JP2017183506A - Resin mold material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin mold material for a semiconductor light-emitting device, which can manufacture a black package without unevenness.SOLUTION: A resin mold material for a semiconductor light-emitting device contains as necessary components: (A) polyorganosiloxane, (B) titanium-based black pigment, and (C) curing catalyst.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a material for a resin molded body used in a semiconductor light emitting device including a light emitting element such as a light emitting diode, and the molded body.

  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. In addition, the structure which consists of conductive metal wirings, such as a lead frame, and an insulating resin molding is called a package.

  Semiconductor light-emitting devices that require directivity for light emission are not only light emitted from a semiconductor light-emitting element in a desired direction, but also light emitted in a direction different from the purpose, such as resin wiring, metal wiring such as a lead frame, In addition, the light is reflected in a desired direction by a reflecting material or the like to increase luminous efficiency. At this time, in order to improve the contrast of the emitted light, a technique for darkening or blackening at least one surface of the substrate, particularly the surface directed forward is disclosed (see Patent Document 1).

  Further, a technique for forming a dark color layer on the upper surface of the package body is disclosed in order to solve the problem that light is reflected on the surface of the sealing resin in the LED and the display contrast is lowered (patent). Reference 2).

JP 2009-239313 A JP 2011-199219 A

  Attempts have been made to improve the contrast by making at least part of the package dark or black, but there are problems that may occur when a black package is actually made using a black pigment or the like. In the above patent document, no particular mention is made.

  The inventors of the present invention have added a black pigment to the resin composition to produce a black resin molding material, and have found a new problem that the black package, which is a molding, is likely to be uneven. It is an object of the present invention to provide a material for a resin molded body for a semiconductor light emitting device that can produce a black package without unevenness.

The present inventors have repeatedly studied to solve the above problems, and by preparing a black resin molded material using a specific base resin and a specific black pigment, the dispersibility of the pigment in the material is good. The present inventors have found that a package without unevenness can be obtained even when formed into a molded body, and completed the invention.
That is, the present invention is as follows.

(1) A resin molded material for a semiconductor light-emitting device containing (A) polyorganosiloxane, (B) a titanium-based black pigment, and (C) a curing catalyst as essential components.
(2) The polyorganosiloxane (A) is an addition type polyorganosiloxane (1
The material for resin moldings as described in).
(3) The resin molded body according to (1) or (2), wherein the content of the (B) titanium-based black pigment is 0.01 to 30% by weight of the entire resin molded body material for a semiconductor light emitting device. material.
(4) The resin molded material according to any one of (1) to (3), wherein the (B) titanium-based black pigment contains titanium nitride.
(5) The resin-molded material according to any one of (2) to (4), wherein (A) the addition-type polyorganosiloxane is a thermosetting polyorganosiloxane that is liquid at normal temperature and normal pressure.
(6) The resin molded material according to any one of (1) to (5), further comprising (D) silica.
(7) The resin molded body material according to any one of (1) to (6), which is an injection molding material.
(8) The resin molded body material according to any one of (1) to (7), further comprising (E) a curing rate control agent.
(9) The resin molded body according to any one of (1) to (8), wherein the viscosity at a shear rate of 100 s ⁻¹ at 25 ° C. is 10 Pa · s or more and 10,000 Pa · s or less. material.
(10) A semiconductor light emitting device package comprising the material for a semiconductor light emitting device according to any one of (1) to (9).

  If the resin molding material of this invention is used, the resin molding material for semiconductor light-emitting devices which can manufacture a black package without a nonuniformity can be obtained.

It is sectional drawing which shows the structure of the one aspect | mode of a semiconductor light-emitting device roughly. It is sectional drawing which shows the structure of the one aspect | mode of a semiconductor light-emitting device roughly.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
<1. Materials for resin moldings for semiconductor light emitting devices>
The resin molded body material for a semiconductor light emitting device is a material used for molding a resin molded body for a semiconductor light emitting device. Specifically, it contains (A) a polyorganosiloxane, (B) a titanium black pigment, and (C) a curing catalyst.
Here, the resin molded body for a semiconductor light emitting device is a molded body obtained by curing a material, and becomes a package for a semiconductor light emitting device by being molded together with a conductive metal wiring such as a lead frame. The semiconductor light emitting device is a light emitting device including a semiconductor light emitting element in the resin molded body for the semiconductor light emitting device. A schematic cross-sectional view of a semiconductor light emitting device is shown in FIG.

<1-1. (A) Polyorganosiloxane>
The polyorganosiloxane refers to a polymer material 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. Here, the polyorganosiloxane is preferably liquid at normal temperature and normal pressure. This is because the material becomes easy to handle when molding the resin molded body for a semiconductor light emitting device. Polyorganosiloxanes that are solid at room temperature and normal pressure generally have a relatively high hardness as a cured product, but have low energy required for destruction and low toughness, light resistance and heat resistance are insufficient, and light This is because many tend to discolor due to heat.
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 one atmospheric pressure. The liquid means a fluid state.

Polyorganosiloxane usually 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 or more and less than 1, and M + D + T + Q = 1.

The unit constituting the main polyorganosiloxane is monofunctional [R ₃ SiO _0.5 ] (triorganosyl hemioxane), bifunctional [R ₂ SiO] (diorganosiloxane), trifunctional [RSiO _1.5 ] (organosilsesquioxane), tetrafunctional [SiO ₂ ] (silicate), and by changing the composition ratio of these four units, the difference in the properties of the polyorganosiloxane appears. The polyorganosiloxane is synthesized by appropriately selecting the desired characteristics.
The above-mentioned polyorganosiloxane having 1 to 3 functional units can be synthesized based on a series of organosilicon compounds called organochlorosilanes (general formula R _n SiCl _4-n (n = 1 to 3)). it can. For example, methylchlorosilane can be synthesized by directly reacting methyl chloride and silicon Si at a high temperature under a Cu catalyst, and silanes having an organic group such as a vinyl group can be synthesized by a general synthetic organic chemistry method. can do.
Silanol is produced when the isolated organochlorosilane is mixed alone or in an arbitrary ratio and hydrolyzed with water. When this silanol is dehydrated and condensed, polyorganosiloxane, which is the basic skeleton of silicone, is synthesized. .

  Polyorganosiloxane can be cured by applying heat energy, light energy, or the like in the presence of a curing catalyst. Here, curing refers to changing from a state showing fluidity to a state showing no fluidity. For example, even if the object is left at an angle of 45 degrees from the horizontal for 30 minutes, it is fluid. The state is referred to as an uncured state, and a state having no fluidity can be determined as a cured state.

When the polyorganosiloxane is classified according to the curing mechanism, polyorganosiloxanes such as an addition polymerization curing type, a condensation polymerization curing type, an ultraviolet curing type, and a peroxide crosslinking type can be generally exemplified. Among these, addition polymerization curing type (addition type polyorganosiloxane) and condensation curing type (condensation type polyorganosiloxane) are preferable. Among these, a polyorganosiloxane type that does not generate by-products and cures by hydrosilylation (addition polymerization) in which the reaction is not reversible is more preferable. This is because when a by-product is generated during the molding process, the pressure in the molded container tends to increase or it remains as foam in the cured material.
Hereinafter, addition-type polyorganosiloxane and condensation-type polyorganosiloxane will be described.

<1-1-1. Addition type polyorganosiloxane>
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 thereof include compounds having a Si—C—C—Si bond at the cross-linking point obtained by mixing in an amount ratio of 5 times or less and reacting in the presence of an addition polymerization catalyst such as (C3) Pt catalyst.

(C1) As a silicon-containing compound having an alkenyl group, the following general formula (2)
R _n SiO [ _{(4-n) / 2} ] (2)
And a polyorganosiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule.
In the formula (2), R is independently the same or different substituted or unsubstituted monovalent hydrocarbon group, alkoxy group or hydroxyl group, and n is a positive value satisfying 0.5 ≦ n <2.5 Is a number.
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 alkyl groups such as methyl group and ethyl group, monovalent hydrocarbon groups having 1 to 20 carbon atoms such as vinyl group and phenyl group. Preferably, they are a methyl group, an ethyl group, and a phenyl group.

  Each may be different, but when UV resistance is required, about 65% of R in the above formula (2) is preferably a methyl group (that is, the number of Si (mol number)). In contrast, the content of functional groups other than methyl groups is preferably 0.35 (mol) or less.) 80% or more of R in the formula (2) is more preferably a methyl group. preferable. 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% by weight or less of the silicon-containing compound having (C1) alkenyl group. In addition, n is a positive number satisfying 0.5 ≦ n <2.5. If this value is 2.5 or more, it is sufficient for adhesion between the resin molding material and a conductor such as a lead frame. Strength cannot be obtained, and if it is less than 0.5, synthesis of this polyorganosiloxane becomes difficult.

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

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

The amount of the silicon compound having (C1) alkenyl group and the silicon compound having (C2) hydrosilyl group is as follows: (C1) hydrosilyl group with respect to 1 mol of silicon compound having alkenyl group (number of moles of alkenyl group) The silicon compound having a group (number of moles of hydrosilyl group) is usually 0.5 mol or more, preferably 0.7 mol or more, more preferably 0.8 mol or more, and usually 5.0 mol or less, preferably 2. 5 mol or less, more preferably 2.0 mol or less. By controlling the number of moles of the hydrosilyl group relative to the alkenyl group, the residual amount of unreacted end groups after curing can be reduced, and a cured product with little change over time such as coloring and peeling during lighting use can be obtained.
In addition, the content of the reaction point (crosslinking point) that causes hydrosilylation is 0.01 mmol / g or more, more preferably 0.1 mmol / g or more, 20 mmol / g in the resin itself that does not contain a pigment for both the alkenyl group and the hydrosilyl group. g or less, more preferably 10 mmol / g or less.

  The viscosity of the resin before the addition of the titanium-based black pigment is usually 100,000 cp or less, preferably 20,000 cp or less, more preferably 10,000 cp or less for ease of handling. The lower limit is not particularly limited, but is generally 5 cp or more in relation to volatility (boiling point).

  Furthermore, as an average molecular weight measurement value in gel permeation chromatography measured using resin polystyrene as a standard substance, the weight average molecular weight of the resin is 500 or more, more preferably 700 or more, and the volatile components are reduced (with other members). Is more preferably 1,000 or more for the purpose). The upper limit is usually 100,000 or less, preferably 50,000 or less, and more preferably 25,000 or less from the viewpoint of easy handling of the material before molding. Most preferably, it is 20,000 or less.

<1-1-2. Condensed polyorganosiloxane>
Examples of the condensed polyorganosiloxane include a compound having a Si—O—Si bond obtained by hydrolysis and polycondensation of an alkylalkoxysilane at a crosslinking point. Specific examples thereof include polycondensates obtained by hydrolysis and polycondensation of compounds represented by the following general formula (3) and / or (4) and / or oligomers thereof.
M ^{m +} X _n Y ¹ _mn (3)
In the formula (3), M represents silicon, X represents a hydrolyzable group, Y ¹ represents a monovalent organic group, and m represents an integer of 1 or more representing the valence of M. , N represents an integer of 1 or more representing the number of X groups. However, m ≧ n.
_{^{(M s + X t Y 1}} s-t-1) u Y 2 ··· (4)
In formula (4), M represents silicon, X represents a hydrolyzable group, Y ¹ represents a monovalent organic group, Y ² represents a u-valent organic group, and s is 1 represents an integer of 1 or more representing the valence of M, t represents an integer of 1 or more and s−1 or less, 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, JP 2006-348284 A,
And the member for semiconductor light-emitting devices described in the international publication 2006/090804 pamphlet is suitable.

  In condensation type polyorganosiloxane, a desorbing component is generated as the condensation reaction proceeds. Use of condensation type polyorganosiloxane is used when the molding process does not affect the molding processability of the component. Is preferred. In that case, the silanol content in the condensed polyorganosiloxane is particularly preferably 0.01% by weight or more and 10% by weight or less.

<1-2. (B) Titanium black pigment>
The titanium-based black pigment may be a black pigment having a titanium atom, and specific examples thereof include low-order titanium oxide and titanium nitride. In the resin molded body material according to the present embodiment, the dispersibility of the black pigment in the resin molded body material becomes extremely good by blending the titanium-based black pigment, and there is no color unevenness when the molded body is formed. A molded body can be obtained. Note that black is a color that absorbs visible light.
Moreover, it is preferable that a titanium-type black pigment has insulation. Insulation means that the electric resistance is large and no current flows even when a voltage is applied.

The titanium-based black pigment can be obtained by reducing titanium oxide at a high temperature to partially remove oxygen in the titanium oxide. Moreover, you may use a commercial item, and as a brand name, titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N (Mitsubishi Materials Electronic Chemicals Co., Ltd.), Tilac D (Ako Kasei Co., Ltd. make) ) Etc.
The titanium-based black pigment preferably includes at least titanium nitride, more preferably includes 40% by weight or more of titanium nitride, and further preferably includes 50% by weight or more of the titanium-based black pigment.
These can be used alone or in admixture of two or more.

  The titanium black pigment may be surface treated with a silane coupling agent or the like. When a titanium black pigment surface-treated with a silane coupling agent is used, the hardness of the entire resin molded material can be improved. Further, extender pigments may be added as necessary.

  The primary particle diameter of the titanium black pigment is usually 10 nm or more, preferably 30 nm or more, and usually 500 nm or less, preferably 100 nm or less. When the primary particle diameter of the titanium black pigment is within the above range, the blackness is increased and the heat resistance and light resistance are excellent, which is preferable. The primary particle diameter of the titanium black pigment is a value measured by observation with an electron microscope.

The specific surface area of the titanium-based black pigment measured by the BET method is usually 1 m ² / g or more, preferably 10 m ² / g or more, and usually 100 m ² / g or less, preferably 60 m ² / g or less. It is preferable that the specific surface area of the titanium black pigment is in the above range so that the blackness is increased and the titanium black pigment is easily dispersed in the resin.

  The compounding amount of the titanium black pigment is usually 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 0.5% by weight or more with respect to the total amount of the resin molded material, and usually 30%. % By weight or less, preferably 20% by weight or less, more preferably 10% by weight or less.

<1-3. (C) Curing catalyst>
(C) A curing catalyst is a catalyst for curing the polyorganosiloxane of (A). The polyorganosiloxane is cured by the catalyst and the polymerization reaction is accelerated. This catalyst includes 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 the hydrosilylation addition reaction between the alkenyl group in the component (C1) and the hydrosilyl group in the component (C2). Examples of the addition polymerization catalyst include platinum black , Platinum chloride, chloroplatinic acid, reaction product of chloroplatinic acid and monohydric alcohol, complex of chloroplatinic acid and olefins, platinum catalyst such as platinum bisacetoacetate, palladium catalyst, rhodium catalyst, etc. And platinum group metal catalysts. The blending amount of the (C3) addition polymerization catalyst can be a catalytic amount. Usually, the platinum group metal is usually 1 ppm or more, preferably 2 ppm or more with respect to the total weight of the components (C1) and (C2). It is usually 100 ppm or less, preferably 50 ppm or less, more preferably 20 ppm or less. Thereby, catalyst activity can be made high.

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 resin molding material for a semiconductor light emitting device, coating hardness, non-yellowing, curability and the like.

The blending amount of the condensation polymerization catalyst is usually 0.01% by weight or more, preferably 0.05% by weight or more, on the other hand, based on the total weight of the components represented by the above formulas (3) and / or (4). Is usually 10% by weight or less, preferably 6% by weight or less.
When the addition amount is in the above range, the curability and storage stability of the resin molded body material for a semiconductor light emitting device are good, and the quality of the resin molded body molded in addition is good. If the added amount exceeds the upper limit value, there may be a problem in the storage stability of the resin molded body material. If it is less than the lower limit value, the curing time becomes longer and the productivity of the resin molded body decreases. There is a tendency for quality to decline.

<1-4. (D) Silica>
The resin molded body material according to the present embodiment preferably further contains (D) silica. By containing silica, the hardness and abrasion resistance of the molded resin molded body can be improved. The silica is preferably spherical, and by making it spherical, it is possible to highly fill the silica into the resin molding material, and the hardness and wear resistance can be further improved.

  The average particle diameter (D50) of silica is not particularly limited, but is usually 0.1 μm or more, preferably 0.3 μm or more, and usually 50 μm or less, preferably 10 μm or less. In addition, silica having a relatively large particle size and fine particle silica may be used in combination, and by using two or more types of silica in combination, silica can be highly filled in the resin molding material. Become.

The specific surface area of the silica measured by the BET method is usually 0.5 m ² / g or more, preferably 1 m ² / g or more, and usually 30 m ² / g or less, preferably 10 m ² / g or less. When the specific surface area of silica is in the above range, it is easy to achieve high packing, which is preferable.

  The amount of silica is usually 50 parts by weight or more, preferably 100 parts by weight or more, more preferably 200 parts by weight or more, and usually 900 parts by weight or less, preferably 100 parts by weight of (A) polyorganosiloxane. 700 parts by weight or less, more preferably 500 parts by weight or less. When the amount of silica is in the above range, it is preferable because the hardness when formed into a molded body can be increased and the linear expansion coefficient of the material can be decreased.

<1-5. (E) Curing rate control agent>
The resin molded body material according to the present embodiment preferably further contains (E) a curing rate control agent. Here, the curing rate control agent is for controlling the curing rate in order to improve the molding efficiency when molding the resin molding material, and includes a curing retarder or a curing accelerator.

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. Of the compounds containing an aliphatic unsaturated bond, compounds having a triple bond are preferred. 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 a curing retarder can be variously set, the lower limit of the preferable addition amount with respect to 1 mol of the (C) curing catalyst to be used is 10 ⁻¹ mol or more, more preferably ¹ mol or more, and the upper limit of the preferable addition amount is 10 ³ mol. Below, more preferably 100 mol or less. Moreover, these hardening retarders may be used independently and may be used together 2 or more types.

The curing accelerator is not particularly limited as long as it cures a thermosetting resin. For example, imidazoles, dicyandiamide derivatives, dicarboxylic acid dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4 -Methylimidazole tetraphenylborate, 1,8-diazabicyclo [5.4.0] undecene-7-tetraphenylborate, and the like can be mentioned. Among them, it is preferable to use imidazoles in view of high reaction acceleration.
Examples of the imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate and the like. 2E4MZ, 2PZ-CN, 2PZ-CNS (Shikoku Chemicals Co., Ltd.) and the like. The addition amount of the curing accelerator may be added in the range of 0.1 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the total of (A) the polyorganosiloxane thermosetting resin and (C) the curing catalyst. preferable.

  By setting the type and blending amount of the curing rate control agent as described above, molding of the resin molded body material becomes easy. For example, there is an advantage that the filling rate into the mold becomes high or there is no leakage from the mold when molding by injection molding, and burrs are hardly generated.

<1-6. Other ingredients>
In the material for a resin molded body according to the present embodiment, in addition to the above (A) polyorganosiloxane, (B) titanium black pigment, (C) curing catalyst, (D) silica, and (E) curing rate control agent. 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, white pigments such as alumina and titania can be contained in an amount necessary to obtain desired thermal conductivity and reflectance for the purpose of improving the thermal conductivity and reflectance of the resin molding material. In addition, solid particles can be included as a fluidity adjusting agent for the purpose of controlling the fluidity of the resin molding material and suppressing the precipitation of the white pigment. The fluidity adjusting agent is not particularly limited as long as it is a solid particle in the vicinity of the molding temperature from the normal temperature at which the viscosity of the resin molding material is increased by inclusion, but the wavelength is converted by the light from the light emitting element or the phosphor. It is preferable that it has no or very small property of absorbing light and does not extremely reduce the reflectivity of the material, and is low in discoloration or alteration due to light or heat and high in durability. Specific examples include silica fine particles, quartz beads, glass beads, inorganic fibers such as glass fibers, boron nitride, and aluminum nitride. Further, for example, a white pigment such as fibrous alumina may be contained.

Among these, silica fine particles having a large thixotropy-imparting effect are easy to control the viscosity and thixotropy of the composition and can be suitably used. Quartz beads, glass beads, glass fibers, etc. are preferred because they can be expected not only as an effect of fluidity control, but also as an effect of increasing the strength and toughness of the material after thermosetting and an effect of reducing the linear expansion coefficient of the material. It may be used in combination with fine particles or may be used alone.
The silica fine particles are not particularly limited, but the specific surface area by the BET method is usually 50 m ² / g or more, preferably 80 m ² / g or more, more preferably 100 m ² / g or more. Moreover, it is 300 m < ² > / g or less normally, Preferably it is 200 m < ² > / g or less. If the specific surface area is too small, the addition effect of silica fine particles is not recognized, and if it is too large, dispersion treatment in the resin becomes difficult. As the silica fine particles, for example, those obtained by hydrophobizing the surface by reacting a silanol group present on the surface of the hydrophilic silica fine particles with a surface modifier may be used.

Examples of the surface modifier include alkylsilane compounds, and specific examples include dimethyldichlorosilane, hexamethyldisilazane, octylsilane, and dimethylsilicone oil.
Examples of the silica fine particles include fumed silica. Fumed silica is produced 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. The primary particles of fumed silica are spherical ultrafine particles mainly composed of amorphous silicon dioxide (SiO ₂ ) having an average particle size of about 5 to 50 nm. Secondary particles that are several hundred nm are formed. Since fumed silica is an ultrafine particle and is produced by rapid cooling, the surface structure is in a chemically active state.

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

Moreover, in order to adjust the viscosity of the material for resin moldings, a polyorganosiloxane having an effect as a liquid thickener can be partly blended with the (A) polyorganosiloxane. As the liquid thickener, the viscosity at 25 ° C. is usually 0.001 Pa · s to 3 Pa · s, preferably 0.001 Pa · s to 1 Pa · s, more preferably 0.001 Pa · s to 0. 7 Pa · s or less, and the hydroxyl value is usually 1.0 × 10 ^{−2 to} 7.7 × 10 ⁻⁵ mol / g, preferably 1.0 × 10 ^{−2 to} 9.5 × 10 ⁻⁵ mol. / G, more preferably 1.0 × 10 ^{−2 to} 10.3 × 10 ⁻⁵ mol / g, containing a hydroxyl group bonded to at least one silicon atom in one molecule (ie, silanol group) A straight-chain organopolysiloxane can be blended.

  The hydroxyl group-containing linear organopolysiloxane as a liquid thickener does not contain a functional group involved in hydrosilylation addition reaction such as alkenyl group and / or SiH group in the molecule. The hydroxyl group may be bonded to the silicon atom at the end of the molecular chain, bonded to the silicon atom at the non-end of the molecular chain (in the middle of the molecular chain), or bonded to both of them. A linear organopolysiloxane containing hydroxyl groups bonded to silicon atoms at both ends of the molecular chain (that is, α, ω-dihydroxydiorganopolysiloxane) is preferable.

Examples of the organic group bonded to the silicon atom include monovalent hydrocarbon groups such as alkyl groups such as methyl, ethyl and propyl, and allyl groups such as phenyl groups, and the diorganosiloxane constituting the main chain of the organopolysiloxane. The repeating unit is preferably one or a combination of two or more of dimethylsiloxane units, diphenylsiloxane units, methylphenylsiloxane units and the like. Specifically, α, ω-dihydroxydimethylpolysiloxane, α, ω-dihydroxydiphenyl polysiloxane, α, ω-dihydroxymethylphenyl polysiloxane, α, ω-dihydroxy (dimethylsiloxane diphenylsiloxane) copolymer, α , Ω-dihydroxy (dimethylsiloxane / methylphenylsiloxane) copolymer, and the like.
The blending amount of the polyorganosiloxane as the liquid thickener is usually 0 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0, when the total amount of the polyorganosiloxane (A) is 100 parts by weight. About 5 to 3 parts by weight.

In addition, for the purpose of increasing the strength and toughness of the material after thermosetting, inorganic fibers such as glass fibers may be included, and in order to increase the thermal conductivity, boron nitride, aluminum nitride having high thermal conductivity, 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, and if the content is too large, the viscosity of the resin molded body material for semiconductor devices increases and affects the workability, so that a sufficient effect is exhibited. The material can be appropriately selected within a range that does not impair the workability of the material. Usually, it is 900 parts by weight or less, preferably 500 parts by weight or less, based on 100 parts by weight of (A) polyorganosiloxane.

  In addition, the above resin molding materials include ion migration (electrochemical migration) inhibitors, anti-aging agents, radical inhibitors, ultraviolet absorbers, adhesion improvers, flame retardants, surfactants, storage stability. Improving agent, antiozonant, light stabilizer, thickener, plasticizer, coupling agent, antioxidant, thermal stabilizer, conductivity imparting agent, antistatic agent, radiation blocking agent, nucleating agent, phosphorus-based excess An oxide 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, as a coupling agent, a silane coupling agent is mentioned, for example. 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.

The preferred contents of the components (A) to (E) in the resin molded body material according to this embodiment are as follows.
The content of (A) polyorganosiloxane is not limited as long as it can be normally used as a material for resin moldings, but is usually 5% by weight or more, preferably 10% by weight or more, more preferably 15% of the whole material. The upper limit is 50% by weight or less, preferably 40% by weight or less, and more preferably 30% by weight or less. In addition, when the liquid thickener which is (E) hardening rate control agent and other components contained in a material is polyorganosiloxane, it shall be contained in content of said (A).

The content of the (B) titanium black pigment is not limited as long as it can be used as a material for a resin molded body, but is usually 0.01% by weight or more and 30% by weight or less of the whole material, preferably Is 0.1 wt% or more and 20 wt% or less, more preferably 0.5 wt% or more and 10 wt% or less.
The content of the fluidity modifier is not limited as long as the effect of the present invention is not impaired, but is usually 0.1% by weight or more and 90% by weight or less, preferably 1% by weight or more and 50% by weight of the whole material. % Or less.
Moreover, the ratio of the total amount of the filler, specifically, the total amount of (D) silica, (B) titanium-based black pigment, fluidity adjusting agent, etc. with respect to the entire resin molded material is 50% by weight or more. It is preferably 60% by weight or more, more preferably 70% by weight or more, more preferably 90% by weight or less, and even more preferably 85% by weight or less.

<1-7. Viscosity of resin molding material>
The resin molded body material according to this embodiment preferably has a viscosity of 10 Pa · s or more and 10,000 Pa · s or less at a shear rate of 100 s ⁻¹ at 25 ° C. The viscosity is more preferably from 50 Pa · s to 5,000 Pa · s, more preferably from 100 Pa · s to 2,000 Pa · s, from the viewpoint of molding efficiency when molding a resin molded body for a semiconductor device. More preferably, it is 150 Pa · s or more and 1,000 Pa · s or less.
In addition, as described later, from the viewpoint of thixotropy, the resin molded body material has a viscosity ratio (1 s ⁻¹⁾ at a shear rate of 1 s ⁻¹ at 25 ° C. to a viscosity at a shear rate of 100 s ⁻¹ at 25 ° C. / 100 s ⁻¹ ) is preferably 5 or more, more preferably 10 or more, and particularly preferably 15 or more. On the other hand, the upper limit is preferably 50 or less, and more preferably 30 or less.

In addition, the viscosity of the material for resin molding is, in particular, that the viscosity at a shear rate of 100 s ⁻¹ at 25 ° C. is 1,000 Pa · s or less, and the viscosity at a shear rate of 100 s ⁻¹ at 25 ° C. The viscosity ratio (1 s ⁻¹ / 100 s ⁻¹ ) at a shear rate of 1 s ⁻¹ at 25 ° C. is preferably 15 or more.
In order to obtain a material with good moldability, it is necessary to give the material a certain level of thixotropy, but the viscosity at a shear rate of 100 s ⁻¹ at 25 ° C. is 10 Pa · s or more and 10
When the ratio of the viscosity at the shear rate of 1 s ⁻¹ to the viscosity at the shear rate of 100 s ⁻¹ is 5 or more, the occurrence of burrs and short molds (unfilled) is small, and at the time of molding The material measurement time and molding cycle can be shortened, the molding is easy to stabilize, and the material has high molding efficiency.

In particular, in LIM molding using a liquid resin material, burrs due to the material seeping out from minute gaps in the mold are likely to occur, and a post-processing step for removing the burrs is necessary. On the other hand, if the gap between the molds is made small in order to suppress the generation of burrs, there is a problem that short mold (unfilled) tends to occur. When the viscosity of the resin molding material is in the above range, such a problem can be solved, and LIM molding of the resin molding can be easily performed with good moldability. If the viscosity at a shear rate of 100 s ^-1 is greater than 10,000 Pa · s, the resin flow is poor and the mold will not be sufficiently filled, and it takes time to supply the material when performing injection molding. The molding efficiency tends to decrease due to a long cycle. If the viscosity is less than 10 Pa · s, the material leaks from the gap between the molds and burrs are generated, or the injection pressure easily escapes into the gap between the molds, making the molding difficult to stabilize. Tend to decrease. In particular, when the molded body is small, post-processing for removing burrs becomes difficult, so it is important for moldability to suppress the generation of burrs.

When the ratio of the viscosity at a shear rate of 1 s ⁻¹ at 25 ° C. to the viscosity at a shear rate of 100 s ⁻¹ at 25 ° C. is less than 5, that is, when the viscosity at the shear rate of 1 s ⁻¹ is relatively small, The material can easily enter the gaps in the mold, the burrs are very likely to occur, the nozzle part is easy to drip, the injection pressure is not easily transmitted to the material, and the molding is difficult to stabilize. Molding control can be difficult. In LIM molding, resin leakage in the parting line of the sprue portion is likely to be a problem, but adjusting to the above viscosity range is effective in suppressing resin leakage.
The viscosity at a shear rate of 100 s ⁻¹ and the viscosity at a shear rate of 1 s ⁻¹ at 25 ° C. are measured using, for example, an ARES-G2-strain-controlled rheometer (manufactured by TI Instruments Japan Co., Ltd.). Can be measured.

  In order to control the viscosity and make the material suitable for liquid injection molding (LIM molding), it is necessary to give the material a certain level of thixotropy. When fine particles in a fine region (primary particle size of 0.005 μm or more and 1.0 μm or less) are blended in the material, a significant increase in viscosity occurs and the effect of imparting thixotropy is great. Therefore, if a fluidity modifier in a fine region such as (D) silica having a primary particle diameter of 0.005 μm or more and 1.0 μm or less, a titanium black pigment, or fumed silica having a large specific surface area is used, the thixotropy of the composition is used. Easy to control sex. Specifically, it is preferable to contain 1% by weight or more of (D) silica having a primary particle size of 0.005 μm or more and 1.0 μm or less, more preferably (D) silica, fumed silica, quartz beads, or the like. By adding 1 to 70% by weight in combination with various fluidity modifiers, the viscosity of the material can be controlled within the above range.

  When using (D) silica with a secondary particle size larger than 1 μm, especially when using a particle with a center particle size of 5 μm or more, a fine region of silica or fluidity modifier having a large thixotropic effect. It is preferable to use together. (D) When the primary particle size of silica itself is sufficiently small, it can be used without being used in combination with a fluidity modifier, and may be combined with a fluidity modifier having a relatively large center particle size of about several μm or more.

<1-8. Thermal conductivity of resin molding material>
The resin molded body material according to the present embodiment preferably has a thermal conductivity of 0.4 to 3.0, more preferably 0.6 to 2.0, at the time of curing. The thermal conductivity at the time of curing can be measured using, for example, Eye Phase Mobile (manufactured by Eye Phase Co.).
Here, the term “cured” refers to the time when the composition is thermally cured at 180 ° C. for 4 minutes.

In a semiconductor light emitting device, heat is generated by light emitted from a semiconductor light emitting element, and the amount of generated heat is larger particularly when the output of the element is large. In this case, the phosphor layer adjacent to the resin molded body is deteriorated due to heat generation, and the durability of the apparatus is lowered.
When the thermal conductivity is less than 0.4, the phosphor layer included in the device tends to be thermally deteriorated due to heat generated by light emitted from the semiconductor light emitting element in the device.
The thermal conductivity can be controlled within the above range by adding a filler having a high thermal conductivity, such as alumina or boron nitride, to the resin molding material.

<1-9. Blackness of resin molding>
The resin molded body using the resin molded body material according to the present embodiment is a black resin molded body. Regarding the blackness of the molded product, L ^* (lightness) of the L ^* a ^* b ^* color system is usually 30 or less, preferably 25 or less. When the blackness is within this range, the appearance of the resin molded body looks black.

<1-10. Shore D hardness of molded resin>
The resin molded body using the resin molded body material according to the present embodiment has a Shore D hardness according to JIS K6253 of usually 60 or more, preferably 70 or more, and usually 90 or less. The Shore D hardness is obtained by quantifying the amount of deformation by pressing an indenter into the surface of the resin molded body using a type D durometer in accordance with JIS K6253.
By setting the Shore D hardness of the resin molded product within this range, the hardness becomes practical. The Shore D hardness of the resin molding can be controlled within the above range by adjusting the crosslink density of the resin or adjusting the amount of filler (silica, pigment, etc.) contained in the resin molding. .

<2. Molding method of resin molding>
Examples of the molding method of the resin molded body according to the embodiment of the present invention include a compression molding method, a transfer molding method, and an injection molding method. Among these, the preferred molding method is that there is no use of a hardened product and secondary processing is unnecessary (that is, burrs are less likely to be generated), so the molding process for resin moldings is automated and the molding cycle is shortened. There is an injection molding method, particularly a liquid injection molding method (LIM molding), which has a great merit such that the cost of the molded product can be reduced. Comparing LIM molding and transfer molding, LIM molding has the advantages that the degree of freedom of the molding shape is high and the molding machine and the mold are relatively inexpensive.

  The injection molding method can be performed using an injection molding machine. The cylinder set temperature may be appropriately selected depending on the material, but is usually 50 ° C. or lower, preferably 30 ° C. or lower, and more preferably 25 ° 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 120 ° C. or higher and 200 ° C. or lower. The injection time varies depending on the material, but is usually several seconds or less than 1 second. The molding time may be appropriately selected according to the gelation speed and curing speed of the material, but usually 3 seconds or more and 600 seconds or less, preferably 5 seconds or more and 200 seconds or less, more preferably 10 seconds or more and 60 seconds or less. It is.

When a resin is molded by liquid injection molding (LIM molding), the cooled resin is fed into a hot mold and the viscosity is increased with a chemical reaction. Therefore, the mold usually reaches the mold with insufficient increase in viscosity. That is, since there is a delay in the increase in viscosity with respect to temperature conditions, in addition to controlling the viscosity of the resin, it is also required that the accuracy of the gap between the molds and between the lead frame and the mold is high. If the increase in viscosity when the resin reaches the mold is insufficient, the resin may leak from the gap between the mold and the gap between the lead frame and the mold, and burrs are likely to occur. Usually 10 μm or less, preferably 5 μm
The mold clearance accuracy of m or less, more preferably 3 μm or less is required. Preheating the lead frame before entering the mold is also effective in suppressing the generation of burrs along the lead.
Further, when the resin is molded, by placing the mold in a vacuum atmosphere, the penetration of the material into the narrow space is promoted, and the generation of air voids in the molded product can be prevented.

  Regarding the curing time in the liquid injection molding (LIM molding), it is preferable that the shape of the graph rises to an S shape when the degree of curing is represented by a graph. If the initial curing rises too early, unfilling of the mold may occur. In order to suppress the generation of burrs and prevent unfilling of the mold, it is very important to control the curing speed of the material and adjust the viscosity. After the mold is filled with the resin material, the molding cycle can be shortened, and the mold release is improved by curing shrinkage. Therefore, the faster the curing, the better.

  The time to completion of curing is usually within 120 seconds, preferably within 60 seconds, and more preferably within 30 seconds. You may post-cure as needed. The curing rate can be adjusted not only by selection of the platinum catalyst species, the amount of catalyst, the use of a curing rate control agent, the degree of crosslinking of the polyorganosiloxane, but also by molding conditions such as mold temperature, filling rate, injection pressure, and the like.

  The compression molding method can be performed using a compression molding machine. The molding temperature may be appropriately selected depending on the material, but is usually 80 ° C. or higher and 300 ° C. or lower, preferably 100 ° C. or higher and 250 ° C. or lower, more preferably 120 ° C. or higher and 200 ° C. or lower. The molding time may be appropriately selected according to the curing rate of the material, but is usually 3 seconds or more and 1200 seconds or less, preferably 5 seconds or more and 900 seconds or less, more preferably 10 seconds or more and 600 seconds or less.

  The transfer molding method can be performed using a transfer molding machine. The molding temperature may be appropriately selected depending on the material, but is usually 80 ° C. or higher and 300 ° C. or lower, preferably 100 ° C. or higher and 250 ° C. or lower, more preferably 120 ° 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 600 seconds or less, preferably 5 seconds or more and 300 seconds or less, more preferably 10 seconds or more and 180 seconds or less. It is.

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

<3. Semiconductor Light Emitting Device Package and Semiconductor Light Emitting Device>
The resin molded body according to the present embodiment is usually used as a semiconductor light emitting device by mounting a semiconductor light emitting element. As shown in FIG. 1, for example, the semiconductor light emitting device 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. In this case, what consists of electroconductive materials, such as lead frame 5, and an insulating resin molding is called a package. The conductive material such as the lead frame 5 includes a ceramic substrate in which a conductive metal is combined.

  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 mounted in FIG. 1, it is possible to arrange a plurality of semiconductor light emitting elements in a linear or planar manner as shown in FIG. By arranging the semiconductor light emitting element 1 in a planar shape, surface illumination can be obtained, and such an embodiment is suitable when it is desired to further increase the output.

  The resin molded body 2 constituting 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. The resin molded body 2 may be made entirely of the resin molded body material according to the present embodiment, or a part thereof may be made of the resin molded body material according to the present embodiment. As a specific example when a part of the resin molded body 2 is made of the resin molded body material according to the present embodiment, the resin molded body of the reflector portion 102 according to the present embodiment is used as shown in FIG. The aspect shape | molded from the resin molding material is mentioned.

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 has a role of fixing 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 as an electrode, the conductive bonding wire 3 plays a role of supplying power to the semiconductor light emitting element 1. The bonding wire 3 is bonded to the lead frame 5 by applying pressure and applying heat and ultrasonic vibration.

The resin molded body 2 constituting the package is mounted with the semiconductor light emitting element 1 and sealed with a sealing material 4 in which a phosphor is mixed. 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 and emits fluorescence having a wavelength different from that of the excitation light. 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 semiconductor light emitting device (white LED) that emits white light, when a semiconductor light emitting element that emits blue light is used as an excitation light source, white light is generated by including green and red phosphors in the phosphor layer. Can do. In the case of a semiconductor light emitting device that emits violet light, white light is generated by including blue and yellow phosphors in the phosphor layer, or by including blue, green, and red phosphors in the phosphor layer. be able to.
The binder resin contained in the sealing material 4 may be appropriately selected from light-transmitting resins that are generally used for sealing materials. Specific examples include an epoxy resin, a silicone resin, an acrylic resin, and a polycarbonate resin, and it is preferable to use a silicone resin.

Another aspect of the semiconductor light emitting device according to the embodiment of the present invention will be described with reference to FIG.
The semiconductor light emitting device 1 </ b> C according to this embodiment includes a casing 101 having a window portion, a reflector portion 102, a light source portion 103, and a heat sink 104. The light source unit 103 includes a light emitting unit 105 on a wiring board. A COB (Chip on Board) format in which a semiconductor light emitting element is directly mounted on the wiring substrate 106, or a type in which a semiconductor light emitting device as shown in FIG. Either of these is acceptable. When the light source unit 103 is in the COB format, the semiconductor light emitting element may be sealed without using a frame material by a sealing resin formed in a dome shape or a flat plate shape. One or more semiconductor light emitting elements may be mounted on the wiring board 106. The reflector unit 102 and the heat sink 104 may be integrated with the housing 101 or may be separate, and can be used as necessary. From the viewpoint of heat dissipation, it is preferable that the light source unit 103, the casing 101, and the heat sink 104 are in contact with each other with a single structure or a high thermal conductive sheet or grease. The window 107 can be made of a known transparent resin, optical glass, or the like, and may be flat or curved.

  In the case where a white LED is provided by providing a phosphor portion, the phosphor portion may be provided in the light source portion 103 or the window portion 107. However, when the phosphor portion is provided in the window portion 107, the phosphor is disposed at a position away from the light emitting element. There is an advantage that it is possible to suppress the deterioration of the phosphor that is easily deteriorated by heat and light, and to obtain white light that is uniform and has high luminance over a long period of time.

When the phosphor layer is provided on the window 107, the phosphor layer can be manufactured on a transparent window material (not shown) by a method such as screen printing, die coating, or spray coating. In such a case, since the semiconductor light emitting element and the phosphor layer are arranged at a distance, it is possible to prevent the phosphor layer from being deteriorated by the energy of light from the semiconductor light emitting element, and to emit light. The output of the device can also be improved. The distance between the semiconductor light emitting element and the phosphor layer of the window 107 is preferably 5 to 50 mm. The phosphor layer in FIG. 2 has a multi-layer structure in which each phosphor color to be used is applied in order to reduce self-resorption of fluorescence and reabsorption between RGB phosphors, or a pattern such as stripes or dots. Or may be formed.
The shape of each part of the semiconductor light emitting device 1C is not limited to that shown in the figure, and may include a curved surface part or an attached device such as a light control device or a circuit protection device if necessary.

  In the semiconductor light emitting device of the present invention described above, the part to which the resin molded body according to the present invention (hereinafter simply referred to as “optical member”) is applied is not particularly limited as described above. For example, in the semiconductor light emitting device 1 </ b> C illustrated in FIG. 2, it can be used for each member of the housing 101, the reflector unit 102, the light source unit 103, the light emitting unit 105, and the wiring substrate 106.

<3-2. Semiconductor Light Emitting Device Package Thickness>
The semiconductor light emitting device package of this embodiment usually has a bottom surface on the side opposite to the chip mounting surface and the chip mounting surface. In this case, the distance between the chip mounting surface and the bottom surface, that is, the thickness of the semiconductor light emitting device package 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, there is a possibility that problems such as insufficient strength of the package and deformation in handling may occur, and if it is too thick, the package itself becomes thick and bulky, so that the application of the semiconductor light emitting device is limited.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, it cannot be overemphasized that this invention is not limited only to the said Example.
<Examples 1 and 2>
[Preparation of resin molding material]
(A) 19.02 parts by weight of LUMISIL 865 manufactured by Asahi Kasei Silicone Co., Ltd. (containing an effective amount of (C) curing catalyst), (D) 70.2 parts by weight of spherical silica having an average particle diameter of 5 μm, average particle 7.8 parts by weight of finely divided spherical silica having a diameter of 0.6 μm, (E) 0.01 part by weight of INHIBITOR PT88 manufactured by Asahi Kasei Wacker Silicone Co., Ltd. as a curing rate control agent, and silica fine particles “AEROSIL RX200” as a fluidity adjusting agent ( 2.97 parts by weight of a specific surface area of 140 m ² / g) was weighed, and a base composition I in which spherical silica and silica fine particles were uniformly dispersed by stirring was obtained. In the obtained base composition I, (B) Titanium Black 13M-T manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd. was blended at a weight ratio shown in Table 1, and after stirring, it was further uniformly dispersed using a mortar to form a black paste. The material for resin molding was obtained.

<Example 3>
(B) A black paste-like resin molded material was obtained in the same manner as in Example 1 except that the Tilac DM type manufactured by Ako Kasei Co., Ltd. was used as the component.

<Comparative Example 1>
(B) Except having used Degussa carbon black SB250 for a component, it operated similarly to Example 1 and obtained the resin paste body material of the black paste form.

<Comparative example 2>
(B) Except having used Degussa carbon black SB550 for a component, it operated similarly to Example 1 and obtained the resin paste body material of the black paste shape.

[Blackness measurement]
The compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were cured using a hot press machine at 180 ° C. and a curing time of 60 seconds to produce a black disk-shaped test piece having a diameter of 13 mm and a thickness of 1 mm. did. The reflectance at a wavelength of 360 nm to 740 nm was measured using SPECTROTOPOMETER CM-2600d manufactured by Konica Minolta, and L ^* (lightness) in the L ^* a ^* b ^* color system was used as an index of blackness. The results are shown in Table 1. The blackness was substantially the same in both Examples and Comparative Examples.

[Shore hardness measurement]
The compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were cured using a hot press machine at 180 ° C. and a curing time of 60 seconds to produce a black disc-shaped test piece having a diameter of 13 mm and a thickness of 3 mm. did. Furthermore, the test piece was heated in an oven at 200 ° C. for 3 hours. Two test pieces were stacked to a thickness of 6 mm, and the Shore hardness was measured. The results are shown in Table 1.

[Evaluation of dispersibility of black pigment]
15 parts by weight of Momentive's dimethyl silicone oil TSF451-100 was added to 1 part by weight of the resin molded body materials of Examples 1 and 3 and Comparative Examples 1 and 2 and diluted uniformly. The diluted dispersion was transferred to a test tube and allowed to stand at room temperature for 26 hours, and the bottom of the test tube was observed. The results are shown in Table 1. In Comparative Examples 1 and 2, a black sediment was observed at the bottom of the test tube.

DESCRIPTION OF SYMBOLS 1 Semiconductor light-emitting device 2 Resin molding 3 Bonding wire 4 Sealing material 5 Lead frame 1C Semiconductor light-emitting device 101 Case 102 Reflector part 103 Light source part 104 Heat sink 105 Light-emitting part 106 Wiring board 107 Window part

Claims (10)

  (A) Polyorganosiloxane, (B) Titanium black pigment, and (C) Material for resin molded body for semiconductor light emitting device containing curing catalyst as essential components.   The material for resin molding according to claim 1, wherein the (A) polyorganosiloxane is an addition type polyorganosiloxane.   The resin molded body material according to claim 1 or 2, wherein the content of the (B) titanium-based black pigment is 0.01 to 30% by weight of the entire resin molded body material for a semiconductor light emitting device.   The resin molded body material according to any one of claims 1 to 3, wherein the (B) titanium-based black pigment contains titanium nitride.   (A) The resin-molded material according to any one of claims 2 to 4, wherein the addition-type polyorganosiloxane is a thermosetting polyorganosiloxane that is liquid at normal temperature and normal pressure.   Furthermore, (D) The resin molding material of any one of Claims 1-5 containing a silica.   The material for resin moldings according to any one of claims 1 to 6, which is a material for injection molding.   Furthermore, the resin molding material of any one of Claims 1-7 containing (E) hardening rate control agent. The resin molding material according to any one of claims 1 to 8, wherein the viscosity at a shear rate of 100 s ^-1 at 25 ° C is 10 Pa · s or more and 10,000 Pa · s or less.   The semiconductor light-emitting device package which consists of the material for resin moldings for semiconductor light-emitting devices as described in any one of Claims 1-9.

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