and a filler different from titanium oxide. . In the white curable composition for optical semiconductor devices according to the present invention, the filler different from titanium oxide is silica (D). The silica (D) includes spherical silica (D1) and crushed silica (D2). That is, the white curable composition for optical semiconductor devices according to the present invention includes both spherical silica (D1) and crushed silica (D2).

  In the white curable composition for optical semiconductor devices according to the present invention, the spherical silica (D1) has an average particle size of 5 μm or more and 100 μm or less.

  By adopting the above-described configuration in the white curable composition for an optical semiconductor device according to the present invention, the quality deteriorates even if the optical semiconductor device using the white curable composition for an optical semiconductor device is used in a harsh environment. It becomes difficult to do. Specifically, the PCT (pressure cooker test) characteristics in the optical semiconductor device can be enhanced. That is, when the optical semiconductor device is subjected to PCT, cracks are unlikely to occur in a member such as a sealant that is in contact with the molded body obtained by curing the curable composition, and the molded body and the member. Is less likely to be peeled off, and poor wiring connection is less likely to occur.

  Furthermore, by adopting the above-described configuration in the white curable composition for optical semiconductor devices according to the present invention, it is possible to suppress discoloration of the electrodes in the optical semiconductor device. In an optical semiconductor device, an electrode plated with silver may be formed on the back surface of the light emitting element in order to reflect light reaching the back side of the light emitting element. By adopting the above-described configuration in the white curable composition for optical semiconductor devices according to the present invention, in the optical semiconductor device, the electrode is discolored by corrosive gas such as hydrogen sulfide gas or sulfurous acid gas present in the atmosphere. Can be suppressed. As a result, a decrease in the reflectance of the electrode is suppressed, and the brightness of the light emitted from the light emitting element is kept high.

  Furthermore, by adopting the above-described configuration in the white curable composition for optical semiconductor devices according to the present invention, a molded body obtained by curing the curable composition, and a sealant in contact with the molded body And adhesion to members such as lead frames.

  Hereinafter, other details of each component contained in the white curable composition for optical semiconductor devices according to the present invention will be described.

[Epoxy compound (A)]
The said curable composition contains the said epoxy compound (A) so that it can harden | cure by provision of a heat | fever. The epoxy compound (A) has an epoxy group. By using the said epoxy compound (A) as a thermosetting compound, the heat resistance and insulation reliability of a molded object become high. As for the said epoxy compound (A), only 1 type may be used and 2 or more types may be used together.

  Specific examples of the epoxy compound (A) include bisphenol type epoxy compounds, novolak type epoxy compounds, glycidyl ester type epoxy compounds obtained by reacting polychloric acid compounds with epichlorohydrin, polyamine compounds and epichlorohydrides. Heterocycles such as glycidylamine type epoxy compounds, glycidyl ether type epoxy compounds, aliphatic epoxy compounds, hydrogenated aromatic epoxy compounds, epoxy compounds having an alicyclic skeleton, triglycidyl isocyanurate obtained by reacting with phosphorus And an epoxy compound of the formula. Examples of the polychloric acid compound include phthalic acid and dimer acid. Examples of the polyamine compound include diaminodiphenylmethane and isocyanuric acid.

  From the viewpoint of increasing the strength of the molded body and further improving the workability of the molded body, the epoxy compound (A) is at least one of an epoxy compound having an aromatic skeleton and an epoxy compound having an alicyclic skeleton. It is preferable to contain. The epoxy compound (A) may contain both an epoxy compound having an aromatic skeleton and an epoxy compound having an alicyclic skeleton.

  From the viewpoint of further enhancing the strength and heat resistance of the molded product, the epoxy compound (A) preferably contains an epoxy compound having an aromatic skeleton. As for the epoxy compound which has the said aromatic skeleton, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of further improving the adhesion between the sealant or the lead frame and the molded article, the epoxy compound (A) preferably contains an epoxy compound having an alicyclic skeleton. As for the epoxy compound which has the said alicyclic skeleton, only 1 type may be used and 2 or more types may be used together.

  Examples of the epoxy compound having an aromatic skeleton include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a cresol novolac type epoxy compound, a phenol novolac type epoxy compound, a polybasic acid compound having an aromatic skeleton, and epichlorohydrin, And a glycidyl ester type epoxy compound obtained by reacting glycidyl ether type epoxy compound having an aromatic skeleton.

  Specific examples of the epoxy compound having the alicyclic skeleton include 2- (3,4-epoxy) cyclohexyl-5,5-spiro- (3,4-epoxy) cyclohexane-m-dioxane, 3,4-epoxy. Cyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, dicyclopentadiene dioxide, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane, 1,2: 8,9-diepoxy limonene, ε -Caprolactone modified tetra (3,4-epoxycyclohexylmethyl) butanetetracarboxylate, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, water Bisphenol A type epoxy compound and hydrogenated bisphenol Lumpur F type epoxy compounds and the like.

  From the viewpoint of further suppressing deterioration of the quality of the optical semiconductor device due to use in a harsh environment and further suppressing discoloration of the electrode, the epoxy compound (A) preferably does not have an aromatic skeleton. . From the viewpoint of further suppressing the deterioration of the quality of the optical semiconductor device due to use in a harsh environment and further suppressing the discoloration of the electrode, the atoms constituting the epoxy compound (A) are carbon atoms, oxygen atoms and hydrogen. It is preferred that there are only three types of atoms. From the viewpoint of further suppressing the deterioration of the quality of the optical semiconductor device due to use in a harsh environment, and further suppressing the discoloration of the electrode, the epoxy compound (A) does not have an aromatic skeleton, and The atoms constituting the epoxy compound (A) are preferably only three kinds of carbon atom, oxygen atom and hydrogen atom.

  The epoxy compound (A) preferably has an alicyclic skeleton. That is, the epoxy compound (A) preferably does not have an aromatic skeleton and has an alicyclic skeleton. The use of an epoxy compound having an alicyclic skeleton further increases the dicing property of the molded product. Further, the optical semiconductor device is used under severe conditions, or the optical semiconductor device is subjected to thermal shock such as a cold cycle. However, the quality of the optical semiconductor device is difficult to deteriorate.

  The two carbon atoms of the epoxy group in the epoxy compound (A) may be an alicyclic skeleton carbon atom or may not be an alicyclic skeleton carbon atom. An epoxy group is called an alicyclic epoxy group when the two carbon atoms of the epoxy group are carbon atoms of an alicyclic skeleton.

  The epoxy compound (A) preferably includes an epoxy compound (A1) having an alicyclic skeleton and two carbon atoms of the epoxy group being carbon atoms of the alicyclic skeleton. The epoxy compound (A1) is an epoxy compound having an alicyclic epoxy group. The epoxy compound (A1) preferably has an epoxycyclohexyl group. As for the said epoxy compound (A1), only 1 type may be used and 2 or more types may be used together.

  In the total 100% by weight of the epoxy compound (A), the content of the epoxy compound (A1) is preferably 0.1% by weight or more, more preferably 1% by weight or more, still more preferably 5% by weight or more, particularly preferably. Is 10% by weight or more, most preferably 20% by weight or more and 100% by weight or less. The entire epoxy compound (A) may be the epoxy compound (A1). As for the said epoxy compound (A1), only 1 type may be used and 2 or more types may be used together.

  The epoxy compound (A) preferably includes an epoxy compound (A2) having an alicyclic skeleton and in which two carbon atoms of the epoxy group are not carbon atoms of the alicyclic skeleton. The epoxy compound (A2) is preferably an epoxy compound having no alicyclic epoxy group. The epoxy compound (A2) has an epoxy group at a site different from the alicyclic skeleton. The content of the epoxy compound (A2) in the total 100% by weight of the epoxy compound (A) is preferably 0.1% by weight or more, more preferably 1% by weight or more, still more preferably 5% by weight or more, particularly preferably. Is 10% by weight or more, most preferably 20% by weight or more and 100% by weight or less. The entire epoxy compound (A) may be the epoxy compound (A2). As for the said epoxy compound (A2), only 1 type may be used and 2 or more types may be used together.

  The total content of the epoxy compound (A1) and the epoxy compound (A2) is preferably 0.1% by weight or more, more preferably 1% by weight or more in the total 100% by weight of the epoxy compound (A). More preferably, it is 5% by weight or more, more preferably 10% by weight or more, still more preferably 20% by weight or more, particularly preferably 30% by weight or more, most preferably 50% by weight or more and 100% by weight or less. The entire epoxy compound (A) may be the epoxy compound (A1) and the epoxy compound (A2).

  The epoxy compound (A) has an alicyclic skeleton, the epoxy compound (A1) in which two carbon atoms of the epoxy group are carbon atoms of the alicyclic skeleton, an alicyclic skeleton, and It is preferable that the two carbon atoms of the epoxy group include both an epoxy compound (A2) that is not a carbon atom of the alicyclic skeleton. The combined use of the epoxy compound (A1) and the epoxy compound (A2) further improves the PCT resistance of the molded article.

  Examples of commercially available products of the epoxy compound (A1) include Celoxide 2021P, Celoxide 2081, Celoxide 3000, Epolide GT301, Epolide GT401 (manufactured by Daicel). Of these, Celoxide 2021P which is 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexenecarboxylate is preferable.

  As a commercial item of the said epoxy compound (A2), EHPE3150 (made by Daicel), ST-4000D (made by Nippon Steel Chemical Co., Ltd.), etc. are mentioned. Among these, EHPE3150 which is a 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of bis (2,3-epoxycyclopentyl) ether and 2,2-bis (hydroxymethyl) -1-butanol is preferable. By using EHPE3150, the heat resistance of the molded body is further increased.

  The epoxy equivalent of the epoxy compound is preferably 50 or more, more preferably 100 or more, preferably 500 or less, more preferably 300 or less, especially for the epoxy compound having the alicyclic skeleton. The epoxy equivalent of the epoxy compound having an alicyclic skeleton is particularly preferably 100 or more and 300 or less. When the epoxy equivalent is not less than the above lower limit and not more than the above upper limit, the adhesion between the molded body and a member such as a sealant or a lead frame in contact with the molded body is further enhanced.

  The compounding quantity of the said epoxy compound (A) is suitably adjusted so that it may harden | cure moderately by provision of heat, and is not specifically limited. In 100% by weight of the white curable composition for optical semiconductor devices, the content of the epoxy compound (A) is preferably 1% by weight or more, more preferably 3% by weight or more, still more preferably 5% by weight or more, preferably It is 99 weight% or less, More preferably, it is 95 weight% or less, More preferably, it is 80 weight% or less. When the content of the epoxy compound (A) is not less than the above lower limit, the curable composition is more effectively cured by heating. When the content of the epoxy compound (A) is not more than the above upper limit, the heat resistance of the molded product is further increased.

  When the epoxy compound (A1) and the epoxy compound (A2) are used in combination, the curable composition contains the epoxy compound (A1) and the epoxy compound (A2) in a weight ratio of 1: 1000. ~ 1000: 1, preferably 1: 100 to 100: 1, more preferably 1:20 to 20: 1, more preferably 1:10 to 10: 1. It is most preferable that it is contained at 1: 5 to 5: 1. When the weight ratio of the epoxy compound (A1) to the epoxy compound (A2) is within the above range, the dicing property of the molded article is further improved.

[Curing agent (B)]
The said white curable composition for optical semiconductor devices contains the said hardening | curing agent (B) so that it can harden | cure efficiently by provision of heat. The curing agent (B) cures the epoxy compound (A). The curing agent (B) is an acid anhydride curing agent. By using the acid anhydride curing agent, adhesion with a member such as a sealant or a lead frame that is in contact with the molded body is increased. Further, by using the acid anhydride curing agent, it is possible to maintain high curability and further suppress the molding unevenness of the molded body. As the acid anhydride curing agent, a known acid anhydride curing agent used as a curing agent for the epoxy compound (A) can be used. As for the said hardening | curing agent (B), only 1 type may be used and 2 or more types may be used together.

  As the acid anhydride curing agent, any of an acid anhydride having an aromatic skeleton and an acid anhydride having an alicyclic skeleton can be used.

  Preferred 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. And methylhexahydrophthalic anhydride and methyltetrahydrophthalic anhydride.

  The acid anhydride curing agent preferably does not have a double bond. Preferable acid anhydride curing agents having no double bond include hexahydrophthalic anhydride and methylhexahydrophthalic anhydride.

  The mixing ratio of the epoxy compound (A) and the curing agent (B) is not particularly limited. The content of the curing agent (B) is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, still more preferably 2 parts by weight or more, particularly preferably 100 parts by weight of the epoxy compound (A). Is 3 parts by weight or more, preferably 500 parts by weight or less, more preferably 300 parts by weight or less, and still more preferably 100 parts by weight or less.

  Moreover, in the said white curable composition for optical semiconductor devices, the equivalent ratio (epoxy equivalent: hardening | curing agent equivalent) of the epoxy equivalent of the said epoxy compound (A) whole and the hardening | curing agent equivalent of the said hardening | curing agent (B) is It is preferably 0.3: 1 to 2: 1, and more preferably 0.5: 1 to 1.5: 1. When the equivalent ratio (epoxy equivalent: curing agent equivalent) satisfies the above range, the heat resistance and weather resistance of the molded article are further enhanced.

(Titanium oxide (C))
Since the said white curable composition for optical semiconductor devices contains the said titanium oxide (C), the molded object with a high reflectance of light can be obtained. Further, by using the titanium oxide (C), it is possible to obtain a molded article having a high light reflectance as compared with the case of using only a filler different from the titanium oxide (C). As for the said titanium oxide (C), only 1 type may be used and 2 or more types may be used together.

  The titanium oxide (C) is preferably rutile titanium oxide or anatase titanium oxide. By using rutile-type titanium oxide, a molded article having further excellent heat resistance can be obtained, and the quality is hardly lowered even when the optical semiconductor device is used in a harsh environment. The anatase type titanium oxide has a lower hardness than the rutile type titanium oxide. For this reason, the moldability of the said curable composition becomes still higher by use of anatase type titanium oxide.

  It is preferable that the said titanium oxide (C) contains the rutile type titanium oxide surface-treated with the aluminum oxide. In 100% by weight of the titanium oxide (C), the content of the rutile titanium oxide surface-treated from the aluminum oxide is preferably 10% by weight or more, more preferably 30% by weight or more and 100% by weight or less. The total amount of titanium oxide (C) may be rutile titanium oxide surface-treated with the aluminum oxide. Use of the rutile type titanium oxide surface-treated with the aluminum oxide further increases the heat resistance of the molded body.

  Examples of the rutile-type titanium oxide surface-treated with the aluminum oxide include, for example, a product number manufactured by Ishihara Sangyo Co., Ltd., which is rutile chlorine method titanium oxide, and a product number manufactured by Ishihara Sangyo Co., Ltd., which is rutile sulfuric acid method titanium oxide. : R-630 and the like.

  In 100% by weight of the white curable composition for optical semiconductor devices, the content of the titanium oxide (C) is preferably 3% by weight or more, more preferably 10% by weight or more, further preferably 15% by weight or more, preferably Is 95% by weight or less, more preferably 90% by weight or less, and still more preferably 85% by weight or less. When the content of the titanium oxide (C) is not less than the above lower limit and not more than the above upper limit, the light reflectance of the molded body is further increased, the heat resistance of the molded body is further increased, and the molded body is heated to a high temperature. It becomes difficult to yellow when exposed.

(Silica (D))
The said white curable composition for optical semiconductor devices contains the said silica (D) as a filler different from a titanium oxide. The silica (D) includes both the spherical silica (D1) and the crushed silica (D2). As for the said spherical silica (D1), only 1 type may be used and 2 or more types may be used together. As for the said crushing silica (D2), only 1 type may be used and 2 or more types may be used together.

  Specific examples of the filler different from the above titanium oxide include silica, alumina, mica, beryllia, potassium titanate, barium titanate, strontium titanate, calcium titanate, zirconium oxide, antimony oxide, aluminum borate, hydroxide Aluminum, magnesium oxide, calcium carbonate, magnesium carbonate, aluminum carbonate, calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, calcium sulfate, barium sulfate, silicon nitride, boron nitride, baked clay clay, talc, silicon carbide Crosslinked acrylic resin particles, silicone particles, and the like. Of these, silica (D) is used.

  When the silica (D) contains both spherical silica (D1) and crushed silica (D2), the deterioration of the quality of the optical semiconductor device due to use in a harsh environment is further suppressed, and further the color change of the electrode The adhesion between the molded body and a member such as a sealant or a lead frame in contact with the molded body can be improved. Furthermore, the combined use of the spherical silica (D1) and the crushed silica (D2) further increases the toughness of the molded body and further improves the workability of the molded body. Further, the combined use of the spherical silica (D1) and the crushed silica (D2) further increases the dicing property of the molded body.

  The spherical silica (D1) is spherical. Spherical silica (D1) refers to silica having an aspect ratio of 2 or less. The spherical silica (D1) may be a true sphere, an elliptic sphere obtained by flattening a sphere, or a shape similar to these.

  The crushed silica (D2) is crushed silica. The aspect ratio of the crushed silica (D2) is not particularly limited. The aspect ratio of the crushed silica (D2) is preferably 1.5 or more, and preferably 20 or less. Since crushed silica having an aspect ratio of less than 1.5 is relatively expensive, the cost of the curable composition increases. The aspect ratio of the crushed silica (D2) may exceed 2. When the aspect ratio is 20 or less, filling of the crushed silica (D2) is easy.

  The aspect ratio of the crushed silica (D2) is determined by measuring the crushed surface of the crushed silica (D2) using, for example, a digital image analysis particle size distribution measuring device (trade name: FPA, manufactured by Nippon Luft). Can be sought.

  The average particle size of the spherical silica (D1) is 5 μm or more and 100 μm or less. When the average particle diameter of the spherical silica (D1) is less than 5 μm, discoloration of the electrode in the optical semiconductor device can be suppressed. Further, when the average particle diameter of the spherical silica (D1) is 5 μm or more and 100 μm or less, the quality is hardly lowered when the optical semiconductor device is used in a harsh environment, and the PCT resistance property of the optical semiconductor device. Becomes higher. From the viewpoint of further suppressing degradation of the quality of the optical semiconductor device due to use in a harsh environment and further suppressing discoloration of the electrode, the average particle diameter of the spherical silica (D1) is preferably 10 μm or more, preferably Is 70 μm or less, more preferably 50 μm or less. Moreover, the moldability of the said curable composition becomes still better that the said average particle diameter is more than the said minimum. When the average particle size is less than or equal to the above upper limit, the appearance defect of the molded body is more difficult to occur.

  The average particle diameter of the crushed silica (D2) is preferably 0.1 μm or more, more preferably 1 μm or more, preferably 100 μm or less, more preferably 30 μm or less. The average particle size of the crushed silica (D2) is particularly preferably 1 μm or more and 30 μm or less. When the average particle size of the crushed silica (D2) is not less than the above lower limit and not more than the above upper limit, the deterioration of the quality of the optical semiconductor device due to use in a harsh environment can be further suppressed, and further the color change of the electrode can be further reduced. It can be suppressed. Moreover, the moldability of the said curable composition becomes still better that the said average particle diameter is more than the said minimum. When the average particle size is less than or equal to the above upper limit, the appearance defect of the molded body is more difficult to occur.

  The average particle diameter in the spherical silica (D1) and the average particle diameter in the crushed silica (D2) are particle diameter values when the integrated value is 50% in the volume-based particle size distribution curve. The average particle size can be measured using, for example, a laser beam type particle size distribution meter. As a commercial product of the laser beam type particle size distribution analyzer, “LS 13 320” manufactured by Beckman Coulter, Inc. can be cited.

  The content of the silica (D) (the total content of spherical silica (D1) and crushed silica (D2)) is preferably 5% by weight or more in 100% by weight of the white curable composition for optical semiconductor devices. More preferably, it is 10% by weight or more, more preferably 20% by weight or more, preferably 95% by weight or less, more preferably 90% by weight or less, still more preferably 85% by weight or less. The moldability of a curable composition becomes still higher that content of the said silica (D) is more than the said minimum and below the said upper limit. When the content of the silica (D) is not more than the above upper limit, the light reflectance of the molded product is further increased.

  In 100% by weight of the white curable composition for optical semiconductor devices, the total content of titanium oxide (C) and silica (D) (titanium oxide (C), spherical silica (D1) and crushed silica (D2 )) Is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 20% by weight or more, preferably 95% by weight or less, more preferably 93% by weight or less, still more preferably Is 90% by weight or less. When the total content of the titanium oxide (C) and the silica (D) is not less than the above lower limit and not more than the above upper limit, the moldability of the curable composition and the light reflectance of the molded body are further increased. .

  In the white curable composition for an optical semiconductor device, the weight ratio of the content of the spherical silica (D1) to the content of the crushed silica (D2) (spherical silica (D1) / crushed silica (D2)) is 0. It is preferably 3 or more and 30 or less, and more preferably 1 or more and 15 or less. The content of the spherical silica (D1) and the content of the crushed silica (D2) indicate the content in 100% by weight of the curable composition. That is, the white curable composition for an optical semiconductor device has a weight ratio (spherical silica (D1): crushed silica (D2)) of the spherical silica (D1) and the crushed silica (D2), from 1:30 to It is preferable to include 30: 1, and it is more preferable to include 1: 15-15: 1. When the content of the spherical silica (D1) is relatively increased, the molded body is less likely to be brittle, the processability of the molded body is further enhanced, and cracks and chips are more unlikely to occur in the molded body. When the content of the crushed silica (D2) is relatively increased, the strength of the molded body is further increased.

(Curing accelerator (E))
The said white curable composition for optical semiconductor devices does not contain or contains a hardening accelerator (E). The white curable composition for optical semiconductor devices preferably contains a curing accelerator (E) in order to promote the reaction between the epoxy compound (A) and the curing agent (B). By using the curing accelerator (E), the curability of the curable composition can be enhanced, and the heat resistance of the molded product can be further enhanced. As for a hardening accelerator (E), only 1 type may be used and 2 or more types may be used together.

  It is preferable that the said hardening accelerator (E) contains the hardening accelerator which has basicity. By using a basic curing accelerator, the curability of the curable composition is further improved.

  Whether or not the curing agent has basicity is determined by putting 1 g of the curing agent in 10 g of a liquid containing 5 g of acetone and 5 g of pure water, heating the mixture with stirring at 80 ° C. for 1 hour, and then after heating. When an insoluble component in the liquid is removed by filtration to obtain an extract, it is judged that the pH of the extract is basic.

  Examples of the curing accelerator (E) include urea compounds, onium salt compounds, imidazole compounds, phosphorus compounds, amine compounds, and organometallic compounds.

  Examples of the urea compound include urea, aliphatic urea compounds, and aromatic urea compounds. Specific examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, and tri-n-. Examples include butylthiourea. Urea compounds other than these may be used.

  Examples of the onium salt compounds include ammonium salts, phosphonium salts, and sulfonium salt compounds.

  Examples of the imidazole compound include 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl- 2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-un Decylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2 ′ -Methyl Midazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6 [2′-Ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine Isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-dihydroxymethylimidazole Can be mentioned.

  The phosphorus compound contains phosphorus and is a phosphorus-containing compound. Examples of the phosphorus compound include triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetra-n-butylphosphonium-o, o-diethylphosphorodithioate, tetra-n-butylphosphonium-tetrafluoroborate, and tetra-n-. Examples thereof include butylphosphonium-tetraphenylborate. Phosphorus compounds other than these may be used.

  Examples of the amine compound include diethylamine, triethylamine, diethylenetetramine, triethylenetetramine, 4,4-dimethylaminopyridine, diazabicycloalkane, diazabicycloalkene, quaternary ammonium salt, triethylenediamine, and tri-2,4. , 6-dimethylaminomethylphenol. You may use the salt of these compounds. Phenylphosphine, tetraphenylphosphonium tetraphenylborate, tetra-n-butylphosphonium-o, o-diethylphosphorodithioate, tetra-n-butylphosphonium-tetrafluoroborate, tetra-n-butylphosphonium-tetraphenylborate It is done.

  Examples of the organometallic compound include alkali metal compounds and alkaline earth metal compounds. Specific examples of the organometallic compound include zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), and trisacetylacetonate cobalt (III).

  From the viewpoint of further improving the curability of the curable composition and further improving the heat resistance of the molded article, the curing accelerator (E) is preferably a urea compound, an onium salt compound or a phosphorus compound. . The curing accelerator (E) is preferably a urea compound, preferably an onium salt compound, and preferably a phosphorus compound.

  The mixing ratio of the epoxy compound (A) and the curing accelerator (E) is not particularly limited. The content of the curing accelerator (E) with respect to 100 parts by weight of the epoxy compound (A) is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, preferably 100 parts by weight or less. More preferably, it is 10 parts by weight or less, and still more preferably 5 parts by weight or less.

  The content of the basic curing accelerator is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, preferably 100 parts by weight with respect to 100 parts by weight of the epoxy compound (A). The amount is more preferably 10 parts by weight or less, still more preferably 5 parts by weight or less. When the content of the curing accelerator having basicity is not less than the above lower limit and not more than the above upper limit, the curability of the curable composition is further increased, and the molding unevenness of the molded body is more unlikely to occur.

(Other ingredients)
The white curable composition for optical semiconductor devices may include a filler different from the titanium oxide (C) and the silica (D).

  The above-mentioned white curable composition for optical semiconductor devices includes a coupling agent, an antioxidant, a release agent, a resin modifier, a colorant, a diluent, a surface treatment agent, a flame retardant, and a viscosity modifier as necessary. , Dispersants, dispersion aids, surface modifiers, plasticizers, antibacterial agents, antifungal agents, leveling agents, stabilizers, anti-sagging agents, or phosphors. The diluent may be a reactive diluent or a non-reactive diluent.

  It does not specifically limit as said coupling agent, A silane coupling agent and a titanate coupling agent are mentioned.

  It does not specifically limit as said antioxidant, A phenolic antioxidant, phosphorus antioxidant, an amine antioxidant, etc. are mentioned.

  The colorant is not particularly limited, and various organic materials such as phthalocyanine, azo compound, disazo compound, quinacridone, anthraquinone, flavantron, perinone, perylene, dioxazine, condensed azo compound, azomethine compound, infrared absorber and ultraviolet absorber. And inorganic pigments such as lead sulfate, chromium yellow, zinc yellow, chromium vermillion, valve shell, cobalt purple, bitumen, ultramarine, carbon black, chromium green, chromium oxide and cobalt green.

(Other details of white curable composition for optical semiconductor device and molded body for optical semiconductor device)
The white curable composition for an optical semiconductor device according to the present invention is a white curable composition for an optical semiconductor device used for obtaining a molded body disposed on a lead frame on which an optical semiconductor element is mounted in the optical semiconductor device. It is preferable that it is a thing. The lead frame is, for example, a component for supporting and fixing the optical semiconductor element and achieving electrical connection between the electrode of the optical semiconductor element and external wiring. The molded body is a molded body for an optical semiconductor device, and is preferably an optical semiconductor element mounting substrate.

  Since a molded article having high light reflectance is obtained, the white curable composition for optical semiconductor devices according to the present invention is provided on the lead frame on which the optical semiconductor element is mounted and on the side of the optical semiconductor element in the semiconductor device. It is preferable that the white curable composition for an optical semiconductor device is used for obtaining a molded body that is disposed on the side and has a light reflecting portion that reflects light emitted from the optical semiconductor element.

  Since a molded article having high light reflectance is obtained, the white curable composition for optical semiconductor devices according to the present invention surrounds the optical semiconductor element on the lead frame on which the optical semiconductor element is mounted in the semiconductor device. It is preferable that the white curable composition for an optical semiconductor device is used for obtaining a molded body that is disposed as described above and has a light reflecting portion that reflects light emitted from the optical semiconductor element on its inner surface. The molded body is preferably an outer wall member surrounding the optical semiconductor element, and is preferably a frame-shaped member. In addition, the said molded object differs from the die-bonding material for joining an optical semiconductor element (die bonding) in an optical semiconductor device.

  The white curable composition for an optical semiconductor device according to the present invention is used for obtaining individual molded bodies by dividing the pre-divided molded bodies after obtaining the molded bodies before division in which a plurality of molded bodies are continuous. It is preferable. Since the processability of the pre-division molded product using the white curable composition for optical semiconductor devices according to the present invention is high, cracks and Chipping can be made difficult to occur.

  The said white curable composition for optical semiconductor devices is conventionally well-known for an epoxy compound (A), a hardening | curing agent (B), a titanium oxide (C), silica (D), and the other component mix | blended as needed. It is obtained by mixing by the method. A general method for producing the curable resin composition includes a method in which each component is kneaded by an extruder, a kneader, a roll, an extruder, etc., and then the kneaded product is cooled and pulverized. From the viewpoint of improving dispersibility, the kneading of each component is preferably performed in a molten state. The kneading conditions are appropriately determined depending on the type and amount of each component. Kneading is preferably performed at 15 to 150 ° C for 5 to 120 minutes, more preferably 15 to 150 ° C for 5 to 40 minutes, and further preferably 20 to 100 ° C for 10 to 30 minutes.

  The molded object for optical semiconductor devices which concerns on this invention is obtained by hardening the white curable composition for optical semiconductor devices mentioned above. The white curable composition for optical semiconductor devices is formed into a predetermined shape. The molded body obtained by curing the white curable composition for optical semiconductor devices is suitably used for reflecting light emitted from the optical semiconductor element in the optical semiconductor device.

  Examples of a method for obtaining the molded article for an optical semiconductor device using the white curable composition for an optical semiconductor device include a compression molding method, a transfer molding method, a laminate molding method, an injection molding method, an extrusion molding method, and a blow molding method. Is mentioned. Of these, transfer molding is preferred.

  In the transfer molding method, for example, the molded product is formed by transfer molding the white curable composition for an optical semiconductor device under the conditions of a molding temperature of 100 to 200 ° C., a molding pressure of 5 to 20 MPa, and a molding time of 60 to 300 seconds. can get.

(Details of optical semiconductor device and embodiment of optical semiconductor device)
An optical semiconductor device according to the present invention includes a lead frame, an optical semiconductor element mounted on the lead frame, and a molded body disposed on the lead frame, and the molded body is for the optical semiconductor device. It is obtained by curing a white curable composition.

  In the optical semiconductor device according to the present invention, the molded body is disposed on a side of the optical semiconductor element, and an inner surface of the molded body is a light reflecting portion that reflects light emitted from the optical semiconductor element. It is preferable.

  1A and 1B are a sectional view and a perspective view of an optical semiconductor device according to an embodiment of the present invention.

  The optical semiconductor device 1 according to this embodiment includes a lead frame 2, an optical semiconductor element 3, a first molded body 4, and a second molded body 5. The optical semiconductor element 3 is preferably a light emitting diode (LED). The first molded body 4 and the second molded body 5 are not formed integrally, but are two other members. The first molded body 4 and the second molded body 5 may be integrally formed.

  An optical semiconductor element 3 is mounted and arranged on the lead frame 2. A first molded body 4 is arranged on the lead frame 2. A second molded body 5 is disposed between the plurality of lead frames 2 and below the lead frames 2. The optical semiconductor element 3 is disposed inside the first molded body 4. A first molded body 4 is disposed on the side of the optical semiconductor element 3, and the first molded body 4 is disposed so as to surround the optical semiconductor element 3. The 1st, 2nd molded objects 4 and 5 are hardened | cured material of the white curable composition for optical semiconductor devices mentioned above, and are obtained by hardening the white curable composition for optical semiconductor devices mentioned above. Therefore, the 1st molded object 4 has light reflectivity, and has a light reflection part in the inner surface 4a. That is, the inner surface 4a of the first molded body 4 is a light reflecting portion. Therefore, the periphery of the optical semiconductor element 3 is surrounded by the inner surface 4 a having the light reflectivity of the first molded body 4.

  The inner surface 4a of the first molded body 4 is formed such that the diameter of the inner surface 4a increases as it goes toward the opening end. Therefore, of the light emitted from the optical semiconductor element 3, the light indicated by the arrow B reaching the inner surface 4 a is reflected by the inner surface 4 a and travels forward of the optical semiconductor element 3.

  The optical semiconductor element 3 is connected to the lead frame 2 using a die bond material 6. A bonding pad (not shown) provided on the optical semiconductor element 3 and the lead frame 2 are electrically connected by a bonding wire 7. A sealing agent 8 is filled in the region surrounded by the inner surface 4 a of the first molded body 4 so as to seal the optical semiconductor element 3 and the bonding wire 7.

  In the optical semiconductor device 1, when the optical semiconductor element 3 is driven, light is emitted as indicated by a broken line A. In the optical semiconductor device 1, not only the light irradiated from the optical semiconductor element 3 to the side opposite to the upper surface of the lead frame 2, that is, the upper side, but also the light reaching the inner surface 4 a of the first molded body 4 is indicated by an arrow B. There is also light that is reflected by the light. Therefore, the brightness of the light extracted from the optical semiconductor device 1 is bright.

  The structure shown in FIG. 1 is merely an example of an optical semiconductor device according to the present invention, and can be appropriately modified to a structure of a molded body, a mounting structure of an optical semiconductor element, and the like.

  Further, as shown in FIG. 2, a pre-division optical semiconductor device component 11 in which a plurality of optical semiconductor device components are connected is prepared, and the pre-division optical semiconductor device component 11 is cut at a portion indicated by a broken line X. Individual optical semiconductor device components may be obtained. The pre-division optical semiconductor device component 11 includes a pre-division lead frame 2A, a pre-division first molded body 4A, and a pre-division second molded body 5A. After obtaining individual components for an optical semiconductor device, the optical semiconductor device 3 may be mounted, and the optical semiconductor device 3 may be sealed with a sealant 8 to obtain the optical semiconductor device 1. When the pre-division lead frame 2A is cut at a portion indicated by a broken line X, the lead frame 2 is obtained. When the first molded body 4A before division is cut at a portion indicated by a broken line X, the first molded body 4 is obtained. When the second molded body 5A before division is cut at a portion indicated by a broken line X, the second molded body 5 is obtained.

  Further, as shown in FIG. 3, a pre-division optical semiconductor device 12 in which a plurality of pre-division optical semiconductor devices are connected is prepared, and the pre-division optical semiconductor device 12 is cut at a portion indicated by a broken line X to obtain individual light. A semiconductor device may be obtained. The pre-division optical semiconductor device 12 includes a pre-division lead frame 2A, a pre-division first molded body 4A, and a pre-division second molded body 5A. As in the optical semiconductor device 1 shown in FIG. 1, in the pre-division optical semiconductor device 12, the optical semiconductor element 3 is mounted and arranged on the pre-division lead frame 2A. 2 and 3, in the pre-division optical semiconductor device component 11 and the pre-division optical semiconductor device 12, a plurality of molded bodies are connected to form a pre-division molded body, but a plurality of molded bodies are connected. The pre-division optical semiconductor device component and the pre-division optical semiconductor device may be divided to obtain the optical semiconductor device component and the optical semiconductor device.

  Hereinafter, the present invention will be clarified by giving specific examples and comparative examples of the present invention. The present invention is not limited to the following examples.

  In the examples and comparative examples, the following materials were used.

(Epoxy compound (A))
1) Celoxide 2021P (epoxy compound (A1), 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, epoxy equivalent 126, manufactured by Daicel)
2) Epolide GT401 (epoxy compound (A1), polyfunctional alicyclic epoxy resin, epoxy equivalent 220, manufactured by Daicel)
3) EHPE3150 (epoxy compound (A2), epoxy resin having an alicyclic skeleton, epoxy equivalent 177, manufactured by Daicel)
4) ST-4000D (epoxy compound (A2), hydrogenated bisphenol A type epoxy resin, epoxy equivalent 700, manufactured by Nippon Steel Chemical Co., Ltd.)
5) TEPIC (triglycidyl isocyanurate, having nitrogen atom, epoxy equivalent of 100, manufactured by Nissan Chemical Co., Ltd.)
6) YD-127 (bisphenol A type epoxy resin, epoxy equivalent 190 having an aromatic skeleton, manufactured by Nippon Steel Chemical Co., Ltd.)

(Curing agent (B))
1) Ricacid MH-700 (a mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride, non-basic, manufactured by Shin Nippon Rika Co., Ltd.)
2) Licacid HH (hexahydrophthalic anhydride, non-basic, manufactured by Shin Nippon Chemical Co., Ltd.)

(Titanium oxide (C))
1) CR-90 (rutile titanium oxide, surface-treated with Al, Si, manufactured by Ishihara Sangyo Co., Ltd.)
2) CR-58 (rutile titanium oxide, surface treated with Al, manufactured by Ishihara Sangyo Co., Ltd.)

(Spherical silica (D1))
1) HS-305 (spherical silica, average particle size 80 μm, manufactured by Micron)
2) MSR-3512 (spherical silica, average particle size 30 μm, manufactured by Tatsumori)
3) MSR-22 (spherical alumina, average particle size 23 μm, manufactured by Tatsumori)
4) SE-8 (spherical silica, average particle size 9 μm, manufactured by Tokuyama Corporation)

(Fractured silica (D2))
1) 3K-S (crushed silica, average particle size 35 μm, aspect ratio 2 to 5, manufactured by Tatsumori)
2) NX-7 (crushed silica, average particle size 13 μm, aspect ratio 2 to 5, manufactured by Tatsumori)
3) CMC-12 (crushed silica, average particle size 5 μm, aspect ratio 2 to 5, manufactured by Tatsumori)

(Other fillers)
1) HSP-2000 (spherical silica, average particle size 2 μm, manufactured by Toagosei Co., Ltd.)

(Curing accelerator (E))
1) PX-4ET (tetra-n-butylphosphonium-o, o-diethyl phosphorodithionate, basic, manufactured by Nippon Chemical Industry Co., Ltd.)

(Examples 1-18 and Comparative Examples 1-8)
The components shown in Tables 1 and 2 below are blended in the blending amounts shown in Tables 1 and 2 (the blending unit is parts by weight) and mixed for 15 minutes with a blender (Laboplast Mill R-60, manufactured by Toyo Seiki Seisakusho). Thus, a kneaded product was obtained.

(Evaluation)
(1) PCT resistance property The obtained kneaded material was heat-treated at 40 ° C. for 30 hours to be solidified. The solidified kneaded product was pulverized to form a tablet (curable composition).

  A circuit was formed on a copper material (TAMAC 194) by etching and then silver plating was performed to obtain a lead frame having a thickness of 0.2 mm. The curable composition is cured on the lead frame by a MAP molding method by transfer molding (molding temperature: 170 ° C., molding time: 3 minutes) using a transfer molding device (“YPS-MP” manufactured by TOWA). The molded body obtained by the above was fabricated, and an optical semiconductor device mounting substrate provided with the molded body was fabricated. As the mold, a batch molding mold having 150 concave portions (optical semiconductor element mounting portions) arranged in a matrix of 15 vertical × 10 horizontal was used. The cavity size was 6 mm × 3 mm per piece and the depth was 5 mm. The obtained molded body was after-cured at 170 ° C. for 2 hours. In the molded article after the after-curing, when there was a burr, the burr was removed using AX-930 (manufactured by Rix Corporation).

  Next, a blue light-emitting element of a sapphire substrate having InGaN as a light-emitting layer was placed on the molded body after the after-curing using a silicone resin adhesive. The light emitting element and the lead frame were electrically connected using a gold wire having a diameter of 30 μm. A sealing agent was dropped into each of the concave portions of the molded body on which the light emitting element was placed on the bottom surface. The sealant contains 100 parts by weight of silicone resin and 30 parts by weight of YAG phosphor. After the dropping, the sealant was cured at 150 ° C. for 3 hours. Finally, it was cut out from the lead frame to obtain an optical semiconductor device emitting white light.

  The obtained optical semiconductor device was subjected to an acceleration test (PCT test) for 60 hours or 120 hours under the conditions of 121 ° C., 100% humidity, and 203 kPa. PCT resistance was determined according to the following criteria.

[Judgment criteria for PCT resistance]
◯: After 120-hour acceleration test, there is no unlit optical semiconductor device, no sealant is peeled off, and no crack is generated in the sealant. ○: Unlit optical semiconductor after 60-hour acceleration test There is no device, there is no peeling of the sealant, and no crack is generated in the sealant, but there is an unlit optical semiconductor device after the 120-hour acceleration test, or the sealant is peeled off Or there is a crack in the sealant ×: After 60-hour acceleration test, there is an unlit optical semiconductor device, peeling of the sealant has occurred, or crack has occurred in the sealant doing

(2) Discoloration of electrode An optical semiconductor device obtained by the evaluation of (1) PCT resistance was prepared. 0.2 g of sulfur was placed in a sealable 200 mL glass bottle, and the above optical semiconductor device was placed therein. The glass bottle was sealed and heated in an oven at 70 ° C. for 15 hours or 30 hours, and then the optical semiconductor device was taken out. The extracted optical semiconductor device was visually observed. The discoloration of the electrode was determined according to the following criteria.

[Criteria for electrode discoloration]
◯: Silver plating is not discolored in the electrode portion that is in contact with the molded product and the sealant after heating for 30 hours. ○: The electrode portion that is in contact with the molded product and the sealant after heating for 15 hours. However, the silver plating is not discolored, but after 30 hours of heating, the silver plating is discolored in the electrode portions that are in contact with the formed body and the sealing agent. The silver plating is discolored in the electrode part in contact with

(3) Adhesion between lead frame and molded body The obtained kneaded material was heat-treated at 40 ° C. for 30 hours to be solidified. The solidified kneaded product was pulverized to form a tablet (curable composition).

  A circuit was formed on a copper material (TAMAC 194) by etching and then silver plating was performed to obtain a lead frame having a thickness of 0.2 mm. On the lead frame, 0.2 g of the curable composition was placed, and a silicon wafer having a size of 3 mm × 3 mm was placed on the curable composition. Then, it heated at 170 degreeC for 2 hours, the said curable composition was hardened, and the sample was obtained.

  The die shear strength of a lead frame and a molded object was measured for the obtained sample using a die shear tester (“PTR-1102” manufactured by Reska Co.). The adhesion between the lead frame and the molded body was determined according to the following criteria.

[Adhesion between lead frame and molded body]
○: Die shear strength is 30N or more ○: Die shear strength is 10N or more and less than 30N ×: Die shear strength is less than 10N

  The results are shown in Tables 1 and 2 below.

DESCRIPTION OF SYMBOLS 1 ... Optical semiconductor device 2 ... Lead frame 2A ... Lead frame before division 3 ... Optical semiconductor element 4 ... 1st molded object 4A ... 1st molded object 4a before division | segmentation 5 ... 2nd molded object 5A ... Before division | segmentation 2nd molded object 6 ... Die bond material 7 ... Bonding wire 8 ... Sealant 11 ... Parts for optical semiconductor devices before division 12 ... Optical semiconductor devices before division

Claims (10)

A lead frame;
An optical semiconductor element mounted on the lead frame;
A molded body disposed on the lead frame,
The molded body is obtained by curing a white curable composition for optical semiconductor devices,
The white curable composition for an optical semiconductor device is a white curable composition for an optical semiconductor device,
The white curable composition for optical semiconductor devices includes an epoxy compound having an epoxy group, an acid anhydride curing agent, titanium oxide, spherical silica, and crushed silica,
An optical semiconductor device, wherein the spherical silica has an average particle size of 5 μm or more and 100 μm or less.   The optical semiconductor device according to claim 1, wherein an aspect ratio of the crushed silica is 1.5 or more and 20 or less.   The optical semiconductor device according to claim 1 or 2, wherein an average particle diameter of the crushed silica is 1 µm or more and 30 µm or less.   The optical semiconductor device according to claim 1, wherein the titanium oxide is rutile titanium oxide. The epoxy compound does not have an aromatic skeleton,
The optical semiconductor device according to any one of claims 1 to 4, wherein the atoms constituting the epoxy compound are only three kinds of carbon atoms, oxygen atoms, and hydrogen atoms.   The optical semiconductor device according to claim 1, wherein the epoxy compound has an alicyclic skeleton.   The optical semiconductor device according to claim 6, wherein the epoxy compound includes an alicyclic skeleton and an epoxy compound in which two carbon atoms of the epoxy group are carbon atoms of the alicyclic skeleton.   The optical semiconductor device according to claim 6, wherein the epoxy compound includes an alicyclic skeleton and an epoxy compound in which two carbon atoms of the epoxy group are not carbon atoms of the alicyclic skeleton.   The epoxy compound has an alicyclic skeleton, and two carbon atoms of the epoxy group are carbon atoms of the alicyclic skeleton, and an alicyclic skeleton and two carbons of the epoxy group The optical semiconductor device according to claim 6, which contains both an epoxy compound whose atoms are not carbon atoms of an alicyclic skeleton.   The said molded object is arrange | positioned at the side of the said optical semiconductor element, The inner surface of the said molded object is a light reflection part which reflects the light emitted from the said optical semiconductor element, The any one of Claims 1-9 2. An optical semiconductor device according to item 1.

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