JP2012049519A - Package for semiconductor light-emitting device, and light-emitting device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a package for a semiconductor light-emitting device made of a material which has extremely high heat resistance and light resistance and can secure a sufficient working life until molding.SOLUTION: The package for a semiconductor light-emitting device at least includes a resin molding 2 containing (A) a polyorganosiloxane resin, (B) a filler, and (C) a curing catalyst. The metal composition content of the curing catalyst in the resin molding except for the filler should be between 0.4 ppm and 25 ppm.

Description

  The present invention relates to an optical device, in particular, a package used for a semiconductor light emitting device including a light emitting element such as a light emitting diode, and a light emitting device.

  As shown in FIG. 1, a semiconductor light emitting device including a semiconductor light emitting element includes a semiconductor light emitting element 1, a resin molded body 2, a bonding wire 3, a sealing material 4, a lead frame 5 and the like, and a package mainly includes a lead frame 5 and the like. Conductive metal wiring and an insulating resin molded body 2.

  Conventionally, an insulating material used for a resin molding has generally been used in which a white pigment is blended with a thermoplastic resin such as polyamide (see, for example, Patent Document 1). Semiconductor light-emitting devices that require directivity for light emission are not only light emitted from the semiconductor light-emitting element in the target direction, but also other light by metal wiring such as resin molded bodies and lead frames, and reflectors, etc. Reflected in the desired direction to increase luminous efficiency. Since a thermoplastic resin such as polyamide is translucent, a white pigment is blended into the resin when reflected by the resin molding, and the difference between the refractive index of the resin and the white pigment is utilized to remove the light from the semiconductor light emitting device. The light is reflected to increase the luminous efficiency of the semiconductor light emitting device.

  In Patent Document 1, even when a white pigment is used, depending on the type of the white pigment, its reflection efficiency is not sufficient, and light rays that are absorbed and transmitted are also emitted. As a result, light from the semiconductor light emitting element is emitted. In some cases, the efficiency of the semiconductor light emitting device may be lowered without being able to concentrate in the intended direction.

  In addition, since polyamide is a thermoplastic resin, lead-free solder with a high melting point is actively used due to environmental problems and the reflow temperature tends to be high, so the package using polyamide is softened by the heat. There is a problem with heat resistance. In addition, since light degradation and thermal degradation occur due to ultraviolet rays and heat in polyamide, a light emitting element having a light emitting region up to a high energy wavelength region such as a blue to near ultraviolet semiconductor light emitting element which has been practically used in recent years was used. In this case, deterioration due to light becomes a particular problem. In the present situation where a brighter light emitting element is demanded, the problem of thermal degradation and light degradation becomes more obvious due to the large light flux and heat generated from the semiconductor light emitting element.

  On the other hand, when heat resistance is required, a ceramic mixed with sintered alumina is used as an insulating material (see, for example, Patent Document 2). A package using ceramic has good heat resistance, but requires a sintering process at a high temperature after molding in the production. In the sintering process, there were problems in terms of cost such as electricity bills, and because the size and shape of the molded body changed due to sintering, defective products were likely to be produced and there was a problem in mass productivity.

  On the other hand, a case where a silicone resin composition using polyorganosiloxane as a resin and titanium oxide as a white pigment is molded has been recently proposed (see, for example, Patent Document 3). By using polyorganosiloxane as the resin, heat resistance can be improved as compared with those using polyamide.

JP 2002-283498 A JP 2004-288937 A JP 2009-155415 A

In the semiconductor light emitting device, heat is generated from the semiconductor light emitting element, and particularly when a bright light emitting element is required, the heat generation is also increased. Therefore, there has been a problem that the resin molded body constituting the package of the semiconductor light emitting device is discolored or cracked due to heat and light from the semiconductor light emitting element. This phenomenon is remarkable in the case of an organic resin such as polyamide, but it still remains a problem even when a silicone resin is used.
Further, it is also required for work reasons that the usable time of the resin itself is long in the LED package molding process. An object of the present invention is to provide a package for a semiconductor light-emitting device that solves such problems and has extremely high heat resistance and light resistance, and can sufficiently ensure the pot life until molding.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved when the metal component concentration of the curing catalyst in the resin molding is a specific value.

That is, the present invention is as follows.
(A) A package for a semiconductor light emitting device comprising at least a resin molded body containing a polyorganosiloxane resin, (B) a filler, and (C) a curing catalyst,
The metal component content of the curing catalyst in the resin molded body excluding the filler is 0.4 ppm or more and 25 ppm or less.

  The metal component of the (C) curing catalyst preferably contains platinum.

  Moreover, it is preferable that the said resin molding is hardened | cured through hydrosilylation.

  The (B) filler preferably contains alumina, and the (B) filler is preferably surface-treated.

  The filler (B) preferably has an aspect ratio of primary particles of 1.0 or more and 4.0 or less.

  Moreover, it is preferable that the weight ratio of the base resin containing the (A) polyorganosiloxane resin and the (B) filler contained in the resin molding is 15 to 60:85 to 40.

  The resin molded body preferably has a light reflectance of 50% or more at a wavelength of 400 nm at a thickness of 0.3 mm.

  The resin molded body preferably further contains a compound having an alicyclic hydrocarbon group, and the resin molded body is consistently at 45 ° C. or lower as an operating temperature before molding processing, and molded. The molding temperature during processing is preferably 300 ° C. or lower.

  Another aspect of the present invention is a semiconductor light emitting device including at least a semiconductor light emitting element, the package described above, and a sealing material.

  According to the present invention, it is possible to obtain a package for a semiconductor light-emitting device that has extremely high heat resistance and light resistance and can sufficiently ensure the pot life until molding.

It is a conceptual diagram showing the one aspect | mode of the semiconductor light-emitting device of this invention. It is a conceptual diagram showing the one aspect | mode of the semiconductor light-emitting device of this invention. It is a graph which shows the lighting durability test result of the package of this invention, and a PPA package. It is a photograph which shows the adhesive evaluation result of the package of this invention and a PPA package (drawing substitute photograph).

<1. Resin molding>
The package of the present invention includes at least a resin molded body containing (A) a polyorganosiloxane resin, (B) a filler, and (C) a curing catalyst. The metal component concentration of the curing catalyst in the resin molded body excluding the filler is 0.4 ppm or more and 25 ppm or less. With such a configuration, the inventor has a new finding that a highly reliable package with high heat resistance and UV (light) resistance can be obtained without shortening the pot life unnecessarily. Got. That is, the problem was solved by making the metal component content of the catalyst in the resin molded body into a specific range.

<1-1. Metal component of curing catalyst>
In the package of the present invention, the metal component content of the curing catalyst in the resin molded body excluding the filler is 0 for the purpose of improving heat resistance and UV (light) resistance without shortening the pot life unnecessarily. 4 ppm or more and 25 ppm or less. Preferably it is 0.5 ppm or more, preferably 20 ppm or less, more preferably 15 ppm or less, still more preferably 10 ppm or less.

When the content of the metal component of the curing catalyst is too small beyond this range, curing is insufficient or it takes a very long time for curing, which is economically undesirable.
Conversely, if the content of the metal component in the curing catalyst exceeds this range and is too high, the cured product itself may be colored or inferior in durability (colored when heated for a long time, or irradiated with long-term ultraviolet rays. In this case, the surface is cracked), the reflectance described later is lowered, the curing rate is difficult to control, and the pot life cannot be secured sufficiently, which is not preferable for industrial processes. In particular, when used as a resin for optical members, it may be a big problem if it is colored.

For example, when platinum is included as the metal component of the curing catalyst, if the platinum content exceeds the above range and is too high, the following disadvantages may occur in the package for a semiconductor light emitting device provided with such a resin molded body. is there.
In a package for a semiconductor light emitting device provided with a resin molded body using addition-type silicone, if the light is lit for tens of thousands of hours in a state where the amount of platinum is large, the package itself may be colored or cracked, There is also a concern that the sealing material in contact may be colored or an unnecessary increase in hardness may be promoted. In particular, when the hardness of the sealing material is unnecessarily increased, stress relaxation at the interface between the hardened sealing material and the package becomes impossible and there is a concern about interface peeling.
Further, when the free excess platinum component is transferred to the sealing layer and reduced or oxidized by an electric field to become platinum fine particles or platinum oxide fine particles, the sealing layer portion may be changed to brown. Further, when the free residual platinum component moves and contacts the die bond material, the decomposition of the die bond material may be promoted to cause discoloration. This is particularly noticeable in the case of a die bond material containing an epoxy resin. In addition, when platinum migrates in the sealing layer or at the interface in an ion state, silver on the electrode surface, which has a greater ionization tendency, and silver used in the die bond material are ionized, and the electrode surface and its vicinity due to silver migration Blackening of the sealing layer occurs, which causes a significant decrease in the luminance of the semiconductor light emitting device.
In addition, when the sealing material to be filled in the package is hardened, there may be a problem that excess residual platinum becomes a catalyst at the interface with the package formed of a material having a large amount of platinum. Specifically, when a compound having a hydroxyl group or alkoxy group such as condensed silicone is used as a sealing material, an explosive hazardous gas such as hydrogen or alkane may be generated, or bubbles (water vapor) may be generated. There is sex. In addition, when addition type silicone is used as the sealing material, only the sealing material in the vicinity of the interface with the package is cured faster, and the stress relaxation function at the package interface may be impaired.

Furthermore, when the platinum component content of the curing catalyst is in the range of 0.4 ppm to 25 ppm as described above, the aspect ratio of the primary particles of the filler used is particularly preferably 1.0 or more and 4.0 or less. . The aspect ratio is preferably in this range from the viewpoint of securing a high reflectance of the material as described later, and from the viewpoint of product properties and processing surfaces that are not related to the platinum concentration, such as reducing the wear rate of the mold. Also, this range is preferable from the relationship with the platinum concentration. In particular, if the platinum content of the curing catalyst is 0.4 ppm or more and 25 ppm or less, and the aspect ratio of the primary particles of the filler used is 1.0 or more and 4.0 or less, the moldability is easy. In addition, it is possible to manufacture a highly reactive material, that is, a material that can satisfy both moldability and economy.
When the aspect ratio of the primary particles of the filler is small beyond this range, it is preferable to increase the filling amount of the filler in order to obtain liquid viscoelasticity that facilitates molding. When the platinum concentration is 0.4 ppm or more and 25 ppm or less, chipping may occur due to a high filler filling amount, the collision frequency between the curing catalyst and the reactive group terminal decreases, and the curing rate becomes slow. There may be disadvantages such as lack of economic efficiency during molding.
On the other hand, when the aspect ratio of the primary particles of the filler is larger than this range, it is preferable to reduce the filling amount of the filler in order to obtain liquid viscoelasticity that facilitates the molding process. At platinum concentrations of 0.4 ppm or more and 25 ppm or less, due to the low filler filling amount and viscosity, the collision frequency between the curing catalyst and the reactive group ends increases, the curing speed increases, and the material liquid fills every corner of the mold. There is a demerit that the curing reaction may progress before being processed and chipping may occur in the molded product, or the filled material liquid penetrates into the gaps of the mold and causes burring errors. There is.
The fact that there is a preferable range for the platinum concentration and the aspect ratio of the primary particles of the filler has not been reported so far.

  Furthermore, when the platinum component content of the curing catalyst is between 0.4 ppm and 25 ppm as described above, the aspect ratio of the primary particles of the filler used as described above is preferably 1.0 or more and 4.0 or less, In order to satisfy both moldability and economy (reactivity), the weight ratio of the base resin containing the polyorganosiloxane resin to the filler is preferably 15 to 60:85 to 40. As will be described later, the weight ratio of the base resin containing the polyorganosiloxane resin to the filler is in the above range, so that it is resistant to temperature shock, the lead frame and the sealing material are difficult to peel off from the resin molded body, and physical impact. A resin molded body that is strongly resistant to cracking and chipping can be obtained, but a good combination range of “the platinum content of the curing catalyst, the aspect ratio of the filler particles, and the filler content” that can obtain such an effect is Even those skilled in the art could not easily conceive.

As the metal component in the curing catalyst, titanium, tantalum, zirconium, aluminum, hafnium, zinc, tin, and the like can be used in addition to the above-described platinum, and platinum is preferable. As a metal component, only one type may be included in the curing catalyst, or two or more types may be included. When two or more kinds are contained, it is preferable that at least platinum is contained, and it is preferable that 70% by weight or more, preferably 90% by weight or more of the metal component is platinum.
Examples of platinum include platinum black, secondary platinum chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and olefins, and platinum bisacetate.

<1-2. Reflectivity>
It is preferable that the resin molding which comprises the package of this invention can maintain a high reflectance about visible light. The reflectance of light having a wavelength of 460 nm at a thickness of 0.3 mm is preferably 60% or more, more preferably 80% or more, and still more preferably 90% or more.
Further, the reflectance of light having a wavelength of 400 nm at a thickness of 0.3 mm is preferably 50% or more, more preferably 70% or more, and further preferably 90% or more.
The reflectance of the resin molding can be controlled by the type of resin, the type of filler, the particle size and content of the filler, and the like.

<1-3. Refractive index>
It is preferable that the resin molding which comprises the package of this invention is 1.41-1.54 as a refractive index of the molding which does not contain a filler, ie, (A) only the polyorganosiloxane resin hardened | cured. When the refractive index of the polyorganosiloxane resin molding is in such a range, the reflection loss of light at the interface between the resin molding and the sealing material can be suppressed due to the balance with the resin used for the sealing material.
The refractive index of the resin molding can be controlled by the type of resin, the functional group contained in the resin, and the type and content of the filler. Specifically, the refractive index can be increased by including a phenyl group as a functional group, and the functional group can be decreased by containing fluorine. Incidentally, about 0.8 (mol) of phenyl group content is added to dimethyl polyorganosiloxane (refractive index: 1.40 to 1.41) having no phenyl group with respect to the number of Si (mol number). It is known that the refractive index reaches approximately 1.53 to 1.54.
Also, particles such as alumina (refractive index: 1.7), zinc oxide (refractive index: 2.0), zirconia (refractive index: 2.4), titania (refractive index: 2.7) are added as fillers. It is also possible to increase the refractive index.

<2. Resin molding material>
In the present invention, the resin molding material used as the raw material of the resin molding contains (A) a polyorganosiloxane resin, (B) a filler, and (C) a curing catalyst. The resin molded body is a molded body obtained by curing a resin molded body material, and becomes a package for a semiconductor light emitting device by being molded together with a metal wiring such as a lead frame.

<2-1. (A) Polyorganosiloxane resin>
The base resin of the resin molded body constituting the package of the present invention is such that the metal component concentration of the curing catalyst in the weight of the resin molded body excluding the filler is in the above range, and (A) a resin containing polyorganosiloxane. The base resin may be a thermoplastic resin or a thermosetting resin, and the type thereof is not particularly limited. Thermoplastic resins used in combination with polyorganosiloxane (as a mixture or copolymer) include aromatic nylon resins, polyphthalamide resins (PPA), sulfone resins, polyamideimide resins (PAI), and polyketone resins (PK). ), Polycarbonate resin, polyphenylene sulfide (PPS), liquid crystal polymer (LCP), ABS resin, PBT resin, and the like. Moreover, as a thermosetting resin used together, an epoxy resin, a modified epoxy resin, various modified silicone resins, an acrylate resin, a urethane resin, etc. can be used.
In the base resin of the resin molded body constituting the package of the present invention, the content of (A) polyorganosiloxane is not particularly limited and can be appropriately selected depending on the properties of the desired package. It is preferable that Here, the main component means that the content in the base resin is 50% by weight or more. Specifically, it is preferably 70% by weight or more, more preferably 80% by weight or more, and still more preferably 90% by weight or more.

  The viscosity of the base resin before adding the filler is preferably 100,000 cp or less at normal temperature because of easy handling. More preferably, it is 20,000 cp or less. More preferably, it is 10,000 cp or less. The lower limit is not particularly limited, but is generally 15 cp or more in relation to volatility (boiling point).

  The average molecular weight of the resin is preferably 500 or more and 100,000 or less as an average molecular weight measurement value in gel permeation chromatography measured using polystyrene of the base resin as a standard substance. More preferably, it is 700 or more and 50,000 or less. Furthermore, it is more preferably 900 or more for the purpose of reducing volatile components (to maintain adhesion to other members) and 10,000 or less for ease of handling of the material before molding. Most preferably, it is 5,000 or less.

The polyorganosiloxane used as the base resin in the resin molded product of the present invention refers to a polymer substance in which an organic group is added to a structure having a portion in which a silicon atom is bonded to another silicon atom through oxygen. Usually, it refers to an organic polymer having a siloxane bond as the main chain, and examples thereof include compounds represented by the following general composition formula (1) and mixtures thereof.
(R ¹ R ² R ³ SiO _1/2 ) _M (R ⁴ R ⁵ SiO _2/2 ) _D (R ⁶ SiO _3/2 ) _T (SiO _4/2 ) _Q (1)
Here, in the above formula (1), R ¹ to R ⁶ are independently selected from an organic functional group, a hydroxyl group, and a hydrogen atom. M, D, T, and Q are 0 to less than 1 and satisfy M + D + T + Q = 1.

The units constituting the main polyorganosiloxane are monofunctional [R ₃ SiO _0.5 ] (triorganosyl hemioxane), bifunctional [R ₂ SiO] (diorganosiloxane), trifunctional [RSiO _1.5 ]. (Organosilsesquioxane), tetrafunctional type [SiO ₂ ] (silicate). By changing the composition ratio of these four units, the difference in the properties of polyorganosiloxane will occur. Is selected as appropriate so that polyorganosiloxane is synthesized.
The polyorganosiloxane of the structural units 1 to 3 functional type, be synthesized based on a series of organic silicon compounds called organochlorosilanes (general formula _{R n SiCl 4-n (n} = 1~3)) it can. For example, methylchlorosilane can be synthesized by directly reacting methyl chloride and silicon Si at a high temperature under a Cu catalyst, and silanes having an organic group such as a vinyl group can be synthesized by a general synthetic organic chemistry method. can do.
Silanol is produced when the isolated organochlorosilane is mixed alone or in an arbitrary ratio and hydrolyzed with water. When this silanol is dehydrated and condensed, polyorganosiloxane, which is the basic skeleton of silicone, is synthesized. .

Polyorganosiloxane can be cured by applying heat energy, light energy, or the like in the presence of a curing catalyst. Here, curing refers to changing from a state showing fluidity to a state showing no fluidity. For example, even if the object is left at an angle of 45 degrees from the horizontal for 30 minutes, it is fluid. The state is referred to as an uncured state, and a state having no fluidity can be determined as a cured state.
When the polyorganosiloxane is classified according to the curing mechanism, polyorganosiloxanes such as an addition polymerization curing type, a condensation polymerization curing type, an ultraviolet curing type, and a peroxide crosslinking type can be generally exemplified. Among these, addition polymerization curing type (addition type polyorganosiloxane) and condensation curing type (condensation type polyorganosiloxane) are preferable. Among these, a polyorganosiloxane type that does not generate by-products and cures by hydrosilylation (addition polymerization) in which the reaction is not reversible is more preferable. This is because when a by-product is generated during the molding process, the pressure in the molded container tends to increase or it remains as foam in the cured material.
The polyorganosiloxane may be liquid at room temperature and normal pressure, or may be solid at room temperature and normal pressure, but is more preferably liquid. The normal temperature refers to a temperature in the range of 20 ° C. ± 15 ° C. (5-35 ° C.), and the normal pressure refers to a pressure equal to atmospheric pressure, which is approximately 1 atm.

  When the polyorganosiloxane is classified according to the curing mechanism, polyorganosiloxanes such as an addition polymerization curing type, a condensation polymerization curing type, an ultraviolet curing type, and a peroxide crosslinking type can be generally exemplified. Among these, addition polymerization curing type (addition type polyorganosiloxane) and condensation curing type (condensation type polyorganosiloxane) are preferable. In particular, there is no generation of by-products (not preferred because it increases the pressure in the molding container or remains as foam in the cured material) during the molding process, and the reaction is not reversible (addition polymerization). The type of polyorganosiloxane that cures by is more preferred.

  The addition-type polyorganosiloxane refers to a polyorganosiloxane chain crosslinked by an organic addition bond. As a typical one, for example, a silicon-containing compound having (C1) alkenyl group such as vinylsilane and a silicon compound containing (C2) hydrosilyl group such as hydrosilane has a total hydrosilyl group amount of 0.5 times or more, A compound having a Si—C—C—Si bond at the cross-linking point obtained by mixing in an amount ratio of 2.0 times or less and reacting in the presence of an addition condensation catalyst represented by (C3) noble metal complex. Can be mentioned.

(C1) As a silicon-containing compound having an alkenyl group, the following general formula (2)
R _n SiO _{[(4-n) / 2]} (2)
And a polyorganosiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule.
In the above formula (2), R is the same or different substituted or unsubstituted monovalent hydrocarbon group, alkoxy group, or hydroxyl group, and n is a positive number satisfying 1 ≦ n <2.
In the silicon-containing compound having the (C1) alkenyl group, the alkenyl group is preferably an alkenyl group having 2 to 8 carbon atoms such as a vinyl group, an allyl group, a butenyl group, or a pentenyl group. When R is a hydrocarbon group, it is selected from an alkyl group such as a methyl group or an ethyl group, a monovalent hydrocarbon group having 1 to 20 carbon atoms such as a vinyl group or a phenyl group. Preferably, they are a methyl group, an ethyl group, and a phenyl group.

  Each may be different, but when UV resistance is required, about 65% of R in the above formula is preferably a methyl group. That is, the content of functional groups other than methyl groups is preferably about 0.5 (mol) with respect to the number of Si (mol number). More preferably, 80% or more is a methyl group. R may be an alkoxy group having 1 to 8 carbon atoms or a hydroxyl group, but the content of the alkoxy group or hydroxyl group is preferably 10% or less of the weight of the silicon-containing compound having (C1) alkenyl group. Further, n is a positive number satisfying 1 ≦ n <2, but if this value is 2 or more, sufficient strength cannot be obtained for bonding between the packaging material and a conductor such as a lead frame, and is less than 1. This makes it difficult to synthesize this polyorganosiloxane.

  Examples of the silicon-containing compound having the (C1) alkenyl group include vinyl silane and vinyl group-containing polyorganosiloxane. These may be used alone or in combination of two or more in any ratio and combination. it can. Among these, a vinyl group-containing polyorganosiloxane having two or more vinyl groups in the molecule is preferable.

Specific examples of the vinyl group-containing polyorganosiloxane having two or more vinyl groups in the molecule include the following.
Both ends vinyl polydimethylsiloxane DMS-V00, DMS-V03, DMS-V05, DMS-V21, DMS-V22, DMS-V25, DMS-V31, DMS-V33, DMS-V35, DMS-V41, DMS-V42, DMS-V46, DMS-V52 (both manufactured by Gelest)
Both-end vinyldimethylsiloxane-diphenylsiloxane copolymer PDV-0325, PDV-0331, PDV-0341, PDV-0346, PDV-0525, PDV-0541, PDV-1625, PDV-1631, PDV-1635, PDV-1641, PDV -2331, PDV-2335 (both manufactured by Gelest)
Both end vinylphenylmethylsiloxane PMV-9925 (manufactured by Gelest)
Trimethylsilyl-blocked vinylmethylsiloxane-dimethylsiloxane copolymer VDT-123, VDT-127, VDT-131, VDT-153, VDT-431, VDT-731, VDT-954 (all manufactured by Gelest)
Vinyl T-structure polymer VTT-106, MTV-124 (both manufactured by Gelest)

  In addition, examples of the (C2) hydrosilyl group-containing silicon compound include hydrosilane and hydrosilyl group-containing polyorganosiloxane, and these may be used alone or in combination of two or more in any ratio and combination. Can do. Of these, hydrosilyl group-containing polyorganosiloxane having two or more hydrosilyl groups in the molecule is preferred.

Specific examples of the polyorganosiloxane containing two or more hydrosilyl groups in the molecule include the following.
Both terminal hydrosilyl polydimethylsiloxane DMS-H03, DMS-H11, DMS-H21, DMS-H25, DMS-H31, DMS-H41 (all manufactured by Gelest)
Both end trimethylsilyl-blocked methylhydrosiloxane-dimethylsiloxane copolymer HMS-013, HMS-031, HMS-064, HMS-071, HMS-082, HMS-151, HMS-301, HMS-501 (all manufactured by Gelest)

The amount of the silicon-containing compound having the (C1) alkenyl group and the silicon compound containing the (C2) hydrosilyl group in the present invention is such that (C2) hydrosilyl group is added to 1 mol of the silicon-containing compound having (C1) alkenyl group. The silicon compound contained is usually 0.5 mol or more, preferably 0.7 mol or more, more preferably 0.8 mol or more. Moreover, it is 2.0 mol or less normally, Preferably it is 1.8 mol or less, More preferably, it is 1.5 mol or less. By reacting at such a ratio, the remaining amount of unreacted end groups after curing can be reduced, and a cured product with little change over time such as coloring or peeling during lighting use can be obtained.
The number of reaction points (crosslinking points) that cause hydrosilylation is preferably 0.15 mmol / g or more and 20 mmol / g or less in the resin itself that does not contain a filler for both alkenyl groups and hydrosilyl groups. More preferably, it is 0.25 mmol / g or more and 10 mmol / g or less.

  Examples of the condensed polyorganosiloxane include a compound having a Si—O—Si bond obtained by hydrolysis and polycondensation of an alkylalkoxysilane at a crosslinking point. Specific examples thereof include polycondensates obtained by hydrolysis and polycondensation of compounds represented by the following general formula (3) and / or (4) and / or oligomers thereof.

M ^{m +} X _n Y ¹ _m-1 (3)
In formula (3), M represents at least one element selected from the group consisting of silicon, aluminum, zirconium, and titanium, X represents a hydrolyzable group, and Y ¹ represents a monovalent organic group. M represents one or more integers representing the valence of M, and n represents one or more integers representing the number of X groups. However, m ≧ n.

_{^{(M S + X t Y 1}} st-1) u Y 2 ··· (4)
In Formula (4), M represents at least one element selected from the group consisting of silicon, aluminum, zirconium, and titanium, X represents a hydrolyzable group, and Y ¹ represents a monovalent organic group. Y ² represents a u-valent organic group, s represents an integer of 1 or more representing the valence of M, t represents an integer of 1 to s−1, and u represents an integer of 2 or more.

  As the condensed polyorganosiloxane, known ones can be used. For example, JP 2006-77234 A, JP 2006-291018 A, JP 2006-316264 A, JP 2006-336010 A, The semiconductor light-emitting device members described in JP-A-2006-348284 and International Publication No. 2006/090804 are suitable.

Among the condensed polyorganosiloxanes, particularly preferred materials will be described below.
When polyorganosiloxane is generally used in a semiconductor light emitting device, the adhesion between the semiconductor light emitting element, the substrate on which the semiconductor element is disposed, the resin molding, etc. may be weak. Therefore, a condensed polyorganosiloxane having at least one of the following [1] and [2] is particularly preferable.
[1] The silicon content is 20% by weight or more.
[2] The measured solid Si-nuclear magnetic resonance (NMR) spectrum has at least one peak derived from Si in the following (a) and / or (b).

(A) A peak whose peak top position is in the region of chemical shift −40 ppm or more and 0 ppm or less with reference to silicone rubber, and the peak half-value width is 0.3 ppm or more and 3.0 ppm or less.
(B) A peak whose peak top position is in the region of chemical shift of −80 ppm or more and −40 ppm or less with respect to the silicone rubber, and the peak half-value width is 0.3 ppm or more and 5.0 ppm or less.

  Further, the base resin of the present invention preferably contains a phenyl group. In addition to increasing the strength of the material by using a polyorganosiloxane having a phenyl group, the refractive index increases so that the resin molded body and the sealing material Light reflection loss at the interface can be suppressed. In particular, when the average number of phenyl groups is 0.8 (mol) or less with respect to the number (mol) of Si contained in one molecule of the polyorganosiloxane represented by (1) above, resin molding The difference between the refractive index of the body and the refractive index of the white filler can be increased, and the difference in refractive index with the sealing resin can be reduced, further reducing the reflection loss of light at the interface between the resin molded body and the sealing material. Since it can suppress, it is still more preferable. The refractive index of a resin material that does not contain a specific white filler is preferably in the range of 1.41 to 1.54.

In addition, among the polyorganosiloxanes having the above characteristics, addition-type polyorganosiloxane that does not have a component that is eliminated as the reaction progresses is moldable when cured in a closed mold. From the standpoint of heat resistance (small weight change), etc., it is preferable. Condensation type polyorganosiloxane can also be used when the molding process does not significantly affect the molding processability of the components generated with the progress of the condensation reaction. Condensed polyorganosiloxanes having a content of from 01% by weight to 10% by weight are preferred. More preferably, the silanol content is 3% by weight or less.

<2-2. (C) Curing catalyst>
The (C) curing catalyst in the present invention is a catalyst for curing the (A) polyorganosiloxane resin. The polyorganosiloxane is cured by adding a catalyst to accelerate the polymerization reaction. The resin molded body of the present invention is cured by a hydrosilylation reaction or a condensation reaction, but is preferably cured via a hydrosilylation reaction. That is, it is preferable to cure by a hydrosilylation reaction, or to cure by combining a hydrosilylation reaction and a condensation reaction.

  When the resin molding of the present invention is mainly composed of a silicone resin, there are an addition polymerization catalyst and a condensation polymerization catalyst depending on the curing mechanism of the polyorganosiloxane. The addition polymerization catalyst is a catalyst for promoting a hydrosilylation addition reaction between the alkenyl group in the component (C1) and the hydrosilyl group in the component (C2). Examples of the addition condensation catalyst include: Platinum black, secondary platinum chloride, chloroplatinic acid, reaction product of chloroplatinic acid and monohydric alcohol, complex of platinum component and olefins, and those dissolved in silicone or hydrocarbon, platinum bisacetoacetate, etc. And platinum-based catalysts, palladium-based catalysts, rhodium-based catalysts, and ruthenium-based catalysts. Of these, platinum-based catalysts are preferable, and chloroplatinic acid is more preferable. The blending amount of the catalyst for addition polymerization is usually 0.4 ppm or more, preferably 0.5 ppm or more, more preferably 1 ppm or more, more preferably, based on the total weight of the components (C1) and (C2) as a platinum group metal. Is 3 ppm or more, usually 25 ppm or less, preferably 20 ppm or less, more preferably 15 ppm or less, and even more preferably 10 ppm or less. As a result, the curing reaction rate can be kept high, and at the same time, low cost due to the use of a large amount of expensive metal catalyst and deterioration of the durability of the material due to the remaining active catalyst species (coloration during heating and storage) UV resistance etc.) and pot life can be secured sufficiently. In particular, inclusion of a platinum component is also preferable from the viewpoint of preventing silver migration commonly used on the electrode surface.

As the catalyst for condensation polymerization, acids such as hydrochloric acid, nitric acid, sulfuric acid, organic acids, alkalis such as ammonia and amines, metal chelate compounds, and the like can be used, and Ti, Ta, Zr, Al, Hf are preferable. A metal chelate compound containing any one or more of Zn, Sn, and Pt can be used. Among them, the metal chelate compound preferably contains one or more of Ti, Al, Zn, and Zr, and more preferably contains Zr.
These catalysts are selected in consideration of stability when blended as a semiconductor light emitting device package material, film hardness, non-yellowing, curability and the like.

The blending amount of the condensation polymerization catalyst is usually 0.01% by weight or more, preferably 0.05% by weight or more with respect to the total weight of the components represented by the above formula (3) and / or (4). The upper limit is usually 10% by weight or less, and preferably 6% by weight or less.
When the addition amount is in the above range, the curability and storage stability of the resin molded body material for a semiconductor light emitting device and the quality of the resin molded body are good. If the amount added exceeds the upper limit value, there will be a problem in the storage stability of the resin molded material. If the amount added is less than the lower limit value, the curing time will become longer and the productivity of the resin molded product will be reduced. Quality deteriorates.

<2-3. (B) Filler>
In the present invention, as the filler, a known inorganic or organic filler that does not inhibit the curing of the resin can be appropriately selected.
In the present invention, the number of fillers having a particle diameter of 0.2 μm or more and 50 μm or less contained in 100 μm ² of the cross section of the resin molded body in the cross section observation of the resin molded body is 100 or more and 350 or less. Is preferred. Controlling the number of fillers present on the fracture surface of the resin molded body within the above range is preferable because it is possible to prevent a decrease in luminance caused by exposure of the filler.

From the viewpoint of further long-term reliability, in the cross-sectional observation of the resin molded body, the number of fillers contained in the resin molded body cross section of 100 μm ² is preferably 120 or more, more preferably 150 or more. preferable. On the other hand, the number is preferably 300 or less, and more preferably 280 or less.

A method for measuring the filler contained in the resin molded body will be described below.
As a specific method for cross-sectional observation, a technique such as SEM, ESCA, TEM, SEM-EDX, or the like is preferably used.

Among them, SEM or ESCA is preferably used from the intention of observing particles having a diameter of 0.2 μm or more over a certain area.
Among them, SEM observation is preferable from the viewpoint of simplicity of measurement.

The SEM observation of the cross section of the resin molded body was performed based on the following method.
1) Cut a small sample with scissors.
2) Embed and fix with two-component mixed epoxy.
3) Using an ultramicrotome UC6 and FC6 manufactured by Leica Microsystems Co., Ltd., and cutting with a diamond knife at a set temperature of −120 ° C. 4) Perform ion etching treatment on the cutting surface with a self-made device.
5) Conductive treatment is performed with an osmium plasma coater manufactured by Philgen.
6) Observe with SEM S800 manufactured by HITACHI.
7) Count the number of particles having a diameter of 0.2 μm or more and 50 μm or less in 100 μm ² .

The number of fillers in the cross section of the resin molded body can be controlled by the adhesiveness between the resin molded body and the filler. That is, when the adhesiveness between the resin molded body and the filler is good, the filler on the fracture surface of the resin molded body is covered with the film of the resin molded body and tends to be difficult to be exposed.
In the resin molded body of the present invention, the number of fillers contained per 100 μm ² in cross section of the resin molded body is the amount of the adsorptive functional group contained in the base resin, the surface treatment for adjusting the activity level of the filler surface, the viscosity It can be controlled by the inclusion of the regulator. For example, a general control method is to introduce in advance functional groups that can form chemical bonds such as a covalent bond, a hydrogen bond, or a coordinate bond with each other on the surface of the base resin and the filler.

Examples of the inorganic filler that can be used in the present invention include metal oxides such as aluminum oxide (alumina), silicon oxide, titanium oxide (titania), zinc oxide, and magnesium oxide; calcium carbonate, barium carbonate, magnesium carbonate, barium sulfate, Metal salts such as aluminum hydroxide, calcium hydroxide, magnesium hydroxide; boron nitride, alumina white, colloidal silica, aluminum silicate, zirconium silicate, aluminum borate, clay, talc, kaolin, mica, synthetic mica and the like.
In addition, examples of the organic filler include resin particles such as fluorine resin particles, guanamine resin particles, melamine resin particles, acrylic resin particles, and silicone resin particles, but they are not limited to these.

Among these, from the viewpoint of exhibiting a high function as a reflecting material, a white pigment exhibiting white is preferable. In particular, the absorption of visible light is weak and the refractive index is preferably high, and specifically, titania, alumina and the like are particularly preferable. When the light emission wavelength of the light emitting element is 410 nm or less, alumina, zirconium oxide, or the like is preferable from the viewpoint of low light absorption in the ultraviolet to near ultraviolet region. From the viewpoint of thermal conductivity, alumina and boron nitride are preferable. A filler can be used individually or in mixture of 2 or more types.

The above-mentioned alumina is an oxide of aluminum, and the crystal form is not limited, but α-alumina having characteristics such as chemically stable, high melting point, high mechanical strength, high hardness, and high electric insulation resistance is used. It can be suitably used.
In addition, when an element other than aluminum or oxygen is contained in alumina as an impurity, it is colored because it has absorption in the visible light region, which is not preferable. Preferably, chromium, iron and titanium contents of 0.02% or less, preferably 0.01% or less can be used. The material preferably has a higher thermal conductivity. In order to increase the thermal conductivity, it is preferable to use alumina having a purity of 98% or more, preferably 99% or more, and particularly preferably low soda alumina.

Specific examples of titania include TA-100, TA-200, TA-300, TA-500, and TR-840 manufactured by Fuji Titanium Industry. Specific examples of alumina include A30 series manufactured by Nippon Light Metal Co., Ltd. , AN series, A40 series, MM series, LS series, AHP series, “Admafine Alumina” manufactured by Admatechs, AO-5 type, AO-8 type, CR series manufactured by Nihon Bikosky Co., Ltd. Aldrich 10 μm ² diameter alumina powder, Showa Denko A-42 series, A-43 series, A-50 series, AS series, AL-43 series, AL-47 series, AL-160SG series, A-170 Series, AL-170 series, AM series made by Sumitomo Chemical, L series, AMS series, AES series, AKP series, AA series, etc. are listed. Specific examples of zirconia include UEP-100 manufactured by Daiichi Rare Chemicals Co., Ltd., and specific examples of zinc oxide include Hakusuitec. 2 types of zinc oxide manufactured by the company are listed.

  The filler preferably has an aspect ratio of primary particles of 1.0 or more and 4.0 or less, and more preferably 1.0 or more and 3.0 or less. More preferably, it is 1.2 or more and 3.0 or less, more preferably 1.3 or more and 2.5 or less, particularly preferably 1.4 or more and 2.2 or less, and 1.4 or less. It is most preferable that it is 1.8 or more. When the aspect ratio of the primary particles is in the above range, high reflectivity is likely to be exhibited by scattering, and in particular, reflection of light having a short wavelength in the near ultraviolet region is large. Furthermore, when the platinum component content is between 0.4 ppm and 25 ppm, this range is preferable from the viewpoint of molding processability and economy as described above.

Moreover, when using a white pigment as said filler, it is preferable that a primary particle diameter is 0.1 to 2 micrometer. The lower limit is preferably 0.15 μm or more, more preferably 0.2 μm or more, and the upper limit is preferably 1 μm or less, more preferably 0.8 μm or less, and particularly preferably 0.5 μm or less.
If the primary particle diameter is too small, the white pigment tends to have low reflectance because the scattered light intensity is small, and if the primary particle diameter is too large, the white pigment tends to scatter forward, although the scattering intensity will increase. The reflectance tends to be small. A white pigment having a primary particle diameter larger than 2 μm can be used in combination for the purpose of increasing the filling rate of the white pigment in the resin composition.

  On the other hand, the white pigment preferably has a median diameter (D50) of secondary particles of 0.2 to 50 μm, more preferably 0.2 to 5 μm. A white pigment having a secondary particle size larger than 50 μm can be used in combination for the purpose of increasing the filling rate of the white pigment in the resin composition.

The primary particles in the present invention are particles that can clearly observe the interface between the particles constituting the powder, and exclude bulk particles in which a plurality of primary particles are aggregated. The primary particle diameter refers to the particle diameter of the primary particles measured by observation with an electron microscope such as SEM. In the case of particles having different areas depending on the observation direction, the length of the major axis when observed from the direction in which the area is maximum. Is the primary particle size. On the other hand, agglomerated particles formed by agglomeration of primary particles are called secondary particles, and the secondary particle size is dispersed in an appropriate dispersion medium (for example, water in the case of alumina) in addition to observation with an electron microscope such as SEM. The particle size measured with a particle size analyzer or the like. The particle diameter or particle diameter described in the present specification refers to the secondary particle diameter unless otherwise specified. When this particle diameter varies, a plurality of points (for example, 10 points) can be observed by SEM, and the average value can be obtained as the particle diameter. In the measurement, when the particle diameter is not spherical, the longest length, that is, the length of the long axis is taken as the particle diameter.

The filler is preferably subjected to a surface treatment in order to improve the adhesiveness with the (A) polyorganosiloxane resin. Examples of the surface treatment include treatment with a coupling agent such as a silane coupling agent and a titanium coupling agent.
Examples of such coupling agents include epoxy functional alkoxy such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. Amino-functional alkoxysilanes such as silane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltri It is preferable to use a mercapto functional alkoxysilane such as methoxysilane.

  In addition, about the surface treatment method of the coupling agent used for surface treatment, what is necessary is just to implement by a normal processing method, and the method is not specifically limited. For example, a method in which a silane coupling agent is dissolved in a suitable solvent, a filler is immersed in this solution, the solvent is distilled off, and heat drying is exemplified.

  Further, when the weight ratio of the filler in the resin molded body is (A) the base resin containing the polyorganosiloxane resin and (B) the filler is 15 to 60:85 to 40, the resin molded body is resistant to temperature shock. It is easy to obtain a resin molded body that is difficult to peel off the lead frame and the sealing material from the body and that is resistant to physical impact and does not crack or chip. The above range is more preferably 30-40: 70-60.

Furthermore, glass fiber, glass fiber, glass powder, etc. can be used for the purpose of increasing the strength of the molded body and as part of the filler.
Specific examples of preferable glass fiber, glass fiber, and glass powder include Denka's large particle size silica FB-40S, Central Glass's EFDE50-31, EGP200-10, EFH75-10, NSG Vetrotex's REV1, REV7, REV8, etc. are mentioned.

  In addition to the addition of these materials, it is possible to select the type suitable for each system and the content in a suitable range.

<2-4. Other ingredients>
In the resin composition of the present invention, as long as the gist of the present invention is not impaired, one or two or more other components can be contained in any ratio and combination as necessary.
For example, silica fine particles having a particle diameter of less than 0.2 μm can be contained for the purpose of controlling fluidity of the resin composition and suppressing sedimentation of the white pigment. This silica fine particle is not defined as a filler in the present invention.
The content of the silica fine particles is usually 60 parts by weight or less, preferably 40 parts by weight or less based on 100 parts by weight of the polyorganosiloxane when the base resin is silicone.

The silica fine particles used in the present invention are not particularly limited, but the specific surface area by the BET method is usually 0.02 m ² / g or more, preferably 10 m ² / g or more, more preferably 50 m ² / g or more. More preferably, it is 100 m ² / g or more. Moreover, it is 500 m < ² > / g or less normally, Preferably it is 200 m < ² > / g or less. If the specific surface area is too small, the addition effect of silica fine particles is not recognized, and if it is too large, dispersion treatment in the resin becomes difficult. As the silica fine particles, for example, those obtained by hydrophobizing the surface by reacting a silanol group present on the surface of the hydrophilic silica fine particles with a surface modifier may be used.

  Examples of the surface modifier include alkylsilane compounds, and specific examples include dimethyldichlorosilane, hexamethyldisilazane, octylsilane, and dimethylsilicone oil.

Examples of the silica fine particles include fumed silica, and fumed silica is obtained by oxidizing and hydrolyzing SiCl 4 gas with a flame of 1100 to 1400 ° C. in which a mixed gas of H ₂ and O ₂ is burned. Produced. The primary particles of fumed silica are spherical ultrafine particles mainly composed of amorphous silicon dioxide (SiO ₂ ) having an average particle size of about 5 to 50 nm. Secondary particles that are several hundred nm are formed. Since fumed silica is an ultrafine particle and is produced by rapid cooling, the surface structure is in a chemically active state.

  Specific examples include “Aerosil” (registered trademark) manufactured by Nippon Aerosil Co., Ltd., and examples of hydrophilic Aerosil (registered trademark) include “90”, “130”, “150”, “200”, Examples of “300” and hydrophobic Aerosil® include “R8200”, “R972”, “R972V”, “R972CF”, “R974”, “R202”, “R805”, “R812”, “R812S”. ”,“ RY200 ”,“ RY200S ”, and“ RX200 ”.

Moreover, in order to adjust the physical characteristic of the molded object which shape | molded the resin composition, a crosslinking agent can also be added. As the crosslinking agent, for example, a compound represented by the following general formula (6) and / or a partial hydrolysis-condensation product thereof is preferably used.
R ⁷ _a SiX _4-a (6)
In the above formula (6), R ⁷ is an unsubstituted or substituted monovalent hydrocarbon group, X is a hydrolyzable group, and a is 0 or 1.

In the general formula (6), the unsubstituted or substituted monovalent hydrocarbon group represented by R ⁷ is, for example, 10 or less carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, preferably 1 -8, particularly preferably 1-6 lower alkyl groups; alkenyl groups such as vinyl group, allyl group, isopropenyl group, butenyl group, hexenyl group; (meth) acryloyl group; (meth) acryloyloxy group; cyclohexyl group, etc. A cycloalkyl group; an allyl group such as a phenyl group, a tolyl group and a naphthyl group; an aralkyl group such as a benzyl group and a 2-phenylethyl group; and a part or all of hydrogen atoms of these groups are substituted with a halogen atom or the like Group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, particularly preferably 1 to 6 carbon atoms such as chloromethyl group and 3,3,3-trifluoropropyl group And the like. Among these, a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group and a phenyl group are preferable, and a methyl group and a phenyl group are particularly preferable.

In the general formula (6), examples of the hydrolyzable group represented by X include alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group, ketoxime groups such as methylethyl ketoxime group, and alkenyl such as isopropenoxy group. Examples include an acyloxy group such as an oxy group and an acetoxy group, and an aminoxy group such as a dimethylaminoxy group. An alkoxy group is preferable, and a methoxy group and an ethoxy group are particularly preferable.

  Specific examples of the compound represented by the general formula (6) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, and vinyltrimethoxysilane. , Trifunctional alkoxysilanes such as phenyltrimethoxysilane and methyltris (methoxyethoxy) silane; tetrafunctional alkoxysilanes such as tetramethoxysilane, tetraethoxysilane and tetrapropoxysilane; methyltripropenoxysilane, methyltriacetoxysilane, Vinyltriacetoxysilane, methyltri (butanoxime) silane, vinyltri (butanoxime) silane, phenyltri (butanoxime) silane, propyltri (butanoxime) silane, tetra (butanoxime) Silane, 3,3,3-trifluoropropyltri (butanoxime) silane, 3-chloropropyltri (butanoxime) silane, methyltri (propanoxime) silane, methyltri (pentanoxime) silane, methyltri (isopentanoxime) silane, vinyltri ( Cyclopentanoxime) silane, methyltri (cyclohexanoxime) silane and partial hydrolysis condensates thereof, and the like, preferably alkoxysilanes and partial hydrolysis condensates thereof.

  When the main component of the base resin is a polyorganosiloxane, the amount of the crosslinking agent contained in the resin composition is usually greater than 0 parts by weight and 30 parts by weight with respect to 100 parts by weight of the polyorganosiloxane. It is as follows. Preferably it is 20 mass parts or less, Most preferably, it is 10 mass parts or less. When the blending amount is within the above range, appropriate hardness and flexibility can be imparted to the resin.

It is also preferable to add a rubbery elastic body such as powdered silicone rubber for the purpose of improving the physical properties by increasing the elasticity of the resin molded body.
As addition amount, it is larger than 0 mass part with respect to 100 mass parts of resin moldings, and is 30 mass parts or less normally. Preferably it is 20 mass parts or less, Most preferably, it is 5 mass parts or less. When the blending amount is in the above range, the strength of the resin molded body is improved.

  Further, a curing retarder (catalyst control agent) can be added for the purpose of adjusting the physical properties of the molded article obtained by molding the resin composition and optimizing the pot life. Examples of the curing retarder include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin-based compound, and an organic peroxide, and these may be used in combination.

  Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols such as 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne and 1-ethynyl-1-cyclohexanol. And maleate esters such as ene-yne compounds and dimethyl malate. Examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite. Examples of organic sulfur compounds include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide and the like. Examples of the nitrogen-containing compound include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like. Examples of tin compounds include stannous halide dihydrate and stannous carboxylate. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

  Among these curing retarders, from the viewpoint of good retarding activity and good raw material availability, benzothiazole, thiazole, dimethyl malate, 3-hydroxy-3-methyl-1-butyne, 1-ethynyl-1- Cyclohexanol is preferred.

Although the addition amount of the curing retarder can be variously set, the lower limit of the preferable addition amount relative to 1 mol of the (C) curing catalyst to be used is 10 ⁻¹ mol, more preferably 1 mol, and the upper limit of the preferable addition amount is 10 ³ mol. More preferably, it is 50 mol. Moreover, these hardening retarders may be used independently and may be used together 2 or more types.

It is also preferable to add a compound having an alicyclic hydrocarbon group in order to adjust the physical properties of the molded article obtained by molding the resin composition. Examples of the compound having an alicyclic hydrocarbon group include a silane coupling agent having a cyclohexyl group or a norbornyl group, and a cyclohexane-based organic compound having a vinyl group, and trivinylcyclohexane, vinylcyclohexane, and vinylnorbornene are particularly preferable. .
The content of the compound having an alicyclic hydrocarbon group can be appropriately set, but is preferably more than 0 parts by weight and 10 parts by weight or less per 100 parts by weight of the resin molded body.

In addition, for the purpose of increasing the strength and toughness of the resin composition after thermosetting, inorganic fibers such as glass fibers may be included. In addition, in order to increase the thermal conductivity, boron nitride or nitride having high thermal conductivity. Aluminum, fibrous alumina or the like can be contained separately from the above-mentioned white pigment. In addition, for the purpose of lowering the linear expansion coefficient of the cured product, quartz beads, glass beads and the like can be contained.
If the content of these additives is too small, the desired effect cannot be obtained. If the content is too large, the viscosity of the resin composition increases and affects processability. Can be appropriately selected within a range not impairing the above. Usually, it is 100 parts by weight or less, preferably 60 parts by weight or less with respect to 100 parts by weight of the polyorganosiloxane.

  In addition, the resin composition includes other ion migration (electrochemical migration) inhibitors, curing accelerators, curing retarders, anti-aging agents, radical inhibitors, ultraviolet absorbers, adhesion improvers, flame retardants, interfaces. Activator, Storage stability improver, Ozone degradation inhibitor, Light stabilizer, Thickener, Plasticizer, Coupling agent, Antioxidant, Thermal stabilizer, Conductivity imparting agent, Antistatic agent, Radiation blocker, Nuclear An agent, a phosphorus peroxide decomposing agent, a lubricant, a pigment, a metal deactivator, a physical property adjusting agent and the like can be contained within a range not impairing the object and effect of the present invention.

  In addition to these, addition of a coupling agent is also preferable from the viewpoint of further controlling the physical properties of the molded body. Some have been introduced in terms of filler surface modifiers and crosslinking agents, but preferred coupling agents include, for example, silane coupling agents. The silane coupling agent is not particularly limited as long as it is a compound having at least one functional group reactive with an organic group and one hydrolyzable silicon group in the molecule. The group reactive with the organic group is preferably at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handling. From the viewpoints of adhesiveness and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

Preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- (Epoxycyclohexyl) alkoxysilanes having an epoxy functional group such as ethyltriethoxysilane; 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Methacrylic or acrylic groups such as triethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Alkoxysilanes having can be exemplified.

<3. Manufacturing Method of Resin Molded Body for Semiconductor Light Emitting Device of the Present Invention>
Examples of the molding method of the resin molded body for a semiconductor light emitting device of the present invention include a compression molding method, a transfer molding method and an injection molding method. Among these, as a preferable molding method, an injection molding method, particularly a liquid injection molding method (LIM molding) is preferable because no unnecessary cured product is generated and secondary processing is unnecessary. According to the injection molding method, there are significant advantages such as automation of the molding process of the resin molded body, shortening of the molding cycle, and cost reduction of the molded product.

  It is preferable that the resin molded body is consistently 45 ° C. or lower as the operating temperature before the molding process, and the molding temperature during the molding process is 300 ° C. or lower.

  The compression molding method can be performed using a compression molding machine. The molding temperature may be appropriately selected according to the material, but is usually 80 ° C. or higher and 300 ° C. or lower, preferably 100 ° C. or higher and 250 ° C. or lower, and more preferably 130 ° C. or higher and 200 ° C. or lower. The molding time may be appropriately selected according to the curing rate of the material, but is usually 3 seconds or more and 1200 seconds or less, preferably 5 seconds or more and 900 seconds or less, more preferably 10 seconds or more and 600 seconds or less.

  The transfer molding method can be performed using a transfer molding machine. The molding temperature may be appropriately selected according to the material, but is usually 80 ° C. or higher and 300 ° C. or lower, preferably 100 ° C. or higher and 250 ° C. or lower, and more preferably 130 ° C. or higher and 200 ° C. or lower. The molding time may be appropriately selected depending on the gelation speed and curing speed of the material, but usually 3 seconds or more and 1200 seconds or less, preferably 5 seconds or more and 900 seconds or less, more preferably 10 seconds or more and 600 seconds or less. It is.

  The injection molding method can be performed using an injection molding machine. The cylinder set temperature may be appropriately selected according to the material, but is usually 100 ° C. or lower, preferably 80 ° C. or lower, and more preferably 60 ° C. or lower. The mold temperature is 80 ° C. or higher and 300 ° C. or lower, preferably 100 ° C. or higher and 250 ° C. or lower, more preferably 130 ° C. or higher and 200 ° C. or lower. The injection time varies depending on the material, but is usually several seconds or less than 1 second. The molding time may be appropriately selected depending on the gelation speed and curing speed of the material, but usually 3 seconds or more and 1200 seconds or less, preferably 5 seconds or more and 900 seconds or less, more preferably 10 seconds or more and 600 seconds or less. It is.

  In any molding method, post-curing can be performed as necessary, and the post-curing temperature is 100 ° C. or higher and 300 ° C. or lower, preferably 150 ° C. or higher and 250 ° C. or lower, more preferably 170 ° C. or higher and 200 ° C. or lower. It is. The post-curing time is usually 3 minutes or more and 24 hours or less, preferably 5 minutes or more and 10 hours or less, more preferably 10 minutes or more and 5 hours or less.

  The resin molded body of the present invention can be made into a package for a semiconductor light-emitting device by molding together with metal wiring during molding. For example, a substrate having wiring as metal wiring is created, and a resin molded body is injection molded using a mold on the substrate, or a resin-molded body is injection molded by placing a lead frame on the mold as metal wiring. It can be manufactured by a method or the like.

<4. Semiconductor light emitting device>
The half-conductor light emitting device package of the present invention is usually used as a semiconductor light emitting device with a semiconductor light emitting element mounted thereon. The outline of the semiconductor light emitting device will be described with reference to the drawings. However, the present invention is not limited to the following embodiments, and can be arbitrarily modified without departing from the gist of the present invention.
1 and 2 show an example of a semiconductor light emitting device, which is composed of a semiconductor light emitting element (LED chip) 1, a package comprising a resin molded body 2 and a metal lead frame 5, a bonding wire 3, a sealing material 4 and the like. Is done.
In FIG. 1, the phosphor particles are dispersed in the sealing material, which also serves as the phosphor layer. On the other hand, as shown in FIG. 2, the phosphor layer 6 can be arranged apart from the semiconductor light emitting element, separately from the sealing material.

  The semiconductor light emitting device 1 uses a near ultraviolet semiconductor light emitting device that emits light having a wavelength in the near ultraviolet region, a purple semiconductor light emitting device that emits light in a purple region, a blue semiconductor light emitting device that emits light in a blue region, and the like. It emits light having a wavelength of 350 nm or more and 520 nm or less. Although only one semiconductor light emitting element is shown in FIGS. 1 and 2, it is also possible to arrange a plurality of semiconductor light emitting elements in a linear or planar shape. By arranging the semiconductor light emitting element 1 in a planar shape, it is possible to easily achieve surface illumination, and this embodiment is suitable when it is desired to further increase the output.

  The resin molded body 2 forming the package is molded together with the lead frame 5. The shape of the package is not particularly limited and may be a planar type or a cup type, but is preferably a cup type from the viewpoint of imparting directivity to light. The lead frame 5 is made of a conductive metal and plays a role of supplying power from outside the semiconductor light emitting device and energizing the semiconductor light emitting element 1.

  The bonding wire 3 fixes the semiconductor light emitting element 1 to the package. As shown in FIG. 2, when the conductor light emitting element 1 is not in contact with the lead frame 5 that serves as an electrode, the conductive bonding wire 3 plays a role of supplying an electrode to the semiconductor light emitting element 1. The bonding wire 3 is bonded to the lead frame 5 by applying pressure and vibration of heat and ultrasonic waves. However, when the surface of the lead frame 5 is made of silver or a silver alloy, the adhesion is improved, which is preferable. .

The encapsulant 4 is a mixture in which a phosphor is mixed with a binder resin, and the phosphor contained in the encapsulant converts excitation light from the semiconductor light emitting element 1 into fluorescence. In the present embodiment, the sealing material also serves as the phosphor layer. The phosphor contained in the sealing material 4 is appropriately selected according to the wavelength of the excitation light of the semiconductor light emitting device 1. In a light emitting device that emits white light, if a semiconductor light emitting element that emits blue excitation light is used as an excitation light source, white light can be generated by including green and red phosphors in the phosphor layer. In the case of a semiconductor light emitting device that emits purple excitation light, there are cases where blue and yellow phosphors are included in the phosphor layer, and blue, green, and red phosphors are included in the phosphor layer. It is done.
As the binder resin contained in the sealing material 4, it is possible to appropriately select a translucent resin conventionally used in sealing materials, and epoxy resins, silicone resins, acrylic resins, polycarbonate resins, and the like are used. However, it is preferable to use a silicone resin.

  An embodiment in which the sealing material 4 does not mix phosphors but has only a sealing role and is configured separately from the phosphor layer is also an embodiment of the present invention. For example, as shown in FIG. 2, a mode in which a transparent substrate (not shown) is prepared so as to cover the resin molded body 2 and the phosphor layer 6 is formed thereon is also conceivable. In such an embodiment, since the semiconductor light emitting element 1 and the phosphor layer 6 are arranged at a distance, the deterioration of the phosphor layer 6 can be prevented, and the output of the light emitting device can be improved. it can. The distance between the semiconductor light emitting element 1 and the phosphor layer 6 is preferably 1 to 500 mm, and more preferably 5 to 500 mm.

In FIG. 1, the semiconductor light emitting element 1 is directly mounted on the resin molded body 2, and the thickness of the resin molded body 2 where the semiconductor light emitting element 1 is mounted is usually 100 μm or more, preferably 20
0 μm or more. Moreover, it is 3000 micrometers or less normally, Preferably it is 2000 micrometers or less. If the thickness is too thin, light tends to be transmitted to the bottom surface and the reflectivity tends to decrease, which may cause problems such as insufficient strength of the package and deformation in handling. If it is too thick, the package itself becomes thick and bulky. Therefore, the application of the semiconductor light emitting device may be limited.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited at all by the following example.

[Preparation of platinum solutions A to D]
To a 10 mL screw tube, phenyl group-free silicone H (vinyl group: 1.2 mmol / g contained, platinum: 6.8 ppm contained) 2.5 g, and 0.1 M Platinum (0) -1,3-divinyl- 0.13 g of 1,1,3,3-tetramethyldisiloxane complex in vinyl terminated poly (dimethylsiloxane) was added and stirred with a rotor at room temperature for 30 minutes to obtain a platinum solution A having a platinum concentration of 1070 ppm.

  To a 10 mL screw tube, phenyl group-free silicone K (vinyl group: 0.04 mmol / g contained) 2.5 g, and 0.1 M Platinum (0) -1,3-divinyl-1,1,3,3 -0.13 g of tetramethyldisiloxane complex in vinyl terminated poly (dimethylsiloxane) was added and stirred with a rotor at room temperature for 30 minutes to obtain a platinum solution B having a platinum concentration of 1064 ppm.

  In a 10 mL screw tube, phenyl group-free silicone H (vinyl group: 1.24 mmol / g contained, platinum: 6.8 ppm contained) 2.5 g, and chloroplatinic acid (IV) 0.0073 g (platinum concentration: 376675 ppm) Was added and stirred with a rotor for 30 minutes at room temperature to obtain a platinum solution C having a platinum concentration of 1094 ppm.

  To a 10 mL screw tube, 6 g of phenyl group-free silicone K (vinyl group: 0.04 mmol / g) and 0.0016 g of chloroplatinic acid (IV) (platinum concentration: 376675 ppm) were added, and the rotor was kept at room temperature for 30 minutes. And a platinum solution D having a platinum concentration of 100.4 ppm was obtained.

[Preparation of Resin Composition 1]
2.94 g of phenyl group-free silicone H was further added to 0.06 g of the obtained platinum solution A, and the mixture was stirred for 30 minutes with a rotor at room temperature. Thereto, 3.0 g of phenyl group-free silicone I (vinyl group: 0.3 mmol / g contained, hydrosilyl group: 1.8 mmol / g contained) was added, and the mixture was stirred at room temperature for 15 minutes with a rotor to obtain a platinum concentration. Obtained the resin composition 1 which is 14.0 ppm. The resin composition 1 was found to have increased viscosity after stirring. Furthermore, the coloring degree was measured about the hardened | cured material which made the resin composition 1 1 mm thick, was pinched | interposed with two slide glasses, and was heat-hardened at 150 degreeC for 30 minutes. As a result of the measurement, the YI value was 1.8 and the APHA value was 30, and almost no coloring was observed.
Here, the YI (Yellowness Index) value, which is an index of the degree of coloring, is an index of yellowness determined by the American Society for Testing and Materials, and is ideal white (completely in the ASTM E313 standard) The diffuse reflection surface) has a yellowness of 0, and the distance from this white is defined as the YI value. The APHA value is a color difference standard value of the American Public Health Association and is an index of yellowishness, which is also called Hazen color number. In the ASTM D 1209 standard, the higher the value, the deeper the yellowishness. . In measuring the YI value and the APHA value, a colorimetry color difference meter (Color Meter) model number ZE-2000 manufactured by Nippon Denshoku Industries Co., Ltd. was used. The same applies to the following embodiments.

[Preparation of Resin Composition 2]
A mixed solution was prepared in the same manner as the resin composition 1 except that 0.03 g of the obtained platinum solution A and 2.97 g of phenyl group-free silicone H were used, and a resin composition having a platinum concentration of 8.7 ppm. Product 2 was obtained. In the resin composition 2, no particularly noticeable change was observed in the stirring process. Furthermore, the coloring degree was measured about the hardened | cured material which made the resin composition 2 1 mm thick, was pinched | interposed with two slide glasses, and was heat-hardened at 150 degreeC for 30 minutes. The measurement results were a YI value of 1.5 and an APHA value of 25, and almost no coloration was observed.

[Preparation of Resin Composition 3]
A mixed solution was prepared in the same manner as the resin composition 1 except that 0.015 g of the obtained platinum solution A and 2.985 g of the phenyl group-free silicone H were used, and a resin composition having a platinum concentration of 6.1 ppm. Product 3 was obtained. In the resin composition 3, no particularly noticeable change was observed in the stirring process. Furthermore, the coloring degree was measured about the hardened | cured material which made the resin composition 3 1 mm thick, was pinched | interposed with two slide glasses, and was heat-hardened at 150 degreeC for 30 minutes. As a result of the measurement, the YI value was 0.5, the APHA value was 5, and almost no coloring was observed.

[Preparation of Resin Composition 4]
Resin having a platinum concentration of 3.4 ppm, prepared in the same manner as the resin composition 1, except that the platinum group-free silicone H was changed to 3.0 g without using the obtained platinum solution A. Composition 4 was obtained. In the resin composition 4, no particularly noticeable change was observed in the stirring process. Furthermore, the coloring degree was measured about the hardened | cured material which made the resin composition 4 1 mm thick, was pinched | interposed with two slide glasses, and was heat-hardened at 150 degreeC for 30 minutes. The measurement results were a YI value of 1.1 and an APHA value of 18, and almost no coloration was observed.

[Preparation of Comparative Resin Composition 1]
2.7 g of phenyl group-free silicone H was further added to 0.3 g of the obtained platinum solution A, and the mixture was stirred for 30 minutes with a rotor at room temperature. Thereto, 3.0 g of phenyl group-free silicone I (vinyl group: 0.3 mmol / g contained, hydrosilyl group: 1.8 mmol / g contained) was added, and the mixture was stirred at room temperature for 15 minutes with a rotor to obtain a platinum concentration. Comparative resin composition 1 having a 56.6 ppm was obtained. The entire comparative resin composition 1 was gelated during the stirring process. Furthermore, the coloring degree was measured about the hardened | cured material which set the comparative resin composition 1 to 1 mm thickness, was pinched | interposed with two slide glasses, and was heat-hardened at 150 degreeC for 30 minutes. The measurement results were a YI value of 13.3 and an APHA value of 245, and a slight degree of coloring was observed.

[Preparation of Comparative Resin Composition 2]
A mixed solution was prepared in the same manner as Comparative Resin Composition 1 except that 0.15 g of the obtained platinum solution A and 2.85 g of phenyl group-free silicone H were used, and the platinum concentration was 30.0 ppm. A resin composition 2 was obtained. Comparative resin composition 2 foamed during the stirring process, and after stirring, it was confirmed that the upper part of the liquid was partially gelled. Furthermore, the coloring degree was measured about the hardened | cured material which set the comparative resin composition 2 to 1 mm thickness, was pinched | interposed with two slide glasses, and was heat-hardened at 150 degreeC for 30 minutes. As a result of measurement, YI value was 8.4, APHA value was 153, and a slight degree of coloring was recognized.

[Preparation of Resin Composition 5]
4.9975 g of phenyl group-free silicone K was further added to 0.0025 g of the obtained platinum solution B, and the mixture was stirred with a rotor at room temperature for 30 minutes. There is a linear silicone L containing 0.07 (mol) of hydrosilyl groups with respect to the number of Si (mol).
0.2160 g (average molecular weight: 2000, viscosity 30 cp) was added, and the mixture was stirred for 15 minutes with a rotor at room temperature to obtain a resin composition 5 having a platinum concentration of 0.5 ppm. In the resin composition 5, no particularly noticeable change was observed in the stirring process. Furthermore, when the resin composition 5 was 1 mm thick and sandwiched between two slide glasses and heated at 150 ° C. for 30 minutes, a colorless and transparent elastomer was obtained. When the degree of coloring of the cured product was measured, the YI value was 0.2, the APHA value was 0, and almost no coloring was observed.

[Preparation of Resin Composition 6]
A mixed solution was prepared in the same manner as in the resin composition 5 except that 0.0050 g of the obtained platinum solution B and 4.9950 g of the phenyl group-free silicone K were changed to a resin composition having a platinum concentration of 1.0 ppm. Product 6 was obtained. In the resin composition 6, no particularly noticeable change was observed in the stirring process. Furthermore, the resin composition 6 having a thickness of 1 mm was sandwiched between two glass slides and heated at 150 ° C. for 30 minutes to obtain a colorless and transparent elastomer. When the degree of coloring of the cured product was measured, the YI value was 1.6, the APHA value was 7, and almost no coloring was observed.

[Preparation of Resin Composition 7]
A mixed solution was prepared in the same manner as the resin composition 5 except that 0.0250 g of the obtained platinum solution B and 4.9750 g of the phenyl group-free silicone K were used, and a resin composition having a platinum concentration of 5.1 ppm. Product 7 was obtained. In the resin composition 7, no particularly noticeable change was observed in the stirring process. Furthermore, when the resin composition 7 was 1 mm thick and sandwiched between two slide glasses and heated at 150 ° C. for 30 minutes, a colorless and transparent elastomer was obtained. When the degree of coloring of the cured product was measured, the YI value was 1.4, the APHA value was 23, and almost no coloring was observed.

[Preparation of Resin Composition 8]
A mixed solution was prepared in the same manner as the resin composition 5 except that 0.0500 g of the obtained platinum solution B and 4.9500 g of the phenyl group-free silicone K were used, and a resin composition having a platinum concentration of 10.2 ppm. Product 8 was obtained. In the resin composition 8, no particularly noticeable change was observed in the stirring process. Furthermore, when the resin composition 8 was 1 mm thick and sandwiched between two slide glasses and heated at 150 ° C. for 30 minutes, a colorless and transparent elastomer was obtained. When the degree of coloring of the cured product was measured, the YI value was 2.6, the APHA value was 45, and almost no coloring was observed.

[Preparation of resin composition 9]
A mixed liquid was prepared in the same manner as in the resin composition 5 except that the obtained platinum solution B was 0.1000 g and the phenyl group-free silicone K was 4.9000 g, and the platinum concentration was 20.4 ppm. Product 9 was obtained. The resin composition 9 was slightly gelled after stirring. Furthermore, when the resin composition 9 was 1 mm thick and sandwiched between two slide glasses and heated at 150 ° C. for 30 minutes, a transparent elastomer with an extremely thin brownish taste was obtained. When the degree of coloring of the cured product was measured, the YI value was 3.7, the APHA value was 64, and almost no coloring was observed.

[Preparation of Comparative Resin Composition 3]
4.9985 g of phenyl group-free silicone K was further added to 0.0015 g of the obtained platinum solution B, and the mixture was stirred with a rotor at room temperature for 30 minutes. 0.2160 g of linear silicone L (average molecular weight: 2000, viscosity of 30 cp) containing 0.07 (mol) of hydrosilyl group with respect to the number of Si (mol number) was added to the rotor at room temperature. The mixture was stirred for 15 minutes to obtain a comparative resin composition 3 having a platinum concentration of 0.3 ppm. In Comparative Resin Composition 3, no noticeable change was observed in the stirring process. Further, the comparative resin composition 3 having a thickness of 1 mm was sandwiched between two slide glasses and cured by heating at 150 ° C. for 30 minutes, but the cured product was very soft and uncured. When the degree of coloring of the cured product was measured, the YI value was 0.1, the APHA value was 0, and almost no coloring was observed.

[Preparation of Comparative Resin Composition 4]
A mixed solution was prepared in the same manner as Comparative Resin Composition 3 except that 0.2500 g of the obtained platinum solution B and 4.7500 g of phenyl group-free silicone K were used, and the platinum concentration was 51.0 ppm. A resin composition 4 was obtained. The entire comparative resin composition 4 was gelated during the stirring process. Further, the comparative resin composition 4 having a thickness of 1 mm was sandwiched between two slide glasses and heated at 150 ° C. for 30 minutes to obtain a thin brownish transparent elastomer. When the degree of coloring of the cured product was measured, the YI value was 6.8, the APHA value was 125, and a slight degree of coloring was recognized.

[Preparation of Resin Composition 10]
2.4875 g of phenyl group-free silicone H was further added to 0.0125 g of the obtained platinum solution C, and the mixture was stirred with a rotor at room temperature for 30 minutes. 2.5 g of phenyl group-free silicone I (vinyl group: 0.3 mmol / g contained, hydrosilyl group: 1.8 mmol / g contained) was added thereto, and the mixture was stirred for 15 minutes with a rotor at room temperature, and the platinum concentration The resin composition 10 which is 6.1 ppm was obtained. In the resin composition 10, no particularly noticeable change was observed in the stirring process. Furthermore, when the resin composition 10 was 1 mm thick and sandwiched between two slide glasses and heated at 150 ° C. for 30 minutes, a colorless and transparent elastomer was obtained. When the degree of coloring of the cured product was measured, the YI value was 1.8, the APHA value was 28, and almost no coloring was observed.

[Preparation of Resin Composition 11]
A mixed solution was prepared in the same manner as the resin composition 10 except that 0.025 g of the obtained platinum solution C and 2.475 g of phenyl group-free silicone H were used, and a resin composition having a platinum concentration of 8.8 ppm. Product 11 was obtained. In the resin composition 11, no particularly noticeable change was observed in the stirring process. Further, when the resin composition 11 was 1 mm thick and sandwiched between two slide glasses and heated at 150 ° C. for 30 minutes, a colorless and transparent elastomer was obtained. When the degree of coloring of the cured product was measured, the YI value was 3.5, the APHA value was 61, and almost no coloring was observed.

[Preparation of Resin Composition 12]
A mixed liquid was prepared in the same manner as the resin composition 10 except that 0.050 g of the obtained platinum solution C and 2.450 g of the phenyl group-free silicone H were used, and a resin composition having a platinum concentration of 14.3 ppm Product 12 was obtained. In the resin composition 12, no particularly noticeable change was observed in the stirring process. Further, the resin composition 12 having a thickness of 1 mm was sandwiched between two glass slides and heated at 150 ° C. for 30 minutes to obtain a colorless and transparent elastomer. When the degree of coloring of the cured product was measured, the YI value was 4.5 and the APHA value was 80, and almost no coloring was observed.

[Preparation of Comparative Resin Composition 5]
A mixed resin was prepared in the same manner as the resin composition 10 except that 0.125 g of the obtained platinum solution C and 2.375 g of phenyl group-free silicone H were used, and a comparative resin having a platinum concentration of 30.6 ppm Composition 5 was obtained. The comparative resin composition 5 became quite high in viscosity after stirring, and the whole started to gel, and the appearance was slightly turbid due to the entrapment of bubbles. Further, when the comparative resin composition 5 was 1 mm thick and sandwiched between two slide glasses and heated at 150 ° C. for 30 minutes, a colorless and transparent elastomer was obtained. When the degree of coloring of the cured product was measured, the YI value was 7.5 and the APHA value was 137, and a slightly yellow coloring was observed.

[Preparation of Comparative Resin Composition 6]
A mixed resin was prepared in the same manner as the resin composition 10 except that 0.25 g of the obtained platinum solution C and 2.25 g of phenyl group-free silicone H were used, and a comparative resin having a platinum concentration of 57.8 ppm. Composition 6 was obtained. The comparative resin composition 6 was gelated as a whole in the stirring process, and was slightly turbid by appearance due to the entrapment of bubbles. Furthermore, the comparative resin composition 6 having a thickness of 1 mm was sandwiched between two glass slides and heated at 150 ° C. for 30 minutes to obtain a colorless and transparent elastomer. When the degree of coloring of the cured product was measured, the YI value was 11.6, the APHA value was 214, and yellow coloring was recognized.

[Preparation of Resin Composition 13]
4.7500 g of phenyl group-free silicone K was further added to 0.2500 g of the obtained platinum solution D, and the mixture was stirred with a rotor at room temperature for 30 minutes. 0.2160 g of linear silicone L (average molecular weight: 2000, viscosity of 30 cp) containing 0.07 (mol) of hydrosilyl group with respect to the number of Si (mol number) was added to the rotor at room temperature. The mixture was stirred for 15 minutes to obtain a resin composition 13 having a platinum concentration of 4.8 ppm. In the resin composition 13, no particularly noticeable change was observed in the stirring process. Furthermore, the resin composition 13 having a thickness of 1 mm was sandwiched between two glass slides and heated at 150 ° C. for 30 minutes to obtain a colorless and transparent elastomer. When the degree of coloring of the cured product was measured, the YI value was 0.5, the APHA value was 4, and almost no coloring was observed.

[Preparation of Resin Composition 14]
A mixed solution was prepared in the same manner as the resin composition 13 except that the obtained platinum solution D was changed to 0.5000 g and the phenyl group-free silicone K was changed to 4.5000 g, and a platinum composition having a platinum concentration of 9.6 ppm Product 14 was obtained. In the resin composition 14, no particularly noticeable change was observed in the stirring process. Furthermore, when the resin composition 14 was 1 mm thick and sandwiched between two slide glasses and heated at 150 ° C. for 30 minutes, a colorless and transparent elastomer was obtained. When the degree of coloring of the cured product was measured, the YI value was 0.8, the APHA value was 11, and almost no coloring was observed.

[Preparation of Comparative Resin Composition 7]
Further, 4.985 g of phenyl group-free silicone K was added to 0.0015 g of the obtained platinum solution D, and the mixture was stirred for 30 minutes with a rotor at room temperature. 0.2160 g of linear silicone L (average molecular weight: 2000, viscosity of 30 cp) containing 0.07 (mol) of hydrosilyl group with respect to the number of Si (mol number) was added to the rotor at room temperature. The mixture was stirred for 15 minutes to obtain a comparative resin composition 7 having a platinum concentration of 0.3 ppm. In Comparative Resin Composition 7, no particularly noticeable change was observed in the stirring process. However, the comparative resin composition 7 having a thickness of 1 mm was sandwiched between two slide glasses, and was cured by heating at 150 ° C. for 30 minutes.

[Preparation of Comparative Resin Composition 8]
A mixed solution was prepared in the same manner as the comparative resin composition 7 except that the obtained platinum solution D was 2.5000 g and the phenyl group-free silicone K was 2.5000 g, and the platinum concentration was 50.2 ppm. A resin composition 8 was obtained. The comparative resin composition 8 was slightly cloudy after stirring. Further, the comparative resin composition 8 gelled when left at room temperature for 6 hours. Further, when the comparative resin composition 8 is 1 mm thick and sandwiched between two slide glasses and heated at 150 ° C. for 30 minutes, a colorless and transparent elastomer is obtained. When the degree of coloring of the cured product is measured, the YI value is 1. 1. APHA value is 17, almost no coloring was observed.

[Example]
[Production of resin molded body and measurement of reflectance and hardness]
In 58 mL of polyethylene ointment basket, 6.0 g of alumina (bulk density: 0.8, average particle size: 1.2 μm, average aspect ratio of primary particles: 1.48, purity: 99.12%), 25 g of surface-treated (trimethylsilyl-treated) fumed silica and 3.5 g of the resin composition 4 were added, and the mixture was stirred with Thinky's Awatake Nitarou ARV-200. 0.25 g of surface-treated (trimethylsilyl-treated) fumed silica was added again, and vacuum defoaming was performed with ARV-200 to obtain white resin composition 1.

The obtained white resin composition 1 was put into a stainless steel mold having a diameter of 1.3 cm and a thickness of 0.3 mm, 1.0 mm, and 3.0 mm, and the pressure was 10 kg / cm ² on a silver plate. White resin molded bodies 1 to 3 were obtained by heating and pressing in air at 150 ° C. for 3 minutes and further post-curing in an air dryer at 200 ° C. for 10 minutes. The ratio of the base resin containing the polyorganosiloxane in the white resin molded bodies 1 to 3 and the filler is 36.8: 63.2.

The reflectance of the white resin molded body 1 having a thickness of 0.3 mm was 94.6% for 400 nm light and 94.6% for 460 nm light. The reflectance of the white resin molded body 2 having a thickness of 1.0 mm was 96.4% for 400 nm light and 97.1% for 460 nm light. Further, the hardness of the white resin molded body 3 having a thickness of 3.0 mm was 90 or more for Shore A and 40 for Shore D.
The reflectance was measured at a measurement diameter of 6 mm using SPECTROTOPOMETER CM-2600d manufactured by Konica Minolta. Also, Shore A and Shore D hardness are measured for each cured sample at a load of 1 kgf using a rubber hardness tester KR-24A and KR-25D manufactured by Furusato Seiki Seisakusho (so that the overlap thickness is 6.0 mm or more, That is, for example, two samples were stacked in the case of a 3.0 mm sample. The same applies to the following embodiments.

The white resin molded body 1 molded to a thickness of 0.3 mm on a silver plate does not peel off or collapse when removed from the mold, and after that, even if a slight force is applied from the side with a spatula There was no peeling or collapse from the silver surface.
Therefore, it turned out that the white resin molding 1 is not brittle and is a material that adheres well to the silver surface.

  Further, in 58 mL of polyethylene ointment jar, 6.0 g of alumina (bulk density: 0.8, average particle size: 1.2 μm, average aspect ratio: 1.48, purity: 99.12%), 0.25 g The surface-treated (trimethylsilyl-treated) fumed silica and 3.5 g of the comparative resin composition 4 were added, and the mixture was stirred with Thinky's Foam Tritaro ARV-200. Again, 0.25 g of surface-treated (trimethylsilyl-treated) fumed silica was added, and vacuum defoaming was performed with ARV-200 to obtain white resin composition 2.

The obtained white resin composition 2 was put into a stainless steel mold having a diameter of 1.3 cm, a thickness of 0.3 mm, and a thickness of 1.0 mm, and 3 mm in air under a pressure of 10 kg / cm ² on a silver plate. Resin molded bodies 4 and 5 were obtained by heating and pressing at 150 ° C. for 10 minutes and further post-curing at 200 ° C. for 10 minutes in an air dryer. The ratio of the base resin containing the polyorganosiloxane and the filler in the resin molded bodies 4 to 5 is 36.8: 63.2.

  The reflectance of the white resin molded body 4 having a thickness of 0.3 mm was 95.1% for 400 nm light and 95.9% for 460 nm light. The reflectance of the white resin molded body 5 having a thickness of 1.0 mm was 95.5% for 400 nm light and 96.8% for 460 nm light. Furthermore, the hardness of six sheets of 1.0 mm thick resin molded bodies 5 was 90 or more for Shore A and 48 for Shore D.

[Evaluation of light resistance (UV) resistance of resin moldings]
Light (2100 mW / cm ² ) from the UV curing apparatus Aicure ANUP5204 made by Matsushita Electric Works and Vision Co., Ltd. was applied to the white resin molded bodies 2 and 5 having a thickness of 1.0 mm at room temperature in the atmosphere. Using this, light of 250 nm or less was cut and irradiated for 20 hours. In the case of the white resin molded body 2, the surface state on the appearance did not change at all before and after the irradiation, whereas in the case of the white resin molded body 5, the surface became rough due to micro cracks. It was.

[Evaluation of heat resistance of molded resin]
When the white resin molded bodies 2 and 5 having a thickness of 1.0 mm were stored in a ventilation dryer at 200 ° C. in the atmosphere, the reflectance of the white resin molded body 2 measured after 400 hours was 400 nm with respect to light. While it was 96.1% (96.4% before irradiation) and 97.0% (97.1% before irradiation) for 460 nm light, the reflectance of the white resin molded body 5 was , 94.8% (95.5% before irradiation) for 400 nm light, and 96.1% (96.8% before irradiation) for 460 nm light. Therefore, it was found that the light reflectance of the white resin molded body 5 is not only low in absolute value with respect to the light reflectance of the white resin molded body 2, but also decreases after the heat test.

[Lighting durability evaluation test]
A cup having a recess having a length of 5 mm, a width of 5 mm, a height of 1.5 mm, and an opening diameter of 3.6 mm, produced by heat-injection molding the obtained white resin composition 1 together with a silver lead-plated copper lead frame. To form a surface mount package in the form of a package. In addition, an LED package (Package 2) using Polyphthalamide (Amodel A4122) PPA manufactured by Solvay Advanced Polymers Co., Ltd. having the same shape was prepared, and an LED lighting durability test was performed.

  Mounting of a semiconductor light emitting device (406 nm emission wavelength, rated current 20 mA) is performed by placing a silicone die bond material (KER-3000-M2 manufactured by Shin-Etsu Chemical Co., Ltd.) at a predetermined position on the inner lead exposed in the recess of the package. The silicone die bond material was cured at 100 ° C. for 1 hour and further at 150 ° C. for 2 hours.

Next, the sealing material was manufactured.
Momentive Performance Materials Japan G.K. both ends silanol dimethyl silicone oil XC96-723 385g, methyltrimethoxysilane 10.28g, and zirconium tetraacetylacetonate powder 0.791g as a catalyst, In a 500 ml three-necked Kolben equipped with a fractionating tube, a Dimroth condenser and a Liebig condenser, the mixture was stirred at room temperature for 15 minutes until the coarse particles of the catalyst were dissolved. Thereafter, the temperature of the reaction solution was raised to 100 ° C. to completely dissolve the catalyst, and initial hydrolysis was performed while stirring at 500 rpm for 30 minutes at 100 ° C. under total reflux.
Subsequently, the distillate was connected to the Liebig condenser side, nitrogen was blown into the liquid with SV20, and methanol, water, and low-boiling silicon components of by-products were distilled off accompanied with nitrogen at 100 ° C. and 500 rpm. Stir for hours. The polymerization reaction was continued for 5 hours while raising and maintaining the temperature at 130 ° C. while blowing nitrogen into the liquid with SV20 to obtain a reaction liquid having a viscosity of 120 mPa · s. Here, “SV” is an abbreviation for “Space Velocity” and refers to the volume of blown volume per unit time. Therefore, SV20 refers to blowing N ₂ in a volume 20 times that of the reaction solution in one hour.
After stopping the blowing of nitrogen and once cooling the reaction solution to room temperature, the reaction solution was transferred to an eggplant-shaped flask, and methanol and moisture remaining in a minute amount at 120 ° C. and 1 kPa on an oil bath using a rotary evaporator, The low boiling silicon component was distilled off to obtain a solvent-free sealing material liquid having a viscosity of 230 mPa · s at room temperature.

  After dripping the obtained silicone sealing material liquid into the package recesses of the package 1 and the package 2 so as to be the same height as the upper edge of the opening, 90 ° C. for 2 hours, then 110 ° C. for 1 hour in a thermostatic chamber, The semiconductor light emitting device was sealed by performing heat curing at 150 ° C. for 3 hours.

The lighting endurance test is performed by setting the above-mentioned sealed packages 1 and 2 on a lighting power source on a 3 mm-thick heat-dissipating aluminum plate with a heat conductive insulating sheet, and an environmental testing machine at a temperature of 60 ° C. and a relative humidity of 90%. A continuous lighting test was conducted by applying a drive current of 60 mA. The semiconductor light emitting device was taken out every predetermined time, and the percentage of output over time (output maintenance rate) with respect to the initial output (mW) was measured offline (luminance measurement was 20 mA energization). The measurement results are shown in FIG.
As shown in FIG. 3, when the package 1 according to the application example 1 is used, it has been found that the output maintenance rate is clearly higher than when the package 2 is used.

  Package 1 and package 2 are stored for 24 hours in an atmosphere of 85 ° C. and 85% RH (relative humidity), and left on a hot plate at 260 ° C. for 1 minute immediately after removal from the atmosphere. Also, a confirmation test of adhesion (peeling) between the sealing material and the package surface or the lead frame surface was also carried out. As a result, as shown in FIG. 4, peeling was recognized only in the case of the package 2 made of PPA (polyphthalamide).

[Adhesion evaluation test]
For the package 1 and the PPA package 2 and the ceramic LED package manufactured by Kyoritsu Elex (M5050N (KA-6)) prepared in the durability test, the adhesion between the lead frame and the resin molded body by the following method (Peeling) confirmation experiment was conducted.
First, each package was washed with ethanol and dried. Next, a test penetrant (Taset Color Check Penetrant FP-S (red)) was sprayed on the dried package and allowed to stand for 5 minutes. About the package after standing, the liquid of the surface was wiped off with a wiper, further cleaned with ethanol, and dried at room temperature for 1 hour.

The package treated by the above procedure was observed for the next peeling.
(I) The metal and the resin are peeled off and the coloring on the resin is observed.
(Ii) Further, Taseto Co., Ltd., a color check developer is sprayed thinly and left for 10 minutes to check the red color that emerges to confirm the presence or absence of peeling.
In the case of the observation of the above (i) and the observation of the above (ii), in the case of the package 1, no red color was observed between the lead frame and the resin molded body, whereas the PPA package In the case of 2 and the ceramic package, red was confirmed in both cases, and it was found that there was peeling between the lead frame and the resin molded body or the ceramic material.

DESCRIPTION OF SYMBOLS 1 Semiconductor light emitting element 2 Resin molding 3 Bonding wire 4 Sealing material 5 Lead frame 6 Phosphor layer

Claims (11)

(A) A package for a semiconductor light emitting device comprising at least a resin molded body containing a polyorganosiloxane resin, (B) a filler, and (C) a curing catalyst,
A package for a semiconductor light-emitting device, wherein a metal component content of the curing catalyst in the resin molded body excluding the filler is 0.4 ppm or more and 25 ppm or less.   The package for a semiconductor light-emitting device according to claim 1, wherein the metal component of the (C) curing catalyst contains platinum.   The package for a semiconductor light-emitting device according to claim 1, wherein the resin molded body is cured through hydrosilylation.   The said (B) filler contains an alumina, The package for semiconductor light-emitting devices of any one of Claims 1-3 characterized by the above-mentioned.   The package for a semiconductor light emitting device according to claim 1, wherein the filler (B) is surface-treated.   The package for a semiconductor light-emitting device according to claim 1, wherein the (B) filler has an aspect ratio of primary particles of 1.0 or more and 4.0 or less.   The resin molded body is characterized in that the weight ratio of (A) a base resin containing a polyorganosiloxane resin and (B) filler contained in the resin molded body is 15 to 60:85 to 40. The package for semiconductor light-emitting devices of any one of 1-6.   The package for a semiconductor light-emitting device according to claim 1, wherein the resin molded body has a light reflectance of 50% or more at a wavelength of 400 nm at a thickness of 0.3 mm.   The package for a semiconductor light-emitting device according to claim 1, wherein the resin molded body further includes a compound having an alicyclic hydrocarbon group.   The said resin molding is 45 degrees C or less consistently as operation temperature before a shaping | molding process, and the shaping | molding temperature at the time of a shaping | molding process is 300 degrees C or less, The any one of Claims 1-9 characterized by the above-mentioned. A package for a semiconductor light emitting device according to the item.   A semiconductor light emitting device comprising at least a semiconductor light emitting element, the package for a semiconductor light emitting device according to claim 1, and a sealing material.