JP2011249786A - Package for semiconductor light emitting device and light emitting device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a package having resistance to a temperature shock, to a peeling of a lead frame or sealing material from a resin molding body, and to a physical shock so as to eliminate a cracking and chipping.SOLUTION: A package for a semiconductor light emitting device comprises: a resin molding body containing a resin (A) and a filler (B). The resin molding body needs to have a damaging index less than or equal to 1.0, where the damaging index is 1000 times the reciprocal of Vickers hardness index. The Vickers hardness index is obtained in a Vickers hardness index measurement test which is conducted by pressing a pyramid-shaped indenter composed by a square quadrangular pyramid diamond having a facing angle α of 136° against a surface of a material by force of 0.3 kgf for 15 seconds to generate a dent thereon.

Description

  The present invention relates to an optical device, in particular, a package used for a semiconductor light emitting device including a semiconductor 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. For this reason, the resin molded body constituting the package of the semiconductor light emitting device expands due to heat generated from the semiconductor light emitting element, which causes a new problem that the lead frame and the sealing material are easily peeled off from the resin molded body. This phenomenon is particularly remarkable when a silicone resin is used.
In addition, if a hard resin molding is used to reduce the expansion coefficient against the thermal expansion as described above, the resin molding becomes brittle, and there are cases where scraps are generated during processing, and cracks occur during mounting. Sometimes chipping occurred. The present invention solves such problems and provides a package in which the lead frame and the sealing material are not easily peeled from the resin molded body, and further a package that is resistant to temperature shock, strong to physical shock, and is less likely to crack or chip. The purpose is to do.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by making the resin molded body used for the package a resin molded body having a specific scratch index.

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 resin and (B) a filler,
The resin molded body is formed with a trace by pressing a pyramid-shaped indenter made of a regular tetragonal pyramid diamond with a facing angle α = 136 ° against the material surface with a force of 0.3 kgf for 15 seconds. A package for a semiconductor light-emitting device, wherein a scratch index (μm ² / gf) represented by 1000 times the reciprocal of Vickers hardness is 1.0 or less in a hardness measurement test.

Further, in the resin molded body, in the cross-sectional observation of the resin molded body, the number of the (B) filler having a particle diameter of 0.2 μm or more and 50 μm or less included in the resin molded body cross section of 100 μm ² is 100 or more and 350 or less. It is preferable that

  Moreover, it is preferable that the said resin molding contains polyorganosiloxane as said (A) resin, and also contains (C) a curing catalyst.

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

  The weight ratio of the (A) resin (hereinafter sometimes referred to as “base resin”) and the (B) filler contained in the resin molded body is 15 to 60:85 to 40. preferable.

  The resin molded body preferably has a reflectance of light of a wavelength of 460 nm of 60% or more and a reflectance of light of a wavelength of 400 nm of 50% or more 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 45 ° C. or lower as an operating temperature before molding and 300 ° C. It is preferable to manufacture by molding at the following temperature.

  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 in which the lead frame and the sealing material are hardly peeled from the resin molded body. In a preferred embodiment, it is possible to obtain a package that is resistant to temperature shocks and that is resistant to physical shocks and is less likely to crack or chip.

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 the figure which observed the cross section of the resin molding which comprises the package of this invention by SEM (drawing substitute photograph). It is a graph which shows the result of having performed the lighting durability test of the semiconductor light-emitting device using the package of this invention. It is a figure which shows the adhesive evaluation result with the sealing material of a package of this invention, and a lead frame (drawing substitute photograph).

<1. Resin molding>
The package of the present invention includes at least a resin molded body containing (A) a resin and (B) a filler. The resin molding is characterized by having a scratch index (unit: μm ² / gf) of 1.0 or less. The resin molded body of the present invention has such a structure and becomes a resin resistant to temperature shock, and when used as a package resin for a semiconductor light emitting device, the lead frame and the sealing material do not peel from the resin molded body. The inventor has obtained a new finding that the package has a high thermal reliability.
So far, there has been no report of a problem that the resin molded body expands due to heat generated from the semiconductor light emitting element, and the resin molded body and the lead frame or the sealing material peel off. According to the present invention, by setting the resin molded body to a specific scratch index range, it is possible to prevent the problem of peeling of the metal wiring such as the resin molded body and the lead frame even when the semiconductor light emitting device is used for a long period of time. It solves new problems.

  In addition, unlike conventional silicone resins, it is resistant to physical impact and can be less likely to be cracked or chipped when mounted on a semiconductor light emitting device. Conventionally, the resin used for the package has been simply increased in hardness of the resin molded body in order to prevent cracking and chipping. The resin molded body provided in the package of the present invention is a resin molded body having the above-described excellent properties regardless of the hardness.

<1-1. Damage index of resin moldings>
The resin molded body provided in the package of the present invention makes a mark by pressing a pyramid-shaped indenter made of a regular quadrangular diamond having a facing angle α = 136 ° against the material surface with a force of 0.3 kgf for 15 seconds. In the Vickers hardness measurement test carried out in this way, 1000 times the reciprocal of Vickers hardness (unit is kgf / mm ² ) (this value is hereinafter defined as “scratch index.” The unit is μm ² / gf.). It is as follows.

Vickers hardness is calculated by the following method and calculation formula.
A trace is made by pressing the material surface with a force of 0.3 kgf for 15 seconds, and the surface area S (mm ² ) is calculated from the length d (mm) of the diagonal line of the dent remaining after removing the load. However, since the material is white, traces are observed using a confocal microscope. Test load F (kgf)
Is the Vickers hardness (HV) divided by the calculated surface area S (mm ² ).
HV (kgf / mm ² ) = F / S
= 2F [sin (α / 2)] / d ²
= 1.8544 (F / d ² )
F: Load (kgf) d: Trace width (mm)

The resin molded body to be measured is obtained by molding a resin composition, which will be described later, to a thickness of 1 mm, for example, and curing it by applying heat energy or light energy. In the present invention, the resin composition before curing is 10 kg / The resin molded body after being cured at 150 ° C. for 3 minutes under a pressure of cm ² and further post-cured at 200 ° C. for 10 minutes is measured. Curing in the present invention means a state change from a state showing fluidity to a state showing no fluidity. For example, even if the object is left to stand for 30 minutes in a state tilted 45 degrees from the horizontal, it is completely fluid. It is assumed that it has been cured.

The resin molded product of the present invention has a scratch index (μm ² / gf) of 1.0 or less, preferably 0.8 or less, more preferably 0.5 or less, particularly preferably 0.2 or less. As a result, the package is highly resistant to temperature shock, and does not peel off the lead frame and the sealing material from the resin molded body even in long-term use as a semiconductor light-emitting device. In addition, when the scratch index is in the above range, it is resistant to physical impact, and when the package is mounted on the semiconductor light emitting device, there is an effect that cracks and chips are hardly generated.

  An event with a low scratch index is generally so hard that it is not scratched (does not deform upon physical impact) (for example, diamond) or is highly elastic and scratches quickly Two types of material systems are shown, returning to their original shape (temporarily deforming in response to a physical impact but returning to their original shape). In any case, when used as a molded body, its shape is difficult to collapse, and it becomes a material that is very suitable for use as a container or as an aggregate. From this point of view, in the present invention, the scratch index is particularly required to be 1.0 or less. When the scratch index exceeds 1.0, when used as a container (especially in the case of a thin wall design), since it does not have sufficient hardness or elasticity, If the container is deformed during transportation on a belt conveyor, etc., and the contents in the container are deformed, or if a precise semiconductor element is mounted, use a gold wire that secures the semiconductor light emitting element to the package. It may be damaged.

  The package for a semiconductor light emitting device of the present invention having a scratch index of 1 or less is adopted as a package for a semiconductor light emitting device because it has the property of being temporarily deformed in response to a physical impact but returning to its original shape. In this case, for example, the following effects can be expected.

In the process of selecting a package after chip mounting, in many cases, it is selected by automatically evaluating the pass / fail of the package performance standards, and immediately after the selection, the package is quickly put into a storage bin according to pass / fail. In some cases, a strong physical shock is applied to the package, and cracking or chipping of the package is a problem. On the other hand, the package having a small scratch index according to the present invention can return to its original shape even when subjected to a physical impact, so that the number of defects can be suppressed and productivity deterioration can be improved.
In addition, when bonding a gold wire, an ultrasonic wave (and heat as necessary) is usually applied, but the ultrasonic wave often causes an extremely small crack in the package. On the other hand, the package having a small scratch index according to the present invention (preferably a package having sufficient elastic force) is not broken even under strong ultrasonic waves because of its strength and / or softness (elasticity). In addition, the ultrasonic wave can be changed to heat while allowing it to escape to some extent, and the melted portion of gold can be settled into a more stable structure, and the disconnection problem when used over a long period of time can be greatly improved.

  In the process of applying the sealing material to the package using a dispenser (applicator), the tip of the thin nozzle approaches the inside of the package and the liquid is applied. After application, the nozzle rises and returns to the standby state. The process of approaching the package is repeated. In this process, in order to stabilize the coating amount, it is desirable to apply the nozzle tip in contact with the package surface, or to make contact once after the application, but this is a reality from the viewpoint of package strength and deformation. Specifically, the tip of the nozzle cannot be applied in contact with the package surface. However, in the package with a small scratch index according to the present invention, even if the nozzle is relatively in contact with the surface of the package, scratches, chips, dents, deformations, etc. occur, or the capacity of the applied sealing material changes. It can be applied without any problems.

Further, a package having a scratch index of 1 or less has a sufficient elastic force. Since it has sufficient elastic force, the effects exemplified below are expected.
A package having a scratch index of 1 or less has the advantage that when it is handled, it can relieve its stress even if it receives an external force accompanied by an impact, and can quickly return to its original state even when deformed (that is, it is resistant to physical impact). Moreover, there is little powdering accompanying a micro crack etc., and the maintenance frequency of a conveying apparatus can be reduced.

  A package with a scratch index of 1 or less has good adhesion and stress relaxation capability in the package. Therefore, it can greatly suppress peeling at the interface with the metal electrode part and the sealing layer. it can. Especially in a semiconductor light emitting device that repeatedly turns on and off, each member repeatedly expands and contracts as the temperature rises and falls, but it is possible to suppress peeling and cracking due to stress at that time, and to improve durability as a semiconductor light emitting device. Can be improved.

When soldering, due to the difference in linear expansion coefficient between each member, for example, a gap is likely to occur between the metal electrode after bonding and the package (resin molded part), and the luminous efficiency is reduced even in a very narrow gap. There was a problem such as. On the other hand, since the package of the present invention can relieve stress and has good stretchability, it is difficult for gaps to occur during solder joining, and even if the temperature rises during lighting, the sealing material containing the phosphor is unlikely to leak. As a result, an effect of being resistant to temperature shock and improving durability can be obtained.
In recent years, an assembly itself as an LED module is increasingly required to have flexibility and flexibility in anticipation of application to a situation. When the material used for the semiconductor light-emitting device of the present invention is used for a resin molded body or other parts, even if a module manufactured in a flat or linear shape is bent at the time of use, it is difficult to cause defects due to destruction. Is obtained.

The scratch index is within the above range by adjusting the type and content of the crosslinking agent and catalyst control agent described later, adjusting the amount of filler to be contained in the resin molded body, or by surface treatment of the filler. Can be controlled. In addition, in order to make the extremely hard material, that is, the scratch index very small, it can be achieved by including a compound having an alicyclic hydrocarbon group, which will be described later, but by adjusting the type and content thereof Even the wound index can be adjusted.
More specifically, a method of making the material elastic by using a polymer in which cross-linking points that extend bonds in three or more directions are connected by long linear molecules, or a resin filled with a lot of fillers to make it harder On the contrary, it is possible to exemplify a method of softening by filling a small amount or adjusting the hardness by introducing a bulky functional group into the polymer side chain.

More specifically, it is preferable to use, for example, a polyorganosiloxane that is cured by hydrosilylation as the base resin. In this case, it is preferable to use a resin molded product having both the amount of vinyl groups and the amount of hydrosilyl groups in the base resin excluding the filler described later in the range of 10 mmol / g or less. That is, it is important to set the number of reaction points (crosslinking points) that cause hydrosilylation within a controlled range.
The amount of vinyl group contained in the base resin is preferably 0.1 to 5 mmol / g, more preferably 0.1 to 2.5 mmol / g, and still more preferably 0.1 to 2 mmol / g. The amount of hydrosilyl group contained in the base resin is preferably 5 mmol / g or less, more preferably 0.1 to 5 mmol / g, and still more preferably 0.2 to 2 mmol / g.
In addition to the amount of vinyl groups and the amount of hydrosilyl groups in the base resin being within the above range, the ratio of polyorganosiloxane to the filler specified later is preferably 15-60: 85-40, more preferably 15 -40: 85-60, more preferably 30-40: 70-60.
By combining these, it becomes possible to make the scratch index 1 or less.

When it is desired to further reduce the value of the scratch index, it is generally easy to take a technique of increasing the elasticity of the material rather than making the material extremely hard. It is preferable to disperse the points and to take a structure in which the cross-linking points are connected by long linear molecular chains. Specifically, a polyorgano having an average molecular weight of 500 or more and 200,000 or less, preferably 700 or more and 100,000 or less, more preferably 1000 or more and 20,000 or less and having vinyl groups only at both ends. It is effective to use a silicone obtained by addition polymerization of siloxane and a polyorganosiloxane having a hydrosilyl group randomly in the molecule.
In addition, a resin molded by liquid injection molding, which will be described later, is usually a thermosetting resin, and unlike a thermoplastic resin, it tends to be a resin having elasticity even under high temperatures and strong ultrasonic waves. For example, silicone that is heat-cured by a reaction of hydrosilylation is an example, and it has elasticity particularly at room temperature, and the damage index tends to be small.

<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 white pigment, the particle size and content of the white pigment, 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 molded object which does not contain a filler, ie, hardened only base resin. When the refractive index of the base resin molded body is within such a range, light reflection loss at the interface between the resin molded body 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.

<1-4. Hardness>
The resin molded body constituting the package of the present invention has a Shore A hardness of preferably 50 or more, more preferably 70 or more. In addition, the resin molded body constituting the package of the present invention has a Shore D hardness of preferably 10 to 95, more preferably 30 to 80.
When the hardness is in the above range, usually, it becomes possible to have elasticity together with necessary strength, and it is possible to make the material difficult to be destroyed by external force.

<2-1. Base resin>
The resin molded body constituting the package of the present invention may be either a thermoplastic resin or a thermosetting resin as long as the scratch index when cured is in the above range, and the type thereof may be There is no particular limitation. As thermoplastic resins, aromatic nylon resins, polyphthalamide resins (PPA), sulfone resins, polyamideimide resins (PAI), polyketone resins (PK), polycarbonate resins, polyphenylene sulfide (PPS), liquid crystal polymers (LCP) ), ABS resin, PBT resin and the like can be used. Moreover, as a thermosetting resin, an epoxy resin, a modified epoxy resin, a silicone resin, a modified silicone resin, an acrylate resin, a urethane resin, etc. can be used. Among these, it is preferable to use a silicone resin from the viewpoint of heat resistance and the like.

When a silicone resin is used as the base resin in the resin molded body of the present invention, polyorganosiloxane is used.
The polyorganosiloxane 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 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, Examples include compounds having Si—C—C—Si bonds at the cross-linking points obtained by mixing in a quantity ratio of 2.0 times or less and reacting in the presence of an addition condensation catalyst such as (C3) Pt catalyst. it can.

(C1) As a silicon-containing compound having an alkenyl group, the following general formula (2)
R _n SiO _{[(4-n) / 2]} (2)
And an organopolysiloxane 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.
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. Therefore, it is difficult to synthesize this organopolysiloxane.

  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 ratio 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 the hydrosilyl group is usually 0.5 mol or more with respect to 1 mol of the alkenyl group, preferably It is 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.

  Further, the viscosity of the base resin before addition of 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, Most preferably, it is 4,000 or less. The lower limit is not particularly limited, but is generally 15 cp or more in relation to volatility (boiling point).

  Furthermore, 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 1000 or more for the purpose of reducing volatile components (to maintain adhesion to other members), and 20,000 or less for ease of handling of the material before molding.

  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 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 _mn (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.

Preferred materials among the condensed polyorganosiloxanes will be described below.
When polyorganosiloxane is used in a semiconductor light emitting device in general, the adhesion to the semiconductor light emitting element, the substrate on which the semiconductor element is arranged, the metal wiring, etc. may be weak. Therefore, in particular, a condensed polyorganosiloxane having one or more features of the following [1] and [2] is also 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 a region where the chemical shift is −80 ppm or more and less than −40 ppm with respect to the silicone rubber, and the half width of the peak is 0.3 ppm or more and 5.0 ppm or less.

In the present invention, in addition to the above features [1] to [2], a polyorganosiloxane having the following feature [3] may also be used.
[3] It has 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. 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 product in the cross section observation of the resin molded product is 100 or more and 350 or less. Is preferred.

A resin molded body used for a package of a semiconductor light emitting device is generally manufactured by blending a filler with a base resin for the purpose of maintaining strength. When such a resin molded body is processed for a package, the filler is likely to be exposed on the fracture surface generated when the conventional resin is processed. When the resin with the exposed filler is used for a long period of time, the resin is deformed by heat generated from the semiconductor light emitting element, and a gap is formed between the filler and the resin, so that contaminants are easily adsorbed. As a result, the present inventors have found that the luminance of the light emitting device decreases. Such a problem has not been conventionally known.
Then, the present inventors have conceived to prevent a decrease in luminance caused by exposure of the filler by controlling the number of fillers present on the fracture surface of the resin molded body.

  Among the fillers contained in the resin molded body, even if they are present, there is almost no influence on the physical property improving effect of the resin molded body of the present invention even if they are present because of their small size and surface area. On the other hand, when the size is 0.2 μm or less, it is difficult to observe with an electron microscope, which will be described below, and the diameter of the filler is too small, and its presence hardly affects the effect of the present invention. The number of fillers of 2 μm or more and 50 μm or less was specified.

In the present invention, in the cross-sectional observation of the resin molded body, when the number of fillers contained per 100 μm ² of the cross section of the resin molded body is 350 or more, the amount of the exposed filler is large, and the light emitting device can be used over a long period of use. In addition to the decrease in brightness, the material becomes brittle. Therefore, when such a resin molded body is used as a package, there is a tendency that a light emitting device having long-term reliability is not obtained.
On the other hand, since the filler content is too small when the number of fillers is 100 or less, the package using such a resin molded body does not have a sufficient function as a reflector, and as a result It tends to cause a decrease in luminance.
From the viewpoint of having further long-term reliability, in the cross-sectional observation of the resin molded body, the number of fillers contained per 100 μm ² of the resin molded body cross section is more preferably 120 to 300, and 150 to 280. More preferably.

A method for measuring the white pigment 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 cut 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 .

Further, the inventors have also found that 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, it was found that the filler on the fracture surface of the resin molded body is covered with the coating of the resin molded body and is not easily 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 alumina (aluminum oxide), 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. 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 1.0 to 4.0, and more preferably 1.0 to 3.0. When the aspect ratio is in the above range, high reflectivity is likely to be manifested by scattering, and the reflection of light having a short wavelength in the near ultraviolet region is particularly large.

Moreover, when using a white pigment as said filler, it is preferable that a primary particle diameter is 0.1 micrometer or more and 2 micrometers or less. 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 a low reflectance because the scattered light intensity is low, and if the primary particle diameter is too large, the white pigment tends to have a forward scattering tendency, although the scattering intensity increases. Therefore, the reflectance tends to be small. A white pigment having a primary particle size 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 μm to 50 μm, and more preferably 0.2 μm 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 particle in the present invention is the smallest unit that can be clearly distinguished from other particles constituting the powder, and the primary particle size is the particle size of the primary particle measured by observation with an electron microscope such as SEM. Say. On the other hand, the agglomerated particles formed by agglomerating the primary particles are called secondary particles, and the secondary particle size is not limited to observation with an electron microscope such as SEM, and the powder is used in an appropriate dispersion medium (for example, water in the case of alumina). The particle diameter measured by a particle size analyzer etc. after being dispersed. The particle diameter or particle diameter described in the present specification refers to the secondary particle diameter unless otherwise specified. When the particle diameter varies, several points (for example, 10 points) can be observed with an 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 adhesion with the base 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.

  In addition, the filler content in the resin molded body is such that the weight ratio of the base resin to the filler is 15 to 60:85 to 40, and it becomes easy to control the scratch index of the resin molded body in a suitable range. As a result, it is easy to obtain a resin molded body that is resistant to temperature impact, difficult to peel off the lead frame and the sealing material from the resin molded body, and is resistant to physical impact and does not crack or chip. The above range is more preferably 30-40: 70-60.

  By selecting a good filler type and a content in a suitable range according to each system, it is possible to maintain the elasticity and reduce the scratch index.

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, and EGP20.
Examples include 0-10, EFH75-10, REV1, REV7, REV8 manufactured by NSG Vetrotex.

  Even when these materials are added, it is possible to reduce the scratch index by selecting a type suitable for each system and a content in a suitable range.

<2-3. Curing catalyst>
The curing catalyst in the present invention is a catalyst for curing the base resin. By adding a curing catalyst, the polymerization reaction is accelerated and cured.

  When the resin molded product of the present invention is 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, platinous chloride, chloroplatinic acid, reaction product of chloroplatinic acid and monohydric alcohol, complex of chloroplatinic acid and olefins, platinum-based catalyst such as platinum bisacetoacetate, palladium-based catalyst, rhodium-based Examples include platinum group metal catalysts such as catalysts. The compounding amount of the addition polymerization catalyst is usually 1 ppm or more, preferably 2 ppm or more, usually 500 ppm or less, preferably 100 ppm or less, based on the total weight of the components (C1) and (C2) as a platinum group metal. Preferably it is 20 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.) can be avoided.

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 preferably 0.01 to 10% by weight, preferably 0.05 to 6% by weight, based on the total weight of the components represented by the above formulas (3) and (4). It is more preferable that
When the addition amount is in the above range, the curability, storage stability, and package quality of the semiconductor light emitting device package material are good. If the amount added exceeds the upper limit value, a problem arises in the storage stability of the package material. If the amount added is less than the lower limit value, the curing time becomes longer, the package productivity decreases, and the package quality decreases due to uncured components.

<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. In order to disperse the silica fine particles uniformly and to obtain a material having sufficient elasticity, the surface of the silica fine particles is preferably subjected to trimethylsilylation treatment. Furthermore, since it becomes a stable material when the remaining acid content is neutralized with an amine component, it is more preferable to treat with hexamethyldisilazane. The balance between the effect of addition dispersibility and wettability, preferably 5m ² / g~400m ² / g as a specific surface area by BET method of the silica fine particles, and more preferably 150m ² / g~250m ² / g.
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 ”.

  It is also preferable to increase the strength of the molded body by using glass fiber, glass fiber, glass powder or the like as an additive.

In addition, a crosslinking agent can be added in order to adjust the scratch index of the molded article obtained by molding the resin composition. 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), as the unsubstituted or substituted monovalent hydrocarbon group represented by R ⁷ , for example,
A lower alkyl group having 10 or less carbon atoms, preferably 1-8, particularly preferably 1-6, such as a methyl group, an ethyl group, a propyl group, a butyl group;
Alkenyl groups such as vinyl group, allyl group, isopropenyl group, butenyl group, hexenyl group; (meth) acryloyl group;
(Meth) acryloyloxy group;
A cycloalkyl group such as a cyclohexyl group;
Aryl groups such as phenyl, tolyl and naphthyl;
Aralkyl groups such as benzyl group and 2-phenylethyl group;
And a group in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms, for example, chloromethyl group, 3,3,3-trifluoropropyl group, etc. 1 to 8, particularly preferably 1 to 6. 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 base resin is silicone, the amount of the crosslinking agent contained in the resin composition is preferably 0 to 30 parts by weight, more preferably 0 to 20 parts per 100 parts by weight of the polyorganosiloxane. Part by weight, particularly preferably 0 to 10 parts by weight. If the blending amount is more than 30 parts by weight, the hardness of the resin increases and the value as a scratch index tends to be too high.

It is also preferable to add a rubbery elastic body such as powdered silicone rubber for the purpose of increasing the elasticity of the resin molded body to improve physical characteristics and reduce the scratch index.
The addition amount is preferably 0 to 30 parts by weight, more preferably 0 to 20 parts by weight, and particularly preferably 0 to 5 parts by weight with respect to 100 parts by weight of the resin molded body. When the blending amount is more than 30 parts by weight, the strength expressed by the covalent bond as the polymer or by the entanglement between the molecules decreases, and conversely, the molded product becomes brittle.

  Further, a curing retarder (catalyst control agent) can be added in order to adjust the value of the scratch index of the molded article obtained by molding the resin composition. 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. . Most preferred is 1,2,4-trivinylcyclohexane from the viewpoint of material that gives sufficient elasticity and the economical viewpoint that it is easily available.
The content of the compound having an alicyclic hydrocarbon group can be appropriately set, but is preferably 0 to 10 parts by weight, more preferably 2 to 5 parts by weight 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. Method for producing resin molded body of the present invention>
The resin molding which the package for semiconductor light-emitting devices of this invention is provided is obtained by shape | molding the resin composition demonstrated below.

<3-1. Manufacturing method of resin composition>
(Raw material)
As a raw material to be used, silica fine particles, a curing catalyst, a curing retarder, and other additives can be appropriately used in addition to the above-described (A) polyorganosiloxane and (B) filler.
Here, the blending amount of each raw material is not particularly limited as long as it is within the range in which the effect of the present invention can be obtained, but is preferably within the above-described range.

(Mixing method)
When mixing each raw material, polyorganosiloxane can be used as a liquid medium. For example, a predetermined amount of polyorganosiloxane, filler, curing catalyst, etc. are weighed and mixed by a conventionally known method such as mixing with a stirrer, mixer, high speed disper, homogenizer, three rolls, kneader, centrifugal defoaming device, etc. can do.
(A) There is no restriction | limiting in particular as a mixing method in the case of mixing a filler with (B) polyorganosiloxane, Even if it uses the apparatus of the system which uses a centrifugal force, the apparatus of the system which stirs and mixes with a stirring blade is used. May be. Among them, as a particularly preferable stirring device for manufacturing a package having a scratch index of 1 or less, a method of mixing by utilizing both rotation and revolution forces from the viewpoint of quickly manufacturing a material having sufficient elasticity. preferable. Specific examples include Nintaro Awatori manufactured by Thinky, and planetary mixers manufactured by Dalton and Primics. By using these apparatuses, (A) a mixture having a high degree of dispersion of the filler can be obtained, and an improvement in the elastic force of the resin composition after mixing is expected. Furthermore, there is little unevenness and uniform mixing is possible, and chipping, cracking, and dusting during use can be suppressed.
Furthermore, in order to obtain a uniform material with no unevenness in filler dispersion, it is preferable to have a vacuum defoaming step when stirring, and even when using a planetary mixer. It is preferable to carry out a stirring and mixing operation.

(Mixing form)
Although all the above-mentioned raw material components may be mixed to produce a one-component resin composition, it may be a two-component type. In the case of the two-component type, for example, (i) a polyorganosiloxane resin composition containing polyorganosiloxane, a filler, and silica fine particles as main components, and (ii) a cross-linking agent containing a curing catalyst and a curing retarder as main components. Two liquids can be prepared, and (i) the polyorganosiloxane resin composition and (ii) the crosslinking agent liquid can be mixed immediately before use.

(Storage of resin composition)
There are no particular restrictions on the method of storing the resin composition, but if the environmental temperature during storage is 15 ° C. or lower, the rapid progress of the curing reaction is suppressed, thereby preventing defective filling of the mold during molding. This is preferable. Among them, if the environmental temperature during storage of the resin composition is higher than 0 ° C, the amount of SiH tends to decrease during storage, and if the environmental temperature is 0 ° C or lower, preferably -20 ° C or lower, Since the SiH abundance tends to increase, it is preferable to adjust the environmental temperature during storage so that the SiH abundance falls within a specific range.

<3-2. Molding method>
Examples of the molding method of the resin molded body of the present invention include a compression molding method, a transfer molding method, and an injection molding method. Among these, when a thermosetting resin (for example, polyorganosiloxane that is heat-cured by a hydrosilylation reaction) is injection-molded, the scratch index tends to be small and cracks and chips are less likely to occur, which is preferable. Further, the injection molding method has a high economic effect because the initial investment amount for the apparatus is small compared to the compression molding method and the like.

  The resin molded body is preferably manufactured by molding at a temperature that is consistently 45 ° C. or lower and 300 ° C. or lower as a process temperature and a storage temperature for manufacturing a material before molding.

  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 speed of the material, but is usually 3 seconds or more and 1200 seconds or less, preferably 5 seconds or more and 1000 seconds or less, more preferably 10 seconds or more and 900 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 according to 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 1000 seconds or less, more preferably 10 seconds or more and 900 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 a few seconds or less. The molding time may be appropriately selected according to 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 1000 seconds or less, more preferably 10 seconds or more and 900 seconds or less. It is.
As a combination of temperature and time during molding, in any molding method, it is preferable to heat at a temperature of 300 ° C. or lower for 20 minutes or less from an economical viewpoint. The short molding time contributes economically, suppresses deterioration of the resin composition, and can suppress the sedimentation of the filler during heating. In addition, by molding after a short period of temperature increase / decrease, it is possible to suppress the generation of a gap between the resin molded body and the electrode surface in the subsequent soldering process, thereby improving adhesion and durability. be able to.

  In any molding method, post-curing can be performed as required, 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 250 ° C. or lower. It is. The post-curing time is usually 1 minute or more and 24 hours or less, preferably 3 minutes or more and 10 hours or less, more preferably 5 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.
FIG. 1 shows an example of a semiconductor light emitting device, which includes a semiconductor light emitting element 1, a package made of a resin molded body 2 and a metal lead frame 5, a bonding wire 3, a sealing material 4, and the like.

  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 illustrated in FIG. 1, a plurality of semiconductor light emitting elements can be arranged in a linear shape or a 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. Further, when the semiconductor light emitting element 1 is not in contact with the lead frame serving 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 sealing material 4 is a mixture in which a phosphor is mixed with a binder resin, and the phosphor 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 0.1 to 10 mm, and more preferably 0.15 to 5 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 200 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.

[Example 1]
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: 1.48, purity: 99.12%), 0.25 g of surface Treated (trimethylsilyl-treated) fumed silica, phenyl group-free silicone (vinyl group: 0.3 mmol / g contained, platinum: 8 ppm contained, viscosity 3700 cp at room temperature. Hereinafter, this silicone is referred to as “phenyl group-free silicone E”. 3.04 g, phenyl group-free silicone (vinyl group: 0.1 mmol / g contained, hydrosilyl group: 4.6 mmol / g contained, viscosity at room temperature: 600 cp. This silicone is hereinafter referred to as “phenyl group”. Non-containing silicone F ”)) 0.30 g, phenyl group-free silicone containing a retarding component (catalyst control component) (Vinyl group: containing 0.2 mmol / g, hydrosilyl group: containing 0.1 mmol / g, alkynyl group: containing 0.2 mmol / g, 500 cp. Hereinafter, this silicone is referred to as “phenyl group-free silicone G”. 0.15 g) was added, and the mixture was stirred with Thinky's Awatori Kentaro ARV-200 in a room temperature atmosphere. 0.25 g of surface-treated (trimethylsilyl-treated) fumed silica was added again, and white resin composition 1 was obtained by carrying out vacuum defoaming with ARV-200 in a room temperature atmosphere.

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. Resin molded bodies 1 to 3 were obtained by heating and pressurizing at 150 ° C. for 3 minutes in the air, and further post-curing for 10 minutes at 200 ° C. in a ventilation dryer. In addition, the ratio of the base resin and the filler in the resin molded bodies 1 to 3 is 36.8: 63.2.

[Measurement of physical properties]
The obtained resin molded body 1 was measured for reflectance, the resin molded body 2 was damaged index, and the resin molded body 3 was measured for hardness.
The reflectance is the reflectance of light having a wavelength of 400 nm and the reflectance of light having a wavelength of 460 nm using a SPECTROPHOTOTER CM-2600d manufactured by Konica Minolta Co., Ltd. with respect to the resin molded body 1 (thickness: 0.3 mm). Was measured.
The hardness was measured according to JIS K6253 by using a durometer for Shore A and Shore D on two sheets of resin molded body 3 (3.0 mm thick).
On the other hand, the scratch index is 0.3 kgf on the surface of the resin molded body with a pyramid-shaped indenter made of a regular quadrangular diamond having a facing angle α = 136 ° with respect to the resin molded body 2 (1.0 mm thick). The surface area S (mm ² ) was calculated from the diagonal length d (mm) of the dent remaining after removing the load, and was measured.

The reflectance of the resin molded body 1 having a thickness of 0.3 mm was 94.2% under light irradiation of 400 nm and 94.3% under light irradiation of 460 nm. The hardness of the resin molded body 3 having a thickness of 3.0 mm was 91 for Shore A and 33 for Shore D, and the scratch index of the resin molded body 2 having a thickness of 1.0 mm was 0 μm ² / gf.

Samples molded to a thickness of 0.3 mm on a silver plate will not be peeled off or destroyed when removed from the mold, and then peeled off from the silver surface even if a slight force is applied from the side with a spatula. There was nothing to do or collapse.
Therefore, it was found that the sample having a scratch index of 1.0 μm ² / gf or less is not brittle and is a material that adheres well to the silver surface.
In addition, the average number of fillers in resin molded body 1 100 μm ² was counted as 183. The measurement method was performed as follows using SEM S800 manufactured by HITACHI.
1) The resin molded body 1 was cut into small pieces with scissors.
2) It was embedded and fixed with a two-component mixed epoxy.
3) Using an ultramicrotome UC6 and FC6 manufactured by Leica Microsystems, cutting was performed with a diamond knife at a set temperature of -120 ° C.
4) The etched surface was ion-etched with a self-made device.
5) Conductive treatment was performed with an osmium plasma coater manufactured by Philgen.
6) Observation was performed with SEM S800 manufactured by HITACHI.
7) The number of particles having a diameter of 0.2 μm or more and 50 μm or less in 100 μm ² was counted. A state observed with an SEM is shown in FIG.

[Example 2]
1.82 g of phenyl group-free silicone E, 0.18 g of phenyl group-free silicone F, 0.09 g of phenyl group-free silicone G containing a curing retarding component (catalyst control component), 1,2,1 from Aldrich 1 linear silicone (average molecular weight: 5600, viscosity at room temperature: 17 cp) containing 0.37 g of 4-trivinylcyclohexane and 0.5 (mol) of hydrosilyl group based on the number of Si (mol number) A resin molded body 4 was prepared in the same manner as in Example 1 except that 0.04 g was used (the number of moles of total hydrosilyl groups was adjusted to 1.1 times the number of moles of total vinyl groups). In addition, the ratio of the base resin and the filler of the resin molded body 4 is 36.8: 63.2.
When the hardness of the resin molded body 4 (3.0 mm thickness) was measured, it was 73 for Shore D, which was higher than that of the resin molded body 3 of Example 1.

[Example 3]
1.75 g of phenyl group-free silicone H (vinyl group: 1.2 mmol / g contained, platinum: 6.8 ppm contained), phenyl group-free silicone I (vinyl group: 0.3 mmol / g contained, hydrosilyl group: 1 .8 mmol / g) was used in the same manner as in Example 1 except that 1.75 g was used (the viscosity at room temperature after mixing both silicones was 1460 cp). In addition, the ratio of the base resin and the filler of the resin molded body 5 is 36.8: 63.2.

As in Example 1, when the physical properties of the resin molded body 5 were measured, the reflectance of the resin molded body 5 having a thickness of 0.3 mm was 94.6% under light irradiation of 400 nm, and under light irradiation of 460 nm. It was 94.6%. Further, the hardness of the resin molded body 5 having a thickness of 3.0 mm was greater than 90 for Shore A, 40 for Shore D, and the scratch index of the resin molded body 5 having a thickness of 1.0 mm was 0 μm ² / gf. .

[Comparative Example 1]
Example 1 A commercially available silicone-based packaging material having a hardness increased so that spherical silica having a diameter of several μm to 100 μm and titania as a white pigment, 80% by weight or more of the resin molded body as a total amount of filler, and Shore D of 90 or more Was molded under the same conditions as above to obtain a resin molded body 6. The damage index of the resin molded body 6 having a thickness of 1.0 mm was 12 μm ² / gf.
When 4 pieces of 5 mm sq. 1 mm thick pieces of the resin molded body 6 were put in a glass sample bottle and shaken 20 times (about 4 times / second) and visually observed, a very large amount of fine powder adhered to the inner wall of the glass bottle. Admitted. Therefore, it was found that this silicone-based package material is high in hardness but brittle.

[Comparative Example 2]
The damage index of the ceramic LED package (M5050N (KA-6)) manufactured by Kyoritsu Elex Co. was 1.3 μm ² / gf. When these four packages were placed in a glass sample bottle and shaken 20 times (about 4 times / second) and visually observed, no chipping or generation of fine powder was observed.

[Comparative Example 3]
The damage index of polyphthalamide (Amodel A4122) manufactured by Solvay Advanced Polymers when the thickness was 1.0 mm was 16 μm ² / gf.

[Comparative Example 4]
Instead of surface-treated (trimethylsilyl-treated) fumed silica, glass fiber (single fiber diameter: 6 μm, average fiber length: 50 μm, surface silane coupling-treated) 1.5 g, phenyl group-free silicone E 2.17 g Resin molded body 7 was prepared in the same manner as in Example 1 except that 0.22 g of phenyl group-free silicone F and 0.11 g of phenyl group-free silicone G containing a curing retardation component (catalyst control component) were used. did. In addition, the ratio of the base resin and the filler of the resin molded body 7 is 25.0: 75.0.

As in Example 1, when the physical properties of the resin molded body 7 were measured, the reflectance of the resin molded body 7 having a thickness of 0.3 mm was 90.7% under light irradiation of 400 nm, and under light irradiation of 460 nm. It was 92.8%. The hardness of the resin molded body 7 having a thickness of 3.0 mm was 96 for Shore A and 58 for Shore D, and the scratch index of the resin molded body 7 having a thickness of 1.0 mm was 487 μm ² / gf.

  The resin molded body 7 molded with a thickness of 0.3 cm on the silver plate was found to be peeled when removed from the mold. Further, the resin molded body 7 molded to a thickness of 0.3 mm on a silver plate whose surface was roughened with # 80 sandpaper was also peeled when removed from the mold. Therefore, it was found that the silicone-based resin molded body 7 having a large scratch index has poor adhesion to silver. In the resin molded body 7, it is estimated that the damage index has increased due to a decrease in the elasticity of the material due to the addition of glass fiber.

[Durability evaluation test]
The white resin composition obtained in Example 3 was formed by heat injection molding together with a silver lead-plated copper lead frame, and 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 was formed. A package 1 was obtained by molding into a cup-shaped surface mount package. In addition, a PPA package (package 2) of Comparative Example 3 having the same shape as this 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, stirring blade Were weighed in a 500 ml three-necked Kolben equipped with a fractionating tube, a Dimroth condenser and a Liebig condenser, and 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. 4, it was found that when the package 1 according to Example 3 was used, the output retention rate was clearly higher than when the package 2 according to Comparative Example 3 was used.

  Further, the package 1 of Example 3 and the package 2 of Comparative Example 3 are stored for 24 hours in an atmosphere at a temperature of 85 ° C. and 85% RH (relative humidity), and immediately after taking out from the atmosphere, on a hot plate at 260 ° C. Then, a test for confirming the adhesion (peeling) between the sealing material and the package surface or the lead frame surface was also conducted. As a result, as shown in FIG. 5, peeling was recognized only in the case of the package 2 made of PPA (polyphthalamide) of Comparative Example 3.

[Adhesion evaluation test]
For the package 1 of Example 3 and the package 2 of Comparative Example 3 and the ceramic LED package of Comparative Example 2 created in the durability test, the adhesion between the lead frame and the resin molded body by the following method ( A confirmation experiment of peeling was performed.
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 derived from Example 3, no red color was observed between the lead frame and the resin molded body. On the other hand, in the case of the package 2 derived from the comparative example 3 and the ceramic package derived from the comparative example 2, both the red color was confirmed and it was found that there was peeling between the lead frame and the resin molded body or the ceramic material. It was.

[Discussion]
From these results, first, even in the same silicone material as in the present invention as in Comparative Example 1, although the hardness is extremely hard based on the conventional idea, the scratch index is 12 μm ² / Since it was gf, it was found that the material was very brittle by checking the hand movement in the glass bottle.
From Comparative Example 4, it can be seen that even with the same silicone type, depending on the difference in addition of filler type and amount, the loss of elasticity increases, the scratch index increases, and the adhesion to the metal frame tends to deteriorate. It was.
Further, in the case of the ceramic LED package having a scratch index of 16 μm ² / gf in Comparative Example 2, peeling was recognized between the resin molded body and the lead frame from the result of the adhesion evaluation test, as described at the beginning. In addition, since a sintering process is required, it is inferior in economic efficiency as compared with those made of silicone or other resin materials.
Further, in the case of the LED package derived from the polyphthalamide material of Comparative Example 3, there is a problem that the actual LED output maintenance rate is low as compared with the case where the silicone LED package is used from the durability evaluation test. From the adhesive evaluation test, it has been found that there is a problem that peeling easily occurs between the lead frame.
Therefore, it has been found that the silicone material is excellent, and in particular, the silicone material having a scratch index of 1.0 μm ² / gf or less is preferable.

DESCRIPTION OF SYMBOLS 1 Semiconductor light-emitting device 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 resin and (B) a filler,
The resin molded body is formed with a trace by pressing a pyramid-shaped indenter made of a regular tetragonal pyramid diamond with a facing angle α = 136 ° against the material surface with a force of 0.3 kgf for 15 seconds. A package for a semiconductor light-emitting device, wherein a scratch index (μm ² / gf) represented by 1000 times the reciprocal of Vickers hardness is 1.0 or less in a hardness measurement test. In the resin molded body, the number of the (B) filler having a particle diameter of 0.2 μm or more and 50 μm or less contained in a cross section of the resin molded body of 100 μm ² in the cross-sectional observation of the resin molded body is 100 or more and 350 or less. The package for a semiconductor light emitting device according to claim 1.   The package for a semiconductor light-emitting device according to claim 1, wherein the resin molded body contains polyorganosiloxane as the resin (A) and further contains (C) a curing catalyst.   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.   6. The resin molded body according to claim 1, wherein a weight ratio of the (A) resin and the (B) filler contained in the resin molded body is 15 to 60:85 to 40. 6. A package for a semiconductor light-emitting device according to claim 1.   The package for a semiconductor light emitting device according to claim 1, wherein the resin molded body has a thickness of 0.3 mm and a reflectance of light having a wavelength of 460 nm is 60% or more.   The package for a semiconductor light-emitting device according to claim 1, wherein the resin molded body has a thickness of 0.3 mm and a reflectance of light having a wavelength of 400 nm is 50% or more.   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 is manufactured by the shaping | molding process in the temperature of 300 degrees C or less, The any one of Claims 1-9 characterized by the above-mentioned. The package for semiconductor light-emitting devices of description.   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.