WO2014004969A1 - Polyorganometallosiloxane, curable polymer compositions, cured product thereof, and optical semiconductor device - Google Patents

Polyorganometallosiloxane, curable polymer compositions, cured product thereof, and optical semiconductor device Download PDF

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Publication number
WO2014004969A1
WO2014004969A1 PCT/US2013/048471 US2013048471W WO2014004969A1 WO 2014004969 A1 WO2014004969 A1 WO 2014004969A1 US 2013048471 W US2013048471 W US 2013048471W WO 2014004969 A1 WO2014004969 A1 WO 2014004969A1
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group
general formula
groups
unit represented
polyorganometallosiloxane
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PCT/US2013/048471
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French (fr)
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Tadashi Okawa
Kazuhiro Nishijima
Kazuhiko Kojima
Haruhiko Furukawa
Masaaki Amako
Nanguo Liu
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Dow Corning Corporation
Dow Corning Toray Co., Ltd.
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Publication of WO2014004969A1 publication Critical patent/WO2014004969A1/en

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    • 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
    • C08G77/58—Metal-containing linkages
    • 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
    • C08L83/14—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/296—Organo-silicon compounds
    • 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
    • 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
    • H01L2224/481—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
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—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
    • H01L24/42—Wire connectors; Manufacturing methods related thereto
    • H01L24/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L24/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/12—Passive devices, e.g. 2 terminal devices
    • H01L2924/1204—Optical Diode
    • H01L2924/12041—LED
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation

Definitions

  • the present invention relates to a polyorganometallosiloxane, a curable polymer composition containing the polyorganometallosiloxane, a cured product of the composition, and an optical semiconductor device using the composition.
  • a resin composition comprising a polyheterosiloxane resin primarily including a unit represented by R m MO( X .
  • M is an atom selected from a group of atoms in the fourth to sixth periods belonging to groups 2A to 5A of the periodic table
  • R represents a group selected from hydrogen atoms, hydroxyl groups, amino groups or substituted or unsubstituted aliphatic groups, alicyclic groups, aryl groups, heterocyclic groups, or groups in which these groups are bonded to M atoms through oxygen
  • x represents the valency of M atoms
  • "m” represents an integer of 0 or from 1 to x-1)
  • Patent Document 1 a curable composition comprising a silylated polymetallosiloxane having at least 2 alkenyl groups in a molecule, a compound having at least 2 silicon-bonded hydrogen atoms in a molecule and having no siloxane bonds, and a curing catalyst
  • these sealing agents have a problem in that the heat resistance and moisture resistance of the resulting cured product are insufficient, which causes the cured product to be discolored to causes discoloration or a decrease in mechanical strength under conditions with high temperature or high humidity. There is also a problem in that when an attempt is made to increase the refractive index of the sealing agent, the cured product becomes hard and brittle, which leads to insufficient stability and mechanical characteristics.
  • Patent Document 1 Japanese Unexamined Patent Application Publication No. 2000-235103 A.
  • Patent Document 2 Japanese Unexamined Patent Application Publication No. 2009-173910A.
  • An object of the present invention is to provide a polyorganometallosiloxane with a high refractive index and excellent heat resistance, moisture resistance, and compatibility with organic polymers. Another object of the present invention is to provide a curable polymer composition which is cured by a hydrosilylation reaction to form a cured product with a high refractive index and excellent visible light transmittance, heat resistance, and moisture resistance. Another object of the present invention is to provide a cured product with a high refractive index and excellent visible light transmittance, heat resistance, and moisture resistance. Yet another object of the present invention is to provide a highly reliable optical semiconductor device using this curable polymer composition.
  • the polyorganometallosiloxane of the present invention comprises a metalloxy unit represented by general formula (1):
  • M 1 is an atom of group 4A or group 5 A of the periodic table, and "x" is the valency of M 1 );
  • organosiloxane unit represented by general formula (3):
  • R 1 is an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a hydrogen atom
  • "a" is a number satisfying: 0 ⁇ a ⁇ 3).
  • the curable polymer composition of the present invention contains the polyorganometallosiloxane described above and is cured by a hydrosilylation reaction.
  • the cured product of the present invention is formed by curing the curable polymer composition.
  • the optical semiconductor device of the present invention is formed by covering or sealing an optical semiconductor element with the cured product of the curable polymer composition described above.
  • the polyorganometallosiloxane of the present invention has a high refractive index and excellent heat resistance, moisture resistance, and compatibility with organic polymers.
  • the curable polymer composition of the present invention is cured by a hydrosilylation reaction to form a cured product with a high refractive index and excellent visible light transmittance, heat resistance, and moisture resistance.
  • the cured product of the present invention has a high refractive index and excellent visible light transmittance, heat resistance, and moisture resistance.
  • the optical semiconductor device of the present invention exhibits excellent reliability.
  • Figure 1 is a cross-sectional drawing of an LED that is an example of the optical semiconductor device of the present invention.
  • the polyorganometallosiloxane of the present invention comprises a metalloxy unit represented by general formula (1): M 1 O x /2, a metalloxy unit represented by general formula (2): M 2 O y /2, and an organosiloxane unit represented by general formula (3): R 1 a SiO(4_ a )/2.
  • the metalloxy unit represented by general formula (1) is a unit which increases the refractive index of the polyorganometallosiloxane of the present invention.
  • M 1 is an atom of group 4 A or group 5 A of the periodic table.
  • M 1 is an atom selected from atoms of group 4 A such as Ti, Zr, and Hf or atoms of group 5A such as V, Nb, and Ta and is preferably Ti or Zr.
  • "x" represents the valency of M 1 , which differs depending on the type of the atom and is an integer of from 1 to 7.
  • the valency of Ti is 3 or 4
  • the valency of Zr or Hf is 4.
  • the metalloxy unit represented by general formula (2) is a unit which improves the heat resistance and moisture resistance of the polyorganometallosiloxane of the present invention.
  • M 2 is an atom of group 2A or group 2B of the periodic table. Specifically, M 2 is an atom selected from atoms of group 2A such as Ca, Sr, and Ba or atoms of group 2B such as Zn, Cd, and Hg. In order to ensure excellent heat resistance, M 2 is preferably Zn, Ca, or Ba and even more preferably Zn.
  • "y" represents the valency of M 2 , which differs depending on the type of the atom and is an integer of from 1 to 7. For example, the valency of Zn, Ca, and Ba is 2.
  • the organosiloxane unit represented by general formula (3) is a unit which improves the heat resistance, moisture resistance, and compatibility with organic polymers of the polyorganometallosiloxane of the present invention.
  • R 1 is an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a hydrogen atom.
  • Examples of the alkyl group of R 1 include methyl groups, ethyl groups, propyl groups, and butyl groups. Of these, methyl groups are preferable.
  • Examples of the alkenyl group of R 1 include vinyl groups, allyl groups, and butenyl groups. Of these, vinyl groups are preferable.
  • aryl group of R 1 examples include phenyl groups, naphthyl groups, anthracenyl groups, phenanthryl groups, pyrenyl groups, and aryl groups in which the hydrogen atoms of these aryl groups are substituted with alkyl groups such as methyl groups or ethyl groups; alkoxy groups such as methoxy groups or ethoxy groups; or halogen atoms such as chlorine atoms or bromine atoms. Of these, phenyl groups and naphthyl groups are preferable.
  • Examples of the aralkyl group of R 1 include naphthyl ethyl groups, naphthyl propyl groups, anthracenyl ethyl groups, phenanthryl ethyl groups, pyrenyl ethyl groups, and aralkyl groups in which the hydrogen atoms of these aralkyl groups are substituted with alkyl groups such as methyl groups or ethyl groups; alkoxy groups such as methoxy groups or ethoxy groups; or halogen atoms such as chlorine atoms or bromine atoms.
  • the polyorganometallosiloxane of the present invention can be made hydrosilylation-reactive, it is preferable for at least one R 1 to be an alkenyl group or a hydrogen atom in a molecule.
  • "a" is a number satisfying: 0 ⁇ a ⁇ 3 and is preferably a number satisfying: 1 ⁇ a ⁇ 3 so that the refractive index of the polyorganometallosiloxane is large and so that the compatibility with organic polymers improves.
  • the respective contents of the metalloxy unit represented by general formula (1), the metalloxy unit represented by general formula (2), and the siloxane unit represented by general formula (3) are not particularly limited, but the ratio of the content of the metalloxy unit represented by general formula (1) to the content of the siloxane unit represented by general formula (3) is preferably within the range of from 0.01: 1 to 99:1 and even more preferably within the range of from 0.01 :1 to 19:1.
  • the ratio of the content of the metalloxy unit represented by general formula (2) to the content of the siloxane unit represented by general formula (3) is preferably within the range of from 0.01:1 to 19:1 and even more preferably within the range of from 0.01 :1 to 9:1. This is because when the content of the metalloxy unit represented by general formula (1) is less than or equal to the lower limit of the range described above, the refractive index of the polyorganometallosiloxane decreases, and when the content is greater than or equal to the upper limit of the range described above, the compatibility of the polyorganometallosiloxane with organic polymers decreases.
  • the content of the metalloxy unit represented by general formula (2) is less than or equal to the lower limit of the range described above, the heat resistance and moisture resistance of the polyorganometallosiloxane decrease, and when the content is greater than or equal to the upper limit of the range described above, the refractive index of the polyorganometallosiloxane decreases and the compatibility with organic polymers decreases.
  • the method of producing such a polyorganometallosiloxane of the present invention is not limited, but an example is a method of hydrolyzing and performing a condensation reaction on a metal compound represented by general formula (4):
  • R 1 is an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a hydrogen atom
  • Z is a hydroxyl group or a hydrolysable group
  • "a" is a number satisfying: 0 ⁇ a ⁇ 3)
  • M 1 is an atom of group 4A or group 5 A of the periodic table, examples of which are the same atoms as those described above.
  • X is a hydroxyl group or a hydrolysable group.
  • hydrolysable group of X examples include alkoxy groups such as methoxy groups and ethoxy groups; enoxy groups such as isopropenoxy groups; acyloxy groups such as acetoxy groups; halogen groups such as chlorine and bromine; sulfuric acid group; (organic) sulfonic acid groups such as methane sulfonic acid groups and tridecyl benzyl sulfonic acid groups; phosphoric acid groups, (organic) phosphonic acid groups, and nitric acid groups.
  • "b" and "c" are numbers satisfying:
  • Examples of such a metal compound represented by general formula (4) include, but are not limited to, zirconium hydroxide, hafnium hydroxide, tantalum hydroxide, titanium alkoxide, zirconium alkoxide, hafnium alkoxide, vanadium alkoxide, niobium alkoxide, tantalum alkoxide, titanium acetate, zirconium acetate, hafnium acetate, vanadium acetate, niobium acetate, tantalum acetate, zirconium methacrylate, titanium chloride, zirconium chloride, hafnium chloride, vanadium chloride, niobium chloride, tantalum chloride, titanium sulfate, zirconium sulfate, vanadium sulfate, zirconium nitrate, hafnium nitrate, tantalum nitrate, titanium methane sulfonate, tridec
  • M 2 is an atom of group 2 A or group 2B of the periodic table, examples of which are the same atoms as those described above.
  • Y is a hydrolysable group, examples of which are the same hydrolysable groups as those of X described above.
  • "d" and "e” are numbers satisfying:
  • Examples of such a metal compound represented by general formula (5) include, but are not limited to, calcium hydroxide, strontium hydroxide, barium hydroxide, zinc hydroxide, cadmium hydroxide, calcium acetate, strontium acetate, barium acetate, zinc acetate, cadmium acetate, mercury acetate, calcium acetylacetonate, strontium acetylacetonate, barium acetylacetonate, calcium chloride, strontium chloride, barium chloride, zinc chloride, cadmium chloride, mercury chloride, calcium nitrate, strontium nitrate, barium nitrate, zinc nitrate, cadmium nitrate, and mercury nitrate.
  • R 1 is an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a hydrogen atom, examples of which are the same groups as those described above.
  • Z is a hydroxyl group or a hydrolysable group, examples of which are the same hydrolysable groups as those of X described above.
  • "a" is a number within the range of 0 ⁇ a ⁇ 3.
  • Examples of such an organosilane compound represented by general formula (6) include, but are not limited to, trimethylmethoxysilane, trimethylethoxysilane, vinyl dimethylmethoxysilane, vinyl dimethylethoxysilane, diphenyl methylmethoxysilane, diphenyl methylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl vinyl dimethoxysilane, methyl vinyl diethoxysilane, methyl phenyl dimethoxysilane, methyl phenyl diethoxysilane, methyl chloropropyl dimethoxysilane, methyl trimethoxysilane, ethyl trimethoxysilane, vinyl trimethoxysilane, phenyl trimethoxysilane, chloropropyl trimethoxysilane, 1-naphthyl trimethoxysilane, vinyl dimethylsilanol
  • the added amounts of the metal compound represented by general formula (4), the metal compound represented by general formula (5), and the organosilane compound represented by general formula (6) are not limited, but are preferably amounts in which the contents of the metalloxy unit represented by general formula (1), the metalloxy unit represented by general formula (2), and the siloxane unit represented by general formula (3) in the resulting polyorganometallosiloxane are within the ranges described above.
  • hydrolysis progresses either at room temperature or under heat, but it is preferable from the perspective of the reaction rate to add an acid or an alkali as a catalyst.
  • examples of usable acids include hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, and phosphoric acid.
  • examples of usable alkalis include organic base compounds such as triethylamine, diethylamine, monoethanolamine, diethanolamine, triethanolamine, ammonia water, tetramethylammonium hydroxide, alkoxysilanes having an amino group, and aminopropyl trimethoxysilane.
  • the curable polymer composition of the present invention contains the polyorganometallosiloxane described above and is cured by a hydrosilylation reaction.
  • An example of such a curable polymer composition is one comprising:
  • M 1 is an atom of group 4A or group 5 A of the periodic table, and "x" is the valency of M 1 );
  • organosiloxane unit represented by general formula (3):
  • R 1 is an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a hydrogen atom
  • "a" is a number satisfying: 0 ⁇ a ⁇ 3).
  • Component (A) is an organopolysiloxane having at least 2 alkenyl groups in a molecule.
  • alkenyl groups in component (A) include vinyl groups, allyl groups, butenyl groups, pentenyl groups, hexenyl groups, and heptenyl groups. Of these, vinyl groups are preferable.
  • groups bonding to silicon atoms other than alkenyl groups in component (A) include alkyl groups, aryl groups, and aralkyl groups.
  • alkyl groups include methyl groups, ethyl groups, propyl groups, and butyl groups. Of these, methyl groups are preferable.
  • aryl groups include phenyl groups, naphthyl groups, anthracenyl groups, phenanthryl groups, pyrenyl groups, and aryl groups in which the hydrogen atoms of these aryl groups are substituted with alkyl groups such as methyl groups or ethyl groups; alkoxy groups such as methoxy groups or ethoxy groups; or halogen atoms such as chlorine atoms or bromine atoms.
  • alkyl groups such as methyl groups or ethyl groups
  • alkoxy groups such as methoxy groups or ethoxy groups
  • halogen atoms such as chlorine atoms or bromine atoms.
  • phenyl groups and naphthyl groups are preferable.
  • aralkyl groups include naphthyl ethyl groups, naphthyl propyl groups, anthracenyl ethyl groups, phenanthryl ethyl groups, pyrenyl ethyl groups, and aralkyl groups in which the hydrogen atoms of these aralkyl groups are substituted with alkyl groups such as methyl groups or ethyl groups; alkoxy groups such as methoxy groups or ethoxy groups; or halogen atoms such as chlorine atoms or bromine atoms.
  • component (A) preferably has aryl groups or aralkyl groups and even more preferably has phenyl groups or naphthyl groups as groups bonding to silicon atoms other than alkenyl groups in component (A).
  • Examples of such component (A) include organopolysiloxanes including a siloxane unit represented by the general formula: R' 3 SiOi 2 and a siloxane unit represented by the general formula: R'R"Si022; organopolysiloxanes including a siloxane unit represented by the general formula: R' 3 SiOi 2 and siloxane units represented by the general formula: R'R"Si0 2/ 2 and the general formula: R' 2 Si0 2 2; organopolysiloxanes including a siloxane unit represented by the general formula: R'2R"SiOi 2 and a siloxane unit represented by the general formula: R' 2 Si0 2 2; organopolysiloxanes including a siloxane unit represented by the general formula: R'2R"SiOi 2, a siloxane unit represented by the general formula: R' 2 Si0 2 2, and a siloxane unit represented by the general formula: R'RR
  • R' is an alkyl group, an aryl group, or an aralkyl group, examples of which are the same groups as those described above.
  • R" is an alkenyl group, examples of which are the same groups as those described above.
  • Component (B) is an organopolysiloxane having at least two silicon-bonded hydrogen atoms in a molecule.
  • groups bonding to silicon atoms other than hydrogen atoms in component (B) include alkyl groups, aryl groups, and aralkyl groups, examples of which are the same groups as those described above.
  • component (B) preferably has aryl groups or aralkyl groups and even more preferably has phenyl groups or naphthyl groups as groups bonding to silicon atoms other than hydrogen atoms in component (B).
  • Examples of such a component (B) include organopolysiloxanes including a siloxane unit represented by the general formula: R' 3 SiOi 2 and a siloxane unit represented by the general formula: R'HSiC>2 / 2; organopolysiloxanes including a siloxane unit represented by the general formula: R' 3 SiOi 2 and siloxane units represented by the general formula: R'HSiC>2 / 2 and the general formula: R'2SiC>2 / 2; organopolysiloxanes including a siloxane unit represented by the general formula: R'2HSiOi 2 and a siloxane unit represented by the general formula: R'2SiC>2 / 2; organopolysiloxanes including a siloxane unit represented by the general formula: R'2HSiOi 2, a siloxane unit represented by the general formula: R'2SiC>2 / 2, and a siloxane unit
  • Component (C) is a hydrosilylation-reaction catalyst, specific examples of which include platinum-based catalysts, rhodium-based catalysts, and palladium- based catalysts.
  • Component (C) is preferably a platinum-based catalyst so that the curing of the present composition can be dramatically accelerated.
  • the platinum-based catalyst include a platinum fine powder, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex and a platinum-carbonyl complex, with a platinum- alkenylsiloxane complex being preferred.
  • Component (D) is a polyorganometallosiloxane comprising a metalloxy unit represented by general formula (1): M 1 O x a, a metalloxy unit represented by general formula (2): M 2 O y/ 2, and an organosiloxane unit represented by general formula (3): R 1 a SiO(4_a ) 2.
  • Component (D) is as described above.
  • component (D) is a polyorganometallosiloxane in which at least one R 1 is an alkenyl group in a molecule
  • component (D) can undergo a hydrosilylation reaction with the silicon-bonded hydrogen atoms in component (B).
  • component (D) is a polyorganometallosiloxane in which at least one R 1 is a hydrogen atom in a molecule
  • component (D) can undergo a hydrosilylation reaction with the alkenyl groups in component (A).
  • the content of component (B) is not particularly limited, but when component (D) does not contain alkenyl groups and silicon-bonded hydrogen atoms, the content is preferably an amount with which the silicon-bonded hydrogen atoms in component (B) are within the range of from 0.2 to 5 mol and even more preferably within the range of from 0.5 to 2 mol with respect to a total of 1 mol of the alkenyl groups in component (A).
  • the content is preferably an amount with which the silicon-bonded hydrogen atoms in component (B) are within the range of from 0.2 to 5 mol and even more preferably within the range of from 0.5 to 2 mol with respect to a total of 1 mol of the alkenyl groups in component (A) and component (D).
  • the content is preferably an amount with which the total silicon-bonded hydrogen atoms in component (B) and component (D) is within the range of from 0.2 to 5 mol and even more preferably within the range of from 0.5 to 2 mol with respect to a total of 1 mol of the alkenyl groups in component (A).
  • component (B) is greater than or equal to the lower limit of the range described above, the curing of the resulting composition becomes sufficient, and when the content is less than or equal to the upper limit of the range described above, the physical characteristics of the resulting cured product improve.
  • the content of component (C) is not particularly limited as long as the curing of the composition can be accelerated. Specifically, the content is preferably an amount with which the catalyst metal in component (C) is within the range of from 0.01 to 500 ppm, even more preferably within the range of from 0.01 to 100 ppm, and yet even more preferably within the range of from 0.01 to 50 ppm in weight units with respect to the composition.
  • the content of component (D) is not particularly limited, but is preferably from 1 to 99 wt. and even more preferably from 10 to 90 wt. of the total amount of component (A), component (B), and component (D). This is because when the content of component (D) is less than the lower limit, the refractive index is insufficient, and when the content is greater than the upper limit, the resulting cured product becomes brittle.
  • curable polymer composition of the present invention is a curable polymer composition comprising:
  • M 1 is an atom of group 4A or group 5 A of the periodic table, and "x" is the valency of M 1 );
  • organosiloxane unit represented by general formula (3):
  • R 1 is an alkyl group, an alkenyl group, an aromatic group-containing group, or a hydrogen atom, and "a" is a number satisfying: 0 ⁇ a ⁇ 3);
  • R 1 are alkenyl groups in a molecule
  • Component (E) is a polyorganometallosiloxane comprising a metalloxy unit represented by general formula (1): M 1 O x a, a metalloxy unit represented by general formula (2): M 2 O y/2 , and an organosiloxane unit represented by general formula (3): R 1 a SiO(4_a)/ 2 , wherein at least two R 1 are alkenyl groups in a molecule.
  • Component (E) is as described above. Since component (E) has at least two alkenyl groups in a molecule, component (E) can undergo a hydrosilylation reaction with the silicon- bonded hydrogen atoms in component (B).
  • Component (B) is an organopolysiloxane having at least two silicon-bonded hydrogen atoms in a molecule, examples of which are the same as those described above.
  • Component (C) is a hydrosilylation-reaction catalyst, examples of which are the same as those described above.
  • the content of component (B) is not particularly limited, but is preferably an amount with which the silicon-bonded hydrogen atoms in the component are within the range of from 0.2 to 5 mol and even more preferably within the range of from 0.5 to 2 mol with respect to 1 mol of the alkenyl groups in component (E). This is because when the content of component (B) is greater than or equal to the lower limit of the range described above, the curing of the resulting composition becomes sufficient, and when the content is less than or equal to the upper limit of the range described above, the physical characteristics of the resulting cured product improve.
  • the content of component (C) is not particularly limited as long as the curing of the composition can be accelerated. Specifically, the content is preferably an amount with which the catalyst metal in component (C) is within the range of from 0.01 to 500 ppm, even more preferably within the range of from 0.01 to 100 ppm, and yet even more preferably within the range of from 0.01 to 50 ppm in weight units with respect to the composition.
  • Such a curable polymer composition of the present invention may also contain (F) a phosphor as another optional component.
  • this component (F) include yellow, red, green, and blue light-emitting phosphors which are widely used in light emitting diodes (LEDs) such as oxide phosphors, oxynitride phosphors, nitride phosphors, sulfide phosphors, oxysulfide phosphors, and mixtures of two or more types of these phosphors.
  • LEDs light emitting diodes
  • oxide phosphors include yttrium, aluminum and garnet-based YAG green to yellow light-emitting phosphors containing cerium ions, terbium, aluminum, and garnet-based TAG yellow light-emitting phosphors containing cerium ions, and silicate green to yellow light-emitting phosphors containing cerium or europium ions.
  • oxide phosphors include yttrium, aluminum and garnet-based YAG green to yellow light-emitting phosphors containing cerium ions, terbium, aluminum, and garnet-based TAG yellow light-emitting phosphors containing cerium ions, and silicate green to yellow light-emitting phosphors containing cerium or europium ions.
  • oxynitride phosphors include silicon, aluminum, oxygen, and nitrogen-based sialon red to green light- emitting phosphors containing europium ions.
  • nitride phosphors include calcium
  • component (F) is not particularly limited, but is preferably within the range of from 0.1 to 70 wt.% and even more preferably within the range of from 1 to 20 wt.% in the composition.
  • the curable polymer composition of the present invention may also contain an adhesion-imparting agent for improving the adhesion of the composition.
  • An organic silicon compound having at least one alkoxy group bonding to silicon atoms in a molecule is preferable as this adhesion-imparting agent.
  • this alkoxy group include methoxy groups, ethoxy groups, propoxy groups, butoxy groups, and methoxyethoxy groups. Of these, methoxy groups are particularly preferable.
  • groups other than alkoxy groups bonding to silicon atoms in this organic silicon compound include substituted or unsubstituted monovalent hydrocarbon groups such as alkyl groups, alkenyl groups, aryl groups, aralkyl groups and halogenated alkyl groups; epoxy group-containing monovalent organic groups such as 3-glycidoxypropyl groups, 4-glycidoxybutyl groups, or similar glycidoxyalkyl groups; 2-(3,4-epoxycyclohexyl)ethyl groups, 3-(3,4-epoxycyclohexyl)propyl groups, or similar epoxycyclohexyl alkyl groups; 4-oxiranylbutyl groups, 8-oxiranyloctyl groups, or similar oxiranylalkyl groups; acrylic group-containing monovalent organic groups such as 3 -methacryloxypropyl groups; and hydrogen atoms.
  • monovalent hydrocarbon groups such as alkyl groups, alkenyl groups, aryl groups, aral
  • This organic silicon compound preferably has silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms.
  • This organic silicon compound also preferably has at least one epoxy group-containing monovalent organic group in a molecule so that good adhesion can be imparted to various base materials.
  • Examples of such an organic silicon compound include organosilane compounds, organosiloxane oligomers, and alkyl silicates.
  • Examples of the molecular structure of this organosiloxane oligomer or alkyl silicate include a straight structure, a partially branched straight structure, a branched structure, a cyclic structure, and a reticulated structure. Of these, straight, branched, and reticulated structures are particularly preferable.
  • Examples of such an organic silicon compound include silane compounds such as 3-glycidoxypropyl trimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, and 3- methacryloxypropyl trimethoxysilane; mixtures of a siloxane compound having at least one of each of a silicon-bonded alkenyl group or a silicon-bonded hydrogen atom and a silicon-bonded alkoxy group in a molecule, a silane compound or a siloxane compound having at least one silicon-bonded alkoxy group, and a siloxane compound having at least one of each of a silicon-bonded hydroxy group and a silicon-bonded alkenyl group in a molecule, methyl polysilicates, ethyl polysilicates, and epoxy-group containing ethyl polysilicates.
  • silane compounds such as 3-glycidoxypropyl trimethoxysilane, 2-(3,4-
  • the content of this adhesion-imparting agent is not particularly limited, but is preferably within the range of from 0.01 to 10 parts by weight per total of 100 parts by weight of the composition.
  • a reaction inhibitor for example, an alkyne alcohol such as 2-methyl-3-butyn- 2-ol, 3,5-dimethyl-l-hexyn-3-ol or 2-phenyl-3-butyn-2-ol; an ene-yne compound such as 3-methyl-3-penten-l-yne or 3,5-dimethyl-3-hexen-l-yne; or 1,3,5,7-tetramethyl- 1 ,3,5,7-tetravinylcyclotetrasiloxane, l,3,5,7-tetramethyl-l ,3,5,7- tetrahexenylcyclotetrasiloxane or a benzotriazole may be incorporated as an optional component in the curable polymer composition of the present invention.
  • an alkyne alcohol such as 2-methyl-3-butyn- 2-ol, 3,5-dimethyl-l-hexyn-3-ol or 2-phenyl-3-butyn-2-ol
  • a content of the reaction inhibitor is not limited, but is preferably from 0.0001 to 5 parts by weight per 100 parts by weight of the present composition.
  • An inorganic filler such as silica, glass, alumina or zinc oxide; an organic resin fine powder of a polymethacrylate resin and the like; a heat-resistant agent, a dye, a pigment, a flame retardant, a solvent and the like may be incorporated as optional components in the curable polymer composition of the present invention at levels that do not impair the objective of the present invention.
  • the curable polymer composition of the present invention is such that curing occurs either at room temperature or under heating, but it is preferable to heat the composition in order to achieve rapid curing.
  • the heating temperature is preferably from 50 to 200°C.
  • Such a curable polymer composition of the present invention may be used as an adhesive, a potting agent, a protective agent, a coating agent, an underfill agent for electrical/electronic use, or a molding agent.
  • the composition is particularly suitable as an adhesive, a potting agent, a protective agent, a coating agent, an underfill agent for a semiconductor element in optical applications, a molding agent for a lens, or the like due to the high optical transmittance of the composition.
  • the cured product of the present invention is formed by curing the curable polymer composition.
  • the shape of such a cured product of the present invention is not particularly limited, and the cured product can be handled in a state in which the cured product covers or seals an optical semiconductor element or the like.
  • the cured product of the present invention can be handled as a stand-alone product, examples of which include a sheet-like product and a film-like product.
  • This device is characterized in that an optical semiconductor element is covered or sealed by a cured product of the curable polymer composition described above.
  • An example of this optical semiconductor element is a light emitting diode (LED) chip.
  • Examples of such an optical semiconductor device include a light emitting diode (LED), a photocoupler, and a CCD.
  • Figure 1 shows a cross-sectional drawing of a surface mounted type LED, which is one example of the optical semiconductor device of the present invention.
  • an LED chip 1 is die-bonded to a lead frame 2, and the LED chip 1 and a lead frame 3 are wire -bonded by a bonding wire 4.
  • This LED chip 1 is covered by a cured product 5 of the curable polymer composition described above.
  • An example of a method of producing the surface mounted type LED illustrated in Figure 1 is a method of die-bonding the LED chip 1 to the lead frame 2, wire-bonding the LED chip 1 and the lead frame 3 with a gold bonding wire 4, applying the curable polymer composition described above to the LED chip 1, and then curing the composition by heating at 50 to 200°C.
  • the polyorganometallosiloxane, the curable polymer composition, the cured product, and the optical semiconductor device of the present invention will be explained in further detail using practical examples.
  • the characteristics of the polyorganometallosiloxane, the curable polymer composition, and the cured product were measured as follows. In the practical examples, Vi represents a vinyl group, Me represents a methyl group, Ph represents a phenyl group, and Naph represents a naphthyl group.
  • the polyorganometallosiloxane was dissolved with a polyphenylmethylsiloxane (viscosity at 25°C, refractive index: 1.545) so as to achieve a prescribed concentration (volume ), and the refractive index was calculated from the refractive index of the mixture.
  • the refractive index of the cured product was measured using the prism coupler method. A 632.8 nm laser light source was used for the measurements.
  • the mixture was distilled under normal pressure while heating until the reaction temperature reached 120°C, and the mixture was reacted for 2 hours at this temperature.
  • the mixture was then cooled to room temperature, and a neutralization reaction was performed by adding 0.08 g (1.3 mmol) of acetic acid. After the salt that was produced was filtered out, the low-boiling matter was removed from the resulting clear solution under reduced pressure while heating, and 14.3 g of a colorless, clear, viscous liquid (yield: 94%) was obtained.
  • this liquid is an organopolysiloxane represented by the average unit formula:
  • This organopolysiloxane had a weight average molecular weight (Mw) of 1,000, a dispersity (Mw/Mn) of 1.05, and a refractive index of 1.603.
  • the mixture was then distilled under normal pressure while heating until the temperature reached 85°C, and the mixture was reacted for 1 hour at this temperature.
  • 0.06 g (1.1 mmol) of potassium hydroxide was loaded.
  • the mixture was distilled under normal pressure while heating until the reaction temperature reached 120°C, and the mixture was reacted for 1 hour at this temperature.
  • the mixture was cooled to room temperature, and a neutralization reaction was performed by adding 0.09 g (1.5 mmol) of acetic acid.
  • this viscous liquid is an organopolysiloxane represented by the average unit formula:
  • This organopolysiloxane had a weight average molecular weight (Mw) of 1,000, a dispersity (Mw/Mn) of 1.08, and a refractive index of 1.622.
  • a reaction was performed in the same manner as in Practical Example 1 with the exception that the zinc acetate of Practical Example 1 was not used. However, when the reaction mixture was heated after 0.1 N of dilute hydrochloric acid was added, the mixture lost fluidity, and gelling occurred.
  • Vinyldimethylsilanol was added to a 50 wt.% toluene solution of the polyorganometallosiloxane (1) prepared in Practical Example 1 to form the respective loading compositions shown in Table 1, and the solutions were heated for 3 hours at 80°C.
  • Vinyldimethylsilanol was added to a 50 wt.% toluene solution of the polyorganometallosiloxane (2) prepared in Practical Example 2 to form the respective loading compositions shown in Table 1, and the solution was heated for 3 hours at 80°C.
  • a polyorganometallosiloxane (15 wt. toluene solution), a vinyl functional polyorganosiloxane, and an SiH functional polyorganosiloxane were mixed at the compounding ratios shown in Table 2.
  • a 1,3-divinyltetramethyl disiloxane platinum complex was mixed at an amount in which the platinum metal was 2 ppm with respect to the solid content in weight units so as to prepare a solution of a curable polymer composition.
  • the evaluation results for the curable polymer compositions and the cured products thereof are shown in Table 2.
  • the SiH/Vi ratio in Table 2 represents the number of mols of silicon-bonded hydrogen atoms in the SiH functional polyorganosiloxane per total of 1 mol of vinyl groups in the vinyl functional polyorganosiloxane in the curable polymer compositions.
  • a polyorganometallosiloxane (15 wt. toluene solution), a vinyl functional polyorganosiloxane, and an SiH functional polyorganosiloxane were mixed at the compounding ratios shown in Tables 3 to 5.
  • a 1,3-divinyltetramethyl disiloxane platinum complex was mixed at an amount in which the platinum metal was 2 ppm with respect to the solid content in weight units so as to prepare a solution of a curable polymer composition.
  • the evaluation results for the curable polymer compositions and the cured products thereof are shown in Table 3 to 5.
  • the SiH/Vi ratio in Tables 3 to 5 represents the number of mols of silicon-bonded hydrogen atoms in the SiH functional polyorganosiloxane per total of 1 mol of vinyl groups in the polyorganometallosiloxane and the vinyl functional polyorganosiloxane in the curable polymer compositions.
  • PPA polyphthalamide
  • the polyorganometallosiloxane of the present invention is cured by a hydrosilylation reaction to form a cured product with a high refractive index and excellent visible light transmittance, heat resistance, and moisture resistance and can therefore be used as an adhesive, a potting agent, a protective coating agent, or an underfill agent for electrical/electronic use.
  • the visible light transmittance is high, which makes the product suitable as a sealing agent or a covering agent for an LED element or as a lens forming material.

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Abstract

A polyorganometallosiloxane comprising a metalloxy unit represented by general formula (1): M1Ox/2 (where M1 is an atom of group 4 A or group 5 A of the periodic table, and "x" is the valency of M1), a metalloxy unit represented by general formula (2): M2Oy/2 (where M2 is an atom of group 2 A or group 2B of the periodic table, and "y" is the valency of M2), and an organosiloxane unit represented by general formula (3): R1aSiO(4-a)/2 (where R1 is an alkyl group, an alkenyl group, a phenyl group, an aralkyl group, or a hydrogen atom, and "a" is a number satisfying: 0 < a < 3), and a curable polymer composition which contains this polyorganometallosiloxane and is cured by a hydrosilylation reaction to form a cured product with a high refractive index, high visible light transmittance, and excellent heat resistance and moisture resistance.

Description

POLYORGANOMETALLOSILOXANE, CURABLE POLYMER COMPOSITION, CURED PRODUCT THEREOF, AND OPTICAL
SEMICONDUCTOR DEVICE
FIELD OF THE INVENTION
[0001] The present invention relates to a polyorganometallosiloxane, a curable polymer composition containing the polyorganometallosiloxane, a cured product of the composition, and an optical semiconductor device using the composition.
DESCRIPTION OF THE RELATED ART
[0002] There is a demand for a material with a high refractive index and excellent long-term stability of characteristics such as visible light transmittance, heat resistance, and moisture resistance as a sealing agent for an optical semiconductor device such as an LED. As such a sealing agent, a resin composition comprising a polyheterosiloxane resin primarily including a unit represented by RmMO(X.m)/2 (where M is an atom selected from a group of atoms in the fourth to sixth periods belonging to groups 2A to 5A of the periodic table, R represents a group selected from hydrogen atoms, hydroxyl groups, amino groups or substituted or unsubstituted aliphatic groups, alicyclic groups, aryl groups, heterocyclic groups, or groups in which these groups are bonded to M atoms through oxygen, x represents the valency of M atoms, and "m" represents an integer of 0 or from 1 to x-1) (see Patent Document 1 below) and a curable composition comprising a silylated polymetallosiloxane having at least 2 alkenyl groups in a molecule, a compound having at least 2 silicon-bonded hydrogen atoms in a molecule and having no siloxane bonds, and a curing catalyst (see Patent Document 2 below) have been proposed.
[0003] However, these sealing agents have a problem in that the heat resistance and moisture resistance of the resulting cured product are insufficient, which causes the cured product to be discolored to causes discoloration or a decrease in mechanical strength under conditions with high temperature or high humidity. There is also a problem in that when an attempt is made to increase the refractive index of the sealing agent, the cured product becomes hard and brittle, which leads to insufficient stability and mechanical characteristics.
[0004] Patent Document 1 : Japanese Unexamined Patent Application Publication No. 2000-235103 A. [0005] Patent Document 2: Japanese Unexamined Patent Application Publication No. 2009-173910A.
SUMMARY OF THE INVENTION AND ADVANTAGES
Technical Problem to be Solved by the Invention
[0006] An object of the present invention is to provide a polyorganometallosiloxane with a high refractive index and excellent heat resistance, moisture resistance, and compatibility with organic polymers. Another object of the present invention is to provide a curable polymer composition which is cured by a hydrosilylation reaction to form a cured product with a high refractive index and excellent visible light transmittance, heat resistance, and moisture resistance. Another object of the present invention is to provide a cured product with a high refractive index and excellent visible light transmittance, heat resistance, and moisture resistance. Yet another object of the present invention is to provide a highly reliable optical semiconductor device using this curable polymer composition.
Disclosure of the Invention
[0007] The polyorganometallosiloxane of the present invention comprises a metalloxy unit represented by general formula (1):
Figure imgf000003_0001
(where M1 is an atom of group 4A or group 5 A of the periodic table, and "x" is the valency of M1);
a metalloxy unit represented by general formula (2):
M2Oy/2
(where M2 is an atom of group 2A or group 2B of the periodic table, and "y" is the valency of M2); and
an organosiloxane unit represented by general formula (3):
R1 aSiO(4- a)/2
(where R1 is an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a hydrogen atom, and "a" is a number satisfying: 0 < a < 3).
[0008] In addition, the curable polymer composition of the present invention contains the polyorganometallosiloxane described above and is cured by a hydrosilylation reaction. [0009] Moreover, the cured product of the present invention is formed by curing the curable polymer composition.
[0010] Further, the optical semiconductor device of the present invention is formed by covering or sealing an optical semiconductor element with the cured product of the curable polymer composition described above.
Effects of Invention
[0011] The polyorganometallosiloxane of the present invention has a high refractive index and excellent heat resistance, moisture resistance, and compatibility with organic polymers. In addition, the curable polymer composition of the present invention is cured by a hydrosilylation reaction to form a cured product with a high refractive index and excellent visible light transmittance, heat resistance, and moisture resistance. Moreover, the cured product of the present invention has a high refractive index and excellent visible light transmittance, heat resistance, and moisture resistance. Furthermore, the optical semiconductor device of the present invention exhibits excellent reliability.
BRIEF DESCRIPTION OF THE DRAWING
[0012] Figure 1 is a cross-sectional drawing of an LED that is an example of the optical semiconductor device of the present invention.
DESCRIPTION OF EMBODIMENTS
[0013] First, the polyorganometallosiloxane of the present invention will be described in detail.
[0014] The polyorganometallosiloxane of the present invention comprises a metalloxy unit represented by general formula (1): M1Ox/2, a metalloxy unit represented by general formula (2): M2Oy/2, and an organosiloxane unit represented by general formula (3): R1 aSiO(4_a)/2.
[0015] The metalloxy unit represented by general formula (1) is a unit which increases the refractive index of the polyorganometallosiloxane of the present invention. In general formula (1), M1 is an atom of group 4 A or group 5 A of the periodic table. Specifically, M1 is an atom selected from atoms of group 4 A such as Ti, Zr, and Hf or atoms of group 5A such as V, Nb, and Ta and is preferably Ti or Zr. In general formula (1), "x" represents the valency of M1, which differs depending on the type of the atom and is an integer of from 1 to 7. For example, the valency of Ti is 3 or 4, and the valency of Zr or Hf is 4.
[0016] The metalloxy unit represented by general formula (2) is a unit which improves the heat resistance and moisture resistance of the polyorganometallosiloxane of the present invention. In general formula (2), M2 is an atom of group 2A or group 2B of the periodic table. Specifically, M2 is an atom selected from atoms of group 2A such as Ca, Sr, and Ba or atoms of group 2B such as Zn, Cd, and Hg. In order to ensure excellent heat resistance, M2 is preferably Zn, Ca, or Ba and even more preferably Zn. In general formula (2), "y" represents the valency of M2, which differs depending on the type of the atom and is an integer of from 1 to 7. For example, the valency of Zn, Ca, and Ba is 2.
[0017] The organosiloxane unit represented by general formula (3) is a unit which improves the heat resistance, moisture resistance, and compatibility with organic polymers of the polyorganometallosiloxane of the present invention. In general formula (3), R1 is an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a hydrogen atom. Examples of the alkyl group of R1 include methyl groups, ethyl groups, propyl groups, and butyl groups. Of these, methyl groups are preferable. Examples of the alkenyl group of R1 include vinyl groups, allyl groups, and butenyl groups. Of these, vinyl groups are preferable. Examples of the aryl group of R1 include phenyl groups, naphthyl groups, anthracenyl groups, phenanthryl groups, pyrenyl groups, and aryl groups in which the hydrogen atoms of these aryl groups are substituted with alkyl groups such as methyl groups or ethyl groups; alkoxy groups such as methoxy groups or ethoxy groups; or halogen atoms such as chlorine atoms or bromine atoms. Of these, phenyl groups and naphthyl groups are preferable. Examples of the aralkyl group of R1 include naphthyl ethyl groups, naphthyl propyl groups, anthracenyl ethyl groups, phenanthryl ethyl groups, pyrenyl ethyl groups, and aralkyl groups in which the hydrogen atoms of these aralkyl groups are substituted with alkyl groups such as methyl groups or ethyl groups; alkoxy groups such as methoxy groups or ethoxy groups; or halogen atoms such as chlorine atoms or bromine atoms. Since the polyorganometallosiloxane of the present invention can be made hydrosilylation-reactive, it is preferable for at least one R1 to be an alkenyl group or a hydrogen atom in a molecule. [0018] In general formula (3), "a" is a number satisfying: 0 < a < 3 and is preferably a number satisfying: 1 < a < 3 so that the refractive index of the polyorganometallosiloxane is large and so that the compatibility with organic polymers improves.
[0019] In the polyorganometallosiloxane of the present invention, the respective contents of the metalloxy unit represented by general formula (1), the metalloxy unit represented by general formula (2), and the siloxane unit represented by general formula (3) are not particularly limited, but the ratio of the content of the metalloxy unit represented by general formula (1) to the content of the siloxane unit represented by general formula (3) is preferably within the range of from 0.01: 1 to 99:1 and even more preferably within the range of from 0.01 :1 to 19:1. In addition, the ratio of the content of the metalloxy unit represented by general formula (2) to the content of the siloxane unit represented by general formula (3) is preferably within the range of from 0.01:1 to 19:1 and even more preferably within the range of from 0.01 :1 to 9:1. This is because when the content of the metalloxy unit represented by general formula (1) is less than or equal to the lower limit of the range described above, the refractive index of the polyorganometallosiloxane decreases, and when the content is greater than or equal to the upper limit of the range described above, the compatibility of the polyorganometallosiloxane with organic polymers decreases. In addition, when the content of the metalloxy unit represented by general formula (2) is less than or equal to the lower limit of the range described above, the heat resistance and moisture resistance of the polyorganometallosiloxane decrease, and when the content is greater than or equal to the upper limit of the range described above, the refractive index of the polyorganometallosiloxane decreases and the compatibility with organic polymers decreases.
[0020] The method of producing such a polyorganometallosiloxane of the present invention is not limited, but an example is a method of hydrolyzing and performing a condensation reaction on a metal compound represented by general formula (4):
M1 b(X)c
(where M1 is an atom of group 4 A or group 5 A of the periodic table, X is a hydroxyl group or a hydrolysable group, and "b" and "c" are numbers satisfying: (valency of M1) x b = (valency of X) x c);
a metal compound represented by general formula (5): M2 d(Y)e
(where M2 is an atom of group 2A or group 2B of the periodic table, Y is a hydrolysable group, and "d" and "e" are numbers satisfying: (valency of M2) x d = (valency of Y) x e); and
an organosilane compound represented by general formula (6):
R1 aSiZ(4_a)
(where R1 is an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a hydrogen atom, Z is a hydroxyl group or a hydrolysable group, and "a" is a number satisfying: 0 < a < 3)
together with a solvent such as water or alcohol.
[0021] In general formula (4), M1 is an atom of group 4A or group 5 A of the periodic table, examples of which are the same atoms as those described above. In general formula (4), X is a hydroxyl group or a hydrolysable group. Examples of the hydrolysable group of X include alkoxy groups such as methoxy groups and ethoxy groups; enoxy groups such as isopropenoxy groups; acyloxy groups such as acetoxy groups; halogen groups such as chlorine and bromine; sulfuric acid group; (organic) sulfonic acid groups such as methane sulfonic acid groups and tridecyl benzyl sulfonic acid groups; phosphoric acid groups, (organic) phosphonic acid groups, and nitric acid groups. In general formula (4), "b" and "c" are numbers satisfying:
(valency of M1) x b = (valency of X) x c.
[0022] Examples of such a metal compound represented by general formula (4) include, but are not limited to, zirconium hydroxide, hafnium hydroxide, tantalum hydroxide, titanium alkoxide, zirconium alkoxide, hafnium alkoxide, vanadium alkoxide, niobium alkoxide, tantalum alkoxide, titanium acetate, zirconium acetate, hafnium acetate, vanadium acetate, niobium acetate, tantalum acetate, zirconium methacrylate, titanium chloride, zirconium chloride, hafnium chloride, vanadium chloride, niobium chloride, tantalum chloride, titanium sulfate, zirconium sulfate, vanadium sulfate, zirconium nitrate, hafnium nitrate, tantalum nitrate, titanium methane sulfonate, tridecyl benzyl titanium, titanium phosphate, and titanium phosphonate.
[0023] In general formula (5), M2 is an atom of group 2 A or group 2B of the periodic table, examples of which are the same atoms as those described above. In general formula (5), Y is a hydrolysable group, examples of which are the same hydrolysable groups as those of X described above. In general formula (5), "d" and "e" are numbers satisfying:
(valency of M2) x d = (valency of Y) x e.
[0024] Examples of such a metal compound represented by general formula (5) include, but are not limited to, calcium hydroxide, strontium hydroxide, barium hydroxide, zinc hydroxide, cadmium hydroxide, calcium acetate, strontium acetate, barium acetate, zinc acetate, cadmium acetate, mercury acetate, calcium acetylacetonate, strontium acetylacetonate, barium acetylacetonate, calcium chloride, strontium chloride, barium chloride, zinc chloride, cadmium chloride, mercury chloride, calcium nitrate, strontium nitrate, barium nitrate, zinc nitrate, cadmium nitrate, and mercury nitrate.
[0025] In general formula (6), R1 is an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a hydrogen atom, examples of which are the same groups as those described above. In general formula (6), Z is a hydroxyl group or a hydrolysable group, examples of which are the same hydrolysable groups as those of X described above. In general formula (6), "a" is a number within the range of 0 < a < 3.
[0026] Examples of such an organosilane compound represented by general formula (6) include, but are not limited to, trimethylmethoxysilane, trimethylethoxysilane, vinyl dimethylmethoxysilane, vinyl dimethylethoxysilane, diphenyl methylmethoxysilane, diphenyl methylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl vinyl dimethoxysilane, methyl vinyl diethoxysilane, methyl phenyl dimethoxysilane, methyl phenyl diethoxysilane, methyl chloropropyl dimethoxysilane, methyl trimethoxysilane, ethyl trimethoxysilane, vinyl trimethoxysilane, phenyl trimethoxysilane, chloropropyl trimethoxysilane, 1-naphthyl trimethoxysilane, vinyl dimethylsilanol, and diphenyl methylsilanol.
[0027] In the production method described above, the added amounts of the metal compound represented by general formula (4), the metal compound represented by general formula (5), and the organosilane compound represented by general formula (6) are not limited, but are preferably amounts in which the contents of the metalloxy unit represented by general formula (1), the metalloxy unit represented by general formula (2), and the siloxane unit represented by general formula (3) in the resulting polyorganometallosiloxane are within the ranges described above. [0028] In addition, in the production method described above, hydrolysis progresses either at room temperature or under heat, but it is preferable from the perspective of the reaction rate to add an acid or an alkali as a catalyst. Examples of usable acids include hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, and phosphoric acid. In addition, examples of usable alkalis include organic base compounds such as triethylamine, diethylamine, monoethanolamine, diethanolamine, triethanolamine, ammonia water, tetramethylammonium hydroxide, alkoxysilanes having an amino group, and aminopropyl trimethoxysilane.
[0029] The curable polymer composition of the present invention will be explained next in detail.
[0030] The curable polymer composition of the present invention contains the polyorganometallosiloxane described above and is cured by a hydrosilylation reaction. An example of such a curable polymer composition is one comprising:
(A) an organopolysiloxane having at least 2 alkenyl groups in a molecule;
(B) an organopolysiloxane having at least 2 silicon-bonded hydrogen atoms in a molecule;
(C) a hydrosilylation-reaction catalyst; and
(D) a polyorganometallosiloxane comprising a metalloxy unit represented by general formula (1):
(where M1 is an atom of group 4A or group 5 A of the periodic table, and "x" is the valency of M1);
a metalloxy unit represented by general formula (2):
M2Oy/2
(where M2 is an atom of group 2A or group 2B of the periodic table, and "y" is the valency of M2); and
an organosiloxane unit represented by general formula (3):
R1 aSiO(4- a)/2
(where R1 is an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a hydrogen atom, and "a" is a number satisfying: 0 < a < 3).
[0031] Component (A) is an organopolysiloxane having at least 2 alkenyl groups in a molecule. Examples of the alkenyl groups in component (A) include vinyl groups, allyl groups, butenyl groups, pentenyl groups, hexenyl groups, and heptenyl groups. Of these, vinyl groups are preferable. Examples of groups bonding to silicon atoms other than alkenyl groups in component (A) include alkyl groups, aryl groups, and aralkyl groups. Examples of alkyl groups include methyl groups, ethyl groups, propyl groups, and butyl groups. Of these, methyl groups are preferable. Examples of aryl groups include phenyl groups, naphthyl groups, anthracenyl groups, phenanthryl groups, pyrenyl groups, and aryl groups in which the hydrogen atoms of these aryl groups are substituted with alkyl groups such as methyl groups or ethyl groups; alkoxy groups such as methoxy groups or ethoxy groups; or halogen atoms such as chlorine atoms or bromine atoms. Of these, phenyl groups and naphthyl groups are preferable. Examples of aralkyl groups include naphthyl ethyl groups, naphthyl propyl groups, anthracenyl ethyl groups, phenanthryl ethyl groups, pyrenyl ethyl groups, and aralkyl groups in which the hydrogen atoms of these aralkyl groups are substituted with alkyl groups such as methyl groups or ethyl groups; alkoxy groups such as methoxy groups or ethoxy groups; or halogen atoms such as chlorine atoms or bromine atoms. From the perspective of the objective of increasing the refractive index of component (A), component (A) preferably has aryl groups or aralkyl groups and even more preferably has phenyl groups or naphthyl groups as groups bonding to silicon atoms other than alkenyl groups in component (A).
[0032] Examples of such component (A) include organopolysiloxanes including a siloxane unit represented by the general formula: R'3SiOi 2 and a siloxane unit represented by the general formula: R'R"Si022; organopolysiloxanes including a siloxane unit represented by the general formula: R'3SiOi 2 and siloxane units represented by the general formula: R'R"Si02/2 and the general formula: R'2Si022; organopolysiloxanes including a siloxane unit represented by the general formula: R'2R"SiOi 2 and a siloxane unit represented by the general formula: R'2Si022; organopolysiloxanes including a siloxane unit represented by the general formula: R'2R"SiOi 2, a siloxane unit represented by the general formula: R'2Si022, and a siloxane unit represented by the general formula: R'R"Si022; organopolysiloxanes including a siloxane unit represented by the general formula: R'2R"SiOi 2 and a siloxane unit represented by the general formula: R'Si03 2; organopolysiloxanes including a siloxane unit represented by the general formula: R'3SiOi 2 and a siloxane unit represented by the general formula: R"Si03 2; organopolysiloxanes including a siloxane unit represented by the general formula: R'3SiOi 2, a siloxane unit represented by the general formula: R"SiC>3/2, and a siloxane unit represented by the general formula: R'SiC^; organopolysiloxanes including a siloxane unit represented by the general formula: R'2R"SiOi 2, a siloxane unit represented by the general formula: R'2SiC>2/2, and a siloxane unit represented by the general formula: R'SiC>3/2; organopolysiloxanes including a siloxane unit represented by the general formula: R'2R"SiOi 2, a siloxane unit represented by the general formula: R'2SiC>2/2, and a siloxane unit represented by the general formula: R'SiC^; organopolysiloxanes including a siloxane unit represented by the general formula: R'R"SiC>2/2 and a siloxane unit represented by the formula: R'SiC>3/2; organopolysiloxanes including a siloxane unit represented by the general formula: R'2R"SiOi/2 and a siloxane unit represented by the formula: S1O4/2; organopolysiloxanes including a siloxane unit represented by the general formula: R'3SiOi 2, a siloxane unit represented by the general formula: R'2R"SiOi 2, and a siloxane unit represented by the formula: S1O4/2; and mixtures of two or more types thereof. In the formulae above, R' is an alkyl group, an aryl group, or an aralkyl group, examples of which are the same groups as those described above. In the formulae above, R" is an alkenyl group, examples of which are the same groups as those described above.
[0033] Component (B) is an organopolysiloxane having at least two silicon-bonded hydrogen atoms in a molecule. Examples of groups bonding to silicon atoms other than hydrogen atoms in component (B) include alkyl groups, aryl groups, and aralkyl groups, examples of which are the same groups as those described above. From the perspective of the objective of increasing the refractive index of component (B), component (B) preferably has aryl groups or aralkyl groups and even more preferably has phenyl groups or naphthyl groups as groups bonding to silicon atoms other than hydrogen atoms in component (B).
[0034] Examples of such a component (B) include organopolysiloxanes including a siloxane unit represented by the general formula: R'3SiOi 2 and a siloxane unit represented by the general formula: R'HSiC>2/2; organopolysiloxanes including a siloxane unit represented by the general formula: R'3SiOi 2 and siloxane units represented by the general formula: R'HSiC>2/2 and the general formula: R'2SiC>2/2; organopolysiloxanes including a siloxane unit represented by the general formula: R'2HSiOi 2 and a siloxane unit represented by the general formula: R'2SiC>2/2; organopolysiloxanes including a siloxane unit represented by the general formula: R'2HSiOi 2, a siloxane unit represented by the general formula: R'2SiC>2/2, and a siloxane unit represented by the general formula: R'HSiC>2/2; organopolysiloxanes including a siloxane unit represented by the general formula: R'2HSiOi 2 and a siloxane unit represented by the general formula: R'SiC>3/2; organopolysiloxanes including a siloxane unit represented by the general formula: R'3SiOi 2 and a siloxane unit represented by the general formula: HS1O3/2; organopolysiloxanes including a siloxane unit represented by the general formula: R'3SiOi/2, a siloxane unit represented by the general formula: HS1O3/2, and a siloxane unit represented by the general formula: R'SiC>3/2; organopolysiloxanes including a siloxane unit represented by the general formula: R'2HSiOi/2, a siloxane unit represented by the general formula: R'2SiC>2/2, and a siloxane unit represented by the general formula: R'SiC>3/2; organopolysiloxanes including a siloxane unit represented by the general formula: R'HSiC>2/2 and a siloxane unit represented by the formula: R'SiC>3/2; organopolysiloxanes including a siloxane unit represented by the general formula: R'2HSiOi 2 and a siloxane unit represented by the formula: S1O4/2; organopolysiloxanes including a siloxane unit represented by the general formula: R'3SiOi 2, a siloxane unit represented by the general formula: R'2HSiOi 2, and a siloxane unit represented by the formula: S1O4/2; and mixtures of two or more types thereof. In the formulae above, R' is an alkyl group, an aryl group, or an aralkyl group, examples of which are the same groups as those described above.
[0035] Component (C) is a hydrosilylation-reaction catalyst, specific examples of which include platinum-based catalysts, rhodium-based catalysts, and palladium- based catalysts. Component (C) is preferably a platinum-based catalyst so that the curing of the present composition can be dramatically accelerated. Examples of the platinum-based catalyst include a platinum fine powder, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex and a platinum-carbonyl complex, with a platinum- alkenylsiloxane complex being preferred.
[0036] Component (D) is a polyorganometallosiloxane comprising a metalloxy unit represented by general formula (1): M1Oxa, a metalloxy unit represented by general formula (2): M2Oy/2, and an organosiloxane unit represented by general formula (3): R1 aSiO(4_a) 2. Component (D) is as described above. When component (D) is a polyorganometallosiloxane in which at least one R1 is an alkenyl group in a molecule, component (D) can undergo a hydrosilylation reaction with the silicon-bonded hydrogen atoms in component (B). When component (D) is a polyorganometallosiloxane in which at least one R1 is a hydrogen atom in a molecule, component (D) can undergo a hydrosilylation reaction with the alkenyl groups in component (A).
[0037] The content of component (B) is not particularly limited, but when component (D) does not contain alkenyl groups and silicon-bonded hydrogen atoms, the content is preferably an amount with which the silicon-bonded hydrogen atoms in component (B) are within the range of from 0.2 to 5 mol and even more preferably within the range of from 0.5 to 2 mol with respect to a total of 1 mol of the alkenyl groups in component (A). When component (D) has alkenyl groups, the content is preferably an amount with which the silicon-bonded hydrogen atoms in component (B) are within the range of from 0.2 to 5 mol and even more preferably within the range of from 0.5 to 2 mol with respect to a total of 1 mol of the alkenyl groups in component (A) and component (D). Further, when component (D) has silicon-bonded hydrogen atoms, the content is preferably an amount with which the total silicon-bonded hydrogen atoms in component (B) and component (D) is within the range of from 0.2 to 5 mol and even more preferably within the range of from 0.5 to 2 mol with respect to a total of 1 mol of the alkenyl groups in component (A). This is because when the content of component (B) is greater than or equal to the lower limit of the range described above, the curing of the resulting composition becomes sufficient, and when the content is less than or equal to the upper limit of the range described above, the physical characteristics of the resulting cured product improve.
[0038] The content of component (C) is not particularly limited as long as the curing of the composition can be accelerated. Specifically, the content is preferably an amount with which the catalyst metal in component (C) is within the range of from 0.01 to 500 ppm, even more preferably within the range of from 0.01 to 100 ppm, and yet even more preferably within the range of from 0.01 to 50 ppm in weight units with respect to the composition.
[0039] The content of component (D) is not particularly limited, but is preferably from 1 to 99 wt. and even more preferably from 10 to 90 wt. of the total amount of component (A), component (B), and component (D). This is because when the content of component (D) is less than the lower limit, the refractive index is insufficient, and when the content is greater than the upper limit, the resulting cured product becomes brittle.
[0040] An example of another curable polymer composition of the present invention is a curable polymer composition comprising:
(E) a polyorganometallosiloxane comprising a metalloxy unit represented by general formula (1):
(where M1 is an atom of group 4A or group 5 A of the periodic table, and "x" is the valency of M1);
a metalloxy unit represented by general formula (2):
M2Oy/2
(where M2 is an atom of group 2A or group 2B of the periodic table, and "y" is the valency of M2); and
an organosiloxane unit represented by general formula (3):
R1 aSiO(4- a)/2
(where R1 is an alkyl group, an alkenyl group, an aromatic group-containing group, or a hydrogen atom, and "a" is a number satisfying: 0 < a < 3);
wherein at least two R1 are alkenyl groups in a molecule;
(B) an organopolysiloxane having at least two silicon-bonded hydrogen groups in a molecule; and
(C) a hydrosilylation-reaction catalyst.
[0041] Component (E) is a polyorganometallosiloxane comprising a metalloxy unit represented by general formula (1): M1Oxa, a metalloxy unit represented by general formula (2): M2Oy/2, and an organosiloxane unit represented by general formula (3): R1 aSiO(4_a)/2, wherein at least two R1 are alkenyl groups in a molecule. Component (E) is as described above. Since component (E) has at least two alkenyl groups in a molecule, component (E) can undergo a hydrosilylation reaction with the silicon- bonded hydrogen atoms in component (B).
[0042] Component (B) is an organopolysiloxane having at least two silicon-bonded hydrogen atoms in a molecule, examples of which are the same as those described above.
[0043] Component (C) is a hydrosilylation-reaction catalyst, examples of which are the same as those described above. [0044] The content of component (B) is not particularly limited, but is preferably an amount with which the silicon-bonded hydrogen atoms in the component are within the range of from 0.2 to 5 mol and even more preferably within the range of from 0.5 to 2 mol with respect to 1 mol of the alkenyl groups in component (E). This is because when the content of component (B) is greater than or equal to the lower limit of the range described above, the curing of the resulting composition becomes sufficient, and when the content is less than or equal to the upper limit of the range described above, the physical characteristics of the resulting cured product improve.
[0045] The content of component (C) is not particularly limited as long as the curing of the composition can be accelerated. Specifically, the content is preferably an amount with which the catalyst metal in component (C) is within the range of from 0.01 to 500 ppm, even more preferably within the range of from 0.01 to 100 ppm, and yet even more preferably within the range of from 0.01 to 50 ppm in weight units with respect to the composition.
[0046] Such a curable polymer composition of the present invention may also contain (F) a phosphor as another optional component. Examples of this component (F) include yellow, red, green, and blue light-emitting phosphors which are widely used in light emitting diodes (LEDs) such as oxide phosphors, oxynitride phosphors, nitride phosphors, sulfide phosphors, oxysulfide phosphors, and mixtures of two or more types of these phosphors. Examples of oxide phosphors include yttrium, aluminum and garnet-based YAG green to yellow light-emitting phosphors containing cerium ions, terbium, aluminum, and garnet-based TAG yellow light-emitting phosphors containing cerium ions, and silicate green to yellow light-emitting phosphors containing cerium or europium ions. Examples of oxynitride phosphors include silicon, aluminum, oxygen, and nitrogen-based sialon red to green light- emitting phosphors containing europium ions. Examples of nitride phosphors include calcium, strontium, aluminum, silicon, and nitrogen-based CASN red light- emitting phosphors containing europium ions. Examples of sulfide phosphors include ZnS-based green coloring phosphors containing copper ions or aluminum ions. Examples of oxysulfide phosphors include Y2C>2S-based red light-emitting phosphors containing europium ions. [0047] The content of component (F) is not particularly limited, but is preferably within the range of from 0.1 to 70 wt.% and even more preferably within the range of from 1 to 20 wt.% in the composition.
[0048] The curable polymer composition of the present invention may also contain an adhesion-imparting agent for improving the adhesion of the composition. An organic silicon compound having at least one alkoxy group bonding to silicon atoms in a molecule is preferable as this adhesion-imparting agent. Examples of this alkoxy group include methoxy groups, ethoxy groups, propoxy groups, butoxy groups, and methoxyethoxy groups. Of these, methoxy groups are particularly preferable. Examples of groups other than alkoxy groups bonding to silicon atoms in this organic silicon compound include substituted or unsubstituted monovalent hydrocarbon groups such as alkyl groups, alkenyl groups, aryl groups, aralkyl groups and halogenated alkyl groups; epoxy group-containing monovalent organic groups such as 3-glycidoxypropyl groups, 4-glycidoxybutyl groups, or similar glycidoxyalkyl groups; 2-(3,4-epoxycyclohexyl)ethyl groups, 3-(3,4-epoxycyclohexyl)propyl groups, or similar epoxycyclohexyl alkyl groups; 4-oxiranylbutyl groups, 8-oxiranyloctyl groups, or similar oxiranylalkyl groups; acrylic group-containing monovalent organic groups such as 3 -methacryloxypropyl groups; and hydrogen atoms. This organic silicon compound preferably has silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms. This organic silicon compound also preferably has at least one epoxy group-containing monovalent organic group in a molecule so that good adhesion can be imparted to various base materials. Examples of such an organic silicon compound include organosilane compounds, organosiloxane oligomers, and alkyl silicates. Examples of the molecular structure of this organosiloxane oligomer or alkyl silicate include a straight structure, a partially branched straight structure, a branched structure, a cyclic structure, and a reticulated structure. Of these, straight, branched, and reticulated structures are particularly preferable. Examples of such an organic silicon compound include silane compounds such as 3-glycidoxypropyl trimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, and 3- methacryloxypropyl trimethoxysilane; mixtures of a siloxane compound having at least one of each of a silicon-bonded alkenyl group or a silicon-bonded hydrogen atom and a silicon-bonded alkoxy group in a molecule, a silane compound or a siloxane compound having at least one silicon-bonded alkoxy group, and a siloxane compound having at least one of each of a silicon-bonded hydroxy group and a silicon-bonded alkenyl group in a molecule, methyl polysilicates, ethyl polysilicates, and epoxy-group containing ethyl polysilicates.
[0049] The content of this adhesion-imparting agent is not particularly limited, but is preferably within the range of from 0.01 to 10 parts by weight per total of 100 parts by weight of the composition.
[0050] A reaction inhibitor, for example, an alkyne alcohol such as 2-methyl-3-butyn- 2-ol, 3,5-dimethyl-l-hexyn-3-ol or 2-phenyl-3-butyn-2-ol; an ene-yne compound such as 3-methyl-3-penten-l-yne or 3,5-dimethyl-3-hexen-l-yne; or 1,3,5,7-tetramethyl- 1 ,3,5,7-tetravinylcyclotetrasiloxane, l,3,5,7-tetramethyl-l ,3,5,7- tetrahexenylcyclotetrasiloxane or a benzotriazole may be incorporated as an optional component in the curable polymer composition of the present invention.
[0051] A content of the reaction inhibitor is not limited, but is preferably from 0.0001 to 5 parts by weight per 100 parts by weight of the present composition.
[0052] An inorganic filler such as silica, glass, alumina or zinc oxide; an organic resin fine powder of a polymethacrylate resin and the like; a heat-resistant agent, a dye, a pigment, a flame retardant, a solvent and the like may be incorporated as optional components in the curable polymer composition of the present invention at levels that do not impair the objective of the present invention.
[0053] The curable polymer composition of the present invention is such that curing occurs either at room temperature or under heating, but it is preferable to heat the composition in order to achieve rapid curing. The heating temperature is preferably from 50 to 200°C.
[0054] Such a curable polymer composition of the present invention may be used as an adhesive, a potting agent, a protective agent, a coating agent, an underfill agent for electrical/electronic use, or a molding agent. In particular, the composition is particularly suitable as an adhesive, a potting agent, a protective agent, a coating agent, an underfill agent for a semiconductor element in optical applications, a molding agent for a lens, or the like due to the high optical transmittance of the composition.
[0055] The cured product of the present invention will be explained next in detail.
[0056] The cured product of the present invention is formed by curing the curable polymer composition. The shape of such a cured product of the present invention is not particularly limited, and the cured product can be handled in a state in which the cured product covers or seals an optical semiconductor element or the like. In addition, the cured product of the present invention can be handled as a stand-alone product, examples of which include a sheet-like product and a film-like product.
[0057] The optical semiconductor device of the present invention will now be explained in detail.
[0058] This device is characterized in that an optical semiconductor element is covered or sealed by a cured product of the curable polymer composition described above. An example of this optical semiconductor element is a light emitting diode (LED) chip. Examples of such an optical semiconductor device include a light emitting diode (LED), a photocoupler, and a CCD.
[0059] Figure 1 shows a cross-sectional drawing of a surface mounted type LED, which is one example of the optical semiconductor device of the present invention. In the LED illustrated in Figure 1 , an LED chip 1 is die-bonded to a lead frame 2, and the LED chip 1 and a lead frame 3 are wire -bonded by a bonding wire 4. This LED chip 1 is covered by a cured product 5 of the curable polymer composition described above.
[0060] An example of a method of producing the surface mounted type LED illustrated in Figure 1 is a method of die-bonding the LED chip 1 to the lead frame 2, wire-bonding the LED chip 1 and the lead frame 3 with a gold bonding wire 4, applying the curable polymer composition described above to the LED chip 1, and then curing the composition by heating at 50 to 200°C.
EXAMPLES
[0061] The polyorganometallosiloxane, the curable polymer composition, the cured product, and the optical semiconductor device of the present invention will be explained in further detail using practical examples. The characteristics of the polyorganometallosiloxane, the curable polymer composition, and the cured product were measured as follows. In the practical examples, Vi represents a vinyl group, Me represents a methyl group, Ph represents a phenyl group, and Naph represents a naphthyl group.
[0062] Refractive index of the polyorganometallosiloxane:
[0063] The polyorganometallosiloxane was dissolved with a polyphenylmethylsiloxane (viscosity at 25°C, refractive index: 1.545) so as to achieve a prescribed concentration (volume ), and the refractive index was calculated from the refractive index of the mixture.
[0064] Appearance of the cured product:
[0065] The transparency of the cured product was confirmed visually.
[0066] Refractive index of the cured product:
[0067] The refractive index of the cured product was measured using the prism coupler method. A 632.8 nm laser light source was used for the measurements.
[0068] Heat resistance of the cured product:
[0069] The appearance was confirmed after the cured product was left to stand for
100 hours in an oven at 150°C.
[0070] Moisture resistance of the cured product:
[0071] The appearance was confirmed after the cured product was left to stand for one week in a constant-temperature, high-humidity oven (85°C, relative humidity: 85%).
[0072] Reference Example 1
[0073] First, 10 g (40.3 mmol) of 1 -naphthyltrimethoxysilane, 2.7 g (26.4 mmol) of vinyldimethylsilanol, 5.8 g (27.1 mmol) of diphenylmethylsilanol, 20 g of toluene, and 0.04 g (0.71 mmol) of potassium hydroxide were loaded into a reaction vessel and heat-refluxed for one hour. Next, the mixture was cooled to room temperature, and a mixture of 1.2 g (66.6 mmol) of water and 10 g of methanol was added. The mixture was distilled under normal pressure while heating until the reaction temperature reached 120°C, and the mixture was reacted for 2 hours at this temperature. The mixture was then cooled to room temperature, and a neutralization reaction was performed by adding 0.08 g (1.3 mmol) of acetic acid. After the salt that was produced was filtered out, the low-boiling matter was removed from the resulting clear solution under reduced pressure while heating, and 14.3 g of a colorless, clear, viscous liquid (yield: 94%) was obtained.
[0074] As a result of NMR analysis, it was ascertained that this liquid is an organopolysiloxane represented by the average unit formula:
( ViMe2SiO i/2)o.28(Ph2MeSiO i 2)o.28(NaphSi03/2)o.44
[0075] This organopolysiloxane had a weight average molecular weight (Mw) of 1,000, a dispersity (Mw/Mn) of 1.05, and a refractive index of 1.603.
[0076] Reference Example 2 [0077] First, 10 g (40.3 mmol) of 1 -naphthyltrimethoxysilane, 4.2 g (13.5 mmol) of l ,3-divinyl-l ,3-diphenyldimethyldisiloxane, and 20 g of toluene were loaded into a reaction vessel and mixed in advance, 2.2 g (122.1 mmol) of water and 10 g of methanol were loaded. Next, 0.069 g (0.46 mmol) of trifluoromethane sulfonic acid was loaded while stirring and heat-refluxed for 2 hours. The mixture was then distilled under normal pressure while heating until the temperature reached 85°C, and the mixture was reacted for 1 hour at this temperature. Next, 0.06 g (1.1 mmol) of potassium hydroxide was loaded. The mixture was distilled under normal pressure while heating until the reaction temperature reached 120°C, and the mixture was reacted for 1 hour at this temperature. The mixture was cooled to room temperature, and a neutralization reaction was performed by adding 0.09 g (1.5 mmol) of acetic acid. After the salt that was produced was filtered out, the low-boiling matter was removed from the resulting clear solution under reduced pressure while heating, and 10.3 g of a colorless, clear, viscous liquid with a viscosity exceeding 10,000 Pa s (yield: 90.4%) was obtained.
[0078] As a result of NMR analysis, it was ascertained that this viscous liquid is an organopolysiloxane represented by the average unit formula:
(MeViPhSiO i/2)o.4o(NaphSi03/2) 0.60
[0079] This organopolysiloxane had a weight average molecular weight (Mw) of 1,000, a dispersity (Mw/Mn) of 1.08, and a refractive index of 1.622.
[0080] Practical Example 1
[0081] First, 49.3 g (0.173 mol) of tetraisopropoxytitanium, 15 g of ethanol, 45 g of toluene, and 10.01 g (0.046 mol) of zinc acetate dihydrate were mixed, and 24.1 g (0.099 mol) of diphenyldimethoxysilane was further added. Next, a mixture of 11.5 g of 0.1 N dilute hydrochloric acid and 64.0 g of ethanol was slowly dripped into the mixture, and after dripping was complete, the mixture was stirred for 1 hour at room temperature. Next, the mixture was heat-refluxed for 1 hour. The solvent was distilled under reduced pressure while heating, and 33.5 g of a colorless solid with a refractive index of 1.670 (yield: 92%) was obtained.
[0082] The reaction rate of the alkoxysilyl groups of this solid was measured by NMR to be 99.4 mol%, and it was ascertained that the solid was a polyorganometallosiloxane (1) with a metalloxy unit (M^metalloxy unit (M2):organosiloxane unit molar ratio of TiC>4/2:ZnC>2/2:Ph2SiC>2/2 = 0.55:0.15:0.30 (= 1.83:0.50: 1).
[0083] The resulting polyorganometallosiloxane (1) was heated for 1 hour in an oven at 220°C, but only slight yellow discoloration was observed.
[0084] Practical Example 2
[0085] First, 81.9 g (0.175 mol) of a 70 wt.% n-propanol solution of tetrapropoxyzirconium, 30 g of ethanol, 90 g of toluene, and 10.1 g (0.046 mol) of zinc acetate dihydrate were mixed, and 24.1 g (0.099 mol) of diphenyldimethoxysilane was further added. Next, a mixture of 9.1 g of 0.1 N dilute hydrochloric acid and 82.0 g of ethanol was slowly dripped into the solution. After dripping was complete, the mixture was stirred for 1 hour at room temperature. Next, the mixture was heat-refluxed for 1 hour. The solvent was distilled under reduced pressure while heating, and 441.9 g of a colorless solid with a refractive index of 1.647 (yield: 94.5%) was obtained.
[0086] The reaction rate of the alkoxysilyl groups of this solid was measured by NMR to be 99.1 mol%, and it was ascertained that the solid was a polyorganometallosiloxane (2) with a metalloxy unit (M^metalloxy unit (M2):organosiloxane unit weight molar ratio of ZrC>4/2:ZnC>2/2:Ph2SiC>2/2 = 0.55:0.15:0.30 (= 1.83:0.50: 1).
[0087] The resulting polyorganometallosiloxane (2) was heated for 1 hour in an oven at 220°C, but no discoloration whatsoever was observed.
[0088] Practical Example 3
[0089] First, 0.88 g (4.0 mmol) of zinc chloride dihydrate was loaded into a mixed solution of 20 g of toluene and 10 g of ethanol and stirred. When 2.87 g (10.1 mmol) of tetraisopropyltitanium was added to the solution and stirred, a colorless, clear solution was obtained. Next, a 2 g toluene solution of 0.76 g (3.53 mmol) of diphenylmethylsilanol was loaded and stirred for 30 minutes at room temperature. Next, a mixture of 0.39 g (21.6 mmol) of water and 2 g of ethanol was slowly dripped into the solution. After dripping was complete, the solution was gradually heated, and low-boiling matter was removed by distillation. When the temperature of the reaction solution reached 110°C, distillation was stopped and heat-aging was performed for 1 hour at 110°C. As a result, 14 g of a toluene solution of an organometallosiloxane (3) with a solid concentration of 13.3 wt.% was obtained. [0090] The molar ratio of the metalloxy unit (M1): metalloxy unit (M2):organosiloxane unit in this organometallosiloxane (3) was TiC>4/2:ZnC>2/2:Ph2MeSiC>i/2 = 0.57:0.23:0.20 (= 2.85: 1.15: 1).
[0091] Practical Example 4
[0092] First, 0.88 g (4.0 mmol) of zinc chloride dihydrate was loaded into a mixed solution of 20 g of toluene and 10 g of ethanol and stirred. When 2.87 g (10.0 mmol) of tetraisopropyltitanium was added to the solution and stirred, a colorless, clear solution was obtained. Next, 2 g of a toluene solution of 0.57 g (2.65 mmol) of diphenylmethylsilanol was loaded and stirred for 30 minutes at room temperature. Next, a mixture of 0.40 g (22.3 mmol) of water and 2 g of ethanol was slowly dripped into the solution. After dripping was complete, the solution was gradually heated, and low-boiling matter was removed by distillation. When the temperature of the reaction solution reached 110°C, distillation was stopped and heat-aging was performed for 1 hour at 110°C. As a result, 14.4 g of a toluene solution of a polyorganometallosiloxane (4) with a solid concentration of 11.7 wt. was obtained. The molar ratio of the metalloxy unit (M ^metalloxy unit (M2):organosiloxane unit in this polyorganometallosiloxane (4) was TiC>4/2:ZnC>2/2:Ph2MeSiC>i/2 = 0.61 :0.24:0.15 (= 4.07: 1.60: 1).
[0093] Comparative Example 1
[0094] A reaction was performed in the same manner as in Practical Example 1 with the exception that the zinc acetate of Practical Example 1 was not used. However, when the reaction mixture was heated after 0.1 N of dilute hydrochloric acid was added, the mixture lost fluidity, and gelling occurred.
[0095] Comparative Example 2
[0096] Without using the zinc acetate of Practical Example 1, a corresponding polyorganometallosiloxane (5) was prepared without any gelling by reducing the amount of 0.1 N dilute hydrochloric acid from 11.5 g to 8 g.
[0097] However, when this polyorganometallosiloxane (5) was heated for 1 hour in an oven at 220°C in the same manner as in Practical Example 1, the solution turned blackish brown.
[0098] Practical Examples 5 to 7
[0099] Vinyldimethylsilanol was added to a 50 wt.% toluene solution of the polyorganometallosiloxane (1) prepared in Practical Example 1 to form the respective loading compositions shown in Table 1, and the solutions were heated for 3 hours at 80°C.
[00100] Next, the solvents were distilled under reduced pressure while heating to prepare polyorganometallosiloxanes (6) to (8). The molar ratios of the metalloxy unit (M ^metalloxy unit (M2):organosiloxane unit in these polyorganometallosiloxanes are shown in Table 1.
[00101] Practical Example 8
[00102] Vinyldimethylsilanol was added to a 50 wt.% toluene solution of the polyorganometallosiloxane (2) prepared in Practical Example 2 to form the respective loading compositions shown in Table 1, and the solution was heated for 3 hours at 80°C.
[00103] Next, the solvent was distilled under reduced pressure while heating to prepare a polyorganometallosiloxane (9). The molar ratios of the metalloxy unit (M ^metalloxy unit (M2):organosiloxane unit in these polyorganometallosiloxanes are shown in Table 1.
Table 1
Figure imgf000024_0001
[00104] Practical Examples 9 to 12 and Comparative Example 3
[00105] A polyorganometallosiloxane (15 wt. toluene solution), a vinyl functional polyorganosiloxane, and an SiH functional polyorganosiloxane were mixed at the compounding ratios shown in Table 2. Next, a 1,3-divinyltetramethyl disiloxane platinum complex was mixed at an amount in which the platinum metal was 2 ppm with respect to the solid content in weight units so as to prepare a solution of a curable polymer composition.
[00106] This solution of a curable polymer composition was dripped onto a glass plate and left to stand all day and night at 40°C to evaporate the toluene, and a colorless, clear, solid film was obtained. Next, the film was heated for 1 hour at 150°C to obtain a colorless, clear cured product. It was confirmed that the products were indeed cured from the fact that the products did not dissolve when immersed in toluene.
[00107] The evaluation results for the curable polymer compositions and the cured products thereof are shown in Table 2. The SiH/Vi ratio in Table 2 represents the number of mols of silicon-bonded hydrogen atoms in the SiH functional polyorganosiloxane per total of 1 mol of vinyl groups in the vinyl functional polyorganosiloxane in the curable polymer compositions.
Table 2
Figure imgf000026_0001
Figure imgf000027_0001
[00108] Practical Examples 13 to 23
[00109] A polyorganometallosiloxane (15 wt. toluene solution), a vinyl functional polyorganosiloxane, and an SiH functional polyorganosiloxane were mixed at the compounding ratios shown in Tables 3 to 5. Next, a 1,3-divinyltetramethyl disiloxane platinum complex was mixed at an amount in which the platinum metal was 2 ppm with respect to the solid content in weight units so as to prepare a solution of a curable polymer composition.
[00110] This solution of a curable polymer composition was dripped onto a glass plate and left to stand all day and night at 40°C to evaporate the toluene, and a colorless, clear, solid film was obtained. Next, the film was heated for 1 hour at 150°C to obtain a colorless, clear cured product. It was confirmed that the products were indeed cured from the fact that the products did not dissolve when immersed in toluene.
[00111] The evaluation results for the curable polymer compositions and the cured products thereof are shown in Table 3 to 5. The SiH/Vi ratio in Tables 3 to 5 represents the number of mols of silicon-bonded hydrogen atoms in the SiH functional polyorganosiloxane per total of 1 mol of vinyl groups in the polyorganometallosiloxane and the vinyl functional polyorganosiloxane in the curable polymer compositions.
Table 3
Figure imgf000029_0001
Table 4
Figure imgf000030_0001
Table 5
Figure imgf000031_0001
[00112] Practical Example 24
[00113] Production of a surface mounted type light emitting diode (LED)
[00114] An MK04545C LED chip 2 measuring 1 mm x 1 mm on each side made by Bridgelux, Inc. was mounted on a TTI-5074 LED lead frame measuring 5 mm x 5 mm on each side made by I-Chiun Precision Industry Co., Ltd. enclosed peripherally by a polyphthalamide (PPA) resin case 1. Next, the LED chip 2 and an inner lead 3 were electrically connected by a gold bonding wire 4 with a thickness of 1.5 mil.
[00115] Next, 3 g of the curable polymer composition prepared in Practical Example 14 and 0.105 g of a terbium-aluminum-garnet-based fluorescent substance (product name: NTAG4851) made by the Intermatix Corporation were mixed to prepare a sealing agent. After this sealing agent was degassed, 14.3 mg of the sealing agent was injected into the polyphthalamide (PPA) resin case 1 using a dispenser and cured by heating for 1 hour at 150°C to form the surface mounted type light emitting diode (LED) illustrated in Figure 1.
INDUSTRIAL APPLICABILITY
[00116] The polyorganometallosiloxane of the present invention is cured by a hydrosilylation reaction to form a cured product with a high refractive index and excellent visible light transmittance, heat resistance, and moisture resistance and can therefore be used as an adhesive, a potting agent, a protective coating agent, or an underfill agent for electrical/electronic use. In particular, the visible light transmittance is high, which makes the product suitable as a sealing agent or a covering agent for an LED element or as a lens forming material.
[00117] Reference Numerals:
1 Polyphthalamide (PPA) resin case
2 LED chip
3 Inner lead
4 Bonding wire
5 Cured product of the curable polymer composition

Claims

1. A polyorganometallosiloxane comprising a metalloxy unit represented by general formula (1): wherein M1 is an atom of group 4 A or group 5 A of the periodic table, and "x" is a valency of M1;
a metalloxy unit represented by general formula (2):
M2Oy/2
wherein M2 is an atom of group 2A or group 2B of the periodic table, and "y" is a valency of M2; and
an organosiloxane unit represented by general formula (3):
R1 aSiO(4- a)/2
wherein R1 is an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a hydrogen atom, and "a" is a number satisfying: 0 < a < 3.
2. The polyorganometallosiloxane according to claim 1, wherein M1 is an atom selected from the group consisting of Ti and Zr, and M2 is an atom selected from the group consisting of Zn, Ca, and Ba.
3. The polyorganometallosiloxane according to any one of claims 1 and 2, wherein a ratio of a content of the metalloxy unit represented by general formula (1) to a content of the siloxane unit represented by general formula (3) is from 0.01 :1 to 99:1 and a ratio of a content of the metalloxy unit represented by general formula (2) to a content of the siloxane unit represented by general formula (3) is from 0.01 :1 to 19:1.
4. A curable polymer composition that is hydrosilylation reaction curable, the composition comprising the polyorganometallosiloxane described in any one of claims 1 to 3.
5. The curable polymer composition according to claim 4, comprising component (A), component (B), component (C), and component (D) below:
(A) an organopolysiloxane having at least 2 alkenyl groups in each molecule;
(B) an organopolysiloxane having at least 2 silicon-bonded hydrogen atoms in a molecule;
(C) a hydrosilylation-reaction catalyst; and
(D) the polyorganometallosiloxane described in any one of claims 1 to 3.
6. The curable polymer composition according to claim 4, comprising component (E), component (B), and component (C) below:
(E) the polyorganometallosiloxane described in any one of claims 1 to 3, wherein at least two R1 in a molecule are alkenyl groups;
(B) an organopolysiloxane having at least two silicon-bonded hydrogen groups in a molecule; and
(C) a hydrosilylation-reaction catalyst.
7. The curable polymer composition according to any one of claims 4 to 6, further comprising (F) a phoshor.
8. A cured product formed by curing the curable polymer composition described in any one of claims 4 to 7.
9. An optical semiconductor device formed by covering or sealing an optical semiconductor element with the cured product of the curable polymer composition described in any one of claims 4 to 7.
10. The curable polymer composition according to claim 7, wherein component (F) is present in an amount of from 0.1 to 70 wt.% based on the total weight of the curable polymer composition.
11. The curable polymer composition according to any one of claims 4-7 and 10 further comprising an adhesion-imparting agent.
12. The curable polymer composition according to claim 11, wherein the adhesion-imparting agent is present in an amount of from 0.01 to 10 parts by weight per total of 100 parts by weight of the curable polymer composition.
PCT/US2013/048471 2012-06-29 2013-06-28 Polyorganometallosiloxane, curable polymer compositions, cured product thereof, and optical semiconductor device WO2014004969A1 (en)

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JP2009173910A (en) 2007-12-27 2009-08-06 Nagase Chemtex Corp Curable composition
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