Classifications

• • 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
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
• • 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
  • C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
  • C08G77/50—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
  • C08G77/52—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages containing aromatic rings
• • 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
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
• • 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
• • 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
• • 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
• • 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
  • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
• • 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
  • 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
  • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
• • 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
  • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
• • 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
  • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
  • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
  • H01L2224/45001—Core members of the connector
  • H01L2224/45099—Material
  • H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
  • H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
  • H01L2224/45144—Gold (Au) as principal constituent
• • 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
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
  • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
  • H10H20/80—Constructional details
  • H10H20/85—Packages
  • H10H20/852—Encapsulations
  • H10H20/854—Encapsulations characterised by their material, e.g. epoxy or silicone resins

Definitions

• This invention relates to curable silicone compositions and light emitting devices encapsulated with silicone products prepared by curing these compositions. More particularly, this invention relates to hydrosilylation-curable compositions that cure to form silicone products having optical clarity, high refractive index, resistance to high temperature, and high mechanical strength. This invention further relates to reliable light emitting devices encapsulated with the silicone products. Background
• Curable silicone compositions giving optically clear silicone products are frequently used in light emitting devices for properties such as their thermal and light resistance. Such curable silicone compositions may have advantages of high reliability over conventional materials such as epoxy resin materials, which may suffer from the drawback of discoloration by the action of heat and light generated from the light source.
• mechanical and adhesion properties of optically clear silicone products may be poorer than epoxy resins and filled silicones. These may cause fracture or delamination of the silicone product, resulting in a drop of the light output.
• One proposed approach to address this is to use a silicone resin compatible to the silicone product as a toughening agent.
• Another approach is to incorporate organic polymer components or functionalities into the silicone polymer structure, however, such modifications of silicone may be unsuitable for thermal and light resistance. Summary of the Invention
• This invention relates to a composition prepared by mixing components comprising: (I) an alkenyl functional, phenyl-containing polyorganosiloxane, an Si-H functional phenyl- containing polyorganosiloxane, or a combination thereof;
• At least one of components (I) and (II) contains alkenyl groups. At least one of components
• This invention further relates to a light emitting device encapsulated or coated with a silicone product prepared by curing the curable silicone composition.
• Light emitting device means a device for lighting.
• Light emitting device includes a light emitting diode (LED) in which a semiconductor chip mounted on a substrate as a light emitting element is encapsulated with an optically transmissive silicone product.
• LED light emitting diode
• Such encapsulation helps to protect against mechanical shock and intrusion of dust or moisture. It also serves at the same time as a medium which improves index matching along the light path and supports propagation of a light signal through its bulk without significant reflection or attenuation of the signal.
• the medium may be transparent or contain a phosphor or other additive to modify transparency.
• Light emitting device also includes devices or system structures in which the other light emitting sources such as a fluorescent lamp is used. [0009] "Delamination" means the tendency of the silicone product to peel off from the light emitting element or the other materials in the light emitting device.
• Frracture means the tendency of the encapsulant to show deformation or cracking, or both, in the light emitting devices.
• Vi means vinyl group.
• Component (I) may comprise an alkenyl functional, phenyl-containing polyorganosiloxane having an average compositional formula given as R*aR ⁇ bSiO(4-a-b)/2-
• the alkenyl functional, phenyl-containing polyorganosiloxane may have a linear, branched, cyclic, or resinous siloxane structure.
• the alkenyl functional, phenyl-containing polyorganosiloxane may be a single component or a combination comprising more than one alkenyl functional, phenyl-containing polyorganosiloxane.
• Component (I) may comprise a branched alkenyl functional, phenyl-containing polyorganosiloxane and a linear alkenyl- functional, phenyl-containing polyorganosiloxane.
• the relative amount of branched alkenyl functional, phenyl-containing polyorganosiloxane may range from 0.01 % to 35 % based on the weight of the composition and alternatively 1 % to 15 %.
• Each R* is independently an alkenyl group having 2 to 12 carbon atoms.
• the alkenyl groups are exemplified by, but not limited to, vinyl, allyl, butenyl, and hexenyl.
• the alkenyl groups in the alkenyl functional, phenyl-containing polyorganosiloxane may be located at monovalent, bivalent, and trivalent siloxane units.
• Each R ⁇ is independently a methyl group or a phenyl group. At least 30 mol% to 90 mol% of R2 may be phenyl groups. Without wishing to be bound by theory, it is thought that the amount of phenyl groups may be selected to improve compatibility of components (I) and (II).
• the methyl and phenyl groups in component (I) may be located at monovalent, bivalent, and trivalent siloxane units.
• Component (I) may comprise polyorganosiloxanes such as ViMe 2 SiO(SiMePhO) n SiMe 2 Vi,
• n, m, 1 are positive numbers less than 200 that mean the average number of each monomer unit in the polymer, and p, q, r, and s mean the average mol percentages of each monomer unit in the total average compositions.
• component (I) may comprise an Si-H functional phenyl-containing polyorganosiloxane having an average compositional formula given as a, and b are as described above.
• the Si-H functional phenyl-containing polyorganosiloxane may have a linear, branched, or cyclic siloxane structure.
• the Si-H functional phenyl-containing polyorganosiloxane may be a single component or a combination comprising more than one SiH functional phenyl-containing polyorganosiloxane.
• Component (I) may comprise polyorganosiloxanes such as HMe2SiO(SiMePhO) n SiMe 2 H,
• n, m, 1 p, q, r and s are as described above.
• component (I) Hydrogendiorganosiloxy terminated oligodiphenylsiloxane
• Component (II) may comprise a hydrogendiorganosiloxy terminated oligodiphenylsiloxane having a molecular formula given as HR 3 2SiO(SiPh2 ⁇ ) x SiR 3 2H.
• Component (II) may be a single component or a combination comprising more than one hydrogendiorganosiloxy terminated oligodiphenylsiloxane.
• Each R 3 is independently a methyl group or a phenyl group.
• each x is an integer from 2 to 8, and x averages from 2 to 4.
• Component (II) may comprise oligodiphenylsiloxanes such as HMe 2 SiO(SiPh 2 O) x SiMe 2 H,
• component (II) may comprise an alkenyl-functional, diorganosiloxy-terminated oligodiphenylsiloxane having a molecular formula given as
• the alkenyl- functional, diorganosiloxy-terminated oligodiphenylsiloxane may be a single component or a combination comprising more than one alkenyl-functional, diorganosiloxy-terminated oligodiphenylsiloxane.
• the alkenyl-functional, diorganosiloxy-terminated oligodiphenylsiloxane is exemplified by ViMe 2 SiO(SiPh 2 O) x SiMe 2 Vi, ViMePhSiO(SiPh 2 O) x SiMePhVi, or a combination thereof, where x is as described above.
• Component (III) is a hydrosilylation catalyst.
• Component (III) is added to the composition in an amount of 0.1 to 1000 ppm of platinum group metal, alternatively 1 to 500 ppm, alternatively 2 to 200, alternatively 5 to 150 ppm, based on the weight of the composition.
• Suitable hydrosilylation catalysts are known in the art and commercially available.
• Component (III) may comprise a platinum group metal selected from platinum, rhodium, ruthenium, palladium, osmium or indium metal or organometallic compound thereof, or a combination thereof.
• Component (III) is exemplified by compounds such as chloroplatinic acid, chloroplatinic acid hexahydrate, platinum dichloride, and complexes of said compounds with low molecular weight organopolysiloxanes or platinum compounds microencapsulated in a matrix or coreshell type structure.
• Complexes of platinum with low molecular weight organopolysiloxanes include 1 ,3-diethenyl-l , 1 ,3,3-tetramethyldisiloxane complexes with platinum.
• Suitable hydrosilylation catalysts for component (III) are described in, for example, U.S. Patents 3,159,601; 3,220,972; 3.296,291; 3,419,593; 3,516,946; 3,814,730; 3,989,668; 4,784,879; 5,036,117; and 5,175,325 and EP 0 347 895 B.
• Optional Components 3,159,601; 3,220,972; 3.296,291; 3,419,593; 3,516,946; 3,814,730; 3,989,668; 4,784,879; 5,036,117; and 5,175,325 and EP 0 347 895 B.
• An optional component may be added to the composition in addition to components (I)-(III). Suitable optional components include (IV) a co-crossHnker (V) an adhesion promoter, (VI) a filler, (VII) a treating agent, (VIII) an optically active agent, (IX) a cure modifier, (X) a rheology modifier, and a combination thereof.
• Suitable optional components include (IV) a co-crossHnker (V) an adhesion promoter, (VI) a filler, (VII) a treating agent, (VIII) an optically active agent, (IX) a cure modifier, (X) a rheology modifier, and a combination thereof.
• Component (IV) is a co-crosslinker.
• Component (IV) may be added to the composition in an amount of 0.01 to 50 weight parts based on the weight of the composition, alternatively 0.01 to 25 weight parts, and alternatively 1 to 5 weight parts.
• Component (IV) may comprise a hydrogensilyl functional polyorganosiloxane having an average compositional formula given as H c R ⁇ t iSiO(4_ c . ⁇ j)/2 other than component (II).
• Each R ⁇ is independently a methyl group or a phenyl group. At least 30 mol% of R 4 are phenyl groups.
• Component (V) is an adhesion promoter.
• Component (V) may be added to the composition in an amount of 0.01 to 50 weight parts based on the weight of the composition, alternatively 0.01 to 10 weight parts, and alternatively 0.01 to 5 weight parts.
• (V) may comprise (i) an alkoxysilane, (ii) a combination of an alkoxysilane and a hydroxy- functional polyorganosiloxane, or (iii) a combination thereof, or a combination of component
• component (V) may comprise an unsaturated or epoxy-functional compound. Suitable epoxy-functional compounds are known in the art and commercially available, see for example, U.S. Pat. Nos. 4,087,585; 5,194,649; 5,248,715; and 5,744,507 col. 4-5. Component (V) may comprise an unsaturated or epoxy-functional alkoxysilane.
• the unsaturated or epoxy-functional alkoxysilane can have the formula
• Each R ⁇ is independently a monovalent organic group with the proviso that at least one R ⁇ is an unsaturated organic group or an epoxy-functional organic group.
• Epoxy-functional organic groups for R ⁇ are exemplified by 3-glycidoxypropyl and (epoxycyclohexyl)ethyl.
• Unsaturated organic groups for R5 are exemplified by 3-methacryloyloxypropyl, 3-acryloyloxypropyl, and unsaturated monovalent hydrocarbon groups such as vinyl, allyl, hexenyl, undecylenyl.
• Each R ⁇ is independently an unsubstituted, saturated hydrocarbon group of 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms.
• R ⁇ is exemplified by methyl, ethyl, propyl, and butyl.
• suitable epoxy-functional alkoxysilanes include 3- glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (epoxycyclohexyl)ethyldimethoxysilane, (e ⁇ oxycyclohexyl)ethyldiethoxysilane and combinations thereof.
• Suitable unsaturated alkoxysilanes include vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hexenyltrimethoxysilane, undecylenyltrimethoxysilane, 3-methacryloyloxypropyl trimethoxysilane, 3- methacryloyloxypropyl triethoxysilane, 3-acryloyloxypropyl trimethoxysilane, 3- acryloyloxypropyl triethoxysilane, and combinations thereof.
• Component (V) may comprise an epoxy- functional siloxane such as a reaction product of a hydroxy-terminated polyorganosiloxane with an epoxy-functional alkoxysilane, as described above, or a physical blend of the hydroxy-terminated polyorganosiloxane with the epoxy-functional alkoxysilane.
• Component (V) may comprise a combination of an epoxy-functional alkoxysilane and an epoxy-functional siloxane.
• component (V) is exemplified by a mixture of 3-glycidoxypropyltrimethoxysilane and a reaction product of hydroxy-terminated methylvinylsiloxane with 3-glycidoxypropyltrimethoxysilane, or a mixture of 3-glycidoxypropyltrimethoxysilane and a hydroxy-terminated methylvinylsiloxane, or a mixture of 3-glycidoxypropyltrimethoxysilane and a hydroxy- terminated methyvinyl/dimethylsiloxane copolymer, or a mixture of 3- glycidoxypropyltrimethoxysilane and a hydroxy-terminated methylvinyl/methylphenylsiloxane copolymer.
• Suitable transition metal chelates include titanates, zirconates such as zirconium acetylacetonate, aluminum chelates such as aluminum acetylacetonate, and combinations thereof. Transition metal chelates and methods for their preparation are known in the art, see for example, U.S. Pat. No. 5,248,715, EP 0493 791 Al, and EP 0497 349 Bl.
• Component (VI) is a filler.
• the amount of component (VI) added to the composition depends on the type of filler selected and the resulting optical transparency.
• Component (VI) may be added to the composition in an amount of 0.1 % to 50 % based on the weight of the composition, alternatively 0.1 % to 25 %.
• Suitable fillers include reinforcing fillers such silica. Suitable reinforcing fillers are known in the art and commercially available, such as a fumed silica sold under the name CAB-O-SIL by Cabot Corporation of Massachusetts.
• Conductive fillers ⁇ i.e., fillers that are thermally conductive, electrically conductive, or both) may also be used as component (VI).
• Suitable conductive fillers include metal particles, metal oxide particles, and a combination thereof.
• Suitable thermally conductive fillers are exemplified by aluminum nitride; aluminum oxide; barium titanate; beryllium oxide; boron nitride; diamond; graphite; magnesium oxide; metal particulate such as copper, gold, nickel, or silver; silicon carbide; tungsten carbide; zinc oxide, and a combination thereof.
• Conductive fillers are known in the art and commercially available, see for example, U.S. Pat. No. 6,169,142 (col. 4, lines 7-33).
• CB-A20S and Al-43- Me are aluminum oxide fillers of differing particle sizes commercially available from Showa- Denko.
• AA-04, AA-2, and AAl 8 are aluminum oxide fillers commercially available from Sumitomo Chemical Company.
• Silver filler is commercially available from Metalor Technologies U.S.A. Corp. of Attleboro, Mass., U.S.A.
• Boron nitride filler is commercially available from Advanced Ceramics Corporation, Cleveland, Ohio, U.S.A.
• the shape of the- filler particles is not specifically restricted, however, rounded or spherical particles may prevent viscosity increase to an undesirable level upon high loading of the filler in the composition.
• a combination of fillers having differing particle sizes and different particle size distributions may be used.
• All or a portion of the filler may comprise spacers.
• Spacers can comprise organic particles such as polystyrene, inorganic particles such as glass, or a combination thereof. Spacers can be thermally conductive, electrically conductive, or both. Spacers can have a particle size of 25 micrometers to 250 micrometers. Spacers can comprise monodisperse beads. The amount of spacer depends on various factors including the distribution of particles, pressure to be applied during placement of the composition, and temperature of placement.
• the filler may optionally be surface treated with component (VII), a treating agent.
• Treating agents and treating methods are known in the art, see for example, U.S. Patent 6, 169, 142 (col.4, line 42 to col. 5, line 2).
• Component (VI) may be treated with the treating agent prior to combining component (VI) with the other components of the composition, or component (VI) may be treated in situ.
• the treating agent can be an alkoxysilane having the formula: R7-fSi(OR8)(4_f ) , where f is 1, 2, or 3; alternatively f is 3.
• Each R? is independently a substituted or unsubstituted monovalent hydrocarbon group of 1 to 50 carbon atoms. R?
• R7 can be saturated or unsaturated, branched or unbranched, and unsubstituted.
• R7 can be saturated, unbranched, and unsubstituted.
• Each R ⁇ is independently an unsubstituted, saturated hydrocarbon group of 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms.
• the treating agent is exemplified by hexyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, dodecyltrimethyoxysilane, tetradecyltrimethoxysilane, phenyltrimethoxysilane, phenylethyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, and a combination thereof.
• Alkoxy-functional oligosiloxanes can also be used as treating agents.
• Alkoxy- functional oligosiloxanes and methods for their preparation are known in the art, see for example, EP 1 101 167 A2.
• suitable alkoxy-functional oligosiloxanes include those of the formula (R 9 O) g Si(OSiR 10 2R 1 ⁇ 4-g- In this formula, g is 1 , 2, or 3, alternatively d is 3.
• Each R ⁇ can independently be an alkyl group.
• Each R ⁇ can be independently selected from saturated and unsaturated monovalent hydrocarbon groups of 1 to 10 carbon atoms.
• Each R* 1 can be a saturated or unsaturated monovalent hydrocarbon group having at least 11 carbon atoms.
• Metal fillers can be treated with alkylthiols such as octadecyl mercaptan and others, and fatty acids such as oleic acid, stearic acid, titanates, titanate coupling agents, zirconate coupling agents, and a combination thereof.
• Treating agents for alumina or passivated aluminum nitride may include alkoxysilyl functional alkylmethyl polysiloxanes (e.g. , partial hydrolysis condensate of or cohydrolysis condensates or mixtures), similar materials where the hydrolyzable group would be silazane, acyloxy or oximo.
• a group tethered to Si is a long chain unsaturated monovalent hydrocarbon or monovalent aromatic-functional hydrocarbon.
• Each R ⁇ is independently a monovalent hydrocarbon group, and each R ⁇ is independently a monovalent hydrocarbon group of 1 to 4 carbon atoms.
• h is 1, 2, or 3 and i is 0, 1, or 2, with the proviso that h+i is 1, 2, or 3.
• i is 0, 1, or 2 with the proviso that h+i is 1, 2, or 3.
• Component (VIII) is an optically active agent.
• component (VIII) include optical diffusants, phosphor powders, photonic crystals, quantum dots, nanoparticles such as titanium dioxide nanoparticles or carbon nanotubes, dyes such as fluorescent dyes or absorbing dyes, and combinations thereof.
• the amount of component (VIII) depends on various factors including the optically active agent selected and the end use application. However, the amount of component (VIII) may range from 0.01 % to 50 % based on the weight of the composition, alternatively 1 % to 10 %.
• Component (IX) Cure Modifier [0045] Component (IX) is a cure modifier.
• Component (IX) can be added to extend the shelf life or working time, or both, of the composition of this invention.
• Component (IX) can be added to raise the curing temperature of the composition.
• Suitable cure modifiers are known in the art and are commercially available.
• Component (DC) is exemplified by acetylenic alcohols, cycloalkenylsiloxanes, eneyne compounds, triazoles phosphines; mercaptans, hydrazines, amines, fumarates, maleates, and combinations thereof. Examples of acetylenic alcohols are disclosed, for example, in EP 0 764703 A2 and U.S.
• Patent 5,449,802 and include methyl butynol, ethynyl cyclohexanol, dimethyl hexynol, 1- butyn-3-ol, l-propyn-3-ol, 2-methyl-3-butyn-2-ol, 3 -methyl- l-butyn-3-ol, 3-methyl-l- pentyn-3-ol, 3 -phenyl- l-butyn-3-ol, 4-ethyl-l-octyn-3-ol, 3,5-diemthyl-l-hexyn-3-ol, and 1- ethynyl-1 -cyclohexanol, and combinations thereof.
• Examples of cycloalkenylsiloxanes include methyl vinylcyclosiloxanes exemplified by l ⁇ S ⁇ -tetramemyl-l ⁇ SJ-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl- 1 ,3,5,7-tetrahexenylcyclotetrasiloxane, and combinations thereof.
• Examples of eneyne compounds include 3-methyl-3-penten-l-yne, 3,5-dimethyl-3-hexen-l-yne, and combinations thereof.
• Examples of triazoles include benzotriazole.
• Examples of phosphines include triphenylphosphine.
• amines include tetramethyl ethylenediamine.
• fumarates include dialkyl fumarates, dialkenyl fumarates, dialkoxyalkyl fumarates, and combinations thereof.
• Suitable cure modifiers are disclosed by, for example, U.S. Pat. Nos. 3,445,420; 3,989,667; 4,584,361; and 5,036,117.
• component (IX) may comprise a silylated acetylenic inhibitor.
• silylated acetylenic inhibitors may have the general formula (IX)(i):
• each R 15 is independently a hydrogen atom or a monovalent organic group
• R 16 is a covalent bond or a divalent hydrocarbon group
• u is 0, 1, 2, or 3
• t is 0 to 10
• v is 4 to 12.
• u is 1 or 3.
• u is 1.
• t is 0.
• v is 5, 6, or 7, and alternatively v is 6.
• monovalent organic groups for R 15 include an aliphatically unsaturated organic group, an aromatic group, or a monovalent substituted or unsubstituted hydrocarbon group free of aromatics and free aliphatic unsaturation, as described above.
• Silylated acetylenic inhibitors are exemplified by (3-methyl-l-butyn-3- oxy)trimethylsilane, ((1,1 -dimethyl-2-propynyl)oxy)trimethylsilane, bis(3 -methyl- 1 -butyn-3 - oxy)dimethylsilane, bis(3 -methyl- 1 -butyn-3 -oxy)silanemethyl vinylsilane, bis(( 1 , 1 -dimethyl- 2- ⁇ ropynyl)oxy)dimethylsilane, methyl(tris( 1 , 1 -dimethyl-2-propynyloxy))silane, methyl(tris(3-methyl-l-butyn-3-oxy))silane, (3-methyl-l-butyn-3-oxy)dimethylphenylsilane, (3-methyl-l-butyn-3-oxy)d ⁇ methylhexenylsilane.
• the silylated acetylenic inhibitor may comprise methyl(tris( 1,1- dimethyl-2-propynyloxy))silane, ((l,l-dimemyl-2-propvnyl)oxy)trimethylsilane., or a combination thereof.
• Silylated acetylenic inhibitors may be prepared by methods known in the art for silylating an alcohol such as reacting a chlorosilane of formula R ls u SiCl4 -u with an acetylenic
• component (IX) added to the composition will depend on the particular cure modifier used, the nature and amount of component (III), and the composition of component (II). However, the amount of component (IX) may range from 0.001 % to 10 % based on the weight of the composition, alternatively 0.001 % to 5 %.
• Component (X) is a rheology modifier. Rheology modifiers can be added to change the thixotropic properties of the composition.
• Component (X) is exemplified by flow control additives; reactive diluents; anti-settling agents; alpha-olefins; hydroxyl- terminated silicone-organic copolymers, including but not limited to hydroxyl-terminated polypropyleneoxide-dimethylsiloxane copolymers; and combinations thereof.
• Other Optional Components [0052] Other optional components may be added in addition to, or instead of, all or a portion of those described above, provided the optional component does not prevent the composition from curing to form a silicone product.
• optional components include, but are not limited to, acid acceptors; anti-oxidants; stabilizers such as magnesium oxide, calcium hydroxide, metal salt additives such as those disclosed in EP 0 950 685 Al, heat stabilizers, and ultra-violet (UV) stabilizers; flame retardants; silylating agents, such as 4-(trimethylsilyloxy)-3-penten-2-one and N-(t-butyl dimethylsilyl)-N- methyltrifluoroacetamide; desiccants, such as zeolites, anhydrous aluminum sulfate, molecular sieves (preferably with a pore diameter of 10 Angstroms or less), kieselguhr, silica gel, and activated carbon; optical diffusants; colloidal silica; and blowing agents, such as water, methanol, ethanol, iso-propyl alcohol, benzyl alcohol, 1,4 butanediol, 1,5 pentanediol, 1 ,7 h
• the components in the composition may be selected such that the molar ratio of the total amount of silicon-bonded hydrogen atoms to aliphatically unsaturated groups in the composition (SiHto/V-tot) * s greater than 0.5 and alternatively at least 0.8.
• SiHt o t/Vit o t may be up to 10.0, alternatively up to 5.0, and alternatively up to 3.0.
• SiHtot ⁇ Vitot * s to ° l° w » men th e composition may not cure or may not adhere to some substrates, and there may be an increase in bleed from within the composition to other surfaces.
• SiHtot ⁇ Vitot * s too high surface properties such as adhesion may be hindered and there may be an increase in bleed from within the composition to other surfaces. Kits
• the composition may be a one-part composition or a multiple-part composition such as a two-part composition.
• component (II) and optional component (IV) when present, are stored in a separate part from component (III). Any of components (I) and (V)-(VIII) can be added to either or both parts.
• One skilled in the art would know how to select components for each part without undue experimentation.
• a kit comprising Part A and Part B can be prepared as follows.
• Part A comprises:
• Part B comprises optionally (I) an alkenyl functional phenyl-containing polyorganosiloxane
• Part A comprises: (II) an alkenyl-functional, diorganosiloxy-terminated oligodiphenylsiloxane having a molecular formula given as where Ph represents a phenyl group, each R* is independently an alkenyl group having 2 to 12 carbon atoms, each R ⁇ is independently a methyl group or a phenyl group, x is an integer from 2 to 8, and x has an average value of 2 to 4, (III) a hydrosilylation catalyst, optionally (V) an adhesion promoter optionally (VI) a filler, optionally (VII) a treating agent, optionally (VIII) a cure modifier, and (IX) a rheology modifier.
• Part B comprises:
• R ⁇ is independently a methyl group or a phenyl group, x is an integer from 2 to 8, and x has an average value of 2 to 4, optionally (IV) a co-crosslinker; optionally (V) an adhesion promoter; optionally (VI) a filler; optionally (VII) a treating agent; optionally (VIII) a cure modifier; and optionally (IX) a rheology modifier.
• the kit may further comprise instructions for mixing Part A and Part B together in a weight ratio.
• Part A and Part B can be mixed together in a ratio of Part A: Part B (A:B) of 0.05:1 to 20:1, alternatively 0.1 :1 to 10:1, alternatively 1 :1 to 5:1.
• compositions described above can be prepared by mixing the components by any convenient means.
• the composition can be prepared by mixing all components at ambient temperature.
• the mixer used is not specifically restricted and will be determined by the viscosity of the components and the composition.
• Suitable mixers include but are not limited to kneader type sigma blade mixers, double planetary mixers, non- intrusive mixers such as those reliant on centrifugal motion, and two- and three-roll rubber mills.
• the compositions may optionally be filtered after mixing.
• One skilled in the art would be able to prepare the composition without undue experimentation by the methods disclosed above and in the examples set forth below.
• composition of this invention is useful for a range of applications where optically transmissive properties or adhesion properties or mechanical properties, or both, are desired.
• the compositions described above cure to form an optically clear material with high adhesion strength and mechanical properties.
• Cured silicone products prepared using the compositions of this invention can vary in properties from rigid resins to elastomers to gels, depending upon various factors including the types and concentrations of components (I) and (II) and any optional components that are added to the composition.
• the cured silicone products are preferably soft elastomers or gels.
• Cured products prepared using the compositions are useful in end- use applications as encapsulants or as coatings.
• Encapsulation or coating techniques for light emitting devices in the present invention are well known to the art and may be used in the present invention. Such techniques comprise casting, dispensing, molding, and the like. For example, after the light emitting device is enveloped in the uncured composition, typically performed in a mold, the composition is cured. These compositions may be cured in one or more stages by heating. For example, cure may be performed at temperatures in one embodiment ranging from room temperature to 200 °C.
• the light emitting devices withstand against thermal shock from soldering condition and thermal and light exposure under light emitting condition.
• transmittance loss of the cured material at 400 nanometers (nm) is smaller than 10 % after soldering at 260 0 C for 5 minutes (Test-1).
• the cured composition show neither delamination nor fracture during the soldering process.
• the similar stability is also observed from following reliability test condition with lighting; a 500 thermal cycle between -40 0 C and 120 0 C (Test-2), exposure at 85 °C/85% relative humidity for 1000 hours (Test-3), and exposure at 150 0 C for 1000 hours (Test-4).
• Reference Example 3 Characterization of Composition and Cured Composition
• a composition was characterized by its viscosity at 25 0 C and refractive index of 587 nm light at 25 0 C.
• the cured silicone product prepared by heating the composition at 150 0 C for 1 min an oven was characterized by its transmittance at 400 nm with 10 mm light path length and durometer A or D hardness.
• Reference Example 4 Preparation of Light Emitting Device [0069] A light emitting diode device shown in Figure 1 was prepared as follows.
• a GaN compound semiconductor (LED) chip 2 was placed in a polyphthalamide (PPA) case 1 and die bonded to an inner lead 3 portion of a lead frame with electroconductive paste, and then the semiconductor chip was wire bonded with gold wire 4.
• PPA polyphthalamide
• a silicone composition as described herein was coated on the semiconductor chip followed by cure at 150 0 C for 1 hour in an oven to form a cured silicone 5.
• Samples for % transmission testing were prepared according to reference example 3, and the samples were separately exposed to following conditions; (1) heating at 260 0 C for 5 min on a hot plate, (2) heating at 150 0 C for 100 h in an oven, (3) heating at 85 0 C under 85% relative humidity for 100 h, and (4) applying a 500 thermal cycle test between -40 0 C and 100 0 C, and (5) heating at 150 0 C for 1000 h. Samples were also prepared according to reference example 4 and exposed to the same conditions. After the exposures, appearance of the encapsulant was observed with microscope in term of delamination, fracture, or the other deformation. % Transmission before and after the exposures were measured, and relative output values based on the initial output value as 100 were obtained.
• Catalyst which is a mixture of 90 % l,3-diethenyl-l,l,3,3-tetramethyldisiloxane and 10 % 1,3-diethenyl-l, 1,3 ,3-tetramethyldisiloxane complexes with platinum, said mixture having a platinum content of 5.0 %, 0.1 parts a hydroxy-terminated poly(methylphenylsiloxane/methylvinylsiloxane) with (glycidoxypropyl)trimethoxysilane as Adhesion Promoter, and 0.01 parts ethynylcyclohexan-1-ol as Cure Modifier to 100 parts of the above mixture yielded a clear composition.
• Catalyst which is a mixture of 90 % l,3-diethenyl-l,l,3,3-tetramethyldisiloxane and 10 % 1,3-diethenyl-l, 1,3,3- tetramethyldisiloxane complexes with platinum, said mixture having a platinum content of 5.0 %, and 0.05 parts ethynylcyclohexan-1-ol as Cure Modifier to 100 parts of the above mixture yielded a clear composition.
• Comparative example 1 Curable Silicone Composition 10074] A mixture of ViMe 2 SiO(SiMePhO) 2 OSiMe 2 Vi (37.54%), ViMe 2 SiO(SiMePhO) 4 SiMe 2 Vi (6.11%),
• Catalyst which is a mixture of 90 % l,3-diethenyl-l,l,3,3-tetramethyldisiloxane and 10 % 1,3-diethenyl- 1,1,3,3-tetramethyldisiloxane complexes with platinum, said mixture having a platinum content of 4.0 %, as Adhesion Promoter, and 0.05 parts ethynyl cyclohexanol as Cure Modifier to 100 parts of the above mixture yielded a clear composition.
• Comparative example 2 - Curable Silicone Composition [00751 A mixture OfViMe 2 SiO(SiMePhO) 5 OSiMe 2 Vi,
• Catalyst which is a mixture of 90 % l,3-diemenyl-l,l,3,3-tetramethyldisiloxane and 10 % 1,3- diethenyl-l,l,3,3-tetramethyldisiloxane complexes with platinum, said mixture having a platinum content of 5.0 %, 0.1 parts a hydroxy-terminated poly(methylphenylsiloxane/methylvinylsiloxane) with (glycidoxypropyl)trimethoxysilane as Adhesion Promoter, and 0.01 parts ethynylcyclohexan-1-ol as Cure Modifier to 100 parts of the above mixture yielded a clear composition.
• Catalyst which is a mixture of 90 % l,3-diemenyl-l,l,3,3-tetramethyldisiloxane and 10 % 1,3- diethenyl-l,l,3,3-tetramethyld
• Comparative example 3 Curable Silicone Composition
• a mixture of (ViMe 2 SiOy 2 )o. 2 5(PhSi ⁇ 3/ 2 )o.75, Ph 2 Si(OSiMe 2 Vi) 2 , and Ph 2 Si(OSiMe 2 H) 2 in ratio of 69.5:2.8:27.7 was prepared by mixing the components.
• Catalyst which is a mixture of 90 % l,3-diethenyl-l,l,3,3- tetramethyldisiloxane and 10 % l,3-diethenyl-l,l,3,3-tetramethyldisiloxane complexes with platinum, said mixture having a platinum content of 5.0 %, and 0.05 parts ethynylcyclohexan-1-ol as Cure Modifier to 100 parts of the above mixture yielded a clear composition.
• Example 4 A mixture of ViMe 2 SiO(MePhSiO 2 / 2 ) ⁇ 9SiMe 2 Vi (54.84 %),
• Catalyst which is a mixture of 99 % ViMe 2 SiO(SiMePhO)IpSiMe 2 Vi, 0.38% 1,3-diethenyl-l, 1,3,3- tetramethyldisiloxane, and 0.62% 1,3-diethenyl-l, 1,3,3-tetramethyldisiloxane complexes with platinum, said mixture having a platinum content of 25.0 %, and 0.39 parts inhibitor which is a mixture of 99 % ViMe 2 SiO(SiMePhO) 19SiMe 2 Vi and 1% 1-ethynyl-l- cyclohexanol as Cure Modifier to 100 parts of the above mixture yielded a clear composition.
• the composition was evaluated according to test (5) in reference example 5. The results are in Table 2.
• FIG. 1 is a cross-section image of light emitting device

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (2)

Family

ID=38459494

Family Applications (1)

Country Status (7)

Cited By (29)

Families Citing this family (76)

Citations (2)

Family Cites Families (94)

• 2007
  • 2007-02-01 CN CN200780006355XA patent/CN101389695B/zh active Active
  • 2007-02-01 JP JP2008556343A patent/JP2009527622A/ja active Pending
  • 2007-02-01 EP EP07749880.6A patent/EP1987084B1/en active Active
  • 2007-02-01 WO PCT/US2007/002966 patent/WO2007100445A2/en not_active Ceased
  • 2007-02-01 US US12/223,133 patent/US8258502B2/en active Active
  • 2007-02-01 KR KR1020087020666A patent/KR20080104279A/ko not_active Ceased
  • 2007-02-15 TW TW96105604A patent/TWI470028B/zh active
• 2012
  • 2012-12-21 JP JP2012279902A patent/JP5669815B2/ja active Active

Patent Citations (2)

Also Published As

Similar Documents

Legal Events