US20120286220A1 - Material for a molded resin for use in a semiconductor light-emitting device - Google Patents

Material for a molded resin for use in a semiconductor light-emitting device Download PDF

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Publication number
US20120286220A1
US20120286220A1 US13/529,587 US201213529587A US2012286220A1 US 20120286220 A1 US20120286220 A1 US 20120286220A1 US 201213529587 A US201213529587 A US 201213529587A US 2012286220 A1 US2012286220 A1 US 2012286220A1
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Prior art keywords
molded resin
semiconductor light
white pigment
light
emitting device
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US13/529,587
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Inventor
Mayuko Takasu
Takeshi Otsu
Kenichi Takizawa
Yutaka Mori
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Assigned to MITSUBISHI CHEMICAL CORPORATION reassignment MITSUBISHI CHEMICAL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: OTSU, TAKESHI, MORI, YUTAKA, TAKASU, MAYUKO, TAKIZAWA, KENICHI
Publication of US20120286220A1 publication Critical patent/US20120286220A1/en
Priority to US14/100,096 priority Critical patent/US9105822B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/56—Materials, e.g. epoxy or silicone resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/016—Additives defined by their aspect ratio
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/49—Structure, shape, material or disposition of the wire connectors after the connecting process of a plurality of wire connectors
    • H01L2224/491—Disposition
    • H01L2224/49105—Connecting at different heights
    • H01L2224/49107—Connecting at different heights on the semiconductor or solid-state body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
    • H01L2933/0091—Scattering means in or on the semiconductor body or semiconductor body package

Definitions

  • the present invention relates to a material for a molded resin that is used in a semiconductor light-emitting device that has a light-emitting element, for example, a light-emitting diode, and to a molding made of the material.
  • a light-emitting element for example, a light-emitting diode
  • a semiconductor light-emitting device made, by mounting a semiconductor light-emitting element is composed of, for example, a semiconductor light-emitting element 1 , a molded resin 2 , a bonding wire 3 , an encapsulant 4 , and a lead frame 5 .
  • the structure comprising the electroconductive metal interconnects, e.g., the lead frame, and the insulating molded resin is referred to as the package.
  • Insulating materials provided by incorporating a white pigment in a thermoplastic resin, e.g., a polyamide, have already entered into general use as insulating materials used for molded resins (refer, for example, to Patent Document 1).
  • a white pigment e.g., a polyamide
  • Patent Document 1 In the case of semiconductor light-emitting devices where directionality is required of the emitted light, the light-emitting efficiency is raised not just by the light emitted in the desired direction from the semiconductor light-emitting element, but also by causing light emitted in undesired directions to be reflected from, e.g., the molded resin, metal interconnects such as the lead frame, and reflectors, into the desired direction.
  • thermoplastic resins such as polyamides are light permeable
  • the light-emitting efficiency of a semiconductor light-emitting device can be raised by incorporating—when light is to be reflected by the molded resin—a white pigment in the resin and reflecting the light emitted from the semiconductor light-emitting element by utilizing the difference in the refractive indices between the resin and white pigment.
  • Polyamides are thermoplastic resins, and polyamides are thus softened by this heat and the heat resistance of the package then becomes a problem in the case of packages that use polyamide.
  • polyamides are subject to photodegradation and thermal degradation by ultraviolet radiation and heat, and degradation by light has become a problem in particular when light-emitting elements are used that have a light-emission range that extends into high-energy wavelength regions, such as the blue to near-ultraviolet semiconductor light-emitting elements whose commercialization has been ongoing in the recent years.
  • thermal degradation and photodegradation have become even more significant problems due to the heat and high luminous flux light generated by the semiconductor light-emitting element as a result of contemporary demands for brighter light-emitting elements.
  • an alumina-containing sintered ceramic may be used as the insulating material in those cases in which heat resistance is required (refer, for example, to Patent Document 2).
  • a package that uses this ceramic does have a good heat resistance, but its production requires a high-temperature sintering step post-molding.
  • This sintering step has posed the following problems: cost problems due, for example, to electricity costs; the ease of appearance of defective products due to changes in the size and shape of the molding caused by sintering; and an impaired productivity.
  • Patent Document 1 Japanese Patent Application Laid-open No. 2002-283498
  • Patent Document 2 Japanese Patent Application Laid-open No. 2004-288937
  • Patent Document 3 Japanese Patent Application Laid-open No. 2009-155415
  • titanium oxide has a low dispersibility in the resin when, during the step of preparing the resin composition, titanium oxide is added to and mixed into the polyorganosiloxane used for the resin. As a consequence, the titanium oxide is not uniformly dispersed in the molded resin provided by the cure of the resin composition and the reflectivity within the molded resin is then not constant, which results in problems with the uniformity of the light emitted from the semiconductor light-emitting device.
  • titanium oxide is photocatalytic
  • the molded resin in proximity to a titanium oxide particle is degraded by the light emitted by the semiconductor light-emitting element and by the light generated by phosphors excited by the light emitted by the semiconductor light-emitting element.
  • the light resistance of the molded resin is seriously impaired when a semiconductor light-emitting element is used that emits light in the blue region and when a semiconductor light-emitting element is used that emits light in the near-ultraviolet region.
  • titanium oxide has an absorption wavelength in the near-ultraviolet region and as a result its color assumes a yellowish tinge. Due to this, the spectrum of the light emitted from the semiconductor light-emitting element is altered, producing a problem with the whiteness and the color rendering property of the light emitted by the semiconductor light-emitting device.
  • the whiteness and the color rendering property in particular are major requirements for the white semiconductor light-emitting devices that are currently the subject of active research, and titanium oxide is also unfavorable from this perspective.
  • a problem for the present invention is to provide a material for a molded resin wherein the material can yield a highly durable (light resistance and heat resistance) molded resin for a semiconductor light-emitting device and can also improve the LED output through an excellent reflectivity.
  • Another problem for the present invention is to provide an easily moldable material for a molded resin for a semiconductor light-emitting device.
  • the present inventors discovered that the problems indicated above could be solved by the use of a white pigment that has specific shape characteristics in the material—wherein this material comprises a polyorganosiloxane, a white pigment, and a curing catalyst—for the molded resin for a semiconductor light-emitting device.
  • a material for a molded resin for a semiconductor light-emitting device comprising (A) a polyorganosiloxane, (B) a white pigment, and (C) a curing catalyst, wherein the white pigment (B) has the following characteristics (a) and (b):
  • a primary particle aspect ratio is 1.2 or more and 4.0 or less
  • a primary particle diameter is 0.1 ⁇ m or more and 2.0 ⁇ m or less.
  • a molded resin for a semiconductor light-emitting device that is obtained by molding the material for a molded resin according to any of (1) to (10).
  • a method of producing a molded resin comprising:
  • a semiconductor light-emitting device that has the molded resin according to any of (11) to (13).
  • a material for a molded resin for a semiconductor light-emitting device comprising (A) a polyorganosiloxane, (B) a white pigment, and (C) a curing catalyst, wherein
  • a viscosity at a shear rate of 100 s ⁇ 1 and at 25° C. is 10 Pa ⁇ s or more and 10,000 Pa ⁇ s or less, and a ratio of a viscosity at a shear rate of 1 s ⁇ 1 to a viscosity at a shear rate of 100 s ⁇ 1 is at least 15.
  • a highly durable (strongly light resistant and heat resistant) molded resin for a semiconductor light-emitting device that also brings about an improved LED output through its excellent reflectivity, can be obtained using the material of the present invention for a molded resin.
  • the present invention provides an easy-to-mold material for a molded resin for a semiconductor light-emitting device.
  • FIG. 1 is a cross-sectional diagram that schematically depicts the structure of one mode of a semiconductor light-emitting device
  • FIG. 2 is a cross-sectional diagram that schematically depicts the structure of another mode of a semiconductor light-emitting device
  • FIG. 3 is a cross-sectional diagram that schematically depicts one mode of a semiconductor light-emitting device that is provided with a conventional package;
  • FIG. 4 is a graph that shows the results of reflectivity measurements on the test pieces of Examples 1 to 7 and Comparative Examples 1 to 6;
  • FIG. 5 is a graph that shows the results of reflectivity measurements on the test pieces of Examples 8 and 9 and Comparative Example 7;
  • FIG. 6 is a graph that shows the results of viscosity measurements on the molded resin materials of Examples 1 to 7 and Comparative Examples 2, 4, and 5.
  • the material of the present invention for a molded resin for a semiconductor light-emitting device is a material that is used to mold a molded resin for a semiconductor light-emitting device. It specifically contains (A) a polyorganosiloxane, (B) a white pigment, and (C) a curing catalyst.
  • the molded resin for a semiconductor light-emitting device is a molding provided by the cure of the material and forms a package for a semiconductor light-emitting device by molding with an electroconductive metal interconnect such as a lead frame.
  • the semiconductor light-emitting device is a light-emitting device that contains a semiconductor light-emitting element in the aforementioned molded resin for a semiconductor light-emitting device.
  • a schematic diagram of the cross section of a semiconductor light-emitting device is shown in FIG. 1 .
  • the polyorganosiloxane in the present invention denotes a polymeric substance in which an organic group is added onto a structure that has a moiety in which a silicon atom is bonded across oxygen to another silicon atom.
  • This polyorganosiloxane is preferably a liquid at normal temperature and normal pressure. This facilitates handling of the material during molding of the molded resin for a semiconductor light-emitting device.
  • a polyorganosiloxane that is solid at normal temperature and normal pressure while generally having a relatively high hardness in the form of the cured material, tends to often have a low toughness due to the low energy required for rupture and to have an inadequate light resistance and heat resistance and thus be susceptible to discoloration by light or heat.
  • the normal temperature referenced above denotes a temperature in the range of 20° C. ⁇ 15° C. (5 to 35° C.), and the normal pressure denotes a pressure equal to atmospheric pressure and is approximately one atmosphere, in addition, liquid denotes a state that exhibits fluidity.
  • the aforementioned polyorganosiloxane generally denotes an organic polymer in which the siloxane bond makes up the main chain and can be exemplified by a compound represented by the following compositional formula (1) and by mixtures thereof.
  • R 1 to R 6 in formula (1) are each independently selected from organic functional groups, the hydroxyl group, and the hydrogen atom.
  • the main units making up the polyorganosiloxane are the monofunctional unit [R 3 SiO 0.5 ] (triorganosilhemioxane), difunctional unit [R 2 SiO] (diorganosiloxane), trifunctional unit [RSiO 1.5 ] (organosiisesquioxane), and tetrafunctional unit [SiO 2 ] (silicate).
  • the properties of the polyorganosiloxane can be changed by altering the constituent proportions of these four units, and the polyorganosiloxane is synthesized using a suitable selection therefrom so as to obtain the desired characteristics.
  • methylchlorosilane can be synthesized, for example, by the direct reaction of silicon Si and methyl chloride at high temperatures in the presence of a Cu catalyst
  • silanes having an organic group, e.g., the vinyl group can be synthesized by standard methods in organic synthetic chemistry.
  • a silanol is produced when the isolated organochlorosilane, either as the individual organochlorosilane or as a mixture of organochlorosilanes in any proportion, is hydrolyzed with water, and the polyorganosiloxane, which is the basic skeleton of a silicone, is synthesized by the dehydration synthesis of the silanol.
  • the polyorganosiloxane can be cured in the presence of a curing catalyst by the application of, for example, thermal energy or light energy.
  • This curing refers to a change from a state that exhibits fluidity to a state that docs not exhibit fluidity.
  • the uncured state refers to a state in which fluidity is present when a specimen is held for 30 minutes while inclined 45° from the horizontal, while a state in which fluidity is entirely absent can be assessed as the cured state.
  • Polyorganosiloxanes can generally be classified by curing mechanism into addition polymerization curing type polyorganosiloxanes, polycondensation curing type polyorganosiloxanes, ultraviolet curing type polyorganosiloxanes, and peroxide vulcanization type polyorganosiloxanes.
  • addition polymerization curing types additional-type polyorganosiloxanes
  • condensation curing types condensation-type polyorganosiloxanes
  • polyorganosiloxanes that cure by hydrosilylation (addition polymerization) which does not produce by-products and is not a reversible reaction, are more favorable. The reason for this is that when by-products are produced during the molding step, they tend to raise the pressure within the molded container and/or to remain as bubbles within the cured material.
  • Addition-type polyorganosiloxanes refer to polyorganosiloxanes in which the polyorganosiloxane chain is crosslinked by an organic addition bond.
  • (C1) a silicon-containing compound having an alkenyl group, e.g., a vinylsilane
  • an addition polymerization catalyst such as a Pt catalyst.
  • the alkenyl group-bearing silicon-containing compound (C1) can be exemplified by a polyorganosiloxane represented by the following general formula (2)
  • Each R in formula (2) is independently selected from identical or different substituted or unsubstituted monovalent hydrocarbon groups and alkoxy groups and the hydroxyl group, and n is a positive number that satisfies 1 ⁇ n ⁇ 2.
  • the alkenyl group in the alkenyl group-bearing silicon-containing compound (C1) is preferably a C 2-8 alkenyl group, for example, the vinyl group, allyl group, butenyl group, pentenyl group, and so forth.
  • R is a hydrocarbon group, it is selected from C 1-20 monovalent hydrocarbon groups, e.g., alkyl groups such as the methyl group and ethyl group, the vinyl group, the phenyl group, and so forth. The methyl group, ethyl group, and phenyl group are preferred.
  • Each may be different, but when UV resistance is required, preferably about 65% of the R in the preceding formula is the methyl group (that is, the number of non-methyl functional groups present with reference to the number of Si (number of moles) is preferably not more than 0.35 (mol)) and more preferably at least 80% of the R in the preceding formula is the methyl group.
  • R may also be a C 1-8 alkoxy group or the hydroxyl group, but the content of the alkoxy group and hydroxyl group is preferably not more than 10 weight % of the alkenyl group-bearing silicon-containing compound (C1).
  • n is a positive number that satisfies 1 ⁇ n ⁇ 2.
  • this value is greater than or equal to 2, an adequate strength is not obtained for the adhesion between the conductors, e.g., the lead frame, and the material for a molded resin, while synthesis of this polyorganosiloxane becomes quite difficult when this value is less than 1.
  • the alkenyl group-bearing silicon-containing compound (C1) can be, for example, a vinylsilane or a vinyl group-containing polyorganosiloxane, and a single one of these can be used by itself or two or more may be used in any ratio and combination.
  • a vinyl group-containing polyorganosiloxane having at least two vinyl groups in the molecule is preferred among the preceding.
  • vinyl group-containing polyorganosiloxanes that have at least two vinyl groups in the molecule.
  • DMS-V00, DMS-V03, DMS-V05, DMS-V21, DMS-V22, DMS-V25, DMS-V31, DMS-V33, DMS-V35, DMS-V41, DMS-V42, DMS-V46, and DMS-V52 all from Gelest, Inc.
  • PDV-0325, PDV-0331, PDV-0341, PDV-0346, PDV-0525, PDV-0541, PDV-1625, PDV-1631, PDV-1635, PDV-1641, PDV-2331, and PDV-2335 all from Gelest, Inc.
  • VDT-123, VDT-127, VDT-131, VDT-153, VDT-431, VDT-731, and VDT-954 all from Gelest, Inc.
  • VTT-106 and MTV-124 both from Gelest, Inc.
  • the hydrosilyl group-bearing silicon-containing compound (C2) can be, for example, a hydrosilane or a hydrosilyl group-bearing polyorganosiloxane, and a single one of these can be used by itself or two or more may be used in any ratio and combination.
  • a hydrosilyl group-bearing polyorganosiloxane that has at least two hydrosilyl groups in the molecule is preferred here.
  • polyorganosiloxanes that contain at least two hydrosilyl groups in the molecule.
  • DMS-H03, DMS-H11, DMS-H21, DMS-H25, DMS-H31, and DMS-H41 all from Gelest, Inc.
  • HMS-013, HMS-031, HMS-064, HMS-071, EMS-082, HMS-151, HMS-301, and HMS-501 all from Gelest, Inc.
  • the alkenyl group-bearing silicon compound (C1) and the hydrosilyl group-bearing silicon compound (C2) are used in the present invention in amounts that provide generally 0.5 mol or more, preferably 0.7 mol or more, and more preferably 0.8 mol or more, but generally 4.0 mol or less, preferably 3.0 mol or less, and even more preferably 2.0 mol or less of the hydrosilyl group-bearing silicon compound (C2) (number of moles of the hydrosilyl group) per 1 mole of the alkenyl group-bearing silicon compound (C1) (number of moles of the alkenyl group).
  • Controlling the number of moles of hydrosilyl group with reference to the alkenyl group makes it possible to lower the post-cure amount of unreacted terminal groups and to thereby obtain a cured material that exhibits little timewise variation, e.g., discoloration or delamination, during use as a light source.
  • reaction sites (crosslinking sites) where hydrosilylation occurs is preferably 0.1 mmol/g or more and 20 mmol/g or less in the resin itself free of the white pigment for both the alkenyl group and hydrosilyl group. 0.2 mmol/g or more and 10 mmol/g or less is more preferred.
  • the viscosity of the resin prior to the addition of the white pigment is generally not more than 100,000 cp and is preferably not more than 20,000 cp and more preferably is not more than 10,000 cp. While there are no particular limitations on the lower limit, it is generally at least 15 cp in view of the relationship with the volatility (boiling point).
  • the weight-average molecular weight of the resin is preferably 500 or more and 100,000 or less. It is more preferably 700 or more and 50,000 or, less. Furthermore, at least 1,000 is even more preferred for the purpose of providing a small volatile component (in order to maintain the adhesiveness with other articles) and not more than 25,000 is also even more preferred from the standpoint of the ease of handling of the material prior to molding. Not more than 20,000 is most preferred.
  • the condensation-type polyorganosiloxanes can be exemplified by compounds that have the Si—O—Si bond at the crosslinking sites and are obtained by the hydrolysis/polycondensation of alkylalkoxysilane.
  • Specific examples are the polycondensates obtained by the hydrolysis/polycondensation of compounds represented by the following general formulas (3) and/or (4), and/or their oligomers.
  • M represents silicon;
  • X represents a hydrolyzable group;
  • Y 1 represents a monovalent organic group;
  • m represents an integer greater than or equal to 1 that represents the valence of M;
  • n represents an integer greater than or equal to 1 that represents the number of X groups.
  • m represents silicon;
  • X represents a hydrolyzable group;
  • Y 1 represents a monovalent organic group;
  • m represents an integer greater than or equal to 1 that represents the valence of M;
  • n represents an integer greater than or equal to 1 that represents the number of X groups.
  • m ⁇ n.
  • M represents silicon;
  • X represents a hydrolyzable group;
  • Y 1 represents a monovalent organic group;
  • Y 2 represents an organic group of valence u;
  • s represents an integer greater than or equal to 1 that represents the valence of M;
  • t represents an integer that is greater than or equal to 1 and less than or equal to s ⁇ 1; and
  • u represents an integer greater than or equal to 2.
  • condensation-type polyorganosiloxanes can be used; for example, the members for semiconductor light-emitting devices described in Japanese Patent Application Laid-open Nos. 2006-77234, 2006-291018, 2006-316264, 2006-336010, and 2006-348284 and WO 2006/090804 are suitable.
  • condensation-type polyorganosiloxanes are described in the following.
  • polyorganosiloxanes In the case of use in semiconductor light-emitting devices, polyorganosiloxanes generally exhibit a weak adhesiveness to, for example, the semiconductor light-emitting elements, the substrates on which the semiconductor light-emitting devices are placed, the molded resins, and so forth, and condensation-type polyorganosiloxanes that have at least one of the following characteristics [1] and [2] are preferred in order to provide a polyorganosiloxane that is highly adhesive to the preceding.
  • the silicon content is at least 20 weight %.
  • the measured solid-state Si-nuclear magnetic resonance (NMR) spectrum has at least one of the following peaks (a) and/or (b) that originate with Si.
  • a condensation-type polyorganosiloxane having characteristic [1] of the preceding characteristics [1] and [2] is preferred in the present invention, while a condensation-type polyorganosiloxane having characteristics [1] and [2] is more preferred.
  • a condensation-type polyorganosiloxane does produce a liberated component as the condensation reaction progresses, but can be used in those cases in which, depending on the molding method, this component does not have a substantial influence on the moldability.
  • the silanol content in the condensation-type polyorganosiloxane is particularly preferably 0.01 weight % or more and 10 weight % or less.
  • a known pigment that does not interfere with resin curing can be selected as appropriate for the white pigment in the present invention.
  • An inorganic material and/or an organic material can be used for the white pigment.
  • white denotes colorlessness and the absence of transparency. Thus, it refers to the color that can cause the diffuse reflection of incident light by a substance that does not exhibit a specific absorption wavelength in the visible region.
  • Inorganic particles that can be used as the white pigment can be exemplified by metal oxides such as alumina (also referred to below as “finely divided alumina powder” or “aluminum oxide”), silicon oxide, titanium oxide (titania), zinc oxide, magnesium oxide, and so forth; metal salts such as calcium carbonate, barium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, and so forth; as well as boron nitride, alumina white, colloidal silica, aluminum silicate, zirconium silicate, aluminum borate, clay, talc, kaolin, mica, synthetic mica, and so forth.
  • metal oxides such as alumina (also referred to below as “finely divided alumina powder” or “aluminum oxide”), silicon oxide, titanium oxide (titania), zinc oxide, magnesium oxide, and so forth
  • metal salts such as calcium carbonate, barium carbonate, magnesium carbonate, barium sul
  • Finely divided organic particles that can be used as the white pigment can be exemplified by resin particles such as fluororosin particles, guanamine resin particles, melamine resin particles, acrylic resin particles, silicone resin particles, and so forth, but there is no limitation to any of the preceding.
  • resin particles such as fluororosin particles, guanamine resin particles, melamine resin particles, acrylic resin particles, silicone resin particles, and so forth.
  • alumina, titanium oxide, and zinc oxide are particularly preferred among the preceding.
  • alumina and boron nitride are particularly preferred.
  • Alumina is particularly preferred also from the perspective of obtaining a high light reflection action for near-ultraviolet radiation with little deterioration induced by the near-ultraviolet radiation.
  • a single one of the preceding may be used or a mixture of two or more of the preceding may be used.
  • titanium oxide when used, it may be incorporated to a degree that does not bring out the problems with photocatalysis, dispersibility, or whiteness.
  • the titanium oxide can be specifically exemplified by the TA series and TR series from Fuji Titanium Industry Co., Ltd., and the TTO series, MC series, CR-EL series, PT series, ST series, and FTL series from Ishihara Sangyo Kaisha, Ltd.
  • the alumina can be specifically exemplified by the A30 series, AN series, A40 series, MM series, LS series, and AHP series from Nippon Light Metal Co., Ltd.; “Admafine Alumina” type AO-5 and AO-8 from Admatechs Co., Ltd.; the CR series from Baikowski Japan Co., Ltd.; Taimicron from Taimei Chemicals Co., Ltd.; alumina powder with a diameter of 10 ⁇ m 2 from Aldrich; the A-42 series, A-43 series, A-50 series, AS series, AL-43 series, AL-47 series, AL-160SG series, A-170 series, and AL-170 series from Showa Denko Kabushiki Kaisha; and the AM series, AL series, AMS series, AES series, AKP series, and AA series from Sumitomo Chemical Co., Ltd.
  • the zirconia can be specifically exemplified by UEP-100 from Daiichi Kigenso Kagaku Kogyo Co., Ltd.
  • the zinc oxide can be specifically exemplified by JIS grade 2 zinc oxide from HakusuiTech Co., Ltd.
  • a larger difference between the refractive index of the polyorganosiloxane (A) and the refractive index of the white pigment (B) provides a higher whiteness, even at small amounts of addition of the white pigment, and makes it possible to obtain a better reflection and scattering efficiency for the molded resin for a semiconductor light-emitting device.
  • the polyorganosiloxane (A) preferably has a refractive index of approximately 1.41, and alumina particles having a refractive index of 1.76 are preferably used as the white pigment (B).
  • the refractive index of the polyorganosiloxane (A) is preferably at least 1.40 from the standpoint of the hardness of the resin, but is preferably not more than 1.50 because smaller differences with the refractive index of alumina result in a declining reflectivity and a declining heat resistance.
  • the white pigment in the present invention is preferably alumina because alumina has a high light reflecting activity for near-ultraviolet radiation and undergoes little near-ultraviolet-induced deterioration.
  • Alumina exhibits a low absorption capacity for ultraviolet radiation and for this reason is well adapted for use in combination with a light-emitting element that emits light in the ultraviolet to near-ultraviolet.
  • alumina denotes the oxide of aluminum, and, while its crystalline form is not critical, ⁇ -alumina, which has such properties as a high chemical stability, a high melting point, a high mechanical strength, a high hardness, and a high electrical insulation resistance, is well suited for use.
  • the crystallite size of the alumina crystals is preferably 500 ⁇ or more and 2,000 ⁇ or less, more preferably 700 ⁇ or more and 1,500 ⁇ or less, and particularly preferably 900 ⁇ or more and 1,300 ⁇ or less.
  • crystallite denotes the largest aggregate that can be regarded as a single crystal.
  • the primary particle diameter of the alumina being in the range indicated above and the crystallite size of the alumina crystals being in the range indicated above mean that the primary particle size is different from the crystallite size, that is, that a primary particle is composed of a plurality of crystallites.
  • the crystallite size of the alumina crystals is preferably in the range indicated above because this results in little wear of the piping, screw, mold, and so forth, during molding, and also inhibits the wear-induced incorporation of impurities.
  • the crystallite size can be checked by X-ray diffraction measurements.
  • a peak is generated in the X-ray diffraction measurement at a position determined in conformity to the crystal form.
  • the crystallite diameter (crystallite size) can be calculated according to the Scherrer equation from the half-width value of this peak.
  • the presence as an impurity of elements other than aluminum and oxygen in the alumina is disfavored as this can lead to coloration due to absorption in the visible light region.
  • chromium when chromium is present, even in trace amounts, this is generally called a ruby and a red color is taken on; when iron or titanium is present as an impurity, this is generally called a sapphire and a blue color is displayed.
  • the alumina used in the present invention preferably has a content of chromium, iron, and titanium of not more than 0.02 weight % each and more preferably not more than 0.01 weight % each.
  • a higher thermal conductivity for the cured material is preferred for the material of the present invention for a molded resin, and the use of at least 98% pure alumina is preferred for raising the thermal conductivity while the use of at least 99% pure alumina is more preferred and the use of low soda alumina is particularly preferred.
  • the use of boron nitride is also preferred for raising the thermal conductivity, and the use of at least 99% pure boron nitride is particularly preferred.
  • Titanium oxide can also be suitably used as the white pigment in particular in semiconductor light-emitting devices that use a light-emitting element that has a peak light emission wavelength at 420 nm or greater. While titanium oxide (titania) does have the ability to absorb ultraviolet radiation, due to its large refractive index and strong light scattering ability it has a high reflectivity for light at wavelengths of 420 nm and above and readily exhibits strong reflection even at small amounts of addition.
  • the rutile type is preferred for the white pigment of the present invention because it is more stable at high temperatures, has a higher refractive index, and has a relatively higher light resistance than the anatase type, which is unstable at high temperatures and exhibits a large capacity to absorb ultraviolet radiation and a high photocatalytic activity.
  • the use of rutile type that has been surface-coated with a thin film of silica or alumina is particularly preferred with the goal of restraining the photoactivity.
  • Alumina and titanium oxide may be used in combination since titanium oxide has a high refractive index and thus provides a large refractive index difference from polyorganosiloxanes and therefore readily provides strong reflection even at small amounts of addition.
  • they can be mixed in proportions that yield a weight ratio of titanium oxide versus alumina (alumina:titanium oxide) of 50:50 to 95:5.
  • the addition of a small amount of titanium oxide to the alumina has the potential to raise the reflectivity for light at wavelengths of 420 nm and greater over that for the use of alumina by itself and also tends to restrain the decline in the reflectivity in the case of small proportions of the white pigment in the material and in the case of a thin material.
  • titania makes it possible to use the white pigment in smaller proportions in the material, which results in greater freedom in the formulation of the material composition and makes it possible to raise the amount of loading with components other than the white pigment.
  • a higher reflectivity by the thin material is very advantageous in terms of raising the degree of freedom for the shape of the molded resin.
  • a high reflectivity for the material even where a large thickness is not possible, as in the case of thin molded resins and fine-structured molded resins, can be expected to have the effect of increasing the brightness of the semiconductor light-emitting device.
  • a surface treatment may be carried out on the white pigment using, for example, a silane coupling agent.
  • the hardness of the molded resin material as a whole can be improved when a white pigment is used that has been surface-treated with a silane coupling agent.
  • the primary particles of the white pigment (B) characteristically have an aspect ratio 1.2 or more and 4.0 or less in the present invention.
  • the aspect ratio of the white pigment (B) is preferably at least 1.25, more preferably at least 1.3, and even more preferably at least 1.4.
  • the upper limit is preferably not more than 3.0, more preferably not more than 2.5, even more preferably not more than 2.2, particularly preferably not more than 2.0, and most preferably not more than 1.8.
  • the aspect ratio is in the range indicated above, a high reflectivity due to scattering is readily manifested and in particular a large reflection is obtained for the short wavelength light of the near-ultraviolet region. This results in an improved LED output for a semiconductor light-emitting device that uses the molded resin under consideration.
  • a white pigment having an aspect ratio in the above-indicated range is also preferred in terms of the moldability, i.e., a low mold wear is obtained.
  • the aspect ratio is larger than the above-indicated range, severe mold wear may occur due to contact with the angular regions of the pigment particles.
  • mold wear is again prone to occur because the frequency of contact between the mold and pigment is increased due to an increase in the packing density of the pigment in the material.
  • the viscosity of the material can be easily adjusted when a white pigment having an aspect ratio in the above-indicated range is used, and adjustment to a viscosity favorable for molding can provide a material with an excellent moldability, i.e., the molding cycle can be shortened and flashing can be inhibited.
  • the aspect ratio is larger than 4.0, it is then difficult to obtain strong reflection; wear of the plumbing, screw, mold, and so forth, will readily occur during molding; and, due to the incorporation of impurities caused by the wear, the molded resin product is prone to have a reduced reflectivity and is also readily susceptible to dielectric breakdown.
  • the aspect ratio is generally used as a convenient method for quantitatively expressing the shape of, for example, a particle, and is determined in the present invention by dividing the length of the major axis (the largest long diameter) of a particle, as measured by observation with an electron microscope, e.g., with an SEM, by the length of the minor axis (the length of the longest part in the direction perpendicular to the long diameter).
  • a plurality of points (10 points, for example) can be measured by SEM and the length of the axis can be determined from their average value. Or, by measuring 30 points or 100 points the same result can be obtained from the calculation.
  • the aspect ratio is an index to whether the shape of the particle is fibrillar or rod-like or is spherical, and a particle with a fibrillar shape has a large aspect ratio while a spherical particle has an aspect ratio of 1.0.
  • the present invention excludes spherical and perfectly spherical shapes from the shapes preferred for the white pigment (B).
  • highly elongated shapes because they instead cause a lowering of the reflectivity, are also excluded from the white pigment (B) according to the present invention.
  • the white pigment tends to block clearances in the mold and thereby inhibits the occurrence of flashing; with a spherical shape, however, clearances in the mold are traversed and flashing tends to occur easily.
  • particles having an aspect ratio encompassed by the previously indicated range preferably account for at least 60 volume %, more preferably at least 70 volume %, and particularly preferably at least 80 volume % of the white pigment (B) as a whole.
  • the individual skilled in the art will naturally understand that this is not a case where the entire white pigment (B) must necessarily satisfy the aspect ratio range indicated above.
  • Ordinary methods e.g., grinding and/or subjecting the white pigment to a surface treatment, may be used to bring the aspect ratio into the range indicated above. This can also be achieved by microfine-sizing by grinding (pulverizing) the white pigment and/or by producing the white pigment by calcination.
  • the white pigment (B) in the present invention encompasses the finely divided inorganic particles/finely divided organic particles provided above as examples in 1-2.
  • its shape is preferably a (c) crushed shape.
  • This (c) crushed shape denotes the shape provided when the white pigment is microfine-sized mainly by grinding (pulverization) and also includes shapes—as provided by a post-grinding treatment—that somewhat take on a roundness having small crystal angles, as well as the nonspherical pigment shapes produced by, for example, calcination.
  • the intent is to exclude, from the standpoint of the nature of the production process, white pigment formed with a spherical or perfectly spherical shape.
  • the material that uses a white pigment having a crushed shape more readily exhibits a high scattering-induced reflectivity than does the material that uses a spherical white pigment and in particular exhibits greater reflection of the short wavelength light in the near-ultraviolet region (particularly light with a wavelength of 360 nm to 460 nm). It can also be more favorable from an economic standpoint than a spherical pigment.
  • the LED output can thus be improved based on the preceding in a semiconductor light-emitting device that uses the molded resin under consideration.
  • the primary particle diameter of the white pigment (B) is preferably 0.1 ⁇ m or more and 2 ⁇ m or less in the present invention.
  • the value of the lower limit is preferably at least 0.15 ⁇ m, more preferably at least 0.2 ⁇ m, and particularly preferably at least 0.25 ⁇ m, while the value of the upper limit is preferably not more than 1 ⁇ m, more preferably not more than 0.8 ⁇ m, and particularly preferably not more than 0.5 ⁇ m.
  • the material can readily exhibit a high reflectivity because it combines the scattered light intensity with a backscattering tendency and in particular strongly reflects short wavelength light, e.g., in the near-ultraviolet region, and is thus preferred.
  • the primary particle diameter of the white pigment When the primary particle diameter of the white pigment is too small, the scattered light intensity is low and as a consequence the reflectivity tends to be low; when the primary particle diameter is too large, the scattered light intensity is high, but the reflectivity tends to be small due to the appearance of a forward scattering tendency.
  • a primary particle diameter in the above-indicated range is also preferred from the standpoint of the moldability, e.g., facile adjustment to a viscosity suitable for molding, low mold wear, and so forth.
  • the primary particle diameter exceeds the range given above, contact with the pigment particles subjects the mold to a large impact and substantial mold wear then tends to occur.
  • a white pigment is used that has a primary particle diameter below the range given above, the material readily assumes a high viscosity and the loading volume by the white pigment cannot be raised, and as a result it tends to be difficult to achieve a balance between the moldability and the properties of the material, e.g., high reflection.
  • the material must be provided with at least a certain degree of thixotropic nature in order to yield a material suitable for use in liquid injection molding.
  • a white pigment with a primary particle diameter 0.1 ⁇ m or more and 2.0 ⁇ m or less has a substantial ability to impart thixotropic nature when added to the composition, and the viscosity and thixotropic nature can then be easily adjusted to provide an easy-to-mold composition that exhibits little flashing or short molding.
  • a combination with a white pigment having a primary particle diameter larger than 2 ⁇ m can also be used in order, for example, to raise the filling rate for the white pigment in the resin composition.
  • the primary particle referenced by the present invention is the smallest solid unit that can be clearly separated from among the other particles that make up a powder, and the primary particle diameter denotes the particle diameter of a primary particle as measured by observation with an electron microscope, e.g., an SEM.
  • a secondary particle refers to an aggregated particle formed by the aggregation of primary particles, and the median diameter of the secondary particles refers to the particle diameter measured using, for example, a particle distribution analyzer, with the powder dispersed in a suitable dispersing medium (for example, water in the case of alumina).
  • a suitable dispersing medium for example, water in the case of alumina.
  • the SEM observation can be performed at several points (for example, 10 points) and the average value thereof can be determined and used as the particle diameter.
  • the longest length i.e., the length of the major axis, is used for the particle diameter.
  • the aspect ratio and primary particle diameter of the white pigment can be measured even after molding (post-curing).
  • a cross section of the molded product can be observed with an electron microscope, e.g., with an SEM, and the primary particle diameter and aspect ratio can be measured on the white pigment exposed in the cross section.
  • a plurality of points (10 points, for example) can be measured by SEM and the length of the axis can be determined from their average value. Or, 30 points or 100 points can be measured and the result can be used from the same calculation.
  • the median diameter of the secondary particles (also referred to below as the “secondary particle diameter”) of the aforementioned white pigment is preferably at least 0.2 ⁇ m and more preferably at least 0.3 ⁇ m.
  • the upper limit is preferably not more than 10 ⁇ m, more preferably not more than 5 ⁇ m, and even more preferably not more than 2 ⁇ m.
  • a preferred material in terms of moldability can be readily obtained when the secondary particle diameter is in the above-indicated range.
  • adjustment to a viscosity suitable for molding can be easily carried out and there is little mold wear.
  • the appearance of flashing is inhibited because the ability of the white pigment to pass through clearances in the mold is inhibited, and the occurrence of problems during molding is inhibited because mold gate clogging is inhibited.
  • the secondary particle diameter exceeds the above-indicated range, the material tends to become nonuniform due to sedimentation of the white pigment and the moldability is impaired due to mold wear and gate clogging and the uniformity of reflection by the material is impaired.
  • a combination with a white pigment having a secondary particle diameter larger than 10 ⁇ m can also be used in order, for example, to raise the filling rate for the white pigment in the resin composition.
  • the median diameter refers to the particle diameter at the point where the volume based particle size distribution curve in cumulative % intersects with the horizontal axis at 50% and is typically referred to as the 50% particle diameter (D 50 ) or the median diameter.
  • the ratio y/x of the median diameter y of the secondary particles to the primary particle diameter x of the white pigment (B) is generally at least 1 in the present invention and is preferably larger than 1 and more preferably is at least 1.2, and is generally not more than 10 and preferably not more than 5.
  • white pigment formed in a spherical or perfectly spherical shape that is, there is almost no aggregation of primary particles and the primary particle diameter and the median diameter of the secondary particles are approximately equal
  • white pigment (B) formed in a spherical or perfectly spherical shape (that is, there is almost no aggregation of primary particles and the primary particle diameter and the median diameter of the secondary particles are approximately equal) is excluded from the preferred shapes for the white pigment (B).
  • the ratio y/x of the median diameter y of the secondary particles to the primary particle diameter x is in the above-indicated range, a high reflectivity is readily manifested due to scattering and in particular short wavelength light in the near-ultraviolet region is substantially reflected. This makes it possible to raise the LED output in a semiconductor light-emitting device that uses the molded resin under consideration. Moreover, adjustment to a material viscosity suitable for molding is also easily carried out.
  • the content of the white pigment (B) in the molded resin material for a semiconductor light-emitting device in the present invention is selected as appropriate as a function of the particle diameter and type of the pigment used and the difference between the refractive indexes of the polyorganosiloxane and pigment.
  • the content of the white pigment (B) is generally at least 20 weight parts, preferably at least 50 weight parts, and more preferably at least 100 weight parts and is generally not more than 900 weight parts, preferably not more than 600 weight parts, and more preferably not more than 400 weight parts.
  • the material must be provided with at least a certain degree of thixotropic nature in order to yield a material suitable for use in liquid injection molding.
  • a white pigment with a primary particle diameter 0.1 ⁇ m or more and 2.0 ⁇ m or less is incorporated in the composition, a substantial increasing viscosity occurs and a large thixotropic nature imparting effect is obtained.
  • the incorporation of at least 30 weight %, with reference to the composition as a whole, of a white pigment with such a shape can provide an easily moldable material that exhibits little flashing or short molding and also facilitates adjustment of the viscosity and thixotropic nature.
  • the addition is preferred, expressed with reference to the total weight of the material for a molded resin, of 40 weight parts or more and 90 weight parts or less of alumina as the white pigment (B).
  • the addition is preferred, expressed with reference to the total weight of the material for a molded resin, of 30 weight parts or more and 90 weight parts or less of boron nitride as the white pigment (B).
  • Alumina and boron nitride may also be used in combination.
  • the curing catalyst (C) in the present invention is a catalyst that cures the polyorganosiloxane (A).
  • the polyorganosiloxane cures with the polymerization reaction being accelerated by the catalyst.
  • This catalyst is an addition polymerization catalyst or a polycondensation catalyst depending on the curing mechanism for the polyorganosiloxane.
  • the addition polymerization catalyst is a catalyst for accelerating the hydrosilylation addition reaction between the alkenyl group in component (C1) and the hydrosilyl group in component (C2), and this addition polymerization catalyst can be exemplified by platinum group metal catalysts such as platinum-based catalysts, e.g., platinum black, platinic chloride, chloroplatinic acid, the reaction product of chloroplatinic acid and a monohydric alcohol, a chloroplatinic acid/olefin complex, and platinum bisacetoacetate; palladium-based catalysts; and rhodium-based catalysts.
  • platinum group metal catalysts such as platinum-based catalysts, e.g., platinum black, platinic chloride, chloroplatinic acid, the reaction product of chloroplatinic acid and a monohydric alcohol, a chloroplatinic acid/olefin complex, and platinum bisacetoacetate
  • palladium-based catalysts e.g., platinum black, platinic chlor
  • the amount of incorporation of this addition polymerization catalyst (C3) can be a catalytic amount, and, expressed as the platinum group metal with reference to the total weight of (C1) and (C2), is generally at least 1 ppm and preferably at least 2 ppm and generally is not more than 100 ppm, preferably not more than 50 ppm, and more preferably not more than 20 ppm. Operating in accordance with the preceding can provide a high catalytic activity.
  • an acid such as hydrochloric acid, nitric acid, sulfuric acid, or an organic acid, or an alkali such as ammonia or an amine, or a metal chelate compound
  • a metal chelate compound containing at least one selection from Ti, Ta, Zr, Al, Hf, Zn, Sn, and Pt can be favorably used as the polycondensation catalyst.
  • the metal chelate compound preferably contains at least one selection from Ti, Al, Zn, and Zr, wherein the use of a metal chelate compound that contains Zr is more preferred.
  • These catalysts are selected considering the stability when incorporated in the molded resin material for a semiconductor light-emitting device, the film hardness, the nonyellowing performance, and the curability.
  • the amount of incorporation of the polycondensation catalyst is generally at least 0.01 weight % and preferably at least 0.05 weight %, while the upper limit is generally not more than 10 weight % and preferably not more than 6 weight %.
  • the molded resin material for a semiconductor light-emitting device has an excellent curability and storage stability and the quality of the molded resin product is also excellent. Problems may appear with the storage stability of the molded resin material when the amount of addition exceeds the upper limit value. At below the lower limit value, long curing times are encountered and the molded resin productivity declines and there is also a tendency for the quality of the molded resin to be reduced due to uncured components.
  • the material of the present invention for a molded resin for a semiconductor light-emitting device preferably also contains a cure rate controlling agent (D).
  • This cure rate controlling agent is used to control the cure rate during molding of the molded resin material in order to improve its molding efficiency and can be exemplified by retarders and hardening accelerators.
  • the retarders can be exemplified by compounds that contain an aliphatically unsaturated bond, organophosphorus compounds, organosulfur compounds, nitrogenous compounds, tin compounds, organoperoxides, and so forth, and these may be used in combination.
  • the compounds that contain an aliphatically unsaturated bond can be exemplified by propargyl alcohols such as 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne, and 1-ethynyl-1-cyclohexanol; ene-yne compounds; and maleic acid esters such as dimethyl maleate.
  • Compounds that contain a triple bond are preferred among these compounds containing an aliphatically unsaturated bond.
  • the organophosphorus compounds can be exemplified by triorganophosphites, diorganophosphines, organophosphines, and triorganophosphites.
  • the organosulfur compounds can be exemplified by organomercaptans, diorgano sulfides, hydrogen sulfide, benzothiazole, thiazole, and benzothiazole disulfide.
  • the nitrogenous compounds can be exemplified by ammonia, primary to tertiary alkylamines, arylamines, urea, and hydrazine.
  • the tin compounds can be exemplified by stannous halide dihydrates and stannous carboxylates.
  • the organoperoxides can be exemplified by di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.
  • benzothiazole, thiazole, dimethyl maleate, 3-hydroxy-3-methyl-1-butyne, and 1-ethynyl-1-cyclohexanol are preferred for their excellent retardation activity and ease of reagent acquisition.
  • the lower limit on the amount of addition is preferably at least 10 ⁇ 1 mol and more preferably at least 1 mol and the upper limit on the amount of addition is preferably not more than 10 3 mol and more preferably not more than 50 mol.
  • a single one of these retarders may be used or two or more may be used in combination.
  • the hardening accelerator can be exemplified by imidazoles, dicyandiamide derivatives, dicarboxylic acid dihydrazides, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, and 1,8-diazabicyclo[5.4.0]undecene-7-tetraphenylborate.
  • the use of the imidazoles is preferred among the preceding because they exhibit a high reaction-promoting activity.
  • the imidazoles can be exemplified by 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-phenylimidazolium trimellitate, and are available under the product names 2E4MZ, 2PZ-CN, and 2PZ-CNS (Shikoku Chemicals Corporation).
  • the amount of addition of the hardening accelerator is preferably 0.1 weight part or more and 10 weight parts or less per 100 weight parts of the total of the heat-curable polyorganosiloxane resin (A) and the curing catalyst (C).
  • the material for a molded resin for a semiconductor device may optionally contain, in any proportion and any combination, one or two or more components other than the polyorganosiloxane (A), white pigment (B), curing catalyst (C), and cure rate controlling agent (D).
  • solid particles can be incorporated as a fluidity controlling agent (E) with the objective of controlling the sedimentation of the white pigment and/or controlling the fluidity of the material for a molded resin for a semiconductor light-emitting device.
  • the fluidity controlling agent (E) should be a particle that is solid from normal temperature to around the molding temperature and that through its incorporation provides a higher viscosity for the material for a molded resin, but is not otherwise particularly limited. However, it preferably has no ability, or only a very small ability, to absorb light from the light-emitting element or light at a phosphor-converted wavelength, does not significantly lower the reflectivity of the material, and is very durable and exhibits little light- or heat-induced discoloration or degradation.
  • a white pigment that does not satisfy one of the following characteristics (a) and (b), or that satisfies neither of them, such as a fibrous alumina, can be incorporated separately from the white pigment already described above.
  • the primary particle aspect ratio is 1.2 or more and 4.0 or less.
  • the primary particle diameter is 0.1 ⁇ m or more and 2.0 ⁇ m or less.
  • Finely divided silica particles which have a significant ability to impart thixotropic nature, are preferred for use among the preceding because they provide facile control of the viscosity and thixotropic nature of the composition.
  • Quartz beads, glass heads, and glass fiber are preferred not only because they can function as a fluidity controlling agent, but also because they can be expected to raise the strength and toughness of the post-thermoset material and to lower the linear expansion coefficient of the material, and they may be used alone or in combination with finely divided silica particles.
  • the finely divided silica particles used by the present invention will have a specific surface area by the BET method generally of at least 30 m 2 /g, preferably at least 50 m 2 /g, and more preferably at least 100 m 2 /g, and generally not more than 300 m 2 /g and preferably not more than 200 m 2 /g.
  • a specific surface area by the BET method generally of at least 30 m 2 /g, preferably at least 50 m 2 /g, and more preferably at least 100 m 2 /g, and generally not more than 300 m 2 /g and preferably not more than 200 m 2 /g.
  • Finely divided silica particles may be used that have been subjected to a surface hydrophobicization by, for example, reacting a surface modifier with the silanol groups that are present on the surface of the hydrophilic finely divided silica particles.
  • the surface modifier can be exemplified by alkylsilane compounds and specifically by dimethyldichlorosilane, hexamethyldisilazane, octylsilane, and dimethylsilicone oil.
  • the finely divided silica particles can be exemplified by fumed silica.
  • Fumed silica is produced by the oxidation and hydrolysis of SiCl 4 gas in an 1100 to 1400° C. flame provided by the combustion of a mixed gas of H 2 and O 2 .
  • the primary particles in fumed silica are spherical ultrafine particles that have an average particle diameter of about 5 to 50 nm and that have amorphous silicon dioxide (SiO 2 ) as their main component; these primary particles aggregate with each other to form secondary particles having a particle diameter of several hundred nanometers.
  • Fumed silica because it is an ultrafine particulate and is produced by quenching, has a surface structure that is in a chemically active state.
  • “Aerosil” (registered trademark) from Nippon Aerosil Co., Ltd., is a specific example, and examples of hydrophilic Aerosil (registered trademark) are “90”, “130”, “150”, “200”, and “300”, while examples of hydrophobic Aerosil (registered trademark) are “PX50”, “NAX50”, “NY90G”, “RY50”, “NY50”, “R8200”, “R972”, “R972V”, “R972CF”, “R974”, “R202”, “R805”, “R812”, “R812S”, “RY200”, “RY200S”, and “RX200”.
  • a polyorganosiloxane that functions as a liquid increasing viscosity agent may be incorporated as a portion of the polyorganosiloxane (A) in order to adjust the viscosity of the material for a molded resin.
  • the following can be incorporated as a liquid increasing viscosity agent: a straight-chain polyorganosiloxane that has a viscosity at 25° C.
  • 0.001 Pa ⁇ s or more and 3 Pa ⁇ s or less generally 0.001 Pa ⁇ s or more and 1 Pa ⁇ s or less, and more preferably 0.001 Pa ⁇ s or more and 0.7 Pa ⁇ s or less, that has a hydroxyl value generally of from 1.0 ⁇ 10 ⁇ 2 to 10.3 ⁇ 10 ⁇ 5 mol/g, preferably from 1.0 ⁇ 10 ⁇ 2 to 9.5 ⁇ 10 ⁇ 5 mol/g, and more preferably from 1.0 ⁇ 10 ⁇ 2 to 7.7 ⁇ 10 ⁇ 5 mol/g, and that has at least one silicon-bonded hydroxyl group (i.e., the silanol group) in each molecule.
  • a hydroxyl value generally of from 1.0 ⁇ 10 ⁇ 2 to 10.3 ⁇ 10 ⁇ 5 mol/g, preferably from 1.0 ⁇ 10 ⁇ 2 to 9.5 ⁇ 10 ⁇ 5 mol/g, and more preferably from 1.0 ⁇ 10 ⁇ 2 to 7.7 ⁇ 10 ⁇ 5 mol/g, and that has at least one silicon-bonded hydroxyl
  • This hydroxyl group-containing straight-chain organopolysiloxane used as a liquid increasing viscosity agent should not contain a functional group that participates in the hydrosilylation addition reaction, e.g., an alkenyl group and/or the SiH group, in the molecule, and the hydroxyl group present in the molecule may be bonded to the silicon at the molecular chain terminals, or may be bonded to the silicon in nonterminal position on the molecular chain (i.e., along the molecular chain), or may be bonded in both positions.
  • a straight-chain organopolysiloxane containing the hydroxyl group bonded to the silicon at both molecular chain terminals that is, an ⁇ , ⁇ -dihydroxydiorganopolysiloxane is preferred.
  • the silicon-bonded organic groups here can be exemplified by monovalent hydrocarbon groups such as alkyl groups, e.g., methyl, ethyl, propyl, and so forth, and aryl groups, the phenyl group and so forth.
  • the diorganosiloxane repeat unit constituting the main chain of the organopolysiloxane under consideration is preferably a single selection or, a combination of two or more selections from the dimethylsiloxane unit, diphenylsiloxane unit, methylphenylsiloxane unit, and so forth.
  • ⁇ , ⁇ -dihydroxydimethylpolysiloxane ⁇ , ⁇ -dihydroxydiphenylpolysiloxane, ⁇ , ⁇ -dihydroxymethylphenylpolysiloxane, ⁇ , ⁇ -dihydroxy(dimethylsiloxane/diphenylsiloxane) copolymer, and ⁇ , ⁇ -dihydroxy(dimethylsiloxane/methylphenylsiloxane) copolymer.
  • the amount of incorporation of the polyorganosiloxane functioning as a liquid increasing viscosity agent, expressed per 100 weight parts of the entire polyorganosiloxane (A), is generally 0 to 10 weight parts, preferably 0.1 to 5 weight parts, and more preferably approximately 0.5 to 3 weight parts.
  • An inorganic fiber e.g., glass fiber
  • boron nitride, aluminum nitride, or fibrous alumina which have high thermal conductivities, may be incorporated separately from the white pigment already described above in order to raise the thermal conductivity.
  • quartz beads, glass beads, and so forth may be incorporated with the objective of lowering the linear expansion coefficient of the cured material.
  • the intended effect is not obtained when their amount of incorporation is too low, while an amount of incorporation that is too large raises the viscosity of the material for a molded resin for a semiconductor light-emitting device and thus affects the processability.
  • their amount of incorporation should be selected as appropriate from within a range where a satisfactory effect is developed and the processability of the material is not impaired. This is generally not more than 500 weight parts and preferably not more than 200 weight parts per 100 weight parts of the polyorganosiloxane.
  • an ion migration (electrochemical migration) inhibitor an ion migration (electrochemical migration) inhibitor, ageing inhibitor, radical inhibitor, ultraviolet absorber, adhesion promoter, flame retardant, surfactant, storage stabilizer, ozone degradation inhibitor, photostabilizer, increasing viscosity agent, plasticizer, coupling agent, oxidation inhibitor, heat stabilizer, agent that provides electroconductivity, static inhibitor, radiation-blocking agent, nucleating agent, phosphorus-based peroxide decomposer, lubricant, pigment, metal inactivator, and property controlling agent.
  • an ion migration (electrochemical migration) inhibitor an ion migration (electrochemical migration) inhibitor, ageing inhibitor, radical inhibitor, ultraviolet absorber, adhesion promoter, flame retardant, surfactant, storage stabilizer, ozone degradation inhibitor, photostabilizer, increasing viscosity agent, plasticizer, coupling agent, oxidation inhibitor, heat stabilizer, agent that provides electroconductivity, static inhibitor, radiation-blocking agent, nu
  • Silane coupling agents are an example of the coupling agent.
  • the silane coupling agent should contain in each molecule at least one hydrolyzable silicon group and at least one functional group reactive with organic groups, but is not otherwise particularly limited.
  • the group reactive with organic groups is preferably at least one functional group selected from the epoxy group, methacryl group, acryl group, isocyanate group, isocyanurate group, vinyl group, and carbamate group, while considered from the standpoint of the curability and adhesiveness the epoxy group, methacryl group, and acryl group are particularly preferred.
  • the hydrolyzable silicon group is preferably an alkoxysilyl group, while the methoxysilyl group and ethoxysilyl group are particularly preferred in terms of reactivity.
  • Examples of preferred silane coupling agents are alkoxysilanes having the epoxy functional group, e.g., 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and alkoxysilanes bearing the methacryl group or acryl group, e.g., 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymeLhyltrimethoxysilane, and acryloxymethyltriethoxysilane
  • the content of the polyorganosiloxane (A) in the material of the present invention for a molded resin should generally be in a range that enables use as a material for a molded resin, but is not otherwise limited, and, expressed with reference to the material as a whole, is generally 10 weight % or more and 50 weight % or less, preferably 15 weight % or more and 40 weight % or less, and more preferably 20 weight % or more and 35 weight % or less.
  • the cure rate controlling agent (D) and liquid increasing viscosity agent, which is an additional component, present in the material are polyorganosiloxanes, they are included in the content of (A).
  • the content of the white pigment (B) in the material of the present invention for a molded resin should generally be in a range that enables use as a material for a molded resin, but is not otherwise limited, and, expressed with reference to the material as a whole, is generally from 30 weight % or more and 85 weight % or less, preferably 40 weight % or more and 80 weight % or less, and more preferably 45 weight % or more and 70 weight % or less, in case of that alumina is used as the white pigment (B).
  • the content of the fluidity controlling agent (E) in the material of the present invention for a molded resin should be in a range that does not impair the effects of the present invention, but is not otherwise limited, and, expressed with reference to the material as a whole, is generally not more than 80 weight, preferably 2 weight % or more and 70 weight % or less, and more preferably 5 weight % or more and 60 weight % or less.
  • the ratio of the total amount of the white pigment (B) and fluidity controlling agent (E) to the molded resin material as a whole is preferably at least 50 weight %, more preferably at least 60 weight %, and particularly preferably at least 65 weight %, and is preferably not more than 85 weight % and more preferably not more than 80 weight.
  • the material of the present invention for a molded resin for a semiconductor light-emitting device preferably has a viscosity at 25° C. and a shear rate of 100 s ⁇ 1 of 10 Pa ⁇ s or more and 10,000 Pa ⁇ s or less. Viewed from the perspective of the molding efficiency during molding of the molded resin for a semiconductor device, this viscosity is more preferably 50 Pa ⁇ s or more and 5,000 Pa ⁇ s or less, even more preferably 100 Pa ⁇ s or more and 2,000 Pa ⁇ s or less, and particularly preferably 150 Pa ⁇ s or more and 1,000 Pa ⁇ s or less.
  • the material of the present invention for a molded resin for a semiconductor light-emitting device has a ratio (1 s ⁇ 1 /100 s ⁇ 1 ) of the viscosity at 25° C. and a shear rate of 1 s ⁇ 1 to the viscosity at 25° C. and a shear rate of 100 s ⁇ 1 preferably of at least 15, more preferably of at least 20, and particularly preferably of at least 30.
  • the upper limit is preferably not more than 500 and more preferably not more than 300.
  • the material of the present invention for a molded resin for a semiconductor light-emitting device particularly preferably has a viscosity at 25° C. and a shear rate of 100 s ⁇ 1 of not more than 1,000 Pa ⁇ s and a ratio (1 s ⁇ 1 /100 s ⁇ 1 ) of the viscosity at 25° C. and a shear rate of 1 s ⁇ 1 to the viscosity at 25° C. and a shear rate of 100 s ⁇ 1 of at least 15.
  • the material In order to provide a material that exhibits a good moldability, the material must be endowed with a certain degree of thixotropic nature, and when the viscosity at 25° C. and a shear rate of 100 s ⁇ 1 is 10 Pa ⁇ s or more and 10,000 Pa ⁇ s or less, and the ratio of the viscosity at a shear rate of 1 s ⁇ 1 to the viscosity at a shear rate of 100 s ⁇ 1 is at least 15, a material is provided that exhibits little flashing and short molding (incomplete filling), that supports a shortening of the molding cycle and the total time for the material in molding, and that has a high molding efficiency and facilitates stable molding.
  • This viscosity at 25° C. and a shear rate of 100 s ⁇ 1 and viscosity at 25° C. and a shear rate of 1 s ⁇ 1 can be measured using, for example, an ARES-G2 strain-controlled rheometer (from TA Instruments Japan Inc.).
  • a certain degree of thixotropic nature must be imparted to the material in order to control the aforementioned viscosity and provide a material suitable for use in liquid injection molding (LIM molding).
  • LIM molding liquid injection molding
  • a substantial increasing viscosity occurs and a large thixotropic nature imparting effect is obtained when finely divided particles in the microscopic range (primary particle diameter 0.1 ⁇ m or more and 2.0 ⁇ m or less) are incorporated in the material.
  • the thixotropic nature of the composition is easily controlled when a white pigment (B) having a primary particle diameter 0.1 ⁇ m or more and 2.0 ⁇ m or less is used and/or when a fluidity controlling agent (E) in the microscopic range, such as fumed silica with its large specific surface area, is used.
  • a white pigment (B) having a primary particle diameter 0.1 ⁇ m or more and 2.0 ⁇ m or less is used and/or when a fluidity controlling agent (E) in the microscopic range, such as fumed silica with its large specific surface area, is used.
  • the incorporation is preferred of at least 30 weight % of the white pigment (B) having a primary particle diameter 0.1 ⁇ m or more and 2.0 ⁇ m or less, while the viscosity of the material can be controlled into the previously indicated range even more preferably by the incorporation of the combination of the white pigment (B) with a fluidity controlling agent (E) that is not a white pigment, such as a fumed silica or quartz beads, at a total of 50 to 85 weight % for the combination.
  • a fluidity controlling agent (E) that is not a white pigment, such as a fumed silica or quartz beads
  • a white pigment When a white pigment is used that has a median diameter for the secondary particles greater than 2 ⁇ m, and particularly when a white pigment is used that has a median diameter of at least 5 ⁇ m, it is preferably used in combination with a fluidity controlling agent in the microscopic range with its large thixotropic nature imparting effect.
  • a fluidity controlling agent in the microscopic range with its large thixotropic nature imparting effect.
  • the primary particle diameter of the white pigment (B) itself it will also be possible to use only the white pigment without the combination with a fluidity controlling agent, or it may be combined with a fluidity controlling agent that has a relatively large median diameter of several micrometers or more.
  • the material of the present invention for a molded resin for a semiconductor light-emitting device has a thermal conductivity when cured preferably 0.4 or more and 3.0 or less, and more preferably 0.6 or more and 2.0 or less.
  • the thermal conductivity when cured can be measured using, for example, an ai-Phase Mobile (from the ai-Phase Co., Ltd.).
  • thermosetting when cured refers to the execution of thermosetting for 4 minutes at 180° C.
  • Heat is produced in a semiconductor light-emitting device by the light that is emitted from the semiconductor light-emitting element, and larger amounts of heat are generated in particular in the case of high-output elements.
  • the phosphor layer adjacent to the molded resin undergoes heat-induced deterioration and the durability of the device is ultimately diminished.
  • the present inventors discovered that by having the thermal conductivity when cured, i.e., when the molded resin has been made by molding, be in the previously indicated range, the thermal radiation characteristics for the heat generated by the light emitted from the semiconductor light-emitting element are improved for the molded resin and the semiconductor light-emitting device constructed using it, and as a consequence the durability of the device is also improved.
  • the phosphor layer present in the device tends to undergo thermal degradation due to the heat generated by the light emitted from the semiconductor light-emitting element in the device.
  • the thermal conductivity here can be controlled into the above-indicated range by the use of alumina or boron nitride for the white pigment (B) present in the material for a molded resin for a semiconductor light-emitting device.
  • the molded resin that uses the molded resin material of the present invention preferably can maintain a high reflectivity for visible light.
  • the reflectivity for light at 460 nm is preferably at least 80% and more preferably is at least 90%.
  • the reflectivity for light at a wavelength of 400 nm is preferably at least 60%, more preferably at least 80%, and even more preferably at least 90%.
  • This reflectivity by the molded resin refers to the reflectivity measured on the 0.4 mm-thick molding provided by thermally curing and molding the molded resin material of the present invention.
  • This thermal curing can be carried out, for example, by curing for 4 minutes at 180° C. under a pressure of 10 kg/cm 2 .
  • the reflectivity of the molded resin can be controlled through, for example, the type of resin (for example, the reflectivity can be controlled by changing the refractive index of the resin), the type of filler, and the particle diameter and content of the filler.
  • the method for molding the molded resin of the present invention for a semiconductor light-emitting device can be exemplified by compression molding methods, transfer molding methods, and injection molding methods.
  • injection molding methods and particularly liquid injection molding (LIM molding) methods are preferred because they do not produce wasted cured material and do not require secondary processing (that is, are resistant to the generation of flash) and because they offer the major advantages of automation of the process for molding the molded resin, a shortening of the molding cycle, and enabling cost reduction for the molded product.
  • LIM molding and transfer molding are compared, LIM molding offers the advantages of a greater freedom for the shape of the molding and a relatively inexpensive molding device and mold.
  • the injection molding methods can be carried out using an injection molding machine.
  • the cylinder setting temperature may be selected as appropriate in conformity to the material, but is generally not more than 100° C., preferably not more than 60° C., and more preferably not more than 60° C.
  • the mold temperature is 80° C. or more and 300° C. or less, and preferably is 100° C. or more and 250° C. or less, and more preferably is 120° C. or more and 200° C. or less.
  • the injection time will vary with the material, but is generally several seconds or not more than 1 second.
  • the molding time may be selected as appropriate in conformity to the gelation rate and cure rate of the material, but is generally 3 seconds or more and 600 seconds or less, preferably 5 seconds or more and 200 seconds or less, and more preferably 10 seconds or more and 60 seconds or less.
  • the penetration of the material into narrow spaces can be promoted and the generation of air voids within the molded product can be prevented by placing the mold under a vacuum when the resin is molded.
  • the graph When the degree of curing is represented graphically as a function of the curing time in liquid injection molding (LIM molding), the graph preferably ascends in an S-shape. Incomplete filling of the mold can occur when the initial rise in the cure is too rapid. Controlling the cure rate of the material and adjusting the viscosity are very important for inhibiting flashing and preventing incomplete filling of the mold. Once the resin material has been filled into the mold, a faster cure is favorable because this can shorten the molding cycle and improve the releasability through cure shrinkage.
  • LIM molding liquid injection molding
  • the time to cure completion is generally within 60 seconds, preferably within 30 seconds, and more preferably within 10 seconds.
  • a post-cure may be implemented as necessary.
  • the cure rate can be adjusted through the selection of the type of platinum catalyst, the amount of catalyst, the use of a cure rate controlling agent, and the degree of crosslinking of the polyorganosiloxane, and also through molding conditions such as the mold temperature, the filling rate, and the injection pressure.
  • Compression molding methods can be carried out using a compression molding machine.
  • the molding temperature may be selected as appropriate in conformity to the material, but is generally 80° C. or more and 300° C. or less, preferably 100° C. or more and 250° C. or less, and more preferably 120° C. or more and 200° C. or less.
  • the molding time may be selected as appropriate in view of the cure rate of the material, but is generally 3 seconds or more and 1200 seconds or less, preferably 5 seconds or more and 900 seconds or less, and more preferably 10 seconds or more and 600 seconds or less.
  • Transfer molding methods can be carried out using a transfer molding machine.
  • the molding temperature may be selected as appropriate in conformity to the material, but is generally 80° C. or more and 300° C. or less, preferably 100° C. or more and 250° C. or less, and more preferably 120° C. or more and 200° C. or less.
  • the molding time may be selected as appropriate in view of the gelation rate or cure rate of the material, but is generally 3 seconds or more and 1200 seconds or less, preferably 5 seconds or more and 900 seconds or less, and more preferably 10 seconds or more and 600 seconds or less.
  • a post-cure may optionally be carried out with any of the molding methods, and the post-cure temperature is 100° C. or more and 300° C. or less, preferably 150° C. or more and 250° C. or less, and more preferably 170° C. or more and 200° C. or less.
  • the post-cure time is generally 3 minutes or more and 24 hours or less, preferably 5 minutes or more and 10 hours or less, and more preferably 10 minutes or more and 5 hours or less.
  • the molded resin of the present invention for a semiconductor light-emitting device is generally used for a semiconductor light-emitting device in which a semiconductor light-emitting element is mounted.
  • the semiconductor light-emitting device is composed of, for example, a semiconductor light-emitting element 1 , a molded resin 2 , a bonding wire 3 , an encapsulant 4 , a lead frame 5 , and so forth, as shown in FIG. 1 .
  • the insulating molded resin and the electroconductive material, e.g., the lead frame 5 are referred to as the package.
  • the semiconductor light-emitting element 1 can be, for example, a near-ultraviolet semiconductor light-emitting element that emits light at a wavelength in the near-ultraviolet region, a violet semiconductor light-emitting element that emits light at a wavelength in the violet region, or a blue semiconductor light-emitting element that emits light at a wavelength in the blue region, and emits light at a wavelength 350 nm or more and 520 nm or less. While only one semiconductor light-emitting element is mounted in FIG. 1 , a plurality of semiconductor light-emitting elements may be positioned, as shown in FIG. 2 , in a linear or planar configuration, vide infra. Area lighting can be provided by positioning the semiconductor light-emitting elements 1 in a planar configuration, and such an embodiment is preferred when it is desired to intensify the output.
  • the molded resin 2 that is a constituent of the package is molded in combination with the lead frame 5 .
  • the entire molded resin 2 may be composed of the molded resin material of the present invention, or a portion thereof may comprise the molded resin material of the present invention.
  • a mode in which the molded resin constituting the reflector component 102 is molded from the molded resin material of the present invention, as shown in FIG. 2 discussed below, is a specific example of the case in which a portion of the molded resin 2 is comprised of the molded resin material of the present invention.
  • the lead frame 5 is composed of an electroconductive metal and functions to energize the semiconductor light-emitting element 1 by feeding power from outside the semiconductor light-emitting device.
  • the bonding wire 3 functions to fix the semiconductor light-emitting element 1 in the package. In addition, in those instances wherein the semiconductor light-emitting element 1 is not in contact with the lead frame, which forms an electrode, the electroconductive bonding wire 3 functions to feed power to the semiconductor light-emitting element 1 .
  • the bonding wire 3 is bonded to the lead frame 5 by compression bonding and the application of heat and ultrasonic vibration.
  • the molded resin 2 which comprises the molded resin material of the present invention, can make the exposed area of the lead frame 5 very small.
  • the molded resin molded from the molded resin material of the present invention tends to have a reflectivity equal to or higher than that of the material of the lead frame (for example, silver), and as a consequence a high package reflectivity can be maintained even when the molded resin presents a large exposed area.
  • a semiconductor light-emitting device with a structure different from that of conventional packages can also be obtained by using a package comprising the material of the present invention for a molded resin.
  • a semiconductor light-emitting device 200 equipped with a conventional package is shown in FIG. 3 .
  • the lead frame 204 has a large exposed area in the semiconductor light-emitting device shown in FIG. 3 . Since the reflectivity of the molded resin 201 has been lower than that of the lead frame 204 , it has been necessary, in order for the semiconductor light-emitting device to realize a high luminance, to provide a large surface area for a lead frame 204 that uses a high reflectivity material. When the lead frame 204 has such a large exposed area, the light emission efficiency may be reduced due to discoloration of the lead frame when the package is used installed in a light-emitting device. However, the decline in the light emission efficiency caused by this discoloration of the lead frame can be stopped by having the exposed area of the lead frame 5 be small, as in FIG. 1 .
  • the molded resin 2 that is a constituent of the package is mounted with the semiconductor light-emitting element 1 and is sealed with a phosphor-admixed encapsulant 4 .
  • the encapsulant 4 is a mixture provided by mixing a phosphor into a binder resin; the phosphor converts the excitation light from the semiconductor light-emitting element 1 and emits fluorescence at a different wavelength from the excitation light.
  • the encapsulant also functions as the phosphor layer.
  • the phosphor present in the encapsulant 4 is selected as appropriate in conformity to the wavelength of the excitation light from the semiconductor light-emitting element 1 .
  • the white light can be produced by incorporating green and red phosphors in the phosphor layer.
  • white light can be produced by incorporating blue and yellow phosphors in the phosphor layer or by incorporating blue, green, and red phosphors in the phosphor layer.
  • binder resin present in the encapsulant 4 an appropriate selection can generally be made from transparent resins known for use in encapsulants. Specific examples are epoxy resins, silicone resins, acrylic resins, polycarbonate resins, and so forth, wherein the use of silicone resins is preferred.
  • FIG. 2 Another mode of the semiconductor light-emitting device of the present invention will be described in detail using FIG. 2 .
  • the semiconductor light-emitting device 1 C of this embodiment is composed of a window-equipped housing 101 , a reflector component 102 , a light source component 103 , and a heat sink 104 .
  • This light source component 103 is provided with a light-emitting component 105 on a circuit substrate, and a chip-on-board (COB) configuration may be used in which the semiconductor light-emitting element is directly mounted on the circuit substrate 106 or a configuration may be used in which the semiconductor light-emitting device is surface mounted, as in FIG. 1 .
  • COB chip-on-board
  • the semiconductor light-emitting element may be sealed, without using a frame, by an encapsulant resin molded in a dome shape or flat plate shape.
  • a single semiconductor light-emitting element or a plurality of semiconductor light-emitting elements may be mounted on the circuit substrate 106 .
  • the reflector component 102 and the heat sink 104 may be formed into a single body with the housing 101 or may each be separate therefrom and can be used as required.
  • the light source component 103 , the housing 101 , and the heat sink 104 preferably have a single body structure or are in gapless contact intermediated by a high thermal conductivity sheet or grease.
  • a known transparent resin or optical glass can be used for the window 107 , and this window 107 may have a flat shape or may have a curved surface.
  • the phosphor component may be disposed at the light source component 103 or may be disposed at the window 107 .
  • the disposition at the window 107 enables the phosphor to be placed at a position that is separated from the light-emitting element and thus offers the advantage of inhibiting deterioration of the phosphor, which is readily degraded by heat and light, and thereby making it possible to obtain uniform, high luminance white light on a long-term basis.
  • the phosphor layer is, for example, screen printed, die coated, or spray coated on (not shown) a transparent window material. Since, in such a configuration, the semiconductor light-emitting element and the phosphor layer are disposed with a distance opened therebetween, deterioration of the phosphor layer by the light energy from the semiconductor light-emitting element can be prevented, while the output of the light-emitting device can also be improved.
  • the distance between the semiconductor light-emitting element and the phosphor layer of the window 107 is preferably from 5 to 50 mm.
  • the phosphor layer for FIG. 2 can be executed as a multilayer structure in which the phosphor for each color used is separately coated or can be formed in a pattern such as stripes or dots.
  • each feature of the semiconductor light-emitting device 1 C is not limited to that shown in the figure, and the device may be fabricated, for example, with a curved surface feature or as necessary with an attached dimmer or circuit protection device.
  • the location where the molded resin according to the present invention (referred to below simply as the “optical member”) is deployed in the semiconductor light-emitting device of the present invention as described hereabove is not particularly limited to that already described above.
  • the optical member can be used for each of the following members in the semiconductor light-emitting device 1 C shown in FIG. 2 ; the housing 101 , the reflector component 102 , the light source component 103 , the light-emitting component 105 , and the circuit substrate 106 .
  • the molded resin according to the present invention exhibits a high reflectivity for ultraviolet-to-visible light and an excellent heat resistance and light resistance, and in consequence thereof can inexpensively provide a highly durable high-luminance lighting device in which the required number of semiconductor light-emitting elements has been brought down.
  • the molded resin of the present invention can effectively reflect the light generated from the semiconductor light-emitting element prior to wavelength conversion by the phosphor and is thus well adapted for embodiments in which the phosphor layer is positioned at a location separated from the light source component.
  • the main component of the reflective filler is preferably alumina, while in the case of a blue emitted light color the main component is preferably alumina and/or titania.
  • a preferred molded resin for a semiconductor light-emitting device said molded resin being provided by molding the material of the present invention for a molded resin for a semiconductor light-emitting device.
  • the semiconductor light-emitting device package of the present invention is characterized by the ability to maintain a high reflectivity not only for visible light, but also for ultraviolet light and near-ultraviolet light having a shorter wavelength than violet.
  • the reflectivity for light at a wavelength of 360, 400, and 460 nm is in each case generally at least 60%, preferably at least 80%, and more preferably at least 90%.
  • a semiconductor light-emitting device package provided with the molded resin of the present invention, which exhibits a high reflectivity from the ultraviolet region to the visible region, has very good characteristics not seen in prior semiconductor light-emitting device packages. Particularly for semiconductor light-emitting device packages made of a resin such as a polysiloxane, these are characteristics that the individual skilled in the art could not heretofore have easily hit upon and the technical significance is quite substantial.
  • the semiconductor light-emitting device package of the present invention generally has a chip-mounting surface and a back surface on the side opposite from this chip-mounting surface.
  • the distance between this chip-mounting surface and the back surface i.e., the thickness of the semiconductor light-emitting device package
  • the thickness of the semiconductor light-emitting device package is generally at least 100 ⁇ m and preferably at least 200 ⁇ m. It is generally not more than 3000 ⁇ m and preferably not more than 2000 ⁇ m.
  • problems can appear such as the penetration of light to the back surface and a reduction in the reflectivity and an inadequate package strength resulting in deformation during handling.
  • the thickness is too large, the package itself is also thick and bulky, resulting in limitations on the uses and applications of the semiconductor light-emitting device.
  • a vinyl group-containing polydimethylsiloxane (vinyl group content: 1.2 mmol/g, viscosity adjusted to 1000 mPa ⁇ s by the addition of finely divided silica particles, contained 6.8 ppm of a platinum complex catalyst) and a hydrosilyl group-containing polydimethylsiloxane (vinyl group content: 0.3 mmol/g, hydrosilyl group content: 1.8 mmol/g, viscosity adjusted to 2100 mPa ⁇ s by the addition of finely divided silica particles) were mixed at 1:1 to obtain a liquid heat-curable polyorganosiloxane (1) having a viscosity of 1500 mPa ⁇ s and a platinum concentration of 3.4 ppm.
  • the finely divided silica particles corresponded to the fluidity controlling agent (E) and were added at a polyorganosiloxane: finely divided silica particle (weight ratio) of from 80:20 to 89.5:10.5 to provide the viscosities indicated above.
  • a vinyl group-containing polydimethylsiloxane (vinyl group content: 0.3 mmol/g, viscosity: 3500 mPa ⁇ s, contained 8 ppm of a platinum complex catalyst), a hydrosilyl group-containing polydimethylsiloxane (vinyl group content: 0.1 mmol/g, hydrosilyl group content: 4.6 mmol/g, viscosity: 600 mPa ⁇ s), and a retarding component (cure rate controlling agent (D))-containing polydimethylsiloxane (vinyl group content: 0.2 mmol/g, hydrosilyl group content: 0.1 mmol/g, alkynyl group content: 0.2 mmol/g, 500 mPa ⁇ s) were mixed at 100:10:5 to obtain a liquid heat-curable polyorganosiloxane (2) having a platinum concentration of 7 ppm.
  • a hydrosilyl group-containing polydimethylsiloxane
  • the refractive index of this liquid heat-curable polyorganosiloxane (2) was 1.41.
  • the primary particle diameter of the white pigments (alumina powder) used in the examples was measured by SEM observation.
  • several points for example, 10 points
  • the average value was then used for the particle diameter.
  • a large variation for example, when the difference between the small particle diameter and the large particle diameter was greater than or equal to about 5 times excluding coarse particles and microfine particles present in trace amounts, the maximum value and minimum value were recorded.
  • the length of the major axis (the largest long diameter) and the length of the minor axis (the length of the longest part in the direction perpendicular to the long diameter) were also measured, and the length of the major axis was used for the primary particle diameter and the value obtained by dividing the length of the major axis (the largest long diameter) by the length of the minor axis (the length of the longest part in the direction perpendicular to the long diameter) was used as the aspect ratio.
  • the results are given in Table 1.
  • the volume-based median diameter D 50 of the secondary particles in the white pigment was measured with a Microtrac MT3000II from Nikkiso Co., Ltd.
  • the median diameter D 50 refers to the particle diameter at the point where the volume based particle size distribution curve in cumulative % intersects with the horizontal axis at 50%. The results are given in Table 1.
  • the crystal system was determined by carrying out X-ray diffraction measurement on the alumina powder using an X'Pert Pro MPD from PANalytical B.V.
  • the (113) crystallite size was calculated for the ⁇ -alumina using the Scherrer equation.
  • Test pieces with the thicknesses shown in Table 3 were obtained using the same conditions as in Example 1, but using the white pigment given in Table 2 and preparing the blend of (A) liquid heat-curable polyorganosiloxane (1) or (2), (B) white pigment, and “AEROSIL RX200” finely divided silica particles as the (E) fluidity controlling agent using the weight ratio shown in Table 2.
  • the white pigments A to J in Table 2 are described in Table 1.
  • Example 1 divided silica particles Comp.
  • G finely 40/60/0 Example 2 divided silica particles Comp.
  • D finely 51/49/0 Example 3 divided silica particles Comp.
  • E finely 40/60/0 Example 4 divided silica particles Comp. (2) H finely 35/60/5
  • Example 5 divided silica particles Comp. (2) H 0 20/80/0
  • Example 6 Comp. (2) J 0 40/60/0
  • Examples 2 and 9 had a higher reflectivity for 460 nm light than did Comparative Example 5 and maintained a relatively high reflectivity even for the thin material. In particular, it was found that little decline in reflectivity occurred for the thin test piece in Example 9, which had titania blended in the alumina.
  • a package for a semiconductor light-emitting device was molded by liquid injection molding using the material of Example 3 in combination with a copper lead frame that had been silver plated over its entire surface.
  • This package was a cup-shaped surface-mount package with the resin portion having length 3.2 mm ⁇ width 2.7 mm ⁇ height 1.4 mm and a concave portion with a diameter of 2.4 mm for the opening. Molding was performed for a curing time of 20 seconds at a mold temperature of 170° C. Observation of the molded package showed the package to be free of flash and free of short molding.
  • a package for a semiconductor light-emitting device was molded by liquid injection molding using the material of Example 3 in combination with a copper lead frame that had been silver plated over its entire surface.
  • This package was a cup-shaped surface-mount package having length 5 mm ⁇ width 5 mm ⁇ height 1.5 mm and a concave portion with a diameter of 3.6 mm for the opening. Molding was performed for a curing time of 180 seconds with a 150° C. mold.
  • the molded package was sectioned with a microtome while frozen with liquid nitrogen and the package cross section was observed by SEM.
  • the primary particle diameter of the alumina exposed in the cross section was 0.3 ⁇ m and the primary particle aspect ratio was 1.42.

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