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WO2012067153A1 - Composition de résine silicone, ainsi que structure contenant une résine silicone, corps d'étanchéité pour élément semi-conducteur optique et procédé de mise en oeuvre de composition de résine silicone associés - Google Patents

Composition de résine silicone, ainsi que structure contenant une résine silicone, corps d'étanchéité pour élément semi-conducteur optique et procédé de mise en oeuvre de composition de résine silicone associés Download PDF

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Publication number
WO2012067153A1
WO2012067153A1 PCT/JP2011/076423 JP2011076423W WO2012067153A1 WO 2012067153 A1 WO2012067153 A1 WO 2012067153A1 JP 2011076423 W JP2011076423 W JP 2011076423W WO 2012067153 A1 WO2012067153 A1 WO 2012067153A1
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Prior art keywords
group
silicone resin
resin composition
zinc
compound
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English (en)
Japanese (ja)
Inventor
吉仁 武井
石川　和憲
丈章 齋木
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Yokohama Rubber Co Ltd
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Yokohama Rubber Co Ltd
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Priority to JP2012507752A priority Critical patent/JP5056998B2/ja
Priority to KR1020137012819A priority patent/KR101296082B1/ko
Priority to CN201180054880.5A priority patent/CN103221485B/zh
Publication of WO2012067153A1 publication Critical patent/WO2012067153A1/fr
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/296—Organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
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    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
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    • 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
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32245—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
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    • 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
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32245—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/32257—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic the layer connector connecting to a bonding area disposed in a recess of the surface of the item
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    • 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
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    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73251—Location after the connecting process on different surfaces
    • H01L2224/73265—Layer and wire connectors
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    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/12—Passive devices, e.g. 2 terminal devices
    • H01L2924/1204—Optical Diode
    • H01L2924/12044—OLED
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    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation

Definitions

  • the present invention relates to a silicone resin composition, a silicone resin-containing structure, an optical semiconductor element sealing body, and a method for using the silicone resin composition using the same.
  • Silicone resins are excellent in heat resistance, but have higher gas permeability than epoxy resins. For this reason, there is a problem that the silver plating to which the silicone resin is applied is discolored and corroded over time with hydrogen sulfide in the air. As countermeasures against discoloration over time, a method of increasing the crosslinking density of the silicone resin to harden the resin and a means of copolymerizing a silicone resin and a resin having high gas barrier properties have been proposed (for example, see Patent Document 1).
  • a silicone resin composition containing a compound obtained by reacting 2 moles or more of an acid with 1 mole of a raw material zinc compound (a compound containing zinc) such as zinc oxide as a zinc compound.
  • Patent Documents 2 to 4 were proposed as the condensation type, Patent Document 5 as the addition type, and Patent Document 6 as the other curing system.
  • JP 2003-188503 A Japanese Patent Application No. 2010-251966 Japanese Patent Application No. 2010-066781 Japanese Patent Application No. 2010-253136 Japanese Patent Application No. 2010-014300 Japanese Patent Application No. 2010-203568
  • an object of the present invention is to provide a silicone resin composition excellent in sulfur resistance (particularly long-term sulfur resistance) and transparency.
  • the present inventor has found that (B) zinc oxide, zinc carbonate, zinc hydroxide, zinc chloride, zinc sulfate and (A) 100 parts by mass of the curable silicone resin composition
  • the present invention has been completed by finding that it is excellent in sulfidation resistance (particularly long-term sulfidation resistance) and transparency.
  • the present invention provides the following 1 to 11.
  • the acid is at least one selected from the group consisting of inorganic acids, organic acids, and esters thereof.
  • the silicone resin composition according to the above 1 or 2 is applied to a thickness of 1 mm and cured to obtain a laminate having the member and the silicone resin layer,
  • the laminated body was subjected to a sulfidation resistance test in a hydrogen sulfide gas having a theoretical value of 560 ppm at 25 ° C., and the spectral reflection of the laminated body before the sulfidation resistance test and 72 hours after the start of the sulfidation resistance test.
  • the silicone resin composition according to 1 or 2 above, wherein the spectral reflectance maintenance factor calculated from the formula is 80% or more. 4).
  • the (A) curable silicone resin composition comprises (a) an organopolysiloxane having at least two hydrolyzable groups bonded to silanol groups or silicon atoms, and (b) a hydrolyzable silane, a hydrolyzate thereof, and 4.
  • the (A) curable silicone resin composition comprises (d) an organopolysiloxane having at least two alkenyl groups bonded to silicon atoms, and (e) a polyorganohydrogen having at least two hydrogen atoms bonded to silicon atoms. 5.
  • the (A) curable silicone resin composition comprises (g) an organopolysiloxane having two or more (meth) acryloyl groups in one molecule, and (h) a thermal polymerization initiator and / or a photopolymerization initiator. 6.
  • the silicone resin composition as described in any one of 1 to 5 above. 7.
  • the silicone resin composition according to any one of 1 to 6 above, wherein the (A) curable silicone resin composition comprises (i) an organopolysiloxane having an epoxy group. 8).
  • a silicone resin-containing structure having a silicone resin layer obtained from the silicone resin composition according to any one of 1 to 8 above and a member containing silver.
  • 11. A method for using a silicone resin composition comprising a curing step of curing the silicone resin composition according to any one of 1 to 8 in the presence of silver.
  • the silicone resin composition of the present invention is excellent in sulfidation resistance (particularly long-term sulfidation resistance) and transparency.
  • the method for using the silicone resin-containing structure of the present invention, the sealed optical semiconductor element of the present invention, and the silicone resin composition of the present invention is excellent in sulfur resistance (particularly long-term sulfur resistance) and transparency.
  • FIG. 1 is a cross-sectional view schematically showing an example of a laminate in the present invention.
  • FIG. 2 is a cross-sectional view schematically showing another example of the laminate in the present invention.
  • FIG. 3 is a cross-sectional view schematically showing an example of the sealed optical semiconductor element of the present invention.
  • FIG. 4 is a cross-sectional view schematically showing another example of the sealed optical semiconductor element of the present invention.
  • FIG. 5 is a cross-sectional view schematically showing another example of the sealed optical semiconductor element of the present invention.
  • FIG. 6 is a diagram schematically showing an example of an LED display using the silicone resin composition of the present invention and / or the sealed optical semiconductor element of the present invention.
  • the silicone resin composition of the present invention is (A) For 100 parts by mass of the curable silicone resin composition, (B) By reacting at least one selected from the group consisting of zinc oxide, zinc carbonate, zinc hydroxide, zinc chloride, zinc sulfate and zinc nitrate: 1 mol to 1.5 mol or more and less than 2 mol of acid. A silicone resin composition containing 0.01 to 5 parts by mass of the obtained zinc compound.
  • the silicone resin composition of the present invention may be hereinafter referred to as “the composition of the present invention”.
  • the curable silicone resin composition will be described below.
  • the curable silicone resin composition contained in the composition of the present invention is not particularly limited as long as it is a composition containing a curable silicone resin (curable silicone resin).
  • curable silicone resins include silanol groups (hydroxy groups bonded to silicon atoms), hydrolyzable groups bonded to silicon atoms, alkenyl groups bonded to silicon atoms, hydrogensilyl groups, (meth) acryloyl groups, and epoxy groups.
  • a reactive functional group such as an amino group, a carbinol group, a mercapto group, a carboxyl group, or a phenol group; a hydrocarbon group.
  • the curable silicone resin can have two or more reactive functional groups in one molecule.
  • the curable silicone resin can have a reactive functional group at its terminal or both terminals and / or side chains.
  • the hydrocarbon group that the curable silicone resin can have is not particularly limited. Examples thereof include an aromatic hydrocarbon group such as a phenyl group which may have a substituent; an alkyl group; an alkenyl group. Examples of the substituent that an aromatic hydrocarbon group (for example, a phenyl group) may have include a hydrocarbon group such as an aliphatic hydrocarbon group; a halogen atom; and a hydroxy group.
  • Examples of the skeleton of the curable silicone resin include silane, silicone oligomer, silicone resin, organosiloxane, diorganosiloxane, organopolysiloxane, and diorganopolysiloxane.
  • the skeleton of the curable silicone resin may be linear or branched.
  • the hydrocarbon group that the curable silicone resin can have can be bonded to the skeleton of the curable silicone resin (for example, the skeleton described above) directly or via an organic group.
  • the amount of the phenyl group which may have a substituent is a group bonded to the silicone skeleton of one molecule of the curable silicone resin.
  • the total of (reactive functional group, hydrocarbon group) is 30 mol% or more from the viewpoint of high refractive index, higher transparency, excellent curability, and ensuring a sufficient pot life. It is preferably 40 to 80 mol%.
  • organosiloxane examples include those represented by the following formula (3).
  • R 4 represents the same or different alkyl group or aryl group having 1 to 18 carbon atoms
  • X 1 , X 2 and X 3 each independently represent a reactive functional group
  • n is an integer of 1 or more
  • M is an integer of 0 or more
  • a and b are 1, 2 or 3, respectively
  • c is 1 or 2
  • a + b + c ⁇ m is 2 or more.
  • examples of the alkyl group having 1 to 18 carbon atoms represented by R 4 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group.
  • examples of the aryl group represented by R 4 include a phenyl group (which may have a substituent) and a naphthyl group (which may have a substituent).
  • the group represented by R 4 is preferably a methyl group or a phenyl group (which may have a substituent), and more preferably a methyl group.
  • R 4 may be the same or different.
  • n can be made into the numerical value corresponding to the weight average molecular weight of organosiloxane.
  • n + m is preferably an integer of 10 to 15,000.
  • the amount of the phenyl group which may have a substituent depends on the silicone skeleton of one molecule of the curable silicone resin.
  • the total of groups (X 1 , R 4 , X 2 , X 3 ) bonded to can be high refractive index, more transparent, excellent curability, and can secure a sufficient pot life. It is preferably 30 mol% or more, and preferably 40 to 80 mol%.
  • Organosiloxanes can be used alone or in combination of two or more. When combining 2 or more types of organosiloxane, 2 or more types of organosiloxane may have the same reactive functional group mutually, and may have a different reactive functional group.
  • an organosiloxane having a reactive functional group that reacts with the reactive functional group and acts as a curing agent can be combined with an organosiloxane having one kind of reactive functional group.
  • the reactive functional group that acts as a curing agent is The amount of the organosiloxane possessed can be such that the reactive functional group is 0.1 to 10 equivalents relative to the reactive functional group possessed by the organosiloxane having one kind of reactive functional group. .
  • curable silicone resin composition examples include the following curable silicone resin compositions [1] to [4].
  • Curable silicone resin composition [1] (a) organopolysiloxane having at least two hydrolyzable groups bonded to silanol groups or silicon atoms, and (b) hydrolyzable silane, hydrolyzate thereof and the same
  • a curable silicone resin composition comprising one or both of at least one silane compound selected from the group consisting of hydrolysis condensates and (c) a condensation catalyst.
  • the curable silicone resin composition [1] can contain one or both of (a) an organopolysiloxane and (b) a silane compound.
  • an organopolysiloxane and / or (b) a silane compound can be a silicone resin.
  • One of preferred embodiments of the curable silicone resin composition [2] is that the amount of the hydrogen atoms is 0.1 to 5.0 moles per mole of the alkenyl group.
  • -Curable silicone resin composition [3] includes an organopolysiloxane having two or more (meth) acryloyl groups in one molecule, and (h) a thermal polymerization initiator and / or a photopolymerization initiator.
  • the curable silicone resin composition [4] may further contain, as an optional component, for example, (j) at least one selected from the group consisting of an acid anhydride, a carboxylic acid, an amine compound, a Lewis acid catalyst, and a Lewis base catalyst.
  • Each component contained in the curable silicone resin compositions [1] to [4] is not particularly limited. For example, a conventionally well-known thing is mentioned.
  • the organosiloxane is not particularly limited for its production.
  • the molecular weight of organosiloxane is excellent in heat-resistant coloring stability (the cured product will not be colored over a long period of time under high temperature conditions, and it will be slightly colored even if it is colored), and the curing time and pot life will be appropriately long. From the viewpoint of excellent curability and excellent physical properties of the cured product, it is preferably 1,000 to 1,000,000, and more preferably 6,000 to 100,000.
  • the molecular weight of the organosiloxane is a weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) using chloroform as a solvent.
  • the production of the curable silicone resin composition is not particularly limited.
  • the curable silicone resin compositions can be used alone or in combination of two or more.
  • One preferred embodiment of the curable silicone resin composition is the curable silicone resin composition [1].
  • the curable silicone resin composition [1] will be described below.
  • the (a) organopolysiloxane contained in the curable silicone resin composition [1] is an organopolysiloxane having at least two hydrolyzable groups bonded to silanol groups or silicon atoms.
  • Organopolysiloxane is a diorgano having at least two hydrolyzable groups bonded to silanol groups or silicon atoms from the viewpoint of excellent transparency and sulfidation resistance, heat resistance coloring stability, thin film curability and adhesion.
  • Polysiloxane and silicone resin are preferable, and organopolydimethylsiloxane having at least two hydrolyzable groups bonded to silanol groups or silicon atoms is more preferable.
  • Examples of the hydrocarbon group bonded to the silicone skeleton in the organopolysiloxane include an aromatic hydrocarbon group such as a phenyl group which may have a substituent; an alkyl group; an alkenyl group.
  • the organopolysiloxane is, for example, one represented by the following formula (1); hydrolyzing a dihalogenated silane compound having an alkyl group such as methylphenyldichlorosilane and an optionally substituted phenyl group.
  • Decomposition condensates such hydrolysis condensates are mentioned as one of preferred embodiments having a silanol group).
  • m can be a numerical value corresponding to the weight average molecular weight of the organopolysiloxane.
  • m is preferably an integer of 10 to 15,000 from the viewpoint of excellent workability and crack resistance.
  • the silane compound (b) contained in the curable silicone resin composition [1] is at least one selected from the group consisting of a hydrolyzable silane, a hydrolyzate thereof, and a hydrolysis condensate thereof.
  • the silane compound (b) may further have a hydrocarbon group.
  • the hydrocarbon group that the silane compound (b) can further include include an aromatic hydrocarbon group such as a phenyl group which may have a substituent; an alkyl group; an alkenyl group.
  • the hydrolyzable silane is not particularly limited as long as it has one silicon atom per molecule and has a hydrolyzable group.
  • the hydrolyzable group include an alkoxy group and a phenoxy group.
  • the hydrolyzable silane may be referred to as “silane compound b1”.
  • the hydrolyzate of hydrolyzable silane is not particularly limited as long as it is obtained by hydrolyzing hydrolyzable silane.
  • the hydrolysis may be partial hydrolysis.
  • the hydrolysis condensate of hydrolyzable silane is not particularly limited as long as it is obtained by hydrolyzing and condensing hydrolyzable silane.
  • the hydrolysis condensation may be a partial hydrolysis condensation.
  • the hydrolysis-condensation product may be referred to as “silane compound b2”.
  • the silane compound can have one or more organic groups in one molecule.
  • the organic group that the silane compound can have include a hydrocarbon group that may contain at least one heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom.
  • Specific examples include alkyl groups (preferably those having 1 to 6 carbon atoms), (meth) acrylate groups, alkenyl groups, aryl groups, and combinations thereof.
  • alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
  • alkenyl group examples include vinyl group, allyl group, propenyl group, isopropenyl group, 2-methyl-1-propenyl group, and 2-methylallyl group.
  • aryl group examples include a phenyl group and a naphthyl group. Of these, a methyl group, a (meth) acrylate group, and a (meth) acryloxyalkyl group are preferable from the viewpoint of excellent heat-resistant coloring stability.
  • Examples of the silane compound b1 include those represented by the following formula (2). Si (OR 1 ) n R 2 4-n (2)
  • n is 2, 3 or 4
  • R 1 is an alkyl group
  • R 2 is an organic group.
  • An organic group is synonymous with what was described regarding the organic group of a silane compound.
  • silane compound b1 examples include dialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane; methyltrimethoxysilane, methyltriethoxysilane Trialkoxysilanes such as ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane and phenyltriethoxysilane; tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane and tetraisopropyloxysilane; ⁇ - (meta ) (Meth) acryloxyalkyltrialkoxysilanes such as acryloxypropyltrimethoxysilane, methyl
  • (meth) acryloxytrialkoxysilane means acryloxytrialkoxysilane or methacryloxytrialkoxysilane.
  • Examples of the hydrolyzate of hydrolyzable silane include a hydrolyzate of silane compound b1.
  • Examples of the silane compound b2 include a compound represented by the formula (3).
  • R is an organic group
  • R ′ is an alkyl group
  • m is 0 ⁇ m ⁇ 2
  • n is 0 ⁇ n ⁇ 2
  • m + n is 0 ⁇ m + n ⁇ 3.
  • An organic group and an alkyl group are as defined above.
  • Examples of the silane compound b2 include silicone alkoxy oligomers such as methyl methoxy oligomer.
  • One preferred embodiment of the silicone alkoxy oligomer is a silicone resin having a main chain of polyorganosiloxane and a molecular terminal blocked with an alkoxysilyl group.
  • the methyl methoxy oligomer corresponds to the compound represented by the formula (3), and specific examples of the methyl methoxy oligomer include those represented by the following formula (4).
  • R ′′ is a methyl group, a is an integer of 1 to 100, and b is an integer of 0 to 100.
  • a commercially available product can be used as the methylmethoxy oligomer.
  • Examples of commercially available methylmethoxy oligomers include x-40-9246 (weight average molecular weight 6,000, manufactured by Shin-Etsu Chemical Co., Ltd.).
  • silane compound b3 a compound having at least one alkoxysilyl group at one end and having three or more alkoxy groups (derived from an alkoxysilyl group) in one molecule (hereinafter referred to as “silane compound b3”). May be mentioned as a preferred form.
  • Silane compound b3 can be obtained, for example, as a reaction product obtained by dealcoholization condensation of 1 mol or more of a silane compound having an alkoxylyl group with respect to 1 mol of polysiloxane having a silanol group at both ends.
  • Examples of the silane compound having an alkoxy group used for producing the compound b3 include the compound represented by the above formula (2): Si (OR 1 ) n R 2 4-n and the above formula ( 3): R m Si (OR ′) n O (4-mn) / 2
  • Examples of the polysiloxane having both silanol groups used for producing the compound b3 include those represented by the above formulas (1) and (4).
  • Examples of the silane compound b3 include those represented by the following formula (IV); methylphenyl silicone having an alkoxy group such as a methoxy group (for example, KR-9218 manufactured by Shin-Etsu Chemical Co., Ltd. as a commercially available product of such silicone). For example).
  • n can be a numerical value corresponding to the molecular weight of the silane compound.
  • the compound represented by the formula (IV) can be produced, for example, by modifying a polysiloxane having silanol groups at both ends with tetramethoxysilane [corresponding to a silane compound represented by the formula (2)]. .
  • the silane compound is preferably represented by the formula (2) or the formula (3) from the viewpoints of excellent transparency and sulfidation resistance, and excellent heat-resistant coloring stability, thin film curability, and heat-crack resistance.
  • Silane compounds are superior in terms of transparency and sulfidation resistance, thin film curability, and heat-resistant coloration stability, such as tetraalkoxysilanes such as tetraethoxysilane; ⁇ - (meth) acryloxypropyltrimethoxysilane.
  • Preferred is a trialkoxy (meth) acryloxyalkylsilane; a methylmethoxy oligomer; and a methylphenyl silicone having an alkoxy group such as a methoxy group.
  • the molecular weight of the silane compound is superior in transparency and sulfidation resistance, excellent in thin film curability and heat-resistant coloration stability, has an appropriate length of curing time and pot life, and is excellent in curability and compatibility. 100 to 1,000,000 is preferable, and 1,000 to 100,000 is more preferable.
  • the silane compound is the silane compound b2
  • the molecular weight is a polystyrene-reduced weight average molecular weight by gel permeation chromatography (GPC) using chloroform as a solvent.
  • GPC gel permeation chromatography
  • the production of the silane compound is not particularly limited, and examples thereof include conventionally known compounds.
  • the silane compounds can be used alone or in combination of two or more.
  • the amount of the silane compound is superior in terms of transparency and sulfidation resistance, excellent in heat-resistant coloration stability, thin film curability, and excellent in crack resistance and compatibility.
  • the amount is preferably 5 to 2,000 parts by mass and more preferably 10 to 1,000 parts by mass with respect to 100 parts by mass of the polysiloxane.
  • the (c) condensation catalyst contained in the curable silicone resin composition [1] is not particularly limited as long as it can hydrolyze and condense a hydrolyzable group-containing silyl group or silanol group.
  • metal compounds containing metals such as tin, aluminum, titanium, zirconium, hafnium, calcium, and barium can be given. Of these, at least one selected from the group consisting of a zirconium compound, a hafnium compound, and a tin compound is preferable from the viewpoint of excellent transparency and sulfidation resistance and excellent surface curability.
  • organometallic compounds include metal alkoxide compounds, metal chelate compounds, and metal alkyl compounds.
  • the curable silicone resin composition other than the curable silicone resin composition [1] can further contain a metal compound as described above.
  • the zirconium compound, hafnium compound and tin compound as the condensation catalyst may be zirconium, hafnium or a compound having tin and an organic group.
  • Zirconium, hafnium or tin can be bonded to the organic group, for example, through a heteroatom such as an oxygen atom, a nitrogen atom, a sulfur atom, and / or via a linking group such as an ester bond.
  • the organic group includes an aliphatic hydrocarbon group (including chain, branched, cyclic, and combinations thereof. The aliphatic hydrocarbon group can have an unsaturated bond), aromatic hydrocarbon groups, and combinations thereof Is mentioned.
  • the organic group can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
  • examples of the organic group include an organic carboxylate (—O—CO—R); an alkoxy group or a phenoxy group in which a hydrocarbon group is bonded to an oxy group (—O—R); a ligand; These combinations are mentioned.
  • R 1 is a hydrocarbon group having 1 to 18 carbon atoms.
  • the hydrocarbon group for R 1 include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and combinations thereof.
  • the hydrocarbon group may be linear or branched.
  • the hydrocarbon group can have an unsaturated bond.
  • the hydrocarbon group can have, for example, a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
  • the compound represented by the formula (1) is more preferably an aliphatic carboxylate and / or an alicyclic carboxylate, and more preferably an alicyclic carboxylate.
  • the aliphatic carboxylate include zirconyl dioctylate and zirconyl dineodecanoate.
  • the alicyclic carboxylate include alicyclic carboxylates such as zirconyl naphthenate and zirconyl cyclohexane.
  • the aromatic carboxylate include zirconyl benzoate.
  • the compound represented by the formula (1) is preferably one or both of zirconyl dioctylate and zirconyl naphthenate from the viewpoint of excellent curability.
  • the zirconium compound represented by the formula (2) as the condensation catalyst will be described below.
  • the zirconium compound include a zirconium compound (metal salt) represented by the following formula (2).
  • n is an integer of 1 to 3, R 1 is a hydrocarbon group having 1 to 16 carbon atoms, and R 2 is a hydrocarbon group having 1 to 18 carbon atoms.
  • the zirconium metal salt represented by the formula (2) the hydrocarbon group as R 1 has 1 to 16 carbon atoms.
  • the number of carbon atoms is 3 to 16 from the viewpoint of being excellent in transparency and resistance to sulfidation, excellent in heat-resistant coloring stability, excellent in thin film curability, and in compatibility (for example, compatibility with curable silicone resin). It is preferably 4 to 16, more preferably.
  • the hydrocarbon group for R 1 include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and combinations thereof.
  • the hydrocarbon group may be linear or branched.
  • the hydrocarbon group can have an unsaturated bond.
  • the hydrocarbon group can have, for example, a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
  • R 1 preferably has a cyclic structure from the viewpoints of transparency and sulfidation resistance, heat resistant coloration stability, thin film curability, and compatibility.
  • the cyclic structure that R 1 can have include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof.
  • R 1 can have, for example, an aliphatic hydrocarbon group in addition to the cyclic structure.
  • the hydrocarbon group in R 1 is preferably an alicyclic hydrocarbon group or an aliphatic hydrocarbon group from the viewpoint of excellent heat-resistant coloring stability and thin film curability, and excellent compatibility.
  • Examples of the alicyclic hydrocarbon group include a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; a naphthene ring (a cycloparaffin ring derived from naphthenic acid); Examples thereof include condensed ring hydrocarbon groups such as an adamantyl group and a norbornyl group.
  • Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and azulene.
  • aliphatic hydrocarbon group examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, and an undecyl group. Is mentioned. Of these, alicyclic hydrocarbon groups and aromatic hydrocarbon groups are preferred from the viewpoints of transparency and sulfidation resistance, heat resistant coloring stability, thin film curability, and compatibility, and cyclopropyl groups and cyclopentyls.
  • cyclohexyl group, adamantyl group, naphthene ring (naphthate group as R 1 COO—) and phenyl group are more preferable, and cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group and naphthene ring are more preferable.
  • the hydrocarbon group as R 2 has 1 to 18 carbon atoms.
  • the number of carbon atoms is preferably 3 to 8 from the viewpoints of excellent heat-resistant coloring stability and thin film curability and excellent compatibility.
  • the hydrocarbon group for R 2 include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and combinations thereof.
  • the hydrocarbon group may be linear or branched.
  • the hydrocarbon group can have an unsaturated bond.
  • the hydrocarbon group can have, for example, a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
  • the hydrocarbon group in R 2 is preferably an aliphatic hydrocarbon group from the viewpoints of excellent transparency and sulfidation resistance, excellent heat-resistant coloring stability, excellent thin film curability, and excellent compatibility.
  • R 2 O— (alkoxy group) having an aliphatic hydrocarbon group examples include methoxy group, ethoxy group, propoxy group (n-propoxy group, isopropoxy group), butoxy group, pentyloxy group, hexyloxy group, An octyloxy group is mentioned. Of these, methoxy, ethoxy, propoxy (n-propoxy, isopropoxy), butoxy are superior in terms of transparency, resistance to sulfidation, heat resistant coloration stability, thin film curability, and compatibility. And a pentyloxy group is preferred.
  • zirconium tributoxy mononaphthate, zirconium tributoxy monoisobutyrate, zirconium are superior in terms of transparency and sulfidation resistance, heat resistant coloring stability, thin film curability, adhesion, and compatibility.
  • Tributoxy mono 2 ethyl hexanoate is preferred.
  • a zirconium compound can be used individually or in combination of 2 or more types, respectively.
  • the zirconium compound is not particularly limited for its production.
  • a commercially available zirconium compound can be used.
  • Zr (OR 2 ) 4 zirconium tetraalkoxide.
  • Each R 2 is a hydrocarbon group having 1 to 18 carbon atoms.
  • R 2 has the same meaning as R 2 in formula (2).
  • Per mole of carboxylic acid represented by R 1 —COOH [R 1 is a hydrocarbon group having 1 to 16 carbon atoms, respectively.
  • R 1 has the same meaning as R 1 in formula (2). It can be produced by stirring at 20 to 80 ° C. under a nitrogen atmosphere using 1 to 4 mol.
  • Regarding the reaction between Zr alcoholate and carboxylic acid see D.C. C. Reference can be made to Bradley's “Metal alkoxide” Academic Press (1978).
  • Examples of Zr (OR 2 ) 4 that can be used for producing the zirconium compound represented by the formula (2) include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetranormal propoxide, and zirconium tetrapropoxy. And zirconium tetranormal butoxide.
  • Examples of the carboxylic acid that can be used for producing the zirconium compound represented by the formula (2) include acetic acid, propionic acid, isobutanoic acid, octylic acid, 2-ethylhexanoic acid, nonanoic acid, and lauric acid.
  • Aliphatic carboxylic acids such as naphthenic acid, cyclopropane carboxylic acid, cyclopentane carboxylic acid, cyclohexyl carboxylic acid (cyclohexane carboxylic acid), adamantane carboxylic acid, norbornane carboxylic acid; benzoic acid and the like Aromatic carboxylic acids can be mentioned.
  • the hafnium compound that the composition of the present invention can contain as the (c) condensation catalyst is not particularly limited as long as it is a compound having a hafnium atom and an organic group.
  • the hafnium compound is preferably a compound represented by the following formula (I) and / or a compound represented by the following formula (II) from the viewpoint of being excellent in sulfidation resistance and excellent in curability.
  • n is an integer of 1 to 4
  • R 1 is a hydrocarbon group
  • R 2 is an alkyl group of 1 to 18 carbon atoms.
  • m is an integer of 1 to 4
  • R 2 is an alkyl group having 1 to 18 carbon atoms
  • R 3 and R 4 are the same or different hydrocarbons having 1 to 18 carbon atoms. Group or alkoxy group.
  • n is an integer of 1 to 4
  • R 1 is a hydrocarbon group
  • R 2 is an alkyl group of 1 to 18 carbon atoms.
  • Examples of the hydrocarbon group in R 1 include aliphatic hydrocarbon groups having 1 to 18 carbon atoms (alkyl groups; including unsaturated aliphatic hydrocarbon groups such as allyl groups), alicyclic hydrocarbon groups, and aryl groups. (Aromatic hydrocarbon group) and combinations thereof.
  • the hydrocarbon group may be linear or branched.
  • the hydrocarbon group can have an unsaturated bond.
  • the hydrocarbon group can have, for example, a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
  • the hydrocarbon group in R 1 has a cyclic structure from the viewpoints of being excellent in sulfidation resistance, excellent in heat resistance (for example, heat-resistant coloring stability), excellent in thin film curability, thermosetting, and compatibility.
  • it is an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof.
  • R 1 can have, for example, an aliphatic hydrocarbon group in addition to the cyclic structure.
  • alicyclic hydrocarbon group, aromatic hydrocarbon group, aliphatic hydrocarbon group is the same as R 1 zirconium compound represented by the above formula (2).
  • alicyclic hydrocarbon groups and aromatic hydrocarbons are superior from the viewpoints of superior sulfidation resistance, excellent heat resistance (for example, heat-resistant coloring stability), excellent thin film curability, thermosetting properties, and compatibility.
  • Group is preferred, at least one selected from the group consisting of cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, naphthene ring, adamantyl group, norbornyl group, phenyl group, naphthyl group and azulene More preferably, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a naphthene ring (naphthate group as R 1 COO—) and a phenyl group are more preferable, and a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group A naphthene ring is particularly preferred.
  • R 2 is an alkyl group having 1 to 18 carbon atoms.
  • the number of carbon atoms is 3 to 8 from the viewpoints of excellent sulfidation resistance, excellent heat resistance (for example, heat resistant color stability), excellent thin film curability, thermosetting property, and compatibility. Is preferred.
  • R 2 examples include a methyl group, an ethyl group, a propyl group (n-propyl group, isopropyl group), a butyl group, a pentyl group, a hexyl group, and an octyl group.
  • methyl group, ethyl group, propyl group (n-propyl group) are preferred from the viewpoints of excellent curability, excellent heat resistance (eg, heat-resistant coloring stability), excellent thin film curability, thermosetting property, and compatibility.
  • hafnium compound having an alicyclic hydrocarbon group as a cyclic structure for example, Hafnium alkoxy (mono-tri) cyclopropanecarboxylate, hafnium tetracyclopropanecarboxylate, Hafnium alkoxy (mono-tri) cyclopentanecarboxylate, hafnium tetracyclopentanecarboxylate, Hafnium alkoxy (mono-tri) cyclohexanecarboxylate, hafnium tetracyclohexanecarboxylate, Hafnium alkoxy (mono-tri) adamantane carboxylate, hafnium tetraadamantane carboxylate, Examples include hafnium alkoxy (mono-tri) naphthate and hafnium tetranaphthate.
  • hafnium compound having an aromatic hydrocarbon group as a cyclic structure examples include hafnium alkoxy (mono-tri) benzene carboxylate and hafnium tetrabenzenecarboxylate.
  • hafnium compound having an aliphatic hydrocarbon group for example, Hafnium alkoxy (mono-tri) butyrate, hafnium tetrabutyrate, Hafnium alkoxy (mono-tri) 2 ethyl hexanoate, hafnium tetra 2 ethyl hexanoate, Examples include hafnium alkoxy (mono-tri) neodecanate and hafnium tetraneodecanate.
  • “(mono to tri)” means any one of mono, di and tri.
  • hafnium trialkoxy mononaphthate and hafnium trialkoxy monoisobutyrate are preferred from the viewpoints of excellent thin film curability, excellent heat resistance (for example, excellent heat-resistant coloring stability), thermosetting property, and compatibility.
  • the hafnium compound represented by the formula (II) will be described below.
  • m is an integer of 1 to 4
  • R 2 is an alkyl group having 1 to 18 carbon atoms
  • R 3 and R 4 are the same or different hydrocarbons having 1 to 18 carbon atoms. Group or alkoxy group.
  • the alkyl group having 1 to 18 carbon atoms is the same as R 2 (the alkyl group having 1 to 18 carbon atoms) in the formula (I).
  • the hydrocarbon group having 1 to 18 carbon atoms is the same as that in which R 1 (hydrocarbon group) in formula (I) has 1 to 18 carbon atoms.
  • Examples of the alkoxy group include those having 1 to 18 carbon atoms such as a methoxy group, an ethoxy group, and a propoxy group.
  • R 3 and R 4 may have a halogen such as a chlorine atom, a bromine atom or a fluorine atom. In formula (II), R 3 and R 4 may be interchanged.
  • hafnium compound represented by the formula (II) examples include: Examples include hafnium alkoxide (mono-tri) 2,4-pentadionate, hafnium-2,4-pentadionate, hafnium alkylpentadionate, and hafnium fluoropentadionate. Among them, hafnium di-n-butoxide (bis-) is preferred from the viewpoints of excellent sulfidation resistance, excellent thin film curability, excellent heat resistance (eg, excellent heat-resistant coloring stability), thermosetting property, and compatibility. 2,4-pentadionate), hafnium-2,4-pentadionate, hafnium tetramethylpentadionate, and hafnium trifluoropentadionate are preferred.
  • the tin compound as the condensation catalyst is not particularly limited.
  • An example is a tetravalent tin compound.
  • Examples of the tetravalent tin compound include a tetravalent tin compound having at least one alkyl group and at least one acyl group.
  • the tin compound can have an acyl group as an ester bond.
  • Examples of the tetravalent tin compound include those represented by the formula (II), bis type and polymer type represented by the formula (II).
  • R 3 is an alkyl group
  • R 4 is a hydrocarbon group
  • a is an integer of 1 to 3.
  • alkyl group examples include those having 1 or more carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and an octyl group.
  • the hydrocarbon group is not particularly limited. Examples thereof include an aliphatic hydrocarbon group such as a methyl group, an ethyl group, and a 2-ethylpentyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and combinations thereof.
  • the hydrocarbon group may be linear or branched.
  • the hydrocarbon group can have an unsaturated bond.
  • the hydrocarbon group can have, for example, a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
  • tin compound examples include dialkyltin compounds such as dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dioctyltin diacetate, and dioctyltin maleate [wherein a is 2 represented by the above formula (II) Dibutyltin oxyacetate dibutytin oxyoctylate, dibutyltin oxylaurate dibutyltin bismethylmalate, dialkyltin dimer such as dibutyltin oxyoleate; or dibutyltin malate polymer, dioctyltin malate polymer; monobutyltin Tris (2-ethylhexanoate) [wherein a is 1 represented by the above formula (II)].
  • dialkyltin compounds such as dibutyltin diacetate, dibutyltin dioctate, dibutyltin dil
  • condensation catalyst dibutyltin diacetate, dibutyltin dioleate, dibutyltin dilaurate, dibutyltin oxyacetate dibutyltin oxyoctylate, dibutyltin oxy Laurate and monobutyltin tris (2-ethylhexanoate) are preferred.
  • the production of the condensation catalyst is not particularly limited.
  • a condensation catalyst can be used individually or in combination of 2 or more types, respectively.
  • the amount of the condensation catalyst is excellent in transparency and sulfidation resistance, excellent in curability, adhesion, heat-resistant coloring stability in a closed system, and balance between transparency and adhesive strength, and excellent in surface curability.
  • the curable silicone resin for example, (a) an organopolysiloxane and / or (b) a silane compound [(a) an organopolysiloxane and (b) a silane compound is used The total of these] is preferably 0.001 to 1 part by mass, more preferably 0.01 to 0.1 part by mass with respect to 100 parts by mass.
  • the amount of the tin compound is superior in terms of transparency and sulfidation resistance, and is excellent in adhesion, stability at room temperature, heat-resistant coloring stability, thin film curability, and adhesion (B )
  • the amount of zinc compound is preferably larger than the amount of tin compound, and the ratio of the amount of tin compound to the amount of (B) zinc compound [tin compound / (B) zinc compound] is 0.01 or more and less than 1. It is preferable that it is 0.01 to 0.1.
  • the zinc compound (B) contained in the composition of the present invention [the zinc compound (B) may be hereinafter referred to as a zinc compound. ], By reacting at least one selected from the group consisting of zinc oxide, zinc carbonate, zinc hydroxide, zinc chloride, zinc sulfate and zinc nitrate: 1 mol to 1.5 mol or more and less than 2 mol of acid. It is obtained.
  • the composition of the present invention is excellent in sulfidation resistance, particularly long-term sulfidation resistance, by containing a zinc compound.
  • Examples of zinc compounds include zinc salts and zinc complexes.
  • the zinc compound may be a binary and / or multi-metal oxide containing zinc, a salt and / or complex thereof, or a combination thereof.
  • the acid used for producing the zinc compound is not particularly limited, and examples thereof include inorganic acids and organic acids [organic carboxylic acids: for example, R- (COOH) n (n is an integer of 1 or more). It is done. ], Any of these esters.
  • examples of the inorganic acid include phosphoric acid and boric acid.
  • the hydrocarbon group that the organic carboxylic acid has other than the carboxyl group is not particularly limited. Examples thereof include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof.
  • Examples of the organic acid include saturated carboxylic acids having 2 to 30 carbon atoms such as stearic acid, palmitic acid, lauric acid and 2-ethylhexanoic acid; and unsaturated carboxylic acids such as (meth) acrylic acid.
  • the hydrocarbon group forming the ester in the ester of the acid is not particularly limited. For example, the same thing as the above is mentioned. Among these, phosphoric acid, 2-ethylhexanoic acid, benzoic acid, and esters thereof are preferable from the viewpoint of excellent transparency and sulfidation resistance (especially sulfidation resistance over a long period of time).
  • the amount of the acid used for producing the zinc compound is at least one selected from the group consisting of zinc oxide, zinc carbonate, zinc hydroxide, zinc chloride, zinc sulfate and zinc nitrate: 1 mol. 1.5 mol or more and less than 2 mol. In such a range, transparency and sulfidation resistance (especially sulfidation resistance over a long period) are excellent.
  • the amount of the acid is 1.5 to 1 with respect to at least one selected from the group consisting of zinc oxide, zinc carbonate, zinc hydroxide, zinc chloride, zinc sulfate and zinc nitrate: 1 mol. 0.9 mol is preferable, and 1.6 to 1.8 mol is more preferable.
  • Examples of the zinc compound include those represented by Zn a (O) x (OH) y (—O—CO—R) z , phosphates having zinc, and borates having zinc.
  • R is a hydrocarbon group. The hydrocarbon group is as defined above. When there are a plurality of R, the plurality of R may be the same or different.
  • a is 1 or more (an integer of 1 or more)
  • x and y are 0 or more (an integer of 0 or more)
  • z is 1 or more (an integer of 1 or more)
  • the zinc compound examples include Zn (OH) (— O—CO—R), R—CO—O—Zn—O—Zn—O—CO—R; O—Zn—OP—, Examples thereof include phosphates having zinc such as Zn—O—Zn—O—P—O—.
  • the zinc compound can have a bond such as —Zn—O—Zn— in its structure. Such bonds can be formed, for example, by dehydration condensation of the product in the production of zinc compounds.
  • Zinc compounds can be used alone or in combination of two or more.
  • the zinc compound can contain as raw materials zinc oxide, zinc carbonate, zinc hydroxide, zinc chloride, zinc sulfate, zinc nitrate; raw acid as an unreacted material.
  • the zinc compound is at least one selected from the group consisting of zinc oxide, zinc carbonate, zinc hydroxide, zinc chloride, zinc sulfate and zinc nitrate, except that the acid is reacted in an amount of 1.5 mol or more and less than 2 mol with respect to 1 mol.
  • the zinc compound can be produced by stirring at least one member selected from the group consisting of zinc oxide, zinc carbonate, zinc hydroxide, zinc chloride, zinc sulfate and zinc nitrate and an acid under room temperature conditions or by heating. it can.
  • the amount of the zinc compound is 0.01 to 5 parts by mass with respect to 100 parts by mass of the curable silicone resin composition. In such a range, transparency and sulfidation resistance (especially sulfidation resistance over a long period) are excellent.
  • the amount of the zinc compound is 0. 0 with respect to 100 parts by mass of the curable silicone resin composition from the viewpoint of being excellent in transparency and sulfidation resistance (especially sulfidation resistance over a long period of time) and excellent in compatibility with the resin.
  • the amount is preferably from 5 to 5 parts by mass, more preferably from 0.1 to 5 parts by mass, and still more preferably from 0.1 to 1 part by mass.
  • the amount of the zinc compound can be 0.01 to 5 parts by mass with respect to 100 parts by mass of the curable silicone resin. In such a range, transparency and sulfidation resistance (especially sulfidation resistance over a long period) are excellent.
  • the amount of the zinc compound is 0.05 to 5 mass with respect to 100 parts by mass of the curable silicone resin from the viewpoint of transparency and sulfidation resistance (especially long-term sulfidation resistance) and excellent compatibility with the resin.
  • Part by weight preferably 0.1 to 5 parts by weight, more preferably 0.1 to 1 part by weight.
  • the composition of the present invention can further contain at least one selected from the group consisting of a phosphate ester, a phosphite ester and a boron compound as component (D).
  • a phosphate ester a phosphite ester and a boron compound as component (D)
  • the composition of the present invention is excellent in transparency, long-term reliability at high temperatures, adhesion, Excellent durability.
  • the composition of the present invention contains at least a boron compound as the component (D)
  • the composition of the present invention has excellent transparency, excellent long-term reliability at high temperatures, and excellent adhesion to an adherend.
  • the phosphoric acid ester as the component (D) contained in the composition of the present invention is an ester of phosphoric acid (orthophosphoric acid) [aliphatic ester (the aliphatic hydrocarbon group of the aliphatic ester is linear or branched. A cyclic ester), an aromatic ester, an ester having an aliphatic hydrocarbon group and an aromatic hydrocarbon group].
  • the phosphate ester may be any of monoester, diester and triester.
  • the phosphoric acid ester means an organic phosphoric acid ester.
  • the phosphate formed only with phosphoric acid and an inorganic substance is not included in this invention.
  • the phosphorous acid ester as the component (D) contained in the composition of the present invention is an ester of phosphorous acid (phosphonic acid) [aliphatic ester (the aliphatic hydrocarbon group is linear, branched or cyclic. An aromatic ester, an aliphatic hydrocarbon group and an ester having an aromatic hydrocarbon group].
  • the phosphite may be any of monoesters, diesters and triesters. In the present invention, phosphite means an organic phosphite. In addition, the phosphite formed only with phosphorous acid and an inorganic substance is not included in this invention.
  • the phosphite ester (organic phosphite ester, the same applies hereinafter) is not particularly limited as long as it is an ester (including monoester, diester, triester) of phosphorous acid and an alcohol or an aromatic compound having a hydroxy group.
  • Examples of the phosphite include those represented by the following formula (dI-1).
  • P- (OR 1 ) 3 (dI-1) In the formula, each R 1 independently represents an alkyl group having 1 to 18 carbon atoms, an aryl group, or a silyl group.
  • alkyl group having 1 to 18 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, various pentyl groups, hexyl group, and 2-ethylhexyl group. , Heptyl group, octyl group, nonyl group, decyl group.
  • aryl group include a phenyl group, a tolyl group, and a naphthyl group.
  • the silyl group is not particularly limited.
  • trialkylsilyl group such as trimethylsilyl group, triethylsilyl group, dimethylethylsilyl group
  • alkoxydialkylsilyl group such as methoxydimethylsilyl group
  • dialkoxyalkylsilyl group such as dimethoxymethylsilyl group
  • trimethoxysilyl group and trialkoxysilyl groups such as
  • R 1 is preferably an alkyl group having 1 to 18 carbon atoms, and preferably an alkyl group having 1 to 18 carbon atoms from the viewpoint of excellent compatibility with (A) polysiloxane and / or (B) silane compound. Is more preferable.
  • phosphites include tri-2-ethyl hexane phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, triethyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite.
  • tris (tridecyl) phosphite diphenyl mono (2-ethylhexyl) phosphite, diphenyl decyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyl dipropylene glycol diphosphite, tetraphenyl tetra (tridecyl) pentaerythritol tetra Phosphite, trilauryl trithiophosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite , Tristearyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) phosphite, hydrogenated bisphenol A
  • the phosphoric acid ester (organic phosphoric acid ester, the same applies hereinafter) is not particularly limited as long as it is an ester (including monoesters, diesters, triesters) of phosphoric acid and an alcohol or an aromatic compound having a hydroxy group.
  • Examples of the phosphoric acid ester include those represented by the following formula (dI-2).
  • O P- (OR 2 ) 3 (dI-2)
  • each R 2 independently represents an alkyl group having 1 to 18 carbon atoms, an aryl group, or a silyl group.
  • An alkyl group having 1 to 18 carbon atoms, an aryl group, and a silyl group are as defined above.
  • R 2 is preferably an alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, from the viewpoint of excellent compatibility with (A) polysiloxane and / or (B) silane compound. Is more preferable.
  • the phosphate ester include monoesters such as propyl phosphate ester, butyl phosphate ester and hexyl phosphate ester; diesters such as dipropyl phosphate ester, dibutyl phosphate ester and dihexyl phosphate ester; triethyl phosphate and tripropyl phosphate.
  • Examples include acid esters, tributyl phosphate esters, trihexyl phosphate esters, triesters such as tris (trimethylsilyl) phosphate; polyethylene oxide alkyl ether phosphate esters such as polyethylene oxide dodecyl ether phosphate esters.
  • Phosphoric acid esters and phosphites are superior in transparency, have excellent adhesion, curability, smoothness, and storage stability, and have a non-phosphorus atom from the viewpoint that the pot life and curing time are appropriately long. It preferably has a shared electron pair, more preferably a phosphite (organic phosphite), more preferably a phosphite (organic phosphite) represented by the above formula (dI-1), Particularly preferred are tri-2-ethylhexane phosphite, triphenyl phosphite, and tris phosphite (trimethylsilyl).
  • the phosphoric ester is superior in transparency, excellent in adhesion, curability, smoothness, and storage stability, and is represented by the above formula (dI-2) from the viewpoint that the pot life and the curing time are appropriately long.
  • the phosphoric acid ester (organic phosphoric acid ester) is preferable, and triethyl phosphate and tris phosphate (trimethylsilyl) are more preferable.
  • the boron compound that can be contained as the component (D) in the composition of the present invention is not particularly limited as long as it is a compound having a boron atom.
  • One preferred embodiment is an organoboron compound.
  • the boron compound include compounds represented by the following formula (dII-1) to the following formula (dII-5).
  • Boron compounds are represented by the following formulas (dII-1) to (dII-5) from the viewpoint of superior transparency, excellent long-term reliability at high temperatures, and excellent adhesion to an adherend. It is preferably at least one selected from the group consisting of compounds.
  • R independently represents a hydrogen atom, an alkyl group, an allyl group, an aryl group, a silyl group or a phosphine group
  • R ′ independently represents A divalent hydrocarbon group, wherein n is 0 or 1 in the formula (dII-2), and when n is 0, the boron atom and R are bonded by a single bond;
  • the alkyl group represented by R in the formulas (dII-1) to (dII-5) is preferably an alkyl group having 1 to 18 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, Isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, Examples thereof include an n-nonyl group and an n-decyl group.
  • Examples of the allyl group represented by R in the formulas (dII-1) to (dII-5) include a 2-propenyl group (—CH 2 CH ⁇ CH 2 ).
  • the aryl group represented by R in the formulas (dII-1) to (dII-5) is preferably an aryl group having 6 to 18 carbon atoms, such as a phenyl group, a tolyl group, a xylyl group, and a cumenyl group. And a mesityl group.
  • Examples of the silyl group represented by R in the formulas (dII-1) to (dII-5) include an unsubstituted silyl group; a monoalkylsilyl group such as a methylsilyl group; a dialkylsilyl group such as a dimethylsilyl group; a trimethylsilyl group A trialkylsilyl group such as methoxydimethylsilyl group; a dialkoxyalkylsilyl group such as dimethoxymethylsilyl group; a trialkylsilyl group such as trimethoxysilyl group; An alkoxysilyl group; and the like.
  • Examples of the phosphine group represented by R in the formulas (dII-1) to (dII-5) include a dimethylphosphine group, a diphenylphosphine group, a ditolylphosphine group, and a dinaphthylphosphine group.
  • the divalent hydrocarbon group represented by R ′ in the formulas (dII-1) to (dII-5) is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, more preferably a carbon number.
  • 1-20 alkylene groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, heptane-1,5-diyl group, hexane-1,6- A diyl group etc. are mentioned.
  • Examples of the boron compounds represented by the formulas (dII-1) to (dII-5) include 2-isopropoxy-4,4,5,5-tetramethyl represented by the following formula (dII-6) -1,3,2-dioxaborolane, tris (trimethylsilyl) borate represented by the following formula (dII-7), 2,4,6-trimethoxyboroxine represented by the following formula (dII-8), Bis (pinacolato) diboron represented by (dII-9), 2-cyclopropyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2- (3,5-dimethylphenyl)- 4,4,5,5-tetramethyl-1,3-dioxaborolane.
  • 2-isopropoxy-4,4,5,5-tetramethyl-1 is preferred because the composition of the present invention has superior long-term reliability at high temperatures and excellent adhesion to an adherend.
  • D component can be used individually or in combination of 2 types or more, respectively.
  • the amount of the component (D) is more excellent in transparency, curability, smoothness, storage stability, excellent long-term reliability under high temperature, and the pot life and curing time are appropriately long.
  • the amount is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the curable silicone resin.
  • component (D) is a phosphate ester and / or a phosphite ester, or contains a phosphate ester and / or a phosphite ester
  • the amount of phosphate ester or phosphite ester (phosphate ester and phosphorous ester) From the viewpoint that the total amount of these when acid esters are used in combination is excellent in transparency, adhesion, curability, smoothness, excellent storage stability, and the pot life and curing time are appropriate lengths.
  • the amount is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the curable silicone resin.
  • phosphoric acid ester and phosphite ester are used in combination, these molar ratios (phosphoric acid ester / phosphorous acid ester) are excellent in transparency, excellent in curability, smoothness, storage stability, and adhesion, and are acceptable. From the viewpoint that the working time and the curing time become appropriate lengths, 1/10 to 10/1 is preferable, and 1/10 to 2/1 is more preferable.
  • the amount of the component (D) is more excellent in transparency, adhesion to the adherend, curability, smoothness, storage stability, under high temperature From the standpoint of excellent long-term reliability at the time of use, and an appropriate working time and curing time, the amount is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the curable silicone resin. More preferred is 5 to 5 parts by mass.
  • the silicone resin composition of the present invention can further contain additives as necessary within a range not impairing the object and effects of the present invention.
  • the additive include a curing agent, a metal compound other than a zinc compound, a catalyst (for example, a condensation catalyst other than the above, a condensation catalyst other than the above; a hydrosilylation catalyst; a Lewis acid catalyst, a Lewis base catalyst; a cationic polymerization catalyst.
  • Polymerization initiators for example, thermal polymerization initiators and photopolymerization initiators
  • inorganic fillers for example, antioxidants, lubricants, ultraviolet absorbers, thermal light stabilizers, dispersants, antistatic agents, Polymerization inhibitors, antifoaming agents, curing accelerators, solvents, fluorescent substances (including inorganic and organic substances), anti-aging agents, radical inhibitors, adhesion improvers, two alkoxysilyl groups and divalent organic groups
  • Compounds excluding the curable silicone resin contained in the composition of the present invention
  • coupling agents adhesion imparting agents (adhesion imparting agents) such as isocyanurate compounds, flame retardants, surfactants, storage Qualitative improver, ozone anti-aging agent, thickener, plasticizer, radiation blocker, nucleating agent, coupling agent, conductivity imparting agent, phosphorus peroxide decomposing agent, pigment, metal deactivator, physical property adjustment Agents.
  • Various additives are not particularly limited. For example,
  • the curing agent that can be further contained in the silicone resin composition of the present invention is not particularly limited. It can select suitably according to the kind of reactive functional group which organopolysiloxane has.
  • the curing agent include amine compounds (polyamine compounds), polyamide compounds, dicyandiamide, acid anhydrides, carboxylic acid compounds, and phenol resins.
  • aliphatic amines such as ethylenediamine, triethylenepentamine, hexamethylenediamine, dimer acid-modified ethylenediamine, N-ethylaminopiperazine, isophoronediamine; metaphenylenediamine, paraphenylenediamine, 3,3′- Aromatic amines such as diaminodiphenyl sulfone, 4,4′-diaminodiphenol sulfone, 4,4′-diaminodiphenol methane, 4,4′-diaminodiphenol ether; mercaptopropionic acid esters, epoxy resins Mercaptans such as terminal mercapto compounds; bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobis
  • aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride
  • imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole And its salts, amine adducts obtained by reacting the above aliphatic amines, aromatic amines, and / or imidazoles with epoxy resins
  • hydrazines such as adipic acid dihydrazide
  • dimethylbenzylamine, 1,8-diazabicyclo Tertiary amines such as [5,4,0] undec-7-ene
  • organics such as triphenylphosphine Sufin like; dicyandiamide, and the like.
  • the above compound can be used as a curing agent for an organopolysiloxane having a reactive functional group selected from, for example, an epoxy group, (meth) acryloyl group, amino group, carbinol group, mercapto group, carboxyl group and phenol group.
  • a reactive functional group selected from, for example, an epoxy group, (meth) acryloyl group, amino group, carbinol group, mercapto group, carboxyl group and phenol group.
  • a compound having two alkoxysilyl groups and a divalent organic group as an additive can be used as an adhesion-imparting agent (adhesion-imparting agent).
  • an adhesion-imparting agent adheresion-imparting agent
  • the composition of the present invention further contains a compound having two alkoxysilyl groups, the adhesion and adhesion are excellent.
  • the alkoxysilyl group can have, for example, an alkyl group such as a methyl group or an ethyl group in addition to the alkoxy group.
  • the divalent organic group can have, for example, a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom, a hydrocarbon group such as a divalent alkane (alkylene group);
  • a group in which two alkylene groups are bonded via an imino group (—NH—)] (for example, a group represented by the following formula (VIII)) can be used.
  • the compound having two alkoxysilyl groups and a divalent organic group include bis (alkoxysilyl) alkanes and bis (alkoxysilylalkyl) amines.
  • Examples of the compound having two alkoxysilyl groups and a divalent organic group include a compound represented by the following formula (VII).
  • each of R 7 to R 8 is an alkyl group
  • R 9 is a divalent organic group which may have a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom (the divalent organic group is And a is an integer of 1 to 3, respectively.
  • the alkyl group include a methyl group and an ethyl group.
  • Specific examples of the divalent organic group as R 9 include an alkylene group having 1 to 10 carbon atoms and a group represented by the following formula (VIII). —R a —NH—R b — (VIII) (In Formula VIII, R a and R b are each an alkylene group having 1 to 10 carbon atoms.)
  • Examples of the compound having two alkoxysilyl groups and a divalent organic group include 1,2-bis (triethoxysilyl) ethane, 1,4-bis (trimethoxysilyl) butane, 1-methyldimethoxysilyl- 4-trimethoxysilylbutane, 1,4-bis (methyldimethoxysilyl) butane, 1,5-bis (trimethoxysilyl) pentane, 1,4-bis (trimethoxysilyl) pentane, 1-methyldimethoxysilyl-5 -Trimethoxysilylpentane, 1,5-bis (methyldimethoxysilyl) pentane, 1,6-bis (trimethoxysilyl) hexane, 1,4-bis (trimethoxysilyl) hexane, 1,5-bis (trimethoxy Silyl) hexane, 2,5-bis (trimethoxysilyl) hexane, 1,6-bis (methyld
  • Compounds having two alkoxysilyl groups and a divalent organic group have excellent transparency, excellent curability, smoothness, and storage stability.
  • the amount of the compound having two alkoxysilyl groups and a divalent organic group is excellent in transparency, curability, smoothness, and storage stability. From the standpoint of excellent performance, pot life and curing time are appropriately long, it is preferably 0.1 to 10 parts by weight, and 0.1 to 5 parts by weight with respect to 100 parts by weight of the curable silicone resin. More preferably, it is part.
  • the isocyanurate compound as an additive is not particularly limited as long as it is a compound that forms an isocyanurate skeleton by a trimer of an isocyanate compound.
  • the composition of the present invention further contains an isocyanurate compound, the adhesiveness and adhesion are excellent.
  • an isocyanurate compound the compound represented by following formula (1) is mentioned, for example.
  • R represents an organic group, a functional group, or a monovalent hydrocarbon group that may have an aliphatic unsaturated bond.
  • R can contain functional groups such as an epoxy group, a glycidoxy group, an alkoxysilyl group, a (meth) acryloyl group, and an isocyanate group.
  • R represents at least one functional group selected from the group consisting of an epoxy group, a glycidoxy group, an alkoxysilyl group, a (meth) acryloyl group and an isocyanate group, and a hydrocarbon group [for example, an aliphatic hydrocarbon group (chain, branched) Any of cyclic groups and unsaturated bonds may be included.), Aromatic hydrocarbon groups, and combinations thereof. ] Can be combined. Examples of the organic group are the same as described above.
  • the alkoxysilyl group can have 1 to 3 alkoxy groups, and the alkoxy group can have 1 or more carbon atoms.
  • the alkoxysilyl group can have a hydrocarbon group in addition to the alkoxy group.
  • the hydrocarbon group is not particularly limited.
  • Examples of the isocyanurate derivative represented by the above formula include tris- (3-trimethoxysilylpropyl) isocyanurate.
  • the isocyanurate compounds can be used alone or in combination of two or more.
  • the amount of the isocyanurate compound is preferably from 0.1 to 10 parts by weight, preferably from 0.1 to 5 parts by weight based on 100 parts by weight of the curable silicone resin, from the viewpoint of excellent adhesiveness, adhesion and transparency. More preferred is part by mass.
  • inorganic fluorescent materials include yttrium, aluminum, garnet-based YAG phosphors, ZnS phosphors, Y 2 O 2 S phosphors, red-emitting phosphors, and blue-emitting phosphors that are widely used in LEDs. Body and green light emitting phosphor.
  • the production of the silicone resin composition of the present invention is not particularly limited. For example, it can manufacture by mixing the said (D) component and additive which can be used as needed, and a curable silicone resin composition and a zinc compound.
  • the silicone resin composition of the present invention can be produced as a one-pack type or a two-pack type.
  • a cured product [silicone resin layer, sealing material] obtained using the composition of the present invention (when the thickness of the cured product is 2 mm) is an ultraviolet / visible absorption spectrum measuring device (Shimadzu) according to JIS K0115: 2004.
  • the transmittance measured at a wavelength of 400 nm using a manufacturing company, the same applies hereinafter) is preferably 80% or more, and more preferably 85% or more.
  • the composition of the present invention can be used, for example, as an adhesive, a primer, or a sealing material (for example, for a semiconductor light emitting device).
  • the semiconductor light emitting device (photo semiconductor device) to which the composition of the present invention can be applied include a light emitting diode (LED), an organic electroluminescent device (organic EL), a laser diode, and an LED array.
  • the LED chip include a high power LED, a high luminance LED, and a general luminance LED.
  • the composition of the present invention is used for, for example, display materials, optical recording medium materials, optical equipment materials, optical component materials, optical fiber materials, optical / electronic functional organic materials, semiconductor integrated circuit peripheral materials, solar cell materials, etc. Can be used.
  • adherends to which the composition of the present invention can be applied include metals (eg, Group 11 metals), glass, plastics (eg, polyphthalamide, polyimide, polycarbonate, (meth) acrylic resin).
  • polyphthalamide is used as a material for a package having an optical semiconductor element such as an LED), rubber, and a semiconductor (for example, a semiconductor light emitting element).
  • the Group 11 metal is preferably at least one selected from the group consisting of copper, silver and gold. From the viewpoint that the composition of the present invention is superior in transparency and sulfidation resistance, it is mentioned as one of preferred embodiments that it is used in the presence of silver.
  • the silicone resin layer obtained from the silicone resin composition of the present invention can be adhered to an adherend.
  • the composition of the present invention is not particularly limited for its use.
  • the usage method including the hardening process which hardens the silicone resin composition of this invention in presence of silver is mentioned. This is the same as the method of using the silicone resin composition of the present invention.
  • a method of using the composition of the present invention will be described below as a method of using the silicone resin composition of the present invention.
  • the silicone resin containing structure of this invention, its manufacturing method; the optical semiconductor element sealing body of this invention, and its manufacturing method shall be demonstrated by demonstrating the usage method of the silicone resin composition of this invention.
  • the usage method of the silicone resin composition of this invention is a usage method of the silicone resin composition including the hardening process which hardens the silicone resin composition of this invention in presence of silver.
  • the usage method of the silicone resin composition of this invention may be called “the usage method of this invention” below.
  • the usage method of this invention includes the hardening process which hardens the silicone resin composition of this invention in presence of silver.
  • the silicone resin composition used in the method of use of the present invention is not particularly limited as long as it is the silicone resin composition of the present invention.
  • the silver used in the method of use of the present invention is not particularly limited. Examples thereof include a silver member, a member containing silver, and silver plating. Specifically, a reflector, an electrode for a solar cell, and the like can be given.
  • the silicone resin composition can be cured after being applied to silver to form a laminate.
  • the method for applying the silicone resin composition to silver is not particularly limited.
  • application by brushing or the like; a method using a dispenser, a potting method, screen printing, transfer molding, or injection molding may be mentioned.
  • the curing step can cure the silicone resin composition by heating and / or light irradiation.
  • the temperature at which the silicone resin composition is heated depends on curability (for example, curability in a closed system), adhesiveness, heat-resistant coloring stability, and balance between transparency and adhesive strength.
  • Excellent, curing time, pot life can be set to an appropriate length, alcohol that is a by-product due to condensation reaction can be further suppressed from foaming, cracks in the cured product can be suppressed, smoothness of the cured product, From the viewpoint of excellent moldability and physical properties, curing is preferably performed at around 80 ° C. to 150 ° C., more preferably around 150 ° C.
  • the light used when the silicone resin composition is cured by light irradiation is not particularly limited. Examples thereof include ultraviolet rays and electron beams.
  • the laminate obtained in the curing step has a silicone resin layer obtained from the silicone resin composition and a member containing silver (a layer containing silver).
  • the laminate obtained in the curing step include the silicone resin-containing structure of the present invention.
  • Specific examples of the laminate (silicone resin-containing structure of the present invention) include, for example, an optical semiconductor element encapsulant (optical semiconductor element encapsulant of the present invention), a solar cell encapsulant, and the like.
  • the laminated body obtained in the curing step is mentioned as one of preferred embodiments in which silver is covered with a silicone resin layer obtained from the silicone resin composition.
  • the silicone resin layer may directly cover silver.
  • a resin layer, a glass layer, an air layer between a silicone resin layer and silver
  • another transparent layer for example, a resin layer, a glass layer, an air layer
  • the optical semiconductor element is not particularly limited.
  • the aspect which exists between the silicone resin layer and the member containing silver may be sufficient as an optical semiconductor element.
  • the optical semiconductor element may be in parallel with the member containing silver, and the silicone resin layer may seal the optical semiconductor element and the member containing silver.
  • the optical semiconductor element is in parallel with a member containing two silver, the optical semiconductor element is located between the first member and the second member, and the silicone resin layer includes the optical semiconductor element and two silver.
  • the aspect which seals a member may be sufficient.
  • FIG. 1 is a cross-sectional view schematically showing an example of a laminate in the present invention.
  • a laminated body 100 includes a member (member containing silver) 120 and a silicone resin layer 102.
  • FIG. 2 is a cross-sectional view schematically showing another example of the laminate in the present invention.
  • the laminate 200 includes a member (a member containing silver) 220, an optical semiconductor element 203, and a silicone resin layer 202.
  • the laminate 200 can further include a transparent layer (not shown) between the optical semiconductor element 203 and the silicone resin layer 202.
  • the transparent layer include a resin layer, a glass layer, and an air layer.
  • the cured product obtained by curing the silicone resin composition of the present invention has sulfur resistance.
  • the sulfidation resistance based on the spectral reflectance maintenance factor is evaluated as follows. First, the silicone resin composition of the present invention is applied to a thickness of 1 mm on a silver member (a metal layer obtained using silver) and cured to form a laminate having the member and the silicone resin layer, A sulfuration resistance test was performed in which the laminate was placed in hydrogen sulfide gas having a theoretical value of 560 ppm at 25 ° C., and the spectrum of the laminate was measured before the sulfurization test and 24 and 72 hours after the start of the sulfurization test.
  • Spectral reflectance maintenance ratio (spectral reflectance after sulfidation test / spectral reflectance before sulfurization test) ⁇ 100].
  • Spectral reflectance maintenance factor is calculated.
  • sulfidation resistance test about 10 g of iron sulfide pulverized in powder form (a large excess with respect to 0.5 mmol of hydrochloric acid) is placed on the bottom of a 10 L desiccator. A dish (having a through-hole) was mounted in a desiccator, and the laminate was placed on the eye dish.
  • the sulfidation resistance in the present invention an evaluation was performed in which the discoloration of silver in the cured sample was confirmed visually after 24 hours and 72 hours from the generation of hydrogen sulfide in the above sulfidation resistance test. It is preferable that no discoloration is confirmed after 24 hours and 72 hours from the start of the sulfidation resistance test.
  • the optical semiconductor element sealing body of the present invention is an optical semiconductor element sealing body that seals an optical semiconductor element and a member containing silver with a silicone resin layer obtained from the silicone resin composition of the present invention. If the silicone resin composition used for the optical semiconductor element sealing body of this invention is a silicone resin composition of this invention, it will not restrict
  • the member containing silver used for the optical semiconductor element sealing body of the present invention is not particularly limited. For example, the same thing as the above is mentioned.
  • the optical semiconductor element used for the sealed optical semiconductor element of the present invention is not particularly limited. For example, the same thing as the above is mentioned.
  • the optical semiconductor element sealing body includes, for example, an optical semiconductor element, a frame having a recess, and a sealing material, and the optical semiconductor element is disposed at the bottom of the recess, and the frame is the recess And a reflector containing silver or the like, wherein the sealing material seals the optical semiconductor element and the reflector, and the sealing material is obtained from the silicone resin composition of the present invention. Is mentioned.
  • FIG. 3 is a cross-sectional view schematically showing an example of the sealed optical semiconductor element of the present invention.
  • an optical semiconductor element sealing body 300 includes an optical semiconductor element 303, a frame 304 having a recess 302, and a sealing material 308, and the optical semiconductor element 303 is a bottom portion of the recess 302 (not shown).
  • the frame 304 is provided with a reflector 320 obtained from a group 11 metal (for example, silver) on the side surface (not shown) of the recess 302, and the sealing material 308 includes the optical semiconductor element 303 and the reflector. 320 is sealed.
  • the sealing material 308 is obtained by curing the silicone resin composition of the present invention.
  • the recessed portion 302 may be filled with the silicone resin composition of the present invention up to the shaded portion 306.
  • the portion denoted by reference numeral 308 may be another transparent layer, and the hatched portion 306 may be a sealing material included in the sealed optical semiconductor element of the present invention.
  • the sealing material can contain a fluorescent substance or the like.
  • Each optical semiconductor element sealing body can have one or a plurality of optical semiconductor elements.
  • the optical semiconductor element may be disposed in the frame with the light emitting layer (the surface opposite to the surface in contact with the mount member) facing up.
  • the optical semiconductor element 303 is disposed on the bottom (not shown) of the recess 302 formed from the frame 304 and the substrate 310, and is fixed by the mount member 301.
  • the reflector there may be mentioned one in which the end portions 312 and 314 included in the frame body 304 are integrally coupled, and the reflector forms a side surface and a bottom portion.
  • the optical semiconductor element can be disposed on the bottom of the reflector.
  • the reflector 320 may have a tapered opening end (not shown) whose cross-sectional dimension increases as the distance from the bottom (not shown) of the recess 302 increases.
  • Examples of the mounting member include silver paste and resin.
  • each electrode (not shown) of the optical semiconductor element 303 and the external electrode 309 are wire bonded by a conductive wire 307.
  • the recess 302 can be sealed with a sealing material 308, 306, or 302 (a portion in which the portion 308 and the portion 306 are combined).
  • a sealing material 308, 306, or 302 a portion in which the portion 308 and the portion 306 are combined.
  • the sealing material has low hardness and small cure shrinkage, so that the sealing material can be prevented from peeling from the recess due to cure shrinkage or the wire being disconnected. it can.
  • FIG. 4 is a cross-sectional view schematically showing another example of the sealed optical semiconductor element of the present invention.
  • the optical semiconductor element sealing body 400 has a lens 401 on the optical semiconductor element sealing body 300 shown in FIG.
  • the lens 401 may be formed using the silicone resin composition of the present invention.
  • FIG. 5 is a cross-sectional view schematically showing another example of the sealed optical semiconductor element of the present invention.
  • the optical semiconductor element sealing body 500 includes an optical semiconductor element 503, a substrate 510 including a frame (not shown) having a recess (not shown), and a sealing material 502.
  • the optical semiconductor element 503 is disposed at the bottom (not shown) of the recess, and the frame includes a reflector 520 obtained from a group 11 metal (for example, silver) on the side surface (not shown) of the recess.
  • a resin 510 having a lamp function has a substrate 510 and inner leads 505.
  • the sealing material 502 is obtained from the above-described silicone resin composition, and the sealing material 502 seals the optical semiconductor element 503 and the reflector 520.
  • the sealing material 502 has sulfidation resistance.
  • a frame (not shown) and the substrate 510 can be integrally formed.
  • the reflector 520 may be formed integrally with the side surface and the bottom (not shown) of the recess.
  • the optical semiconductor element 503 is fixed on the substrate 510 with a mount member 501. Examples of the mount member include silver paste and resin.
  • Each electrode (not shown) of the optical semiconductor element 503 is wire-bonded by a conductive wire 507.
  • Resin 506 can be formed using the silicone resin composition of the present invention.
  • FIG. 6 is a diagram schematically showing an example of an LED display using the silicone resin composition of the present invention and / or the sealed optical semiconductor element of the present invention.
  • an LED display 600 includes an optical semiconductor element sealing body 601 arranged in a matrix in a housing 604, the optical semiconductor element sealing body 601 is sealed with a sealing material 606, and the housing 604.
  • the light shielding member 605 is arranged in a part of the structure.
  • the silicone resin composition of the present invention can be used for the sealing material 606.
  • the optical semiconductor element sealing body of this invention can be used as the optical semiconductor element sealing body 601.
  • silicone resin-containing structure of the present invention or the sealed optical semiconductor element of the present invention examples include automobile lamps (head lamps, tail lamps, directional lamps, etc.), household lighting fixtures, industrial lighting fixtures, Stage lighting fixtures, displays, signals, projectors.
  • Polysiloxane 2 A 500 mL three-necked flask equipped with a stirrer and reflux condenser and a polysiloxane having silanol groups at both ends (polydimethylsiloxane- ⁇ , ⁇ -diol, weight average molecular weight 49,000, trade name ss10, manufactured by Shin-Etsu Chemical Co., Ltd.) The same applies hereinafter.) 100 parts by weight, 10 parts by weight of tetramethoxysilane, and 0.1 parts by weight of acetic acid were added, and the reaction was carried out under a nitrogen atmosphere at 100 ° C.
  • polysiloxane 2 The main structure of polysiloxane 2 is represented by the following formula. Polysiloxane 2 is a trimethoxysilylsiloxane at both ends. The weight average molecular weight of polysiloxane 2 (weight average molecular weight expressed in terms of polystyrene by gel permeation chromatography (GPC) using chloroform as a solvent. The same applies hereinafter) was 55,000.
  • Polysiloxane 3 A 500 mL three-necked flask was equipped with a stirrer and a reflux condenser, and 100 parts by weight of polysiloxane (ss10) having silanol groups at both ends and 10 methoxy oligomers having a methoxy group (KC-89, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.1 parts by weight of acetic acid and 0.1 parts by weight of acetic acid were added and reacted under a nitrogen atmosphere at 140 ° C for 15 hours. The disappearance of the silanol group of ss10 was confirmed by 1 H-NMR analysis. The obtained polysiloxane was designated as polysiloxane 3.
  • the main structure of the polysiloxane 3 is represented by the following formula. Organosiloxane 3 is a terminal polymethoxysilylsiloxane. The weight average molecular weight of polysiloxane 3 was 60,000.
  • Polysiloxane 8 100 parts by mass of polydimethylsiloxane having silanol groups at both ends (weight average molecular weight 28,000, trade name ss70, manufactured by Shin-Etsu Chemical Co., Ltd.), methacryloxypropyltrimethoxysilane (trade name KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 mass And 0.01 parts by mass of tin 2-ethylhexanoate (manufactured by Kanto Chemical Co., Ltd.) as a catalyst were placed in a reaction vessel and reacted for 6 hours while maintaining the pressure at 10 mmHg and the temperature at 80 ° C.
  • the obtained reaction product was subjected to 1 H-NMR analysis, and it was confirmed that both ends of polydimethylsiloxane were methacryloxypropyldimethoxysilyl groups.
  • the obtained polydimethylsiloxane having methacryloxypropyldimethoxysilyl groups at both ends is designated as polysiloxane 8 (M-ss70).
  • the weight average molecular weight of polysiloxane 8 was 35,000.
  • Spectral reflectance maintenance factor Sulfurization resistance was evaluated by spectral reflectance maintenance factor. Using a URE-30 manufactured by USHIO INC. As a spectral reflectometer, a cured sample before the sulfidation test and after the sulfidation test (24 and 72 hours after generation of hydrogen sulfide) The spectral reflectance at 475 nm (measurement wavelength) was measured. Spectral reflectance maintenance ratio was calculated by applying the spectral reflectance before and after the sulfuration resistance test to the following equation.
  • Spectral reflectance maintenance factor (Spectral reflectance after anti-sulfurization test / Spectral reflectance before anti-sulfurization test) ⁇ 100
  • ⁇ the resistance to sulfidation was excellent
  • x the resistance to sulfidation was excellent
  • Curing conditions (cured sample for measuring transmittance and cured sample for evaluating sulfidation resistance) -When the silicone resin composition contains (c) condensation catalysts 1 to 3: heated for 24 hours at 150 ° C-When the silicone resin composition contains a hydrosilyl catalyst (addition-type curing catalyst): 150 ° C Heat for 6 hours under the conditions ⁇ When the silicone resin composition contains a thermal radical initiator: for 3 hours under the condition of 150 ° C.
  • the silicone resin composition contains a radical photoinitiator: under high-pressure mercury lamp irradiation conditions in case the accumulated amount of light 8,000 mJ / cm 2 irradiation, the silicone resin composition contains an acid anhydride and an amine compound: 150 If 5 hours, the silicone resin composition under conditions of °C contains a Lewis acid catalyst: Heat for 3 hours at 150 ° C
  • Condensation catalyst 2 monobutyltris 2-ethylhexanoate tin (manufactured by Nitto Kasei)
  • Curing catalyst 3 Tributoxy hafnium mononaphthate [tetrabutoxy hafnium (manufactured by Gelst) 4.71 g (0.01 mol), naphthenic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.54 g (0.01 Mol) was put into a three-necked flask and stirred at room temperature for about 2 hours under a nitrogen atmosphere to obtain the target compound.
  • Polysiloxane 6 dimethylpolysiloxane having a vinyl group, trade name DMS-V35 (manufactured by Gelest), weight average molecular weight 49,500, average number of functional groups having a vinyl group as a reactive functional group 2
  • Polysiloxane 7 methylposilyloxane having a hydrogensilyl group, trade name KF-9901 (manufactured by Shin-Etsu Chemical Co., Ltd.), weight average molecular weight 1,500, average having a hydrogensilyl group as a reactive functional group
  • Hydrosilyl catalyst platinum-cyclovinylmethylsiloxane complex, SIP6832.2, manufactured by Gelest
  • Polysiloxane 8 polysiloxane having methacryloxypropyldimethoxysilyl groups at both ends Dimethylsiloxane (M-ss70), weight average molecular weight 35,000 , Having a methacryloxy group as
  • Comparative Example I-3, Comparative Example II-2, Comparative Example III-2, and Comparative Example IV-2 containing 5 parts by mass of the zinc compound with respect to 100 parts by mass of the curable silicone resin composition were obtained.
  • the cured sample became cloudy.
  • Reference Example I-1 ⁇ 4, II-1 to 3, III-1, and IV-1 discolored silver after 72 hours, and the sulfuration resistance over a long period was low.
  • the silicone resin layers obtained by using the compositions of Examples I-1 to 10, Example II-1 to 3, Example III-1 to 4, and Example IV-1 to 4 were covered.
  • the broken silver member has no discoloration after 72 hours and has a high resistance to sulfuration over a long period of time. Therefore, the composition of the present invention can trap hydrogen sulfide for a long time. Further, cracks were generated in the silicone resin layers obtained by using the compositions of Examples I-1 to 10, Example II-1 to 3, Example III-1 to 4, and Example IV-1 to 4. There was no.

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Abstract

L'invention a pour objectif de fournir une composition de résine silicone présentant d'excellentes propriétés de transparence et de résistance au soufre. Plus précisément, l'invention concerne une composition de résine silicone, ainsi qu'une structure contenant une résine silicone, un corps d'étanchéité pour élément semi-conducteur optique et un procédé de mise en œuvre de composition de résine silicone associés à cette composition de résine silicone. Ladite composition de résine silicone comprend pour (A) 100 parties en masse de composition de résine silicone durcissable, (B) 0,01 à 5 parties en masse d'un composé zinc obtenu par réaction d'un acide à raison d'au moins 1,5 moles et de moins de 2 moles, pour 1 mole d'au moins un élément choisi dans un groupe constitué d'un oxyde de zinc, d'un carbonate de zinc, d'un hydroxyde de zinc, d'un chlorure de zinc, d'un sulfate de zinc et d'un nitrate de zinc.
PCT/JP2011/076423 2010-11-17 2011-11-16 Composition de résine silicone, ainsi que structure contenant une résine silicone, corps d'étanchéité pour élément semi-conducteur optique et procédé de mise en oeuvre de composition de résine silicone associés Ceased WO2012067153A1 (fr)

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KR1020137012819A KR101296082B1 (ko) 2010-11-17 2011-11-16 실리콘 수지 조성물, 이것을 이용하는, 실리콘 수지 함유 구조체, 광반도체 소자 봉지체, 실리콘 수지 조성물의 사용 방법
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WO2014088115A1 (fr) 2012-12-07 2014-06-12 東レ・ダウコーニング株式会社 Composition de silicone durcissable et dispositif optique à semi-conducteur
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EP2876138A1 (fr) * 2013-11-20 2015-05-27 Samsung SDI Co., Ltd. Matériau silicone pour protéger des appareils électroniques, module de circuit l'utilisant et procédé de fabrication de module de circuit
JP2018519673A (ja) * 2015-07-07 2018-07-19 ルミレッズ ホールディング ベーフェー 光を発するデバイス
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JP2014001344A (ja) * 2012-06-20 2014-01-09 Kyocera Chemical Corp 光半導体部品用組成物
WO2014088115A1 (fr) 2012-12-07 2014-06-12 東レ・ダウコーニング株式会社 Composition de silicone durcissable et dispositif optique à semi-conducteur
TWI650378B (zh) * 2013-10-17 2019-02-11 道康寧東麗股份有限公司 硬化性聚矽氧組合物及光半導體裝置
WO2015056726A1 (fr) * 2013-10-17 2015-04-23 東レ・ダウコーニング株式会社 Composition de silicone pouvant durcir et dispositif à semi-conducteur optique
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EP2876138A1 (fr) * 2013-11-20 2015-05-27 Samsung SDI Co., Ltd. Matériau silicone pour protéger des appareils électroniques, module de circuit l'utilisant et procédé de fabrication de module de circuit
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JP2018519673A (ja) * 2015-07-07 2018-07-19 ルミレッズ ホールディング ベーフェー 光を発するデバイス
JP7038039B2 (ja) 2015-07-07 2022-03-17 ルミレッズ ホールディング ベーフェー 光を発するデバイス
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JP2019192782A (ja) * 2018-04-25 2019-10-31 三菱電機株式会社 映像表示ユニット及び映像表示装置
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CN112313282B (zh) * 2018-06-28 2023-09-05 信越化学工业株式会社 有机硅组合物和使用其的纤维处理剂

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