JP6038236B2 - White curable material for optical semiconductor device and method for producing white curable material for optical semiconductor device - Google Patents

Description

  The present invention relates to a white curable material for an optical semiconductor device and a white curable material for an optical semiconductor device, which are used to obtain a molded body disposed on a lead frame on which an optical semiconductor element is mounted in an optical semiconductor device. Regarding the method. Moreover, this invention relates to the molded object for optical semiconductor devices using the said white curable material for semiconductor devices, and an optical semiconductor device.

  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 compound for optical semiconductor devices. 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 body, the following Patent Document 1 includes a curable composition containing an epoxy resin, a curing agent, a curing accelerator, an inorganic filler, a white pigment, and a coupling agent. It is disclosed. The length of the burr produced when the curable composition is transfer molded under the conditions of a molding temperature of 100 to 200 ° C., a molding pressure of 20 MPa or less, and a molding time of 60 to 120 seconds is 5 mm or less. The light reflectance at a wavelength of 350 to 800 nm of the molded product after the above-mentioned curable composition is thermally cured is 80% or more.

  Patent Document 2 below discloses a curable composition containing a triazine derivative epoxy resin, an acid anhydride, an antioxidant, a curing catalyst, a reflective member, and an inorganic filler.

  Patent Document 3 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 3, 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 a 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.

JP 2008-144127 A WO2007 / 015426A1 JP2011-009519A

  In the case of transfer molding a conventional curable composition as described in Patent Documents 1 to 3, there is a problem that the handleability of the curable composition is low or the moldability of the molded body is low. There is. Furthermore, when the molded body is continuously molded, the cured product of the curable composition adheres to the mold, or the releasability of the molded body from the mold may be low. That is, the conventional curable composition has a problem of low continuous moldability.

  An object of the present invention is to provide a white curable material for an optical semiconductor device that is excellent in handleability, filling into a mold during molding, and continuous moldability, a method for producing the white curable material for an optical semiconductor device, and the light. An object of the present invention is to provide an optical semiconductor device molded body and an optical semiconductor device using a white curable material for a semiconductor device.

  A limited object of the present invention is a white curable material for optical semiconductor devices and a white color for optical semiconductor devices, which are excellent in handling properties, suppression of burrs during transfer molding, filling into a mold, and continuous moldability. It is providing the manufacturing method of a curable material, the molded object for optical semiconductor devices using the white curable material for optical semiconductor devices, and an optical semiconductor device.

  According to a wide aspect of the present invention, there is provided a white curable material for optical semiconductor devices, which is a white curable composition or a heat-treated product obtained by heat-treating the white curable composition, the curable composition described above. The product includes an epoxy compound, a curing agent, titanium oxide, a filler different from titanium oxide, and a curing accelerator, and has a softening point of 60 ° C. or higher and lower than 120 ° C., and a viscosity at 170 ° C. of 120 Pa.・ After s, 300 Pa · s or less, gel time at 170 ° C. is 30 seconds or more and 100 seconds or less, mold after transfer molding in the mold under the conditions of molding temperature 170 ° C. and molding time 100 seconds. A white curable material for optical semiconductor devices is provided in which when the molded product is taken out from the mold, the hardness of the molded product 5 seconds after being taken out from the mold is 70 or more in Shore D.

  On the specific situation with the white curable material for optical semiconductor devices which concerns on this invention, the said hardening | curing agent is an acid anhydride hardening | curing agent.

  In another specific aspect of the white curable material for an optical semiconductor device according to the present invention, the epoxy compound includes at least one of an epoxy compound having an aromatic skeleton and an epoxy compound having an alicyclic skeleton.

  In still another specific aspect of the white curable material for an optical semiconductor device according to the present invention, the epoxy compound includes both the epoxy compound having the aromatic skeleton and the epoxy compound having the alicyclic skeleton.

  In another specific aspect of the white curable material for an optical semiconductor device according to the present invention, the titanium oxide is a rutile type titanium oxide.

  In still another specific aspect of the white curable material for an optical semiconductor device according to the present invention, the filler has a first filler having an average particle diameter of 1 μm or more and less than 10 μm, and an average particle diameter of 10 μm or more. , And a second filler that is 50 μm or less.

  In another specific aspect of the white curable material for optical semiconductor devices according to the present invention, the white curable material is kneaded at a temperature of 60 to 100 ° C. for 10 to 60 minutes and then 1 to 48 at 50 to 80 ° C. A heat-treated product obtained by heat-treating the curable composition by time-aging.

  The white curable material for optical semiconductor devices according to the present invention is a white curable material for optical semiconductor devices used for obtaining a molded body disposed on a lead frame on which an optical semiconductor element is mounted in an optical semiconductor device. It is preferable.

  The white curable material 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 a side of the optical semiconductor element in the optical semiconductor device, and is emitted from the optical semiconductor element. It is preferably a white curable material for an optical semiconductor device used for obtaining a molded body having a light reflecting portion that reflects light.

  According to a broad aspect of the present invention, using a white curable composition comprising an epoxy compound, a curing agent, titanium oxide, a filler different from titanium oxide, and a curing accelerator, the white curing The composition is heat-treated to obtain a white curable material for an optical semiconductor device that is a heat-treated product, the softening point is 60 ° C. or higher and lower than 120 ° C., and the viscosity at 170 ° C. exceeds 120 Pa · s, 300 Pa · s or less, gel time at 170 ° C. being 30 seconds or more and 100 seconds or less, transfer molding in a mold under conditions of a molding temperature of 170 ° C. and a molding time of 100 seconds, and then removing the molded body from the mold Method for producing a white curable material for an optical semiconductor device, wherein the hardness of the molded product 5 seconds after removal from the mold is 70 or more on Shore D But It is subjected.

  In a specific aspect of the method for producing a white curable material for an optical semiconductor device according to the present invention, after kneading at a temperature of 60 to 100 ° C. for 10 to 60 minutes, aging at 50 to 80 ° C. for 1 to 48 hours. A white curable material for an optical semiconductor device, which is a heat-treated product obtained by heat-treating the curable composition, is obtained.

  The molded article for an optical semiconductor device according to the present invention is a white for an optical semiconductor device obtained by curing the above-described white curable material for an optical semiconductor device or the above-described method for producing a white curable material for an optical semiconductor device. It is obtained by curing a curable material.

  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. It is obtained by curing a white curable material for a semiconductor device or curing a white curable material for an optical semiconductor device obtained by the above-described method for producing a white curable material for an optical semiconductor device.

  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 material for optical semiconductor devices according to the present invention is a white curable composition or a heat-treated product obtained by heat-treating the white curable composition, and the curable composition is an epoxy compound and And a curing agent, titanium oxide, a filler different from titanium oxide, and a curing accelerator, and the white curable material has a softening point of 60 ° C. or higher and lower than 120 ° C., and a viscosity at 170 ° C. Is over 120 Pa · s, 300 Pa · s or less, the gel time at 170 ° C. is 30 seconds or more and 100 seconds or less, and after transfer molding in a mold under the conditions of a molding temperature of 170 ° C. and a molding time of 100 seconds. When the molded body is taken out from the mold, the hardness of the molded body after 70 seconds from the mold is 70 or more on Shore D. And ream It is excellent in formability.

  In the method for producing a white curable material for an optical semiconductor device according to the present invention, a white curable composition comprising an epoxy compound, a curing agent, titanium oxide, a filler different from titanium oxide, and a curing accelerator. The white curable composition is heat-treated to obtain a white curable material for optical semiconductor devices, which is a heat-treated product, and has a softening point of 60 ° C. or higher and lower than 120 ° C., 170 The viscosity at 120 ° C. exceeds 120 Pa · s, is 300 Pa · s or less, the gel time at 170 ° C. is 30 seconds or more and 100 seconds or less, and is transferred in the mold under the conditions of a molding temperature of 170 ° C. and a molding time of 100 seconds. After molding, when the molded body is taken out from the mold, a white curable material for an optical semiconductor device having a hardness of 70 or more on Shore D after 5 seconds from the removal from the mold is obtained. , It is possible to obtain handling properties, a white curable material having excellent filling properties and continuous moldability during molding and.

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 material for an optical semiconductor device according to an embodiment of the present invention. is there. FIG. 2 schematically shows 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 material for an optical semiconductor device according to an embodiment of the present invention are connected. It is sectional drawing. 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 material for an optical semiconductor device according to an embodiment of the present invention are connected. It is. FIGS. 4A and 4B are a schematic perspective view and a cross-sectional view for explaining a burr length evaluation method in Examples and Comparative Examples.

  Hereinafter, the present invention will be described in detail.

(White curable material for optical semiconductor devices and method for producing white curable material for optical semiconductor devices)
The white curable material for optical semiconductor devices according to the present invention is a white curable composition or a heat-treated product obtained by heat-treating the white curable composition. The curable composition includes an epoxy compound (A), a curing agent (B), titanium oxide (C), a filler (D) different from titanium oxide, and a curing accelerator (E).

  Furthermore, the softening point before thermosetting of the white curable material for optical semiconductor devices according to the present invention is 60 ° C. or higher and lower than 120 ° C. The viscosity at 170 ° C. of the white curable material for optical semiconductor devices according to the present invention is more than 120 Pa · s and not more than 300 Pa · s. The gel time at 170 ° C. of the white curable material for optical semiconductor devices according to the present invention is 30 seconds or more and 100 seconds or less. After the white curable material for optical semiconductor devices according to the present invention is transfer molded in a mold under the conditions of a molding temperature of 170 ° C. and a molding time of 100 seconds, it is taken out from the mold when the molded body is taken out from the mold. After 5 seconds, the hardness of the molded product is 70 or more on Shore D.

  In the method for producing a white curable material for an optical semiconductor device according to the present invention, an epoxy compound (A), a curing agent (B), titanium oxide (C), a filler different from titanium oxide (D), A white curable composition containing a curing accelerator (E) is used. The manufacturing method of the white curable material for optical semiconductor devices which concerns on this invention comprises the process of heat-processing this white curable composition, and obtaining the white curable material for optical semiconductor devices which is heat processing material.

  Furthermore, in the manufacturing method of the white curable material for optical semiconductor devices which concerns on this invention, the white curable material whose softening point is 60 degreeC or more and less than 120 degreeC is obtained. Moreover, in the manufacturing method of the white curable material for optical semiconductor devices which concerns on this invention, the white curable material whose viscosity in 170 degreeC exceeds 120 Pa.s and is 300 Pa.s or less is obtained. In the method for producing a white curable material for an optical semiconductor device according to the present invention, a white curable material having a gel time at 170 ° C. of 30 seconds or more and 100 seconds or less is obtained. In the method for producing a white curable material for an optical semiconductor device according to the present invention, when the molded body is taken out from the mold after transfer molding in the mold at a molding temperature of 170 ° C. and a molding time of 100 seconds, A white curable material having a hardness of 70 or more on Shore D after 5 seconds from removal from the mold is obtained.

  The white curable material for optical semiconductor devices according to the present invention and the white curable material for optical semiconductor devices obtained by the method for producing a white curable material for optical semiconductor devices according to the present invention are: It is preferably a white curable material for an optical semiconductor device used for obtaining a molded body disposed on a lead frame to be mounted. The molded body is a cured product molded into a predetermined shape.

  A white curable material for an optical semiconductor device according to the present invention and a white curable material for an optical semiconductor device obtained by the method for producing a white curable material for an optical semiconductor device according to the present invention are molded to produce a molded body, An optical semiconductor device is obtained using the molded body.

  By adopting the above-described configuration in the white curable material for optical semiconductor devices according to the present invention and the method for producing the white curable material for optical semiconductor devices according to the present invention, the handleability of the white curable material is improved. Furthermore, the filling property to the metal mold | die at the time of shaping | molding of the said white curable material becomes favorable. And when a molded object is shape | molded continuously using the said white curable material, hardened | cured material becomes difficult to adhere to a metal mold | die, and the mold release property from the metal mold | die becomes high. That is, by adopting the above-described configuration in the white curable material for an optical semiconductor device according to the present invention and the method for producing the white curable material for an optical semiconductor device according to the present invention, continuous formability can be improved.

  Furthermore, by adopting the above-described configuration in the method for producing the white curable material for optical semiconductor devices according to the present invention and the white curable material for optical semiconductor devices according to the present invention, it is possible to suppress the generation of burrs during transfer molding. .

  Moreover, the white curable material for optical semiconductor devices is cured by adopting the above-described configuration in the method for producing the white curable material for optical semiconductor devices according to the present invention and the white curable material for optical semiconductor devices according to the present invention. Thus, the light reflectance of the molded product obtained can be increased. Since the obtained molded body has a high reflectance of light, the light is effectively reflected when the light emitted from the optical semiconductor element reaches the molded body. For this reason, the brightness of the light extracted from the optical semiconductor device can be increased.

  The softening point of the said white curable material is 60 degreeC or more and less than 120 degreeC. When the softening point is less than 60 ° C., the handleability of the white curable material is deteriorated. For this reason, workability | operativity at the time of obtaining a molded object worsens. When the softening point is 120 ° C. or higher, the filling property of the white curable material into the mold is deteriorated.

  The white curable material has a viscosity at 170 ° C. of more than 120 Pa · s and not more than 300 Pa · s. When the viscosity is 120 Pa · s or less, the transfer moldability of the molded article deteriorates. Specifically, burrs are likely to occur during transfer molding. When the viscosity exceeds 300 Pa · s, the filling property of the white curable material into the mold is deteriorated.

  The gel time at 170 ° C. of the white curable material is 30 seconds or more and 100 seconds or less. When the gel time is less than 30 seconds, the filling property of the white curable material into the mold is deteriorated. When the gel time exceeds 100 seconds, the take-out property of the molded body from the mold is deteriorated, and the releasability of the molded body from the mold is deteriorated.

  The gel time means a time until the white curable material loses fluidity when 0.5 g of the white curable material is mixed with a stirring bar on a hot plate heated to 170 ° C.

  The white curable material is molded by transfer molding in a mold under conditions of a molding temperature of 170 ° C. and a molding time of 100 seconds, and then molding is performed 5 seconds after the molded body is removed from the mold. The hardness of the body is 70 or more on Shore D. When the Shore D is less than 70, the take-out property of the molded product from the mold is deteriorated, and the releasability of the molded product from the mold is deteriorated.

  The Shore D is a hardness defined by durometer type D of JIS K6253.

  The white curable material for optical semiconductor devices according to the present invention is heat-treated by kneading at a temperature of 60 to 100 ° C. for 10 to 60 minutes and then aging at 50 to 80 ° C. for 1 to 48 hours. The heat-treated product is preferably used. The manufacturing method of the white curable material for optical semiconductor devices which concerns on this invention knead | mixes for 10 to 60 minutes at the temperature of 60-100 degreeC, Then, the said curable composition is carried out by aging at 50-80 degreeC for 1-48 hours. It is preferable to obtain a heat-treated product obtained by heat-treating the product. By such aging, it is easy to obtain a white curable material excellent in handleability, filling property in a mold during molding, and continuous moldability.

  Hereinafter, the detail of each component contained in the white curable composition (white curable composition) used for the white curable material for optical semiconductor devices which concerns on this invention is demonstrated.

[Epoxy compound (A)]
The white curable composition contains the epoxy compound (A) so that it can be cured by application of heat. The epoxy compound (A) has an epoxy group. By using an epoxy compound (A) as a thermosetting compound, the heat resistance and insulation reliability of a molded object become high. As for an 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.

  The epoxy equivalent of the whole epoxy compound (A) contained in the white resin composition is preferably 200 or more, preferably 20000 or less. When the epoxy equivalent is 200 or more, the moldability of the white curable material is further improved, the molded body is hardly brittle, and the processability of the molded body is further improved. When the epoxy equivalent is 20000 or less, the moldability of the white curable material is further improved, and the strength of the molded body is further increased. The epoxy equivalent is measured according to JIS K7236.

  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 composed of an epoxy compound (A1) having an aromatic skeleton and an epoxy compound (A2) having an alicyclic skeleton. It is preferable that at least one of these is included. The epoxy compound (A) may contain both an epoxy compound (A1) having an aromatic skeleton and an epoxy compound (A2) having an alicyclic skeleton. The said white curable composition may contain only the epoxy compound (A1) which has an aromatic skeleton, and may contain only the epoxy compound (A2) which has an alicyclic skeleton.

  From the viewpoint of further enhancing the strength and heat resistance of the molded article, the epoxy compound (A) preferably contains an epoxy compound (A1) having an aromatic skeleton. As for the epoxy compound (A1) 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 lead frame and the molded body, the epoxy compound (A) preferably includes an epoxy compound (A2) having an alicyclic skeleton. As for the epoxy compound (A2) which has the said alicyclic skeleton, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of further improving the heat resistance of the molded body and further improving the adhesion between the lead frame and the molded body, the epoxy compound (A) is an alicyclic epoxy compound (A1) having an aromatic skeleton. It is particularly preferable that both the epoxy compound (A2) having a skeleton be included.

  Examples of the epoxy compound (A1) having an aromatic skeleton include bisphenol A type epoxy compound, bisphenol F type epoxy compound, cresol novolac type epoxy compound, phenol novolac type epoxy compound, polybasic acid compound having aromatic skeleton and epichloro Examples thereof include glycidyl ester type epoxy compounds obtained by reacting with hydrin and glycidyl ether type epoxy compounds having an aromatic skeleton.

  From the viewpoint of further enhancing the strength and heat resistance of the molded article, the epoxy compound (A1) having the aromatic skeleton preferably has a bisphenol skeleton or a novolak skeleton.

  The epoxy equivalent of the epoxy compound (A1) having an aromatic skeleton is preferably 400 or more, and preferably 3000 or less. When the epoxy equivalent is 400 or more, the moldability of the white curable material is further improved. When the epoxy equivalent is 3000 or less, the strength of the molded product is further increased.

  Specific examples of the epoxy compound (A2) having the alicyclic skeleton include 2- (3,4-epoxy) cyclohexyl-5,5-spiro- (3,4-epoxy) cyclohexane-m-dioxane, 3, 4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, dicyclopentadiene dioxide, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane, 1,2: 8,9-diepoxy Limonene, ε-caprolactone modified tetra (3,4-epoxycyclohexylmethyl) butanetetracarboxylate, 2,2-bis (hydroxymethyl) -1-butanol added with 1,2-epoxy-4- (2-oxiranyl) cyclohexane Thing etc. are mentioned. From the viewpoint of further improving the heat resistance of the molded article, the epoxy compound (A2) having the alicyclic skeleton is 1,2-epoxy-4- (2,2-bis (hydroxymethyl) -1-butanol. 2-oxiranyl) cyclohexane adduct (“EHPE-3150” manufactured by Daicel Chemical Industries, Ltd.) is preferable.

  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, the content of the epoxy compound (A) is preferably 3% by weight or more, more preferably 5% by weight or more, still more preferably 10% by weight or more, preferably 99% by 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 white curable material 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.

[Curing agent (B)]
The said white curable composition contains a hardening | curing agent (B) so that it can harden | cure efficiently by provision of heat. The curing agent (B) cures the epoxy compound (A). As the curing agent (B), a known 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 curing agent (B), triphenylphosphine is formed by a shell formed of an acid anhydride, dicyandiamide, a phenol compound, a hydrazide compound, an imidazole compound, a compound having a triazine ring, a methyl (meth) acrylate resin, a styrene resin, or the like. A latent curing agent (for example, “EPCAT-P” and “EPCAT-PS” manufactured by Nippon Kayaku Co., Ltd.), a polyurea polymer or a radical polymer formed by a shell formed with a (curing agent) is coated with an amine. It is obtained by dispersing a curing agent such as a latent curing agent (described in Japanese Patent No. 3031897 and Japanese Patent No. 3199818) coated with a curing agent such as modified imidazole in an epoxy resin and confining and grinding. Latent curing agent ("Novakyu" manufactured by Asahi Kasei E-materials HXA3792 "and" HXA3932HP "), a latent curing agent in which a curing agent is dispersed and contained in a thermoplastic polymer (described in Japanese Patent No. 3098061), and an imidazole latency coated with a tetrakisphenol compound or the like Examples thereof include curing agents (for example, “TEP-2E4MZ” and “HIPA-2E4MZ” manufactured by Nippon Soda Co., Ltd.). A curing agent (B) other than these may be used.

  From the viewpoint of further improving the adhesion between the lead frame and the molded body, the curing agent (B) preferably contains an acid anhydride curing agent. The white curable composition preferably contains an acid anhydride curing agent. By using an acid anhydride curing agent, it is possible to maintain high curability and further suppress molding unevenness of the molded body. 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). 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, the equivalent ratio (epoxy equivalent: hardener equivalent) of the epoxy equivalent of the whole epoxy compound (A) and the hardener equivalent of a hardening | curing agent (B) is 0.3: 1. 2: 1 is preferable, and 0.5: 1 to 1.5: 1 is more preferable. 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 contains a titanium oxide (C), a 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 a case where only a filler different from the titanium oxide (C) is used. The titanium oxide (C) contained in the white curable composition is not particularly limited. As for 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 type titanium oxide or anatase type titanium oxide, and more preferably rutile type titanium oxide. By using rutile-type titanium oxide, a molded article having more excellent heat resistance and light resistance can be obtained. The anatase type titanium oxide has a lower hardness than the rutile type titanium oxide. For this reason, the moldability of the said white curable material 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 a rutile chlorine method titanium oxide, and a product number manufactured by Ishihara Sangyo Co., Ltd., which is a rutile sulfuric acid method titanium oxide. : R-630 and the like.

  It is preferable that the said titanium oxide (C) contains the rutile type titanium oxide surface-treated with the silicon oxide. By using the rutile type titanium oxide surface-treated with the silicon oxide, the heat resistance of the molded body is further enhanced.

  The content of the titanium oxide (C) in 100% by weight of the white curable composition is preferably 3% by weight or more, more preferably 10% by weight or more, still more preferably 15% by weight or more, preferably 95% by weight. Hereinafter, it is more preferably 90% by weight or less, and still more preferably 85% by weight or less. When the content of 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 exposed to a high temperature. When it is done, it becomes difficult to yellow.

(Filler (D))
The filler (D) is a filler different from titanium oxide. The filler (D) is not particularly limited. As for the said filler (D), only 1 type may be used and 2 or more types may be used together.

  Any of an inorganic filler and an organic filler can be used as the filler (D). Specific examples of the filler (D) include silica, alumina, mica, beryllia, potassium titanate, barium titanate, strontium titanate, calcium titanate, zirconium oxide, antimony oxide, aluminum borate, aluminum hydroxide, Magnesium oxide, calcium carbonate, magnesium carbonate, aluminum carbonate, calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, calcium sulfate, barium sulfate, silicon nitride, boron nitride, calcined clay, talc, silicon carbide, cross-linked Examples include acrylic resin particles and silicone particles. As for the said filler (D), only 1 type may be used and 2 or more types may be used together.

  The filler (D) is preferably silica. Use of silica further increases the strength of the molded body.

  From the viewpoint of further improving the moldability of the white curable material, the filler (D) preferably includes a filler having an average particle size of 10 μm or more and 50 μm or less. From the viewpoint of further improving the moldability of the white curable material, the filler (D) preferably includes a filler having an average particle diameter of 1 μm or more and less than 10 μm. From the viewpoint of further improving the moldability of the white curable material, the filler (D) includes a first filler having an average particle size of 10 μm or more and 50 μm or less, and an average particle size of 1 μm or more and less than 10 μm. It is particularly preferable to include both the second filler and the second filler. Due to the combined use of the first and second fillers, burrs are more unlikely to occur during transfer molding.

  The average particle size is a particle size value 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, “LS13 320” manufactured by Beckman Coulter, Inc., and the like can be given.

  The filler (D) may include a spherical filler, may include a crushed filler, or may include both a spherical filler and a crushed filler.

  The content of the filler (D) in 100% by weight of the white curable composition 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. Hereinafter, it is more preferably 90% by weight or less, and still more preferably 85% by weight or less. When the content of the filler (D) is not less than the above lower limit and not more than the above upper limit, the moldability of the white curable material is further enhanced.

(Curing accelerator (E))
The white curable composition 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 white curable material can be enhanced, and the heat resistance of the molded body 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.

  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 enhancing the curability of the white curable material and further enhancing the heat resistance of the molded body, 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) 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, based on 100 parts by weight of the epoxy compound (A). Preferably it is 10 weight part or less, More preferably, it is 5 weight part or less.

(Antioxidant (F))
As said antioxidant (F), a phenolic antioxidant, a phosphorus antioxidant, an amine antioxidant, etc. are mentioned.

  Examples of commercially available phenolic antioxidants include IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, and IRGANOX 295 (all of which are manufactured by BASF), ADK STAB AO-30, and ADK STAB AO. -40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-90, and ADK STAB AO-330 (all of which are manufactured by ADEKA), Sumilizer GA-80, and Sumizer MDP -S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), and Sumilizer G (All are manufactured by Sumitomo Chemical Co., Ltd.), HOSTANOX O10, HOSTANOX O16, HOSTANOX O14, and HOSTANOX O3 (all are manufactured by Clariant), Antage BHT, Antage W-300, Antage W-400, and Antage W500 (All as described above, manufactured by Kawaguchi Chemical Industry Co., Ltd.), SEENOX 224M, and SEENOX 326M (all as described above, manufactured by Sipro Kasei Co., Ltd.).

  Examples of the phosphorus antioxidant include cyclohexylphosphine and triphenylphosphine. Commercially available products of the above phosphorus antioxidants include Adeastab PEP-4C, Adeastab PEP-8, Adeastab PEP-24G, Adeastab PEP-36, Adeastab HP-10, Adeastab 2112, Adeastab 260, Adeastab 522A, Adeastab 1178, Adeastab 1500, Adeastab C, Adeastab 135A, Adeastab 3010, and Adeastab TPP (all of which are manufactured by ADEKA), Sandstub P-EPQ, and Hostanox PAR24 (all of which are manufactured by Clariant), and JP-312L, JP -318-0, JPM-308, JPM-313, JPP-613M, JPP-31, JPP-2000PT, and JPH-3800 (all of which are Johoku Manabu Kogyo Co., Ltd.), and the like.

  Examples of the amine-based antioxidant include triethylamine, melamine, ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-tolyl-S-triazine, and 2,4-diamino- Examples include 6-xylyl-S-triazine and quaternary ammonium salt derivatives.

  Of the above-described antioxidants (F), phenolic antioxidants are more preferable. By using a phenol-based antioxidant, a molded article having more excellent heat resistance can be obtained. As for the said phenolic antioxidant, only 1 type may be used and 2 or more types may be used together.

  The content of the antioxidant (F) is preferably 0.1 parts by weight or more, more preferably 5 parts by weight or more, preferably 50 parts by weight or less, more preferably 100 parts by weight of the epoxy compound (A). Is 30 parts by weight or less. When the content of the antioxidant (F) is not less than the above lower limit and not more than the upper limit, a molded body that is more excellent in heat resistance can be obtained.

(Coupling agent (G))
The white curable composition may further contain a coupling agent (G). By using the coupling agent (G), the adhesiveness between the thermosetting component, titanium oxide (C) and the filler (D) is improved in the molded body. As for a coupling agent (G), only 1 type may be used and 2 or more types may be used together.

  Although it does not specifically limit as said coupling agent (G), For example, a silane coupling agent and a titanate coupling agent are mentioned. As the silane coupling agent, generally an epoxy silane coupling agent, an amino silane coupling agent, a cationic silane coupling agent, a vinyl silane coupling agent, an acrylic silane coupling agent, a mercapto silane coupling agent and These composite coupling agents are mentioned. The coupling agent (G) is preferably a silane coupling agent.

  In 100% by weight of the white curable composition, the content of the coupling agent (G) is preferably 0.01% by weight or more, and preferably 5% by weight or less.

(Other ingredients)
The white curable composition comprises a mold release agent, a resin modifier, a colorant, a diluent, a surface treatment agent, a flame retardant, a viscosity modifier, a dispersant, a dispersion aid, and a surface modifier as necessary. , A plasticizer, an antibacterial agent, an antifungal agent, a leveling agent, a stabilizer, an anti-sagging agent or a phosphor may be contained. The diluent may be a reactive diluent or a non-reactive diluent.

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

(Other details of white curable material for optical semiconductor device, other details of manufacturing method of white curable material for optical semiconductor device, and molded article for optical semiconductor device)
The white curable material for optical semiconductor devices according to the present invention and the white curable material for optical semiconductor devices obtained by the method for producing a white curable material for optical semiconductor devices according to the present invention are: It is a white curable material for optical semiconductor devices used for obtaining a molded body placed on a lead frame to be mounted. 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 material for optical semiconductor devices obtained by the method for producing the white curable material for optical semiconductor devices according to the present invention and the white curable material for optical semiconductor devices according to the present invention is obtained. In the semiconductor device, the conductive material is formed on the lead frame on which the optical semiconductor element is mounted and on the side of the optical semiconductor element, and has a light reflecting portion that reflects the light emitted from the optical semiconductor element. It is preferable that it is a white curable material for optical semiconductor devices used for obtaining.

  Since a molded article having high light reflectance is obtained, the white curable material for optical semiconductor devices obtained by the method for producing the white curable material for optical semiconductor devices according to the present invention and the white curable material for optical semiconductor devices according to the present invention is obtained. The conductive material is disposed on the lead frame on which the optical semiconductor element is mounted in the semiconductor device so as to surround the optical semiconductor element, and has a light reflecting portion that reflects light emitted from the optical semiconductor element on the inner surface. It is preferably a white curable material for optical semiconductor devices used for obtaining a molded body. 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.

  A white curable material for an optical semiconductor device according to the present invention and a white curable material for an optical semiconductor device obtained by the method for producing a white curable material for an optical semiconductor device according to the present invention have a lead frame and a white molded body. It is preferably used for obtaining individual molded bodies by dividing the pre-division shaped bodies after obtaining the pre-division shaped bodies connected via at least one of the curable materials. Examples of the dividing method include punching with a mold and dicing.

  The white curable composition or the white curable material comprises an epoxy compound (A), a curing agent (B), titanium oxide (C), a filler (D), and other components blended as necessary. It can be obtained by mixing by a conventionally known method. As a general method for producing the white curable composition or the white curable material, there is 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. Can be mentioned. 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 60 minutes, and more preferably kneading at 20 to 100 ° C. for 10 to 30 minutes. It is more preferable to knead for 10 to 60 minutes at a temperature of 60 to 100 ° C.

  An optical semiconductor device molded body according to the present invention is an optical semiconductor obtained by curing the white curable material for an optical semiconductor device according to the present invention or the method for producing a white curable material for an optical semiconductor device according to the present invention. It is obtained by curing a white curable material for equipment. The white curable material for optical semiconductor devices is formed into a predetermined shape. The molded body for an optical semiconductor device according to the present invention is preferably used so as to contact a metal part in the optical semiconductor device, and more preferably used so as to contact an electrode. The molded body obtained by curing the white curable material for an optical semiconductor device 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 body for an optical semiconductor device using the white curable material for the 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. Can be mentioned. Of these, transfer molding is preferred.

  In the transfer molding method, for example, a molded body is obtained by transfer molding the white curable material for optical semiconductor devices 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. It is done. The molding temperature is more preferably 150 to 190 ° C., and the molding time is more preferably 60 to 200 seconds. The conditions for obtaining a molded body for measuring the Shore D are set at a molding temperature of 170 ° C. and a molding time of 100 seconds. The molding temperature and molding time during transfer molding of the white curable material are as follows. This is because it is generally within the above-mentioned range.

(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. A white curable material for an optical semiconductor device obtained by the method, wherein the molded body cures the white curable material for an optical semiconductor device according to the present invention or is produced by the method for producing a white curable material for an optical semiconductor device according to the present invention. It is obtained by curing.

  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 material for optical semiconductor devices mentioned above, and are obtained by hardening the white curable material 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 and the pre-division optical semiconductor device, a plurality of molded bodies are connected to form a pre-division molded body, but a plurality of molded bodies are not connected to each other. The front 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) YD-013 (bisphenol A type epoxy resin having an aromatic skeleton, epoxy equivalent 850, manufactured by Nippon Steel Chemical Co., Ltd.)
2) YDCN704 (Cresol novolac type epoxy resin having an aromatic skeleton, epoxy equivalent 210, manufactured by Nippon Steel Chemical Co., Ltd.)
3) EHPE3150 (epoxy resin having an alicyclic skeleton, epoxy equivalent 180, manufactured by Daicel Chemical Industries)

(Curing agent (B))
1) Ricacid HH (hexahydrophthalic anhydride, manufactured by Shin Nippon Chemical Co., Ltd.)
2) Ricacid MH-700 (mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride, manufactured by Shin Nippon Rika Co., Ltd.)
3) DICY7 (dicyandiamide, manufactured by Mitsubishi Chemical Corporation)

(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.)

(Filler (D))
1) SE-40 (spherical silica, average particle size 37 μm, manufactured by Tokuyama Corporation)
2) 3K-S (crushed silica, average particle size 35 μm, manufactured by Tatsumori)
3) MSS-7 (spherical silica, average particle size 7 μm, manufactured by Tatsumori)
4) XJ-7 (crushed silica, average particle size 6 μm, manufactured by Tatsumori)

(Curing accelerator (E))
1) SA102 (DBU-octylate, manufactured by San Apro)
2) PX-4ET (tetra-n-butylphosphonium-o, o-diethyl phosphorodithionate, manufactured by Nippon Chemical Industry Co., Ltd.)

(Antioxidant (F))
1) Irganox 1010 (phenolic antioxidant, manufactured by BASF)

(Examples 1-12 and Comparative Examples 1-5)
The components shown in Tables 1 and 2 below are blended in the blending amounts shown in Tables 1 and 2 below, and mixed at 100 ° C. for 20 minutes in a mixer (Laboplast Mill R-60, manufactured by Toyo Seiki Seisakusho). I got a thing. After pulverizing the melt-kneaded material at room temperature, after aging in the time shown in Tables 1 and 2 below in an oven at 70 ° C. or after aging was not performed (aging time: 0 hour), tableting was performed. Thus, a white curable material was obtained.

(Measurement)
(1) Softening point 20 mg of the obtained white curable material was taken out into an aluminum pan for DSC (differential scanning calorimetry). The softening point was measured from the endothermic peak due to softening of the white curable material by DSC at a temperature rising rate of 10 ° C./min in the temperature range of 0 to 150 ° C.

(2) Gel time 0.5 g of the obtained white curable material was taken out. The mixture was stirred with a stainless spatula while being heated on a hot plate heated to 170 ° C., and the time until the fluidity of the white curable material was lost due to the curing reaction was evaluated. The time until fluidity was lost was defined as gel time.

(3) Viscosity Using a high-pressure flow tester manufactured by Shimadzu Corporation, the viscosity of the obtained white curable material at 170 ° C. under the conditions of a temperature of 170 ° C., a load of 20 kgf, a die hole diameter of 1 mm and a die length of 1 mm. It was measured.

(4) Shore D (hardness)
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. A substrate for mounting an optical semiconductor device provided with a molded body was produced on the lead frame by transfer molding (molding temperature: 170 ° C., molding time: 100 seconds) by the MAP molding method. 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 taken out of the mold, and 5 seconds later, the hardness of the cull portion in the molded body was measured. In this hardness measurement, Shore D, which is the hardness defined by the durometer type D, was obtained in accordance with JIS K6253.

(Evaluation)
(1) Handling property A white curable material (hereinafter referred to as a tablet) obtained by tableting was placed on an aluminum bat, placed in an oven at 40 ° C., and taken out after 2 hours. Thereafter, the tablet was taken out from the aluminum bat, and the handleability of the tablet was determined according to the following criteria.

[Handling criteria]
○: The tablet is not softened, and the tablet is not attached to the aluminum bat after taking out. ×: The tablet surface is partially softened, and part of the tablet is attached to the aluminum bat after taking out.

(2) Formability (fillability into mold)
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. A substrate for mounting an optical semiconductor device provided with a molded body was produced on the lead frame by transfer molding (molding temperature: 170 ° C., molding time: 100 seconds) by the MAP molding method. 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 substrate for mounting an optical semiconductor device was visually inspected, and formability was determined according to the following criteria.

[Criteria for moldability]
○: There is no appearance abnormality such as chipping and weld due to poor filling in the molded body ×: There is one or more appearance abnormality such as chipping and welding due to poor filling in the molded body

(3) Continuous moldability Each of the obtained white curable materials was molded 50 times under the same molding conditions as the above (2) moldability. The number of continuous molding was counted and the continuous moldability was determined according to the following criteria.

[Criteria for continuous formability]
○: Molding was possible 50 times continuously, the cured product did not adhere to the mold, and the release property of the molded body from the mold was good. Object stuck

(4) Burr length A mold for burr evaluation shown in FIGS. 4 (a) and (b) was prepared. An upper die 51 having a 50 μm slit 51a, a lower die 52, and a plunger 53 were prepared. A cylindrical molded body X having a diameter of 11 mm and a height of 5 mm, on which the obtained white curable material was molded, was prepared. Using a flow tester, press the obtained molded body X with the plunger 53 under the conditions of a temperature of 170 ° C., a load of 300 kgf, and a heating time of 100 seconds, and use a caliper to determine the length of the burr produced by flowing out of the slit 51a. It was. The burr length was determined according to the following criteria.

[Burr length criteria]
○○: Burr length is less than 1 mm ○: Burr length is 1 mm or more and less than 2 mm ×: Burr length is 2 mm or more

  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 (5)

A white curable composition for optical semiconductor devices, which is a white curable composition or a heat-treated product obtained by heat-treating the white curable composition,
The curable composition includes an epoxy compound, a curing agent, titanium oxide, a filler different from titanium oxide, and a curing accelerator,
The softening point is 60 ° C. or higher and lower than 120 ° C.,
Viscosity that will be measured at a pressure of 170 ° C. and a load 20kgf exceeds 120 Pa · s, or less 300 Pa · s,
Gel time at 170 ° C. is 30 seconds or more and 100 seconds or less,
When the molded body is taken out from the mold after transfer molding in the mold at a molding temperature of 170 ° C. and a molding time of 100 seconds, the hardness of the molded body after 5 seconds from the mold is Shore A white curable material for optical semiconductor devices having a D of 70 or more.   The white curable material for optical semiconductor devices according to claim 1, wherein the epoxy compound includes at least one of an epoxy compound having an aromatic skeleton and an epoxy compound having an alicyclic skeleton.   The white curable material for optical semiconductor devices according to claim 1, wherein the titanium oxide is rutile titanium oxide.   4. The heat-treated product obtained by heat-treating the curable composition by aging at 50 to 80 ° C. for 1 to 48 hours after kneading at a temperature of 60 to 100 ° C. for 10 to 60 minutes. Item 1. A white curable material for an optical semiconductor device according to item 1. Using the white curable composition containing an epoxy compound, a curing agent, titanium oxide, a filler different from titanium oxide, and a curing accelerator, the white curable composition is heated to 60 to 100 ° C. A step of obtaining a white curable material for an optical semiconductor device, which is a heat-treated product obtained by heat-treating the curable composition by aging at a temperature of 50 to 80 ° C. for 1 to 48 hours after kneading at a temperature for 10 to 60 minutes. Prepared,
Softening point 60 ° C. or more and less than 120 ° C., exceed 170 ° C. and the load measured Ru viscosity of 120 Pa · s under a pressure of 20 kgf, or less 300 Pa · s, gel time 30 seconds or more at 170 ° C., 100 The molded product is 5 seconds after being taken out from the mold when the molded product is taken out from the mold after transfer molding in the mold at a molding temperature of 170 ° C. and a molding time of 100 seconds. The manufacturing method of the white curable material for optical semiconductor devices which obtains the white curable material for optical semiconductor devices whose hardness is 70 or more by Shore D is.

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