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WO2013035736A1 - Composition durcissable destinée à un dispositif semi-conducteur optique - Google Patents

Composition durcissable destinée à un dispositif semi-conducteur optique Download PDF

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Publication number
WO2013035736A1
WO2013035736A1 PCT/JP2012/072603 JP2012072603W WO2013035736A1 WO 2013035736 A1 WO2013035736 A1 WO 2013035736A1 JP 2012072603 W JP2012072603 W JP 2012072603W WO 2013035736 A1 WO2013035736 A1 WO 2013035736A1
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WIPO (PCT)
Prior art keywords
group
organopolysiloxane
optical semiconductor
formula
curable composition
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/JP2012/072603
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English (en)
Japanese (ja)
Inventor
穣 末▲崎▼
康成 日下
秀文 保井
亮介 山▲崎▼
良隆 国広
満 谷川
貴志 渡邉
靖 乾
千鶴 金
佑 山田
小林　祐輔
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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Priority to KR1020137029657A priority Critical patent/KR20140071961A/ko
Publication of WO2013035736A1 publication Critical patent/WO2013035736A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C08K5/5455—Silicon-containing compounds containing nitrogen containing at least one group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C08K5/5465—Silicon-containing compounds containing nitrogen containing at least one C=N bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
    • H01L2224/45099—Material
    • H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/45144—Gold (Au) as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • 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
    • 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
    • H10H20/855—Optical field-shaping means, e.g. lenses

Definitions

  • the present invention relates to a curable composition for an optical semiconductor device used for sealing an optical semiconductor element or forming a lens above the optical semiconductor element in an optical semiconductor device.
  • the present invention also relates to an optical semiconductor device using the curable composition for optical semiconductor devices.
  • An optical semiconductor device such as a light emitting diode (LED) device has low power consumption and long life. Moreover, the optical semiconductor device can be used even in a harsh environment. Accordingly, optical semiconductor devices are used in a wide range of applications such as mobile phone backlights, liquid crystal television backlights, automobile lamps, lighting fixtures, and signboards.
  • LED light emitting diode
  • optical semiconductor element for example, LED
  • LED which is a light emitting element used in an optical semiconductor device
  • Patent Document 1 discloses an epoxy resin material containing hydrogenated bisphenol A glycidyl ether, an alicyclic epoxy monomer, and a latent catalyst as a sealant for an optical semiconductor device. This epoxy resin material is cured by thermal cationic polymerization.
  • a lens may be formed using a lens material for an optical semiconductor device in order to control the light emission direction or to prevent the front luminance from becoming too high.
  • the lens is disposed on the surface of the sealant, for example.
  • the lens may be disposed on the optical semiconductor element or so as to cover the optical semiconductor element.
  • Patent Document 2 includes (A) an organopolysiloxane having two or more aliphatic unsaturated bonds and (B) two or more hydrogen atoms bonded to silicon atoms as the lens material for an optical semiconductor device.
  • a lens material including an organohydrogenpolysiloxane, (C) a platinum group metal catalyst, and (D) a release agent is disclosed.
  • Patent Document 3 (1) optical transparency that is 90% or higher transmittance for light having a wavelength of 400 nm with an optical path length of 1.0 cm, and (2) after being exposed to 150 ° C. for 6 hours. , Thermal stability retaining 90% or higher transmission for light of 400 nm wavelength with 1.0 cm path length, and (3) thermal stability having a refractive index of 1.545 or higher at 589 nm A polysiloxane composition is disclosed.
  • Patent Document 4 discloses an LED encapsulant composition
  • an LED encapsulant composition comprising (1) at least one polyorganosiloxane and an effective amount of (2) an addition reaction catalyst, which is cured to form a resin.
  • the average composition formula of the mixture of (1) at least one polyorganosiloxane is (R 1 R 2 R 3 SiO 1/2 ) M ⁇ (R 4 R 5 SiO 2/2 ) D ⁇ (R 6 SiO 3 / 2 ) T ⁇ (SiO 4/2 ) Q
  • the light intensity (brightness) emitted from the optical semiconductor device may gradually decrease.
  • An object of the present invention is to provide a curable composition for an optical semiconductor device capable of improving the pot life of the composition, and an optical semiconductor device using the curable composition for an optical semiconductor device.
  • a first organopolysiloxane having two or more alkenyl groups a second organopolysiloxane having two or more hydrogen atoms bonded to a silicon atom, a hydrosilylation reaction catalyst, And a first silane compound having a ureido group or an isocyanate group, and a curable composition for an optical semiconductor device.
  • the curable composition for optical semiconductor devices according to the present invention is preferably an encapsulant for optical semiconductor devices or a lens material for optical semiconductor devices.
  • the first silane compound has a ureido group.
  • the first silane compound is a first silane compound represented by the following formula (S1) or the following formula (S2).
  • X1 represents an alkoxy group
  • X2 and X3 each represents an alkoxy group or a hydrocarbon group having 1 to 8 carbon atoms
  • R4 is a single bond directly bonding a nitrogen atom and a silicon atom. Or a hydrocarbon group having 1 to 8 carbon atoms.
  • X1 represents an alkoxy group
  • X2 and X3 each represents an alkoxy group or a hydrocarbon group having 1 to 8 carbon atoms
  • R4 represents a single bond directly connecting a nitrogen atom and a silicon atom. It represents a bond or a hydrocarbon group having 1 to 8 carbon atoms.
  • the first silane compound is a first silane compound represented by the above formula (S1).
  • the first silane compound represented by the above formula (S1) is a first silane compound represented by the following formula (S1-1). Silane compound.
  • R1 to R3 each represent a hydrocarbon group having 1 to 8 carbon atoms
  • R4 represents a single bond directly bonding a nitrogen atom and a silicon atom, or 1 to 8 hydrocarbon groups are represented.
  • the number average molecular weight of the first organopolysiloxane is 500 or more and 200,000 or less, and the number average of the second organopolysiloxane.
  • the molecular weight is 500 or more and 20000 or less.
  • a second silane compound having an epoxy group, a vinyl group, or a (meth) acryloyl group is further included.
  • the second silane compound is 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl. Trimethoxysilane, vinyltrimethoxysilane or 3- (meth) acryloxypropyltrimethoxysilane.
  • the content of the second silane compound is 0 with respect to a total of 100 parts by weight of the first and second organopolysiloxanes. 0.01 parts by weight or more and 5 parts by weight or less.
  • the first organopolysiloxane does not have a hydrogen atom bonded to a silicon atom
  • the second organopolysiloxane is alkenyl. Has a group.
  • the first organopolysiloxane has a methyl group represented by the following formula (1A) and bonded to an alkenyl group and a silicon atom.
  • a second organopolysiloxane which is a first organopolysiloxane and the second organopolysiloxane is represented by the following formula (51A) and has a hydrogen atom bonded to a silicon atom and a methyl group bonded to a silicon atom.
  • siloxane or the first organopolysiloxane is represented by the following formula (1B), is a first organopolysiloxane having an aryl group and an alkenyl group, and the second organopolysiloxane is A second organopolysiloxane represented by the following formula (51B) and having a hydrogen atom bonded to an aryl group and a silicon atom.
  • R1 to R6 each represents at least one alkenyl group, at least one represents a methyl group, and R1 to R6 other than the alkenyl group and the methyl group represent a hydrocarbon group having 2 to 8 carbon atoms. .
  • R51 to R56 each represents at least one hydrogen atom, at least one represents a methyl group, and R51 to R56 other than the hydrogen atom and the methyl group are hydrocarbon groups having 2 to 8 carbon atoms. Represents.
  • R51 to R56 represents an aryl group
  • R51 to R56 other than the aryl group and the hydrogen atom are carbon atoms having 1 to 8 carbon atoms. Represents a hydrogen group.
  • the first organopolysiloxane represented by the above formula (1A) or the above formula (1B) is a hydrogen atom bonded to a silicon atom.
  • the second organopolysiloxane represented by the formula (51A) or the formula (51B) has an alkenyl group, and in the formula (51A), at least one of R51 to R56 is Represents a hydrogen atom, at least one represents a methyl group, at least one represents an alkenyl group, R51 to R56 other than a hydrogen atom, a methyl group and an alkenyl group represent a hydrocarbon group having 2 to 8 carbon atoms;
  • at least one of R51 to R56 represents an aryl group, at least one represents a hydrogen atom, at least one represents an alkenyl group, an aryl group, a hydrogen atom and an alkyl group.
  • the second organopolysiloxane represented by the above formula (51A) or the above formula (51B) is represented by the following formula (51-a). ).
  • R52 and R53 each represent a hydrocarbon group having 1 to 8 carbon atoms.
  • first organopolysiloxane is represented by the above formula (1A) and the second organopolysiloxane is represented by the above formula (51A). It is also preferred that the first organopolysiloxane is represented by the formula (1B) and the second organopolysiloxane is represented by the formula (51B).
  • the content of the second organopolysiloxane is 10 parts by weight or more with respect to 100 parts by weight of the first organopolysiloxane. 400 parts by weight or less, and the content of the catalyst for hydrosilylation reaction in the curable composition is 0.01 ppm or more and 1000 ppm or less by weight unit of metal atom,
  • the content of the first silane compound is 0.01 parts by weight or more and 5 parts by weight or less with respect to a total of 100 parts by weight of siloxane.
  • the curable composition for optical semiconductor devices according to the present invention includes a first organopolysiloxane having an alkenyl group, a second organopolysiloxane having a hydrogen atom bonded to a silicon atom, a hydrosilylation reaction catalyst, Even if the optical semiconductor device using the curable composition for optical semiconductor devices is used in a harsh environment under high temperature and high humidity, since it contains the first silane compound having a ureido group or an isocyanate group The peeling from the adhesion target object of the hardened
  • FIG. 1 is a front sectional view showing an optical semiconductor device according to the first embodiment of the present invention.
  • FIG. 2 is a front sectional view showing an optical semiconductor device according to the second embodiment of the present invention.
  • FIG. 3 is a front sectional view showing an optical semiconductor device according to the third embodiment of the present invention.
  • the curable composition for optical semiconductor devices includes a first organopolysiloxane having an alkenyl group, a second organopolysiloxane having a hydrogen atom bonded to a silicon atom, a hydrosilylation reaction catalyst, And a first silane compound having a ureido group or an isocyanate group.
  • the optical semiconductor device using the curable composition for optical semiconductor devices is cured even when used in harsh environments under high temperature and high humidity.
  • cured can be suppressed.
  • the curable composition when the optical semiconductor device is sealed using the curable composition for optical semiconductor devices according to the present invention or a lens is formed above the optical semiconductor device, the curable composition is cured. It becomes difficult for the object to peel from the object to be bonded.
  • the material of a package such as a sealant or a housing material in contact with a lens may be polyphthalamide (PPA).
  • PPA polyphthalamide
  • an electrode plated with silver may be formed on the back surface of the light emitting element.
  • the present inventors do not sufficiently increase the adhesiveness of the cured product to the object to be bonded. I found out. In particular, in the optical semiconductor device used for the curable composition for optical semiconductor devices, it is difficult to sufficiently enhance the adhesion of the cured product to the object to be bonded.
  • the inventor has a ureido group or an isocyanate group together with a first organopolysiloxane having an alkenyl group, a second organopolysiloxane having a hydrogen atom bonded to a silicon atom, and a catalyst for hydrosilylation reaction. It has been found that by adopting a composition further containing the first silane compound, the adhesion of the cured product to the object to be bonded can be sufficiently enhanced.
  • the present inventors use the first silane compound having a ureido group out of the first silane compound having a ureido group and the first silane compound having an isocyanate group, so that the cured product can be bonded. It has been found that the adhesion to objects is even higher.
  • the present inventors provide a ureido group in a composition comprising a first organopolysiloxane having an alkenyl group, a second organopolysiloxane having a hydrogen atom bonded to a silicon atom, and a catalyst for hydrosilylation reaction.
  • a first silane compound having an isocyanate group is used, the viscosity of the curable composition for optical semiconductor devices hardly changes, and the pot life of the curable composition for optical semiconductor devices is improved.
  • a curable composition for an optical semiconductor device comprising a first organopolysiloxane having an alkenyl group, a second organopolysiloxane having a hydrogen atom bonded to a silicon atom, and a hydrosilylation reaction catalyst is also obtained at room temperature.
  • the polymerization reaction proceeds slowly. For this reason, the viscosity of the curable composition gradually increases even at room temperature. Therefore, the first organopolysiloxane having an alkenyl group and the second organopolysiloxane having a hydrogen atom bonded to a silicon atom are provided as two separate liquids (first and second liquids). There is. These two liquids are mixed and used immediately before use by the user.
  • the hydrosilylation reaction catalyst is contained in at least one of the first liquid containing the first organopolysiloxane and the second liquid containing the second organopolysiloxane.
  • the reaction starts when the two liquids are mixed, so that the viscosity increases.
  • the discharge amount when dispensing the curable composition changes, and it becomes difficult to maintain a certain shape.
  • the sealing agent may be insufficiently filled or the lens shape may be deteriorated.
  • the ratio ( ⁇ 1 / ⁇ 2) of the curable composition (the curable composition immediately after preparation) to the viscosity ⁇ 2 is preferably 2 or less, more preferably 1.5 or less, and still more preferably 1.3 or less.
  • the ratio ( ⁇ 1 / ⁇ 2) is generally 1 or more, but may be 0.7 or more, for example, or 0.8 or more.
  • the viscosity change of the curable composition is small, that is, if the pot life of the curable composition is good, it is easy to manufacture an optical semiconductor device of a certain quality under a certain production condition.
  • the first organopolysiloxane is represented by the formula (1A) and is a first organopolysiloxane having an alkenyl group and a methyl group bonded to a silicon atom, or represented by the formula (1B) and an aryl
  • a first organopolysiloxane having a group and an alkenyl group is preferred.
  • a first organopolysiloxane different from the first organopolysiloxane represented by the formula (1A) or the formula (1B) may be used.
  • the second organopolysiloxane has an alkenyl group
  • the first organopolysiloxane preferably does not have a hydrogen atom bonded to a silicon atom.
  • the first organopolysiloxane preferably does not have a hydrogen atom bonded to a silicon atom.
  • the second organopolysiloxane is a second organopolysiloxane represented by the formula (51A) and having a hydrogen atom bonded to a silicon atom and a methyl group bonded to a silicon atom, or the formula (51B) And is preferably a second organopolysiloxane having an aryl group and a hydrogen atom bonded to a silicon atom.
  • a second organopolysiloxane different from the second organopolysiloxane represented by the formula (51A) or the formula (51B) may be used.
  • the organopolysiloxane represented by the formula (1A) is a first organopolysiloxane having a methyl group bonded to an alkenyl group and a silicon atom
  • the second organopolysiloxane is represented by the formula (51A)
  • a second organopolysiloxane having a hydrogen atom bonded to a silicon atom and a methyl group bonded to a silicon atom, or the first organopolysiloxane is represented by the formula (1B) and is aryl
  • the first organopolysiloxane having a group and an alkenyl group, and the second organopolysiloxane is represented by the formula (51B). It is preferred aryl group and a silicon atom is
  • a cured product of a conventional curable composition for optical semiconductor devices when used in a harsh environment such as a temperature cycle that repeatedly receives heating and cooling, the cured product is cracked or the cured product is a housing material. It may peel off from etc.
  • a cured product of a conventional curable composition for optical semiconductor devices has a problem that heat resistance is low.
  • the first organopolysiloxane is a first organopolysiloxane represented by the formula (1A) and having an alkenyl group and a methyl group bonded to a silicon atom.
  • the second organopolysiloxane is preferably the second organopolysiloxane represented by the formula (51A) and having a hydrogen atom bonded to a silicon atom and a methyl group bonded to a silicon atom.
  • the content ratios of methyl groups bonded to silicon atoms in the first organopolysiloxane and the second organopolysiloxane are each 80 mol% or more. preferable.
  • the content ratio of the methyl group bonded to the silicon atom is represented by the following formula (X).
  • the “functional group” means a group directly bonded to a silicon atom in the first organopolysiloxane or the second organopolysiloxane.
  • “average molecular weight of functional groups” means the sum of “average number of functional groups ⁇ functional group molecular weight” of each functional group. The same applies to “functional group” and “average molecular weight of functional group” in the following formula (Y).
  • a silver-plated electrode may be formed on the back surface of the light emitting element in order to reflect the light reaching the back side of the light emitting element. If a crack occurs in the sealant or the lens, or the sealant is peeled off from the housing material, the silver-plated electrode is exposed to the atmosphere or easily exposed to the atmosphere. As a result, the silver plating may be discolored by a corrosive gas such as hydrogen sulfide gas or sulfurous acid gas present in the atmosphere. When the color of the electrode changes, the reflectance decreases, which causes a problem that the brightness of the light emitted from the light emitting element decreases.
  • a corrosive gas such as hydrogen sulfide gas or sulfurous acid gas
  • the sealant or lens formed by the cured product of the curable composition has a high gas barrier property against corrosive gas, thereby suppressing discoloration of silver plating and lowering the brightness of light emitted from the light emitting element. Can be suppressed.
  • the first organopolysiloxane is the first organopolysiloxane represented by the formula (1B) and having an aryl group and an alkenyl group
  • the first The second organopolysiloxane represented by the formula (51B) is preferably a second organopolysiloxane having an aryl group and a hydrogen atom bonded to a silicon atom.
  • the content ratios of aryl groups in the first organopolysiloxane and the second organopolysiloxane are 30 mol% or more and 85 mol% or less, respectively. preferable.
  • the content ratio of the aryl group is represented by the following formula (Y).
  • aryl group (mol%) ⁇ (average number of aryl groups contained in one molecule of the first organopolysiloxane or the second organopolysiloxane ⁇ molecular weight of the aryl group) / (the first The average number of functional groups bonded to silicon atoms contained in one molecule of the second organopolysiloxane or the average molecular weight of the functional groups) ⁇ ⁇ 100 Formula (Y)
  • the content ratio of the aryl group indicates the content ratio of the phenyl group.
  • an optical semiconductor device using the above-described curable composition for optical semiconductor devices is provided. That is, according to a broad aspect of the present invention, an optical semiconductor element and a sealing agent disposed so as to seal the optical semiconductor element or a lens disposed on the optical semiconductor element are provided, and the sealing is performed.
  • An optical semiconductor device is provided in which the stopper or the lens is formed by curing a curable composition for an optical semiconductor device.
  • the curable composition for an optical semiconductor device used in the optical semiconductor device includes a first organopolysiloxane having two or more alkenyl groups and a second organopolysiloxane having two or more hydrogen atoms bonded to silicon atoms. And a hydrosilylation reaction catalyst and a first silane compound having a ureido group or an isocyanate group.
  • the cured product obtained by curing the curable composition can be prevented from being peeled off from the adhesion target, and further cured for an optical semiconductor device. Since the pot life of the composition is good, a homogeneous optical semiconductor device can be provided.
  • the first organopolysiloxane contained in the curable composition for optical semiconductor devices according to the present invention has two or more alkenyl groups.
  • the alkenyl group is preferably directly bonded to the silicon atom.
  • the carbon atom in the carbon-carbon double bond of the alkenyl group may be bonded to the silicon atom, and the carbon atom different from the carbon atom in the carbon-carbon double bond of the alkenyl group is bonded to the silicon atom. It may be bonded.
  • As for said 1st organopolysiloxane only 1 type may be used and 2 or more types may be used together.
  • the first organopolysiloxane is represented by the following formula (1A), and includes a first organopolysiloxane having an alkenyl group and a methyl group bonded to a silicon atom.
  • Siloxane hereinafter sometimes referred to as first organopolysiloxane A
  • the first organopolysiloxane A is preferably a first organopolysiloxane which does not have a hydrogen atom bonded to a silicon atom but has an alkenyl group and a methyl group bonded to a silicon atom.
  • R1 to R6 each represents at least one alkenyl group, at least one represents a methyl group, and R1 to R6 other than the alkenyl group and the methyl group represent a hydrocarbon group having 2 to 8 carbon atoms. .
  • the first organopolysiloxane is represented by the following formula (1B) and has a first organopolysiloxane having an aryl group and an alkenyl group (hereinafter referred to as the first organopolysiloxane). 1 may be referred to as organopolysiloxane B).
  • the first organopolysiloxane B is preferably a first organopolysiloxane which does not have a hydrogen atom bonded to a silicon atom and has an aryl group and an alkenyl group.
  • the aryl group include an unsubstituted phenyl group and a substituted phenyl group.
  • the structural unit represented by (R4R5SiO 2/2 ) and the structural unit represented by (R6SiO 3/2 ) each have an alkoxy group. It may have a hydroxy group.
  • the above formula (1A) and the above formula (1B) show an average composition formula.
  • the hydrocarbon group in the above formula (1A) and the above formula (1B) may be linear or branched.
  • R1 to R6 in the above formula (1A) and the above formula (1B) may be the same or different.
  • the oxygen atom part in the structural unit represented by (R4R5SiO 2/2 ) and the oxygen atom part in the structural unit represented by (R6SiO 3/2 ) are respectively siloxane.
  • An oxygen atom part forming a bond, an oxygen atom part of an alkoxy group, or an oxygen atom part of a hydroxy group is shown.
  • the content of alkoxy groups is small, and the content of hydroxy groups is also small.
  • an organosilicon compound such as an alkoxysilane compound is hydrolyzed and polycondensed to obtain a first organopolysiloxane
  • most of the alkoxy groups and hydroxy groups are converted into a partial skeleton of siloxane bonds. It is to be done. That is, most of oxygen atoms of the alkoxy group and oxygen atoms of the hydroxy group are converted into oxygen atoms forming a siloxane bond.
  • alkenyl group examples include vinyl group, allyl group, butenyl group, pentenyl group, and hexenyl group.
  • the alkenyl group in the first organopolysiloxane and the alkenyl group in the above formula (1A) and the above formula (1B) are preferably vinyl groups or allyl groups. More preferably, it is a group.
  • the first organopolysiloxane preferably has a vinyl group.
  • the hydrocarbon group having 2 to 8 carbon atoms in the above formula (1A) is not particularly limited, and examples thereof include ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, and n-heptyl. Group, n-octyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, isohexyl group, cyclohexyl group and aryl group.
  • Examples of the hydrocarbon group having 1 to 8 carbon atoms in the above formula (1B) include the same groups as the hydrocarbon group having 2 to 8 carbon atoms in the above formula (1A), and further includes a methyl group.
  • the first organopolysiloxane contains one vinyl group and two carbon atoms per silicon atom. It preferably contains a structural unit bonded to a hydrocarbon group of 1 to 8 (methyl group or hydrocarbon group of 2 to 8 carbon atoms).
  • (R1R2R3SiO 1 / The structural unit represented by 2 ) includes a structural unit in which R1 represents a vinyl group, and R2 and R3 represent a hydrocarbon group having 1 to 8 carbon atoms (methyl group or hydrocarbon group having 2 to 8 carbon atoms). It is preferable.
  • the structural unit represented by (R1R2R3SiO 1/2 ) may contain only the structural unit represented by the following formula (1-a), and the structural unit represented by the following formula (1-a) and And a structural unit other than the structural unit represented by the formula (1-a).
  • the presence of the structural unit represented by the following formula (1-a) allows a vinyl group to be present at the terminal, and the presence of the vinyl group at the terminal increases the opportunity for reaction, and the curability of the curable composition. Can be further increased.
  • the terminal oxygen atom generally forms a siloxane bond with an adjacent silicon atom, and shares an oxygen atom with the adjacent structural unit. Therefore, one oxygen atom at the terminal is defined as “O 1/2 ”.
  • R2 and R3 each represent a hydrocarbon group having 1 to 8 carbon atoms.
  • the content ratio of methyl groups bonded to silicon atoms in the first organopolysiloxane A is preferably 80 mol% or more.
  • the content ratio of the methyl group bonded to the silicon atom is obtained from the following formula (X1).
  • the content ratio of the methyl group is 80 mol% or more, the heat resistance of the cured product becomes considerably high, and even if the optical semiconductor device is used in a harsh environment under high temperature and high humidity, Is difficult to decrease and discoloration of the cured product is difficult to occur.
  • the content ratio of the methyl group bonded to the silicon atom in the first organopolysiloxane A is preferably 85 mol% or more, preferably 99.9 mol% or less, more preferably 99 mol% or less, and still more preferably 98 mol%. It is less than mol%.
  • the content ratio of the methyl group is not less than the above lower limit, the heat resistance of the cured product is further enhanced.
  • the content ratio of the methyl group is not more than the above upper limit, alkenyl groups can be sufficiently introduced, and it is easy to improve the curability of the curable composition.
  • the content ratio of the aryl group in the first organopolysiloxane B is preferably 30 mol% or more, and preferably 85 mol% or less.
  • the content ratio of this aryl group is calculated
  • the content ratio of the aryl group is 30 mol% or more, the gas barrier property of the cured product is further enhanced, and cracks and peeling are less likely to occur in the cured product.
  • the content ratio of the aryl group is 85 mol% or less, peeling of the cured product is more difficult to occur.
  • the content ratio of the aryl group in the first organopolysiloxane B is more preferably 35 mol% or more.
  • the content ratio of the aryl group in the first organopolysiloxane B is more preferably 80 mol% or less, still more preferably 75 mol% or less, and particularly preferably 70 mol%. Hereinafter, it is most preferably 65 mol% or less.
  • the first organopolysiloxane A preferably has an aryl group.
  • the aryl group include an unsubstituted phenyl group and a substituted phenyl group.
  • the content ratio of the aryl group in the first organopolysiloxane A is preferably 0.5 mol% or more, preferably 10 mol% or less, more preferably 5 mol% or less.
  • the heat resistance of the cured product is further improved.
  • the structural unit represented by (R4R5SiO 2/2 ) (hereinafter also referred to as a bifunctional structural unit) has the following formula ( The structure represented by 1-2), that is, a structure in which one of the oxygen atoms bonded to the silicon atom in the bifunctional structural unit forms a hydroxy group or an alkoxy group may be included.
  • the structural unit represented by (R4R5SiO 2/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (1-b), and is further represented by the following formula (1-2-b). A portion surrounded by a broken line of the structural unit may be included. That is, a structural unit having a group represented by R4 and R5 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R4R5SiO 2/2 ).
  • the structural unit represented by (R4R5SiO 2/2 ) is a broken line of the structural unit represented by the following formula (1-b) The part enclosed by is shown.
  • the structural unit represented by (R4R5SiO 2/2 ) having the remaining alkoxy group or hydroxy group has the following formula: A portion surrounded by a broken line in the structural unit represented by (1-2-b) is shown.
  • the oxygen atom in the Si—O—Si bond forms a siloxane bond with the adjacent silicon atom, and the adjacent structural unit and oxygen atom Sharing. Accordingly, one oxygen atom in the Si—O—Si bond is defined as “O 1/2 ”.
  • X represents OH or OR
  • OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms.
  • R4 and R5 in formula (1-b), formula (1-2), and formula (1-2-b) are the same groups as R4 and R5 in formula (1A) and formula (1B). It is.
  • the structural unit represented by (R6SiO 3/2 ) (hereinafter also referred to as trifunctional structural unit) has the following formula ( 1-3) or a structure represented by formula (1-4), that is, a structure in which two oxygen atoms bonded to a silicon atom in a trifunctional structural unit each constitute a hydroxy group or an alkoxy group, or a trifunctional
  • One of the oxygen atoms bonded to the silicon atom in the structural unit may include a structure constituting a hydroxy group or an alkoxy group.
  • the structural unit represented by (R6SiO 3/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (1-c), and further includes the following formula (1-3-c) or formula ( A portion surrounded by a broken line of the structural unit represented by 1-4-4-c) may be included. That is, a structural unit having a group represented by R6 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R6SiO 3/2 ).
  • R6 in the above formula (1-c), formula (1-3), formula (1-3-c), formula (1-4) and formula (1-4-c) represents the above formula (1A) and It is the same group as R6 in the above formula (1B).
  • the linear or branched alkoxy group having 1 to 4 carbon atoms is not particularly limited.
  • the lower limit of a / (a + b + c) is 0, and the upper limit is 0.30.
  • a / (a + b + c) is less than or equal to the above upper limit, the heat resistance of the cured product is further increased, and peeling of the cured product can be further suppressed.
  • a / (a + b + c) becomes like this. Preferably it is 0.25 or less, More preferably, it is 0.20 or less.
  • the lower limit of b / (a + b + c) is 0.70, and the upper limit is 1.0.
  • b / (a + b + c) is not less than the above lower limit, the cured product does not become too hard, and cracks hardly occur in the cured product.
  • b / (a + b + c) is preferably 0.75 or more, more preferably 0.80 or more.
  • the lower limit of c / (a + b + c) is 0, and the upper limit is 0.10.
  • c / (a + b + c) is not more than the above upper limit, it is easy to maintain an appropriate viscosity of the curable composition, and the adhesiveness of the cured product is further enhanced.
  • c / (a + b + c) is preferably 0.05 or less.
  • the structural unit of (R6SiO 3/2 ) does not exist in the above formula (1A).
  • C / (a + b + c) in the above formula (1A) is preferably 0. That is, the first organopolysiloxane represented by the above formula (1A) is preferably the first organopolysiloxane represented by the following formula (1Aa). As a result, cracks are less likely to occur in the cured product, and the cured product is more difficult to peel from the housing material or the like.
  • a / (a + b) is preferably 0.25 or less, more preferably 0.20 or less, and still more preferably 0.15 or less.
  • b / (a + b) is preferably 0.75 or more, more preferably 0.80 or more, and further preferably 0.85 or more.
  • a / (a + b + c) is 0 or more and 0.50 or less.
  • a / (a + b + c) is less than or equal to the above upper limit, the heat resistance of the cured product is further increased, and peeling of the cured product can be further suppressed.
  • a / (a + b + c) is preferably 0.45 or less, more preferably 0.40 or less.
  • b / (a + b + c) is 0.40 or more and 1.0 or less.
  • b / (a + b + c) is not less than the above lower limit, the cured product does not become too hard, and cracks hardly occur in the cured product.
  • b / (a + b + c) is preferably 0.50 or more.
  • c / (a + b + c) is 0 or more and 0.50 or less.
  • c / (a + b + c) is not more than the above upper limit, it is easy to maintain an appropriate viscosity of the curable composition, and the adhesiveness of the cured product is further enhanced.
  • c / (a + b + c) is preferably 0.45 or less, more preferably 0.40 or less, and still more preferably 0.35 or less.
  • the structural unit of (R6SiO 3/2 ) does not exist in the above formula (1B).
  • C / (a + b + c) in the above formula (1B) is preferably 0. That is, the first organopolysiloxane represented by the above formula (1B) is preferably the first organopolysiloxane represented by the following formula (1Bb). As a result, cracks are less likely to occur in the cured product, and peeling of the cured product is further less likely to occur.
  • a / (a + b) in the above formula (1Bb) is preferably 0.45 or less, more preferably 0.40 or less.
  • b / (a + b) is preferably 0.55 or more, more preferably 0.60 or more.
  • NMR si-nuclear magnetic resonance analysis
  • TMS tetramethylsilane
  • Each peak corresponding to the structural unit represented by (R4R5SiO 2/2 ) and the bifunctional structural unit of the above formula (1-2) appears in the vicinity of ⁇ 10 to ⁇ 50 ppm, and the above formula (1A) and the above formula (1B )
  • the ratio of each structural unit in the above formula (1A) and the above formula (1B) can be measured by measuring 29 Si-NMR and comparing the peak areas of the respective signals.
  • the second organopolysiloxane contained in the curable composition for optical semiconductor devices according to the present invention has two or more hydrogen atoms bonded to silicon atoms.
  • the hydrogen atom is directly bonded to the silicon atom.
  • As for said 2nd organopolysiloxane only 1 type may be used and 2 or more types may be used together.
  • the second organopolysiloxane may contain a structural unit in which three oxygen atoms are bonded to one silicon atom.
  • one hydrogen atom may be bonded to the silicon atom to which three oxygen atoms are bonded, and one hydrocarbon group having 1 to 8 carbon atoms (methyl group or hydrocarbon having 2 to 8 carbon atoms). Group) may be bonded.
  • the second organopolysiloxane is represented by the following formula (51A) and has a hydrogen atom bonded to a silicon atom and a methyl group bonded to the silicon atom.
  • a second organopolysiloxane (hereinafter sometimes referred to as a second organopolysiloxane A) is preferred.
  • R51 to R56 each represents at least one hydrogen atom, at least one represents a methyl group, and R51 to R56 other than the hydrogen atom and the methyl group are hydrocarbon groups having 2 to 8 carbon atoms. Represents.
  • the second organopolysiloxane is represented by the following formula (51B), and includes a second organopolysiloxane having an aryl group and a hydrogen atom bonded to a silicon atom.
  • Siloxane hereinafter sometimes referred to as second organopolysiloxane B
  • the aryl group include an unsubstituted phenyl group and a substituted phenyl group.
  • R51 to R56 represents an aryl group
  • R51 to R56 other than the aryl group and the hydrogen atom are carbon atoms having 1 to 8 carbon atoms. Represents a hydrogen group.
  • the structural unit represented by (R54R55SiO 2/2 ) and the structural unit represented by (R56SiO 3/2 ) each have an alkoxy group. It may have a hydroxy group.
  • the above formula (51A) and the above formula (51B) show the average composition formula.
  • the hydrocarbon group in the above formula (51A) and the above formula (51B) may be linear or branched.
  • R51 to R56 in the above formula (51A) and the above formula (51B) may be the same or different.
  • the oxygen atom part in the structural unit represented by (R54R55SiO 2/2 ) and the oxygen atom part in the structural unit represented by (R56SiO 3/2 ) are respectively siloxane.
  • An oxygen atom part forming a bond, an oxygen atom part of an alkoxy group, or an oxygen atom part of a hydroxy group is shown.
  • the hydrocarbon group having 2 to 8 carbon atoms in the formula (51A) is not particularly limited, and examples thereof include an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and an n-heptyl group.
  • Examples of the hydrocarbon group having 1 to 8 carbon atoms in the above formula (51B) include the same groups as the hydrocarbon group having 2 to 8 carbon atoms in the above formula (51A), and further includes a methyl group.
  • the second organopolysiloxane contains one hydrogen atom and two carbon atoms in one silicon atom. It preferably contains a structural unit bonded to a hydrocarbon group of 1 to 8 (methyl group or hydrocarbon group of 2 to 8 carbon atoms).
  • (R51R52R53SiO 1 / The structural unit represented by 2 ) includes a structural unit in which R51 represents a hydrogen atom, and R52 and R53 represent a hydrocarbon group having 1 to 8 carbon atoms (a methyl group or a hydrocarbon group having 2 to 8 carbon atoms). It is preferable.
  • the second organopolysiloxane has a structural unit represented by (HR52R53SiO 1/2 ). In other words, it preferably has a structural unit represented by the following formula (51-a).
  • the structural unit represented by (R51R52R53SiO 1/2 ) may contain only the structural unit represented by the following formula (51-a), and the structural unit represented by the following formula (51-a) And a structural unit other than the structural unit represented by the formula (51-a). Due to the presence of the structural unit represented by the following formula (51-a), a hydrogen atom can be present at the terminal.
  • the terminal oxygen atom generally forms a siloxane bond with an adjacent silicon atom, and shares an oxygen atom with the adjacent structural unit. Therefore, one oxygen atom at the terminal is defined as “O 1/2 ”.
  • R52 and R53 each represent a methyl group or a hydrocarbon group having 2 to 8 carbon atoms.
  • the first organopolysiloxane is a structural unit represented by the above formula (1-a). It is particularly preferable that the second organopolysiloxane has a structural unit represented by the above formula (51-a).
  • the second organopolysiloxane preferably has an alkenyl group, and more preferably has a vinyl group.
  • at least one of R51 to R56 represents a silicon atom, at least one represents a methyl group, at least one represents an alkenyl group, a hydrogen atom, a methyl group, and R51 to R56 other than the alkenyl group represent a hydrocarbon group having 2 to 8 carbon atoms.
  • At least one of R51 to R56 represents an aryl group, at least one represents a silicon atom, at least one represents an alkenyl group, and other than an aryl group, a hydrogen atom, and an alkenyl group R51 to R56 each represents a hydrocarbon group having 2 to 8 carbon atoms.
  • the content ratio of methyl groups bonded to silicon atoms in the second organopolysiloxane A is preferably 80 mol% or more.
  • the content ratio of the methyl group bonded to the silicon atom is obtained from the following formula (X51).
  • the content ratio of the methyl group bonded to the silicon atom in the second organopolysiloxane is preferably 85 mol% or more, preferably 99.9 mol% or less, more preferably 99 mol% or less, and still more preferably 98 mol%. % Or less.
  • the content ratio of the methyl group is not less than the preferable lower limit, the heat resistance of the cured product is further enhanced.
  • the content ratio of the methyl group is not more than the above upper limit, hydrogen atoms bonded to silicon atoms can be sufficiently introduced, and it is easy to improve the curability of the curable composition.
  • the content ratio of the aryl group in the second organopolysiloxane B is preferably 30 mol% or more, and preferably 85 mol% or less.
  • the content ratio of this aryl group is calculated
  • the content ratio of the aryl group is 30 mol% or more, the gas barrier property of the cured product is further enhanced, and cracks and peeling are less likely to occur in the cured product.
  • the content ratio of the aryl group is 85 mol% or less, peeling of the cured product is more difficult to occur.
  • the content ratio of the aryl group in the second organopolysiloxane B is more preferably 35 mol% or more.
  • the content ratio of the aryl group in the second organopolysiloxane B is more preferably 80 mol% or less, still more preferably 75 mol% or less, and particularly preferably 70 mol%. Hereinafter, it is most preferably 65 mol% or less.
  • Aryl group content (mol%) (average number of aryl groups contained in one molecule of the second organopolysiloxane ⁇ molecular weight of aryl group / included in one molecule of the second organopolysiloxane) Average number of functional groups bonded to silicon atoms ⁇ average molecular weight of functional groups) ⁇ 100 Formula (Y51)
  • the second organopolysiloxane A preferably has an aryl group.
  • the aryl group include an unsubstituted phenyl group and a substituted phenyl group.
  • the content ratio of the aryl group in the second organopolysiloxane A is preferably 0.5 mol% or more, preferably 10 mol% or less, more preferably 5 mol% or less.
  • the heat resistance of the cured product is further improved.
  • the structural unit represented by (R54R55SiO 2/2 ) (hereinafter also referred to as a bifunctional structural unit) has the following formula ( 51-2), that is, a structure in which one of oxygen atoms bonded to a silicon atom in the bifunctional structural unit constitutes a hydroxy group or an alkoxy group may be included.
  • the structural unit represented by (R54R55SiO 2/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (51-b), and is further represented by the following formula (51-2-b). A portion surrounded by a broken line of the structural unit may be included. That is, a structural unit having a group represented by R54 and R55 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R54R55SiO 2/2 ).
  • X represents OH or OR
  • OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms.
  • R54 and R55 in the formula (51-b), formula (51-2) and formula (51-2-b) are the same groups as R54 and R55 in the formula (51A) and the formula (51B). It is.
  • the structural unit represented by (R56SiO 3/2 ) (hereinafter also referred to as trifunctional structural unit) has the following formula ( 51-3) or a structure represented by formula (51-4), that is, a structure in which two oxygen atoms bonded to a silicon atom in a trifunctional structural unit each constitute a hydroxy group or an alkoxy group, or a trifunctional
  • One of the oxygen atoms bonded to the silicon atom in the structural unit may include a structure constituting a hydroxy group or an alkoxy group.
  • the structural unit represented by (R56SiO 3/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (51-c), and further includes the following formula (51-3-c) or formula ( A part surrounded by a broken line of the structural unit represented by 51-4-c) may be included. That is, a structural unit having a group represented by R56 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R56SiO 3/2 ).
  • R56 in the above formula (51-c), formula (51-3), formula (51-3-c), formula (51-4) and formula (51-4-c) represents the above formula (51A) and It is the same group as R56 in the above formula (51B).
  • the linear or branched alkoxy group having 1 to 4 carbon atoms is not particularly limited.
  • the lower limit of p / (p + q + r) is 0.10 and the upper limit is 0.50.
  • p / (p + q + r) is less than or equal to the above upper limit, the hardness of the cured product is increased, adhesion of scratches and dust can be prevented, the heat resistance of the cured product is further increased, and peeling of the cured product can be further suppressed.
  • p / (p + q + r) becomes like this. Preferably it is 0.45 or less, More preferably, it is 0.40 or less.
  • the lower limit of q / (p + q + r) is 0, and the upper limit is 0.40.
  • q / (p + q + r) exceeds 0, the cured product does not become too hard and cracks are hardly generated in the cured product.
  • q / (p + q + r) becomes like this.
  • it is 0.10 or more, More preferably, it is 0.15 or more.
  • the structural unit of (R54R55SiO 2/2 ) does not exist in the above formula (51A).
  • the lower limit of r / (p + q + r) is 0.40, and the upper limit is 0.90.
  • r / (p + q + r) is not less than the above lower limit, the hardness of the cured product is increased, and scratches and dust can be prevented from adhering.
  • r / (p + q + r) is not more than the above upper limit, it is easy to maintain an appropriate viscosity of the curable composition, and the adhesiveness of the cured product is further enhanced.
  • p / (p + q + r) is 0.05 or more and 0.50 or less.
  • p / (p + q + r) is less than or equal to the above upper limit, the heat resistance of the cured product is further increased, and peeling of the cured product can be further suppressed.
  • p / (p + q + r) becomes like this.
  • it is 0.10 or more, Preferably it is 0.45 or less.
  • q / (p + q + r) is 0.05 or more and 0.50 or less.
  • q / (p + q + r) is not less than the above lower limit, the cured product does not become too hard and cracks are hardly generated in the cured product.
  • q / (p + q + r) is not more than the above upper limit, the gas barrier property of the cured product is further enhanced.
  • q / (p + q + r) is preferably 0.10 or more, and preferably 0.45 or less.
  • r / (p + q + r) is 0.20 or more and 0.80 or less.
  • r / (p + q + r) is equal to or greater than the above lower limit, the hardness of the cured product is increased, scratches and dust can be prevented, the heat resistance of the cured product is increased, and the thickness of the cured product is less likely to decrease in a high temperature environment.
  • r / (p + q + r) is not more than the above upper limit, it is easy to maintain an appropriate viscosity of the curable composition, and the adhesiveness of the cured product is further enhanced.
  • the ratio of each structural unit in the above formula (51A) and the above formula (51B) can be measured by measuring 29 Si-NMR and comparing the peak areas of the respective signals.
  • the content of the second organopolysiloxane is preferably 10 parts by weight or more, more preferably 15 parts by weight or more, still more preferably 20 parts by weight or more, preferably 100 parts by weight of the first organopolysiloxane. 400 parts by weight or less, more preferably 300 parts by weight or less, still more preferably 200 parts by weight or less.
  • a curable composition more excellent in curability can be obtained.
  • the number average molecular weight (Mn) of the first organopolysiloxane is preferably 500 or more, more preferably 1000 or more, still more preferably 5000 or more, preferably 200000 or less, more preferably 100000 or less, still more preferably 60000 or less, Particularly preferred is 10,000 or less, and most preferred is 8000 or less.
  • the number average molecular weight (Mn) of the first organopolysiloxane represented by the above formula (1A) is preferably 500 or more, more preferably 1000 or more, further preferably 5000 or more, preferably 200000 or less, more preferably 100000. Hereinafter, it is more preferably 60000 or less.
  • the number average molecular weight (Mn) of the first organopolysiloxane represented by the above formula (1B) is preferably 500 or more, more preferably 1000 or more, preferably 10,000 or less, more preferably 8000 or less.
  • the number average molecular weights (Mn) of the second organopolysiloxane, the second organopolysiloxane represented by the formula (51A), and the second organopolysiloxane represented by the formula (51B) are each preferably Is 500 or more, more preferably 1000 or more, preferably 20000 or less, more preferably 10,000 or less.
  • the number average molecular weight is not less than the above lower limit, the volatile components are reduced at the time of thermosetting, and the thickness of the cured product is hardly reduced under a high temperature environment.
  • the number average molecular weight is not more than the above upper limit, viscosity adjustment is easy.
  • the number average molecular weight (Mn) is a value obtained by using polystyrene as a standard substance using gel permeation chromatography (GPC).
  • the number average molecular weight (Mn) is determined by two measuring devices manufactured by Waters (column: Shodex GPC LF-804 (length: 300 mm) manufactured by Showa Denko KK), measuring temperature: 40 ° C., flow rate: 1 mL / min, solvent: Tetrahydrofuran, standard substance: polystyrene) means a value measured.
  • the method for synthesizing the first and second organopolysiloxanes is not particularly limited, and examples thereof include a method in which an alkoxysilane compound is hydrolyzed and subjected to a condensation reaction, and a method in which a chlorosilane compound is hydrolyzed and condensed. Especially, the method of hydrolyzing and condensing an alkoxysilane compound from a viewpoint of reaction control is preferable.
  • Examples of the method of hydrolyzing and condensing the alkoxysilane compound include a method of reacting an alkoxysilane compound in the presence of water and an acidic catalyst or a basic catalyst. Further, the disiloxane compound may be hydrolyzed and used.
  • organosilicon compound for introducing an alkenyl group into the first organopolysiloxane examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, methoxydimethylvinylsilane, vinyldimethylethoxysilane, and 1,3-divinyl. -1,1,3,3-tetramethyldisiloxane and the like.
  • organosilicon compound for introducing a hydrogen atom bonded to a silicon atom into the second organopolysiloxane examples include trimethoxysilane, triethoxysilane, methyldimethoxysilane, methyldiethoxysilane, and 1,1,3, Examples include 3-tetramethyldisiloxane.
  • organosilicon compound for introducing an aryl group into the first and second organopolysiloxanes as necessary include triphenylmethoxysilane, triphenylethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methyl (phenyl) ) Dimethoxysilane, phenyltrimethoxysilane and the like.
  • organosilicon compounds examples include silane, cyclohexyl (methyl) dimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, and octyltrimethoxysilane.
  • Examples of the acidic catalyst include inorganic acids, organic acids, acid anhydrides of inorganic acids and derivatives thereof, and acid anhydrides of organic acids and derivatives thereof.
  • Examples of the inorganic acid include hydrochloric acid, phosphoric acid, boric acid, and carbonic acid.
  • examples of the organic acid include formic acid, acetic acid, propionic acid, butyric acid, lactic acid, malic acid, tartaric acid, citric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid and oleic acid. Is mentioned.
  • Examples of the basic catalyst include alkali metal hydroxides, alkali metal alkoxides, and alkali metal silanol compounds.
  • alkali metal hydroxide examples include sodium hydroxide, potassium hydroxide and cesium hydroxide.
  • alkali metal alkoxide include sodium-t-butoxide, potassium-t-butoxide, and cesium-t-butoxide.
  • alkali metal silanol compound examples include a sodium silanolate compound, a potassium silanolate compound, and a cesium silanolate compound.
  • a potassium catalyst or a cesium catalyst is preferable.
  • the hydrosilylation reaction catalyst contained in the curable composition for optical semiconductor devices according to the present invention is bonded to an alkenyl group in the first organopolysiloxane and a silicon atom in the second organopolysiloxane. It is a catalyst for the hydrosilylation reaction between the hydrogen atom.
  • hydrosilylation reaction catalyst various catalysts that cause the hydrosilylation reaction to proceed can be used.
  • the said catalyst for hydrosilylation reaction only 1 type may be used and 2 or more types may be used together.
  • hydrosilylation reaction catalyst examples include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Since the transparency of the cured product is increased, a platinum-based catalyst is preferable.
  • platinum-based catalyst examples include platinum powder, chloroplatinic acid, platinum-alkenylsiloxane complex, platinum-olefin complex, and platinum-carbonyl complex.
  • platinum-alkenylsiloxane complex or a platinum-olefin complex is preferred.
  • Examples of the alkenylsiloxane in the platinum-alkenylsiloxane complex include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 1,3,5,7-tetramethyl-1,3,5. , 7-tetravinylcyclotetrasiloxane and the like.
  • Examples of the olefin in the platinum-olefin complex include allyl ether and 1,6-heptadiene.
  • alkenylsiloxane is preferably 1,3-divinyl-1,1,3,3-tetramethyldisiloxane.
  • the organosiloxane oligomer is preferably a dimethylsiloxane oligomer.
  • the olefin is preferably 1,6-heptadiene.
  • the content of the catalyst for hydrosilylation reaction is preferably 0.01 ppm or more, more preferably 1 ppm or more, preferably in terms of weight units of metal atoms (platinum atoms in the case of platinum alkenyl complexes). Is 1000 ppm or less, more preferably 500 ppm or less.
  • the content of the hydrosilylation reaction catalyst is not less than the above lower limit, it is easy to sufficiently cure the curable composition.
  • the content of the catalyst for hydrosilylation reaction is not more than the above upper limit, the problem of coloring of the cured product hardly occurs.
  • the curable composition for optical semiconductor devices according to the present invention includes a first silane compound having a ureido group or an isocyanate group.
  • a first silane compound having a ureido group or an isocyanate group By using the first silane compound having this specific group, even if the optical semiconductor device is used in a harsh environment under high temperature and high humidity, the curable composition is cured from the bonded object of the cured product. Peeling is less likely to occur.
  • the first silane compound may have a ureido group or an isocyanate group.
  • the composition comprising the first organopolysiloxane having an alkenyl group, the second organopolysiloxane having a hydrogen atom bonded to a silicon atom, and a catalyst for hydrosilylation reaction, the second organopolysiloxane having an ureido group or an isocyanate group.
  • 1 silane compound By using 1 silane compound, the viscosity of the curable composition for optical semiconductor devices hardly changes, and the pot life of the curable composition for optical semiconductor devices is improved.
  • the first silane compound may have a ureido group or an isocyanate group. From the viewpoint of further increasing the adhesiveness of the cured product to the object to be bonded, the first silane compound preferably has a ureido group. In addition, the use of the first silane compound having a ureido group can further suppress electrode discoloration due to sulfur-containing gas in the atmosphere in the optical semiconductor device.
  • the first silane compound is a first silane compound represented by the following formula (S1) or the following formula (S2). preferable.
  • the first silane compound is represented by the following formula (S1). It is preferable that it is the 1st silane compound represented.
  • X1 represents an alkoxy group
  • X2 and X3 each represents an alkoxy group or a hydrocarbon group having 1 to 8 carbon atoms
  • R4 is a single bond directly bonding a nitrogen atom and a silicon atom. Or a hydrocarbon group having 1 to 8 carbon atoms.
  • X1 represents an alkoxy group
  • X2 and X3 each represents an alkoxy group or a hydrocarbon group having 1 to 8 carbon atoms
  • R4 represents a single bond directly connecting a nitrogen atom and a silicon atom. It represents a bond or a hydrocarbon group having 1 to 8 carbon atoms.
  • the number of carbon atoms of the alkoxy group in X1 in the formula (S1) and the formula (S2) is preferably 1-8.
  • the alkoxy group in X2 and X3 preferably has 1 to 8 carbon atoms.
  • the first silane compound represented by the above formula (S1) is preferably the first silane compound represented by the following formula (S1-1).
  • S1-1 the adhesion of the cured product to the object to be bonded is further enhanced.
  • R1 to R3 each represent a hydrocarbon group having 1 to 8 carbon atoms
  • R4 represents a single bond directly bonding a nitrogen atom and a silicon atom, or 1 to 8 hydrocarbon groups are represented.
  • the first silane compound represented by the above formula (S2) is preferably the first silane compound represented by the following formula (S2-1).
  • S2-1 the adhesion of the cured product to the object to be bonded is further enhanced.
  • R1 to R3 each represent a hydrocarbon group having 1 to 8 carbon atoms
  • R4 represents a single bond directly bonding a nitrogen atom and a silicon atom, or 1 carbon atom. Represents 8 to 8 hydrocarbon groups.
  • the content of the first silane compound is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, preferably 100 parts by weight in total for the first and second organopolysiloxanes. 5 parts by weight or less, more preferably 3 parts by weight or less.
  • the content of the first silane compound is equal to or higher than the lower limit, peeling of the cured product from the adhesion target can be further suppressed.
  • the content of the first silane compound is not more than the above upper limit, it is possible to prevent the surface stickiness of the sealing agent from being deteriorated due to the excessive first silane coupling agent.
  • the curable composition for optical semiconductor devices according to the present invention preferably contains a second silane compound different from the first silane compound having a ureido group or an isocyanate group.
  • the second silane compound does not have a ureido group and an isocyanate group.
  • the second silane compound is not particularly limited, and examples thereof include vinyltriethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Examples include 3- (meth) acryloxypropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane.
  • (meth) acryloyl indicates acryloyl and methacryloyl.
  • (meth) acryloxy refers to acryloxy and methacryloxy.
  • the second silane compound preferably has an epoxy group, a vinyl group or a (meth) acryloyl group.
  • the second silane compound is 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Vinyltrimethoxysilane or 3- (meth) acryloxypropyltrimethoxysilane is preferable.
  • the content of the second silane compound is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, preferably 100 parts by weight based on the total of the first and second organopolysiloxanes. 5 parts by weight or less, more preferably 3 parts by weight or less.
  • the content of the second silane compound is equal to or more than the lower limit, peeling of the cured product from the adhesion target can be further suppressed.
  • the content of the second silane compound is not more than the above upper limit, it is possible to prevent the surface stickiness of the sealing agent from being deteriorated due to an excessive second silane coupling agent.
  • the curable composition for optical semiconductor devices according to the present invention preferably further contains silicon oxide particles.
  • the encapsulant preferably further contains silicon oxide particles.
  • the primary particle diameter of the silicon oxide particles is preferably 5 nm or more, more preferably 8 nm or more, preferably 200 nm or less, more preferably 150 nm or less.
  • the primary particle diameter of the silicon oxide particles is not less than the above lower limit, the dispersibility of the silicon oxide particles is further increased, and the transparency of the cured product is further increased.
  • the primary particle diameter of the silicon oxide particles is not more than the above upper limit, it is possible to sufficiently obtain the effect of increasing the viscosity at 25 ° C. and to suppress the decrease in the viscosity due to the temperature increase.
  • the primary particle diameter of the silicon oxide particles is measured as follows.
  • the cured product of the curable composition for optical semiconductor devices is observed using a transmission electron microscope (“JEM-2100” manufactured by JEOL Ltd.).
  • the size of the primary particles of 100 silicon oxide particles in the visual field is measured, and the average value of the measured values is defined as the primary particle diameter.
  • the primary particle diameter means an average value of the diameters of the silicon oxide particles when the silicon oxide particles are spherical, and an average value of the major diameters of the silicon oxide particles when the silicon oxide particles are non-spherical.
  • the BET specific surface area of the silicon oxide particles is preferably 30 m 2 / g or more, and preferably 400 m 2 / g or less.
  • the BET specific surface area of the silicon oxide particles is 30 m 2 / g or more, the viscosity at 25 ° C. of the curable composition can be controlled within a suitable range, and the decrease in the viscosity due to a temperature rise can be suppressed.
  • the BET specific surface area of the silicon oxide particles is 400 m 2 / g or less, the aggregation of the silicon oxide particles hardly occurs, the dispersibility can be increased, and the transparency of the cured product can be further increased. it can.
  • the silicon oxide particles are not particularly limited, and examples thereof include silica produced by a dry method such as fumed silica and fused silica, and silica produced by a wet method such as colloidal silica, sol-gel silica and precipitated silica. It is done.
  • fumed silica is suitably used as the silicon oxide particles from the viewpoint of obtaining a cured product with less volatile components and higher transparency.
  • Examples of the fumed silica include Aerosil 50 (specific surface area: 50 m 2 / g), Aerosil 90 (specific surface area: 90 m 2 / g), Aerosil 130 (specific surface area: 130 m 2 / g), Aerosil 200 (specific surface area). : 200 m 2 / g), Aerosil 300 (specific surface area: 300 m 2 / g), Aerosil 380 (specific surface area: 380 m 2 / g) (all manufactured by Nippon Aerosil Co., Ltd.) and the like.
  • the silicon oxide particles are preferably surface-treated with an organosilicon compound. By this surface treatment, the dispersibility of the silicon oxide particles becomes very high, and it is possible to further suppress the decrease in the viscosity due to the temperature rise of the curable composition.
  • the content of the silicon oxide particles is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight with respect to a total of 100 parts by weight of the first organopolysiloxane and the second organopolysiloxane. More preferably, it is 1 part by weight or more, preferably 40 parts by weight or less, more preferably 35 parts by weight or less, and still more preferably 20 parts by weight or less.
  • the content of the silicon oxide particles is equal to or higher than the lower limit, it is possible to suppress a decrease in viscosity at the time of curing.
  • the content of the silicon oxide particles is not more than the above upper limit, the viscosity of the curable composition can be controlled to a more appropriate range, and the transparency of the cured product is further enhanced.
  • the curable composition for optical semiconductor devices according to the present invention may further contain a phosphor.
  • the curable composition for optical semiconductor devices according to the present invention is an encapsulant for optical semiconductor devices
  • the encapsulant preferably further contains a phosphor.
  • the curable composition for optical semiconductor devices which concerns on this invention does not need to contain fluorescent substance. In this case, a phosphor may be added when the curable composition is used.
  • the phosphor absorbs light emitted from a light-emitting element that is sealed using the curable composition for optical semiconductor devices, and generates fluorescence to finally obtain light of a desired color. Acts as follows. The phosphor is excited by light emitted from the light emitting element to emit fluorescence, and light of a desired color is obtained by a combination of light emitted from the light emitting element and fluorescence emitted from the phosphor.
  • the content of the phosphor can be adjusted as appropriate so as to obtain light of a desired color, and is not particularly limited.
  • the content of the phosphor is preferably 0.1 parts by weight or more and preferably 40 parts by weight or less with respect to 100 parts by weight of the curable composition for optical semiconductor devices according to the present invention.
  • the content of the phosphor is preferably 0.1 parts by weight or more and preferably 40 parts by weight or less with respect to 100 parts by weight of all components excluding the phosphor of the curable composition for optical semiconductor devices.
  • the curable composition for an optical semiconductor device includes a dispersant, an antioxidant, an antifoaming agent, a colorant, a modifier, a leveling agent, a light diffusing agent, a heat conductive filler, or a flame retardant as necessary. Etc. may further be included.
  • said 1st organopolysiloxane, said 2nd organopolysiloxane, said hydrosilylation reaction catalyst, and said 1st silane compound are the liquids containing these 1 type, or 2 or more types separately.
  • the curable composition for optical semiconductor devices according to the present invention may be prepared by preparing and mixing a plurality of liquids immediately before use. For example, the first liquid containing the first organopolysiloxane and the second liquid containing the second organopolysiloxane are prepared separately, and the first liquid and the second liquid are prepared just before use.
  • the curable composition for optical semiconductor devices according to the present invention may be prepared by mixing with a liquid. At least one of the first liquid and the second liquid contains the hydrosilylation reaction catalyst.
  • the first liquid preferably contains a hydrosilylation reaction catalyst.
  • the first silane compound may be added to the first liquid or may be added to the second liquid. At least one of the first liquid and the second liquid contains the first silane compound.
  • the second silane compound, the silicon oxide particles, or the phosphor is used, the second silane compound, the silicon oxide particles, or the phosphor may be added to the first liquid, respectively. It may be added to the second liquid. It is preferable that at least one of the first liquid and the second liquid contains the second silane compound.
  • storage stability improves by making said 1st organopolysiloxane and said 2nd organopolysiloxane into 2 liquids of a 1st liquid and a 2nd liquid separately.
  • the curing temperature of the curable composition for optical semiconductor devices according to the present invention is not particularly limited.
  • the curing temperature of the curable composition for optical semiconductor devices is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, preferably 180 ° C. or lower, more preferably 150 ° C. or lower.
  • the curing temperature is not less than the above lower limit, curing of the curable composition proceeds sufficiently.
  • the curing temperature is not more than the above upper limit, the package is unlikely to be thermally deteriorated.
  • the curing method is not particularly limited, but it is preferable to use a step cure method.
  • the step cure method is a method in which the resin is temporarily cured at a low temperature and then cured at a high temperature. By using the step cure method, curing shrinkage of the cured product can be suppressed.
  • mixers such as a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, a triple roll, or a bead mill.
  • the light-emitting element is not particularly limited as long as it is a light-emitting element using a semiconductor.
  • the light-emitting element is a light-emitting diode
  • a structure in which an LED-type semiconductor material is stacked on a substrate is exemplified.
  • the semiconductor material include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, and SiC.
  • Examples of the material of the substrate include sapphire, spinel, SiC, Si, ZnO, and GaN single crystal. Further, a buffer layer may be formed between the substrate and the semiconductor material as necessary. Examples of the material of the buffer layer include GaN and AlN.
  • optical semiconductor device examples include a light emitting diode device, a semiconductor laser device, and a photocoupler.
  • Such optical semiconductor devices include, for example, backlights such as liquid crystal displays, illumination, various sensors, light sources such as printers and copiers, vehicle measuring instrument light sources, signal lights, indicator lights, display devices, and light sources for planar light emitters. It is suitably used for displays, decorations, various lights and switching elements.
  • the curable composition for optical semiconductor devices according to the present invention is preferably an encapsulant for optical semiconductor devices or a lens material for optical semiconductor devices.
  • the curable composition for optical semiconductor devices according to the present invention may be an encapsulant for optical semiconductor devices or a lens material for optical semiconductor devices.
  • the curable composition for optical semiconductor devices according to the present invention is also used as a coating material for optical semiconductor devices for forming a coating layer on the surface of an optical semiconductor element.
  • An optical semiconductor device includes an optical semiconductor element and a sealing agent disposed so as to seal the optical semiconductor element or a lens disposed on the optical semiconductor element.
  • the sealing agent or the lens is formed by curing the above-described curable composition for optical semiconductor devices.
  • a cured product of the curable composition for an optical semiconductor device is disposed so as to seal a light emitting element formed of an optical semiconductor such as an LED, the cured product is effectively peeled from the housing or the like. Can be suppressed.
  • the lens may be directly laminated on the optical semiconductor element, or may be disposed on the optical semiconductor element via a sealant or the like disposed so as to seal the optical semiconductor element. That is, the lens may be disposed on the surface of the sealant.
  • the shape of the lens is not particularly limited. From the viewpoint of controlling the light emission direction in the optical semiconductor device and further suppressing the front luminance from becoming too high, the shape of the lens may be a part of a sphere or a part of a spheroid. preferable.
  • FIG. 1 is a front sectional view showing an optical semiconductor device according to the first embodiment of the present invention.
  • the optical semiconductor device 1 of this embodiment has a housing 2.
  • An optical semiconductor element 3 is disposed in the housing 2.
  • the optical semiconductor element 3 is surrounded by an inner surface 2 a having light reflectivity of the housing 2.
  • the optical semiconductor element 3 is a light emitting element such as an LED.
  • the inner surface 2a is formed such that the diameter of the inner surface 2a increases toward the opening end. Therefore, of the light emitted from the optical semiconductor element 3, the light that has reached the inner surface 2 a is reflected by the inner surface 2 a and travels forward of the optical semiconductor element 3.
  • a sealing agent 4 that is a cured product of the curable composition for optical semiconductor devices is filled.
  • the sealant 4 is formed by curing the sealant that is the curable composition for optical semiconductor devices according to the present invention, and is a cured product of the sealant.
  • FIG. 2 is a front sectional view showing an optical semiconductor device according to the second embodiment of the present invention.
  • the optical semiconductor device 11 shown in FIG. An optical semiconductor element 3 is disposed in the housing 2.
  • a sealing agent 12 is filled in a region surrounded by the inner surface 2 a of the housing 2 so as to seal the optical semiconductor element 3. That is, the optical semiconductor element 3 is sealed with the sealant 12 in the housing 2.
  • a sealing agent 12 is disposed so as to seal the optical semiconductor element 3.
  • a lens 13 is disposed on the surface 12 a of the sealant 12.
  • the lens 13 is formed by curing a lens material that is a curable composition for optical semiconductor devices according to the present invention, and is a cured product of the lens material.
  • FIG. 3 is a front sectional view showing an optical semiconductor device according to the third embodiment of the present invention.
  • an optical semiconductor element 23 is arranged on a substrate 22 on which a terminal 22a is provided.
  • An electrode 23 a provided on the upper surface of the optical semiconductor element 23 and a terminal 22 a provided on the upper surface of the substrate 22 are electrically connected by a bonding wire 24.
  • a lens 25 is disposed on the optical semiconductor element 23.
  • the lens 25 covers the surface of the optical semiconductor element 23 and the bonding wire 24.
  • the lens 25 is formed by curing a lens material that is a curable composition for optical semiconductor devices according to the present invention, and is a cured product of the lens material.
  • FIGS. 1 to 3 are merely examples of the optical semiconductor device according to the present invention, and the mounting structure of the optical semiconductor device can be modified as appropriate.
  • the number average molecular weight of the obtained polymer (A) was 37400.
  • the polymer (A) had the following average composition formula (A1).
  • Me represents a methyl group
  • Vi represents a vinyl group.
  • the content ratio of the methyl group of the obtained polymer (A) was 99 mol%.
  • the molecular weight of each polymer obtained in Synthesis Example 1 and Synthesis Examples 2 to 6 was measured by GPC measurement by adding 1 mL of tetrahydrofuran to 10 mg, stirring until dissolved.
  • GPC measurement a measuring device manufactured by Waters (column: Shodex GPC LF-804 (length: 300 mm) x 2 manufactured by Showa Denko KK), measuring temperature: 40 ° C., flow rate: 1 mL / min, solvent: tetrahydrofuran, standard substance: Polystyrene) was used.
  • the number average molecular weight (Mn) of the obtained polymer (B) was 1700.
  • the polymer (B) had the following average composition formula (B1).
  • Me represents a methyl group
  • Ph represents a phenyl group
  • Vi represents a vinyl group.
  • the content ratio of the phenyl group of the obtained polymer (B) was 80.8 mol%.
  • the polymer was obtained by removing the volatile component under reduced pressure.
  • 150 g of hexane and 150 g of ethyl acetate were added, washed 10 times with 300 g of ion-exchanged water, reduced in pressure to remove volatile components, and polymer (C) was obtained.
  • the number average molecular weight of the obtained polymer (C) was 3420.
  • the polymer (C) had the following average composition formula (C1).
  • Me represents a methyl group
  • Vi represents a vinyl group.
  • the content ratio of methyl groups of the obtained polymer (C) was 90 mol%.
  • Synthesis Example 4 Synthesis of Second Organopolysiloxane A 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer was charged with 31 g of trimethylmethoxysilane, 40 g of 1,1,3,3-tetramethyldisiloxane, diphenyl. 110 g of dimethoxysilane, 268 g of phenyltrimethoxysilane, and 45 g of vinyltrimethoxysilane were added and stirred at 50 ° C. Into this, a solution of 1.4 g of hydrochloric acid and 116 g of water was slowly added dropwise, and after the addition, the mixture was stirred at 50 ° C.
  • the number average molecular weight (Mn) of the obtained polymer (D) was 1100.
  • the polymer (D) had the following average composition formula (D1).
  • Me represents a methyl group
  • Ph represents a phenyl group
  • Vi represents a vinyl group.
  • the content ratio of the phenyl group of the obtained polymer (D) was 82.5 mol%.
  • Synthesis Example 5 Synthesis of First Organopolysiloxane
  • a 1 L separable flask equipped with a thermometer, a dropping device and a stirrer was charged with 474 g of dimethyldimethoxysilane, 10 g of diphenyldimethoxysilane, 1,3-divinyl-1,1, 1.2 g of 3,3-tetramethyldisiloxane and 200 g of dimethylformamide were added and stirred at 50 ° C.
  • a solution prepared by dissolving 2.2 g of potassium hydroxide in 144 g of water was slowly added dropwise thereto, and after the dropwise addition, the mixture was stirred at 50 ° C. for 2 hours to react, further heated to 85 ° C.
  • the number average molecular weight of the obtained polymer (E) was 52300.
  • the polymer (E) had the following average composition formula (E1).
  • Me represents a methyl group
  • Ph represents a phenyl group
  • Vi represents a vinyl group.
  • the content ratio of the methyl group of the obtained polymer (E) was 99 mol%.
  • the polymer was obtained by removing the volatile component under reduced pressure.
  • 150 g of hexane and 150 g of ethyl acetate were added, washed 10 times with 300 g of ion-exchanged water, reduced in pressure to remove volatile components, and polymer (F) was obtained.
  • the number average molecular weight of the obtained polymer (F) was 5480.
  • the polymer (F) had the following average composition formula (F1).
  • Me represents a methyl group
  • Vi represents a vinyl group.
  • the content ratio of the methyl group of the obtained polymer (F) was 90 mol%.
  • Example 1 Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) And 3-ureidopropyltriethoxysilane (0.2 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.
  • Example 2 Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) And 3-isocyanatopropyltriethoxysilane (0.2 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.
  • Example 3 Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) 2), 3-ureidopropyltriethoxysilane (0.15 g), and 3-glycidoxypropyltrimethoxysilane (0.15 g) are mixed and defoamed to obtain a curable composition for optical semiconductor devices. Obtained.
  • Example 4 Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) ), 3-ureidopropyltriethoxysilane (0.15 g), and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (0.15 g) are mixed and degassed for use in an optical semiconductor device. A curable composition was obtained.
  • Example 5 Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) ), 3-ureidopropyltriethoxysilane (0.15 g), and vinyltrimethoxysilane (0.15 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.
  • Example 6 Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) 2), 3-ureidopropyltriethoxysilane (0.15 g), and 3-methacryloxypropyltrimethoxysilane (0.15 g) are mixed and degassed to obtain a curable composition for an optical semiconductor device. It was.
  • Example 7 Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) 3), 3-ureidopropyltriethoxysilane (0.10 g), 3-glycidoxypropyltrimethoxysilane (0.10 g), and vinyltrimethoxysilane (0.10 g) are mixed and defoamed.
  • a curable composition for an optical semiconductor device was obtained.
  • Example 8 Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) ), 3-isocyanatopropyltriethoxysilane (0.15 g), and 3-glycidoxypropyltrimethoxysilane (0.15 g) are mixed and degassed to obtain a curable composition for optical semiconductor devices. Obtained.
  • Example 9 Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) ), 3-isocyanatopropyltriethoxysilane (0.15 g), and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (0.15 g) are mixed and degassed for use in an optical semiconductor device. A curable composition was obtained.
  • Example 10 Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) ), 3-isocyanatopropyltriethoxysilane (0.15 g), and vinyltrimethoxysilane (0.15 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.
  • Example 11 Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) 2), 3-isocyanatopropyltriethoxysilane (0.15 g), and 3-methacryloxypropyltrimethoxysilane (0.15 g) are mixed and defoamed to obtain a curable composition for optical semiconductor devices. It was.
  • Example 12 Polymer A (10 g), Polymer C (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal is 10 ppm by weight with respect to the entire curable composition) 3), 3-isocyanatopropyltriethoxysilane (0.10 g), 3-glycidoxypropyltrimethoxysilane (0.10 g), and vinyltrimethoxysilane (0.10 g) are mixed and defoamed.
  • a curable composition for an optical semiconductor device was obtained.
  • Example 15 Polymer B (10 g), Polymer D (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) 2), 3-ureidopropyltriethoxysilane (0.15 g), and 3-glycidoxypropyltrimethoxysilane (0.15 g) are mixed and defoamed to obtain a curable composition for optical semiconductor devices. Obtained.
  • Example 16 Polymer B (10 g), Polymer D (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) ), 3-ureidopropyltriethoxysilane (0.15 g), and vinyltrimethoxysilane (0.15 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.
  • platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition)
  • 3-ureidopropyltriethoxysilane (0.15 g)
  • vinyltrimethoxysilane (0.15 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.
  • Example 17 Polymer B (10 g), Polymer D (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) 3), 3-ureidopropyltriethoxysilane (0.10 g), 3-glycidoxypropyltrimethoxysilane (0.10 g), and vinyltrimethoxysilane (0.10 g) are mixed and defoamed.
  • a curable composition for an optical semiconductor device was obtained.
  • Example 18 Polymer B (10 g), Polymer D (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) ), 3-isocyanatopropyltriethoxysilane (0.15 g), and 3-glycidoxypropyltrimethoxysilane (0.15 g) are mixed and degassed to obtain a curable composition for optical semiconductor devices. Obtained.
  • Example 20 Polymer B (10 g), Polymer D (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) 3), 3-isocyanatopropyltriethoxysilane (0.10 g), 3-glycidoxypropyltrimethoxysilane (0.10 g), and vinyltrimethoxysilane (0.10 g) are mixed and defoamed.
  • a curable composition for an optical semiconductor device was obtained.
  • Example 21 Polymer E (10 g), Polymer F (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) And 3-ureidopropyltriethoxysilane (0.2 g) were mixed and defoamed to obtain a curable composition for optical semiconductor devices.
  • Example 25 Polymer E (10 g), Polymer F (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) 3), 3-ureidopropyltriethoxysilane (0.10 g), 3-glycidoxypropyltrimethoxysilane (0.10 g), and vinyltrimethoxysilane (0.10 g) are mixed and defoamed.
  • a curable composition for an optical semiconductor device was obtained.
  • Example 28 Polymer E (10 g), Polymer F (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal is 10 ppm by weight with respect to the entire curable composition) 3), 3-isocyanatopropyltriethoxysilane (0.10 g), 3-glycidoxypropyltrimethoxysilane (0.10 g), and vinyltrimethoxysilane (0.10 g) are mixed and defoamed.
  • a curable composition for an optical semiconductor device was obtained.
  • the obtained optical semiconductor device was placed in a chamber at 40 ° C. and a relative humidity of 90% RH, and the chamber was filled with gas so that the concentration of hydrogen sulfide gas was 5 ppm and the concentration of sulfur dioxide gas was 15 ppm. . From the gas filling, the lead electrodes plated with silver were visually observed after 24 hours, 48 hours, 96 hours, 168 hours and 500 hours.
  • Thermal shock test Using the obtained optical semiconductor device and using a liquid bath thermal shock tester (“TSB-51” manufactured by ESPEC), the temperature was maintained at ⁇ 50 ° C. for 5 minutes, and then the temperature was increased to 135 ° C. A cold cycle test was conducted in which the process of holding at 5 ° C. for 5 minutes and then lowering the temperature to ⁇ 50 ° C. was 1 cycle. 20 samples were taken out after 500 cycles, 1000 cycles, 1500 cycles, 2000 cycles and 3000 cycles, respectively.
  • TTB-51 liquid bath thermal shock tester
  • the sample was observed with a stereomicroscope ("SMZ-10" manufactured by Nikon Corporation). It is observed whether cracks are generated in the cured products obtained by curing 20 samples of the curable composition for optical semiconductor devices, or whether the cured products are separated from the package or the electrode. The number of samples produced (NG number) was counted.
  • Viscosity ratio A curable composition for optical semiconductor devices immediately after fabrication (a curable composition immediately after fabrication) was prepared. Furthermore, the curable composition immediately after preparation was allowed to stand at room temperature (23 ° C.) for 3 hours to prepare a curable composition after 3 hours. Using a viscosity measuring device (“VISCOMETER TV-22” manufactured by Toki Sangyo Co., Ltd.), the viscosity of the curable composition immediately after preparation at 23 ° C. and 10 rpm, and the temperature of the curable composition after 3 hours at 23 ° C. and 10 rpm And the viscosity was measured. The viscosity ratio (viscosity value after 3 hours / initial viscosity value) to the viscosity value in the curable composition immediately after production of the viscosity value in the curable composition after 3 hours was determined.
  • VISCOMETER TV-22 manufactured by Toki Sangyo Co., Ltd.
  • the luminous intensity when a current of 20 mA was passed through the light emitting element was measured using a photometric measuring device (“OL770” manufactured by Optronic Laboratories) at a temperature of 23 ° C. (hereinafter, “initial” Called “luminosity”).
  • the optical semiconductor device was placed in a chamber under an atmosphere of 85 ° C. and a relative humidity of 85 RH% with a current of 20 mA flowing through the light emitting element, and left for 1000 hours.
  • the light intensity when a current of 20 mA was passed through the light emitting element was measured using a light intensity measuring device (“OL770” manufactured by Optronic Laboratories), and the rate of decrease in light intensity relative to the initial light intensity Calculated.
  • the rate of decrease in luminous intensity is less than 5%, it is “ ⁇ ”, when it is 5% or more and less than 10%, “ ⁇ ”, when it is 10% or more and less than 20%, “ ⁇ ”, when it is 20% or more It was determined as “x”.
  • the obtained optical semiconductor device was fixed with a double-sided tape on a slide glass with the light emitting surface facing up.
  • 0.2 g of sulfur was placed in a glass container with a lid having a capacity of 120 mL, and a slide glass on which the optical semiconductor device was fixed was placed in the glass container so that the optical semiconductor device and sulfur were not in direct contact.
  • the glass container was sealed and placed in an oven at 80 ° C. After being placed in the oven, changes in the silver-plated lead electrode were visually observed after 4 hours, 8 hours, 16 hours, 24 hours and 48 hours, respectively.
  • the gas corrosion test 2 was determined according to the following criteria. In addition, when the adhesiveness with respect to the adhesion target object of hardened

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Led Device Packages (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

L'invention concerne une composition durcissable destinée à un dispositif semi-conducteur optique au moyen de laquelle il est possible de durcir la composition durcissable et d'obtenir un produit durci qui ne se décollera pas lors de la liaison à un autre objet, même lorsque le dispositif semi-conducteur optique est utilisé dans un environnement rude sous des températures élevées et une humidité élevée, et au moyen de laquelle la durée de vie en pot de la composition durcissable destinée à un dispositif semi-conducteur optique est bonne. La composition durcissable destinée à un dispositif semi-conducteur optique relative à la présente invention comprend un premier organopolysiloxane présentant deux groupes alcényle ou plus, un deuxième organopolysiloxane présentant deux atomes d'hydrogène liés à des atomes de silicium ou plus, un catalyseur d'hydrosilylation et un premier composé de silane présentant des groupes uréido ou des groupes isocyanate.
PCT/JP2012/072603 2011-09-08 2012-09-05 Composition durcissable destinée à un dispositif semi-conducteur optique Ceased WO2013035736A1 (fr)

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Publication number Priority date Publication date Assignee Title
CN103694709A (zh) * 2013-12-09 2014-04-02 华南理工大学 加成型液体硅橡胶用耐漏电起痕剂及其制备方法和应用
EP3162864A1 (fr) * 2015-11-02 2017-05-03 Shin-Etsu Chemical Co., Ltd. Promoteur d'adhésion, composition de résine organopolysiloxane durcissable par addition et dispositif à semi-conducteurs
JP2020070391A (ja) * 2018-11-01 2020-05-07 株式会社ダイセル 硬化性エポキシ樹脂組成物
JP2020070390A (ja) * 2018-11-01 2020-05-07 株式会社ダイセル 硬化性エポキシ樹脂組成物

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JP2000017042A (ja) * 1998-06-30 2000-01-18 Ge Toshiba Silicones Co Ltd 硬化性組成物
JP2004519544A (ja) * 2001-01-03 2004-07-02 ヘンケル ロックタイト コーポレイション 低温高速硬化シリコーン組成物
JP2007246842A (ja) * 2006-03-17 2007-09-27 Shin Etsu Chem Co Ltd 熱硬化性組成物及び該組成物から得られる層を備えたフィルム
JP2011099090A (ja) * 2009-10-05 2011-05-19 Shin-Etsu Chemical Co Ltd 付加硬化型自己接着性シリコーンゴム組成物
JP4951147B1 (ja) * 2011-09-08 2012-06-13 積水化学工業株式会社 光半導体装置用硬化性組成物

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JPH03223362A (ja) * 1989-12-05 1991-10-02 Shin Etsu Chem Co Ltd 自己接着型シリコーンゴム組成物及びシリコーンゴム被覆布
JP2000017042A (ja) * 1998-06-30 2000-01-18 Ge Toshiba Silicones Co Ltd 硬化性組成物
JP2004519544A (ja) * 2001-01-03 2004-07-02 ヘンケル ロックタイト コーポレイション 低温高速硬化シリコーン組成物
JP2007246842A (ja) * 2006-03-17 2007-09-27 Shin Etsu Chem Co Ltd 熱硬化性組成物及び該組成物から得られる層を備えたフィルム
JP2011099090A (ja) * 2009-10-05 2011-05-19 Shin-Etsu Chemical Co Ltd 付加硬化型自己接着性シリコーンゴム組成物
JP4951147B1 (ja) * 2011-09-08 2012-06-13 積水化学工業株式会社 光半導体装置用硬化性組成物

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103694709A (zh) * 2013-12-09 2014-04-02 华南理工大学 加成型液体硅橡胶用耐漏电起痕剂及其制备方法和应用
CN103694709B (zh) * 2013-12-09 2016-04-13 华南理工大学 加成型液体硅橡胶用耐漏电起痕剂及其制备方法和应用
EP3162864A1 (fr) * 2015-11-02 2017-05-03 Shin-Etsu Chemical Co., Ltd. Promoteur d'adhésion, composition de résine organopolysiloxane durcissable par addition et dispositif à semi-conducteurs
US10040924B2 (en) 2015-11-02 2018-08-07 Shin-Etsu Chemical Co., Ltd. Adhesion promoter, addition curable organopolysiloxane resin composition and semiconductor apparatus
JP2020070391A (ja) * 2018-11-01 2020-05-07 株式会社ダイセル 硬化性エポキシ樹脂組成物
JP2020070390A (ja) * 2018-11-01 2020-05-07 株式会社ダイセル 硬化性エポキシ樹脂組成物
JP7329320B2 (ja) 2018-11-01 2023-08-18 株式会社ダイセル 硬化性エポキシ樹脂組成物
JP7329319B2 (ja) 2018-11-01 2023-08-18 株式会社ダイセル 硬化性エポキシ樹脂組成物

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