JP5798839B2 - Optical semiconductor device - Google Patents

Description

  The present invention relates to an optical semiconductor device, 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, and the white curable composition for an optical semiconductor device. The present invention relates to a molded body and an optical semiconductor device using the composition.

  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, Patent Document 1 below discloses a curable composition containing an epoxy resin, a curing agent, a curing catalyst, and an inorganic filler. 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.

  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.

JP 2009-141327 A JP 2011-9519 A

  When the conventional curable composition as described in Patent Documents 1 and 2 is transfer molded, there is a problem that the curing rate of the curable composition is slow. For this reason, there exists a problem that it is difficult to take out the molded object after shaping | molding from a metal mold | die.

  Furthermore, when a molded body is obtained using a conventional curable composition, uneven molding tends to occur in the obtained molded body.

  Moreover, when carrying out transfer molding of the conventional curable composition as described in Patent Document 1, it is necessary to separate the LED package including the transfer molded molded body from the runner portion. However, since the molded body using the conventional curable composition containing titanium oxide is brittle, when the LED package is separated from the runner portion, the molded body is damaged or deformed, or the molded body is cracked or chipped. Sometimes.

  Moreover, in the manufacturing method of an optical semiconductor device as described in Patent Document 2, it is necessary to divide a molded body before division in which a plurality of molded bodies are continuous into individual molded bodies. However, when the pre-division molded body is divided into individual molded bodies, the molded body may be cracked or chipped. That is, when the conventional curable composition is used, there exists a problem that the workability of a molded object is low.

  An object of the present invention is to use a white curable composition for an optical semiconductor device capable of obtaining a molded article having excellent curability and suppressed molding unevenness, and the white curable composition for an optical semiconductor device. And providing an optical semiconductor device.

  A limited object of the present invention is to provide a white curable composition for an optical semiconductor device capable of obtaining a molded article excellent in processability, and a molded article and an optical semiconductor using the white curable composition for an optical semiconductor device. Is to provide a device.

  According to a wide aspect of the present invention, in an optical semiconductor device, there is provided 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. A compound, a curing agent, titanium oxide, and a filler different from titanium oxide, with or without a curing accelerator, and when the curing accelerator is not included, the curing agent is basic When the curing accelerator is included, the curing agent contains a basic curing agent, or the curing accelerator contains a basic curing accelerator. At least one of the titanium oxide and the filler is heated by boiling a liquid obtained by adding 5 g of the component to 100 mL of pure water and boiling for 5 minutes. Get the liquid and then get White for an optical semiconductor device containing a component having a pH value of 4 or more and less than 7 when the pH of a solution obtained by adding water in an amount of water evaporated by boiling to a boiling treatment solution to make the amount of water 100 mL is measured. A curable composition is provided.

  In a specific aspect of the white curable composition for an optical semiconductor device according to the present invention, at least one of the titanium oxide and the filler is coated with an acidic metal oxide or an acidic metal hydroxide.

  In another specific aspect of the white curable composition for an optical semiconductor device according to the present invention, at least one of the titanium oxide and the filler is coated with a coating material containing silicon oxide.

  In another specific aspect of the white curable composition for optical semiconductor devices according to the present invention, the curing agent contains an acid anhydride curing agent.

  The epoxy compound preferably includes at least one of an epoxy compound having an aromatic skeleton and an epoxy compound having an alicyclic skeleton. The epoxy compound preferably includes an epoxy compound having an aromatic skeleton. The epoxy equivalent of the epoxy compound having an aromatic skeleton is preferably 400 or more and 3000 or less. The epoxy compound preferably includes an epoxy compound having an alicyclic skeleton.

  In another specific aspect of the white curable composition for optical semiconductor devices according to the present invention, the filler includes both a spherical filler and a crushed filler.

  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.

  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 composition for semiconductor devices.

  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, a curing agent, titanium oxide, and a filler different from titanium oxide, and does not include a curing accelerator or includes the curing agent. When the accelerator is not included, the curing agent contains a basic curing agent, and when the curing accelerator is included, the curing agent contains a basic curing agent, Or the said hardening accelerator contains the hardening accelerator which has basicity, and also the component in which at least one component of the said titanium oxide and the said filler shows the value of 4 or more and less than 7 by boiling method. Since it contains, the molding which has favorable sclerosis | hardenability and the shaping | molding nonuniformity was suppressed can be obtained.

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 includes an epoxy compound (A), a curing agent (B), titanium oxide (C), and a filler (D) different from titanium oxide. The white curable composition for optical semiconductor devices according to the present invention does not contain or contains a curing accelerator (E). It is preferable that the white curable composition for optical semiconductor devices which concerns on this invention contains a hardening accelerator (E). In the white curable composition for optical semiconductor devices according to the present invention, when the curing accelerator (E) is not included, the curing agent (B) contains a basic curing agent, and the curing acceleration is performed. When the agent (E) is included, the curing agent (B) contains a basic curing agent, or the curing accelerator (E) contains a basic curing accelerator. When the said hardening accelerator (E) is contained, the said hardening agent (B) contains the hardening agent which has basicity, and the said hardening accelerator (E) contains the hardening accelerator which has basicity. May be.

  In the white curable composition for optical semiconductor devices according to the present invention, at least one of the titanium oxide (C) and the filler (D) has a pH measured by boiling method of 4 or more and less than 7. The component which shows is contained. In the white curable composition for optical semiconductor devices according to the present invention, the titanium oxide (C) may contain titanium oxide having a pH measured by boiling method of 4 or more and less than 7, and the filler ( D) may contain a filler having a pH measured by boiling method of 4 or more and less than 7, and titanium oxide (C) has a pH measured by boiling method of 4 or more and less than 7. And the filler (D) may include a filler having a pH measured by boiling method of 4 or more and less than 7. Further, the whole of titanium oxide (C) may have a pH measured by boiling method of 4 or more and less than 7, and a part of titanium oxide (C) has a pH measured by boiling method. A value of 4 or more and less than 7 may be indicated. The whole of the filler (D) may have a pH measured by boiling method of 4 or more and less than 7, and a part of the filler (D) has a pH measured by boiling method of 4 or more. , A value less than 7 may be indicated.

  In the boiling method, a solution obtained by adding 5 g of the above component to 100 mL of pure water is heated and boiled for 5 minutes, and then left to stand until reaching 23 ° C. to obtain a boiling treatment liquid, and then the obtained boiling treatment This is a method of measuring the pH of a liquid in which the amount of water evaporated by boiling is added to the liquid to bring the amount of water to 100 mL.

  In the present specification, a liquid obtained by adding 5 g of the above component to 100 mL of pure water is heated and boiled for 5 minutes, and then left to stand until reaching 23 ° C. to obtain a boiling treatment liquid, and then the obtained boiling treatment liquid In addition, the method of measuring the pH of a solution in which the amount of water evaporated by boiling is added to make the amount of water 100 mL may be called a boiling method.

  In the boiling method, specifically, a solution obtained by adding 5 g of the above component to 100 mL of pure water is placed in a container having an opening. The liquid in the container is heated by heating the container, and the liquid in the container is boiled. Maintain boiling for 5 minutes after starting to boil. Thereafter, a stopper is attached to the opening of the container and left to reach 23 ° C. to obtain a boiling treatment liquid. The stopper is removed from the opening of the container, and the amount of water evaporated by boiling is added to the obtained boiling treatment liquid to make the amount of water 100 mL. A stopper is attached to the opening of the container, shaken for 1 minute, and allowed to stand for 5 minutes. In this way, a measurement liquid is obtained. The pH of the obtained measuring solution is JIS Z8802 7. Can be measured in accordance with the operation described in 1.

  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 molded body is a cured product molded into a predetermined shape.

  By adopting the above-described configuration in the white curable composition for optical semiconductor devices according to the present invention, particularly by using a component having a pH of 4 or more and less than 7 in the boiling method, the curability of the white curable composition is good. And uneven molding of the molded body can be suppressed. When the curability is improved by increasing the basicity of components other than the components having a pH of 4 or more and less than 7 in the boiling method, uneven molding tends to occur. By using a component having a pH of 4 or more and less than 7, molding unevenness can be sufficiently suppressed.

  In general, there are acid points and base points on the surfaces of titanium oxide and the filler, respectively. The surface of a component having a pH of 4 or more and less than 7 in the boiling method has more acid sites than base sites. A component having a pH of 4 or more and less than 7 in the boiling method greatly contributes to suppression of molding unevenness. In addition, even if it uses the component whose pH in the said boiling method is 7 or more with the component whose pH in the said boiling method is 4 or more and less than 7, hardening by the component whose pH in the said boiling method is 4 or more and less than 7 The effect of improving the property is sufficiently obtained.

  Titanium oxide (C) preferably contains a component having a pH measured by boiling method of 4 or more and less than 7. Moreover, it is also preferable that a filler (D) contains the component in which pH measured by the boiling method shows the value of 4 or more and less than 7.

  The total content of titanium oxide (C) and filler (D) is 100% by weight or more, and the content of the above component having a pH measured by boiling method of 4 or more and less than 7 is preferably 10% by weight or more. More preferably, it is 30 weight% or more and 100 weight% or less. When the content of the above component having a pH measured by boiling method of 4 or more and less than 7 is not less than the above lower limit, the curability of the white curable composition is further enhanced, and the molding unevenness of the molded product is caused. It becomes even less likely to occur. The above-mentioned component in which the pH of the whole of titanium oxide (C) and filler (D) measured by boiling method is 4 or more and less than 7 may be used.

  In 100% by weight of the white curable composition for an optical semiconductor device, the content of the component having a pH measured by boiling method of 4 or more and less than 7 is preferably 1% by weight or more, more preferably 3%. % By weight or more, more preferably 5% by weight or more, particularly preferably 10% by weight or more, most preferably 20% by weight or more, preferably 95% by weight or less, more preferably 93% by weight or less, still more preferably 90% by weight or less. It is. When the content of the component having a pH measured by boiling method of 4 or more and less than 7 is not less than the above lower limit and not more than the above upper limit, the curability of the white curable composition is further increased, and the molded product This makes it more difficult to form unevenness.

  Of the total of 100% by weight of the curing agent (B) and the curing accelerator (E), the total content of the basic curing agent and the basic curing accelerator is preferably 0.1% by weight or more, More preferably, it is 0.5 weight% or more and 100 weight% or less. When the total content of the basic curing agent and the basic curing accelerator is not less than the above lower limit, the curability of the white curable composition is further enhanced.

  In 100% by weight of the white curable composition for optical semiconductor devices, the total content of the basic curing agent and the basic curing accelerator is preferably 0.01% by weight or more, more preferably 0.8%. It is at least 05% by weight, preferably at most 20% by weight, more preferably at most 10% by weight. When the total content of the basic curing agent and the basic curing accelerator is not less than the above lower limit, the curability of the white curable composition is further enhanced.

  Furthermore, by adopting the above-described configuration in the white curable composition for optical semiconductor devices according to the present invention, a molded article having excellent processability can be obtained. Since the white curable composition for optical semiconductor devices according to the present invention is excellent in moldability, the use of the white curable composition for optical semiconductor devices according to the present invention makes it easy to form a molded body having a uniform and good shape. Can get to.

  In the present invention, for example, after molding the white curable composition for optical semiconductor devices according to the present invention, when separating the LED package including the molded product from the runner part, the molded product is damaged, deformed, Cracks and chips are less likely to occur. Furthermore, when the pre-division molded body having a plurality of molded bodies is divided into individual molded bodies to obtain a post-division molded body, cracks and chips are less likely to occur in the molded body. That is, by using the white curable composition for optical semiconductor devices according to the present invention, a molded body using the white curable composition for optical semiconductor devices can be diced satisfactorily.

  Moreover, the reflectance of the molded object obtained by hardening the white curable composition for optical semiconductor devices is improved by employ | adopting the said composition in the white curable composition for optical semiconductor devices which concerns on this invention. Can do. 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.

  In order to make the surface acidic, it is preferable that at least one of titanium oxide (C) and filler (D) is coated with an acidic metal oxide or acidic metal hydroxide. In this case, the curability of the white curable composition is further increased, and the molding unevenness of the molded body is further less likely to occur. Titanium oxide (C) is preferably coated with an acidic metal oxide or acidic metal hydroxide, and the filler (D) may be coated with an acidic metal oxide or acidic metal hydroxide. preferable. As for the said acidic metal oxide or acidic metal hydroxide, only 1 type may be used and 2 or more types may be used together.

  Examples of the acidic metal oxide or acidic metal hydroxide include metal compounds containing aluminum, silicon, zinc, tin, lead, or the like. In this specification, silicon is included in a metal element. From the viewpoint of further enhancing the curability of the white curable composition and further suppressing the molding unevenness of the molded body, the metal elements constituting the acidic metal oxide or acidic metal hydroxide are aluminum and silicon. Of these, at least one of them is preferred. From the viewpoint of further enhancing the curability of the white curable composition and further suppressing the molding unevenness of the molded body, at least one of the titanium oxide (C) and the filler (D) contains silicon oxide. It is preferable that the coating material is coated with the coating material. Titanium oxide (C) is preferably coated with a coating material containing silicon oxide, and the filler (D) is also preferably coated with a coating material containing silicon oxide. Silicon oxide is preferably used as the acidic metal oxide or acidic metal hydroxide.

  From the standpoint of further enhancing the curability of the white curable composition and further suppressing the molding unevenness of the molded body, the titanium oxide (C) is a rutile titanium oxide, and the rutile titanium oxide is an acidic metal. It is preferably coated with an oxide or an acidic metal hydroxide.

  Examples of the coating method using the acidic metal oxide or acidic metal hydroxide include the following methods.

  Titanium oxide or a filler is dispersed in water or a liquid containing water as a main component to obtain a slurry. If necessary, the titanium oxide or filler is pulverized by a sand mill or a ball mill. The pH of the slurry is then made neutral or acidic, optionally alkaline. Thereafter, a water-soluble salt serving as a raw material for the coating material is added to the slurry to coat the surface of the titanium oxide or filler. Thereafter, the slurry is neutralized and the titanium oxide or filler is recovered. The recovered titanium oxide or filler may be dried or dry pulverized.

  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 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 for an optical semiconductor device is preferably 500 or more, and preferably 20000 or less. When the epoxy equivalent is 500 or more, the moldability of the white curable composition is further improved, the molded body is not easily 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 composition 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.

  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 composition 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) of 2,2-bis (hydroxymethyl) -1-butanol. -Oxiranyl) cyclohexane adduct ("EHPE-3150" manufactured by Daicel Chemical Industries) 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 for optical semiconductor devices, 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 95% by weight or less, still more preferably 80% by weight or less. When the content of the epoxy compound (A) is not less than the above lower limit, the white 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.

[Curing agent (B)]
The said white curable composition for optical semiconductor devices 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 or a styrene resin. 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 curing agent (B) preferably contains a basic curing agent. By using a basic curing agent, the curability of the white 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.

  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.

  The content of the basic curing agent with respect to 100 parts by weight of the epoxy compound (A) is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and still more preferably 2 parts by weight or more. The amount is particularly preferably 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. When the content of the basic curing agent is not less than the above lower limit and not more than the above upper limit, the curability of the white curable composition is further increased, and the molding unevenness of the molded body is further less likely to occur.

  The content of the acid anhydride curing agent with respect to 100 parts by weight of the epoxy compound (A) 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. The amount is preferably 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. When the content of the acid anhydride curing agent is not less than the above lower limit and not more than the above upper limit, the curability can be kept high and the molding unevenness of the molded body can be further suppressed.

  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 whole epoxy compound (A) and the hardening | curing agent equivalent of a hardening | curing agent (B) is 0.00. The ratio is preferably 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 a 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 a case where only a filler different from the titanium oxide (C) is used. As for the titanium oxide (C) contained in the said white curable composition for optical semiconductor devices, 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 body having further excellent heat 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 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 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.

  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 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.

  In 100% by weight of the white curable composition for optical semiconductor devices, the content of titanium oxide having a pH measured by the boiling method of 4 or more and less than 7 is 0% by weight or more, preferably 1% by weight. Or more, more preferably 3% by weight or more, still more preferably 10% by weight or more, particularly preferably 15% 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. . When the content of titanium oxide having a pH measured by the boiling method of 4 or more and less than 7 is not less than the above lower limit (excluding 0% by weight) and not more than the above upper limit, curability of the white curable composition. Becomes even higher, and the molding unevenness of the molded body becomes even less likely to occur.

(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.

  From the viewpoint of enhancing the toughness of the molded body and further improving the workability of the molded body, the filler (D) preferably includes both the spherical filler (D1) and the crushed filler (D2). .

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

  The crushed filler (D2) is a crushed filler. The aspect ratio of the crushing filler (D2) is not particularly limited. The aspect ratio of the crushed filler (D2) is preferably 1.5 or more, and preferably 20 or less. The crushed filler (D2) having an aspect ratio of less than 1.5 is relatively expensive. Therefore, the cost of a white curable composition becomes high. When the aspect ratio is 20 or less, the crushing filler (D2) can be easily filled.

  The aspect ratio of the crushed filler (D2) is, for example, measuring the crushed surface of the crushed filler (D2) using a digital image analysis particle size distribution measuring device (trade name: FPA, manufactured by Nippon Luft). It can ask for.

  Preferred examples of the spherical filler (D1) include silica, alumina, potassium titanate, zirconium oxide, strontium titanate, aluminum borate, magnesium oxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium phosphate and Examples include inorganic spherical fillers such as calcium sulfate, and organic spherical fillers such as crosslinked acrylic resin particles. As for the said spherical filler (D1), only 1 type may be used and 2 or more types may be used together.

  Preferred examples of the crushed filler (D2) include silica, antimony oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, barium carbonate, alumina, mica, beryllia, barium titanate, titanate. Potassium, strontium titanate, calcium titanate, aluminum carbonate, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, calcined clay, etc., talc, aluminum borate, silicon carbide, etc. Can be mentioned. As for the said crushing filler (D2), only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of improving the moldability and obtaining a molded article excellent in thermal conductivity and light reflection characteristics, the crushed filler (D2) is composed of silica, alumina, magnesium oxide, antimony oxide, zirconium oxide, aluminum hydroxide or Magnesium hydroxide is preferred.

  The average particle diameter of the filler (D), the average particle diameter of the spherical filler (D1), and the average particle diameter of the crushed filler (D2) are each preferably 0.1 μm or more, preferably 100 μm or less. . When the average particle size is not less than the above lower limit, the moldability of the white curable composition is further improved. 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 filler (D) in the spherical filler (D1) and the average particle diameter of the crushed filler (D2) are the particle diameter values when the integrated value is 50% in the volume-based particle size distribution curve. It is. The average particle size can be measured using, for example, a laser beam type particle size distribution meter. As a commercially available product of the laser beam type particle size distribution analyzer, a product “LS 13 320” manufactured by Beckman Coulter, Inc. may be mentioned.

  In 100% by weight of the white curable composition for optical semiconductor devices, the content of the filler (D) is preferably 5% by weight or more, more preferably 10% by weight or more, and further preferably 20% 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 filler (D) is not less than the above lower limit and not more than the above upper limit, the moldability of the white curable composition is further enhanced. When the content of the filler (D) is not more than the above upper limit, the light reflectance of the molded body is further increased.

  In 100% by weight of the white curable composition for optical semiconductor devices, the content of the filler different from titanium oxide having a pH measured by the boiling method of 4 or more and less than 7 is 0% by weight or more, Preferably 1% by weight or more, more preferably 3% by weight or more, still more preferably 5% by weight or more, particularly preferably 10% by weight or more, most preferably 20% by weight or more, preferably 95% by weight or less, more preferably 90% by weight. % By weight or less, more preferably 85% by weight or less. When the content of the filler different from titanium oxide having a pH measured by the boiling method of 4 or more and less than 7 is not less than the above lower limit (excluding 0% by weight) and not more than the above upper limit, white curability The curability of the composition is further increased, and the molding unevenness of the molded body is further less likely to occur.

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

  When the spherical filler (D1) and the crushed filler (D2) are used in combination, in the white curable composition for optical semiconductor devices, the crushed filler having a content of the spherical filler (D1) is used. The weight ratio to the content of (D2) (spherical filler (D1) / crushed filler (D2)) is preferably 0.3 or more and 30 or less, more preferably 1 or more and 15 or less. . Content of the said spherical filler (D1) and content of the said crushing filler (D2) show content in 100 weight% of the said white curable composition. That is, in the white curable composition for optical semiconductor devices, the spherical filler (D1) and the crushed filler (D2) are in a weight ratio (spherical filler (D1): crushed filler (D2)). It is preferable to contain by 10-30: 1, and it is more preferable to contain by 1: 1-15: 1. When the content of the spherical filler (D1) is relatively increased, the molded body is less likely to be brittle, the processability of the molded body is further improved, and cracks and chips are less likely to occur in the molded body. When the content of the crushing filler (D2) is relatively increased, the strength of the molded body is further increased.

(Curing 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 white curable composition can be increased, and the heat resistance of the molded body can be further increased. 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. Use of the curing accelerator having basicity further improves the curability of the white curable composition.

  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 enhancing the curability of the white curable composition and further enhancing the heat resistance of the molded article, the curing accelerator (E) may be a urea compound, an onium salt compound, or a phosphorus compound. preferable. 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.

  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 basic curing accelerator is not less than the above lower limit and not more than the above upper limit, the curability of the white curable composition is further increased, and the molding unevenness of the molded body is further less likely to occur.

(Coupling agent (F))
It is preferable that the said white curable composition for optical semiconductor devices further contains a coupling agent (F). By using the coupling agent (F), the adhesiveness between the thermosetting component, titanium oxide (C) and the filler (D) is improved in the molded body. As for a coupling agent (F), 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 (F), 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 (F) is preferably a silane coupling agent.

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

(Other ingredients)
The white curable composition for an optical semiconductor device includes an antioxidant, a release agent, a resin modifier, a colorant, a diluent, a surface treatment agent, a flame retardant, a viscosity modifier, a dispersant, if necessary. It may contain a dispersion aid, a surface modifier, a plasticizer, an antibacterial agent, an antifungal agent, a leveling agent, a stabilizer, an anti-sagging agent or a phosphor. The diluent may be a reactive diluent or a non-reactive diluent.

  Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, and amine antioxidants.

  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.

  The content of the antioxidant 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 30 parts by weight with respect to 100 parts by weight of the epoxy compound (A). Or less. When the content of the antioxidant 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.

  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 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 the epoxy compound (A), a hardening | curing agent (B), a titanium oxide (C), a filler (D), and the other component mix | blended as needed conventionally. It can be obtained by mixing by a known method. As a general method for producing the white curable resin composition, 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. 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 40 minutes, and more preferably kneading at 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, the light reaching the inner surface 4 a of the first molded body 4 as indicated by the arrow B as well as 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. 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-012 (bisphenol A type epoxy resin having an aromatic skeleton, epoxy equivalent 650, manufactured by Nippon Steel Chemical Co., Ltd.)
2) YD-019 (bisphenol A type epoxy resin having an aromatic skeleton, epoxy equivalent 2900, manufactured by Nippon Steel Chemical Co., Ltd.)
3) YDCN704 (Cresol novolac type epoxy resin having an aromatic skeleton, epoxy equivalent 210, manufactured by Nippon Steel Chemical Co., Ltd.)
4) EHPE3150 (epoxy resin having an alicyclic skeleton, epoxy equivalent 180, manufactured by Daicel Chemical Industries)

(Curing agent (B))
1) DICY7 (dicyandiamide, basic, manufactured by Mitsubishi Chemical Corporation)
2) 2MZ-A (2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, basic, manufactured by Shikoku Chemicals)
3) Licacid HH (hexahydrophthalic anhydride, non-basic, manufactured by Shin Nippon Chemical Co., Ltd.)
4) Ricacid MH-700 (mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride, non-basic, manufactured by Shin Nippon Rika)

(Titanium oxide (C))
1) CR-90 (rutile titanium oxide, pH 6.2 by boiling method, surface-treated with Al, Si, manufactured by Ishihara Sangyo Co., Ltd.)
2) CR-50-2 (rutile titanium oxide, pH 8.0 by boiling method, surface treatment with Al, organic treatment, manufactured by Ishihara Sangyo Co., Ltd.)
The titanium oxides 1) and 2) are coated with an acidic metal compound or acidic metal hydroxide. In the surface treatment of titanium oxide, aluminum hydroxide or aluminum oxide is used when the metal species is Al, and silicon oxide is used when the metal species is Si.

(Filler (D))
1) MSR-3512 (spherical silica, pH 6.5 by boiling method, average particle size 30 μm, manufactured by Tatsumori)
2) HSP-2000 (spherical silica, pH 6.5 by boiling method, average particle size 2 μm, manufactured by Toagosei Co., Ltd.)
3) A-1 (crushed silica, pH 6.8 by boiling method, average particle size 11 μm, manufactured by Tatsumori)
4) B-55 (barium sulfate as a crushing filler, pH 8.5 by boiling method, average particle size 1.2 μm, manufactured by Sakai Chemical Industry Co., Ltd.)

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

(Examples 1-12 and Comparative Examples 1-4)
The components shown in the following Tables 1 and 2 are blended in the blending amounts shown in the following Tables 1 and 2, and mixed for 15 minutes with a mixer (Laboplast Mill R-60, manufactured by Toyo Seiki Seisakusho) to obtain a melt-kneaded product. It was. When the melt-kneaded product was liquid at ordinary temperature (23 ° C.), the melt-kneaded product was used as a white curable composition. When the melt-kneaded material was solid at ordinary temperature (23 ° C.), it was pulverized at ordinary temperature and then tableted to obtain a white curable composition.

(Evaluation)
(1) Curability After forming a circuit on a copper material (TAMAC 194) by etching, silver plating was applied 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 180 ° C., molding time 4 minutes) on the lead frame 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. From the state at the time of removing the obtained optical semiconductor device mounting substrate from the mold, the curability was determined according to the following criteria.

[Criteria for curability]
○: It was possible to remove from the mold. ×: When removed from the mold, adhesion of the molded body to the mold or deformation of the molded body was observed.

(2) Molding unevenness The molded product (molded product before division) obtained by the above evaluation of curability was visually observed, and the molding unevenness was determined according to the following criteria.

[Criteria for forming unevenness]
○○: No abnormality in the appearance ○: Chipping of the molded body, voids in the molded body and poor filling of the molded body were found in one place ×: Chipping of the molded body, voids in the molded body and filling of the molded body 2 or more defects were seen in total

(3) Workability The molded body obtained by the above evaluation of curability was after-cured at 170 ° C. for 2 hours. An optical semiconductor mounting having a single optical semiconductor element mounting portion by dividing a pre-division molded body in which a plurality of molded bodies are arranged in a matrix form into individual molded bodies using a dicing apparatus ("DAD3350" manufactured by DISCO). 150 substrates were obtained.

  The dicing surfaces of the molded bodies on the 150 optical semiconductor mounting substrates were observed, and the workability was determined according to the following criteria.

[Criteria for workability]
○○: No more than 3 out of 150 optical semiconductor mounting substrates with cracks or chips in the molded body ○: 4 or more optical semiconductor mounting substrates with cracks or chips in the molded body, 10 or less ×: 11 or more of 150 optical semiconductor mounting substrates in which cracks or chips occurred in the molded body

  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 (9)

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 includes an epoxy compound, a curing agent, titanium oxide, and a filler different from titanium oxide,
The white curable composition for an optical semiconductor device does not contain or contains a curing accelerator,
When the curing accelerator is not included, the curing agent contains a basic curing agent, and when the curing accelerator is included, the curing agent contains a basic curing agent. Or the curing accelerator contains a basic curing accelerator,
At least one of the titanium oxide and the filler is heated to a solution obtained by adding 5 g of the component to 100 mL of pure water, boiled for 5 minutes, and then allowed to stand until reaching 23 ° C. Next, when the pH of the liquid obtained by adding water of the amount of water evaporated by boiling to the obtained boiling treatment liquid to make the amount of water 100 mL was measured, a component showing a value of 4 or more and less than 7 was obtained. The component having a pH of 4 or more and less than 7 is a component having a pH of 4 or more and 6.8 or less,
The optical semiconductor device, wherein the content of a component having a pH of 4 or more and 6.8 or less is 30 % by weight or more in a total of 100% by weight of the titanium oxide and the filler.   The optical semiconductor device according to claim 1, wherein at least one of the titanium oxide and the filler is covered with an acidic metal oxide or an acidic metal hydroxide.   The optical semiconductor device according to claim 1, wherein at least one of the titanium oxide and the filler is covered with a coating material containing silicon oxide.   The optical semiconductor device according to claim 1, wherein the curing agent contains an acid anhydride curing agent.   The optical semiconductor device according to any one of claims 1 to 4, 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 optical semiconductor device according to claim 5, wherein the epoxy compound includes an epoxy compound having an aromatic skeleton.   The optical semiconductor device according to claim 5 or 6, wherein an epoxy equivalent of the epoxy compound having an aromatic skeleton is 400 or more and 3000 or less.   The optical semiconductor device according to claim 5, wherein the epoxy compound includes an epoxy compound having an alicyclic skeleton.   The optical semiconductor device according to claim 1, wherein the filler includes both a spherical filler and a crushed filler.

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