JP2014517110A - Thermosetting light reflecting resin composition and manufacturing method thereof, optical semiconductor element mounting reflector manufactured by thermosetting light reflecting resin composition, and optical semiconductor device including the same - Google Patents

Abstract

The present invention relates to a thermosetting light reflecting resin composition and a method for producing the same, a reflecting plate for mounting an optical semiconductor element manufactured using the thermosetting light reflecting resin composition, and an optical semiconductor device including the same. More specifically, the present invention is a thermosetting light reflecting resin composition containing a polyol having a hydroxyl group as a curing accelerator, having good discoloration resistance and low light reflectivity reduction. The present invention relates to a resin composition, a manufacturing method thereof, a reflecting plate for mounting an optical semiconductor element manufactured by a thermosetting light reflecting resin composition, and an optical semiconductor device including the same.
[Selection] Figure 1

Description

The present invention relates to a thermosetting light reflecting resin composition and a method for producing the same, a reflecting plate for mounting an optical semiconductor element manufactured using the thermosetting light reflecting resin composition, and an optical semiconductor device including the same. More specifically, the present invention includes a polyhydric polyol having two or more hydroxy groups as a curing accelerator in the thermosetting light reflecting resin composition, and yellowing or discoloration occurs due to good discoloration resistance. Without reducing the light reflectivity, a thermosetting light reflecting resin composition and a method for manufacturing the same, a reflecting plate for mounting an optical semiconductor element manufactured using the thermosetting light reflecting resin composition, and an optical semiconductor including the same Relates to the device.

An LED (light emitting diode) is a light emitting device in which a light emitting element is mounted on a reflection plate and sealed with an epoxy resin or the like. These LEDs are small and lightweight, so they can be easily mounted on various instruments, and they are not only long-lived because they are strong against vibration and repeated on / off, but also have excellent visibility because the color is clear and conspicuous. And has the advantage of low power consumption. Among such LEDs, a white LED including an ultraviolet light emitting element and a phosphor that emits white light by ultraviolet light generated from the ultraviolet light emitting element is a backlight for liquid crystal display screens of mobile phones, computers, televisions, and the like. It is attracting attention as a light source for automobile headlights, instrument panels, and lighting fixtures.

The LED reflector used in such a device is generally required to have a good light reflectance that reflects light or ultraviolet rays emitted from a light emitting element with high efficiency. In order to prevent a decrease in light reflectance, the reflector itself must not turn yellow or discolor. Further, since the LED reflector is exposed to high heat for a long time, it must have a high light reflectance even after heat treatment.

In a conventional LED reflector, a metal wiring (lead frame) is plated from a metal foil by a method such as punching or etching, and then a molded product is manufactured using a thermoplastic resin containing a white pigment. However, in response to consumer demand for high brightness, the rated output of LEDs has recently increased, and the high heat and ultraviolet rays generated at this time cause discoloration such as yellowing in the reflector, resulting in light reflectance and brightness. It is reported that it becomes a factor to decrease The reflector for light reflection manufactured with the existing thermoplastic resin molded product has a limit in maintaining light reflectivity especially at high temperature.

An object of the present invention is to provide a thermosetting light reflecting resin composition having good discoloration resistance that does not cause yellowing or discoloration.

Another object of the present invention is to provide a thermosetting light reflecting resin composition in which the light reflectance does not decrease after heat treatment.

Still another object of the present invention is to provide a method for producing a thermosetting light reflecting resin composition.

Still another object of the present invention is to provide an optical semiconductor element mounting reflector including the reflector composed of the thermosetting light reflecting resin composition.

Still another object of the present invention is to provide an optical semiconductor device including the optical semiconductor element mounting reflector.

The thermosetting light reflecting resin composition which is one aspect of the present invention contains a polyhydric polyol having about 2 or more hydroxy groups as a curing accelerator, and a test piece produced from the composition has the following formula 1 The light reflectance maintenance factor displayed on the screen can be about 70% or more.

<Formula 1>
Light reflectance maintenance rate (%) = light reflectance after heat treatment at 180 ° C. for 168 hours / light reflectance before heat treatment × 100

In one embodiment, the composition may have a light reflectance maintenance ratio of 70% or more after transfer molding, curing at 150 ° C. for 3 hours, and heat treatment at 180 ° C. for 168 hours.

In one embodiment, the composition may have a S / F (spiral flow length) of about 15 inches to about 45 inches during transfer molding.

In one embodiment, the composition may have a G / T (Gelation time) of about 30 seconds to about 70 seconds during transfer molding.

In one embodiment, the composition may include the curing accelerator, an epoxy resin, a curing agent, an inorganic filler, and a white pigment.

In one specific example, the curing accelerator may have a structure of Formula 3 below.

<Chemical Formula 3>
_{OH- (CH 2) m - [} CR1-OH] n - (CH 2) p -OH
(In the above formula, R1 is hydrogen or a linear or branched alkyl group having 1 to 30 carbon atoms, n is an integer of 0 to 20, and m and p are independently integers of 0 to 10. (However, when n, m, and p are all 0, they are excluded.)

In one embodiment, the curing accelerator may not contain an aromatic functional group.

In one embodiment, the curing accelerator may be included in an amount of about 3 parts by weight to about 49 parts by weight with respect to about 100 parts by weight of the epoxy resin.

In one embodiment, the epoxy resin may not contain an aromatic functional group.

In one embodiment, the curing agent may not contain an aromatic functional group.

In one embodiment, the composition may further include one or more selected from the group consisting of a release agent and an additive.

In one embodiment, the inorganic filler is included as a mixture of an inorganic filler having an average particle diameter (D50) of less than about 10 μm and an inorganic filler having an average particle diameter (D50) of about 10 μm to about 35 μm. Can do.

In one embodiment, the composition may include the white pigment and the inorganic filler in a weight ratio of about 1: 0.1 to about 1: 4.

According to still another aspect of the present invention, there is provided a method for producing a thermosetting light reflecting resin composition, comprising: melting and mixing an epoxy resin and a curing agent; curing containing a polyhydric polyol having about 2 or more hydroxy groups in the mixture A step of adding an accelerator, an inorganic filler, and a white pigment and melt-kneading can be included.

In one embodiment, the melt-kneading step may be performed at a temperature of about 30 ° C. to about 50 ° C. for about 30 minutes to about 180 minutes.

The reflecting plate for mounting an optical semiconductor element, which is still another aspect of the present invention, can include the thermosetting light reflecting resin composition.

An optical semiconductor device which is still another aspect of the present invention can include the optical semiconductor element mounting reflector.

The present invention provides a thermosetting light-reflective resin composition that has good discoloration resistance and does not cause yellowing or discoloration. In addition, the present invention provides a thermosetting light reflecting resin composition in which the light reflectance does not decrease even when exposed to a high temperature for a long time.

Samples prepared from the compositions of Examples 1 to 3 of the present invention and the composition of Comparative Example 4 containing a curing accelerator containing an aromatic functional group were heat treated at 180 ° C. for 168 hours, and then aged. It is the graph which showed the light reflectivity in 430 nm wavelength by time. Specimens manufactured with the compositions of Examples 1 to 3 of the present invention and the compositions of Comparative Examples 5 to 7 containing thermoplastic resins that are used in the past were heat-treated at 180 ° C. for 168 hours, and then depending on the aging time. It is the graph which showed the light reflectivity in 430 nm wavelength.

The light reflectance maintenance factor of the thermosetting light reflecting resin composition which is one aspect of the present invention can be about 70% or more. In this specification, the “light reflectance maintenance factor” means the light reflectance after heat treating the specimen at 180 ° C. for 168 hours with respect to the light reflectance before heat treating the specimen manufactured with the resin composition. The ratio value of The light reflectance maintenance factor can be expressed as the following formula 1.

<Formula 1>
Light reflectance maintenance rate (%) = light reflectance after heat treatment at 180 ° C. for 168 hours / light reflectance before heat treatment × 100

In general, when a specimen made of a resin composition for light reflection is heat-treated, the color changes from white to yellow, which is indicated as a decrease in light reflectance. The lower the light reflectivity, the higher the discoloration resistance. That is, the higher the light reflectance maintenance rate, the higher the discoloration resistance.

The composition may have a light reflectance maintenance factor of about 70% or more, desirably about 72% to about 85%.

The light reflectance maintenance factor is not particularly limited, but the composition was molded by using a transfer molding machine at 150 ° C. for 240 seconds, removed from the mold, and then post-cured at 150 ° C. for 3 hours. Manufacture pieces. Thereafter, the light reflectance before heat treatment is measured, and after heat treatment at 180 ° C. for 168 hours, the light reflectance can be measured and obtained. In the present invention, the light reflectance is based on a value measured at a wavelength of about 430 nm.

In one embodiment, the thermosetting light reflecting resin composition may have an S / F (spiral flow length) of about 15 inches to about 45 inches, preferably about 24 inches to about 45 inches during transfer molding. .

In one embodiment, the thermosetting light reflecting resin composition may have a G / T (Gelation time) during transfer molding of about 30 seconds to about 70 seconds, preferably about 57 seconds to about 68 seconds.

The resin composition of the present invention can contain an epoxy resin, a curing agent, a curing accelerator, an inorganic filler, and a white pigment.

In the present invention, as the epoxy resin, those usually used as an epoxy resin molding material can be used. For example, novolaks of phenols and aldehydes including phenol novolac type epoxy resins, orthocresol novolac type epoxy resins and the like. Epoxidized resin; diglycidyl ether such as bisphenol A, bisphenol F, bisphenol S, alkyl-substituted bisphenol; glycidylamine type epoxy resin obtained by reaction of polyamine such as diaminodiphenylmethane and isocyanuric acid with epichlorohydrin; olefin A linear aliphatic epoxy resin obtained by molding a bond with a peracid such as peracetic acid; and an alicyclic epoxy resin can be used. As the epoxy resin, a mixture of two or more kinds can be used.

As the epoxy resin, an epoxy resin having an epoxy equivalent of about 50 g / eq to about 500 g / eq, desirably about 80 g / eq to about 450 g / eq can be used.

Desirably, as an epoxy resin, what does not contain an aromatic functional group can be used. When an aromatic functional group is contained, when it is applied to a reflector of a light-emitting element, yellowing occurs due to high heat of the light-emitting element, and it may not be used as a reflector. For example, as the epoxy resin, a linear aliphatic epoxy resin obtained by molding an olefin bond with a peracid such as peracetic acid; and an alicyclic epoxy resin can be used.

For example, among the epoxy resins, a triglycidyl isocyanurate resin represented by the following chemical formula 1 or an epoxy resin represented by the following chemical formula 2 that is excellent in transparency and discoloration resistance can be used.

<Chemical formula 1>

（前記式において、ｎは０〜２０の整数である。） <Chemical formula 2>

(In the above formula, n is an integer of 0 to 20.)

In particular, since the epoxy resin of Formula 2 contains one or more hydroxy groups in the epoxy molecular structure, it is not gelled by a partial esterification reaction with a curing agent and can be melted again by heat. It is suitable for manufacturing in the B stage state.

In the present invention, the curing agent is not particularly limited, and any compound that can react with the epoxy resin can be used. As the curing agent, an acid anhydride curing agent, an isocyanuric acid curing agent, a phenol curing agent, or the like can be used. As a hardening | curing agent, what mixed 2 or more types can be used.

Examples of the acid anhydride curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, glutaric anhydride, Dimethyl glutaric anhydride, diethyl glutaric anhydride, succinic anhydride, methyl hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride and the like can be used.

Isocyanuric acid curing agents include 1,3,5-tris (1-carboxymethyl) isocyanurate, 1,3,5-tris (2-carboxyethyl) isocyanurate, 1,3,5-tris (3-carboxyl). Propyl) isocyanurate, 1,3-bis (2-carboxyethyl) isocyanurate, and the like.

Examples of phenolic curing agents include phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene, and formaldehyde. , Benzaldehyde, salicylaldehyde, and other novolak-type phenol resins obtained by condensation or cocondensation in the presence of an acidic catalyst; synthesized from phenols and / or naphthols and dimethoxyparaxylene or bis (methoxy) biphenyl Phenol aralkyl resins; aralkyl type phenol resins such as biphenylene type phenol aralkyl resins and naphthol aralkyl resins; phenols and / or naphth Dicyclopentadiene-type phenolic resins such as dicyclopentadiene-type phenol novolak resin and dicyclopentadiene-type 4-naphthol novolak resin synthesized by copolymerization of tols with dicyclopentadiene; triphenylmethane-type phenol resin; terpene-modified phenol resin Paraxylene and / or metaxylene modified phenolic resin; melamine modified phenolic resin; or cyclopentadiene modified phenolic resin can be used.

Desirably, as a hardening | curing agent, what does not contain an aromatic functional group can be used. When an aromatic functional group is contained, when it is applied to a reflector of a light emitting diode, yellowing occurs due to the high heat of the light emitting diode, and it may not be used as a reflector. For example, as the curing agent, one or more selected from the group consisting of an acid anhydride curing agent and an isocyanuric acid curing agent can be used, and an acid anhydride curing agent can be desirably used.

As the acid anhydride curing agent, it is desirable to use a colorless or light yellow curing agent.

The curing agent may be included in an amount of about 50 parts by weight to about 250 parts by weight with respect to about 100 parts by weight of the epoxy resin. Within the above range, there can be an effect that the high temperature stability and electrical performance are excellent, the heat distortion temperature is high, and the mechanical properties are good. The curing agent may be included in an amount of about 50 parts by weight to about 200 parts by weight, more preferably about 50 parts by weight to about 170 parts by weight.

In compounding a curing agent for an epoxy resin, particularly an acid anhydride curing agent, an active group capable of reacting with an epoxy group, for example, an acid anhydride group, from about 0.5 equivalents to 1 equivalent of an epoxy group in the epoxy resin. Desirably about 1.5 equivalents. Within the said range, the cure rate of an epoxy resin composition does not become slow, the glass transition temperature of hardened | cured material does not fall, and the moisture resistance of hardened | cured material does not fall. Desirably, the active group can be about 0.7 equivalents to about 1.2 equivalents.

In addition to the curing agent for the epoxy resin, the acid anhydride curing agent described above partially esterified with alcohol or a carboxylic acid curing agent can be used together.

The curing accelerator that can be used in the present invention serves to promote the crosslinking reaction by reacting with the epoxy resin and the curing agent. As the curing accelerator, a polyhydric polyol having about 2 or more hydroxy groups can be used. Desirably, the curing accelerator can have about 3 or more hydroxy groups.

The curing accelerator is not particularly limited, but may have a structure represented by the following chemical formula 3.

<Chemical Formula 3>
_{OH- (CH 2) m - [} CR1-OH] n - (CH 2) p -OH
(In the above formula, R1 is hydrogen or a linear or branched alkyl group having 1 to 30 carbon atoms, n is an integer of 0 to 20, and m and p are independently integers of 0 to 10. (However, when n, m, and p are all 0, they are excluded.)

Desirably, R1 is hydrogen or a linear or branched alkyl group having 1 to 10 carbon atoms, and n is an integer of 0 to 3.

As the curing accelerator of the present invention, a curing accelerator having a hydroxyl group equivalent of about 30 or more, desirably about 30 to about 200, more desirably about 30 to about 150 can be used.

The curing accelerator of the present invention may not contain an aromatic functional group. When an aromatic functional group is included, discoloration may occur when the reflector is manufactured.

The curing accelerator of the present invention may be included in an amount of about 3 parts by weight to about 49 parts by weight with respect to about 100 parts by weight of the epoxy resin. Within the said range, since the crosslinked bond of an epoxy resin and a hardening | curing agent does not generate | occur | produce, the uncured state of a composition can be prevented. The curing accelerator may be included in an amount of about 5 parts by weight to about 45 parts by weight.

The inorganic filler is not particularly limited, and for example, one or more selected from the group consisting of silica, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, and barium carbonate can be used. From the viewpoint of moldability and flame retardancy of the resin composition, it is desirable to use one or more of silica, aluminum hydroxide, and magnesium hydroxide as the inorganic filler.

The average particle size (D50) of the inorganic filler can be about 35 μm or less, desirably about 1 μm to about 22 μm. As the inorganic filler, a mixture of two or more kinds having different average particle diameters may be used. For example, an inorganic filler having an average particle diameter (D50) of less than about 10 μm, preferably about 1 μm to about 10 μm. And an inorganic filler having an average particle diameter (D50) of about 10 μm to about 35 μm can be used. When the average particle diameter (D50) contains an inorganic filler having a particle size of about 10 μm to about 35 μm, there is an effect of reducing burrs generated between the molds during transfer molding. However, if there is too much inorganic filler, unfilling can occur by easily closing the cavity inlet. In this case, an inorganic filler having an average particle size (D50) of less than about 10 μm and an inorganic filler having an average particle size (D50) of about 10 μm to about 35 μm have a weight of about 1: 0.1 to about 1: 2.0. Ratios can be included.

The inorganic filler is about 1 to about 90 parts by weight, preferably about 5 to about 70 parts by weight, more preferably about 40 parts by weight, of about 100 parts by weight of the total thermosetting light reflecting resin composition. Or about 45 parts by weight.

The white pigment is not particularly limited, and titanium oxide, alumina, magnesium oxide, antimony oxide, zirconium oxide, inorganic hollow particles, and the like can be used.

The average particle size (D50) of the white pigment can be from about 0.1 μm to about 50 μm. Within the above range, since the particles do not aggregate, the dispersibility is good and the light reflection property of the cured product does not deteriorate. As the white pigment, a mixture of two or more kinds having different average particle diameters can be used. The white pigment is about 5 parts by weight to about 50 parts by weight, preferably about 10 parts by weight to about 40 parts by weight, more preferably about 15 parts by weight to about 100 parts by weight of the total thermosetting light reflecting resin composition. About 35 parts by weight can be included.

The white pigment and the inorganic filler can be included in a weight ratio of about 1: 0.1 to about 1: 4. Within the above range, the light reflection property of the cured product does not deteriorate, which is advantageous for tablet molding suitable for the transfer molding method, and when the melt is injected into the mold, the light reflection is inhibited on the surface of the molded product. The formation of bubbles can be reduced, the resin burrs leaking between the molds can be reduced, and the metal wiring (lead frame) can be prevented from being contaminated by the resin burrs. There can be an effect that the operation of connecting the work and the gold wire is performed well. The white pigment and the inorganic filler may desirably be included in a weight ratio of about 1: 0.2 to about 1: 3.

In another embodiment, the composition of the present invention may further include one or more selected from the group consisting of a release agent and an additive.

The release agent is not particularly limited and is selected from the group consisting of aliphatic carboxylic acids, aliphatic carboxylic acid esters, aliphatic polyethers, non-oxidized polyolefins, and oxidized polyolefins having a carboxy group. The above can be used. As the mold release agent, it is desirable to use a mold release agent with little colorless or pale yellow coloring.

As the aliphatic carboxylic acid, a monovalent organic acid having 10 to 50 carbon atoms such as lauric acid, myristic acid, palmitic acid, stearic acid, and montanic acid can be used.

As the aliphatic carboxylic acid ester, a polyalkylene ether compound having a structure of the following chemical formula 4 and having 3 to 500 carbon atoms can be used.

（前記式において、ｑ１は１〜２０で、Ｒは、水素、メチル基、炭素数２〜１０の有機基である。） <Chemical formula 4>

(In the above formula, q1 is 1 to 20, and R is hydrogen, a methyl group, or an organic group having 2 to 10 carbon atoms.)

As the oxidized or non-oxidized polyolefin, a low molecular weight polyolefin having a number average molecular weight of about 500 g / mol to about 10,000 g / mol can be used.

The release agent may be included in an amount of about 0.01 to about 8 parts by weight with respect to about 100 parts by weight of the epoxy resin. Within the said range, the adhesiveness with respect to a reflecting plate does not deteriorate. The release agent may be included in an amount of about 1 to about 7 parts by weight.

The additive is excellent in heat and cold resistance and can maintain the elasticity of the product in a wide temperature range of about -50 ° C to about 250 ° C. As the additive, one having a crosslinked linear dimethylpolysiloxane structure can be used.

For example, as the additive, fine silicon powder containing a structural unit represented by the following formula 5 can be used. Alternatively, as the additive, a hybrid silicon powder obtained by coating a fine silicon powder represented by the following formula 5 with a silicon resin represented by the following formula 6 can be used.

<Chemical formula 5>

<Chemical formula 6>
(RSiO _3/2 ) n
(In the above formula, R is a methyl group, a phenyl group, a vinyl group, or hydrogen. N is an integer of 2 to 10,000.)

The average particle size (D50) of the silicon powder may be about 0.8 μm to about 40 μm.

The additive may be contained in an amount of about 0.01 to about 10 parts by weight out of about 100 parts by weight of the entire thermosetting light reflecting resin composition. Within the above range, the molded product has impact absorption, and has an effect of improving wear resistance and mold release. The additive may be included at about 0.1 to about 7 parts by weight.

The thermosetting light reflecting resin composition according to the present invention further includes various additives in addition to the epoxy resin, the curing agent, the curing accelerator, the inorganic filler, the white pigment, the release agent, and the additive. Can do. For example, a coupling agent can be used as needed from the viewpoint of improving the interfacial adhesion between the resin, the inorganic filler, and the white pigment. The coupling agent is not particularly limited, and a silane coupling agent and a titanate coupling agent can be used. As the silane coupling agent, epoxy silane, amino silane, cationic silane, vinyl silane, acrylic silane, mercapto silane, or the like can be used. It is desirable that the coupling agent is appropriately adjusted in consideration of the surface coating amount on the inorganic filler. The coupling agent is desirably about 5% by weight or less in the resin composition. In addition to the coupling agent, additives such as an antioxidant and an ion scavenger can be included.

A method for producing a thermosetting light reflecting resin composition according to another aspect of the present invention is provided. In the said method, the epoxy resin mentioned above, a hardening | curing agent, a hardening accelerator, an inorganic filler, and a white pigment can be mixed and manufactured, and a mixing means, conditions, etc. are not restrict | limited especially. In general, various components can be kneaded using an apparatus such as a mixing roll, an extruder, a kneader, a roll or an extruder, and the obtained kneaded product can be produced by cooling and pulverizing. The kneading method is not particularly limited, but melt kneading can be performed, and the temperature and time at the time of melt kneading can be adjusted according to the type and amount of various components used.

As a specific example, there is no limitation on the order of blending the components, but a predetermined temperature, for example, about 100 ° C. to about 100 ° C., so that the mixture of the epoxy resin, the curing agent, the release agent, and the additive can be melted. Maintain at 150 ° C. to obtain a liquid molten mixture. The resulting molten mixture is again cooled to about 30 ° C to about 60 ° C. The remaining raw material curing accelerator, various additives that are unmelted solid powder, white pigment, inorganic filler, and the like are added, and the melt-kneading process proceeds. In the melt kneading process, the mixture can be maintained at a temperature of about 30 ° C. to about 50 ° C., desirably about 35 ° C. to about 45 ° C., and kneaded at about 50 rpm to about 300 rpm for about 30 minutes to about 180 minutes. If the melt-kneading time is less than 30 minutes, the dispersibility of the mixture decreases, and if it exceeds 180 minutes, reaction heat is generated due to the reaction of the composition, so that the reaction control is difficult, and gel may be generated in the mixture. There are no restrictions on the order of blending the components, but first, an epoxy resin, a curing agent, a release agent and various additives are premixed, and then a curing accelerator, a white pigment, an inorganic filler, and an unmelted solid. It is desirable to add an additive.

Still another aspect of the present invention provides a reflector for mounting an optical semiconductor element. The said optical semiconductor element mounting reflector can be comprised using the thermosetting type light reflecting resin composition which concerns on this invention. Specifically, the optical semiconductor element mounting reflector includes one or more recesses, and at least an inner side surface of the recess includes a reflector made of the thermosetting light reflecting resin composition of the present invention. Can do.

Still another aspect of the present invention provides a method for manufacturing a reflecting plate for mounting an optical semiconductor element. The method may include a step of forming an inner side surface of the optical semiconductor element mounting reflector with the thermosetting light reflecting resin composition. Specifically, a thermosetting light reflecting resin composition or a tablet molded body thereof can be produced by transfer molding. In the optical semiconductor element mounting reflector, metal wiring is formed from a metal foil by a known method such as punching or etching. Nickel / silver plating is performed on the metal wiring (lead frame). Thereafter, the metal wiring is arranged in a mold, and the thermosetting light reflecting resin composition of the present invention, that is, the dissolved product of the tablet molding is injected into the resin injection port of the mold. Thereafter, the injected resin composition is cured at a mold temperature of about 145 ° C. to about 190 ° C. and a molding pressure of about 10 Kgf / cm ^{2 to} about 80 Kgf / cm ² for about 100 seconds to about 240 seconds, and then removed from the mold. Heat curing is performed at a curing temperature of about 120 ° C. to about 180 ° C. for about 1 hour to about 5 hours. In addition, after undergoing a process of removing organic contamination such as resin burrs on the metal wiring (lead frame) of the optical semiconductor device, the thermosetting light reflecting resin composition is used for the purpose of improving the optical semiconductor reflectance and maintaining it for a long time. Nickel / silver plating can be performed again at a predetermined position of a recess surrounded by a reflecting mirror made of a cured product and serving as an optical semiconductor element mounting region.

Still another aspect of the present invention relates to an optical semiconductor device including the optical semiconductor element mounting reflector. The optical semiconductor device includes a reflection plate for mounting an optical semiconductor element, an optical semiconductor element mounted on a bottom surface of the recess of the reflection plate for mounting an optical semiconductor element, and a phosphor containing the phosphor formed in the recess so as to cover the optical semiconductor element A transparent sealing resin layer can be included. An LED can be used as the optical semiconductor element.

Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, this is provided as a preferred example of the present invention and cannot be construed as limiting the present invention in any way.

The contents not described here can be sufficiently technically analogized by those skilled in this technical field, and the description thereof will be omitted.

Specific specifications of the components used in the following examples and comparative examples are as shown below.

(1) TEPIC-S (Nissan Chemical Industry Co., Ltd.) was used as an epoxy resin.

(2) MH-700G (Shin Nihon Rikagaku) was used as a curing agent.

(3-1) PEP550 (tetrahydric alcohol) (BASF Corporation) was used as a curing accelerator.

(3-2) TPP-PB (Hokuko Chemical Co., Ltd.) (phosphorus catalyst) was used as a curing accelerator.

(4) SiO ₂ (a 1: 1 weight ratio mixture of average particle diameter (D50) 1 μm and average particle diameter (D50) 22 μm) was used as the inorganic filler.

(5) TiO ₂ (average particle size 0.17 μm) was used as a white pigment.

(6) PED-522 (Clariant) was used as a release agent.

(7) KBM-403 (epoxysilane) (Shin-Etsu Chemical Co., Ltd.) was used as an additive.

(8) PA-9T TA-112 (Kuraray) as the thermoplastic resin 1, PA-9T TA-113 (Kuraray) as the thermoplastic resin 2, PA-9T TA-124 (Kuraray) as the thermoplastic resin 3 It was used.

Examples 1-3

A mixture of the epoxy resin, the curing agent, the release agent, and the additive added in the contents shown in Table 1 below was heated to 120 ° C. and melt mixed. The temperature of the resulting mixture was allowed to cool to 40 ° C. White pigments, curing accelerators and inorganic fillers were added in the amounts listed in Table 1 below. The resulting mixture was kneaded for 80 minutes at rpm 100 while maintaining the temperature at 35 ° C. The obtained mixture was put in a tray and aged in an oven at 70 ° C. for 3 hours, and each specimen was produced using a transfer molding machine at 150 ° C. for 240 seconds.

Comparative Examples 1-4

Except having changed the content of each component in the following Table 1, the composition was manufactured by the same method as the said Example, and the test piece was manufactured.

Comparative Example 5

  A polyamide-based thermoplastic resin 1 having high heat resistance that can be applied in the industry as a reflector for light reflection is injected into a 0.5 watt LED by an injection molding method using a 300 ° C. mold. Pieces were produced.

Comparative Examples 6-7

In Comparative Examples 6 to 7, specimens were produced in the same manner as in Comparative Example 5 except that the thermoplastic resins 2 to 3 were used in place of the thermoplastic resin 1, respectively.

Example: Physical property evaluation

The following physical properties were evaluated for the specimens produced in the above Examples and Comparative Examples, and the results are shown in Table 2 below.

<Method for measuring physical properties>

(1) S / F (Spiral flow length) (inch): The flowability at the time of transfer molding at a mold temperature of 150 ° C. using an EMMI standard mold for the compositions produced in the examples and comparative examples. It was measured. In addition, S / F was measured by aging time while aging at 70 ° C.

(2) G / T (Gelation time) (sec): The amount of time required for gelation is determined by placing a certain amount of the compositions produced in the examples and comparative examples on a hot plate at 150 ° C. It was measured. Further, G / T was measured by aging time while aging at 70 ° C.

(3) High-temperature hardness (Shore-A): 50 mm × 50 mm × 3 mm (length × width × thickness) using a transfer molding machine at a mold temperature of 150 ° C. with respect to the compositions produced in the above examples and comparative examples. The sample of No. 3) was transfer molded, and after 240 seconds had passed, the hardness was measured on a 150 ° C. mold.

(4) Light reflectance (Reflectance, R) (%): 50 mm × 50 mm × 1 mm (length × width × thickness) specimen was transfer molded at 150 ° C. for 240 seconds and cured at 150 ° C. for 3 hours. . The initial light reflectance was measured at 430 nm using a V-670 spectrometer (JASCO). After measuring the initial light reflectivity, heat treatment was performed at 180 ° C. for 168 hours, and the light reflectivity was measured again at 430 nm. FIG. 1 shows the light reflectance at 430 nm depending on the aging time after heat treatment at 180 ° C. for 168 hours on the specimens prepared with the compositions of Examples 1 to 3 and the composition of Comparative Example 4. It is. FIG. 2 shows the light reflectance at 430 nm depending on the aging time after heat treatment at 180 ° C. for 168 hours on the specimens produced with the compositions of Examples 1 to 3 and Comparative Examples 5 to 7. It is a thing.

(5) Discoloration resistance (light reflectivity maintenance rate) (%): Color change resistance (light reflectivity maintenance rate) was calculated using the measured light reflectivity and the following formula.

Light reflectance maintenance ratio (%) = light reflectance after heat treatment at 180 ° C. for 168 hours / light reflectance before heat treatment × 100

(6) Peeling evaluation: A contact portion of a cup-shaped molded product having a size of 3 mm × 2.5 mm × 2 mm (length × width × thickness) was immersed in water-based ink, and the presence or absence of ink intrusion due to capillary action was confirmed. When the ink soaked, it was indicated by ○, and when the ink did not soak, it was indicated by ×.

As shown in Table 2, the composition of Comparative Example 1 in which the curing accelerator of the present invention is not added is in an uncured state even after 3 hours because the reaction hardly occurs at an aging temperature of 70 ° C. It was difficult to make. In the case of the composition of Comparative Example 2 containing 2 parts by weight as an addition amount with respect to 100 parts by weight of epoxy, the reaction occurred at a temperature of 70 ° C., unlike Comparative Example 1 in which no curing accelerator was contained. However, S / F was 103 inches or more and G / T was manufactured on the B stage in 100 seconds. However, since the high temperature hardness after transfer molding is 10, a phenomenon of sticking to the mold occurs, and it is difficult to manufacture a specimen for evaluating physical properties, so that it is difficult to measure light reflectance and evaluate peeling. When 100 parts by weight of the epoxy contained 50 parts by weight of the curing accelerator, the reaction occurred at the same aging temperature, but sufficient crosslinking reaction of the composition did not occur, so the high temperature hardness after transfer molding was as low as 12. Similarly, since it is difficult to manufacture the B stage, it is difficult to measure the light reflectance and evaluate the peeling. On the other hand, in the case of Examples 1, 2 and 3, since the reaction occurs at the aging temperature of 70 ° C., there is no problem in the production of the B stage, and the hardness at the high temperature after transfer molding is 50 or more. There was no difficulty in production. In any of Examples 1, 2, and 3, the initial light reflectance was measured as high as 90% or more, and the light reflectance was measured after heat treatment at 180 ° C. for 168 hours. In all of 1, 2, and 3, it was shown to be 70% or more. In the case of Comparative Example 4 using a phosphorus curing accelerator containing an aromatic functional group, a sufficient reaction occurred at an aging temperature of 70 ° C., and a B stage was produced after 30 minutes. Since the hardness at high temperature at the time of transfer molding was high, there was no difficulty in the production of specimens, and no peeling phenomenon was found. However, in the case of discoloration resistance, the initial light reflectance was measured to be high, but the light reflectance after the high-temperature heat treatment was significantly lower than that of the present invention. That is, discoloration such as yellowing occurred after heat treatment at high temperature, and the initial light reflectance could not be maintained, so the discoloration resistance was not good. In addition, as shown in the results of Comparative Examples 5 to 7 and FIG. 2, specimens made of a polyamide series thermoplastic resin having high heat resistance that can be applied in the industry as a light reflecting reflector are also provided. It can be seen that the color reflectance is not good because the light reflectance after the heat treatment is abruptly lowered.

Moreover, S / F and G / T were measured by the aging time at 70 ° C. for the compositions produced in the above Examples and Comparative Examples, and the results are shown in Tables 3 and 4 below.

As described above, the composition of the present invention was manufactured on a B stage having an appropriate S / F value and G / T value, while the compositions of Comparative Examples 1 to 3 were in an uncured state. Even if it was manufactured on the B stage, it could not have proper S / F and G / T values. However, in the case of Comparative Example 4, after 0.5 hours, the B stage has appropriate S / F value and G / T value at a relatively fast time, and after that, there is no fluidity and gelation has already occurred. G / T could not be measured due to progress.

The present invention provides a thermosetting light-reflective resin composition that has good discoloration resistance and does not cause yellowing or discoloration. In addition, the present invention provides a thermosetting light reflecting resin composition in which the light reflectance does not decrease even when exposed to a high temperature for a long time.

Although the embodiments and drawings of the present invention have been described above, the present invention is not limited to the above-described embodiments and drawings, and can be manufactured in various forms different from each other in the technical field to which the present invention belongs. Those skilled in the art will understand that the present invention can be implemented in other specific forms without changing the technical idea and essential features of the present invention. Thus, it should be understood that the above-described embodiments are illustrative in all aspects and not limiting.

Claims (20)

A thermosetting light reflecting resin composition comprising a polyhydric polyol having two or more hydroxy groups as a curing accelerator,
Thermosetting light-reflective resin composition having a light reflectance maintenance ratio represented by the following formula 1 of the specimen produced from the composition of 70% or more:
<Formula 1>
Light reflectance maintenance rate (%) = light reflectance after heat treatment at 180 ° C. for 168 hours / light reflectance before heat treatment × 100 The thermosetting light reflecting resin composition according to claim 1, wherein the number of hydroxy groups is 3 or more. The composition according to claim 1, wherein the composition has a light reflectance maintenance ratio of 70% or more after transfer molding, curing at 150 ° C for 3 hours, and heat treatment at 180 ° C for 168 hours. Thermosetting light reflecting resin composition. 2. The thermosetting light reflecting resin composition according to claim 1, wherein the composition has an S / F (spiral flow length) of about 15 inches to about 45 inches at the time of transfer molding. The thermosetting light reflecting resin composition according to claim 1, wherein the composition has a G / T (Gelation time) of about 30 seconds to about 70 seconds at the time of transfer molding. The thermosetting light-reflecting resin composition according to claim 1, wherein the curing accelerator has a hydroxy group equivalent of 30 or more. The thermosetting light reflecting resin composition according to claim 1, wherein the curing accelerator does not contain an aromatic functional group. The thermosetting light-reflecting resin composition according to claim 1, wherein the curing accelerator has a structure represented by the following chemical formula 3:
<Chemical Formula 3>
_{OH- (CH 2) m - [} CR1-OH] n - (CH 2) p -OH
(In the above formula, R1 is hydrogen or a linear or branched alkyl group having 1 to 30 carbon atoms, n is an integer of 0 to 20, and m and p are independently integers of 0 to 10. (However, when n, m, and p are all 0, they are excluded.) The thermosetting light reflecting resin composition according to claim 1, wherein the composition includes the curing accelerator, an epoxy resin, a curing agent, an inorganic filler, and a white pigment. The thermosetting light reflecting resin composition according to claim 9, wherein the curing accelerator is included in an amount of about 3 parts by weight to about 45 parts by weight with respect to about 100 parts by weight of the epoxy resin. Production method. The thermosetting light reflecting resin composition according to claim 9, wherein the epoxy resin does not contain an aromatic functional group. The thermosetting light reflecting resin composition according to claim 9, wherein the curing agent does not contain an aromatic functional group. The thermosetting light reflecting resin composition according to claim 9, wherein the composition comprises the white pigment and the inorganic filler in a weight ratio of 1: 0.1 to 1: 4. The inorganic filler is included as a mixture of an inorganic filler having an average particle size (D50) of less than about 10 μm and an inorganic filler having an average particle size (D50) of about 10 μm to about 35 μm. Item 10. The thermosetting light reflecting resin composition according to Item 9. The thermosetting light-reflecting resin composition according to claim 9, wherein the composition further comprises one or more selected from the group consisting of a release agent and an additive. The thermosetting light reflecting resin composition according to claim 15, wherein the additive has a crosslinked linear dimethylpolysiloxane structure. Melt mixing the epoxy resin and curing agent;
A thermosetting light-reflective resin composition comprising a step of adding a curing accelerator containing a polyhydric polyol having about 2 or more hydroxy groups, an inorganic filler, and a white pigment to the mixture and melt-kneading; Manufacturing method. The method of claim 17, wherein the melt-kneading step is performed at a temperature of about 30 ° C to about 50 ° C for about 30 minutes to about 180 minutes. Method. A reflecting plate for mounting an optical semiconductor element, comprising the thermosetting light reflecting resin composition according to any one of claims 1 to 16. 20. An optical semiconductor device comprising the optical semiconductor element mounting reflector according to claim 19.

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