JP6917570B2 - Light emitting device - Google Patents

Description

The present invention relates to a light emitting device including a light emitting element such as a light emitting diode.

In recent years, the use of light emitting devices including light emitting elements such as light emitting diodes for electronic devices, vehicles, lighting devices, and the like has been expanding.

In the light emitting device, for example, a resin composition is molded to produce a reflector having a recess, a lead frame is embedded in the reflector, a light emitting element is mounted in the recess, and the light emitting element is electrically connected to the lead frame. Then, it is manufactured by filling the recess with a sealing material. The sealing material protects the light emitting element and transmits the light emitted by the light emitting element to the outside.

The encapsulant is often made of a low-viscosity resin such as a silicone resin, and often contains a fluorescent substance for wavelength conversion of the light emitted by the light emitting element. Therefore, it is necessary that the resin and the fluorescent substance do not leak from the recess.

However, as described above, the lead frame is embedded in the reflector, and since the two have different coefficients of thermal expansion, the lead frame and the reflector have poor adhesion. Therefore, the resin and the fluorescent substance may leak to the outside from the inside of the recess through between the base and the lead frame. Then, the light emitting element may not be protected, or the sealing material may not have the desired wavelength conversion performance.

In order to improve the adhesion between the reflector and the lead frame, it has been proposed to roughen the surface of the lead frame by laser processing the lead frame (see Patent Document 1).

Japanese Patent No. 5083472

In particular, when the reflector is made of a resin having low adhesion to a metal such as an unsaturated polyester resin or a silicone resin, sufficient adhesion may not be obtained only by roughening the lead frame.

An object of the present invention is to provide a light emitting device capable of having a high adhesion between a lead frame and a reflector.

The light emitting device according to one aspect of the present invention includes a reflector and a lead frame embedded in the reflector, has a recess, and a part of the lead frame is exposed on the bottom surface of the recess. A base, a light emitting element mounted in the recess of the base, and a sealing material filled in the recess of the base and sealing the light emitting element are provided. The region in contact with the reflector on the surface of the lead frame has a roughened surface having Ra in the range of 0.5 to 1.5 μm. The reflector is a molded product of a resin composition containing silica powder having an average particle size of 9 to 25 μm and a proportion of particles having a particle size of 6 μm or less of 25 to 40% by volume.

According to one aspect of the present invention, high adhesion between the reflector and the lead frame in the light emitting device can be realized.

It is sectional drawing which shows the light emitting device which concerns on one Embodiment of this invention. It is a partially broken perspective view which shows the base in the light emitting device shown in FIG. FIG. 3A is a plan view showing a lead frame in the light emitting device shown in FIG. 1, and FIG. 3B is a bottom view showing the lead frame.

Hereinafter, an embodiment of the present invention will be described.

The light emitting device 1 according to the present embodiment includes a base 2, a light emitting element 5, and a sealing material 6. The base 2 includes a reflector 3 and a lead frame 4 embedded in the reflector 3. The base 2 has a recess 21, and a part of the lead frame 4 is exposed on the bottom surface of the recess 21. The light emitting element 5 is mounted in the recess 21 of the base 2 and is electrically connected to the lead frame 4. The sealing material 6 is filled in the recess 21 of the base 2 to seal the light emitting element 5. The region in contact with the reflector 3 on the surface of the lead frame 4 has a roughened surface 8 having Ra in the range of 0.5 to 1.5 μm. The reflector 3 is a molded product of a resin composition (hereinafter referred to as composition (X)) containing silica powder having an average particle size of 9 to 25 μm and a proportion of particles having a particle size of 6 μm or less of 25 to 40% by volume. be.

In the light emitting device 1 according to the present embodiment, as described above, not only the lead frame 4 has a roughened surface 8 having a specific roughness, but also the reflector 3 contains silica powder having a specific particle size. Since it is a molded product of the object (X), high adhesion between the reflector 3 and the lead frame 4 can be realized. Therefore, even if a material such as a resin or a fluorescent substance is arranged in the recess 21 to produce the sealing material 6, such a material is unlikely to leak to the outside through between the reflector 3 and the lead frame 4. .. As a result, the light emitting element 5 can be sufficiently protected by the sealing material 6. It is also possible to maintain the original concentration of the fluorescent substance in the encapsulant 6 and maintain the desired wavelength conversion performance of the encapsulant 6. Further, since it becomes difficult for water to pass between the reflector 3 and the lead frame 4, it is possible to prevent the water that has entered from the outside from reaching the light emitting element 5. Therefore, deterioration of the light emitting element 5 due to moisture is suppressed.

The light emitting device 1 according to the present embodiment will be described in more detail.

First, the structure of the light emitting device 1 will be described.

FIG. 1 shows a cross-sectional view of a light emitting device 1 according to the present embodiment, FIG. 2 shows a broken perspective view of a base 2 in the light emitting device 1, and FIG. 3A shows a plan view of a lead frame 4 in the light emitting device 1. FIG. 3B shows a bottom view of the lead frame 4.

The base 2 includes a reflector 3 and a lead frame 4 embedded in the reflector 3.

The lead frame 4 has a first surface 43 and a second surface 44 on the opposite side of the first surface 43. The lead frame 4 includes a first lead 41 and a second lead 42 that are arranged at intervals in one direction along the first surface 43. A step 45 is formed on the outer peripheral edge of each of the first lead 41 and the second lead 42 on the second surface 44 side over the entire circumference thereof. In the present embodiment, the lead frame 4 is formed with the step 45 in this way, but the step 45 may not be formed.

In the present embodiment, the reflector 3 includes a reflector portion 31 and an insulating portion 32. The reflector portion 31 has a tubular shape and is formed so as to protrude from the first surface 43 of the lead frame 4. The insulating portion 32 is interposed between the first lead 41 and the second lead 42 to electrically insulate both of them, and meshes with each stage 45 of the first lead 41 and the second lead 42. There is. Further, the reflector 3 is engaged with the step 45 at the outer peripheral portion of the lead frame 4. As a result, the lead frame 4 is embedded in the reflector 3 and supported by the reflector 3. The inside surrounded by the tubular reflector portion 31 constitutes the recess 21 of the base 2. The inner diameter of the recess 21 becomes larger toward the opening of the recess 21, and the inner peripheral surface of the reflector portion 31 is inclined so as to be so. Therefore, the light emitted from the light emitting element 5 is easily reflected by the inner peripheral surface of the reflector portion 31, and as a result, the light emitting device 1 can have a high light extraction efficiency. On the bottom surface of the recess 21, the first lead 41 and the second lead 42 are exposed, whereby a part of the first surface 43 of the lead frame 4 is exposed on the bottom surface of the recess 21. The insulating portion 32 is also exposed on the bottom surface of the recess 21. The second surface 44 of the lead frame 4 is exposed to the outside except for the step 45.

The light emitting element 5 mounted in the recess 21 of the base 2 is arranged on the first lead 41 in the recess 21, as shown in FIG. 1, for example, and the wire 71 and the wire 72 are the first leads. It is electrically connected to the 41 and the second lead 42, respectively. As a result, the light emitting element 5 is electrically connected to the lead frame 4.

The recess 21 is filled with a sealing material 6, and the sealing material 6 seals the light emitting element 5. The sealing material 6 is made of, for example, a silicone resin. Further, the sealing material 6 may contain a fluorescent substance for wavelength-converting the light emitted by the light emitting element 5.

In this embodiment, the lead frame 4 is made of metal and is made of, for example, copper or a copper alloy. The lead frame 4 may include a metal film formed by a plating method or the like. The metal coating is, for example, a silver coating or a gold coating, but is not limited to this. When the lead frame 4 has a silver film, the adhesion between the lead frame 4 and the reflector 3 is particularly high. The thickness of the silver film is, for example, in the range of 1 to 10 μm.

As described above, the region in contact with the reflector 3 on the surface of the lead frame 4 has a roughened surface 8 having Ra in the range of 0.5 to 1.5 μm. Ra is the arithmetic mean height defined by JIS B0601: 2001.

The roughened surface 8 is formed in, for example, a region of the first surface 43 in contact with the reflector portion 31. The roughened surface 8 on the first surface 43 is preferably formed in a band shape so as to surround the bottom surface of the recess 21. In this case, leakage of the resin, fluorescent substance, etc. from the inside of the recess 21 to the outside is effectively suppressed.

The width of the roughened surface 8 on the first surface 43 is preferably in the range of 60 to 80 μm. When the width of the roughened surface 8 is 60 μm or more, the roughened surface 8 particularly improves the adhesion between the reflector 3 and the lead frame 4. Further, when the width of the roughened surface 8 is larger than 80 μm, the effect of improving the adhesion is almost saturated in spite of the increase in labor required for laser processing.

The roughened surface 8 may be formed in the step 45 on the second surface 44. In this case, the reflector 3 meshes with the step 45 and comes into contact with the roughened surface 8 at this step 45, so that the adhesion between the reflector 3 and the lead frame 4 becomes higher. The width of the roughened surface 8 in the step 45 depends on the dimensions of the step 45, but is in the range of, for example, 30 to 50 μm.

In a preferred embodiment of the present embodiment, the lead frame 4 is provided with a silver film, and the roughened surface 8 is formed on the silver film. In this case, the adhesion between the lead frame 4 and the reflector 3 is particularly high.

The roughened surface 8 is formed by, for example, performing laser processing at a position on the lead frame 4 where the roughened surface 8 should be formed. That is, for example, the roughened surface 8 is composed of laser machining marks. The laser type used when forming the roughened surface 8 by laser processing is, for example, a FAYb laser or a YAG laser, but is not limited thereto. The laser irradiation conditions are such that when a YAG laser is used and the lead frame 4 having a silver coating is laser-processed, the oscillation wavelength is in the range of 950 to 1100 nm, preferably in the range of 1000 to 70 nm, and the peak output. Is, for example, 8 kW or more, preferably 10 kW or more, but is not limited to this, and is appropriately set according to conditions such as the type of laser and the material of the lead frame 4.

As described above, the reflector 3 in this embodiment is a molded product of the composition (X). The composition (X) contains, for example, a molding resin and a filler.

The molding resin may be either a thermosetting resin or a thermoplastic resin. The molding resin can contain an appropriate resin such as an unsaturated polyester resin, a silicone resin, an epoxy resin, a phenol resin, an acrylic resin, a vinyl ester resin, a polyamide resin, and a PCT resin.

In particular, the molding resin preferably contains at least one of an unsaturated polyester resin and a silicone resin. The cured products of these resins originally have low adhesion to metals. However, even if the molding resin contains at least one of the unsaturated polyester resin and the silicone resin, the lead frame 4 has a roughened surface 8 having a specific roughness and the reflector 3 has a roughened surface 8 as in the present embodiment. In the case of the molded product of the composition (X) containing the silica powder having a specific particle size, the adhesion between the reflector 3 and the lead frame 4 is particularly improved as compared with the case where it is not.

An unsaturated polyester resin that can be blended in the composition (X) will be described.

The unsaturated polyester resin is made of unsaturated polyester (A), or is made of unsaturated polyester (A) and a cross-linking agent (B).

The unsaturated polyester (A) is a copolymer of a carboxylic acid (a1) and an alcohol (a2). That is, the unsaturated polyester (A) comprises a residue of the carboxylic acid (a1) and a residue of the alcohol (a2).

The carboxylic acid (a1) is, for example, fumaric acid, 1,4-cyclohexanedicarboxylic acid, maleic acid, citraconic acid, mesaconic acid, itaconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, glutaconic acid, phthalic acid, isophthalic acid, It contains at least one compound selected from the group consisting of terephthalic acid, succinic acid, adipic acid, sebatic acid, azelaic acid, endomethylenetetrahydrophthalic acid, hetic acid and tetrabromphthalic acid.

The alcohol (a2) is, for example, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, cyclohexane1,4-dimethanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1, Consists of 3-butanediol, 1,5-pentanediol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, hydride bisphenol A, bisphenol A propylene oxide compound, dibromneopentyl glycol, and trimethylolpropane diallyl ether. Contains at least one compound selected from the group.

In a preferred embodiment of the present embodiment, the carboxylic acid (a1) contains fumaric acid and 1,4-cyclohexanedicarboxylic acid, and the alcohol (a2) contains 1,6-hexanediol. In this case, the unsaturated polyester (A) can have crystallinity. Therefore, the storage stability of the composition (X) containing the unsaturated polyester (A) at room temperature is improved, and the viscosity at the time of melting is reduced. Therefore, the fluidity of the composition (X) at the time of molding is increased, and for example, the moldability of the composition (X) when it is molded by the transfer molding method is improved. Further, the discoloration resistance of the reflector 3 which is a molded product produced from the composition (X) is improved. That is, when the reflector 3 is heated and when the reflector 3 is irradiated with light, the reflector 3 is less likely to be discolored. Further, the flexural modulus of the reflector 3 is reduced. This improves the crack resistance of the reflector 3. As a result, the reflector 3 can have high discoloration resistance and high crack resistance even if it is small in size. The total amount of fumaric acid and 1,4-cyclohexanedicarboxylic acid with respect to the entire carboxylic acid (a1) is preferably 99% by mass or more. The mass ratio of fumaric acid to 1,4-cyclohexanedicarboxylic acid is preferably in the range of 63:27 to 81:19. In this case, the unsaturated polyester (A) has an appropriate amount of ethylenically unsaturated bonds, so that the fluidity of the composition (X) at the time of melting is improved and the thermosetting property is also improved. The amount of 1,6-hexanediol with respect to the total alcohol (a2) is preferably 99% by mass or more.

The glass transition temperature of the unsaturated polyester (A) is preferably in the range of 30 to 50 ° C. When the glass transition temperature is 30 ° C. or higher, the storage stability of the composition (X) becomes particularly high. That is, for example, when the composition (X) is pulverized into granules and then stored, the particles of the composition (X) are suppressed from being fused to each other at a high temperature such as in summer. Further, when the glass transition temperature becomes higher than 50 ° C., the melting point of the unsaturated polyester (A) may become too high, which is not preferable. The glass transition temperature of the unsaturated polyester (A) can be easily adjusted by adjusting the composition ratio and the molecular weight of the constituent components.

The melting point of the unsaturated polyester (A) is preferably in the range of 70 to 100 ° C. When the melting point is 100 ° C. or lower, the unsaturated polyester (A) can be easily melted during heat kneading for the preparation of the composition (X) without proceeding with the curing reaction. Therefore, the composition (X) containing no cured product can be easily prepared. Further, when the melting point is 70 ° C. or higher, the decrease in the light reflectance of the molded product such as the reflector 3 is suppressed. The reason is presumed to be as follows. When the melting point of the unsaturated polyester (A) is low, when the composition (X) is crushed by the crushing device, the unsaturated polyester (A) is melted by the heat generated by the crushing device, frictional heat, etc. X) is partially melted. When the partially melted composition (X) collides with a metal component such as a rotary blade in a pulverizer, the composition (X) tends to rub against each other in contact with the metal component. When a hard component such as a filler in the composition (X) and a metal part rub against each other, metal powder is generated from the metal part and is easily mixed in the molding material. It is considered that this metal powder causes a decrease in the light reflectance of the reflector 3. On the other hand, when the melting point of the unsaturated polyester (A) is 70 ° C. or higher, the unsaturated polyester (A) is less likely to melt when the composition (X) is pulverized by a pulverizer. Then, when the composition (X) collides with a metal part such as a rotary blade, the composition (X) is easily crushed quickly. Therefore, the composition (X) and the metal parts are less likely to rub against each other. As a result, the metal powder is less likely to be mixed into the composition (X), and the decrease in the light reflectance of the molded product is suppressed.

Further, when the unsaturated polyester (A) has a melting point in the range of 70 to 100 ° C., the composition (X) can be imparted with particularly excellent fluidity during molding. Therefore, the moldability is improved even when the composition (X) is molded by the transfer molding method.

The iodine value of the unsaturated polyester (A) is preferably in the range of 75 to 100. In this case, the unsaturated polyester (A) has particularly good fluidity when melted and also has good thermosetting property. Therefore, the fluidity, thermosetting property, moldability, and mold releasability of the composition (X) at the time of molding are improved. The iodine value can be easily adjusted by adjusting the mass ratio of fumaric acid and 1,4-cyclohexanedicarboxylic acid in the carboxylic acid (a1).

The ICI viscosity (high shear viscosity) of the unsaturated polyester (A) at 150 ° C. is preferably in the range of 0.1 to 5 Pa · s, preferably in the range of 0.5 to 3 Pa · s. More preferred. In this case, an appropriate fluidity is imparted to the composition (X) at the time of molding, the moldability is particularly good, and the generation of burrs is effectively suppressed. The ICI viscosity of the unsaturated polyester (A) can be easily adjusted by appropriately adjusting the composition of the unsaturated polyester (A).

The cross-linking agent (B) is a component that constructs a cross-linked structure by reacting with an unsaturated bond of the unsaturated polyester (A). The cross-linking agent (B) can contain, for example, at least one compound selected from the group consisting of a vinyl-based polymerizable monomer, a methacrylate-based polymerizable monomer, an acrylate-based polymerizable monomer, and a prepolymer. The prepolymer is a polymer of at least one compound selected from the group consisting of, for example, a vinyl-based polymerizable monomer, a methacrylate-based polymerizable monomer, and an acrylate-based polymerizable monomer. The vinyl-based polymerizable monomer can contain at least one component selected from the group consisting of, for example, styrene, vinyltoluene, divinylbenzene, α-methylstyrene, methyl methacrylate and vinyl acetate. The methacrylate-based and acrylate-based polymerizable monomers are, for example, a group consisting of diallyl phthalate, isodialyl phthalate, triallyl cyanurate, diallyl tetrabromphthalate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate and 1,6-hexanediol diacrylate. Can contain at least one component selected from.

In particular, the cross-linking agent (B) preferably contains a compound having a boiling point of 150 ° C. or higher. In this case, the volatilization of the cross-linking agent (B) from the composition (X) is suppressed. Therefore, the generation of odor from the composition (X) is suppressed, and the working environment is improved. In addition, the stability of the composition of the composition (X) is increased.

The cross-linking agent (B) comprises a group consisting of a polymer of at least one compound selected from the group consisting of diallyl phthalate, isodialyl phthalate, diethylene glycol diacrylate, and these compounds as a compound having a boiling point of 150 ° C. or higher. It is particularly preferred to contain at least one compound of choice. The compound having a boiling point of 150 ° C. or higher includes a compound that does not boil under normal pressure and has a thermal decomposition temperature of 150 ° C. or higher.

The cross-linking agent (B) also preferably contains at least one compound of diallyl phthalate monomer and triallyl cyanurate. In this case, not only the effect of the high volatilization temperature can be obtained, but also mold stains are suppressed when the composition (X) is molded by a mold molding method such as a transfer molding method.

When the unsaturated polyester resin contains the cross-linking agent (B), the amount of the cross-linking agent (B) is in the range of 2 to 15% by mass with respect to the total amount of the unsaturated polyester (A) and the cross-linking agent (B). Is particularly preferable. When this amount is 2% by mass or more, the glass transition point of the molded product such as the reflector 3 becomes particularly high. Further, when this amount is 15% by mass or less, the heat-resistant discoloration property of the molded product becomes particularly high.

When the composition (X) contains an unsaturated polyester resin, the composition (X) may further contain a curing catalyst. In this case, the curing reaction of the unsaturated polyester resin is promoted. Therefore, the moldability of the composition (X) and the shape stability of the molded product are improved. The curing catalyst contains, for example, at least one of a curing accelerator and a polymerization initiator.

The polymerization initiator can contain, for example, a heat-decomposable organic peroxide. Organic peroxides include, for example, t-butylperoxy-2-ethylhexyl monocarbonate, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) -3,3. Contains at least one compound selected from the group consisting of 5-trimethylcyclohexane, t-butylperoxyoctate, benzoyl peroxide, methylethylketone peroxide, acetylacetone peroxide, t-butylperoxybenzoate, and dicumyl peroxide. can.

The polymerization initiator preferably contains an organic peroxide having a 10-hour half-life temperature of 100 ° C. or higher. Specifically, the polymerization initiator preferably contains dicumyl peroxide. When the polymerization initiator contains such an organic peroxide, the decrease in reflectance of the molded product over time is further suppressed.

The amount of organic peroxide with respect to the entire unsaturated polyester resin is preferably in the range of 1 to 3% by mass. When this amount is 1% by mass or more, the curing reaction of the unsaturated polyester resin can be effectively promoted. Further, when this amount is 3% by mass or less, excessive shortening of the molding time can be suppressed, and defects such as blurring in the molded product such as the reflector 3 can be suppressed.

When the composition (X) contains an unsaturated polyester resin, the composition (X) may contain a polymerization inhibitor. The polymerization inhibitor can contain, for example, at least one compound selected from the group consisting of quinones and phenolic compounds. Examples of quinones include hydroquinone, monomethyl ether hydroquinone, toluhydroquinone, di-t-4-methylphenol, phenothiazine, t-butylcatechol, parabenzoquinone, and pyrogallol. Phenolic compounds include, for example, 2,6-di-t-butyl-p-cresol, 2,2-methylene-bis- (4-methyl-6-t-butylphenol), and 1,1,3-tris-( It can contain at least one component selected from the group consisting of 2-methyl-4-hydroxy-5-t-butylphenyl) butane.

The silicone resin that can be blended in the composition (X) will be described.

The silicone resin contains at least one component selected from the group consisting of, for example, a condensation / addition reaction curable silicone resin, a heteroatom-containing modified silicone resin, an addition reaction curable silicone resin, and an inorganic oxide-containing silicone resin.

The condensation / addition reaction curable silicone resin can be cured by the condensation reaction and the addition reaction. The condensation reaction is, for example, a silanol condensation reaction, and the addition reaction is, for example, an epoxy ring opening reaction or a hydrosilylation reaction.

The condensation / addition reaction curable silicone resin contains, for example, a silanol group-terminal polysiloxane, an ethylene-based unsaturated hydrocarbon group-containing silicon compound, an epoxy group-containing silicon compound, and an organohydrogensiloxane.

The silanol group double-ended polysiloxane is an organosiloxane containing a silanol group (SiOH group) at both ends of the molecule. The silanol group-terminal polysiloxane is represented by, for example, the following formula (1).

HO-Si (R ¹ ) _2- O- [Si (R ¹ ) _2- O] _n ^{-Si (R 1} ) _2- OH ... (1)
In formula (1), R ¹ is independently a monovalent saturated hydrocarbon group or a monovalent aromatic hydrocarbon group. R ¹ is a linear or branched alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group and a hexyl group; a cyclopentyl group and a cyclohexyl. A cycloalkyl group having 3 to 6 carbon atoms such as a group; or an aryl group having 6 to 10 carbon atoms such as a phenyl group or a naphthyl group.

In equation (1), n is an integer of 1 or more. n is preferably an integer of 1 to 10000, more preferably an integer of 1 to 1000.

Examples of silanol group-terminal polysiloxanes include silanol group-terminal polydimethylsiloxanes, silanol group-terminal polymethylphenylsiloxanes, and silanol group-terminal polydiphenylsiloxanes. The number average molecular weight of the silanol group-terminal polysiloxane is, for example, in the range of 100 to 1000000, preferably in the range of 200 to 100,000. The silanol group equivalent of the silanol group-terminal polysiloxane is, for example, in the range of 0.002 to 25 mmol / g, preferably in the range of 0.02 to 25 mmol / g.

The amount of the silanol group-terminal polysiloxane is, for example, in the range of 1 to 99.99 parts by mass, preferably in the range of 50 to 99.9 parts by mass, and more preferably 80 to 99 parts by mass with respect to 100 parts by mass of the silicone resin. It is within the range of 5.5 parts by mass.

The ethylene-based silicon compound is a silane compound having an ethylene-based unsaturated hydrocarbon group and a leaving group in a silanol condensation reaction. The ethylene-based silicon compound is represented by, for example, the following formula (2).

R ^2- Si (X ¹ ) ₃ ... (2)
In formula (2), R ² is a monovalent ethylene-based unsaturated hydrocarbon group. R ² is, for example, a substituted or unsubstituted ethylene-based unsaturated hydrocarbon group, and more specifically, for example, an alkenyl group or a cycloalkenyl group. The alkenyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, and an octenyl group, and a vinyl group is particularly preferable. Examples of cycloalkenyl groups include cycloalkenyl groups having 3 to 10 carbon atoms, such as cyclohexenyl groups and norbornenyl groups.

In formula (2), X ¹ is a leaving group in the silanol condensation reaction, and SiX ¹ is a reactive functional group in the silanol condensation reaction. X ¹ is, for example, a halogen atom, an alkoxy group, a phenoxy group, or an acetoxy group independently of each other. The halogen atom is, for example, bromine, chlorine, fluorine, or iodine. Examples of alkoxy groups include linear or branched alkyl groups having 1 to 6 carbon atoms such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, pentyloxy group and hexyloxy group. It contains an alkoxy group having an alkoxy group having a cycloalkyl group having 3 to 6 carbon atoms, such as a cyclopentyloxy group and a cyclohexyloxy group. X ¹ is particularly preferably an alkoxy group, and particularly preferably a methoxy group.

Such ethylene-based silicon compounds include, for example, ethylene-based unsaturated hydrocarbon group-containing trialkoxysilane, ethylene-based unsaturated hydrocarbon group-containing trihalogenated silane, ethylene-based unsaturated hydrocarbon group-containing triphenoxysilane, and ethylene-based It contains at least one component selected from the group consisting of unsaturated hydrocarbon group-containing triacetoxysilanes. In particular, it is preferable that the ethylene-based silicon compound contains an ethylene-based unsaturated hydrocarbon group-containing trialkoxysilane.

Examples of ethylene-based unsaturated hydrocarbon group-containing trialkoxysilanes are vinyltrialkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltripropoxysilane; allyltrimethoxysilane; propenyltrimethoxysilane; butenyltrimethoxysilane. Also contains cyclohexenyltrimethoxysilane. The ethylene-based unsaturated hydrocarbon group-containing trialkoxysilane preferably contains vinyltrialkoxysilane, and is particularly preferably containing vinyltrimethoxysilane.

The amount of the ethylene-based silicon compound is, for example, in the range of 0.01 to 90 parts by mass, preferably in the range of 0.01 to 50 parts by mass, more preferably with respect to 100 parts by mass of the condensation / addition reaction curing type silicone resin. Is in the range of 0.01 to 10 parts by mass.

The epoxy group-containing silicon compound is a silane compound having an epoxy group and a leaving group in a silanol condensation reaction. The epoxy group-containing silicon compound is represented by, for example, the following formula (3).

R ^3- Si (X ² ) ₃ ... (3)
In formula (3), R ³ is a group having an epoxy group. R ³ is an epoxycycloalkyl group such as a glycidyl ether group or an epoxycyclohexyl group, preferably a glycidyl ether group.

The glycidyl ether group is, for example, a glycidoxyalkyl group represented by the following formula (4).

-[R ^4- O-Gr] ... (4)
In formula (4), Gr is a glycidyl group (C ₃ H ₃ O). R ⁴ is a divalent hydrocarbon group, for example a saturated hydrocarbon group or an aromatic hydrocarbon group. Examples of the saturated hydrocarbon group include an alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group, a propylene group and a butylene group, and a cycloalkylene group (a cyclopentylene group and a cyclohexylene group having 3 to 8 carbon atoms). Examples of the aromatic hydrocarbon group include an arylene group having 6 to 10 carbon atoms such as a phenylene group and a naphthylene group. R ⁴ is preferably an alkylene group having 1 to 6 carbon atoms, and particularly a propylene group. preferable.

The glycidyl ether group is, for example, a glycidoxymethyl group, a glycidoxyethyl group, a glycidoxypropyl group, a glycidoxycyclohexyl group, or a glycidoxyphenyl group, preferably a glycidoxypropyl group.

In formula (3), X ² is a leaving group in the silanol condensation reaction, and SiX ² is a reactive functional group in the silanol condensation reaction. X ² is, for example, a halogen atom, an alkoxy group, a phenoxy group, or an acetoxy group independently of each other. The halogen atom is, for example, bromine, chlorine, fluorine, or iodine. Examples of alkoxy groups include linear or branched alkyl groups having 1 to 6 carbon atoms such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, pentyloxy group and hexyloxy group. It contains an alkoxy group having an alkoxy group having a cycloalkyl group having 3 to 6 carbon atoms, such as a cyclopentyloxy group and a cyclohexyloxy group. X ² is particularly preferably an alkoxy group, and particularly preferably a methoxy group.

The epoxy group-containing silicon compound contains at least one component selected from the group consisting of, for example, an epoxy group-containing trialkoxysilane, an epoxy group-containing trihalogenated silane, an epoxy group-containing triphenoxysilane, and an epoxy group-containing triacetoxysilane. do. The epoxy group-containing silicon compound preferably contains an epoxy group-containing trialkoxysilane. Examples of epoxy group-containing trialkoxysilanes are glycidoxyalkyltrimethoxysilanes such as glycidoxymethyltrimethoxysilane, (2-glycidoxyethyl) trimethoxysilane, and (3-glycidoxypropyl) trimethoxysilane; Includes (3-glycidoxypropyl) triethoxysilane; (3-glycidoxypropyl) tripropoxysilane; and (3-glycidoxypropyl) triisopropoxysilane. The epoxy group-containing trialkoxysilane preferably contains glycidoxymethyltrialkoxysilane, and is particularly preferably containing (3-glycidoxypropyl) trimethoxysilane.

The amount of the epoxy group-containing silicon compound is, for example, in the range of 0.01 to 90 parts by mass, preferably in the range of 0.01 to 50 parts by mass, and further, with respect to 100 parts by mass of the condensation / addition reaction curing type silicone resin. It is preferably in the range of 0.01 to 1 part by mass.

The silanol group SiOH group of the silanol group both-terminal polysiloxane with respect to the total of ^{SiX 1} group which is a reactive functional group of the ethylene-based silicon compound ^{and SiX 2} group which is the reactive functional group of the epoxy group-containing silicon compound. The molar ratio value is, for example, in the range of 20/1 to 0.2 / 1, preferably in the range of 10/1 to 0.5 / 1, and particularly preferably substantially 1/1. .. The molar ratio of the ethylene-based silicon compound to the epoxy group-containing silicon compound is, for example, in the range of 10/90 to 99/1, preferably in the range of 50/50 to 97/3, and further. It is preferably in the range of 80/20 to 95/5.

The organohydrogensiloxane is an organosiloxane that does not contain an ethylene-based unsaturated hydrocarbon group and has at least two hydrosilyl groups in one molecule. For example, a hydrogen side chain-containing organopolysiloxane and a hydrogen-terminal organopolysiloxane. Contains at least one of them.

The hydrogen side chain-containing organopolysiloxane is an organohydrogensiloxane having a hydrogen atom as a side chain branched from the main chain. Examples of hydrogen side chain containing organopolysiloxanes include methylhydrogenpolysiloxane, dimethylpolysiloxane-co-methylhydrogenpolysiloxane, ethylhydrogenpolysiloxane, and methylhydrogenpolysiloxane-co-methylphenylpolysiloxane. .. The number average molecular weight of the hydrogen side chain-containing organopolysiloxane is, for example, in the range of 100 to 1000000.

Hydrogen-terminal organopolysiloxane is an organohydrogensiloxane having hydrogen atoms at both ends of the main chain, for example, hydrosilyl group both-terminal polydimethylsiloxane, hydrosilyl group both-terminal polymethylphenylsiloxane, and hydrosilyl group both-terminal polydiphenyl. It contains at least one component selected from the group consisting of siloxane. The number average molecular weight of the hydrogen-terminal organopolysiloxane is, for example, in the range of 100 to 1000000, preferably in the range of 100 to 100,000.

The organohydrogensiloxane preferably contains a hydrogen side chain-containing organopolysiloxane, and more preferably contains dimethylpolysiloxane-co-methylhydrogenpolysiloxane.

The viscosity of the organohydrogensiloxane measured by a B-type viscometer at 25 ° C. is, for example, in the range of 10 to 100,000 mPa · s, preferably in the range of 20 to 50,000 mPa · s. The hydrosilyl group equivalent of the organohydrogensiloxane is, for example, in the range of 0.1 to 30 mmol / g, preferably in the range of 1 to 20 mmol / g.

The amount of the organohydrogensiloxane is, for example, in the range of 10 to 10000 parts by mass, preferably in the range of 100 to 1000 parts by mass with respect to 100 parts by mass of the ethylene-based silicon compound. ^{The molar ratio of the ethylene-based unsaturated hydrocarbon group R 2} of the ethylene-based silicon compound to the hydrosilyl group SiH group of the organohydrogensiloxane is, for example, in the range of 20/1 to 0.05 / 1, preferably in the range of 20/1 to 0.05 / 1. Within the range of 20 / 1-0.1 / 1, more preferably within the range of 10 / 1-0.1 / 1, particularly preferably within the range of 10 / 1-0.2 / 1, most preferably 5 /. It is in the range of 1 to 0.2 / 1. The molar ratio value may be less than 1/1 or 0.05 / 1 or more.

The condensation / addition reaction curable silicone resin is prepared by blending the above-mentioned silanol group-terminal polysiloxane, ethylene-based silicon compound, epoxy group-containing silicon compound and organohydrogensiloxane together with a catalyst and stirring and mixing. ..

The catalyst contains, for example, at least one of a condensation catalyst and an addition catalyst (hydrosilylation catalyst).

The condensation catalyst promotes the condensation reaction between the ^{silanol group and the 1} SiX group and ² SiX groups which are reactive functional groups. The condensation catalyst is selected from the group consisting of acids such as hydrochloric acid, acetic acid, formic acid and sulfuric acid; bases such as potassium hydroxide, sodium hydroxide, potassium carbonate and tetramethylammonium hydroxide: and metals such as aluminum, titanium, zinc and tin. Contains at least one ingredient. The condensation catalyst preferably contains a base, and more preferably contains tetramethylammonium hydroxide. The amount of the condensation catalyst is, for example, in the range of 0.1 to 50 mol, preferably in the range of 0.5 to 5 mol, with respect to 100 mol of the silanol group-terminal polysiloxane.

The addition catalyst promotes an addition reaction, that is, a hydrosilylation reaction between an ethylene-based unsaturated hydrocarbon group and SiH. The addition catalyst is at least selected from the group consisting of platinum catalysts such as platinum black, platinum chloride, platinum chloride acid, platinum-olefin complex, platinum monocarbonyl complex, platinum-acetylacetate, and metal catalysts such as palladium catalyst and rhodium catalyst. Contains a type of ingredient. The addition catalyst preferably contains a platinum catalyst, and more preferably contains a platinum-carbonyl complex. The amount of the addition catalyst is such that the amount of metal contained in the addition catalyst is in ^{the range of, for example, 1.0 × 10 -4 to} 1.0 part by mass, preferably 1.0 × 10 with respect to 100 parts by mass of organohydrogensiloxane. ^{The amount is in the range of -4 to} 0.5 parts by mass, more preferably 1.0 × 10 ^{-4 to} 0.05 parts by mass.

In order to prepare a condensation / addition reaction curable silicone resin, the above-mentioned condensation raw material and additional raw material are mixed with a catalyst, and if necessary, they are mixed while being heated. The catalyst may be blended as it is, or may be blended after being dissolved or dispersed in a solvent from the viewpoint of handleability. The solvent is, for example, water or an alcohol such as methanol or ethanol.

The heteroatom-containing modified silicone resin contains, for example, a silanol group-terminal polysiloxane and a heteroatom complex.

The silanol group-terminal polysiloxane may be, for example, the same as the silanol group-terminal polysiloxane represented by the above formula (1).

The heteroatom complex is, for example, a complex of heteroatoms other than Si, O, C and H. The heteroatom complex is represented by, for example, the following formula (5).

M- (OY) _n ... (5)
In formula (5), M is a heteroatom other than Si, O, C, and H, and is a metal atom such as aluminum or titanium, boron, or phosphorus. M is preferably a metal atom, and more preferably aluminum.

In formula (5), Y is a hydrogen atom, a monovalent saturated hydrocarbon group or a monovalent aromatic hydrocarbon group. More specifically, Y is a linear or branched hydrogen atom having 1 to 6 carbon atoms, such as a hydrogen atom; a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, or a hexyl group. Alkyl group; cycloalkyl group having 3 to 6 carbon atoms such as cyclopentyl group and cyclohexyl group; or aryl group having 6 to 10 carbon atoms such as phenyl group and naphthyl group. Y is preferably a monovalent saturated hydrocarbon group, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an isopropyl group.

In formula (5), n is the same number as the valence of the heteroatom. n is, for example, an integer in the range of 1 to 6, preferably an integer in the range of 3 to 5.

Heteroatom complexes contain, for example, at least one component selected from the group consisting of aluminum alkoxides, titanium alkoxides, boron alkoxides, and phosphorus alkoxides. The heteroatomic complex preferably contains an aluminum alcoside and is at least one selected from the group consisting of aluminum trimethoxydo, aluminum triethoxydo, aluminum tripropoxide, aluminum triisopropoxide, and aluminum tributoxide. It is more preferable if it contains a component, and it is particularly preferable that it contains aluminum triisopropoxide.

The amount of the heteroatom complex is, for example, in the range of 0.01 to 20 parts by mass, preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the silanol group-terminal polysiloxane.

The heteroatom-containing modified silicone resin is prepared, for example, by blending a silanol group-terminal polysiloxane and a heteroatom complex and stirring and mixing them at room temperature.

The filler will be described.

In the present embodiment, the filler contains an inorganic filler, and the inorganic filler contains silica powder. That is, the composition (X) contains silica powder.

As described above, the average particle size of the silica powder is in the range of 9 to 25 μm. The proportion of particles having a particle size of 6 μm or less in the silica powder is in the range of 25 to 40% by volume. When the average particle size of the silica powder is 25 μm or less, the adhesion between the reflector 3 and the roughened surface 8 can be improved. Further, when the average particle size of the silica powder is 9 μm or more, good moldability of the composition (X) can be ensured. Further, when the proportion of particles having a particle size of 6 μm or less in the silica powder is 40% by volume or less, the adhesion between the reflector 3 and the roughened surface 8 can be improved. Further, when this ratio is 25% by volume or more, good moldability of the composition (X) can be ensured.

note that. The average particle size of the silica powder is a volume-based arithmetic mean diameter calculated from the measurement result of the particle size distribution of the silica powder measured by the laser diffraction scattering method. The proportion of particles having a particle size of 6 μm or less in the silica powder is calculated from the measurement result of the particle size distribution of the silica powder measured by the laser diffraction / scattering method.

The amount of silica powder with respect to the entire composition (X) is preferably in the range of 10 to 75% by mass. In this case, the adhesion between the reflector 3 and the lead frame 4 is particularly high. The amount of the silica powder is more preferably in the range of 15 to 70% by mass.

The silica powder preferably contains amorphous molten silica. In this case, the adhesion between the lead frame 4 and the reflector 3 is particularly high. The silica powder may contain amorphous molten silica and crushed silica. In this case, the crushed silica particles are likely to pierce the roughened surface 8, so that the adhesion between the lead frame 4 and the reflector 3 can be further improved. Further, the whiteness of the reflector 3 is further increased by filling the gaps between the molten silica particles with the crushed silica particles.

The filler may contain components other than silica powder.

In particular, it is preferable that the filler contains a white pigment. That is, the composition (X) preferably contains a white pigment. The white pigment can impart good light reflectivity to the reflector 3 which is a molded product produced from the composition (X). The white pigment contains, for example, at least one material selected from the group consisting of titanium oxide, barium titanate, strontium titanate, aluminum oxide, magnesium oxide, zinc oxide, zinc sulfide, barium sulfate, magnesium carbonate, and barium carbonate. can.

In particular, the white pigment preferably contains at least one material selected from the group consisting of titanium oxide, barium titanate, barium sulfate, zinc oxide, and zinc sulfide. When the white pigment contains zinc oxide, the thermal conductivity of the molded product is particularly high, which is preferable. It is also preferable that the white pigment contains aluminum oxide having high thermal conductivity.

When the white pigment contains titanium oxide, the titanium oxide can contain at least one material selected from the group consisting of, for example, anatase-type titanium oxide, rutile-type titanium oxide, and blusite-type titanium oxide. In particular, since rutile-type titanium oxide is excellent in thermal stability, it is preferable that the rutile-type titanium oxide contains rutile-type titanium oxide.

The white pigment may be surface-treated with a fatty acid, a coupling agent or the like. In this case, aggregation of the white pigment, oil absorption, and the like are suppressed, and the filling property of the white pigment in the composition (X) is improved.

The average particle size of the white pigment is preferably 2.0 μm or less. The average particle size is preferably 0.01 μm or more. The average particle size is more preferably in the range of 0.03 to 1.0 μm, and more preferably in the range of 0.1 to 0.7 μm. Further, the average particle size is preferably in the range of 0.2 to 0.5 μm. The average particle size of the white pigment is a volume-based arithmetic mean diameter calculated from the particle size distribution measured by the laser diffraction / scattering method.

The amount of the white pigment with respect to the composition (X) is preferably in the range of 15 to 40% by mass. In this case, the heat-resistant discoloration property of the molded product is particularly high, and the light reflectivity of the molded product is also particularly high.

The inorganic filler may further contain a material other than silica powder. In this case, by selecting an appropriate material as the material other than the silica powder, the light reflectivity of the molded product such as the reflector 3 can be further enhanced, and the shape stability of the molded product can be further enhanced. In addition, the thermal conductivity of the molded product can be increased by selecting an appropriate material other than the silica powder. As a result, discoloration, deterioration, etc. due to heat of the molded product are further suppressed.

Materials other than silica powder contain at least one component selected from the group consisting of, for example, calcium carbonate, calcium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, boron nitride, mica, and hollow glass particles.

The average particle size of the material other than the silica powder is preferably 100 μm or less. In this case, the moldability of the composition (X) is particularly good, and the heat-resistant discoloration and moisture resistance of the molded product are particularly high. The average particle size is preferably 0.1 μm or more. In this case, the handleability of the composition (X) is improved. The average particle size of the inorganic filler is more preferably 80 μm or less, and even more preferably 50 μm or less. Further, the average particle size of the material other than the silica powder is more preferably 0.3 μm or more. Further, when the average particle size of the material other than the silica powder is in the range of 8 to 20 μm, the injection moldability of the composition (X) becomes particularly good. The average particle size of the material other than the silica powder is a volume-based arithmetic mean diameter calculated from the particle size distribution measured by the laser diffraction / scattering method.

The total amount of the silica powder and the inorganic filler with respect to the total molding resin in the composition (X) is preferably 40% by mass or more. In this case, the shape stability of the molded product is particularly high. Further, the total amount is preferably 300% by mass or less. In this case, the moldability of the composition (X) becomes particularly high. This total amount is particularly preferable as long as it is in the range of 50 to 250% by mass.

The amount of the white pigment with respect to the filler is preferably 30% by mass or more. In this case, the light reflectivity of the reflector 3 becomes particularly high. This amount is preferably 95% by mass or less. This amount is more preferably in the range of 35 to 90% by mass, and even more preferably in the range of 40 to 85% by mass.

The amount of the filler in the composition (X) with respect to the total molding resin is preferably 500% by mass or less. In this case, the fluidity of the composition (X) becomes particularly high during molding. The filler is preferably 100% by mass or more. In this case, the light reflectivity of the molded product such as the reflector 3 becomes particularly high. The amount of the filler is more preferably in the range of 100 to 400% by mass, and even more preferably in the range of 200 to 300% by mass.

The filler may contain a fibrous filler. When the filler contains the fibrous filler, the curing shrinkage of the composition (X) is suppressed during molding, the strength of the reflector 3 is increased, and the dimensional stability of the reflector 3 is further enhanced.

The amount of the fibrous filler in the composition (X) with respect to the total molding resin is preferably in the range of 10 to 200% by mass. In this case, the curing shrinkage of the composition (X) is particularly suppressed during molding, and the strength of the molded product is particularly high. The amount of the fibrous filler is more preferably in the range of 20 to 100% by mass, and even more preferably in the range of 30 to 80% by mass.

The average fiber diameter of the fibrous filler is preferably in the range of 6 to 12 μm, and more preferably in the range of 6 to 8 μm. In this case, the strength of the molded product is particularly high. The average fiber length of the fibrous filler is preferably in the range of 100 to 300 μm, more preferably in the range of 150 to 250 μm. In this case, the strength of the molded product is particularly improved, and the light reflectance thereof is also particularly improved. The average fiber diameter and average fiber length of the fibrous filler are arithmetic average values of the fiber diameter and fiber length obtained by image-processing the electron micrographs of the fibers in the fibrous filler, respectively.

The fibrous filler is selected from the group consisting of, for example, glass fiber, vinylon fiber, aramid fiber, polyester fiber, wallastnite, potassium titanate whiskers, whiskers of carbonates such as calcium carbonate, and hydrotalcite. Can contain a kind of material. In particular, the fibrous filler preferably contains glass fibers.

The glass fibers include, for example, silicate glass, E glass (non-alkali glass for electricity), C glass (alkali-containing glass for chemicals), A glass (acid resistant glass), and S glass (high-strength glass) made from silicate glass. ) And the like, which can contain at least one material selected from the group consisting of glass fibers. The glass fiber may be a long fiber (roving) or a short fiber (chopped strand). The glass fiber may be surface-treated with a converging agent or the like.

The amount of the fibrous filler is preferably in the range of 3 to 20% by mass, more preferably in the range of 5 to 15% by mass with respect to the composition (X). In these cases, the bending strength of the separator is particularly improved. Furthermore, in these cases, the material shrinkage rate can be reduced. That is, the occurrence of cracks in the separator is suppressed in a temperature cycle test or the like.

The amount of the filler with respect to the composition (X) is preferably in the range of 20 to 90% by mass. In this range, excellent fluidity of the composition (X) is ensured during molding.

The composition (X) preferably contains a silane coupling agent. When the composition (X) contains a silane coupling agent, the adhesion between the reflector 3 and the lead frame 4 becomes particularly high.

The silane coupling agent contains at least one component selected from the group consisting of, for example, aminosilane, epoxysilane, methacrylsilane, vinylsilane, mercaptosilane and isocyanatesilane. The silane coupling agent preferably contains at least one component selected from the group consisting of epoxysilane, methacrylsilane and vinylsila, and more preferably contains at least one of epoxysilane and methacrylsilane. It is more preferable if it is contained. These components can particularly improve the adhesion between the reflector 3 and the lead frame 4. Further, the silane coupling agent preferably contains at least one of methacrylsilane and vinylsilane. In this case, the heat-resistant discoloration property of the reflector 3 can be improved. In order to achieve a good balance between the improvement of the adhesion between the reflector 3 and the lead frame 4 and the improvement of the heat-resistant discoloration property of the reflector 3, the silane coupling agent preferably contains methacrylsilane.

The amount of the silane coupling agent is preferably in the range of 0.3 to 1% by mass with respect to the total amount of the inorganic filler and the white pigment. When the amount of the silane coupling agent is 0.3% by mass or more, the adhesion between the reflector 3 and the lead frame 4 becomes particularly high. Further, when the amount of the silane coupling agent is 1% by mass or less, discoloration of the reflector 3 due to the coupling agent is suppressed, and when the composition (X) is molded, the composition (X) is removed from the composition (X). Volatilization of the coupling agent is suppressed and good continuous moldability can be ensured.

The silane coupling agent may be dispersed in the composition (X), and at least a part of the inorganic filler and the white pigment is treated with the silane coupling agent to make the composition (X) silane. Coupling agents may be included.

The composition (X) preferably contains an antioxidant. In this case, the discoloration of the molded product is further suppressed, and the deterioration of the light reflectivity of the molded product with time is less likely to occur. The antioxidant may contain, for example, at least one of a phenolic antioxidant and a phosphorus-based antioxidant. It is preferable that the antioxidant does not contain a compound that produces a chromophore.

The composition (X) preferably contains a phosphorus-based antioxidant. In this case, the yellowing of the molded product during processing and the yellowing over time are further suppressed, whereby the decrease in the light reflectance of the molded product is further suppressed. In particular, when the composition (X) contains triglycidyl isocyanurate, and further containing a phosphorus-based antioxidant, the decrease in light reflectance of the molded product is significantly suppressed.

Phosphoric antioxidants include, for example, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy)-. Selected from the group consisting of 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, bis (nonylphenyl) pentaerythritol-di-phosphite and distearyl pentaerythritol-di-phosphite. Can contain at least one compound. The amount of the phosphorus-based antioxidant with respect to the composition (X) is preferably in the range of 0.1 to 0.5% by mass.

The composition (X) also preferably contains a sulfur-based antioxidant. Specific examples of the sulfur-based antioxidant include ADEKA CORPORATION's product name ADEKA STAB AO-412S. The amount of the sulfur-based antioxidant with respect to the composition (X) is preferably 0.5% by mass or less, and more preferably in the range of 0.01 to 0.5% by mass.

The composition (X) may contain a release agent. The release agent can contain, for example, at least one material selected from the group consisting of general fatty acid-based waxes, fatty acid metal salt-based waxes, and mineral-based waxes. In particular, the release agent preferably contains at least one of a fatty acid-based wax and a fatty acid metal salt-based wax, which are excellent in heat-resistant discoloration.

The release agent preferably contains at least one material selected from the group consisting of stearic acid, zinc stearate, aluminum stearate, and calcium stearate.

The amount of the mold release agent with respect to 100 parts by mass of the molding resin in the composition (X) is preferably in the range of 1 to 15 parts by mass. In this case, good releasability of the molded product at the time of molding and excellent appearance of the molded product are compatible, and the light reflectivity of the molded product is particularly high.

In addition to the above components, the composition (X) may contain appropriate additives such as a colorant, a thickener, a flame retardant, and a flexibility-imparting agent.

In preparing the composition (X), for example, first, the above-mentioned raw materials are mixed in a predetermined ratio and mixed with a mixer such as a mixer or a blender to prepare a mixture. This mixture is kneaded with a kneader, an extruder or the like capable of heating and pressurizing. As the kneader, a pressure kneader, a heat roll, an extruder and the like can be used. The heating temperature during kneading is, for example, in the range of 80 to 120 ° C. Subsequently, the bulk body of the mixture is pulverized, sized, or further granulated as necessary to obtain a composition (X) in the form of granules, powder, pellets, or the like.

The reflector 3 is produced, for example, by molding and curing the composition (X). As a molding method for the composition (X), an appropriate melt heating molding method such as an injection molding method, an injection compression molding method, or a transfer molding method can be applied. Although it depends on the composition of the composition (X), it is particularly preferable to apply a transfer molding method which is low in cost and easy to mass-produce. The molding conditions in the transfer molding method are, for example, a molding temperature in the range of 130 to 180 ° C., a transfer pressure in the range of 5 to 20 MPa, and a curing time in the range of 30 to 300 seconds, preferably 30 to 180 seconds. .. Post-cure treatment may be applied if necessary.

When producing the reflector 3, it is preferable to embed the lead frame 4 in the reflector 3 by insert molding. That is, it is preferable to manufacture the reflector 3 by an appropriate melt heating molding method using this mold with the lead frame 4 set in the mold. As a result, the base 2 including the lead frame 4 and the reflector 3 can be manufactured.

The light emitting element 5 is, for example, a light emitting diode, but is not limited to this, and may be, for example, a laser diode. The light emitting element 5 is mounted in the recess 21 by being die-bonded on the first lead 41 on the bottom surface of the recess 21, for example. As described above, in the present embodiment, the light emitting element 5 is electrically connected to the first lead 41 and the second lead 42 by the wires 71 and 72. The diameters of the wires 71 and 72 are, for example, in the range of 25 to 35 μm in diameter, and the material thereof is, for example, aluminum, copper, platinum or gold.

The encapsulant 6 is produced from, for example, a fluid reaction-curable resin composition (hereinafter referred to as composition (Y)). The composition (Y) has, for example, thermosetting, but may also have photocurability.

When the composition (Y) is thermosetting, the composition (Y) contains, for example, a thermosetting silicone resin. This silicone resin may be the same as the silicone resin that can be contained in the composition (X) described above. The composition (Y) may contain a thermosetting resin other than the silicone resin.

The composition (X) preferably contains a fluorescent substance. In this case, a sealing material 6 containing a fluorescent substance can be produced. When the encapsulant 6 contains a fluorescent substance, a part of the light emitted by the light emitting element 5 is wavelength-converted by the fluorescent substance when passing through the encapsulant 6. Therefore, the emission color of the light emitting device 1 can be controlled by the fluorescent substance. Fluorescent material, for example YAG: Ce, or of Eu and Cr is a nitrogen-containing CaO-Al ₂ O ₃ -SiO _2, which is activated with at least one, but not limited thereto.

When producing the sealing material 6, the composition (Y) is first filled in the recess 21. At this time, if the adhesion between the reflector 3 and the lead frame 4 is low, components such as the resin and the fluorescent substance in the composition (Y) may leak from the recess 21. However, in the present embodiment, since the adhesion between the reflector 3 and the lead frame 4 is high, leakage of the component in the composition (Y) from the recess 21 is suppressed.

Subsequently, the composition (Y) in the recess 21 is cured by a method according to the composition of the composition (Y). For example, when the composition (Y) has thermosetting property, the composition (Y) is cured by heating. As a result, the sealing material 6 is produced.

Hereinafter, specific examples of the present invention will be presented.

(1) Preparation of composition The raw material shown in the column of "resin component composition" in the table was prepared as a resin component, and the raw material shown in the column of "filler composition" was prepared as a filler component. The resin component and the filler component were blended so that the total amount of the filler component with respect to all the raw materials became the value shown in the column of "ratio of the filler in the molding material" to obtain a compound. The compound was uniformly mixed using a sigma blender and then kneaded with a hot roll heated to 100 ° C. to prepare a sheet-shaped kneaded product. This kneaded product was cooled, crushed, and sized. As a result, a granular resin composition was prepared.
The details of the raw materials are as follows.
-Unsaturated polyester: Terephthalic acid-based unsaturated polyester, manufactured by Japan U-Pica, product name Yupica 8552, softening point 50 ° C or higher.
Cross-linking agent: diallyl phthalate monomer, manufactured by Daiso Co., Ltd., product name Dapp monomer, molecular weight 246.3, viscosity 8.5 mPa · s at 30 ° C, iodine value 202, liquid at room temperature, boiling point 290 ° C.
-Polymerization initiator: Dicumyl peroxide, manufactured by NOF CORPORATION, 1-minute half-life temperature of 179 ° C.
-Release agent: Zinc stearate, manufactured by Sakai Chemical Industry Co., Ltd., product name SZ-P.
-Antioxidant 1: Phenolic antioxidant, manufactured by ADEKA Corporation, product name ADEKA STAB AO-80.
-Antioxidant 2: Phosphorus-based antioxidant, manufactured by ADEKA Corporation, product name ADEKA STAB PEP-36.
-Antioxidant 3: Sulfur-based antioxidant, manufactured by ADEKA Corporation, product name ADEKA STAB AO-412S.
-Silicone resin 1: Toray Dowcorn Co., Ltd., product number OE6351A.
-Silicone resin 2: Made by Toray Dowcorn Co., Ltd., product number OE6351B.
-Silicone resin 3: Toray Dowcorn Co., Ltd., product number OE6652A.
-Silicone resin 4: Toray Dowcorn Co., Ltd., product number OE6652B.
-Curing retarder: 1-ethynyl-1-cyclohexanol.
-Titanium oxide: rutile type titanium oxide, average particle size 0.4 μm, manufactured by Thai Oxide Japan Co., Ltd., product name Tioxide RTC-30.
-Zinc oxide: Manufactured by Sakai Chemical Industry Co., Ltd., specific gravity 5.6, average particle size 0.6 μm, trade name "Zinc oxide 1 type".
-Silica powder 1: Amorphous spherical molten silica, 29% by volume of particles having an average particle size of 16 μm and a particle size of 6 μm or less.
-Silica powder 2: Amorphous spherical molten silica, an average particle size of 11 μm, and a proportion of particles having a particle size of 6 μm or less of 39% by volume.
-Silica powder 3: Amorphous spherical molten silica, an average particle size of 23 μm, and a proportion of particles having a particle size of 6 μm or less 28% by volume.
-Silica powder 4: Amorphous spherical molten silica, 20% by volume of particles having an average particle size of 12 μm and a particle size of 6 μm or less.
-Silica powder 5: Amorphous spherical molten silica, an average particle size of 10 μm, a proportion of particles having a particle size of 6 μm or less, 45% by volume.
-Silica powder 6: Amorphous spherical molten silica, an average particle size of 8 μm, a proportion of particles having a particle size of 6 μm or less, 30% by volume.
-Silica powder 7: Amorphous spherical molten silica, an average particle size of 26 μm, a proportion of particles having a particle size of 6 μm or less, 33% by volume.
-Vinylsilane: manufactured by Shin-Etsu Chemical Co., Ltd., product number KBM-1003.
-Epoxy silane: manufactured by Shin-Etsu Chemical Co., Ltd., product number KBM-403.
-Methacrylic silane: manufactured by Shin-Etsu Chemical Co., Ltd., product number KBM-503.
-Fibrous filler: Glass fibers with an average fiber length of 3 mm, an average fiber diameter of 6.0 μm, a moisture content of 0.02%, and a strong heat loss of 0.28%, surface-treated with an aminosilane coupling agent and converging on an aliphatic urethane system. A treated product obtained by sequentially performing surface treatment with an agent.

(2) Evaluation test (2-1) Preparation and evaluation of lead frame Lead frames having the shapes shown in FIGS. 3A and 3B were prepared. The lead frame was made of copper, and a silver film was formed on the surface by a plating method.

Except for the case of Comparative Example 1, laser machining is performed using a laser machining machine (laser marker manufactured by Panasonic Corporation, model number LP-S500) at a position on the first surface of the lead frame that matches the position of the roughened surface in FIG. 3A. Was given. The laser type used was a YAG laser, and the laser irradiation conditions are as shown in the "Laser irradiation setting conditions" column of the table. That is, it is described in the "machining speed" column while irradiating the lead frame with the laser beam at the output described in the "output" column and the pulse frequency described in the "pulse frequency" column. Laser processing was performed by moving the laser irradiation position on the lead frame at a high speed. The output is the ratio (percentage) of the output during laser processing to the maximum output (42W) of the laser processing machine. The width of the roughened surface formed on the first surface by laser processing is as shown in the column of "Roughened surface width of the first surface". In addition, when "Yes" is described in the "Presence / absence of irradiation to the stage" column, laser processing was also performed on the inner surface of the stage on the second surface of the lead frame. The width of the roughened surface formed on the second surface by laser processing is as shown in the column of "Roughened surface width of the first surface".

Ra of the roughened surface formed by this laser processing was measured using a laser microscope (model number OLS3500) manufactured by Olympus according to JIS B0633; 2001. The result is shown in the column of "Ra of roughened surface".

(2-2) Fabrication and Evaluation of Base A reflector was produced by transferring the composition with the lead frame set in a mold, and the lead frame was embedded in the reflector. As a result, a base including a lead frame and a reflector was produced. The transfer molding conditions are a molding temperature of 150 ° C., a transfer pressure of 8 MPa, and a curing time of 90 seconds.

Twenty-four hours after dropping red ink (stamp ink red manufactured by Lion Office Equipment Co., Ltd.) into the recess of the base, it was confirmed whether or not the red ink leaked from the recess of the base to the outside of the base. The same test was performed on 200 samples to determine the number of samples in which red ink leakage was confirmed. The results are shown in the "Ink test water-based" column.

Further, the recess of the base is filled with a potting agent (transparent sealing resin for photo devices manufactured by Shin-Etsu Chemical Co., Ltd., product number SCR1011), heated at 70 ° C. for 1 hour, and then heated at 150 ° C. for 5 hours. Twenty hours after curing with, it was confirmed whether or not the potting agent leaked out of the base from the recess of the base. The same test was performed on 200 samples to determine the number of samples in which potting agent leakage was confirmed. The results are shown in the "Potting agent leak" column.

In Comparative Examples 3 and 4, the reflector could not be produced because the fluidity of the composition was too low, and therefore the evaluation was not performed.

(2-3) Manufacture and evaluation of light emitting device A product number B2632 manufactured by Genelites Co., Ltd. was mounted as a light emitting element in the recess of the base. Subsequently, a potting agent (transparent sealing resin for photo devices manufactured by Shin-Etsu Chemical Co., Ltd., product number SCR1011) is filled in the recess of the base, heated at 70 ° C. for 1 hour, and then heated at 150 ° C. for 5 hours. It was cured by this to prepare a sealing material. As a result, a light emitting device was manufactured.

The light emitting device was exposed to exposure at 85 ° C. and 85% RH for 1000 hours. Before and after this process, the emission brightness of the light emitting device when a current of 400 mA was applied to the light emitting element to cause light emission was measured using a luminance meter manufactured by Otsuka Electronics. The ratio (percentage) of the emission brightness of the light emitting device after the treatment to the emission brightness of the light emitting device before the treatment was calculated. The result is shown in the column of "85 ° C. 85% RH1000h LED deterioration rate". Since the reflector could not be produced in Comparative Examples 3 and 4, the evaluation was not performed.

1 Light emitting device 2 Base 21 Recessed part 3 Reflector 4 Lead frame 5 Light emitting element 6 Encapsulant

Claims (6)

A base that includes a reflector and a lead frame embedded in the reflector, has a recess, and a part of the lead frame is exposed on the bottom surface of the recess.
A light emitting element mounted in the recess of the base and a sealing material filled in the recess of the base and sealing the light emitting element are provided.
The region in contact with the reflector on the surface of the lead frame has a roughened surface having Ra in the range of 0.5 to 1.5 μm.
The reflector, Ri moldings der tree fat composition containing a filler,
The filler contains silica powder having an average particle size of 9 to 25 μm and a proportion of particles having a particle size of 6 μm or less of 25 to 40% by volume, and a white pigment, and the amount of the silica powder with respect to the entire resin composition is In the range of 10 to 75% by volume,
Light emitting device. A base that includes a reflector and a lead frame embedded in the reflector, has a recess, and a part of the lead frame is exposed on the bottom surface of the recess.
A light emitting element mounted in the recess of the base, and
A sealing material that is filled in the recess of the base and seals the light emitting element is provided.
The region in contact with the reflector on the surface of the lead frame has a roughened surface having Ra in the range of 0.5 to 1.5 μm.
The reflector is a molded product of a resin composition containing a filler.
The ratio of the filler to the resin composition is 65 to 90% by mass.
The filler contains silica powder having an average particle size of 9 to 25 μm and a particle size of 6 μm or less of 25 to 40% by volume, and a white pigment, and the mass ratio of the silica powder in the total filler is 24.5 / 104-75 / 100,
Light emitting device. The resin composition contains a silane coupling agent.
The light emitting device according to claim 1 or 2. The resin composition contains at least one of an unsaturated polyester resin and a silicone resin.
The light emitting device according to any one of claims 1 to 3. The lead frame has a silver film, and the roughened surface is formed on the silver film.
The light emitting device according to any one of claims 1 to 4. The roughened surface is composed of laser processing marks.
The light emitting device according to any one of claims 1 to 5.

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