TW201526296A - Method of manufacturing optical semiconductor device and optical semiconductor device - Google Patents

Abstract

The present invention relates to a method of manufacturing an optical semiconductor device comprising a step of sealing an optical semiconductor element using a curable silicone composition, the curable silicone composition, although cured by a hydrosilylation reaction, being hydrosilylation reaction catalyst free, or, if containing a hydrosilylation reaction catalyst, a content of the curable silicone composition being insufficient to cure the composition, and the optical semiconductor element being sealed in a state in which the curable silicone composition contacts a cured silicone that contains a hydrosilylation reaction catalyst. According to the present invention, a method of manufacturing an optical semiconductor device of which the sealing agent realizes storage stability, has good heat resistance, and can greatly resist discoloration can be provided; and an optical semiconductor device obtained by the manufacturing method can be provided.

Description

Optical semiconductor device manufacturing method and optical semiconductor device

The present invention relates to a method of fabricating an optical semiconductor device, and more particularly to a method of fabricating an optical semiconductor device in which the storage stability of an encapsulant of an optical semiconductor device can be achieved, and the encapsulant has good heat resistance and can greatly resist fading. And an optical semiconductor device obtained by the manufacturing method.

The present invention claims priority to Japanese Patent Application No. 2013-184438, filed on Sep. 5, 2013, the content of which is hereby incorporated by reference.

A curable polysiloxane composition cured by a hydrogenation reaction is used as a sealant, a coating agent, a lens molding material, a light reflective material, and the like for an optical semiconductor device (for example, an optical coupler, a light-emitting diode, a solid-state image) Optical semiconductor components in sensors and the like. For example, in Patent Document 1, a curable polydecene oxide composition is proposed which is composed of an organopolysiloxane having an average of not less than 0.2 fluorenyl alkenyl groups per molecule, having a three-dimensional shape The organic polyoxane of the network structure, the organic polyoxane having no less than two hydrazine-bonded hydrogen atoms per molecule, and the hydrazine hydrogenation reaction catalyst. Further, Patent Document 2 proposes a curable polydecene oxide composition which is composed of an organopolysiloxane having a fluorene-bonded phenyl group and a fluorenyl-bonded alkenyl group, having a hydrazine-bonded hydrogen group. Atomic organic polyoxane and hydrazine hydrogenation catalyst.

In the curable polyoxo composition, a reaction control agent is added to suppress hydrogenation The reaction is because the hydrazine hydrogenation reaction can be carried out even at room temperature; however, the compositions have a problem that the viscosity increases with time.

Further, in the curable polyoxosiloxane compositions, the rhodium hydrogenation reaction cannot be carried out unless a rhodium hydrogenation catalyst is added, so that the viscosity is increased. However, it is considered in the art that since the reaction cannot be started, it is necessary to add a rhodium hydrogenation catalyst, and it is also considered that a sealant composed of a composition containing no rhodium hydrogenation catalyst or the like cannot be provided as a product.

Further, in addition to the above problems, the conventional curing polyfluorene has the following problems. Although high heat resistance is necessary for the sealing agent of the optical semiconductor element, since the sealant directly receives the heat generated by the element, the conventional cured polyfluorene oxide is yellowed upon exposure to high temperature.

Prior technical document Patent document

Patent Document 1: Japanese Unexamined Patent Application Publication No. 2006-213789

Patent Document 2: Japanese Unexamined Patent Application Publication No. 2009-185226

In view of the above factors, an object of the present invention is to provide an optical semiconductor in which the storage stability of an encapsulant of an optical semiconductor device can be achieved, and the encapsulant has good heat resistance, and can be greatly resistant to fading even when exposed to a high temperature. A method of manufacturing a device, and an optical semiconductor device obtained by the method.

As a result of diligent research to solve the above problems, the inventors have found that by using a curable polysiloxane composition which is cured by a hydrogenation reaction and contains little or no hydrogenation catalyst, it is used as a sealing of an optical semiconductor element. Further, by disposing the cured polyfluorene oxygen containing the hydrazine hydrogenation reaction catalyst as a member separate from the sealant, fading due to the fact that the sealant contains a hydrogenation reaction catalyst can be suppressed, and good heat resistance can be achieved. It also found that Since the curable polyoxynoxy composition forming the sealant itself does not cure, the curable polyoxynoxy composition which is usually provided in two parts can be provided in part, and thus the mixing operation and mixing of the two parts can be avoided. The complexity of the degassing operation and the prevention of compounding errors during mixing.

That is, the first embodiment of the present invention is a method of manufacturing an optical semiconductor device comprising the step of sealing an optical semiconductor element using a curable polydecene oxide composition, wherein the curable polyoxo composition is hydrogenated by a hydrazine reaction Curing, but it does not contain a rhodium hydrogenation catalyst, or if the curable polyoxo composition does contain a rhodium hydrogenation catalyst, the rhodium hydrogenation catalyst is insufficient to cure the composition; and the optical semiconductor component is sealed It is in a state in which the curable polyoxynene composition is contacted with the cured polyfluorene containing a hydrogenation-reactive catalyst.

Further, the curable polydecene oxide composition comprises: (A) at least one type of organopolyoxyalkylene having at least two fluorenyl alkenyl groups per molecule, and (B) at least one type per molecule An organopolysiloxane having not less than two hydrazine-bonded hydrogen atoms, and which does not contain a hydrazine hydrogenation catalyst, or a hydrazine hydrogenation catalyst if the viscous polyoxyl composition does contain a hydrazine hydrogenation catalyst The amount is preferably insufficient to cure the composition.

The rhodium hydrogenation catalyst is preferably a platinum-based catalyst, and the curable polydecane oxygen composition is preferably free of the rhodium hydrogenation reaction inhibitor.

Further, the cured polyfluorene is preferably a light-reflecting material, a substrate, a dam material or a plate containing a fluorescent substance.

Further, the cured polyfluorene preferably contains at least one type of white pigment selected from the group consisting of titanium oxide, zinc oxide, barium titanate, barium sulfate, and zirconium oxide, and preferably contains at least one type selected from the following Inorganic fillers of the group: non-spherical cerium oxide, spherical cerium oxide and glass fiber.

Another embodiment of the present invention is an optical semiconductor device manufactured by the above method of manufacturing an optical semiconductor device.

According to the present invention, it is possible to provide a method of manufacturing an optical semiconductor device in which a sealant of an optical semiconductor device achieves storage stability, has good heat resistance, and can greatly resist fading; and an optical semiconductor device obtained by the manufacturing method can be provided.

Since the encapsulant is optically transparent or white even when exposed to high temperatures, the optical semiconductor device obtained by the manufacturing method of the present invention can be used alone or in combination with a plurality of substrates for electrical and electronic components or optical components.

1‧‧‧Optical semiconductor components

2‧‧‧ lead frame

3‧‧‧ lead frame

4‧‧‧bonding line

4'‧‧‧bonding line

5‧‧‧Light Reflective Material / Curing Polyoxygen

6‧‧‧Sealant

7‧‧‧Substrate

8‧‧‧ dam material

9‧‧‧Frame materials

10‧‧‧Board containing fluorescent substances

1 is a cross-sectional view of an LED of an example of an optical semiconductor device of the present invention.

2 is a cross-sectional view showing an LED of another example of the optical semiconductor device of the present invention.

3 is a cross-sectional view showing an LED of another example of the optical semiconductor device of the present invention.

4 is a cross-sectional view showing an LED of another example of the optical semiconductor device of the present invention.

Hereinafter, a method of manufacturing an optical semiconductor device and an optical semiconductor device of the present invention will be clearly described using the drawings.

[Method of Manufacturing Optical Semiconductor Device]

The method of manufacturing an optical semiconductor device of the present invention comprises the step of sealing an optical semiconductor element using a curable polydecene oxide composition.

As a first embodiment of the present invention, as shown in FIG. 1, the optical semiconductor element 1 is sealed by disposing a cured polyfluorene oxide (light-reflecting material 5 in FIG. 1) containing a hydrogenation-reactive catalyst, And then using a curable polyanthracene composition which is solidified by a hydrogenation reaction and which does not contain a rhodium hydrogenation catalyst, or which is insufficient in amount to cure the composition if the curable polyoxon composition does contain a rhodium hydrogenation catalyst, The sealant 6 composed of the curable polydecene oxide composition is brought into contact with the cured polyfluorene oxide 5.

Since the curable polyoxynoxy composition contains little or no rhodium hydrogenation catalyst, fading caused by the rhodium hydrogenation catalyst at high temperatures can be suppressed. In addition, since the curing reaction of the curable polydecene oxide composition itself can be effectively cured by contact with the sealant Since the hydrogenation reaction catalyst is carried out, a sealant which ensures desired heat resistance and storage stability can be formed.

As explained above, the following technical concept exists in the industry: Generally, the composition does not contain a rhodium hydrogenation catalyst from the standpoint of fading at high temperatures. In any case, where the composition inevitably contains a rhodium hydrogenation catalyst and for some reasons the composition contains traces, it is stated that "the composition is not only free of the rhodium hydrogenation catalyst" and "if combined The substance does contain a rhodium hydrogenation catalyst and is insufficient in amount to cure the composition."

[cured polyoxyl]

In the manufacturing method of the present invention, the cured polyfluorene oxide is disposed at a position to contact the sealant around the periphery of the semiconductor element.

The cured polyfluorene oxygen means herein a material obtained by curing the specified curable polyoxynoxy composition, and in the optical semiconductor device, the cured polyfluorene oxide is not limited to a specific one, provided that the cured polyfluorinated oxygen is arranged To contact the parts of the sealant. Specific examples include light reflective materials, substrates, dam materials, and plates containing fluorescent materials.

The composition forming the cured polyfluorene oxide is not limited to the curable system, and may be any system, provided that the system contains a rhodium hydrogenation reaction catalyst. However, it preferably comprises a curable polydecaneoxy composition of the following: (a) an organopolyoxyalkylene having not less than two fluorenyl alkenyl groups per molecule, (b) having one molecule per molecule Not less than two organopolyoxanes bonded to a hydrogen atom, and (c) a hydrogenation catalyst.

Examples of the oxime-bonded alkenyl group in the component (a) are a vinyl group, an aryl group, a butenyl group, a pentenyl group and a hexenyl group, and a vinyl group is preferred. Examples of the group (a) in which a group other than an alkenyl group is bonded to a halogen atom includes a monovalent hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group or a similar alkyl group. Cyclopentyl, cyclohexyl or similar cycloalkyl; phenyl, tolyl, xylyl, naphthyl or similar aryl; benzyl, phenethyl, 3-phenylpropyl or similar aralkyl; chlorine Methyl, 3-chloropropyl, 3,3,3-trifluoropropyl, nonafluorobutylethyl or the like Halogenated hydrocarbon groups. Examples of the molecular structure of component (a) include a linear, cyclic, partially branched linear chain and a branched chain, but from the viewpoint that it can impart sufficient hardness and strength to the obtained cured polyfluorene, It is preferred to use at least one type of branched organopolyoxyalkylene as component (a). The viscosity of component (a) at 25 ° C is preferably 1 mPa. s to 10,000mPa. s.

Examples of the group of the component (b) which is bonded to the oxime other than the hydrogen atom contain the same monovalent hydrocarbon group as explained above. Examples of the molecular structure of the component (b) include a linear chain, a cyclic chain, a partially branched linear chain, and a branched chain. From the viewpoint of adjusting the hardness and strength of the cured polyfluorene obtained, the component (b) having a plurality of structures is preferably used in combination. At 25 ° C, the viscosity of the linear, cyclic and partially branched linear component (b) is preferably 1 mPa. s to 10,000mPa. s.

The compounding amount of the component (b) in the composition may be an amount sufficient to cure the curable polyoxynoxy composition, and the amount of the hydrazine-bonded hydrogen atom in the component (b) is preferably in the component (a). From 1 mol to 10 mol in 1 mol of the alkenyl group. If the amount of the hydrazine-bonded hydrogen atom in the component (b) in the 1 mol of the alkenyl group in the component (a) is less than this range, it is not desirable because the composition tends to be insufficiently cured. On the other hand, if it exceeds this range, it is undesired because the mechanical strength of the obtained cured polyfluorene is often lowered.

The hydrogenation reaction catalyst of component (c) is used to accelerate the crosslinking of the composition, preferably based on a platinum catalyst. Examples of platinum-based catalysts include chloroplatinic acid, an alcohol solution of chloroplatinic acid, an olefin complex of platinum, an alkenyl alkane complex of platinum, platinum black, and platinum supported ruthenium dioxide. The compounding amount is preferably from 1 ppm to 1,000 ppm based on the mass of the platinum metal in the composition. From the standpoint of curing of the cured polyoxymethylene composition as the sealant, it is preferably not less than 5 ppm, and is not more than 100 ppm from the viewpoint of increasing the heat resistance of the cured polyfluorene.

Examples of other optional components which the composition may contain include hydrazine hydrogenation inhibitors such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol , 3-phenyl-1-butyn-3-ol or similar alkyne alcohol; 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexene-1-yne Or class Iso-alkyne compound; 1,3,5,7-tetramethyl-1,3,5-tetravinylcyclotetraoxane, 1,3,5,7-tetramethyl-1,3,5 , 7-tetrahexenylcyclotetraoxane and benzotriazole. The content of the hydrazine reaction inhibitor is preferably from 10 ppm to 50,000 ppm based on the mass of the composition.

When the cured polyfluorene oxide is used as the light-reflecting material of the optical semiconductor device, it is preferred to contain a white pigment in the composition constituting the cured polysiloxane for the purpose of increasing whiteness. Examples of the white pigment include metal oxides such as titanium oxide, aluminum oxide, zinc oxide, zirconium oxide, and magnesium oxide; and barium sulfate, zinc sulfate, barium titanate, aluminum nitride, boron nitride, tantalum nitride, and the like. From the viewpoint of high light reflectance and blocking ability, titanium oxide is preferred, and zinc oxide or barium titanate is preferred from the viewpoint of light reflectance in the UV range.

Although the shape and average particle diameter of the white pigment are not limited, the average particle diameter is preferably from 0.05 μm to 10.0 μm, and particularly preferably from 0.1 μm to 5.0 μm. In order to increase the compatibility and dispersibility of the white pigment containing the resin and the inorganic filler, the white pigment may be surface-treated with a decane coupling agent, cerium oxide, aluminum oxide or the like.

The white pigment is added in an amount of not less than 50 parts by mass, and preferably not less than 60 parts by mass per 100 parts by mass of the array parts (a) and (b). This is because the light reflectance of the cured polyfluorene is good when the content is not less than the lower limit.

When the cured polyfluorene oxide is used as the light reflective material, the composition constituting the cured polyfluorene oxide is used for the purpose of reducing the linear expansion coefficient of the obtained cured polyfluorene oxygen due to the dimensional stability of the cured polyfluorene oxide. It is preferred to contain an inorganic filler. Examples of the inorganic filler include spherical cerium oxide, non-spherical cerium oxide, and glass fiber. Examples of the spherical cerium oxide of the inorganic filler include dry cerium oxide, wet cerium oxide, fumed cerium oxide, and deflagration cerium oxide, but fumed cerium oxide is exhibited in the composition of the present invention. Good filling characteristics are preferred. Examples of the non-spherical cerium oxide of the inorganic filler include quartz powder and glass beads, but quartz powder is preferred. Examples of the glass fiber of the inorganic filler include the cut glass fiber and the ground glass fiber, but the ground glass fiber is preferred.

The particle size of the spherical cerium oxide used for the inorganic filler is not limited, but the average particle diameter It is preferably from 0.1 μm to 50 μm, and particularly preferably from 0.5 μm to 30 μm. The particle diameter of the non-spherical cerium oxide used for the inorganic filler is not limited, but the average particle diameter is preferably from 0.1 μm to 50 μm, and particularly preferably from 0.5 μm to 30 μm. The shape of the glass fibers used for the inorganic filler is not limited, but the diameter of the fibers is preferably from 1 μm to 50 μm, and particularly preferably from 5 μm to 20 μm, and the length of the fibers is preferably from 5 μm to 500 μm. Preferably, the system is 10 μm to 300 μm.

The content of the inorganic filler is not less than 100 parts by mass, and preferably not less than 120 parts by mass per 100 parts by mass of the array parts (a) and (b). When the content of the inorganic filler is not less than the lower limit of the range, the obtained cured product has a low linear expansion coefficient and good dimensional stability.

The total content of the pigment component and the inorganic filler component is not more than 700 parts by mass, and preferably not more than 600 parts by mass per 100 parts by mass of the array parts (a) and (b). When the total content of the pigment component and the inorganic filler component is not more than the upper limit mentioned above, the viscosity of the obtained composition is good.

Further, when the cured polyfluorene oxide is used as the light-reflecting material, various additives may be compounded in the composition constituting the cured polyfluorene oxide as needed. Other optional components which may be contained include inorganic fillers other than spherical cerium oxide, non-spherical cerium oxide and glass fibers; fine powders of organic resins (for example, polymethacrylate resin and polyoxyl resin) a release agent such as palm wax, a high carbon number fatty acid, a metal salt of a high carbon number fatty acid, and a methyl polyoxyphthalic acid; a heat resistant agent; a flame retardant; a solvent; and the like.

When solidified polyfluorene oxide is used as a material other than the light-reflecting material (for example, a plate containing a phosphor), a plurality of additives may be compounded in the composition constituting the cured polysiloxane as needed. Other optional components which may be contained include inorganic fillers other than spherical cerium oxide, non-spherical cerium oxide and glass fibers; fine powders of organic resins (for example, polymethacrylate resin and polyoxyl resin) ; heat resistant agent; dye; pigment, fluorescent substance; flame retardant; solvent; and the like.

[curable polyoxyl composition]

By using the production method of the present invention, a curable poly group which is solidified by a hydrogenation reaction and which does not contain a rhodium hydrogenation catalyst, or which is insufficient in content to cure the composition if the curable polyoxon composition does contain a rhodium hydrogenation catalyst The ruthenium oxygen composition seals the semiconductor component.

Similar to the composition constituting the cured polyfluorene oxide, the curable polydecene oxide composition used in the present invention comprises: (A) at least one type of organic polycondensation having not less than two fluorene-bonded alkenyl groups per molecule a siloxane, and (B) at least one type of organopolyoxy siloxane having not less than two hydrazine-bonded hydrogen atoms per molecule, and which does not contain a hydrazine hydrogenation catalyst, or a curable polyoxygen combination The material does contain a rhodium hydrogenation catalyst, and the amount is preferably insufficient to cure the composition. The composition mentioned above preferably does not contain a rhodium hydrogenation catalyst, or if the curable polyoxo composition does contain a rhodium hydrogenation catalyst, the rhodium hydrogenation catalyst contains no more than the mass of the composition. 0.1ppm metal atom.

Additionally, the curable polyoxynoxy composition that forms the cured polyoxo or sealant can contain a variety of adhesion promoters to improve adhesion to a variety of materials. Examples of such adhesion promoters include: an organic decane having from about 4 to 20 germanium atoms or a linear, branched or cyclic organooxyalkylene oligomer having a trialkoxymethoxy group (for example, Trimethoxymethoxy or triethoxymethoxy) or trialkoxyalkylalkyl (for example, trimethoxydecylethyl or triethoxydecylethyl) and hydroquinone or alkene a base (for example, a vinyl or allyl group); an organodecane having from about 4 to 20 ruthenium atoms or a linear, branched or cyclic organooxane oligomer having a trialkoxymethoxy group Or a trialkoxyalkylalkyl group and a methacryloxyalkyl group (for example, 3-methacryloxypropyl); an organic decane having about 4 to 20 ruthenium atoms or a straight chain a chain or cyclic organooxane oligomer having a trialkoxymethoxy or tripaloxyalkylalkyl group and an epoxy-bonded alkyl group (eg, 3-glycidoxypropyl group, 4-glycidoxybutyl, 2-(3,4-epoxycyclohexyl)ethyl or 3-(3,4-epoxycyclohexyl)propyl); and amine The reaction product of an alkylalkyltrialkoxydecane with an epoxy-bonded alkyltrialkoxydecane and an epoxy group-containing polycaprate. Specific examples of adhesion promoters include: vinyl trimethoxy decane, allyl trimethoxy decane, allyl triethoxy decane, hydrogen triethoxy decane, 3-glycidoxy propyl trimethoxy Decane, 3-glycidoxypropyltriethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane , a reaction product of 3-methacryloxypropyltriethoxydecane, 3-glycidoxypropyltriethoxydecane and 3-aminopropyltriethoxydecane, a sterol group Condensation reaction product of blocked methyl vinyl siloxane oligomer with 3-glycidoxypropyl trimethoxy decane, sterol group terminated methyl vinyl siloxane oligomer and 3-methyl The condensation reaction product of propylene methoxy propyl triethoxy decane, bismuth (3-trimethoxymercaptopropyl) isocyanurate, an acid anhydride, and the like. The adhesion promoters are preferably low viscosity liquids, and are not particularly limited in viscosity at 25 ° C but preferably 1 mPa. s to 500mPa. s. The content of the adhesion promoter is not particularly limited, but is preferably 0.01 to 10 parts by mass relative to the total of 100 parts by mass of the composition (A) and (B) in the composition. If the respective adhesion promoters mentioned above are added to the curable polydecene oxide composition, it is not important that they are the same or different.

Additionally, the curable polydecene oxide composition is preferably free of the rhodium hydrogenation reaction inhibitor. This is because since the curable polyoxynoxy composition of the present invention is initially free of or substantially free of the rhodium hydrogenation catalyst, it is not necessary to add a rhodium hydrogenation inhibitor. It is believed in the art that the curing of the curable polyanthracene composition can be carried out even without the hydrogenation reaction catalyst in that the rhodium hydrogenation catalyst migrates from the solidified polyoxane which contacts it during curing. However, when the curable polydecaneoxy composition contains a hydrazine hydrogenation reaction inhibitor, this migration is hindered and the curing eventually becomes slow.

When a curable polydecene oxide composition is used as a sealant or lens material for an optical semiconductor device, a plurality of fillers may be compounded into optional components other than the above-mentioned mandatory components to improve the aggregation obtained by curing the composition. The mechanical strength of the helium oxide layer is premised on the preservation of the object of the present invention.

Examples of the filler include inorganic reinforcing fillers such as precipitated cerium oxide, fumed cerium oxide, fumed cerium oxide, and fumed titanium oxide; inorganic non-reinforced fillers such as crushed quartz, diatomaceous earth, aluminum Citrate, iron oxide, zinc oxide and calcium carbonate; organic fillers such as polymethacrylate resins; and by using organic antimony compounds (eg hexamethylguanidine, trimethylchlorodecane, polydimethylene) An inorganic or organic filler obtained by treating the surface with a sulfoxane or polymethylhydroquinone.

The initial particle diameter of the fillers is preferably not more than 0.5 μm, and more preferably not more than 0.1 μm. The content thereof is controlled so that the light transmittance of the cured polyfluorene oxide of the curable polydecene oxide composition is not less than 80%, but it is usually not more than 10% by mass, preferably not more than 5% by mass of the curable polydecene oxide composition. And more preferably not more than 1% by mass. If it is considered that the transparency of the sealant and the lens material is critical, it is preferred not to compound any inorganic filler.

Further, if a curable polydecene oxide composition is used as a sealant or lens material of an optical semiconductor device, as a component other than the above-mentioned filler, a plurality of additives may be compounded as needed. Other optional components that may be included include fine powders of organic resins such as polymethacrylate resins and polyoxyxylene resins, heat resistant agents, dyes, pigments, fluorescent materials, flame retardants, solvents, and the like.

[Polyfluorene composite material]

The above-mentioned cured polyfluorene oxide and sealant or the like (polyoxynitride composite) obtained by using the curable polyoxyl composition mentioned above will now be explained.

The shape of the cured polyfluorene oxide constituting the polyfluorene oxide composite material of the present invention is not particularly limited, but if a shape as shown in FIG. 1 is used, any one of the sealant 6 to the sealant 6 and the cured polyfluorene oxide 5 The minimum distance between the interfaces is preferably not more than 5 mm, and more preferably not more than 3 mm. According to the present invention, the curing catalyst required for the heat-curable curable polyoxo composition is derived from the adjacent disposed cured polyfluorene; therefore, when it is too far from the interface with the cured polyfluorene, the curing catalyst may not reach The polydecene oxide composition can be cured and curing will be insufficient. Due to this fact, a sealant composed of a curable polydecene oxide composition can be used in a coating application in which it is dispersed on a cured polyfluorene oxide or in which the polyoxynitride itself is less (for example, light for an optical semiconductor device) In the application of electronic materials for composites of reflective materials and sealants.

The curing temperature of the polyoxymethylene composition constituting the cured polyfluorene oxide and the curing temperature of the above-mentioned curable polyoxynoxy composition are not particularly limited, but good curing is usually obtained from room temperature to 220 °C. Curing at a temperature of from 60 ° C to 180 ° C is preferred, and curing at a temperature of from 80 ° C to 150 ° C is preferred because of the strong adhesion between the polysilicon layer and the substrate. Further, stepwise curing is preferred, wherein the composite is heated at room temperature to 100 ° C, preferably 60 ° C to 80 ° C, and then heated at 80 ° C to 180 ° C, preferably 100 ° C to 150 ° C. In some cases, the adhesion between the polysilicon layer and the substrate is further improved.

In the case where the polyfluorene oxide composite material of the present invention is used in combination with another material such as a substrate, the material and shape of the substrate are not particularly limited. The substrate may be constructed from organic materials (eg, heat curable resins and thermoplastic resins) or a variety of structural bodies (eg, woven, non-woven fabric, or porous bodies), and the substrate may have a variety of shapes, such as plates, rods, hemispheres, balls, and the like. . In addition, a plurality of other layers, such as a transparent acrylic resin layer, may be provided on the surface of the polyoxyxene composite of the present invention as needed.

The polyoxyn composite material of the present invention is not limited to being incorporated into an optical semiconductor device. The polyoxygen composite material itself can be used as a variety of electrical and electronic components or medical products (such as bandages), or can be used in combination with a variety of substrates (such as metal substrates, metal oxide substrates, glass substrates, and plastic films). In addition, since the polyfluorene oxide composite material of the present invention can have both a light transparent portion and a reflective portion, a polyoxynitride composite material can be used as a part or the entire member of the optical element.

[Optical semiconductor device]

The optical semiconductor device of the present invention will now be explained.

The optical semiconductor device of the present invention is characterized in that it is manufactured by the above-described manufacturing method.

An example of such an optical semiconductor device of the present invention is a light emitting diode (LED) (see Figs. 1 to 4). In the optical semiconductor device of FIG. 1, the light-reflecting material 5 composed of the cured polyfluorene oxide functions as a frame material (encapsulation material) of the optical semiconductor device, and the sealant 6 functions as a protective agent for the optical semiconductor element 1. In the optical semiconductor device of FIG. 2, the substrate 7 having the cured polyfluorene oxide functions as a substrate on which the optical semiconductor element 1 is mounted, and the sealant 6 functions as a protective agent and a lens material of the optical semiconductor element 1. In the optical semiconductor device of FIG. 3, the dam material 8 composed of the cured polyfluorene oxide controls the outflow of the sealant 6 as a frame material of the optical semiconductor device, and the sealant 6 functions as a protective agent for the optical semiconductor element 1. In the optical semiconductor device of FIG. 4, the phosphor-containing plate composed of the cured polyfluorene oxide converts the wavelength of light from the optical semiconductor element and diffuses the light, and the sealant 6 functions as a protective agent for the optical semiconductor element 1. .

In the optical semiconductor device of the present invention, as illustrated in FIG. 1, the optical semiconductor element 1 is die-bonded to the lead frame 2 by a die bonding material, and the optical semiconductor element is bonded by bonding wires 4, 4' One wire is bonded to the lead frames 2, 3. Around the periphery of the optical semiconductor element 1, except for the upper portion thereof, there is a light reflecting material 5 composed of solidified polyfluorene oxide. The optical semiconductor element 1 in the light-reflecting material 5 is sealed by a sealant 6.

The flow chart for manufacturing the surface mount type LED shown in Fig. 1 is exemplified by the following method, which comprises the following steps: (1) Curable polycondensation by transfer molding, compression molding or injection molding hydrazine hydrogenation reaction The oxygen composition forms the light-reflecting material 5 integrated with the lead frames 2, 3, (2) the die-bonding material is used to bond the optical semiconductor element 1 to the lead frame 2, and (3) the bonding wires 4, 4' are used. The optical semiconductor element 1 is bonded to the lead frames 2, 3, and (4) the optical semiconductor element 1 is sealed using a sealant 6.

If the light-reflecting material is formed by transfer molding, compression molding or injection molding as mentioned above, the molding is preferably carried out at a temperature of from 110 ° C to 170 ° C for from 60 seconds to 300 seconds. Curing can be carried out at a temperature of from 130 ° C to 180 ° C for about 1 hour to 8 hours.

In addition, in another optical semiconductor device of the present invention, as illustrated in FIG. 2 The optical semiconductor element 1 is die-bonded to the lead frame 2 by a die bonding material, and the optical semiconductor element 1 is wire-bonded to the lead frames 2, 3 by bonding wires 4, 4'. On the portion of the substrate 7 that contacts the mounted optical semiconductor element 1 of the encapsulant 6, there is the above-mentioned cured polyfluorene oxide, and the optical semiconductor element 1 is sealed by the encapsulant 6.

The flow chart for manufacturing the surface mount type LED shown in Fig. 2 is exemplified by the following method, which comprises the following steps: (1) Curable polycondensation by transfer molding, compression molding or injection molding hydrazine hydrogenation reaction The oxygen composition forms the substrate 7 integrated with the lead frames 2, 3, (2) the die bonding of the optical semiconductor element 1 onto the lead frame 2 using a die bonding material, and (3) bonding the light using the bonding wires 4, 4' The semiconductor element 1 and the lead frames 2, 3, and (4) seal the optical semiconductor element 1 using a sealant 6 composed of a curable polysiloxane composition.

Further, in another optical semiconductor device of the present invention, as illustrated in FIG. 3, the optical semiconductor element 1 is die-bonded to the lead frame 2 by a die bonding material, and by bonding wires 4, 4' This optical semiconductor element 1 is wire-bonded to the lead frames 2, 3. Around the periphery of the optical semiconductor element 1, except for the upper portion thereof, there is a dam material 8 composed of solidified polyfluorene oxide. The optical semiconductor element 1 in the dam material 8 is sealed by a sealant 6.

The flow chart for manufacturing the surface mount type LED shown in FIG. 3 is exemplified by the following method, which comprises the steps of: (1) bonding the optical semiconductor element 1 to the lead frame 2 using a die bonding material, ( 2) bonding the optical semiconductor element 1 and the lead frames 2, 3 using the bonding wires 4, 4', and (3) forming a curable polyoxyxene composition by distributing a hydrogenation reaction around the periphery of the optical semiconductor element 1 on the substrate The dam material 8, and (4) seals the optical semiconductor element 1 using a sealant 6 composed of a curable polyoxynoxy composition.

Further, in another optical semiconductor device of the present invention, as illustrated in FIG. 4, the optical semiconductor element 1 is die-bonded to the lead frame 2 by a die bonding material, and by bonding wires 4, 4' This optical semiconductor element 1 is wire-bonded to the lead frames 2, 3. The optical semiconductor element 1 is covered by a plate 10 containing a fluorescent substance composed of a cured polyfluorene oxide, and the fluorescent material-containing plate 10 and the optical semiconductor element 1 are sealed by a sealant 6.

The flow chart for manufacturing the surface mount type LED shown in Fig. 4 is exemplified by the following method, which comprises the following steps: (1) Curable polycondensation by transfer molding, compression molding or injection molding hydrazine hydrogenation reaction The oxygen composition forms the frame material 9 integrated with the lead frames 2, 3, (2) the die bonding of the optical semiconductor element 1 onto the lead frame 2 using a die bonding material, and (3) bonding using bonding wires 4, 4' The optical semiconductor element 1 and the lead frames 2, 3, (4) cover the optical semiconductor element 1 using the plate 10 containing the fluorescent substance, and (5) the optical semiconductor element is filled with the sealant 6 composed of the curable polyoxygen oxide composition. 1 and a plate 10 containing a phosphor.

The curing temperature of the sealant 6 is not particularly limited, but usually it is possible to obtain good curing from room temperature to 220 °C. Curing at a temperature of from 60 ° C to 180 ° C is preferred, and curing at a temperature of from 80 ° C to 150 ° C is preferred because of the strong adhesion between the polysilicon layer and the substrate. Further, stepwise curing is preferred, wherein the composite is heated at room temperature to 100 ° C, preferably 60 ° C to 80 ° C, and then heated at 80 ° C to 180 ° C, preferably 100 ° C to 150 ° C. In some cases, the adhesion between the polysilicon layer and the substrate is further improved.

Instance

A method of manufacturing an optical semiconductor device and an optical semiconductor device of the present invention will now be described in detail using examples. Further, the curability and storage stability of the curable polydecene oxide composition and the heat resistance of the cured polyfluorene oxide were evaluated by the following methods.

[(1) Evaluation of Curability of Curable Polyanthracene Composition]

The light-reflecting material 5 (cured polyoxymethylene) illustrated in Fig. 1 was produced by a transfer molding machine at 150 ° C by a hydrogenation reaction-curable polyoxyxene composition which was integrated with the lead frames 2, 3 by molding. . After the post-curing of the light-reflecting material at 130 ° C for 3 hours, it was filled by dispensing the specified curable poly-xyloxy composition to form the sealant 6. Curing of the curable polyoxynene composition was initiated at 150 °C using a light reflective material filled with a curable polydecene oxide composition. The surface tack of the cured sealant 6 was examined at 5 minutes, 10 minutes, 30 minutes, 60 minutes, and 120 minutes after the start of curing, and the time until the tack-free property was taken as the curing time.

[(2) Evaluation of long-term storage capacity of curable polyoxyl composition]

The viscosity of the curable polyanthracene composition was measured immediately after preparation using a rheometer (AR550, manufactured by TA Instruments) using a shear rate of 20 (1/sec). After the composition was prepared and then allowed to stand at 25 ° C for 24 hours, the viscosity was measured by the same method and compared with the initial viscosity.

[(3) Evaluation of heat resistance of cured polyfluorene oxide of curable polydecane oxide composition]

The manufactured optical semiconductor device was placed in a 300 ° C oven for 20 minutes, and the degree of fading of the sealant was visually inspected.

Curing polyfluorene oxide and encapsulant will now be specifically described using each of the practical examples and comparative examples. It should be noted that in the equation, Me, Ph, Vi and Ep represent a methyl group, a phenyl group, a vinyl group and a 3-glycidoxypropyl group, respectively.

[Manufacturing Example 1 - Preparation of Curable Polydecane Oxide Composition 1 Forming Curing Polyoxyl Oxide]

Uniformly blended with 100.0 parts by mass of methylvinylphenyl polyoxyalkylene represented by the following average unit formula: (Me ₂ ViSiO _1/2 ) _0.20 (PhSiO _3/2 ) _0.80 (HO _1/2 ) _0.02 ; 8.0 parts by mass of 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetraoxane represented by the formula: (MeViSiO) ₄ ; 20.0 parts by mass The following average formula represents a dimethylvinyl methoxy-terminated methylphenyl polyoxyalkylene: ViMe ₂ SiO (MePhSiO) _17.5 SiViMe ₂ ; 35.0 parts by mass of 1,1,5 represented by the following formula: 5-tetramethyl-3,3-diphenyltrioxane: (HMe ₂ SiO) ₂ SiPh ₂

(amount such that the hydrazine-bonded hydrogen atom in this component is relative to the above-mentioned methylvinylphenyl polysiloxane, 1,3,5,7-tetramethyl-1,3,5, 1 mol of the total vinyl group of 7-tetravinylcyclotetraoxane and dimethylvinyloxyl-terminated methylphenyl polyoxyalkylene is 0.76 mol.); 7.5 parts by mass of the following average unit Methylphenyl polyoxane containing a hydrazine-bonded hydrogen atom: (Me ₂ HSiO _1/2 ) _0.6 (PhSiO _3/2 ) _0.4

(amount such that the hydrazine-bonded hydrogen atom in this component is relative to the above-mentioned methylvinylphenyl polysiloxane, 1,3,5,7-tetramethyl-1,3,5, 7-tetravinylcyclotetraoxane and dimethylvinyloxyl-terminated methylphenyl polyoxyalkylene have 1 mol of total vinyl group of 0.18 mol); platinum 1,3-divinyl- 1,1,3,3-tetramethyldioxane complex 1,3-divinyl-1,1,3,3-tetramethyldioxane solution (the amount should be The mass of the platinum metal in the composition of the invention is 5 ppm); 1-ethynyl-1-cyclohexanol (in an amount such that it is 250 ppm by mass in the composition of the present invention); 110 parts by mass has an average initial of 0.2 μm Titanium oxide of particle size (SX-3103, manufactured by Sakai Chemical Industry Co., Ltd.); 100 parts by mass of crushed quartz powder having an average particle diameter of 5 μm (SILICIC SAB-500, manufactured by Yamamori Tsuchimoto Mining Co., Ltd.); And 180 parts by mass of spherical ceria (HS-202, manufactured by Nippon Steel & Sumikin Materials Co., Ltd.) having an average particle diameter of 15 μm to prepare a curable polydecane oxide composition 1.

[Manufacturing Example 2 - Preparation of Curable Polydecane Oxide Composition 2 Forming Curing Polyoxyl Oxide]

Uniformly blended with 100.0 parts by mass of methylvinylphenyl polyoxyalkylene represented by the following average unit formula: (Me ₂ ViSiO _1/2 ) _0.20 (PhSiO _3/2 ) _0.80 (HO _1/2 ) _0.02 ; 8.0 parts by mass of 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetraoxane represented by the formula: (MeViSiO) ₄ ; 20.0 parts by mass The following average formula shows a dimethylvinyl methoxy-terminated methylphenyl polyoxyalkylene: ViMe ₂ SiO(MePhSiO) _17.5 SiViMe ₂ ; 35.0 parts by mass of 1,1,5 represented by the following formula: 5-tetramethyl-3,3-diphenyltrioxane: (HMe ₂ SiO) ₂ SiPh ₂

(amount such that the hydrazine-bonded hydrogen atom in this component is relative to the above-mentioned methylvinylphenyl polysiloxane, 1,3,5,7-tetramethyl-1,3,5, 7-tetravinylcyclotetraoxane and dimethylvinyloxyl-terminated methylphenyl polyoxyalkylene have a total vinyl group of 0.76 mol); 7.5 parts by mass of the following average unit Methylphenyl polyoxane represented by a hydrazine-bonded hydrogen atom: (Me ₂ HSiO _1/2 ) _0.6 (PhSiO _3/2 ) _0.4

(amount such that the hydrazine-bonded hydrogen atom in this component is relative to the above-mentioned methylvinylphenyl polysiloxane, 1,3,5,7-tetramethyl-1,3,5, 7-tetravinylcyclotetraoxane and dimethylvinyloxyl-terminated methylphenyl polyoxyalkylene have 1 mol of total vinyl group of 0.18 mol); platinum 1,3-divinyl- a solution of 1,1,3,3-tetramethyldioxane complex 1,3-divinyl-1,1,3,3-tetramethyldioxane in an amount such that The mass of the platinum metal in the composition is 10 ppm); 1-ethynyl-1-cyclohexanol (in an amount such that it is 250 ppm by mass in the composition of the present invention); 110 parts by mass of the average initial particle having 0.2 μm Titanium oxide (SX-3103, manufactured by Sakai Chemical Industry Co., Ltd.); 100 parts by mass of crushed quartz powder having an average particle diameter of 5 μm (SILICIC SAB-500, manufactured by Yamamori Tsuchimoto Mining Co., Ltd.); 180 parts by mass of spherical ceria (HS-202, manufactured by Nippon Steel & Sumikin Materials Co., Ltd.) having an average particle diameter of 15 μm to prepare a curable polydecene composition 2.

[Manufacturing Example 3 - Preparation of Curable Polyanthracene Composition 3 Forming Curing Polyoxyl Oxide]

Uniformly blended with 100.0 parts by mass of methylvinylphenyl polyoxyalkylene represented by the following average unit formula: (Me ₂ ViSiO _1/2 ) _0.20 (PhSiO _3/2 ) _0.80 HO _1/2 ) _0.02 ; 8.0 The mass fraction is 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetraoxane represented by the following formula: (MeViSiO) ₄ ; 20.0 parts by mass of the following The dimethylvinyl methoxy-terminated methylphenyl polyoxy siloxane of the average formula: ViMe ₂ SiO (MePhSiO) _17.5 SiViMe ₂ ; 35.0 parts by mass of 1,1,5,5 represented by the following formula -tetramethyl-3,3-diphenyltrioxane: (HMe ₂ SiO) ₂ SiPh ₂

(amount such that the hydrazine-bonded hydrogen atom in this component is relative to the above-mentioned methylvinylphenyl polysiloxane, 1,3,5,7-tetramethyl-1,3,5, 7-tetravinylcyclotetraoxane and dimethylvinyloxyl-terminated methylphenyl polyoxyalkylene have a total vinyl group of 0.76 mol); 7.5 parts by mass of the following average unit Methylphenyl polyoxane represented by a hydrazine-bonded hydrogen atom: (Me ₂ HSiO _1/2 ) _0.6 (PhSiO _3/2 ) _0.4

(amount such that the hydrazine-bonded hydrogen atom in this component is relative to the above-mentioned methylvinylphenyl polysiloxane, 1,3,5,7-tetramethyl-1,3,5, 7-tetravinylcyclotetraoxane and dimethylvinyloxyl-terminated methylphenyl polyoxyalkylene have 1 mol of total vinyl group of 0.18 mol); platinum 1,3-divinyl- a solution of 1,1,3,3-tetramethyldioxane complex 1,3-divinyl-1,1,3,3-tetramethyldioxane in an amount such that The mass of the platinum metal in the composition is 10 ppm); and 1-ethynyl-1-cyclohexanol (in an amount such that it is 250 ppm by mass in the composition of the present invention) to prepare a curable polydecene oxide composition 3.

[Manufacturing Example 4 - Preparation of Curable Polyanthracene Composition 4 Forming Curing Polyoxyl Oxide]

Uniformly blended 48.4 parts by mass of methyl vinyl phenyl polyoxyalkylene represented by the following average unit formula: (MeViSiO _2/2 ) _0.25 (Ph ₂ SiO _2/2 ) _0.30 (PhSiO _3/2 ) _0.45 ( HO _1/2 ) _0.02 ; 51.6 parts by mass of methyl vinyl phenyl polyoxyalkylene represented by the following average unit formula: (Me ₂ ViSiO _1/2 ) _0.20 (PhSiO _3/2 ) _0.80 (HO _{1/ 2} ) _0.01 ; 12.9 parts by mass of dimethylvinyl methoxy-terminated methylphenyl polyoxyalkylene represented by the following average formula: ViMe ₂ SiO (MePhSiO) _17.5 SiViMe ₂ ; 29.0 parts by mass 1,1,5,5-tetramethyl-3,3-diphenyltrioxane represented by the formula: (HMe ₂ SiO) ₂ SiPh ₂

(Amount such that the hydrazine-bonded hydrogen atom in this component is relative to the methylvinyl phenyl polyoxy siloxane described above and the dimethylvinyl hydroxy terminated methyl phenyl polyoxy siloxane 1 mol of total vinyl is 0.94 mol); platinum 1,3-divinyl-1,1,3,3-tetramethyldioxane complex 1,3-divinyl-1, a solution of 1,3,3-tetramethyldioxane in an amount such that it is 5 ppm by mass of the platinum metal in the composition of the present invention; 1-ethynyl-1-cyclohexanol (the amount thereof is such that The mass in the composition was 250 ppm); 118 parts by mass of titanium oxide (SX-3103, manufactured by Sakai Chemical Industry Co., Ltd.) having an average primary particle diameter of 0.2 μm; and 213 parts by mass of an average particle diameter of 15 μm. Spherical cerium oxide (HS-202, manufactured by Nippon Steel & Sumikin Materials Co., Ltd.) was used to prepare a curable polydecane oxidizing composition 4.

[Production Example 5 - Preparation of Curable Polydecane Oxide Composition 5 Forming Curing Polyoxyl Oxide]

Uniformly blended 48.4 parts by mass of methyl vinyl phenyl polyoxyalkylene represented by the following average unit formula: (MeViSiO _2/2 ) _0.25 (Ph ₂ SiO _2/2 ) _0.30 (PhSiO _3/2 ) _0.45 ( HO _1/2 ) _0.02 ; 51.6 parts by mass of methyl vinyl phenyl polyoxyalkylene represented by the following average unit formula: (Me ₂ ViSiO _1/2 ) _0.20 (PhSiO _3/2 ) _0.80 (HO _{1/ 2} ) _0.01 ; 12.9 parts by mass of dimethylvinyl methoxy-terminated methylphenyl polyoxyalkylene represented by the following average formula: ViMe ₂ SiO (MePhSiO) _17.5 SiViMe ₂ ; 29.0 parts by mass 1,1,5,5-tetramethyl-3,3-diphenyltrioxane represented by the formula: (HMe ₂ SiO) ₂ SiPh ₂

(The amount is such that the ruthenium atom in the component is bonded to the hydrogen atom relative to the methylvinyl phenyl polyoxy siloxane mentioned above and the dimethylvinyl hydroxy terminated methyl phenyl polyoxyl 1 mol of total vinyl in the alkane is 0.94 mol); 1,3-divinyl-1 of platinum 1,3-divinyl-1,1,3,3-tetramethyldioxane complex a 1,3,3-tetramethyldioxane solution (in an amount such that 10 ppm by mass of the platinum metal in the composition of the present invention); 1-ethynyl-1-cyclohexanol (the amount thereof The mass in the composition of the present invention is 250 ppm); 118 parts by mass of titanium oxide having an average primary particle diameter of 0.2 μm (SX-3103, manufactured by Sakai Chemical Industry Co., Ltd.); and 213 parts by mass having an average of 15 μm Spherical cerium oxide (HS-202, manufactured by Nippon Steel & Sumikin Materials Co., Ltd.) having a particle size to prepare a curable polyoxyn composition 5.

[Manufacturing Example 6 - Preparation of Curable Polyanthracene Composition 6 as Sealant]

100 parts by mass of methyl vinyl phenyl polyoxyalkylene represented by the following average unit formula: (Me ₂ ViSiO _1/2 ) _0.20 (PhSiO _3/2 ) _0.80 (HO _1/2 ) _0.02 ; 0.35 parts by mass of 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetraoxane represented by the following formula: (MeViSiO) ₄ ; 30.4 parts by mass The following average formula represents a dimethylvinyl methoxy-terminated methylphenyl polyoxyalkylene: ViMe ₂ SiO(MePhSiO) _17.5 SiViMe ₂ ; 4.17 parts by mass of an epoxy group represented by the following average unit formula Polyoxane: (Me ₂ ViSiO _1/2 ) _0.2 (Ph ₂ SiO _2/2 ) _0.4 (EpSiO _3/2 ) _0.4 ; 34.7 parts by mass of 1,1,5,5- represented by the following formula Tetramethyl-3,3-diphenyltrioxane: (HMe ₂ SiO) ₂ SiPh ₂

(amount such that the hydrazine-bonded hydrogen atom in this component is relative to the above-mentioned methylvinylphenyl polysiloxane, 1,3,5,7-tetramethyl-1,3,5, 7-tetravinylcyclotetraoxane, dimethylvinyloxy-terminated methylphenyl polyoxyalkylene, and 1 mole of total vinyl group in the epoxy group-containing polyoxyalkylene are 1.03 mol); And 4.17 parts by mass of methyl phenyl polyoxy siloxane containing hydrazine-bonded hydrogen represented by the following average unit formula: (Me ₂ HSiO _1/2 ) _0.6 (PhSiO _3/2 ) _0.4

(amount such that the hydrazine-bonded hydrogen atom in this component is relative to the above-mentioned methylvinylphenyl polysiloxane, 1,3,5,7-tetramethyl-1,3,5, 7-tetravinylcyclotetraoxane, dimethylvinyloxy-terminated methylphenyl polyoxyalkylene, and 1 mole of total vinyl group in the epoxy group-containing polyoxyalkylene are 0.14 mol), To obtain a viscosity of 2,400 mPa. The curable polyanthracene composition 6 of s. After the curable polyoxynoxy composition 6 was allowed to stand at 25 ° C for 24 hours, its viscosity was 2,400 mPa. s.

[Manufacturing Example 7 - Preparation of Curable Polyoxynoxy Composition 7 as Sealant]

100 parts by mass of methyl vinyl phenyl polyoxyalkylene represented by the following average unit formula: (Me ₂ ViSiO _1/2 ) _0.20 (PhSiO _3/2 ) _0.80 (HO _1/2 ) _0.02 ; 1.59 parts by mass of 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetraoxane represented by the formula: (MeViSiO) ₄ ; 21.4 parts by mass The dimethylvinyl methoxy-terminated methylphenyl polyoxane represented by the following average formula: ViMe ₂ SiO(MePhSiO) _17.5 SiViMe ₂ ; 3.94 parts by mass of the epoxy group represented by the following average unit formula Polyoxyalkylene: (Me ₂ ViSiO _1/2 ) _0.2 (Ph ₂ SiO _2/2 ) _0.4 (EpSiO _3/2 ) _0.4 ; 28.7 parts by mass of 1,1,5,5- represented by the following formula Tetramethyl-3,3-diphenyltrioxane: (HMe ₂ SiO) ₂ SiPh ₂

(amount such that the hydrazine-bonded hydrogen atom in this component is relative to the above-mentioned methylvinylphenyl polysiloxane, 1,3,5,7-tetramethyl-1,3,5, 7-tetravinylcyclotetraoxane, dimethylvinyloxy-terminated methylphenyl polyoxyalkylene, and 1 mole of total vinyl group in the epoxy group-containing polyoxyalkylene are 0.82 mol); And 3.44 parts by mass of methyl phenyl polyoxy siloxane containing hydrazine-bonded hydrogen represented by the following average unit formula: (Me ₂ HSiO _1/2 ) _0.6 (PhSiO _3/2 ) _0.4

(amount such that the hydrazine-bonded hydrogen atom in this component is relative to the above-mentioned methylvinylphenyl polysiloxane, 1,3,5,7-tetramethyl-1,3,5, 7-tetravinylcyclotetraoxane, dimethylvinyloxy-terminated methylphenyl polyoxyalkylene, and 1 mole of total vinyl group in the epoxy group-containing polyoxyalkylene are 0.11 mol), To obtain a viscosity of 4,600 mPa. The curable polyoxynoxy composition 7 of s. After the curable polyoxynoxy composition 7 was allowed to stand at 25 ° C for 24 hours, the viscosity was 4,600 mPa. s.

[Manufacturing Example 8 - Preparation of Curable Polydecane Oxide Composition 8 as Sealant]

100 parts by mass of methyl vinyl phenyl polyoxyalkylene represented by the following average unit formula: (Me ₂ ViSiO _1/2 ) _0.20 (PhSiO _3/2 ) _0.80 (HO _1/2 ) _0.02 ; 0.35 The mass fraction is 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetraoxane: (MeViSiO) ₄ ; 30.4 parts by mass of the following The dimethyl vinyl methoxy-terminated methylphenyl polyoxy siloxane of the average formula: ViMe ₂ SiO (MePhSiO) _17.5 SiViMe ₂ ; 4.17 parts by mass of the epoxy group-containing olefinic group represented by the following average unit formula Polyoxane: (Me ₂ ViSiO _1/2 ) _0.2 (Ph ₂ SiO _2/2 ) _0.4 (EpSiO _3/2 ) _0.4 ; 34.7 parts by mass of 1,1,5,5-four represented by the following formula Methyl-3,3-diphenyltrioxane: (HMe ₂ SiO) ₂ SiPh ₂

(amount such that the hydrazine-bonded hydrogen atom in this component is relative to the above-mentioned methylvinylphenyl polysiloxane, 1,3,5,7-tetramethyl-1,3,5, 7-tetravinylcyclotetraoxane, dimethylvinyloxy-terminated methylphenyl polyoxyalkylene, and 1 mole of total vinyl group in the epoxy group-containing polyoxyalkylene are 1.03 mol); 4.17 parts by mass of methyl phenyl polyoxy siloxane containing hydrazine-bonded hydrogen represented by the following average unit formula: (Me ₂ HSiO _1/2 ) _0.6 (PhSiO _3/2 ) _0.4

(amount such that the hydrazine-bonded hydrogen atom in this component is relative to the above-mentioned methylvinylphenyl polysiloxane, 1,3,5,7-tetramethyl-1,3,5, 7-tetravinylcyclotetraoxane, dimethylvinyloxy-terminated methylphenyl polyoxyalkylene, and 1 mole of total vinyl group in the epoxy group-containing polyoxyalkylene are 0.14 mol); And 1-ethynyl-1-cyclohexanol (in an amount such that it is 250 ppm by mass in the composition of the invention) to obtain a viscosity of 2,400 mPa. The curable polydecaneoxy composition 8 of s. After the curable polyoxynoxy composition 8 was allowed to stand at 25 ° C for 24 hours, its viscosity was 2,400 mPa. s.

[Manufacturing Example 9 - Preparation of Curable Polydecane Oxide Composition 9 as Sealant]

100 parts by mass of methyl vinyl phenyl polyoxyalkylene represented by the following average unit formula: (Me ₂ ViSiO _1/2 ) _0.20 (PhSiO _3/2 ) _0.80 (HO _1/2 ) _0.02 ; 1.59 The mass fraction is 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetraoxane represented by the following formula: (MeViSiO) ₄ ; 21.4 parts by mass of the following The dimethyl vinyl methoxy-terminated methyl phenyl polyoxy siloxane of the average formula: ViMe ₂ SiO (MePhSiO) _17.5 SiViMe ₂ ; 3.94 parts by mass of the epoxy group-containing group represented by the following average unit formula Polyoxane: (Me ₂ ViSiO _1/2 ) _0.2 (Ph ₂ SiO _2/2 ) _0.4 (EpSiO _3/2 ) _0.4 ; 28.7 parts by mass of 1,1,5,5-four represented by the following formula Methyl-3,3-diphenyltrioxane: (HMe ₂ SiO) ₂ SiPh ₂

(amount such that the hydrazine-bonded hydrogen atom in this component is relative to the above-mentioned methylvinylphenyl polysiloxane, 1,3,5,7-tetramethyl-1,3,5, 7-tetravinylcyclotetraoxane, dimethylvinyloxy-terminated methylphenyl polyoxyalkylene, and 1 mole of total vinyl group in the epoxy group-containing polyoxyalkylene are 0.82 mol); 3.44 parts by mass of methyl phenyl polyoxyalkylene containing hydrazine-bonded hydrogen represented by the following average unit formula: (Me ₂ HSiO _1/2 ) _0.6 (PhSiO _3/2 ) _0.4

(The amount is such that the halogen atom in this component is bonded to the hydrogen atom relative to the above-mentioned methyl vinyl phenyl polyoxyalkylene, 1,3,5,7-tetramethyl-1,3,5 , 7-tetravinylcyclotetraoxane, dimethylvinyloxy-terminated methylphenyl polyoxyalkylene, and 1 mole of total vinyl group in the epoxy group-containing polyoxyalkylene are 0.11 mol) And 1-ethynyl-1-cyclohexanol (in an amount such that it is 250 ppm by mass in the composition of the invention) to obtain a viscosity of 4,600 mPa. The curable polydecaneoxy composition 9 of s. After the curable polyoxynoxy composition 9 was allowed to stand at 25 ° C for 24 hours, the viscosity was 4,600 mPa. s.

[Manufacturing Example 10 - Preparation of Curable Polydecane Oxide Composition 10 as Sealant]

100 parts by mass of methyl vinyl phenyl polyoxyalkylene represented by the following average unit formula: (Me ₂ ViSiO _1/2 ) _0.20 (PhSiO _3/2 ) _0.80 (HO _1/2 ) _0.02 ; 0.35 The mass fraction is 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetraoxane: (MeViSiO) ₄ ; 30.4 parts by mass of the following The dimethyl vinyl methoxy-terminated methylphenyl polyoxy siloxane of the average formula: ViMe ₂ SiO (MePhSiO) _17.5 SiViMe ₂ ; 4.17 parts by mass of the epoxy group-containing olefinic group represented by the following average unit formula Polyoxane: (Me ₂ ViSiO _1/2 ) _0.2 (Ph ₂ SiO _2/2 ) _0.4 (EpSiO _3/2 ) _0.4 ; 34.7 parts by mass of 1,1,5,5-four represented by the following formula Methyl-3,3-diphenyltrioxane: (HMe ₂ SiO) ₂ SiPh ₂

(amount such that the hydrazine-bonded hydrogen atom in this component is relative to the above-mentioned methylvinylphenyl polysiloxane, 1,3,5,7-tetramethyl-1,3,5, 7-tetravinylcyclotetraoxane, dimethylvinyloxy-terminated methylphenyl polyoxyalkylene, and 1 mole of total vinyl group in the epoxy group-containing polyoxyalkylene are 1.03 mol); 4.17 parts by mass of methyl phenyl polyoxy siloxane containing hydrazine-bonded hydrogen represented by the following average unit formula: (Me ₂ HSiO _1/2 ) _0.6 (PhSiO _3/2 ) _0.4

(amount such that the hydrazine-bonded hydrogen atom in this component is relative to the above-mentioned methylvinylphenyl polysiloxane, 1,3,5,7-tetramethyl-1,3,5, 7-tetravinylcyclotetraoxane, dimethylvinyloxy-terminated methylphenyl polyoxyalkylene, and 1 mole of total vinyl group in the epoxy group-containing polyoxyalkylene are 0.14 mol); 1,3-divinyl-1,1,3,3-tetramethyldifluoride of platinum 1,3-divinyl-1,1,3,3-tetramethyldioxane complex An oxane solution (in an amount such that 5 ppm by mass of the platinum metal in the composition of the present invention); and 1-ethynyl-1-cyclohexanol (in an amount such that it is 250 ppm by mass in the composition of the present invention), To obtain a viscosity of 2,400 mPa. The curable polydecene oxide composition 10 of s. After the curable polyoxynoxy composition 10 was allowed to stand at 25 ° C for 24 hours, the viscosity was 5,800 mPa. s.

[Manufacturing Example 11 - Preparation of Curable Polydecane Oxide Composition 11 as Sealant]

100 parts by mass of methyl vinyl phenyl polyoxyalkylene represented by the following average unit formula: (Me ₂ ViSiO _1/2 ) _0.20 (PhSiO _3/2 ) _0.80 (HO _1/2 ) _0.02 ; 1.59 The mass fraction is 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetraoxane: (MeViSiO) ₄ ; 21.4 parts by mass of the following The dimethyl vinyl methoxy-terminated methyl phenyl polyoxy siloxane of the average formula: ViMe ₂ SiO (MePhSiO) _17.5 SiViMe ₂ ; 3.94 parts by mass of the epoxy group-containing group represented by the following average unit formula Polyoxane: (Me ₂ ViSiO _1/2 ) _0.2 (Ph ₂ SiO _2/2 ) _0.4 (EpSiO _3/2 ) _0.4 ; 28.7 parts by mass of 1,1,5,5-four represented by the following formula Methyl-3,3-diphenyltrioxane: (HMe ₂ SiO) ₂ SiPh ₂

(amount such that the hydrazine-bonded hydrogen atom in this component is relative to the above-mentioned methylvinylphenyl polysiloxane, 1,3,5,7-tetramethyl-1,3,5, 7-tetravinylcyclotetraoxane, dimethylvinyloxy-terminated methylphenyl polyoxyalkylene, and 1 mole of total vinyl group in the epoxy group-containing polyoxyalkylene are 0.82 mol); 3.44 parts by mass of methyl phenyl polyoxyalkylene containing hydrazine-bonded hydrogen represented by the following average unit formula: (Me ₂ HSiO _1/2 ) _0.6 (PhSiO _3/2 ) _0.4

(amount such that the hydrazine-bonded hydrogen atom in this component is relative to the above-mentioned methylvinylphenyl polysiloxane, 1,3,5,7-tetramethyl-1,3,5, 7-tetravinylcyclotetraoxane, dimethylvinyloxy-terminated methylphenyl polyoxyalkylene, and 1 mole of total vinyl group in the epoxy group-containing polyoxyalkylene are 0.11 mol); 1,3-divinyl-1,1,3,3-tetramethyldifluoride of platinum 1,3-divinyl-1,1,3,3-tetramethyldioxane complex Oxytomane solution The mass of the platinum metal in the composition of the invention is 5 ppm); and 1-ethynyl-1-cyclohexanol (in an amount such that it is 250 ppm by mass in the composition of the present invention) to obtain a viscosity of 4,600 mPa. The curable polydecene oxide composition 11 of s. After the curable polyoxyl composition 11 was allowed to stand at 25 ° C for 24 hours, the viscosity was 10,600 mPa. s.

[Practical example 1]

The curable polyxanylene composition 1 prepared in Production Example 1 was molded and molded with a lead frame at 150 ° C for 2 minutes, and then post-cured in an oven at 150 ° C for 1 hour to obtain a light-reflecting material. This material was filled by dispensing the curable polyelectrolytic composition 6 prepared in Production Example 6, and then cured in a furnace at 150 ° C for a predetermined period of time, and the curability was evaluated based on the surface tackiness. The obtained optical semiconductor device was placed in a 300 ° C furnace, and a heat resistance test was performed for 20 minutes. Visually check the degree of fading of the sealant. The evaluation results are shown in Table 1.

[Practical example 2]

The curable polyxanylene composition 1 prepared in Production Example 1 was molded and molded with a lead frame at 150 ° C for 2 minutes, and then post-cured in an oven at 150 ° C for 1 hour to obtain a light-reflecting material. This material was filled by dispensing the curable polysiloxane composition 7 prepared in Production Example 7, and then cured in a furnace at 150 ° C for a predetermined period of time, and the curability was evaluated in terms of surface tackiness. The obtained optical semiconductor device was placed in a 300 ° C furnace, and a heat resistance test was performed for 20 minutes. Visually check the degree of fading of the sealant. The evaluation results are shown in Table 1.

[Practical example 3]

The curable polyxanylene composition 2 prepared in Production Example 2 was molded with the lead frame molding at 150 ° C for 2 minutes, and then post-cured in an oven at 150 ° C for 1 hour to obtain a light reflective material. This material was filled by dispensing the curable polyelectrolytic composition 6 prepared in Production Example 6, and then cured in a furnace at 150 ° C for a predetermined period of time, and the curability was evaluated based on the surface tackiness. The obtained optical semiconductor device was placed in a 300 ° C furnace and carried out for 20 minutes. Heat resistance test. Visually check the degree of fading of the sealant. The evaluation results are shown in Table 1.

[Practical Example 4]

The curable polyxanylene composition 2 prepared in Production Example 2 was molded with the lead frame molding at 150 ° C for 2 minutes, and then post-cured in an oven at 150 ° C for 1 hour to obtain a light reflective material. This material was filled by dispensing the curable polysiloxane composition 7 prepared in Production Example 7, and then cured in a furnace at 150 ° C for a predetermined period of time, and the curability was evaluated in terms of surface tackiness. The obtained optical semiconductor device was placed in a 300 ° C furnace, and a heat resistance test was performed for 20 minutes. Visually check the degree of fading of the sealant. The evaluation results are shown in Table 1.

[Practical example 5]

The curable polyxanylene composition 3 prepared in Production Example 3 was molded with the lead frame molding at 150 ° C for 2 minutes, and then post-cured in an oven at 150 ° C for 1 hour to obtain a light reflective material. This material was filled by dispensing the curable polyelectrolytic composition 6 prepared in Production Example 6, and then cured in a furnace at 150 ° C for a predetermined period of time, and the curability was evaluated based on the surface tackiness. The obtained optical semiconductor device was placed in a 300 ° C furnace, and a heat resistance test was performed for 20 minutes. Visually check the degree of fading of the sealant. The evaluation results are shown in Table 1.

[Practical example 6]

The curable polyanthracene composition 4 prepared in Production Example 4 was molded with the lead frame molding at 150 ° C for 2 minutes, and then post-cured in an oven at 150 ° C for 1 hour to obtain a light reflective material. This material was filled by dispensing the curable polyelectrolytic composition 6 prepared in Production Example 6, and then cured in a furnace at 150 ° C for a predetermined period of time, and the curability was evaluated based on the surface tackiness. The obtained optical semiconductor device was placed in a 300 ° C furnace, and a heat resistance test was performed for 20 minutes. Visually check the degree of fading of the sealant. The evaluation results are shown in Table 1.

[Practical example 7]

The curable polyanthracene composition 4 prepared in Production Example 4 was molded with the lead frame molding at 150 ° C for 2 minutes, and then post-cured in an oven at 150 ° C for 1 hour to obtain a light reflective material. This material was filled by dispensing the curable polysiloxane composition 7 prepared in Production Example 7, and then cured in a furnace at 150 ° C for a predetermined period of time, and the curability was evaluated in terms of surface tackiness. The obtained optical semiconductor device was placed in a 300 ° C furnace, and a heat resistance test was performed for 20 minutes. Visually check the degree of fading of the sealant. The evaluation results are shown in Table 1.

[Practical Example 8]

The curable polyfluorene oxide composition 5 prepared in Production Example 5 was molded and laminated with a lead frame at 150 ° C for 2 minutes, and then post-cured in an oven at 150 ° C for 1 hour to obtain a light reflective material. This material was filled by dispensing the curable polyelectrolytic composition 6 prepared in Production Example 6, and then cured in a furnace at 150 ° C for a predetermined period of time, and the curability was evaluated based on the surface tackiness. The obtained optical semiconductor device was placed in a 300 ° C furnace, and a heat resistance test was performed for 20 minutes. Visually check the degree of fading of the sealant. The evaluation results are shown in Table 1.

[Practical Example 9]

The curable polyfluorene oxide composition 5 prepared in Production Example 5 was molded and laminated with a lead frame at 150 ° C for 2 minutes, and then post-cured in an oven at 150 ° C for 1 hour to obtain a light reflective material. This material was filled by dispensing the curable polysiloxane composition 7 prepared in Production Example 7, and then cured in a furnace at 150 ° C for a predetermined period of time, and the curability was evaluated in terms of surface tackiness. The obtained optical semiconductor device was placed in a 300 ° C furnace, and a heat resistance test was performed for 20 minutes. Visually check the degree of fading of the sealant. The evaluation results are shown in Table 1.

[Practical Example 10]

The curable polyfluorene oxide composition 1 prepared in Example 1 and the lead were fabricated at 150 °C. The frame molding was integrated for 2 minutes and then post-cured in a 150 ° C oven for 1 hour to obtain a light reflective material. This material was filled by dispensing the curable polyoxyl composition 8 prepared in Production Example 8, and then cured in a furnace at 150 ° C for a predetermined period of time, and the curability was evaluated in terms of surface tack. The obtained optical semiconductor device was placed in a 300 ° C furnace, and a heat resistance test was performed for 20 minutes. Visually check the degree of fading of the sealant. The evaluation results are shown in Table 1.

[Practical Example 11]

The curable polyxanylene composition 2 prepared in Production Example 2 was molded with the lead frame molding at 150 ° C for 2 minutes, and then post-cured in an oven at 150 ° C for 1 hour to obtain a light reflective material. This material was filled by dispensing the curable polydecane oxide composition 9 prepared in Production Example 9, and then cured in a furnace at 150 ° C for a predetermined time, and the curability was evaluated in terms of surface tackiness. The obtained optical semiconductor device was placed in a 300 ° C furnace, and a heat resistance test was performed for 20 minutes. Visually check the degree of fading of the sealant. The evaluation results are shown in Table 1.

[Comparative Example 1]

The curable polyanthracene composition 4 prepared in Production Example 4 was molded with the lead frame molding at 150 ° C for 2 minutes, and then post-cured in an oven at 150 ° C for 1 hour to obtain a light reflective material. This material was filled by dispensing the curable polyelectrolytic composition 10 prepared in Production Example 10, and then cured in a furnace at 150 ° C for a predetermined period of time, and the curability was evaluated in terms of surface tackiness. The obtained optical semiconductor device was placed in a 300 ° C furnace, and a heat resistance test was performed for 20 minutes. Visually check the degree of fading of the sealant. The evaluation results are shown in Table 1.

[Comparative Example 2]

The curable polyfluorene oxide composition 5 prepared in Production Example 5 was molded and laminated with a lead frame at 150 ° C for 2 minutes, and then post-cured in an oven at 150 ° C for 1 hour to obtain a light reflective material. This was filled by dispensing the curable polyoxyl composition 11 prepared in Production Example 11. The material was then cured in a furnace at 150 ° C for a predetermined period of time, and the curability was evaluated based on the surface tackiness. The obtained optical semiconductor device was placed in a 300 ° C furnace, and a heat resistance test was performed for 20 minutes. Visually check the degree of fading of the sealant. The evaluation results are shown in Table 1.

As can be seen from the results shown in Table 1, Practical Examples 1 to 11 exhibited results superior to those of Comparative Examples 1 and 2 in the fading of the sealant. Therefore, in the optical semiconductor device relating to the practical example manufactured by the method of the present invention, fading caused by the hydrogenation reaction catalyst at a high temperature can be suppressed, and also since the curing reaction of the curable polysiloxane composition itself can be effectively By carrying out the hydrogenation reaction catalyst in the solidified polyoxo oxygen which is contacted with the sealant, a sealant which ensures desired heat resistance and storage stability can be formed.

Industrial applicability

According to the present invention, a method of manufacturing an optical semiconductor device in which a sealant achieves storage stability, has good heat resistance, and can greatly resist fading can be provided; and an optical semiconductor device obtained by the manufacturing method can be provided.

1‧‧‧Optical semiconductor components

2‧‧‧ lead frame

3‧‧‧ lead frame

4‧‧‧bonding line

4'‧‧‧bonding line

5‧‧‧Light Reflective Material / Curing Polyoxygen

6‧‧‧Sealant

Claims (8)

A method of manufacturing an optical semiconductor device, comprising: a step of sealing an optical semiconductor element using a curable polydecene oxide composition; although the curable polyoxynoxy composition is cured by a hydrogenation reaction, it does not contain hydrogen peroxide a reaction catalyst, or if a ruthenium hydrogenation catalyst is contained, the content of the ruthenium hydrogenation reaction catalyst is insufficient to cure the composition; and the optical semiconductor element is sealed in a state in which the curable polyoxynoxy composition is contacted with ruthenium The state of the polycondensation of the hydrogenation reaction catalyst. The method of producing an optical semiconductor device according to claim 1, wherein the curable polyoxynoxy composition comprises: (A) at least one type of organopolyoxane having not less than two fluorene-bonded alkenyl groups per molecule And (B) at least one type of organopolyoxane having not less than two hydrazine-bonded hydrogen atoms per molecule, and which does not contain a hydrazine hydrogenation catalyst, or if it contains a hydrazine hydrogenation catalyst, 矽The amount of hydrogenation catalyst is insufficient to cure the composition. The method of manufacturing an optical semiconductor device according to claim 1 or 2, wherein the cured polyfluorene-based light-reflecting material, the substrate, the dam material or the plate containing the phosphor. The method of producing an optical semiconductor device according to claim 1 or 2, wherein the hydrazine hydrogenation reaction catalyst is based on a platinum catalyst. The method of producing an optical semiconductor device according to claim 1 or 2, wherein the curable polyoxynoxy composition does not contain a hydrazine hydrogenation reaction inhibitor. The method of producing an optical semiconductor device according to claim 1 or 2, wherein the cured polyfluorene contains at least one type of white pigment selected from the group consisting of titanium oxide, zinc oxide, barium titanate, barium sulfate, and zirconium oxide. . The method of manufacturing an optical semiconductor device according to claim 1 or 2, wherein the cured polyfluorene contains at least one type of inorganic filler selected from the group consisting of non-spherical cerium oxide, spherical cerium oxide, and glass. fiber. An optical semiconductor device manufactured by the manufacturing method as set forth in any one of claims 1 to 7.