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WO2008065786A1 - Dispositif optique à semiconducteur et élément optique transparent - Google Patents

Dispositif optique à semiconducteur et élément optique transparent Download PDF

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Publication number
WO2008065786A1
WO2008065786A1 PCT/JP2007/066028 JP2007066028W WO2008065786A1 WO 2008065786 A1 WO2008065786 A1 WO 2008065786A1 JP 2007066028 W JP2007066028 W JP 2007066028W WO 2008065786 A1 WO2008065786 A1 WO 2008065786A1
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WO
WIPO (PCT)
Prior art keywords
group
formula
compound
cage
carbon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2007/066028
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English (en)
Japanese (ja)
Inventor
Ken-Ichi Shinotani
Takao Hayashi
Shunpei Fujii
Norihiro Takamura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Electric Works Co Ltd
Original Assignee
Panasonic Electric Works Co Ltd
Matsushita Electric Works Ltd
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Filing date
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Priority claimed from JP2006319018A external-priority patent/JP5204393B2/ja
Priority claimed from JP2006319019A external-priority patent/JP5204394B2/ja
Application filed by Panasonic Electric Works Co Ltd, Matsushita Electric Works Ltd filed Critical Panasonic Electric Works Co Ltd
Publication of WO2008065786A1 publication Critical patent/WO2008065786A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/30—Coatings
    • H10F77/306—Coatings for devices having potential barriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/50—Encapsulations or containers
    • 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
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/852—Encapsulations
    • H10H20/854—Encapsulations characterised by their material, e.g. epoxy or silicone resins

Definitions

  • the present invention relates to a semiconductor optical device using a silsesquioxane compound as a sealing material, and a transparent optical member using a silsesquioxane compound as a molding material.
  • semiconductor light emitting devices such as light emitting diodes, laser diodes, and semiconductor lasers have been used as light emission sources.
  • light-emitting diodes are widely used as long-life, compact light sources for sine light sources and display light sources.
  • Semiconductor light-emitting elements are also being developed as lighting fixtures incorporating white LED units, and are expected to become increasingly widespread in the future.
  • the white LED light source used in the white LED unit is a blue / near-ultraviolet LED, and development to achieve high output and high brightness is being promoted in order to satisfy the requirements of lighting equipment. It has been.
  • Patent Document 1 discloses a semiconductor device obtained by encapsulating a semiconductor light emitting element using metalloxane, which is a metal oxide obtained by a sol-gel method, as a material having excellent heat resistance and light resistance.
  • metalloxane which is a metal oxide obtained by the sol-gel method, has a problem in that it has a porous structure and therefore has a high water absorption rate and may absorb moisture and cause cracks during use.
  • a DVD device that records light by irradiating light onto a resin disk is used as information recording.
  • light in the blue region and near ultraviolet region is used.
  • a device that records and reads data by irradiating is being studied. When reading information recorded on a resin disc, the laser light in the blue / near ultraviolet region is irradiated onto the recording surface of the resin disc, and the light reflected on the recording surface is received by the semiconductor light receiving element.
  • Such semiconductor light receiving elements are generally sealed and protected with a sealing material, and are irradiated with a single laser beam with a higher output than those using conventional red laser light.
  • a sealing material When using this sealing material, there was a problem that the sealing material was likely to deteriorate.
  • Patent Document 1 Japanese Patent No. 3412152
  • the present invention has been made in view of the above points, and in a semiconductor optical device in which a semiconductor light emitting element or a semiconductor light receiving element is sealed with a sealing material, the sealing material is unlikely to deteriorate and has an excellent lifetime.
  • a transparent optical member used for a portion irradiated with light in a blue region (near ultraviolet region) a transparent optical member that is hardly deteriorated and has an excellent lifetime is provided. It is intended to provide.
  • the present inventors have developed a glass-like inorganic property when a desired force and a silsesquioxane compound are used as a sealant, and a blue region- It has resistance to near-ultraviolet light and can also be formed into a desired shape due to its organic properties, and its power and type silsesquioxane compounds are used as sealing agents for semiconductor optical devices.
  • the inventors have found that the present invention is optimal and have completed the present invention.
  • the semiconductor optical device includes a cage silsesquioxane compound represented by the following formula (1), or a force obtained by partial addition reaction of this compound, a cage silsesquioxane compound.
  • equation (1) is (AR R SiOSiO) (R R HSiOSiO) (BR R SiOSiO
  • A is a group having a carbon-carbon unsaturated bond
  • B is a substituted or unsubstituted saturated alkyl group or hydroxyl group
  • R 1, R 2, R 3, R 4, R 5 and R 5 are each independently a lower alkyl group.
  • the invention of claim 2 is characterized in that, in claim 1, in addition to the cage silsesquioxane compound of the above formula (1), a compound represented by the following formula (2) is contained.
  • X represents a divalent functional group or an oxygen atom
  • R 1, R 2, R 3, and R 5 are each independently carbon
  • ⁇ represents a divalent functional group
  • the invention of claim 4 is the invention according to any one of claims 1 to 3, wherein ⁇ in formula (1) is carbon.
  • the semiconductor optical device is a chain hydrocarbon group having a carbon unsaturated bond.
  • the transparent optical member according to claim 5 of the present invention is a cage-type silsesquioxane compound represented by the following formula (1) or a partial polymer of a cage-type silsesquioxane compound obtained by partial addition reaction of this compound. It is characterized by polymerizing the contained key compound.
  • A is a group having a carbon-carbon unsaturated bond
  • B is a substituted or unsubstituted saturated alkyl group or hydroxyl group
  • R 1, R 2, R 3, R 4, R 5 and R 5 are each independently a lower alkyl group.
  • the invention of claim 6 is characterized in that, in claim 5, it contains a compound represented by the following formula (2) in addition to the cage silsesquioxane compound of the above formula (1).
  • X represents a divalent functional group or an oxygen atom
  • R 1, R 2, R 3, and R 5 are each independently carbon
  • the invention of claim 7 is characterized in that, in claim 5, it contains a compound represented by the following formula (3) in addition to the cage silsesquioxane compound of the above formula (1).
  • ⁇ represents a divalent functional group
  • the invention of claim 8 is the transparent optical member according to any one of claims 5 to 7, wherein ⁇ in formula (1) is a chain hydrocarbon group having a carbon-carbon unsaturated bond. It is.
  • the cage silsesquioxane compound of the formula (1) has a polyhedral structure formed of silicon atoms and oxygen atoms, a hydrogen atom bonded to the silicon atom via a siloxane bond, and a siloxane bond. And a group having a carbon-carbon unsaturated bond bonded to each other, so that a hydrogen atom is subjected to a hydrosilylation reaction with a group having a carbon-carbon unsaturated bond of another cage-type silsesquioxane compound, and added.
  • It has a more uniform network structure with fewer unreacted residues, and can form a three-dimensional cross-linked structure of the silsesquioxane compound, which can suppress stress cracking of the cured product and is tough In addition, it can improve the irradiation resistance against short wavelength high energy light such as Blu-ray.
  • the cage silsesquioxane compound can be cross-linked and cured with the compound of formula (3), and it has a more uniform network structure with fewer unreacted residues and a cage silsess Can form a three-dimensional cross-linked structure of a xanthone compound, suppresses stress cracking of the cured product, enhances toughness, and improves irradiation resistance to short wavelength high energy light such as Blu-ray It is something that can be done.
  • a semiconductor optical device can be formed with a sealing material that does not easily deteriorate and has a long life, and a transparent optical member can be obtained with a material that does not easily deteriorate and has a long life.
  • the affinity of the surface with a heavy metal sol such as TiO or ZrO whose surface is covered with the hydroxyl group can be increased.
  • a cured product having an increased refractive index can be obtained.
  • FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of a semiconductor optical device of the present invention.
  • FIG. 2 is a view schematically showing a three-dimensional crosslinked structure polymer crosslinked by a cage silsesquioxane compound of the present invention.
  • FIG. 3 is a graph showing the wavelength dependence of the transmittance of the cage silsesquioxane compound according to Example 1.
  • FIG. 4 is a schematic cross-sectional view illustrating the force according to Example 1 and a method for sealing a cage silsesquioxane compound.
  • FIG. 5 is a graph showing the luminous flux maintenance factor of the cage silsesquioxane compound according to Example 1.
  • FIG. 7 Color-printed images of senalmon observation in the Blu-ray irradiation test.
  • A is for Example 4 and
  • B is for Reference Example 2.
  • FIG. 8 Far-field images are color-printed in the Blu-ray irradiation test.
  • (A) is for Example 5 and (b) is for Example 1.
  • FIG. 9 Color-printed images of senalmon observation in the Blu-ray irradiation test.
  • FIG. 1 shows an example of a semiconductor optical device.
  • a semiconductor light emitting element 2 is mounted on the surface of a substrate 1, and the entire semiconductor light emitting element 2 and a part of the surface of the substrate 1 are sealed with a sealing material 3. It is.
  • a phosphor layer 4 is formed on the surface of the sealing material 3.
  • An electronic circuit 5 is formed on the substrate 1, and in the embodiment shown in FIG. 1, the electrical circuit 5 is electrically connected to the semiconductor light emitting element 2 by a bonding wire 6.
  • the semiconductor light-emitting element 2 when a device that outputs light having a wavelength in the blue region or near-ultraviolet region of 450 nm or less, which can use the known semiconductor light-emitting device 2, is obtained. It is preferable because it can increase the illuminance of the light device and enhance the color rendering.
  • a semiconductor substrate such as GaAlN, ZnS, ZnSe, SiC, GaP, GaAlAs, AlInGaP, InGaN, GaN, AlInGaN formed as a light emitting layer is used. Can do.
  • the mounting of the semiconductor light emitting element 2 can be performed by placing the semiconductor light emitting element 2 on the portion of the substrate 1 where the semiconductor light emitting element 2 is mounted and performing wire bonding mounting or flip chip mounting.
  • the substrate 1 can be obtained by molding a resin material such as a ceramic material, a thermoplastic resin or a thermosetting resin into a desired shape by various molding methods. It is not limited. Examples of the ceramic material that can be used for the substrate 1 include alumina, aluminum nitride, zirconium oxide, and carbide carbide. These are formed by known compression molding, injection molding (CIM), etc., and sintered. Can be formed as a substrate 1 by the force S. Since the ceramic material is excellent in thermal conductivity, it can be preferably used from the viewpoint that the heat generated by the semiconductor light emitting element 2 can be diffused throughout the substrate 1 and efficiently radiated.
  • a resin material such as a ceramic material, a thermoplastic resin or a thermosetting resin into a desired shape by various molding methods. It is not limited. Examples of the ceramic material that can be used for the substrate 1 include alumina, aluminum nitride, zirconium oxide, and carbide carbide. These are formed by known compression molding, injection molding (CIM), etc.
  • thermoplastic resins such as polyphenylene sulfide (PPS), polyphthalimide (PPA), or liquid crystal polymer (LCP), and thermosetting resins such as epoxy resin and phenol resin can be used.
  • thermosetting resins such as epoxy resin and phenol resin
  • a filler such as glass, silica, or alumina
  • a predetermined pattern connected to the semiconductor light emitting element 2 as described above is formed on the surface of the substrate 1.
  • the electric circuit 5 is formed! /,
  • the force to be formed is not particularly limited, and a known method is used to reduce the force S.
  • the semiconductor optical device according to the present invention has been described using a semiconductor light emitting device in which the semiconductor light emitting element 2 is sealed with the sealing material 3.
  • the semiconductor light receiving element is made of the sealing material. Even a semiconductor light-receiving device that is sealed! /, Noha! /, Undo! /.
  • the sealing material 3 includes a cage silsesquioxane compound represented by the following formula (1), or a force obtained by partial addition reaction of this compound, a cage silsesquioxane. It is formed by crosslinking a key compound containing a partial polymer of the compound.
  • Equation (1) is expressed as (AR R SiOSiO) (R R HSiOSiO) (BR R SiOSiO)
  • A represents a group having a carbon-carbon unsaturated bond, and is not particularly limited as long as it includes a carbon-carbon double bond or a carbon-carbon triple bond as part of the group.
  • those containing an alkenyl group, an alkynyl group, and a cyclohexenyl group can be exemplified.
  • the group containing an alkenyl group or an alkynyl group include a group having a carbon-carbon double bond such as a bur group and an aryl group, Examples thereof include a group having a carbon-carbon triple bond such as an ether group and a vinyl group.
  • a group in which a group having a carbon-carbon double bond or a carbon-carbon triple bond and a divalent group not having an unsaturated group are bonded, and a divalent group not having an unsaturated group is bonded examples include cyclohexenylethyldimethyloxy group.
  • B represents a substituted or unsubstituted saturated alkyl group or hydroxyl group.
  • substituted or unsubstituted saturated alkyl group include a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, which is substituted or unsubstituted.
  • an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; Group, alkoxy group such as ethoxy group; aralkyl group such as 2-phenylethyl group, 2 phenylpropyl group, 3-phenylpropyl group; chloromethyl group,
  • Illustrative examples include halogen-substituted hydrocarbon groups such as ⁇ -chloropropyl group and 3,3,3-trifluoropropyl group.
  • a methyl group which is preferably an alkyl group having 1 to 4 carbon atoms, is particularly preferable from the viewpoint of reducing steric hindrance during the reaction.
  • each B group may be the same or different.
  • R 1, R 2, R 3, R 4, R 5 and R 5 are each independently a lower alkyl group.
  • a phenyl group is preferable from the viewpoint of reducing the steric hindrance of the reaction, and a methyl group preferably increasing the refractive index.
  • n l to m
  • 1 represents an integer of 1
  • p represents an integer of l to m-n
  • q represents an integer of 0 to m-n-p.
  • cage silsesquioxane compound examples include those represented by the following formula (4) and formula (5).
  • R force A compound of S methyl group (Me), approximately 6 faces formed by silicon atom and oxygen atom
  • a groups are bonded to 4 silicon atoms via siloxane bonds (O Si), and the other 4 silicon atoms are bonded to siloxane bonds (O — Si). It has a structure in which hydrogen atoms are bonded.
  • the structural formula of formula (4) is as follows. (One OS iMe-A) is bonded to four silicon atoms out of eight silicon atoms constituting an approximately hexahedral structure, and is bonded to the other four silicon atoms. (One O SiMe H)
  • R, R, R, R and B are methyl group compounds formed by silicon and oxygen atoms
  • the structural formula of formula (5) is that, among the eight silicon atoms constituting the substantially hexahedral structure, (O SiMe-A) is bonded to three silicon atoms one by one, and the other three silicon atoms (- ⁇
  • SiMe H are bonded to each other, and (O SiMe) is connected to the remaining two silicon atoms.
  • an octacanion with an approximately hexahedral structure (such as Si O 8 and chlorohydridodimethylsilane).
  • the hydridodimethylsiloxy group is bonded to the eight silicon atoms of octanion to form octakis [hydridodimethylsilane] silsesquioxane ⁇ . OHSS). Then, by using this OHSS, a compound having two or more carbon-carbon unsaturated groups in the molecule, such as 4-butyl1-1-cyclohexene, is reacted in an amount less than the equivalent, so that some hydridodimethylsiloxy groups are inactivated.
  • Addition reaction of a compound having two or more saturated groups in the molecule forms an approximately hexahedral structure formed by silicon atoms and oxygen atoms. A group having a carbon-carbon unsaturated bond is bonded to some of the eight silicon atoms. Then, a caged silsesquioxane compound represented by the formula (4) in which a hydridodimethylsiloxy group is bonded to another silicon atom can be prepared.
  • the octacanion can be obtained by hydrolytic polycondensation of tetraethoxysilane in the presence of tetramethylammonium hydroxide.
  • a reactive halogen having a carbon-carbon unsaturated group such as dimethylvinylchlorosilane, dimethylallylchlorosilane, chlorocycloalkenyldimethylsilane and chlorohydridodimethylsilane with octacanion
  • a group having a carbon-carbon unsaturated bond is bonded to a part of eight silicon atoms constituting a substantially hexahedral structure formed of silicon atoms and oxygen atoms, and a hydridodimethylsiloxy group is bonded to other silicon atoms.
  • a cage-type silsesquioxane compound such as formula (4) can be prepared.
  • an approximately hexahedral structure is formed by mixing and reacting an unsaturated group such as chlorotrimethylsilane and a reactive halogen having no active hydrogen.
  • an unsaturated group such as chlorotrimethylsilane and a reactive halogen having no active hydrogen.
  • a cage-type silsesquioxane compound represented by the formula (5) in which a non-reactive group is bonded to a part of one silicon atom can be prepared.
  • the gale silsesquioxane compound in a substantially hexahedral structure formed of silicon atoms and oxygen atoms, has hydrogen atoms bonded to the silicon atoms via siloxane bonds. And a group having a carbon-carbon unsaturated bond group, so that this hydrogen atom is subjected to a hydrosilylation reaction with an unsaturated group contained in the carbon-carbon unsaturated bond group of another cage-type silsesquioxane compound. Then, it is cross-linked and cured by addition polymerization to form a three-dimensional cross-linked structure.
  • Figure 2 schematically shows a three-dimensional cross-linked structure in which an approximately hexahedral structure (symbol 7) formed by silicon atoms and oxygen atoms is cross-linked.
  • [Chemical Formula 2] shows the cross-linking reaction of a three-dimensional cross-linked structure of a cage silsesquioxane compound in which A in formula (4) is a cyclohexenyl group.
  • This three-dimensional cross-linking structure is a nano-sac made of silica (glass). It has a structure in which the cage structure is connected by an organic segment, and can exhibit a glass-like function.
  • the reacting carbon-carbon unsaturated bond group and the hydrogen atom are both bonded to the polyhedral structure part of silsesquioxane (Si 2 O 3) via a siloxane bond (1 O—Si—).
  • the crosslinked structure of the cured product obtained as described above has a structure in which silicon atoms constituting the polyhedral structure of silsesquioxane are bonded to four oxygen atoms to form a glass which is an inorganic material.
  • the structure is close, and the organic group is not directly bonded to the silicon atom, so it is difficult to deteriorate even if it is used under irradiation with light in the blue and near ultraviolet regions.
  • the sealing material 3 for sealing the semiconductor light emitting element 2 or the like a light transmitting epoxy resin, polyester, polyacrylate, organopolysiloxane or the like that has been used conventionally is used.
  • a light transmitting epoxy resin, polyester, polyacrylate, organopolysiloxane or the like that has been used conventionally is used.
  • the cage silsesquioxane compound of the present invention In sealing the semiconductor light emitting device 2 using the cage silsesquioxane compound of the present invention, it is particularly limited as long as the polymerization / crosslinking reaction of the cage silsesquioxane compound proceeds. Any method can be adopted without any reaction, and the reaction may be carried out using an addition reaction catalyst such as platinum or noradium as necessary.
  • the cage silsesquioxane compound according to the present invention is a liquid at room temperature or a solid that melts at a relatively low temperature until it is crosslinked, the semiconductor light-emitting element 2 and the like can be easily sealed. Is possible.
  • the partial polymer of the cage silsesquioxane compound obtained by partial addition reaction of the cage silsesquioxane compound represented by the above formula (1) of the present invention is represented by the formula (1).
  • the sealing material 3 can be formed of a cured product that is hardly deteriorated and has a low water absorption even when used in a state of being irradiated with light in the blue region and near-ultraviolet region.
  • the encapsulant 3 for encapsulating the semiconductor light emitting device 2 and the like has a cage-type silsesquioxane compound represented by the above formula (1) or a force obtained by partial addition reaction of this compound,
  • a key compound having addition reactivity may be contained as long as desirable optical and physical properties of the cured product are maintained.
  • the substituted or unsubstituted alkyl group of the basket-type silsesquioxane compound represented by formula (1) B is an alkoxy group and q 2
  • the bond between a group having a carbon unsaturated bond and a hydrogen atom it is also possible to crosslink by a hydrolysis / polycondensation bond between these alkoxy groups. Increased properties are preferable.
  • the bond between a group having a carbon-carbon unsaturated bond and a hydrogen atom becomes a main cross-linked structure, it is preferable that the thickness of the cured product becomes relatively easy.
  • the decomposition / polycondensation bond is a main cross-linked structure because of relatively high transparency.
  • [Chemical Formula 3] shows an example of a crosslinking reaction of a three-dimensional crosslinked structure when A in the formula (1) is a cyclohexenyl group and B is an ethoxy group.
  • the cage silsesquioxane compound of the formula (1) or a portion of a cage silsesquioxane compound obtained by partial addition reaction of this compound The semiconductor optical device in which the semiconductor light emitting element or the semiconductor light receiving element is sealed with the polymer has been described.
  • the cage silsesquioxane compound represented by the formula (1) or a partial addition reaction of this compound A transparent optical member such as a lens or a prism can be produced by using a partially polymerized product of a cage-type silsesquioxane compound as a molding material and molding and polymerizing and curing it. .
  • a transparent optical member such as a protective layer of a Blu-ray disc by coating and polymerizing on the surface of the optical disc.
  • the cured product of the force-type silsesquioxane compound is transparently sealed for LED white illumination replacement paper (Rule 26)
  • LED white illumination replacement paper When applied to optical applications such as materials, it is necessary to improve the refractive index, and in order to form a cured product of a rugged silsesquioxane compound to have a high refractive index, It is preferable to mix a heavy metal sol such as TiO or ZrO and introduce the heavy metal sol into the cured product of the cage silsesquioxane compound.
  • the cage-type silsesquioxane compound is generally incompatible with heavy metal sols such as TiO and ZrO, and it is difficult to uniformly disperse the heavy metal sol, and as a result, the transparency of the cured product tends to be impaired.
  • A is an aryl group, R, R,
  • aryl groups are bonded to three silicon atoms via siloxane bonds (—O—Si—). It has a structure in which a hydrogen atom is bonded to three silicon atoms via a siloxane bond (one O—Si—) and a hydroxyl group is bonded to two silicon atoms.
  • Such a cage silsesquioxane having a hydroxyl group bonded to a part of eight silicon atoms constituting an approximately hexahedral structure can be obtained as follows.
  • the cage silsesquioxane compound such as the above [Chemical 4] is prepared by reacting with the following [Chemical 12] and [Chemical 13] reaction, and eight reaction sites of S and Octanion.
  • the amount of allyl dimethyl chlorosilane or dimethyl chlorosilane should be a large excess (for example, 30 times equivalent or more) with respect to octacanion. Must be set.
  • the force-type silsesquioxane compounds are directly crosslinked by hydrosilylation reaction between a carbon-carbon unsaturated bond and a hydrogen atom.
  • the cage silsesquioxane compound represented by the formula (1) is blended with the following formula (2) or formula (3) as a reactive monomer, and the cage silsesquioxane compound is obtained.
  • the compound is cured by crosslinking with the compound of formula (2) or formula (3).
  • X represents a divalent functional group or an oxygen atom.
  • R 1, R 2, R 3 and R 5 are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom.
  • the compound represented by the formula (2) is not particularly limited, but examples thereof include those represented by the following [Chemical Formula 6].
  • the amount of the compound of the formula (2) with respect to the force of the formula (1) and the type silsesquioxane compound is not particularly limited.
  • the amount equivalent to the amount of the unreacted A unsaturated group remaining when the hydrosilylation reaction with a hydrogen atom is performed is preferably set slightly higher than the equivalent amount.
  • the cage-type silsesquioxane compound is blended with the compound of the formula (2) as a reactive monomer and reacted, thereby producing a force-type silsesquioxane as shown in [Chemical Formula 7].
  • the cage-type silsesquioxane compound can be cross-linked with the compound of formula (2) and hardened, and the nano-sized cage structure with silica power is connected by organic segments.
  • Such a three-dimensional crosslinked structure can be formed.
  • the aryl group is bonded to the X silicon atoms through a siloxane bond (one O—Si—) and the other 8—X atoms. It has a structure in which a hydrogen atom is bonded to a silicon atom via a siloxane bond (one O—Si—).
  • Y represents a divalent functional group
  • the compound represented by the formula (3) is not particularly limited, but is represented by the following [Chemical Formula 8]. It can be illustrated.
  • the amount of the compound of formula (3) to the cage silsesquioxane compound of formula (1) is not particularly limited, but the cage silsesquioxane compound of formula (1) It is preferable to set the amount to be equivalent to the amount of unreacted hydrogen atoms remaining when the carbon-carbon unsaturated bond and the hydrogen atom are subjected to a hydrosilylation reaction, or a little less than the equivalent.
  • the cage-type silesquioxane compound is compounded with the compound of the formula (3) as a reactive monomer and subjected to an X reaction, as shown in [Chemical Formula 9].
  • One CH CH group hydrosilylation reaction at both ends of the compound of formula (3) on one SiH group of the compound
  • cage-type silsesquioxane compound can be cross-linked with the compound of formula (3) and cured, and the nano-sized cage structure composed of silica is connected by organic segments.
  • a three-dimensional crosslinked structure can be formed.
  • a force-type silsesquioxane compound having one SiH group in the reactive monomer sea gradually reacts with the compound of formula (3).
  • the progress of the reaction can be controlled more mildly, and even if one unreacted SiH group occurs during the course of the crosslinking reaction, the formula (3) The compound moves to the residue and undergoes a crosslinking reaction.
  • the freezing of the reaction can be controlled mildly to delay the structure freezing, and more uniform network structure with fewer unreacted residues and the cage-type cinresesquioxane compound It is possible to form a tertiary five-crosslinked structure, to suppress stress cracking of the cured body and to improve toughness, and to improve irradiation resistance against short wavelength high-energy energy such as Blu-ray. it can.
  • the force-type silsesquioxane compound according to Embodiment 2 is a group in which A in the cage-type silsesquioxane compound represented by Formula (1) in Embodiment 1 has a carbon-carbon unsaturated bond.
  • A is a chain hydrocarbon group having a carbon-carbon unsaturated bond. Different from sesquioxane compounds.
  • 'Encapsulant 3 is a cage-type silsesquioxane compound represented by the following formula (1), or a portion of a cage-type silsesquioxane compound obtained by partial addition reaction of this compound. It is formed by cross-linking a key compound containing a polymer.
  • A is a chain hydrocarbon group having a carbon-carbon unsaturated bond.
  • A is not particularly limited as long as it contains a carbon-carbon double bond or a carbon-carbon triple bond as part of the group.
  • Examples include groups containing alkenyl groups and alkynyl groups.
  • groups containing alkenyl groups or alkynyl groups include groups having a carbon-carbon double bond such as a buyl group and an allyl group, an ether group, and a vinyl group.
  • groups having a carbon-carbon triple bond such as a group.
  • a group in which a group having a carbon-carbon double bond or a carbon-carbon triple bond and a divalent group not having an unsaturated group are bonded can also be exemplified.
  • the position of the carbon-carbon unsaturated bond of the chain hydrocarbon group having these carbon-carbon unsaturated bonds is preferably at the terminal from the viewpoint of reducing steric hindrance during hydrolysis.
  • OHSS octakis [hydridodimethyloxy] silsesquioxane
  • a chain-like group having a carbon-carbon unsaturated bond is bonded to some of the eight silicon atoms that form an approximately hexahedral structure formed by silicon atoms and oxygen atoms, and the other silicon atoms are bonded to other silicon atoms.
  • a cage-type silsesquioxane compound represented by the formula (4) to which a hydridodimethylsiloxy group is bonded can be prepared.
  • the above octanion can be obtained by hydrolysis polycondensation reaction of tetraethoxysilane in the presence of tetramethylammonium salt.
  • a silicon atom and Carbon is carbon-saturated to some of the eight silicon atoms that make up the nearly hexahedral structure formed by oxygen atoms.
  • a cage-type silsesquioxane compound represented by the formula (4) in which a chain group having a sum bond is bonded and a hydridodimethylsiloxy group is bonded to another silicon atom can be prepared.
  • the gale silsesquioxane compound includes a hydrogen atom bonded to a silicon atom having a substantially hexahedral structure formed of a silicon atom and an oxygen atom through a siloxane bond; And a chain hydrocarbon group having a carbon-carbon unsaturated bond, so that this hydrogen atom is included in the chain hydrocarbon having a carbon-carbon unsaturated bond of another cage silsesquioxane compound. Hydrosilylation reaction with an unsaturated group, followed by addition polymerization to crosslink and cure to form a three-dimensional crosslinked structure.
  • FIG. 2 schematically shows a three-dimensional cross-linked structure in which a substantially hexahedral structure (symbol 7) formed of silicon atoms and oxygen atoms is cross-linked.
  • the cross-linking of the oxane compound is shown.
  • the power of [Chemical Formula 15] is that the silsesquioxane of the hexagonal structure has four hydrogen atoms bonded to eight silicon atoms of approximately hexahedral structure via siloxane bonds, and via siloxane bonds. Four hexenyl groups are bonded, and a hydrogen atom and an unsaturated group of hexenyl are crosslinked by hydrosilylation reaction.
  • This three-dimensional cross-linking structure has a structure in which nano-sized cage structures made of silica (glass) are connected by organic segments, and can exhibit a glass-like function.
  • the crosslinked structure of the cured product obtained as described above has a structure close to that of glass, which is an inorganic material, in which the silicon atoms constituting the polyhedral structure of silsesquioxane are bonded to four oxygen atoms.
  • glass which is an inorganic material, in which the silicon atoms constituting the polyhedral structure of silsesquioxane are bonded to four oxygen atoms.
  • the organic group is not directly bonded to the silicon atom, it is difficult to deteriorate even if it is used in the state of being irradiated with light in the blue region and near ultraviolet region.
  • the cured product since it has a nano-sized cage structure that also has silica (glass) force, the cured product has a higher crosslink density and lower water absorption than metalloxane obtained by the sol-gel method. Obtain power S. [0082] [Chemical 15]
  • Tetramethylammonium hydroxide (334 mL), methanol (164 mL), and water (123 mL) were added to an lOOOOmL flask equipped with a reflux tube and a dropping funnel and stirred.
  • the dropping funnel was charged with 179 mL of tetraethoxysilane (TEOS), and the whole flask was cooled to about 5 ° C in an ice bath, and when the temperature reached about 5 ° C, TEOS was added dropwise. The dripping of 179 mL of TEOS was completed in about 1 hour from the start of dripping.
  • TEOS tetraethoxysilane
  • the mixture was stirred for 10 minutes in an ice bath, while the stirring was continued, the ice bath was removed, and the mixture was further stirred at room temperature for 6 hours to proceed the reaction.
  • the solution in the flask was transferred to a 2 L separatory funnel, and the lower methanol layer was taken out.
  • the upper hexane layer was transferred to a 2 L Erlenmeyer flask, sodium sulfate was added, and the mixture was allowed to stand for about 10 minutes to dry the water in the solution.
  • the upper hexane layer formed by standing was transferred to the 2 L Erlenmeyer flask to which the above hexane layer was transferred, The water in the solution was dried.
  • the dried hexane layer was transferred to a 1 L eggplant type flask, and the hexane was volatilized from the solution using a rotary evaporator and removed from the system.
  • the damp white solid remaining in the 1 L eggplant type flask where hexane was volatilized was further dried under reduced pressure (133 Pa (lmmHg), room temperature) using a vacuum pump.
  • Acetonitrile was added to a 1 L eggplant-shaped flask containing a white solid, the white solid was stirred, and then the solid was filtered off with a suction filter bottle. Next, this filtered white solid was transferred to a lOOmL beaker, further washed with acetonitrile lOOmL, and suction filtered to take out the white solid. This washing operation was repeated twice, followed by drying under reduced pressure using a vacuum pump to obtain white solid octakis [hydridodimethylsiloxy] silsesquioxane (OHSS). The yield at this time was 56%.
  • the basket-type silsesquioxane compound thus obtained was purified by adding a acetonitrile solvent, and then the white precipitate was filtered. This procedure was repeated three times for purification, and the resulting white powder was dried in vacuo.
  • the purified force, yield of the gale silsesquioxane compound was 3.5 g (2.4 mmol, 24.5%).
  • the cage-type silsesquioxane compound thus obtained was poured into a mold made of Teflon (registered trademark), heated and melted at 90 ° C, degassed under reduced pressure, and further maintained under vacuum. The temperature was raised to 00 ° C. and heated for 5 hours to cure to obtain a resin plate.
  • the resin plate had a size of 5 cm x 3 cm and a thickness of about 1 mm.
  • the wavelength dependence of the light transmittance of the resin plate was measured using an ultraviolet, visible, and near-infrared spectrophotometer ("UV-3100PC” manufactured by Shimadzu Corporation) at a slit width of 20 nm. For comparison, it does not contain an aromatic component!
  • a resin plate molded and cured using a silicone resin (“KE-006” manufactured by Shin-Etsu Chemical Co., Ltd.) and a light-transmitting alicyclic epoxy resin The same measurement was conducted on a resin plate that was molded and cured. The results are shown in Figure 3. As can be seen in FIG. 3, it was confirmed that the resin plate of this example has high transparency up to a low wavelength.
  • a semiconductor light-emitting element 2 having an emission wavelength peak of 380 ⁇ m is mounted on the bottom of the cavity la of the substrate 1, and the cage silsesquioxane obtained as described above is mounted.
  • the compound was filled into the cavity la and heated at 200 ° C. for 5 hours to cure, thereby sealing the semiconductor light emitting element 2 and fabricating a semiconductor optical device. Then, with this semiconductor optical device at room temperature, the semiconductor light emitting element 2 was turned on, and the maintenance rate of the luminous flux with respect to the illuminance at the start of lighting was measured.
  • a semiconductor optical device sealed with a silicone resin containing no aromatic component (“KE-006” manufactured by Shin-Etsu Chemical Co., Ltd.) and a light-transmitting alicyclic epoxy resin are used for sealing.
  • the semiconductor optical device encapsulated with the cage-type silsesquioxane compound obtained in this example maintains a light flux of nearly 90% even after 1000 hours. It was confirmed that it was high! / And resistant! /.
  • the lifetime defined by the time when the luminous flux maintenance factor falls to 50% of the initial value was predicted by the following Lehmann equation, and it was confirmed that the lifetime was 60,000 hours or more. It was.
  • ⁇ (t) luminous flux after t time
  • ⁇ (0) initial luminous flux
  • ⁇ time constant of degradation
  • ⁇ constant
  • Example 2 The OHSS obtained in Example 1 was charged to lg (lmmol) in a lOOmL Schlenk flask having a reflux condenser. The flask was heated under vacuum to remove residual air and moisture, then flushed with nitrogen, and then 5 mL of toluene, 0.32 g of 4-Buyl 1-cyclohexene (2. 9 mmol), 0.25 g (l. 9 mmol) of dimethyl butylethoxysilane, and 2 mM Pt (dcp) -toluene solution as a catalyst were added to a 0 ⁇ l mL (Pt: 0.02 ppm) flask. The mixture was reacted with stirring at 90 ° C. for 4 hours, and the solvent was evaporated in vacuum at room temperature to obtain 1.49 g (0.95 mmol) of a white powder. The yield at this time was 95%.
  • the composition obtained by concentrating the obtained hydrolyzate was poured into a 10 mL Teflon (registered trademark) mold and cured by heating at 200 ° C. for 5 hours to obtain a resin plate.
  • the resin plate had a size of 5 cm x 3 cm and a thickness of about 1 mm.
  • the tris [cyclohexenylethyldimethylsilane] tris [dimethylsilaneoxy] di [dimethyl ethersilylethyldimethylsiloxy] cinolesesquioxane obtained as described above was used for curing. It was confirmed that the addition reaction could be cured after hydrolysis polycondensation, and it was confirmed that the addition could be cured by hydrolysis polycondensation after the addition reaction.
  • Hexalylsilsesquioxane 1 ⁇ Og synthesized as shown in [Chemical Formula 12] was mixed with 0.24 g of tetramethyldisiloxane as the compound of formula (2), and 3.0 Add 10% to 3 % by weight Pt (cts) toluene solution to the entire system and mix evenly, then in the air, 12 replacement paper (Rule 26) It was cured by heating at 0 ° C. for 3 hours to obtain a colorless and transparent resin plate.
  • Example 3 in the method of synthesizing hexarylsilsesquioxane having two SiH groups in [Chemical Formula 12], 19.8 mL of allyldimethylchlorosilane was added to 376 mL of hexane. As shown in the above [Chemical 4], except that 14.6 mL of dimethylchlorosilane was added and octanion was allowed to react, it was shown in the above [Chemical 4]. Axane was synthesized.
  • Example 3 and Reference Example 1 were immersed in an acetone solution (RT), and stress cracking was evaluated based on the presence or absence of cracks in the resin plate during the immersion.
  • RT acetone solution
  • the resin plate of Reference Example 1 in which the cage-type silsesquioxane compound was directly crosslinked was cross-linked with a reactive monomer.
  • the cage-type silsesquioxane compound was instantly cracked by immersion in an acetone solution.
  • the resin plate of Example 3 was not cracked.
  • the obtained reaction solution was extracted 3 times with 40 mL of hexane, and the hexane layer was dried with a desiccant (sodium sulfate) and then filtered with suction. As shown in [Chemical Formula 14], the obtained filtrate is evaporated to remove hexane, and the reaction product power obtained is removed by purification while heating at 50 ° C with a vacuum pump. A tetrahexenyl silsesquioxane having four SiH groups was obtained.
  • diallyl silsesquioxane obtained in [Chemical Formula 13] above and tetrahexenylsilsesquioxane are mixed in a mass ratio of 30:70, By heating at 120 ° C for 4 hours, the spaces were directly crosslinked and cured to obtain a colorless and transparent resin plate.
  • Example 4 The resin plate obtained in Example 4 and the resin plate obtained in Reference Example 2 were evaluated for BluRay irradiation resistance.
  • each resin plate was irradiated with 405 nm Blu-ray under the conditions of power density 1.1 W / wake 2 and spot size 200 m, and the time-dependent change of the irradiated part screen enlarged image (far field image) was observed. Senna / lemon observation was performed on the sample after completion of the irradiation test.
  • FIG. 6 (a) shows the time-dependent change of the far field image of Example 4
  • FIG. 6 (b) shows the time-dependent change of the far field image of Reference Example 2.
  • the example 4 crosslinked with a reactive monomer was used before the Blu-ray irradiation ( The change in far-field image was small compared to O r). After 240 hours of irradiation (240 r), the change was almost unchanged. .
  • Fig. 7 (a) shows the senalmon observation of Example 4
  • Fig. 7 (b) shows the senalmon observation of Reference Example 2.
  • Reference Example 2 a slight irradiation mark is seen at the center as shown in Fig. 7 (b), but in the case of Example 4, the irradiation mark was not seen as shown in Fig. 7 (a). .
  • Example 4 and Reference Example 2 were immersed in an acetone solution (RT), and stress cracking was evaluated based on the presence or absence of cracks in the resin plate during the immersion. As a result, the resin plate of Reference Example 2 was instantly cracked when immersed in an aceto solution.
  • RT acetone solution
  • An apparatus equipped with a dropping funnel, thermometer, and reagent injection valve was assembled in a three-necked flask, and 376 mL of hexane, 33.8 mL of allyldimethyl chronolesilane, and 4.3 niL of dimethinorechlorsilane were added to the three-flask.
  • the whole system in the three-necked flask is cooled in an ice bath to 5 ° C or less, and after confirming that the temperature in the system is 5 ° C or less, the dropping funnel replacement paper ( (Rule 26) Force Octanion 140 mL was added dropwise at a rate of 1-2 drops per second.
  • the whole system in the three-necked flask is cooled in a water bath so that the temperature is 5 ° C or less, and when the temperature in the system becomes 5 ° C or less, it is 70 m from the dropping funnel.
  • each resin plate obtained in Example 5 and the resin plate obtained in Example 1 was irradiated with benoray ray under the conditions of a power density of 1.1 W, ⁇ 2 and a spot size of 200 am, and the time-dependent changes in the screen image of the irradiated area (far field image) were observed. did.
  • FIG. 8 (a) shows the time-dependent change of the far field image of Example 5
  • FIG. 8 (b) shows the time-dependent change of the far field image of Example 1.
  • FIG. 8 (a) and 8 (b) shows the time-dependent change of the far field image of Example 1.
  • FIG. 9 (a) shows the senalmon observation of Example 5
  • FIG. 9 (b) shows the senalmon observation of Example 1.
  • Example 1 there is an irradiation mark as shown in FIG.
  • the force of Example 5 shows a slight damage after 183 hr irradiation as shown in FIG. 9 (a). The damage is extremely small compared to that of Example 1.
  • X 1CT Add 3 ppm by mass of Pt (cts) toluene solution at a concentration of 3 % by mass, mix uniformly, and then cure by heating at 120 ° C for 4 hours in air to obtain a colorless and transparent resin plate It was.
  • Example 6 in a method for synthesizing hexarylsilsesquioxane having two SiH groups of [Chemical Formula 17], 19.8 mL of allyldimethylchlorosilane was added to 376 mL of hexane. The reaction was purified in the same manner except that 14.6 mL of dimethylchlorosilane was mixed and reacted with octananion, so that tetraallylsilsesquioxane having four SiH groups shown in [Chemical 4] above was obtained.
  • Example 6 in a method for synthesizing hexarylsilsesquioxane having two SiH groups of [Chemical Formula 17].

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Abstract

L'invention concerne un dispositif optique à semi-conducteur comprenant un élément électroluminescent semi-conducteur ou un élément récepteur de lumière semi-conducteur maintenu étanche à l'aide d'un matériau de scellage, le matériau d'étanchéité étant difficilement détérioré et présentant une faible capacité d'absorption d'eau. Un composé de silicium contenant un composé-cage de silsesquioxane représenté par la formule décrite ci-après, ou un produit de polymérisation partielle du composé est utilisé pour maintenir étanche un élément électroluminescent semi-conducteur ou un élément récepteur de lumière semi-conducteur. Dans la formule (AR1R2SiOSiO1,5)n(R3R4HSiOSiO1,5)p(BR5R6SiOSiO1,5)q(HOSiO1,5)m-n-p-q, A représente un groupe présentant une liaison insaturée carbone-carbone ou un groupe hydrocarbure linéaire présentant une liaison insaturée carbone-carbone; B représente un groupe alkyle saturé substitué ou non substitué ou un groupe hydroxy; R1, R2, R3, R4, R5 et R6 représentent indépendamment un groupe fonctionnel sélectionné parmi un groupe alkyle inférieur, un groupe phényle et un groupe arylakyle inférieur; m représente un nombre sélectionné parmi 6, 8, 10 et 12; n représente un entier compris entre 1 et m-1; p représente un entier compris entre 1 et m-n; et q représente un entier compris entre 0 et m-n-p.
PCT/JP2007/066028 2006-11-27 2007-08-17 Dispositif optique à semiconducteur et élément optique transparent Ceased WO2008065786A1 (fr)

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JP2008201832A (ja) * 2007-02-16 2008-09-04 Shin Etsu Chem Co Ltd シロキサン重合体とその製造方法、該重合体を含有する多孔質膜形成用塗布液ならびに多孔質膜と、該多孔質膜を用いた半導体装置
WO2011125463A1 (fr) * 2010-03-31 2011-10-13 積水化学工業株式会社 Agents de scellement pour semi-conducteurs optiques et dispositif semi-conducteur optique
JP2012067160A (ja) * 2010-09-22 2012-04-05 Kaneka Corp 多面体構造ポリシロキサン変性体およびこれから得られる組成物
WO2012144480A1 (fr) * 2011-04-20 2012-10-26 セントラル硝子株式会社 Composé siloxane et produit durci obtenu à partir de celui-ci
JP2013010807A (ja) * 2011-06-02 2013-01-17 Nitto Denko Corp シリコーン樹脂組成物、シリコーン樹脂シート、光半導体素子装置、および、シリコーン樹脂シートの製造方法。
JP2019505603A (ja) * 2015-12-18 2019-02-28 ワッカー ケミー アクチエンゲゼルシャフトＷａｃｋｅｒ Ｃｈｅｍｉｅ ＡＧ シロキサン樹脂組成物

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