JP5834519B2 - Material for resin molded body for semiconductor light emitting device and molded body thereof - Google Patents

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 thereof.

  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.

  Conventionally, as an insulating material used for a resin molded body, a material in which a white pigment is blended with a thermoplastic resin such as polyamide has been generally used (see, for example, Patent Document 1). 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. Since a thermoplastic resin such as polyamide is translucent, when reflecting light with a resin molding, a semiconductor light-emitting element is used by using a difference in refractive index between the resin and the white pigment by blending the resin with a white pigment. The luminous efficiency of the semiconductor light emitting device is increased by reflecting light from the light.

  In Patent Document 1, even when a white pigment is used, the reflection efficiency is not sufficient depending on the type of the white pigment, and a light beam absorbed by the resin molded body and a light beam transmitted through the resin molded body are also emitted. Therefore, as a result, the light from the semiconductor light emitting element cannot be concentrated in the intended direction, and the light emission efficiency as the semiconductor light emitting device may be lowered.

  In addition, polyamide is a thermoplastic resin, and lead-free solder with a high melting point is actively used due to environmental problems, and the reflow temperature tends to increase. The heat softens the polyamide resin. Therefore, there is a problem with the heat resistance of the package. 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 above-mentioned Patent Document 3 in which polyorganosiloxane is used for the resin, titanium oxide is used for the white pigment, which causes the following problems.
First, in the step of preparing the resin composition, when titanium oxide is added to and mixed with polyorganosiloxane that is a resin, there is a problem that titanium oxide has low dispersibility in the resin. For this reason, in the resin molded body after curing the resin composition, titanium oxide is not uniformly dispersed and the reflectance in the resin molded body is not constant, and as a result, the light rays emitted from the semiconductor light emitting device are uniform. There is a problem in terms of sex.

  In addition, since titanium oxide has photocatalytic properties, when a semiconductor light emitting device having a wavelength of about 470 nm or less is used, titanium oxide particles are generated by light emitted from the semiconductor light emitting device or light emitted from a phosphor excited by the light. A nearby resin molded body deteriorates. Therefore, when a semiconductor light emitting device that emits light in the blue region and a semiconductor light emitting device that emits light in the near ultraviolet region are used, the light resistance of the resin molded product is significantly impaired.

  Furthermore, since titanium oxide has an absorption wavelength in the near ultraviolet region, its color is yellowish. For this reason, the emission spectrum from the semiconductor light emitting element is changed, causing problems in the whiteness and color rendering of the light emitted from the semiconductor light emitting device. In particular, in white semiconductor light emitting devices that are being actively researched, whiteness and color rendering are important requirements, and this is also disadvantageous.

  The present invention provides a material for a resin molded body that can be used as a resin molded body for a semiconductor light-emitting device that has high durability (light resistance, heat resistance) and improves LED output due to excellent reflectance. Let it be an issue. It is another object of the present invention to provide a resin molding material for a semiconductor light emitting device that has flow characteristics suitable for molding and can be easily molded.

  As a result of intensive studies to solve the above problems, the inventors of the present invention provide a resin molding material for a semiconductor light-emitting device containing (A) a polyorganosiloxane, (B) a white pigment, and (C) a curing catalyst. (B) By using a white pigment blended with alumina having different average secondary particle diameters in a specific quantitative ratio, a well-balanced resin molded body having a particularly high hardness and a sufficiently high reflectance can be obtained. I found out. The present invention has been accomplished based on these findings.

That is, the gist of the present invention is as follows [1] to [ 8 ].
[1] A resin molding material for a semiconductor light emitting device containing (A) a polyorganosiloxane, (B) a white pigment and (C) a curing catalyst, wherein the (A) polyorganosiloxane is an addition polymerization curing type The content of the (B) white pigment is 80 parts by weight or more and 900 parts by weight or less per 100 parts by weight of the (A) polyorganosiloxane, and the (B) white pigment is
(A) an alumina,
(B) The alumina contains (B1) a component having an average secondary particle size of 0.2 μm or more and 1.5 μm or less, and (B2) a component having an average secondary particle size of 2 μm or more and 30 μm or less,
(C) the (B1) the amount of the component and (B2) weight ratio of the content of the component [(B1) / (B2)] is Ri Der range from 1/5 of 3/1,
(D) The secondary particles of the component (B1) are composed of primary particles having an aspect ratio of 1.2 to 4.0, and (e) the primary particle diameter x of the component (B1) and the central particles of the secondary particles A resin molded body material, wherein a ratio (y / x) of the diameter y is 1 or more and 10 or less .
[ 2 ] The ratio [D (B1) / D (B2)] of the average secondary particle diameter D (B1) of the component (B1) to the average secondary particle diameter D (B2) of the component (B2) is 1 / The material for resin moldings according to [1 ], which is in a range of 2.5 to 1/10.
[ 3 ] The resin molded body material according to [1] or [2] , further comprising (D) a curing rate modifier and / or (E) a fluidity modifier.
[4] The resin molded material according to any one of [1] to [3], which is for liquid injection molding.
[ 5 ] A resin molded body for a semiconductor light-emitting device, which is formed by molding the material according to any one of [1] to [ 4 ].
[ 6 ] A method for producing a resin molded body for a semiconductor light emitting device, which comprises subjecting the material according to any one of [1] to [ 4 ] to liquid injection molding.
[ 7 ] The resin molded product according to [ 5 ], which is used for a package of a semiconductor light emitting device.
[ 8 ] A semiconductor light-emitting device comprising the resin molded body according to [ 7 ].

  If the resin molding material of the present invention is used, resin molding for a semiconductor light emitting device which improves durability (light resistance, heat resistance), hardness, thermal conductivity of the resin part, and improves LED output by excellent reflectance. You can get a body. Furthermore, according to the present invention, it is possible to provide a resin molding material for a semiconductor light-emitting device that has a small linear expansion coefficient, has flow characteristics suitable for molding, and can be easily molded.

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 schematically the structure of another aspect of a semiconductor light-emitting device. It is sectional drawing which shows schematically the structure of another aspect of a semiconductor light-emitting device.

  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>
In the present invention, the resin molded body material for a semiconductor light emitting device is a material used for molding a resin molded body for use in a semiconductor light emitting device. Specifically, it is a material containing (A) a polyorganosiloxane, (B) a white pigment, and (C) a curing catalyst, wherein the (B) white pigment is a white color mainly composed of (a) alumina. A component having (B1) an average secondary particle diameter of 0.2 μm or more and 1.5 μm or less; and (B2) a component having an average secondary particle diameter of 2 μm or more and 30 μm or less. (C) The mass ratio [(B1) / (B2)] of the content of the component (B1) and the content of the component (B2) is in the range of 1/5 to 3/1. It is characterized by.

  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 in the present invention refers to a polymer substance in which an organic group is added to a structure having a portion in which a silicon atom is bonded to another silicon atom through oxygen. Here, the polyorganosiloxane is preferably liquid at room temperature and normal pressure. This is because the material can be easily handled when molding a resin molded body for a semiconductor light emitting device. In addition, solid 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, and light resistance and heat resistance are insufficient. 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.

The 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 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 _1/2 ] (triorganosylhemioxane), bifunctional [R ₂ SiO _2/2 ] (diorganosiloxane), trifunctional Type [RSiO _3/2 ] (organosilsesquioxane), tetrafunctional type [SiO _4/2 ] (silicate), and the difference in the properties of polyorganosiloxane by changing the constitution ratio of these four units Therefore, it is selected as appropriate so as to obtain desired characteristics, and polyorganosiloxane is synthesized.

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. In the present invention, the polyorganosiloxane is preferably a thermosetting material that can be cured by applying thermal energy.

  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, A compound having Si—C—C—Si bond at the cross-linking point, obtained by mixing in an amount ratio of 2.0 times or less and reacting in the presence of an addition condensation catalyst such as (C3) platinum (Pt) catalyst Can be mentioned.

(C1) As a silicon-containing compound having an alkenyl group, the following general formula (2)
R _n SiO [ _{(4-n) / 2} ] (2)
And a polyorganosiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule.
In the 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 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.

  In the above formula, each of R may be different from each other, but when UV resistance is required, about 65% of R is preferably a methyl group (that is, the number of Si (mol) The number of functional groups other than methyl groups is preferably 0.35 (mol) or less with respect to the number), and 80% or more of R in the above formula is more preferably 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% by mass or less 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 adhesion between the resin molding material and a conductor such as a lead frame, If it is less than 1, 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 group-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-terminal 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 in the present invention is (C1) 1 mol of silicon compound having alkenyl group (the number of moles of alkenyl group). C2) The silicon compound having a hydrosilyl group (the 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 2.0 mol or less, preferably 1.8 mol or less, more preferably 1.5 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.

  Further, the content of the reaction point (crosslinking point) that causes hydrosilylation is preferably 0.1 mmol / g or more and 20 mmol / g or less in the resin itself that does not contain a white pigment for both the alkenyl group and the hydrosilyl group. More preferably, it is 0.2 mmol / g or more and 10 mmol / g 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 include compounds represented by the following general formula (3) and / or (4) and polycondensates obtained by hydrolysis and polycondensation of oligomers of these compounds.

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, The semiconductor light emitting device members described in JP-A-2006-348284 and International Publication No. 2006/090804 are suitable.

<1-1-2-1. Particularly preferred condensed polyorganosiloxane>
Among the condensed polyorganosiloxanes, particularly preferred materials will be described below.
In general, polyorganosiloxane may have weak adhesion to semiconductor light emitting devices, substrates on which semiconductor light emitting devices are arranged, and resin moldings when used in semiconductor light emitting devices. In order to obtain siloxane, condensed polyorganosiloxane having at least one of the following [1] and [2] is particularly preferable.
[1] The silicon content is 20% by mass or more.
[2] The measured solid Si-nuclear magnetic resonance (NMR) spectrum has at least one peak derived from Si of the following (i) and / or (ii).

(I) A peak whose peak top position is in a region where the chemical shift is −40 ppm or more and 0 ppm or less with respect to dimethylsiloxysilicon of the dimethyl silicone rubber, and the half width of the peak is 0.3 ppm or more and 3.0 ppm or less.
(Ii) A peak whose peak top position is in a region where the chemical shift is −80 ppm or more and less than −40 ppm based on dimethylsiloxysilicon of the dimethyl silicone rubber, and the peak half-value width is 0.3 ppm or more and 5.0 ppm or less.

Of the above features [1] and [2], a condensed polyorganosiloxane having the feature [1] is preferable. More preferred is a condensed polyorganosiloxane having the above features [1] and [2].
In the condensation type polyorganosiloxane, a desorbing component is generated as the condensation reaction proceeds. However, the condensation type polyorganosiloxane can be used when the molding process does not significantly affect the molding processability of the component. In that case, the silanol content in the condensed polyorganosiloxane is particularly preferably 0.01% by mass or more and 10% by mass or less.

  In the present invention, the viscosity of the polyorganosiloxane (A) before adding the white pigment is usually 100,000 mPa · s or less, preferably 20,000 mPa · s or less, more preferably 10,000 mPa, for ease of handling. -S or less. The lower limit is not particularly limited, but is generally 15 mPa · s or more in relation to volatility (boiling point). In the present specification, the viscosity is a value at 23 ° C. unless otherwise specified.

  The mass average molecular weight of (A) polyorganosiloxane is preferably 500 or more and 100,000 or less, more preferably 700 or more and 50, or less as an average molecular weight measurement value in gel permeation chromatography measured using polystyrene as a standard substance. 000 or less. Furthermore, it is more preferably 1,000 or more for the purpose of reducing volatile components (to maintain adhesion to other members) and 25,000 or less for ease of handling of the material before molding. Most preferably, it is 20,000 or less.

<1-2. (B) White pigment>
In the present invention, the white pigment is (a) a white pigment mainly composed of alumina,
(B) The alumina has (B1) a component having an average secondary particle size of 0.2 μm or more and 1.5 μm or less [(B1) component] and (B2) an average secondary particle size of 2 μm or more and 30 μm or less. Component [(B2) component], and the mass ratio [(B1) / (B2)] of the content of component (c) (B1) and component (B2) is from 1/5 to 3 / Within the range of 1.

  As the white pigment, an inorganic and / or organic material can be used in combination with the components (B1) and (B2) as necessary. These components may be appropriately selected from known substances that do not inhibit the curing of the resin. Here, white means colorless and not transparent. That is, it means a color that can diffusely reflect incident light by a substance that does not have a specific absorption wavelength in the visible light region.

The amount of alumina in the white pigment is not particularly limited as long as alumina is the main component constituting the white pigment, that is, the amount that is the main component, but with respect to the total amount of the components constituting the white pigment. In general, it is particularly preferably 60% by mass or more, preferably 70% by mass or more, more preferably 85% by mass or more, and the total amount of the white pigment being alumina.
Moreover, content of an alumina is 40 mass% or more and 90 mass% or less normally with respect to the resin material whole material quantity as it mentions later.

Alumina is particularly preferable as a white pigment from the viewpoint of a high near-ultraviolet light reflection effect and a small alteration due to near-ultraviolet light. Further, by using alumina as the main component of the white pigment, the thermal conductivity of the resin molded body material described later is in the range of 0.4 W / (m · K) to 3.0 W / (m · K). Can be controlled.
By setting the content of alumina in the above range, a resin molded material having a sufficiently high reflectivity and good moldability can be obtained. If the alumina content is less than 40% by mass relative to the total amount of the resin molded material, sufficient light reflection effect cannot be obtained, and if it exceeds 90% by mass, the viscosity of the material becomes high and molding is difficult. It may become.

The (B1) component and (B2) component alumina are secondary particles formed by agglomeration of primary particles. The average secondary particle size of the component (B1) is usually 0.2 μm or more, preferably 0.3 μm or more, more preferably 0.5 μm or more, and usually 1.5 μm or less, preferably 1.3 μm or less, More preferably, it is 1.2 μm or less.
The average secondary particle size of the component (B2) is usually 2 μm or more, preferably 2.5 μm or more, more preferably 3 μm or more, and usually 30 μm or less, preferably 10 μm or less, more preferably 5 μm or less. is there.

  The component (B1) alumina has a large hiding power and greatly contributes to improving the reflectance of the material. However, if the amount added is increased, the material tends to become highly viscous, so the component (B1) alone cannot increase the filling rate. . The alumina of component (B2) can be highly filled because the viscosity of the material is difficult to increase, but the reflectance cannot be increased to the same level as component (B1) even if the filling rate is increased. By combining the (B1) component and the (B2) component, high reflection can be ensured with the (B1) component, and the combined use of the (B2) component can achieve high filling without excessively increasing the material viscosity.

  When the filling rate of alumina is high, the coefficient of linear expansion of the material is small, so that the change in dimensions during heat curing is small and molding becomes easy. Moreover, since the hardness after hardening becomes high, the intensity | strength of a resin molding increases, and also the heat dissipation of a resin molding increases because thermal conductivity becomes high. Thus, when the filling rate of alumina is increased, there is a merit that the material cost is lowered because the amount of (A) polyorganosiloxane which is generally more expensive than alumina is reduced.

The mass ratio [(B1) / (B2)] of the content of the component (B1) and the content of the component (B2) in the white pigment is usually in the range of 1/5 to 3/1, preferably 1/4. In the range of 2/1, more preferably in the range of 1/3 to 1/1.
If the component (B1) is less than 1/5, the reflectance of the resin molded product is low, and if it is more than 3/1, the viscosity of the material tends to increase, and high filling is difficult.

Further, the ratio [D (B1) / D (B2)] of the average secondary particle diameter D (B1) of the component (B1) and the average secondary particle diameter D (B2) of the component (B2) is not particularly limited. Preferably, it is in the range of 1 / 2.5 to 1/10, more preferably in the range of 1/3 to 1/5, and particularly preferably in the range of 1/3 to 1/4.
When the ratio of the average secondary particle diameter is smaller than the above range, there is a tendency that it is difficult to obtain an effect for sufficiently high filling.

  When the average secondary particle size is in the above range, a material preferable from the viewpoint of moldability is easily obtained. In addition, it is easy to adjust to a viscosity suitable for molding, and there is little wear on the mold. In addition, since the white pigment does not easily pass through the gap between the molds, burrs are not easily generated, and the mold gate is not easily clogged, so that troubles during molding hardly occur. When the secondary particle size of the component (B2) is larger than the above range, the material tends to be non-uniform due to the precipitation of the white pigment, and the moldability is impaired due to wear of the mold or clogging of the gate, The uniformity of the reflection of the material may be impaired.

The average secondary particle size is the center particle size. The center particle diameter means the particle diameter at the point where the volume-based particle size distribution curve of cumulative% intersects the horizontal axis of 50%, and generally refers to what is called 50% particle diameter (D ₅₀ ) and median diameter.

The aspect ratio of the primary particles of the component (B1) in the present invention is preferably 1.2 or more and 4.0 or less.
The aspect ratio of the primary particles of the component (B1) is more preferably 1.25 or more, further preferably 1.3 or more, and particularly preferably 1.4 or more. On the other hand, the upper limit is preferably 3.0 or less, more preferably 2.5 or less, still more preferably 2.2 or less, particularly preferably 2.0 or less. Most preferably, it is 8 or less.

  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. Thereby, in the semiconductor light-emitting device using this resin molding, LED output can be improved.

  In addition, the use of a white pigment having an aspect ratio in the above range is preferable from the viewpoint of moldability, such as less wear of the mold. When the aspect ratio is larger than the above range, the mold may be worn by contact with the corners of the pigment particles. Conversely, when a white pigment with a small aspect ratio is used, the white pigment There is a tendency for burrs to easily pass through the gaps in the mold. Furthermore, the use of a white pigment with an aspect ratio in the above range makes it easy to adjust the material viscosity. By adjusting to a viscosity suitable for molding, the molding cycle can be shortened and burrs can be suppressed. Or a material excellent in moldability.

  In particular, when the aspect ratio is larger than 4.0, it is difficult to be highly reflective, and wear of pipes, screws, molds, etc. is likely to occur during molding. There is a tendency for the reflectivity to decrease and dielectric breakdown to occur easily. The aspect ratio of the primary particles of the component (B2) is not particularly limited, and fibrous or plate-like alumina can be selected for the purpose of increasing the thermal conductivity of the material. For the purpose of suppressing wear and increasing the filling without increasing the viscosity as much as possible, it is desirable to select alumina having a small aspect ratio close to a spherical shape.

  The aspect ratio is generally used as a simple method for quantitatively expressing the shape of a particle. In the present invention, the major axis length (maximum major axis) of a particle measured by observation with an electron microscope such as SEM is the minor axis length. It is obtained by dividing by the length (the length of the longest part perpendicular to the major axis). When the axial length varies, a plurality of points (for example, 10 points) can be measured with an SEM and calculated from the average value. Alternatively, the same calculation result can be obtained by measuring 30 points and 100 points.

  The aspect ratio is an indicator of whether the shape of the particle is fibrous, rod-like, or spherical. The aspect ratio is large when the particle is fibrous, and is 1.0 when the particle is spherical.

  When the aspect ratio is in the above range, spherical and true spherical shapes are excluded from the preferable shape of the component (B1). In addition, an extremely long and narrow shape may lower the reflectance. When the aspect ratio is in the above range, the white pigment tends to clog the mold gap and hardly generates burrs, but in the case of a spherical shape, it tends to pass through the mold gap and easily generate burrs.

  The particles having an aspect ratio within the above range are preferably 60% by volume or more, more preferably 70% by volume or more, and particularly preferably 80% by volume or more based on the entire component (B1).

  In order to set the aspect ratio of the primary particles within the above range, a general method such as surface treatment or polishing of the white pigment may be employed. It can also be achieved by crushing (pulverizing) the white pigment to make it finer, or generating the white pigment by firing and crushing. Using the primary particles having a specific aspect ratio thus obtained, secondary particles may be prepared by a method known per se.

  Moreover, it is preferable that the primary particle diameter of (B1) component in this invention is 0.1 to 1.5 micrometer. The lower limit is preferably 0.15 μm or more, more preferably 0.2 μm or more, particularly preferably 0.25 μm or more, and the upper limit is preferably 1 μm or less, more preferably 0.8 μm or less, particularly preferably 0. .5 μm or less.

  When the primary particle size is in the above range, the material is easy to express high reflectivity by combining the backscattering tendency and the scattered light intensity, and the reflection with respect to light having a short wavelength particularly in the near ultraviolet region is increased, which is preferable. .

  When the particle size is too small, the white pigment tends to have a low reflectance because the scattered light intensity is low. When the particle size is too large, the scattered light intensity tends to increase, but the reflectance tends to decrease because it tends to scatter forward. There is a tendency.

  In order to obtain a material that can be suitably used for liquid injection molding, it is necessary that the material has a thixotropic property of a certain level or more. When the component (B1) having a primary particle size of 0.1 μm or more and 1.5 μm or less is added to the composition, the effect of imparting thixotropy is great, and the viscosity and thixotropy are improved in order to make the composition easy to mold with little burr and short. Can be adjusted easily.

  However, when only the component (B1) having a small particle size is used, the material tends to be highly viscous, and the filling amount of the white pigment cannot be increased. It tends to be difficult. By using the component (B2) having a secondary particle diameter of 2.0 μm or more for the purpose of increasing the filling ratio of the white pigment in the resin composition, it is possible to achieve both material properties such as high reflection and moldability. It becomes possible.

  As described above, the resin molded body material of the present invention contains, as a white pigment, two-component alumina [(B1) component and (B2) component] having different average secondary particle diameters in a specific mass ratio. It is. In the present invention, even when two components of white pigment (alumina) [(B1) component and (B2) component] having different average secondary particle diameters are mixed and used, the components (B1) and (B2) When a white pigment (alumina) having a particle size distribution of 2 or broad and containing a corresponding component in a mass ratio [(B1) / (B2)] in the range of 1/5 to 3/1 is used alone. included.

  Here, the primary particle in the present invention refers to an individual of the smallest unit that can be clearly distinguished from others among the particles constituting the powder, and the primary particle diameter is the primary particle measured by observation with an electron microscope such as SEM. The particle diameter. On the other hand, agglomerated particles formed by aggregating primary particles are called secondary particles. The center particle diameter of the secondary particles is the center particle diameter as described above, and refers to the particle diameter measured with a particle size analyzer or the like by dispersing the powder in an appropriate dispersion medium (for example, water in the case of alumina). When the primary particle size varies, several points (for example, 10 points) can be observed with an SEM, and the average value can be obtained as the particle size. In the measurement, when the particle diameter is not spherical, the longest length, that is, the length of the major axis is taken as the particle diameter.

  The aspect ratio and particle diameter of the white pigment can be measured even after molding (after curing). What is necessary is just to observe the cross section of a molded article with electron microscopes, such as SEM, and to measure the particle diameter and aspect ratio of the white pigment exposed to the cross section.

  In the present invention, the major axis length (maximum major axis) of the particles measured by observation with an electron microscope such as SEM is divided by the minor axis length (the length of the longest part perpendicular to the major axis). When the axial length varies, a plurality of points (for example, 10 points) can be measured with an SEM and calculated from the average value. Alternatively, the same calculation result can be obtained by measuring 30 points and 100 points.

  In addition, by detecting the characteristic X-rays generated by electron beam irradiation and spectrally diffusing with energy, alumina and other white pigments or silica fine particles (silica fine particles (silica fine particles) (SEM / EDX, etc.) are used for elemental analysis and composition analysis of the observed site A fluidity modifier).

  In the present invention, the ratio y / x of the primary particle diameter x of the component (B1) and the central particle diameter y of the secondary particles is usually 1 or more, preferably more than 1, particularly preferably 1.2 or more, Moreover, it is 10 or less normally, Preferably it is 5 or less.

  Here, since the ratio y / x of the primary particle diameter x and the center particle diameter y of the secondary particles is in the above range, the preferable shape of the component (B1) is formed into a spherical shape or a true spherical shape (that is, The primary particles are hardly agglomerated, and the primary particle size and the center particle size of the secondary particles are substantially equal).

  When the ratio y / x between the primary particle size x and the center particle size y of the secondary particles is in the above range, high reflectivity is likely to be manifested by scattering, and particularly the reflection of short-wavelength light in the near ultraviolet region is large. . Thereby, in the semiconductor light-emitting device using this resin molding, LED output can be improved. Moreover, adjustment to the material viscosity suitable for molding is also easy.

  In addition, when alumina contains elements other than aluminum and oxygen as impurities, it may be colored due to absorption in the visible light region. For example, if it contains even a small amount of chromium, it is generally called a ruby and exhibits a red color. If iron or titanium is contained as an impurity, it is generally called a sapphire and exhibits a blue color. As the alumina in the present invention, it is preferable to use chromium, iron and titanium having a content of 0.02% by mass or less, preferably 0.01% by mass or less.

  The heat conductivity at the time of curing of the resin molded body material of the present invention is preferably high, but in order to increase the heat conductivity, it is preferable to use alumina having a purity of 98% or more, and a purity of 99% or more. It is more preferable to use alumina, and it is particularly preferable to use low soda alumina. In order to increase the thermal conductivity, it is also preferable to use boron nitride together, and it is particularly preferable to use boron nitride having a purity of 99% or more.

  As the refractive index difference between (A) the polyorganosiloxane and (B) the white pigment is larger, the whiteness is higher even when a small amount of white pigment is added, and a resin molded product for a semiconductor light-emitting device with good reflection and scattering efficiency is obtained. be able to. The polyorganosiloxane (A) preferably has a refractive index of about 1.41, and alumina particles having a refractive index of 1.76 can be suitably used as the (B) white pigment. (A) The refractive index of the polyorganosiloxane is preferably 1.40 or more from the viewpoint of the hardness of the resin, and the refractive index difference with alumina tends to decrease and the reflectance tends to decrease, and the heat resistance tends to decrease. For reasons, 1.50 or less is preferable.

  In the present invention, it is preferable that the white pigment is mainly composed of alumina as described above from the viewpoint that the near-ultraviolet ray has a high light reflection effect and the alteration by the near-ultraviolet ray is small. Alumina has a low ability to absorb ultraviolet rays, and therefore can be suitably used particularly when used with a light emitting element emitting ultraviolet to near ultraviolet light. In the present invention, alumina refers to an oxide of aluminum, and its crystal form is not limited, but it is chemically stable, has a high melting point, high mechanical strength, high hardness, and high electrical insulation resistance. Alumina can be suitably used.

As the white pigment, other inorganic particles (inorganic particles other than alumina) and organic fine particles can be used as long as the effects of the present invention are not impaired.
Examples of other inorganic particles include metal oxides such as silicon oxide, titanium oxide (titania), zinc oxide, and magnesium oxide; calcium carbonate, barium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, calcium hydroxide, water Metal salts such as magnesium oxide; boron nitride, alumina white, colloidal silica, aluminum silicate, zirconium silicate, aluminum borate, clay, talc, kaolin, mica, synthetic mica and the like.

Examples of the organic fine particles 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. .
These inorganic particles and organic particles can be used alone or in combination of two or more.

  Of these, titanium oxide, zinc oxide, and the like are particularly preferable from the viewpoint that the whiteness is high and the light reflection effect is high even with a small amount, and it is difficult to change quality. Also, boron nitride and the like are particularly preferable from the viewpoint of improving the thermal conductivity when the material is cured. When titanium oxide is used, it can be contained to such an extent that problems such as photocatalytic properties, dispersibility, and whiteness do not occur.

Specific examples of titanium oxide include TA series and TR series manufactured by Fuji Titanium Industry Co., Ltd., TTO series, MC series, CR-EL series, PT series, ST series, FTL series, and TYPE WHITE manufactured by Ishihara Sangyo Co., Ltd. Specific examples of alumina include A30 series, AN series, A40 series, MM series, LS series, AHP series, “Admafine Alumina” AO-5 type, AO-8 made by Admatechs Type, CR series manufactured by Nippon Bikosky Co., Ltd., Tymicron manufactured by Daimyo Chemical Industry Co., Ltd., 10 μm ² diameter alumina powder manufactured by Aldrich, A-42 series, A-43 series, A-50 series, AS series manufactured by Showa Denko KK AL-43 series, AL-47 series , AL-160SG series, A-170 series, AL-170 series, Sumitomo Chemical AM series, AL series, AMS series, AES series, AKP series, AA series, etc. Includes UEP-100 manufactured by Daiichi Elemental Chemical Co., Ltd.
Specific examples of zinc oxide include two types of zinc oxide manufactured by Hakusui Tech Co., Ltd.

  In particular, in a semiconductor light emitting device using a light emitting element having an emission peak wavelength of 420 nm or more, titanium oxide can also be suitably used as a white pigment. Titanium oxide (titania) has an ultraviolet absorbing ability, but has a high refractive index and a strong light scattering property. Therefore, the reflectance of light having a wavelength of 420 nm or more is high, and high reflection is easily exhibited even with a small addition amount. The white pigment of the present invention is preferably a rutile type that is stable at high temperatures, has a high refractive index, and has a relatively high light resistance, rather than an anatase type that has a large ultraviolet absorption ability and photocatalytic ability and is unstable at high temperatures. A rutile type having a surface coated with a thin film of silica or alumina is particularly preferred for the purpose of suppressing the above.

  Titanium oxide has a high refractive index and a large difference in refractive index from polyorganosiloxane, so that even a small addition amount is likely to be highly reflective. Therefore, titanium oxide may be used in combination with alumina as a white pigment. For example, the mass ratio of titanium oxide to alumina (alumina: titanium oxide) can be mixed at a ratio of 60:40 to 95: 5.

  By adding a small amount of titanium oxide to alumina, there is a possibility that the reflectance of light having a wavelength of 420 nm or more will be higher than when alumina is used alone, and the ratio of white pigment in the material is small or Even when the thickness of the material is thin, the reflectance tends not to decrease. Since the ratio of the white pigment in the material can be reduced by the combined use of titania, the degree of freedom of the material composition is increased, and the filling amount of components other than the white pigment can be increased. Moreover, the high reflectance of a thin material is very advantageous in that the degree of freedom of the shape of the resin molded body is increased. Further, even a thin resin molded body that cannot be increased in thickness or a resin molded body having a fine structure can be expected to have an effect of increasing the brightness of the semiconductor light-emitting device due to the high reflectance of the material.

  The white pigment may be surface treated with a silane coupling agent or the like. When a white pigment surface-treated with a silane coupling agent is used, the hardness of the entire resin molded material can be improved.

<1-2-1. (B) Addition amount of white pigment>
In the present invention, the content of the white pigment (B) in the resin molded body material for a semiconductor light-emitting device is appropriately selected depending on the particle size and type of the pigment used and the difference in refractive index between the polyorganosiloxane and the pigment. (A) It is 20 mass parts or more normally with respect to 100 mass parts of polyorganosiloxane, Preferably it is 80 mass parts or more, More preferably, it is 100 mass parts or more, Usually 900 mass parts or less, Preferably it is 600 mass parts or less, More preferably 400 parts by mass or less.

  When it is within the above range, reflectivity, moldability and the like are good. If it is less than the above lower limit, light tends to be transmitted and the reflection efficiency of the semiconductor light emitting device tends to decrease, and if it is larger than the upper limit, the fluidity of the material tends to deteriorate and the moldability tends to decrease. is there.

  In particular, in order to obtain a material that can be suitably used for liquid injection molding, it is necessary that the material has a thixotropic property of a certain level or more. When a white pigment having a primary particle size of 0.1 μm or more and 1.5 μm or less is blended in the composition, the viscosity increases markedly and the effect of imparting thixotropy is great. By containing at least%, it is possible to make the material easy to mold with few burrs and shorts, and it becomes easy to adjust the viscosity and thixotropy. In order to control thermal conductivity, boron nitride may be used in combination with alumina as a white pigment.

<1-3. (C) Curing catalyst>
The (C) curing catalyst in the present invention 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). It is in this addition polymerization catalysts, such as platinum black, platinic chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid with olefins, platinum bisacetoacetate and the like And platinum group metal catalysts such as platinum-based catalysts, palladium-based catalysts, and rhodium-based catalysts. The blending amount of the (C3) addition polymerization catalyst can be a catalytic amount, but is usually 1 ppm or more, preferably 2 ppm or more with respect to the total mass of the components (C1) and (C2) as a platinum group metal. 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 mass or more, preferably 0.05% by mass or more, on the other hand, based on the total mass of the components represented by the formula (3) and / or (4). Is usually 10% by mass or less, preferably 6% by mass 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) Curing rate control agent>
The resin molding material for a semiconductor light emitting device of the present invention preferably further contains (D) 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 such as 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne and 1-ethynyl-1-cyclohexanol. Examples include alcohols, ene-yne compounds, and maleic esters such as 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 the organic sulfur compound 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.

  A modified silicone in which a functional group having an effect as a curing retarder such as an aliphatic unsaturated bond is introduced into a part of the polyorganosiloxane by a covalent bond can also be suitably used as the curing retarder. Such a polymer-type curing retarder is preferable because it has characteristics such as being easily mixed with the base polyorganosiloxane and being less likely to volatilize than a low-molecular curing retarder.

  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 50 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 0.1 to 10 parts by mass with respect to 100 parts by mass of the total of (A) polyorganosiloxane thermosetting resin and (C) 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.

<1-5. Other ingredients>
The material for a resin molded body for a semiconductor light emitting device of the present invention can further contain one or more other components in any ratio and combination as necessary.

  For example, solid particles can be included as the (E) fluidity adjusting agent for the purpose of controlling the fluidity of the resin molded body material for a semiconductor light emitting device and suppressing the precipitation of 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.

  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 used in the present invention 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 (that is, silanol group) bonded to at least one silicon atom in one molecule. Linear 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 desirable.

  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. The diorganosiloxane repeating unit constituting the main chain of the organopolysiloxane 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-dihydroxydiphenylpolysiloxane, α, ω-dihydroxymethylphenylpolysiloxane, α, ω-dihydroxy (dimethylsiloxane / diphenylsiloxane) copolymer, α , Ω-dihydroxy (dimethylsiloxane / methylphenylsiloxane) copolymer, and the like.

  The compounding amount of the polyorganosiloxane as a liquid thickener is usually 0 to 10 parts by mass, preferably 0.1 to 5 parts by mass, more preferably 0, when the total amount of (A) polyorganosiloxane is 100 parts by mass. About 5 to 3 parts by mass.

  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 500 mass parts or less with respect to 100 mass parts of polyorganosiloxane, Preferably it is 200 mass parts or less.

  In addition, the 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 above components (A) to (E) in the material for a resin molded product of the present invention are as follows.
The content of (A) polyorganosiloxane in the resin molded body material of the present invention is not limited as long as it can be used as a normal resin molded body material. It is 20 mass% or less, Preferably it is 20 mass% or more and 40 mass% or less, More preferably, it is 25 mass% or more and 35 mass% or less. In addition, when the liquid thickener which is (D) 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 white pigment (B) in the resin molded material of the present invention is not limited as long as it can be used as a normal resin molded material, but is usually 30% by mass or more and 85% by mass of the entire material. %, Preferably 40% to 80% by mass, more preferably 45% to 70% by mass.

  The content of the (E) fluidity modifier in the resin molded material of the present invention is not limited as long as it does not impair the effects of the present invention, but is usually 55% by mass or less of the entire material, preferably They are 2 mass% or more and 50 mass% or less, More preferably, they are 5 mass% or more and 45 mass% or less.

  Further, the ratio of the total amount of (B) white pigment and (E) fluidity modifier to the whole resin molded material is preferably 50% by mass or more, more preferably 60% by mass or more. 65% by mass or more is particularly preferable, 90% by mass or less is preferable, and 85% by mass or less is more preferable.

<1-6. Viscosity of resin molding material>
The resin molded material of the present invention preferably has a viscosity of 10 Pa · s to 10,000 Pa · s 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 of the present invention has a viscosity ratio 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. ( 1s- ¹ / 100s- ¹ ) is preferably 15 or more, more preferably 20 or more, and particularly preferably 30 or more. On the other hand, the upper limit is preferably 500 or less, and more preferably 300 or less.

Further, the viscosity of the resin molded body material of the present invention is, in particular, a viscosity at a shear rate of 100 s ⁻¹ at 25 ° C. of 1,000 Pa · s or less, and at a shear rate of 100 s ⁻¹ at 25 ° C. It is preferable that the ratio of the viscosity at a shear rate of 1 s ⁻¹ at 25 ° C. (1 s ⁻¹ / 100 s ⁻¹ ) to the viscosity of 15 is 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 10,000 Pa · s or less. 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 15 or more, the occurrence of burrs and short molds (unfilled) is small, and the measurement time of the material at the time of molding, The 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 15, that is, when the viscosity at a 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 0.1 μm or more and 1.5 μm or less) are blended in the material, a significant increase in viscosity occurs and the effect of imparting thixotropy is great. Therefore, when (B) white pigment having a primary particle size of 0.1 μm or more and 1.5 μm or less, or (E) fluidity modifier in a fine region such as fumed silica having a large specific surface area, thixotropy of the composition is used. Easy to control sex. Specifically, it is preferable to contain 20% by mass or more of (B1) white pigment having a primary particle size of 0.1 μm or more and 1.5 μm or less, more preferably (B) white pigment, fumed silica or quartz beads. The viscosity of the material can be controlled within the above range by combining 50 to 85% by mass in total with the (E) fluidity modifier other than the white pigment.

  When using a white pigment with a secondary particle size larger than 2 μm, especially when using a pigment with a central particle size of 5 μm or more, use a fluidity modifier in a fine region with a large thixotropic effect. However, when the primary particle size of the white pigment itself is sufficiently small, it can be used only with the white pigment without being used in combination with the fluidity adjusting agent, and the flow having a relatively large central particle size of about several μm or more. You may combine with a sex modifier.

<1-7. Thermal conductivity of resin molding material>
The resin molded body material of the present invention preferably has a thermal conductivity at curing of 0.4 W / (m · K) or more and 3.0 W / (m · K) or less, 0.6 W / More preferably, it is not less than (m · K) and not more than 2.0 W / (m · K) . 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.

  In response to such a problem, the present inventors have a resin molded body and a semiconductor light emitting device configured using the resin molded body because the thermal conductivity at the time of curing, that is, when the resin molded body is formed by molding, is in the above range. The present inventors have found that the durability of the device is improved because heat dissipation against heat generated by light emitted from the semiconductor light emitting element is improved.

When the thermal conductivity is less than 0.4 W / (m · K) , 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 using alumina or boron nitride as the white pigment (B) contained in the resin molding material for a semiconductor light emitting device.

<1-8. Reflectivity of resin molding>
Moreover, it is preferable that the resin molding using the resin molding material of the present invention can maintain a high reflectance with respect to visible light. Specifically, the reflectance of light at 460 nm is preferably 80% or more, and more preferably 90% or more. The reflectance of light having a wavelength of 400 nm is preferably 60% or more, more preferably 80% or more, and further preferably 90% or more.

Here, the reflectance of the resin molded body refers to the reflectance when the molded body obtained by thermosetting the resin molded body material of the present invention and molded to a thickness of about 0.4 mm to 0.5 mm or less is measured. . The thermosetting can be performed, for example, by curing at 180 ° C. for 4 minutes under a pressure of 10 kg / cm ² .

  The reflectance of the resin molded body is the type of resin (for example, the reflectance can be controlled by changing the refractive index of the resin), the type of white pigment (filler), the particle size of the white pigment (filler), It can be controlled by the content.

<2. Manufacturing method of resin molding>
The resin molding which the package for semiconductor light-emitting devices of this invention is provided is obtained by shape | molding the resin composition (material for resin moldings) demonstrated below.

<2-1. Manufacturing method of resin composition>
As a raw material to be used, as described above, in addition to (A) polyorganosiloxane, (B) white pigment and (C) curing catalyst, (D) a curing rate control agent (curing retarder or curing accelerator), (E) Fluidity modifiers and other additives can be used.

  Here, the blending amount of each raw material is not particularly limited as long as the effect of the present invention is obtained, but the blending amount of (A) polyorganosiloxane is 15 to 70 with respect to 100 parts by mass of the resin composition. The blending amount of the white pigment (B) is 20 to 80 parts by mass, preferably 30 to 70 parts by mass with respect to 100 parts by mass of the resin composition, and (E) The compounding quantity of a fluidity modifier is 1-50 mass parts with respect to 100 mass parts of resin compositions, Preferably it is 3-30 mass parts. Moreover, the compounding quantity of (C) curing catalyst is 1-20 ppm as a platinum concentration with respect to polyorganosiloxane, for example, if it is a platinum-type catalyst, Preferably it is 2-10 ppm. (D) The compounding quantity of a cure rate control agent (curing retarder) is 0.1-1000 mol with respect to 1 mol of the curing catalysts to be used, Preferably it is 1-50 mol. Moreover, these hardening retarders may be used independently and may be used together 2 or more types.

  When mixing each raw material, polyorganosiloxane can be used as a liquid medium. For example, a predetermined amount of polyorganosiloxane, a white pigment (filler), a curing catalyst, and the like are weighed and mixed with a mixer, a high-speed disper, a homogenizer, a three-roller, a kneader, a centrifugal defoaming device, or the like. Can be mixed.

  In the present invention, the method of mixing the inorganic particles is not particularly limited, but it is preferable to mix while defoaming using a planetary stirring mixer, a rotation / revolution vacuum mixer, a thin film swirl mixer, or the like. For example, as a planetary mixer, T.M. K. Hibismix, Iwata Iron Works' planetary mixer and planetary despa, Inoue's planetary mixer and trimix, PD mixer, Ashizawa Finetech's 2-axis planetary mixer PLM, 3-axis planetary mixer 3PLM, etc. Can be mentioned. In the case of centrifugal stirring, a rotating / revolving vacuum mixer (specifically, ARV310 manufactured by Sinky, V-mini300V manufactured by EME, Mazerustar manufactured by Kurabo Industries, etc.) can be used. As a thin film swirl type mixer, T.M. K. Examples of the mortar mold kneader include Miracle KCK manufactured by Iwata Iron Works.

  In addition, when mixing small particles such as aerosil which are easy to aggregate, after the small particles are mixed, the aggregated particles are crushed using a bead mill or three rolls as necessary, and then a white pigment (filler Large particle components that are easy to mix may be mixed.

  In the step of mixing each raw material, if the resin composition to be produced contains a large amount of moisture, the amount of SiH present in the resin molded body decreases, and if the amount of moisture decreases, the amount of SiH present in the resin molded body tends to increase. Therefore, it is preferable to adjust the moisture content so that the SiH abundance is in a specific range. In order to reduce the mixing of moisture into the resin composition, the mixing can be performed under a reduced pressure atmosphere. The pressure during decompression is usually 0 kPa or more, preferably 0.1 kPa or more, more preferably 0.5 kPa or more, and usually 40 kPa or less, preferably 30 kPa or less, more preferably 20 kPa or less. Below this range, it is difficult to maintain the degree of decompression, requiring a highly accurate device, which may not be economical. Moreover, when it exceeds this range, the removal of moisture tends to be insufficient.

Moreover, as an atmosphere at the time of decompression, air, an inert gas such as nitrogen or a rare gas, or the like is preferable.
The relative humidity of the atmosphere at the time of depressurization varies depending on the temperature and pressure, the type of equipment used in the depressurization process and the operation method, but generally cannot be said, but generally the relative humidity before the depressurization operation is 25 ° C., usually 0% or more, Preferably it is 5% or more, and is usually 80% or less, preferably 70% or less, more preferably 60% or less. Below this range, a special desiccant device is used although the water removal efficiency is increased, which may be uneconomical and inferior in productivity. Moreover, when it exceeds this range, the removal of moisture tends to be insufficient.

  Moreover, when the material temperature at the time of mixing is made too low compared with the temperature of the atmosphere, the moisture content of the resin composition is increased by local condensation.

  Moreover, the moisture content to a resin composition can also be reduced by drying with hot air before mixing a white pigment (filler) and a fluidity modifier, for example, silica fine particles. The temperature during hot air drying is preferably 150 ° C. or higher, and more preferably 250 ° C. or higher.

  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-pack type, for example, (i) a polyorganosiloxane resin composition mainly composed of a polyorganosiloxane, a white pigment (filler), and a fluidity modifier, and (ii) a curing catalyst and a curing retarder. It is also possible to prepare two liquids of a crosslinking agent liquid as a main component and mix (i) the polyorganosiloxane resin composition and (ii) the crosslinking agent liquid immediately before use.

  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 be difficult to decrease, it is preferable to adjust the environmental temperature during storage so that the SiH abundance falls within a specific range.

<2-2. Molding method>
Examples of the molding method for the resin molded body 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 100 ° C. or lower, preferably 80 ° C. or lower, more preferably 60 ° C. or lower. The mold temperature is 80 ° C to 300 ° C, preferably 100 ° C to 250 ° C, more preferably 120 ° C to 200 ° C. 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 is usually 3 seconds to 600 seconds, preferably 5 seconds to 200 seconds, and more preferably 10 seconds to 60 seconds.

  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, mold gap accuracy of 10 μm or less, preferably 5 μm 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 property is improved by curing shrinkage.

  The time to completion of curing is usually within 60 seconds, preferably within 30 seconds, and more preferably within 10 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 to 1200 seconds, preferably 5 seconds to 900 seconds, and more preferably 10 seconds to 600 seconds.

  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 is usually 3 seconds to 1200 seconds, preferably 5 seconds to 900 seconds, and more preferably 10 seconds to 600 seconds.

  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, and more preferably 170 ° C. or higher and 200 ° C. or lower. The post-curing time is usually from 3 minutes to 24 hours, preferably from 5 minutes to 10 hours, more preferably from 10 minutes to 5 hours.

<3. Semiconductor Light Emitting Device Package and Semiconductor Light Emitting Device>
The resin molded body for a semiconductor light emitting device of the present invention is usually used as a semiconductor light emitting device with a semiconductor light emitting element mounted thereon. 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 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 entirely made of the resin molded body material of the present invention, or a part thereof may be made of the resin molded body material of the present invention. As a specific example when a part of the resin molded body 2 is made of the resin molded body material of the present invention, the resin molded body of the reflector portion 102 is replaced with the resin molded body material of the present invention as shown in FIG. The mode which shape | molds from 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 made of the resin molded body material of the present invention can make the exposed area of the lead frame 5 extremely small. Since the resin molded body obtained by molding the resin molded body material of the present invention tends to have the same or higher reflectivity as the lead frame material (for example, silver), the package can be obtained even if the exposed area of the resin molded body is increased. High reflectance can be maintained. Therefore, by using a package made of the resin molded body material of the present invention, a semiconductor light emitting device having a configuration different from that of the conventional package can be obtained.

  For example, FIG. 3 shows a semiconductor light emitting device 200 with a conventional package. In the semiconductor light emitting device of FIG. 3, the exposed area of the lead frame 204 is large. This is because the reflectance of the resin molded body 201 is lower than that of the lead frame 204, so that the surface area of the lead frame 204 using a material with high reflectance is increased in order for the semiconductor light emitting device to achieve high brightness. There was a need to do. When such an exposed area of the lead frame 204 is large, when the package is used in the light emitting device, the lead frame may be discolored due to discoloration, but as shown in FIG. By reducing the exposed area of the lead frame 5, it is possible to prevent a decrease in light emission efficiency due to such discoloration of the lead frame.

  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 embodiment of the semiconductor light emitting device 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 them 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 part, the phosphor part may be provided in the light source part 103 or the window part 107. 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 multilayer structure in which each color of the phosphor to be used is divided, striped, or dot-like in order to reduce self-absorption of fluorescence and reabsorption between RGB phosphors. A pattern 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. Since the resin molded body according to the present invention has a high reflectance of ultraviolet to visible light and is excellent in heat resistance and light resistance, the number of necessary semiconductor light-emitting elements can be reduced to provide an inexpensive, high-brightness, and highly durable lighting device. . In particular, since the resin molded body of the present invention has a high reflectance of ultraviolet to blue light, it can effectively reflect light emitted from the semiconductor light emitting element before being wavelength-converted by the phosphor, and the phosphor layer can be reflected from the light source section. It is suitable for an embodiment installed at a remote position. When the emission color of the semiconductor light emitting device is from ultraviolet to near ultraviolet, the reflector filler (white pigment) is preferably composed mainly of alumina, and when it is blue, it is preferable to use titania in combination with alumina.

  A resin molded body for a semiconductor light emitting device formed using the material for a resin molded body for a semiconductor light emitting device of the present invention preferably has the following characteristics.

<3-1. Reflectivity of semiconductor light emitting device package>
The semiconductor light emitting device package of the present invention is characterized in that it can maintain a high reflectance not only for visible light but also for near ultraviolet light and ultraviolet light having a wavelength shorter than purple. The reflectance of light having wavelengths of 360, 400, and 460 nm is usually 60% or more, preferably 80% or more, and more preferably 90% or more. The semiconductor light emitting device package provided with the resin molding of the present invention having a high reflectance from the ultraviolet light region to the visible light region has extremely excellent characteristics that cannot be recognized by the conventional semiconductor light emitting device package. In particular, the semiconductor light emitting device package made of a resin such as polysiloxane has characteristics that have not been easily conceived by those skilled in the art, and has extremely high technical significance.

<3-2. Semiconductor Light Emitting Device Package Thickness>
The semiconductor light emitting device package of the present invention normally has a chip mounting surface and a bottom surface on the opposite side of 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 risk that light will be transmitted to the bottom surface and the reflectance will decrease, and the package will have insufficient strength and will be deformed due to handling, etc. If it is too thick, the package itself will be thick and bulky. Application application of the semiconductor light emitting device is limited.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Incidentally, various production conditions and evaluation result values in the following examples have meanings as preferred values of the upper limit or lower limit in the embodiment of the present invention, and the preferred range is the above-described upper limit or lower limit value. It may be a range defined by a combination of values of the following examples or values of the examples.

1. Preparation of liquid thermosetting polyorganosiloxane A vinyl polydimethylsiloxane having both ends containing a platinum compound as a curing catalyst [vinyl group: 0.3 mmol / g, the total of trifunctional silicon and tetrafunctional silicon is about 15 of the total silicon. %, Viscosity: 4200 mPa · s, mass average molecular weight (MW): 9600. Platinum concentration: 14 ppm] and hydrosilyl group-containing polydimethylsiloxane [vinyl group: 0.04 mmol / g, hydrosilyl group: 4.8 mmol / g, and the total of trifunctional silicon and tetrafunctional silicon is about 20% of the total silicon. , Viscosity 700 mPa · s, mass average molecular weight (MW): 9800], and polydimethylsiloxane (vinyl group: 0.2 mmol / g, hydrosilyl group: 0) bonded with an alkynyl group acting as a curing rate control agent (curing retarder) 0.1 mmol / g, the total of trifunctional silicon and tetrafunctional silicon is 0%, the alkynyl group of the curing retarder: 0.2 mmol / g, the viscosity of 500 mPa · s, and the mass average molecular weight (MW): 10800] The mixture was mixed at 100: 10: 5 and stirred at normal temperature to obtain a liquid thermosetting polyorganosiloxane having a platinum concentration of 12 ppm.

  The liquid thermosetting polyorganosiloxane had a refractive index of 1.41. Moreover, the mass mean molecular weight (MW) of a raw material compound is a measured value in gel permeation chromatography measured using polystyrene as a standard substance.

2. Preparation of composition for semiconductor light emitting device package and preparation of test piece <Example 1>
The liquid thermosetting polyorganosiloxane obtained above, (B1) α-alumina (primary particle diameter 0.3 μm, purity 99.1%, aspect ratio 1.48) with an average secondary particle diameter of 1.2 μm, (B2) α-alumina having an average secondary particle size of 3.6 μm (primary particle size of 3 to 5 μm, purity of 99.9%), silica fine particles “AEROSIL RX200” (manufactured by Nippon Aerosil Co., Ltd .: specific surface area) : 140 m ² / g) at a mass ratio shown in Table 1 and agitated to disperse the white pigment and the silica fine particles in the liquid thermosetting polyorganosiloxane. Resin molding material) was obtained.
This composition was heated and cured at 150 ° C. for 3 minutes with a hot press so as to have a predetermined thickness to obtain a circular test piece (test piece) having a diameter of 13 mm.

<Examples 2-4, Comparative Examples 1-3>
Liquid thermosetting polyorganosiloxane, (B) (B1) or (B2) as white pigment, (E) Other than changing the blending amount of silica fine particles “AEROSIL RX200” as fluidity adjusting agent as shown in Table 1 Obtained a test piece under the same conditions as in Example 1. “(A) Silicone” in Table 1 is the amount of “liquid thermosetting polyorganosiloxane containing curing catalyst and retarder”.

3. Evaluation (1) Viscosity The viscosity before curing of the compositions of Examples 1 and 2 and Comparative Examples 1 to 3 was evaluated based on the viscosity of the composition of Comparative Example 1 that can be molded by injection molding. . The results are shown in Table 2.

(2) Linear expansion coefficient About each composition of the said Examples 1 and 2 and Comparative Examples 1-3, liquid thermosetting polyorganosiloxane [(A) silicone], (B) white pigment, (E) fluidity | liquidity adjustment agent linear expansion coefficient (RX200) were respectively ^{300 (× 10 -6 /℃),8.5(×10 -6 /℃),0.5(×10} -6 / ℃), the volume ratio (vol% ) To calculate the linear expansion coefficient of the composition. The calculated values are shown in Table 2.

(3) Shore D hardness Each test piece (thickness 3 mm) obtained in the above example and comparative example was post-cured in a thermostat at 200 ° C. for 20 minutes, and then the two test pieces were stacked. The Shore D hardness near the center of the test piece was measured according to JIS K6753 using a plastic hardness meter KORI Durometer KR-25D. The results are shown in Table 2.

(4) Reflectance For each of the test pieces of Examples 1 and 2 and Comparative Examples 1 to 3, the reflectance of light at a wavelength of 360 nm to 740 nm is measured at a measurement diameter of 6 mm using SPECTROTOPOMETER CM-2600d manufactured by Konica Minolta. did. Table 2 shows the thickness and reflectance of each test piece.

<Evaluation of results>
According to Table 2, in Examples 1 and 2 using the component (B1) and the component (B2) as the white pigment (B), the filling rate of the white pigment in the composition while maintaining a good moldability viscosity. Compared with Comparative Example 1 containing only the component (B1), the cured product had a higher hardness and a smaller linear expansion coefficient. Although the reflectivity was lower than that of Comparative Example 1, a sufficiently high reflectivity of about 90% or more was shown, and a well-balanced molding material was obtained.

In Comparative Example 2 in which only the component (B1) was used as the white pigment and the filling rate of the white pigment in the composition was increased, the hardness of the cured product was increased, but the viscosity of the composition was increased and molding became difficult. . In Comparative Example 3 in which only the component (B2) was used as the white pigment, the reflectance was low despite increasing the white pigment filling rate up to (A) / (B) = 100/567. It was found that it was difficult to guarantee the reflectance.
From these results, it is possible to obtain a highly reflective and moldable material by using together the component (B1) contributing mainly to high reflection and the component (B2) contributing to high filling as the white pigment. It was.

DESCRIPTION OF SYMBOLS 1 Semiconductor light-emitting element 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 200 Semiconductor light-emitting device 201 Resin molding 202 Semiconductor light emitting element 203 Encapsulant 204 Lead frame

Claims (8)

(A) a polyorganosiloxane, (B) a white pigment, and (C) a resin molding material for a semiconductor light-emitting device containing a curing catalyst, wherein (A) the polyorganosiloxane is an addition polymerization curing type, The content of the (B) white pigment is 80 parts by weight or more and 900 parts by weight or less per 100 parts by weight of the (A) polyorganosiloxane, and the (B) white pigment is
(A) an alumina,
(B) The alumina contains (B1) a component having an average secondary particle size of 0.2 μm or more and 1.5 μm or less, and (B2) a component having an average secondary particle size of 2 μm or more and 30 μm or less,
(C) the (B1) the amount of the component and (B2) weight ratio of the content of the component [(B1) / (B2)] is Ri Der range from 1/5 of 3/1,
(D) The secondary particles of the component (B1) are composed of primary particles having an aspect ratio of 1.2 to 4.0, and (e) the primary particle diameter x of the component (B1) and the central particles of the secondary particles A resin molded body material, wherein a ratio (y / x) of the diameter y is 1 or more and 10 or less . The ratio [D (B1) / D (B2)] of the average secondary particle diameter D (B1) of the component (B1) to the average secondary particle diameter D (B2) of the component (B2) is 1/2. The resin molded body material according to claim 1, wherein the material is in a range of 1/10 to 1/10. Furthermore, (D) hardening rate modifier and / or (E) fluidity modifier are contained, The material for resin moldings of Claim 1 or 2 characterized by the above-mentioned.   The material for resin moldings according to any one of claims 1 to 3, wherein the material is for liquid injection molding. It claims 1 to resin molding for semiconductor light-emitting device which is characterized in that by molding the material according to any one of 4. A method for producing a resin molded body for a semiconductor light-emitting device, wherein the material according to any one of claims 1 to 4 is subjected to liquid injection molding. 6. The resin molded body according to claim 5 , which is used for a package of a semiconductor light emitting device.   A semiconductor light-emitting device comprising the resin molded body according to claim 7.

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