[go: up one dir, main page]

WO2017126199A1 - Composition de résine de silicone durcissable et son produit durci, et dispositif semi-conducteur optique l'utilisant - Google Patents

Composition de résine de silicone durcissable et son produit durci, et dispositif semi-conducteur optique l'utilisant Download PDF

Info

Publication number
WO2017126199A1
WO2017126199A1 PCT/JP2016/083317 JP2016083317W WO2017126199A1 WO 2017126199 A1 WO2017126199 A1 WO 2017126199A1 JP 2016083317 W JP2016083317 W JP 2016083317W WO 2017126199 A1 WO2017126199 A1 WO 2017126199A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
silicone resin
group
formula
represented
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/083317
Other languages
English (en)
Japanese (ja)
Inventor
亘 河合
勝宏 秋山
佑 松野
真 情野
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central Glass Co Ltd
Original Assignee
Central Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2016200588A external-priority patent/JP2017128707A/ja
Application filed by Central Glass Co Ltd filed Critical Central Glass Co Ltd
Publication of WO2017126199A1 publication Critical patent/WO2017126199A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • C08G77/06—Preparatory processes
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • 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
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/852—Encapsulations
    • H10H20/854—Encapsulations characterised by their material, e.g. epoxy or silicone resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched

Definitions

  • the present invention relates to a curable silicone resin composition that can be suitably used as a raw material for a sealing material of an optical semiconductor element such as a light emitting diode, a raw material for an adhesive, a cured product thereof, and an optical semiconductor device using these.
  • a cured product such as a silicone resin composition is used as a sealing material of a light emitting device using an optical semiconductor element such as a light emitting diode (abbreviation: LED).
  • LED light emitting diode
  • an addition-curable silicone resin composition using an addition reaction (hydrosilylation reaction) between an H—Si group and an alkenyl group is used as a raw material, which is cured and used as a sealing material (patent) Literature 1, Patent Literature 2).
  • potting molding is generally performed using a dispenser or the like.
  • the thread may be pulled during the operation, and labor may be required for the sealing operation. Therefore, in order to improve working efficiency, it is preferable that the silicone resin composition before curing has a low viscosity.
  • silicone resin compositions having many branched structures often have good cured properties and durability required for white LED encapsulant applications.
  • the silicone resin composition often has a higher viscosity as it has more branched structures in the molecule.
  • the viscosity of the entire composition has been reduced by adding a small amount of low-viscosity long-chain silicone (for example, polydimethylsilicone).
  • long-chain silicone for example, polydimethylsilicone
  • the crosslinking density in the molecular structure often decreases in the silicone resin composition.
  • the silicone resin is easily broken by external force, and the function as a sealing material may be impaired.
  • the present invention has been made in view of the above circumstances, and provides a low-viscosity curable silicone resin composition, a cured product having sufficient durability in sealing material applications, and an optical semiconductor device using these. For the purpose.
  • the present inventors have intensively studied to achieve the above object. As a result, the inventors have found that the above object can be achieved by using a predetermined curable silicone resin composition, and completed the present invention.
  • the present invention includes the following inventions.
  • a curable silicone resin composition comprising at least the following component (A), component (B) and component (C).
  • component (A) component a silicone resin represented by the following formula [1] and having a viscosity of 10,000 cP or less
  • component (B) component a silicone resin represented by the following formula [2] and having a viscosity of 10,000 cP or less
  • Me represents a methyl group
  • Ph represents a phenyl group
  • Vi represents a vinyl group
  • Me represents a methyl group
  • Ph represents a phenyl group
  • Each oxygen atom in the structural unit represented forms a siloxane bond Or oxygen atom forming a silanol group.
  • the content ratio of the component (A) and the component (B) is expressed as a ratio of the number of moles of H—Si groups contained in the component (A) / the number of moles of Vi—Si groups contained in the component (B).
  • Invention 7 Cure retarder, antioxidant, light stabilizer, adhesion promoter, phosphor, inorganic particles, release agent, resin modifier, colorant, diluent, antibacterial agent, antifungal agent, leveling agent and anti-sagging agent
  • [Invention 10] A silicone resin represented by the following formula [1] and having a viscosity of 10,000 cP or less.
  • Me represents a methyl group
  • Ph represents a phenyl group
  • the oxygen atoms in the structural units are each an oxygen atom forming a siloxane bond. Or an oxygen atom forming a silanol group.
  • [Invention 11] A silicone resin represented by the following formula [2] and having a viscosity of 10,000 cP or less.
  • Vi represents a vinyl group
  • Me represents a methyl group
  • Ph represents a phenyl group
  • the oxygen atoms in the structural units represented by (Vi-SiMe 2 O 1/2 ), (Me 2 SiO 2/2 ), (PhSiO 3/2 ) and (SiO 4/2 ) are each siloxane bonds Represents an oxygen atom that forms a silanol group or an oxygen atom that forms a silanol group.)
  • [Invention 12] A method for producing a curable silicone resin composition, comprising at least the following first to fifth steps.
  • First step a step of obtaining a first hydrolyzed polycondensate by reacting a dialkoxysilane represented by the following general formula [3] and a trialkoxysilane represented by the following general formula [4].
  • Second step A step of obtaining a second hydrolyzed polycondensate by reacting the first hydrolyzed polycondensate with a tetraalkoxysilane represented by the following general formula [5] under strong acid conditions.
  • Third step By reacting the second hydrolyzed polycondensate with the silane compound represented by the following general formula [6], [7] or [8] under strong acid conditions, A step of obtaining a silicone resin having a viscosity of 10,000 cP or less.
  • Me represents a methyl group
  • R 5 represents an alkyl group having 1 to 3 carbon atoms
  • two R 5 s may be the same or different from each other.
  • Ph represents a phenyl group
  • R 6 represents an alkyl group having 1 to 3 carbon atoms
  • three R 6 may be the same or different from each other.
  • R 7 represents carbon In the formulas [6] to [8], Me represents a methyl group, and in the formula [7], four R 7 s may be the same or different from each other.
  • R 8 represents an alkyl group having 1 to 3 carbon atoms.
  • [Invention 13] A method for producing a silicone resin, comprising at least the following first to third steps, wherein the viscosity is 10,000 cP or less.
  • First step a step of obtaining a first hydrolyzed polycondensate by reacting a dialkoxysilane represented by the following general formula [3] and a trialkoxysilane represented by the following general formula [4].
  • Second step A step of obtaining a second hydrolyzed polycondensate by reacting the first hydrolyzed polycondensate with a tetraalkoxysilane represented by the following general formula [5] under strong acid conditions.
  • Third step The second hydrolysis polycondensate and the silane compound represented by the following general formula [6], [7] or [8] are reacted under strong acid conditions, whereby the viscosity is 10,000 cP or less.
  • a step of obtaining a silicone resin In formula [3], Me represents a methyl group, R 5 represents an alkyl group having 1 to 3 carbon atoms, and two R 5 s may be the same or different from each other. , Ph represents a phenyl group, R 6 represents an alkyl group having 1 to 3 carbon atoms, and three R 6 may be the same or different from each other.
  • R 7 represents carbon In the formulas [6] to [8], Me represents a methyl group, and in the formula [7], four R 7 s may be the same or different from each other.
  • R 8 represents an alkyl group having 1 to 3 carbon atoms.
  • [Invention 14] A method for producing a silicone resin, comprising at least the following first step, second step and fourth step, wherein the viscosity is 10,000 cP or less.
  • First step a step of obtaining a first hydrolyzed polycondensate by reacting a dialkoxysilane represented by the following general formula [3] and a trialkoxysilane represented by the following general formula [4].
  • Second step A step of obtaining a second hydrolyzed polycondensate by reacting the first hydrolyzed polycondensate with a tetraalkoxysilane represented by the following general formula [5] under strong acid conditions.
  • the second hydrolysis polycondensate is reacted with a silane compound represented by the following general formula [9], [10] or [11] under strong acid conditions, whereby the viscosity is 10,000 cP or less.
  • a step of obtaining a silicone resin In formula [3], Me represents a methyl group, R 5 represents an alkyl group having 1 to 3 carbon atoms, and two R 5 s may be the same or different from each other. , Ph represents a phenyl group, R 6 represents an alkyl group having 1 to 3 carbon atoms, and three R 6 may be the same or different from each other.
  • R 7 represents carbon an alkyl group having 1 to 3, four R 7 may be the same or different types from each other, wherein [9] to the formula [11], Me represents a methyl group, Vi represents a vinyl group In the formula [10], R 9 represents an alkyl group having 1 to 3 carbon atoms.
  • Vi represents a vinyl group (CH 2 ⁇ CH group)
  • Me represents a methyl group
  • Et represents an ethyl group
  • Ph represents a phenyl group.
  • the curable silicone resin composition of the present invention contains at least the components (A) to (C). Hereinafter, each component contained in the composition of this invention is demonstrated.
  • the component (A) is a silicone resin represented by the following formula [1] and having a viscosity of 10,000 cP or less.
  • the oxygen atoms in the structural units represented by (H—SiMe 2 O 1/2 ), (Me 2 SiO 2/2 ), (PhSiO 3/2 ) and (SiO 4/2 ) each form a siloxane bond.
  • the value of a is preferably 0.05 to 0.40, and more preferably 0.10 to 0.30.
  • the value of b is preferably 0.10 to 0.80, particularly preferably 0.10 to 0.40.
  • the value of c is preferably 0.10 to 0.80, particularly preferably 0.30 to 0.60.
  • the value of d is preferably 0.0005 to 0.40, particularly preferably 0.005 to 0.30. If the values of a, b, c and d are in the above-mentioned ranges, the composition and the cured product of the present invention have good moldability and good mechanical strength.
  • a, b, c and d were determined by measuring the 29 Si-NMR spectrum and 1 H-NMR spectrum of the silicone compound represented by the formula [1] using a nuclear magnetic resonance apparatus. These are used for calculation.
  • the structural unit represented by (Me 2 SiO 2/2 ) is a structure represented by the following formula [1-2], that is, a structure represented by (Me 2 SiO 2/2 ).
  • One of the oxygen atoms bonded to the silicon atom in the unit may include a structure in which a silanol group is formed.
  • the structural unit represented by (Me 2 SiO 2/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula [1-b], and further represented by the following formula [1-2-b].
  • the part enclosed by the broken line of the structural unit represented may be included. That is, a structural unit having a group represented by Me (methyl group) and having a hydroxy group remaining at the terminal to form a silicon atom and a silanol group is also represented by (Me 2 SiO 2/2 ). Included in the structural unit.
  • the oxygen atom in the Si—O—Si bond forms a siloxane bond with an adjacent silicon atom, It shares an oxygen atom with an adjacent structural unit. Therefore, one oxygen atom in the Si—O—Si bond is defined as “O 1/2 ”.
  • the structural unit represented by (PhSiO 3/2 ) is a structure represented by the following formula [1-2] or a structure represented by the formula [1-3], that is, (PhSiO 3 / 2 )
  • the structure may include a structure in which one of the oxygen atoms forms a silanol group.
  • the structural unit represented by (PhSiO 3/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula [1-c], and further includes the following formula [1-3 A portion surrounded by a broken line of the structural unit represented by -c] or [1-4-c] may be included. That is, a structural unit having a group represented by Ph (phenyl group) and having a hydroxy group remaining at the terminal to form a silicon atom and a silanol group is also represented by (PhSiO 3/2 ). Included in the unit.
  • structural units represented by (SiO 4/2) may include a moiety surrounded by dashed lines of a unit represented by the following formula [1-d], further the following formula [1-5 -D], [1-6-d], or a portion surrounded by a broken line of the structural unit represented by [1-7-d] may be included. That is, a structural unit in which a hydroxy group remains at the terminal to form a silicon atom and a silanol group is also included in the structural unit represented by (SiO 4/2 ).
  • the viscosity of the component (A) is not particularly limited as long as it is 10,000 cP (centipoise) or less in the standard state (25 ° C., 1 atm). From the viewpoint of handling workability, it is preferably 7,000 cP or less.
  • the lower limit is not particularly limited, and the lower the viscosity, the lower the viscosity of the resulting composition of the present invention, and the easier the sealing operation of the semiconductor device.
  • the viscosity of component (A) may be greater than 0 cP and 10,000 cP or less, and preferably greater than 0 cP and 7,000 or less in the standard state (25 ° C., 1 atm).
  • the viscosity of component (A) is measured with a rotational viscometer or the like.
  • a rotational viscometer manufactured by ANTON® PAAR, product name: PHYSICA® MCR 51, measurement range 200 to 1,000,000 cP
  • a temperature control unit manufactured by ANTON PAAR, product name: P-PTD200
  • measurement was performed at a shear rate of 30 [1 / s] in a standard state (25 ° C., 1 atm), and obtained 1 minute after the start of measurement.
  • the value is the viscosity of component (A).
  • the component (A) contains at least a hydrogen atom (H—Si group) bonded to a silicon atom, and the amount thereof is not particularly limited. It is preferable to contain 2 or more in one molecule. In order to obtain a good cured product, it is particularly preferably 0.5 to 4.0 mmol / g.
  • the mass average molecular weight of the component (A) is not particularly limited. 500 to 10,000 is preferable, and 800 to 7,000 is more preferable. If the mass average molecular weight is 500 or more, the cured product of the present invention has good resin strength, and if it is 10,000 or less, the composition of the present invention has good moldability.
  • the mass average molecular weight is a value obtained by measuring by a gel permeation chromatography (abbreviation: GPC) method and converting by a standard polystyrene calibration curve (the same applies hereinafter).
  • GPC gel permeation chromatography
  • the amount of HO—Si group contained in the component (A) is not particularly limited. 0.5 to 4.5 mmol / g is preferable, and 1.0 to 3.5 mmol / g is particularly preferable. If the HO—Si group content exceeds 4.5 mmol / g, bubbles may be observed in the cured product.
  • the component (B) is a silicone resin represented by the following formula [2] and having a viscosity of 10,000 cP or less.
  • the oxygen atoms in the structural units represented by (Vi-SiMe 2 O 1/2 ), (Me 2 SiO 2/2 ), (PhSiO 3/2 ) and (SiO 4/2 ) each form a siloxane bond.
  • the value of e is preferably 0.05 to 0.40, more preferably 0.10 to 0.30.
  • the value of f is preferably 0.10 to 0.80, particularly preferably 0.10 to 0.40.
  • the value of g is preferably 0.10 to 0.80, particularly preferably 0.30 to 0.60.
  • the value of h is preferably 0.001 to 0.40, particularly preferably 0.05 to 0.30. If the values of e, f, g, and h are in the ranges described above, the composition and the cured product of the present invention have good moldability and good mechanical strength.
  • the viscosity of the component (B) is not particularly limited as long as it is 10,000 cP (centipoise) or less in the standard state (25 ° C., 1 atm). From the viewpoint of handling workability, it is preferably 7,000 cP or less.
  • the lower limit is not particularly limited, and the lower the viscosity, the lower the viscosity of the resulting composition of the present invention, and the easier the sealing operation of the semiconductor device.
  • the viscosity of component (B) may be more than 0 cP and 10,000 cP or less, and preferably more than 0 cP and 7,000 or less in the standard state (25 ° C., 1 atm).
  • the viscosity of the component (B) is measured by the same method as the viscosity of the component (A).
  • the component (B) contains at least a vinyl group (Vi-Si group) bonded to a silicon atom, and the amount thereof is not particularly limited. It is preferable to contain 2 or more in one molecule. In order to obtain a good cured product, it is particularly preferably 0.5 to 4.0 mmol / g.
  • the mass average molecular weight of the component (B) is not particularly limited. 500 to 10,000 is preferable, and 800 to 7,000 is more preferable. If the mass average molecular weight is 500 or more, the cured product of the present invention has good resin strength, and if it is 10,000 or less, the composition of the present invention has good moldability.
  • the amount of HO—Si group contained in the component (B) is not particularly limited. 0.5 to 6.0 mmol / g is preferable, and 1.0 to 3.5 mmol / g is particularly preferable. If the content of the HO—Si group exceeds 6.0 mmol / g, bubbles may be observed in the cured product.
  • the (C) component hydrosilylation catalyst is added to accelerate the hydrosilylation reaction (addition curing reaction) between the H—Si group in the (A) component and the Vi—Si group in the (B) component described later. Is done.
  • the kind of component will not be specifically limited if the said hydrosilylation reaction is accelerated
  • platinum-based catalyst examples include platinum powder, complexes of platinum components such as chloroplatinic acid and chloroplatinic acid, alcohols, aldehydes, ketones and the like, platinum-olefin complexes, platinum-alkenylsiloxane complexes, platinum-carbonyl complexes, and the like. It is done. Examples thereof include platinum-carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex (cursed catalyst), platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde complex, platinum-phosphine complex, dicarbonyldichloroplatinum and the like. Of these, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex and the like are preferable.
  • component (D) component: cure retarder As other additives, for example, in the composition of the present invention, for the purpose of improving the storage stability and handling workability of the composition, adjusting the hydrosilylation reactivity in the curing process, etc.
  • a curing retarder hereinafter sometimes referred to as component (D)
  • component (D) may be blended.
  • the composition of the present invention can be made into a cured product at a relatively low temperature, it can be suitably used for coating / sealing on a heat-sensitive optical semiconductor member.
  • it may be preferable to blend a curing retarder in order to adjust the curing rate from the viewpoint of storage stability over time and handling workability of the composition of the present invention.
  • component (D) is not particularly limited as long as it is a compound having a curing delay effect with respect to component (C).
  • curing retardants can be used, and examples thereof include compounds containing aliphatic unsaturated bonds, organic phosphorus compounds, nitrogen-containing compounds, organic sulfur compounds, and organic peroxides. These compounds may be used alone or in combination.
  • the content of the component (D) in the composition of the present invention is not particularly limited. Usually, 20 to 200 equivalents of a curing retarder may be added to 1 equivalent of platinum atom in component (C) contained in the composition.
  • the degree of the retarding effect of the retarder varies depending on the chemical structure of the retarder. Therefore, it is preferable to adjust the blending amount to an optimal amount depending on the type of the curing retarder used.
  • the composition of the present invention can be stored for a long period of time at room temperature (especially an ambient temperature not heated or cooled, usually 15 to 30 ° C., the same applies hereinafter). In addition, the heat curability is excellent.
  • the composition of the present invention contains an adhesion-imparting agent (hereinafter sometimes referred to as (E) component) in addition to the components (A) to (C) described above. May be.
  • a conventionally well-known silane coupling agent, its hydrolysis condensate, etc. can be used, for example, an epoxy group containing silane coupling agent, a (meth) acryl group containing silane coupling agent, Examples include isocyanate group-containing silane coupling agents, isocyanurate group-containing silane coupling agents, amino group-containing silane coupling agents, and mercapto group-containing silane coupling agents. These may be used alone or in combination.
  • the content of the component (E) in the composition of the present invention is not particularly limited. It is preferable to add 1 to 20% by mass, particularly preferably 5 to 15% by mass, based on the total mass of the components (A) to (C).
  • antioxidant antioxidant
  • a conventionally well-known antioxidant can be used,
  • group acid antioxidant, phosphorus antioxidant, etc. are mentioned.
  • phenolic antioxidants and thioether antioxidants are preferred, and thioether antioxidants are particularly preferred. These antioxidants may be used individually by 1 type, and may use 2 or more types together.
  • the content of the component (F) in the composition of the present invention is not particularly limited as long as it is in an amount that does not impair characteristics such as transparency of the cured product of the present invention and is an effective amount as an antioxidant.
  • 0.001 to 2 mass% may be blended with respect to the total mass of components (A) to (C), and 0.01 to 1 mass% is preferably blended. If it is in this range, the antioxidant ability is sufficiently exhibited, so that a cured product excellent in engineering characteristics can be obtained while suppressing the occurrence of coloring, white turbidity, oxidative degradation and the like.
  • (G) component light stabilizer
  • a light stabilizer hereinafter sometimes referred to as (G) component
  • (G) component may be added to the composition of the present invention.
  • (G) As a kind of component, a conventionally well-known light stabilizer can be used. Especially, the hindered amine stabilizer which capture
  • the blending amount of the component (G) in the composition of the present invention is not particularly limited as long as it is in an amount that does not impair the characteristics such as transparency of the cured product of the present invention and is an effective amount as a light stabilizer. It may be blended in an amount of 0.01 to 5% by weight, preferably 0.05 to 0.5% by weight, based on the total weight of the components (A) to (C).
  • H black, which is widely used for light emitting diodes (LEDs), is made of an oxide phosphor, an oxynitride phosphor, a nitride phosphor, a sulfide phosphor, an oxysulfide phosphor, etc. , Red, green, and blue light emitting phosphors.
  • the blending amount of the component (H) is not particularly limited as long as it is within the range that does not impair the characteristics such as transparency of the cured product of the present invention and is an effective amount as a phosphor.
  • the blending amount is preferably 10 to 70% by weight, particularly preferably 20 to 50% by weight, based on the total weight of the components (A) to (C).
  • component (I) component inorganic particles
  • the composition of the present invention may be referred to as inorganic particles (hereinafter referred to as component (I)) for the purpose of improving the optical properties, workability, mechanical properties, and physicochemical properties of the cured product. ) May be blended.
  • component (I) The kind of component should just be selected according to the objective, may mix
  • the inorganic particles may be surface-treated with a surface treatment agent such as a silane coupling agent.
  • Component types include silica, barium titanate, titanium oxide, zirconium oxide, niobium oxide, aluminum oxide, cerium oxide, yttrium oxide and other inorganic oxide particles, silicon nitride, boron nitride, silicon carbide, nitride Examples thereof include nitride particles such as aluminum, carbon compound particles, and diamond particles, but other materials can be selected according to the purpose, and the present invention is not limited thereto.
  • the form of the component (I) may be any form depending on the purpose, such as powder or slurry. Depending on the required transparency, it is preferable that the composition of the present invention is blended so that the refractive index of the cured product of the present invention is as equal as possible. Moreover, it is preferable to mix
  • the average particle size of the component (I) to be blended is not particularly limited, and those having an average particle size according to the purpose are used. Usually, it is about 1/10 or less of the particle diameter of the aforementioned phosphor.
  • the particle diameter is a value obtained by measuring the minor axis and major axis of the particle by SEM (scanning electron microscope) observation and calculating (minor axis + major axis) / 2. This operation is performed on the particles in a certain section in the SEM image, and the arithmetic average value of the obtained particle diameters is defined as the average particle diameter of the component (I).
  • the blending amount of the component (I) is arbitrary as long as the characteristics such as heat-resistant transparency of the cured product of the present invention are not impaired. If the blending amount of component (I) is too small, the desired effect may not be obtained, and if it is too large, it will adversely affect various properties such as heat-resistant transparency, adhesion, transparency, moldability and hardness of the cured product. Sometimes. About 1 to 50% by mass may be blended with respect to the total mass of components (A) to (C), and preferably about 5 to 35% by mass.
  • the composition of the present invention includes a release agent, a resin modifier, a colorant, a diluent, as long as the characteristics such as transparency of the cured product are not impaired. You may mix
  • the compounding ratio of the component (A) and the component (B) in the composition of the present invention is not particularly limited. Basically, it is blended based on the molar ratio of the H—Si group contained in the component (A) and the Vi—Si group contained in the component (B). Specifically, the number of moles of H—Si groups contained in component (A) / the number of moles of Vi—Si groups contained in component (B) is preferably in the range of 1 to 4. 3 is particularly preferred. Within this range, the composition of the present invention exhibits good moldability, and the cured product of the present invention has excellent heat-resistant transparency.
  • the amount of component (C) in the composition of the present invention is not particularly limited. Based on the total mass of component (A), component (B) and component (C), the amount of metal atoms in component (C) is preferably in the range of 0.003 to 30 ppm in terms of mass unit. Among them, the obtained cured product tends to have excellent heat-resistant transparency, so 0.003-5.0 ppm is more preferable, 0.003-3.0 ppm is more preferable, and 0.003-2.0 ppm is more preferable. Particularly preferred. If the amount of component (C) is 0.003 to 30 ppm, the hydrosilylation reaction of component (A) and component (B) proceeds smoothly.
  • the viscosity of the composition of the present invention is not particularly limited as long as it is 10,000 cP (centipoise) or less in a standard state (25 ° C., 1 atm). If it is 10,000 cP or less, it is preferably 7,000 cP or less.
  • the lower limit is not particularly limited, and the lower the viscosity, the easier the sealing operation of the semiconductor device is preferable.
  • the viscosity of the composition of the present invention may be more than 0 cP and 10,000 cP or less, and preferably more than 0 cP and 7,000 or less in a standard state (25 ° C., 1 atm).
  • the viscosity of the composition of the present invention is measured by the same method as the viscosity of the component (A).
  • the composition of the present invention is a low-viscosity resin composition, it has good fluidity.
  • the resin composition is hardly interrupted and bubbles are not easily entrained, and is easy to apply. Therefore, the sealing work can be performed efficiently.
  • cured material obtained from the composition of this invention has sufficient durability in the sealing material use of a semiconductor device. For this reason, the composition of this invention is suitable for the sealing material use of a semiconductor device.
  • the total content of HO—Si groups in the component (A) and the component (B) in the composition of the present invention is not particularly limited. It may be 0.5 to 5.0 mmol / g, preferably 1.0 to 4.5 mmol / g, particularly preferably 1.5 to 4.5 mmol / g. If it exists in this range, hardening of a composition will fully advance and a desired hardened
  • composition of this invention can be prepared by mix
  • the component (A), the component (B), the component (C), and additives added as necessary are dispersed substantially uniformly by mixing.
  • the mixing method is not particularly limited, and a conventionally known mixing method can be employed.
  • a mixing method using a mixing device such as a universal kneader or a kneader can be employed.
  • component (C) may be previously mixed with the component (A) and / or the component (B).
  • (B) component and (C) component are preserve
  • the second composition containing the remainder of the component (A) and the component (B) is stored in separate containers and mixed immediately before use to prepare the composition of the present invention for use.
  • the prepared composition may be further degassed under reduced pressure for use.
  • the component (A) can be produced by a method including at least the following first to third steps.
  • First step a step of obtaining a first hydrolyzed polycondensate by reacting a dialkoxysilane represented by the following general formula [3] and a trialkoxysilane represented by the following general formula [4].
  • Second step A step of obtaining a second hydrolyzed polycondensate by reacting the first hydrolyzed polycondensate with a tetraalkoxysilane represented by the following general formula [5] under strong acid conditions.
  • the component (A) is obtained by reacting the second hydrolysis polycondensate with the silane compound represented by the following general formula [6], [7] or [8] under strong acid conditions.
  • R 5 represents an alkyl group having 1 to 3 carbon atoms, and the two R 5 may be the same or different from each other.
  • R 6 represents an alkyl group having 1 to 3 carbon atoms, and the three R 6 may be the same or different from each other.
  • R 7 represents an alkyl group having 1 to 3 carbon atoms, and the four R 7 may be the same or different from each other.
  • R 8 represents an alkyl group having 1 to 3 carbon atoms.
  • first step In the first step, first, a dialkoxysilane represented by the general formula [3] (hereinafter sometimes referred to as “dialkoxysilane [3]”) and a trialkoxysilane represented by the general formula [4] (hereinafter referred to as “dialkoxysilane [3]”). , Sometimes referred to as “trialkoxysilane [4]”) in a reaction vessel at room temperature, water for hydrolysis polycondensation is added, and a reaction solvent is added as desired. To add a catalyst for smoothly proceeding the condensation reaction to obtain a reaction solution. The order in which the reaction materials are charged at this time is not particularly limited, and can be charged in any order to obtain a reaction solution.
  • the first hydrolyzed polycondensate can be obtained by advancing the reaction at a predetermined temperature for a predetermined time while stirring the reaction solution.
  • the reaction vessel is preferably equipped with a reflux device. .
  • the amount of dialkoxysilane [3] and trialkoxysilane [4] used is not particularly limited.
  • the dialkoxysilane [3]: trialkoxysilane [4] is preferably blended at a molar ratio of 85:15 to 15:85, particularly preferably 85:15 to 30:70.
  • the molar ratio of dialkoxysilane [3] is less than 15, it may be higher than the desired molecular weight, and when it exceeds 85, the hydrolysis polycondensation reaction is difficult to proceed and may be lower than the desired molecular weight. is there.
  • the amount of water used is not particularly limited.
  • the alkoxy group contained in the alkoxysilane compound of the reaction raw material that is, the total molar equivalent of the alkoxy group contained in dialkoxysilane [3] and trialkoxysilane [4] is 1 It is preferably 5 times or more and 5 times or less. If it is 1.5 times molar equivalent or more, dialkoxysilane [3] and trialkoxysilane [4] are efficiently hydrolyzed, and it is not necessary to add more than 5 times molar equivalent.
  • the reaction can be carried out even under solvent-free conditions, but a reaction solvent can also be used.
  • the kind of the reaction solvent is not particularly limited as long as the reaction for obtaining the first hydrolysis polycondensate is not inhibited.
  • hydrophilic organic solvents such as alcohols are preferable.
  • Specific examples of the alcohols include methanol, ethanol, normal propanol, isopropanol, and butanol, but are not limited thereto.
  • the amount of the reaction solvent used is preferably 0.1 to 1000% by mass, particularly preferably 1 to 300% by mass, based on the total amount of the alkoxysilane compound as a reaction raw material.
  • alcohols generated from the alkoxysilane compound as a reaction raw material in the reaction process function as a reaction solvent, it may not always be necessary.
  • an acidic catalyst or a basic catalyst can be used.
  • the use of an acidic catalyst is preferable because the molecular weight control of the obtained first hydrolyzed polycondensate is easy.
  • the kind of acidic catalyst is not particularly limited.
  • acetic acid, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, trifluoromethanesulfonic acid, tosylic acid, trifluoroacetic acid and the like can be mentioned.
  • acetic acid, hydrochloric acid, nitric acid, sulfuric acid, and hydrofluoric acid are preferable, and acetic acid is more preferable because the removal of the acid catalyst after the reaction is easy.
  • the kind of basic catalyst is not specifically limited. Examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, triethylamine, pyridine and the like.
  • the amount of the catalyst used is preferably from 0.001 to 5% by mass, particularly preferably from 0.005 to 1% by mass, based on the total amount of the alkoxysilane compound, water and solvent as the reaction raw materials.
  • the reaction time and reaction temperature are not particularly limited.
  • the reaction time is usually 3 to 15 hours.
  • the reaction temperature is usually 60 to 120 ° C, preferably 80 to 100 ° C.
  • the separation method includes an extraction method. Specifically, the first hydrolyzed polycondensate present in the reaction system is extracted by lowering the temperature of the reaction solution after the above reaction to room temperature and then bringing it into contact with a water-insoluble organic solvent as an extraction solvent. . Next, the catalyst contained in the solution after extraction is removed.
  • the method for removing the catalyst is not particularly limited. For example, if the catalyst (for example, acetic acid) used is water-soluble, this catalyst can be removed by washing the solution after extraction with water.
  • a desiccant is added to the solution after removing the catalyst to remove water dissolved in the system. Furthermore, the high-purity first hydrolyzed polycondensate can be separated by removing the desiccant and removing the extraction solvent under reduced pressure. At this time, water may be simultaneously removed under reduced pressure in the process of removing the extraction solvent from the solution after removing the catalyst under reduced pressure without using a desiccant.
  • a water-insoluble organic solvent can be used as the extraction solvent.
  • the type of the water-insoluble organic solvent is not particularly limited. Examples thereof include aromatic hydrocarbons and ethers. Specific examples include toluene, diethyl ether, isopropyl ether, dibutyl ether, and the like, but are not limited thereto.
  • the desiccant is not particularly limited as long as water can be removed from the system and separated from the first hydrolyzed polycondensate.
  • a solid desiccant is preferably used, and specific examples thereof include magnesium sulfate, but are not limited thereto.
  • the separated and purified first hydrolyzed polycondensate may be further subjected to a condensation reaction by heating and stirring in a solvent or under heating without solvent. Thereby, the molecular weight of the first hydrolyzed polycondensate can be increased.
  • the first hydrolysis polycondensate and the solvent are put into a reaction vessel capable of heating and refluxing to obtain a solution.
  • the solution is heated to reflux and azeotroped with water generated in the system as the condensation proceeds.
  • tosylic acid or the like may be added to the solution and heated to reflux.
  • the type of the solvent to be used is not particularly limited as long as it can dissolve the first hydrolysis polycondensate and can be heated to reflux.
  • Aromatic hydrocarbons include toluene, xylene, benzene, etc.
  • ethers include diethyl ether, diisopropyl ether, and the like
  • esters include ethyl acetate and the like.
  • “Second step” In the second step, the first hydrolyzed polycondensate obtained in the first step and the tetraalkoxysilane represented by the general formula [5] (hereinafter sometimes referred to as “tetraalkoxysilane [5]”). Are reacted in the presence of a strong acid to obtain a second hydrolyzed polycondensate. Specifically, after a predetermined amount of the first hydrolyzed polycondensate and tetraalkoxysilane [5] are placed in a reaction vessel at room temperature, a reaction solvent is added as desired to serve as a catalyst for advancing the condensation reaction. Add strong acid to make reaction solution.
  • the order of charging at this time is not limited to this, and the reaction solution can be prepared by charging in any order.
  • the second hydrolyzed polycondensate can be obtained by advancing the reaction at a predetermined temperature for a predetermined time while stirring the reaction solution.
  • the reaction vessel is preferably equipped with a reflux device.
  • the amount of the first hydrolyzed polycondensate and tetraalkoxysilane [5] used is not particularly limited.
  • the tetraalkoxysilane [5] is preferably 0.001 to 600% by mass, particularly preferably 0.01 to 400% by mass, based on the first hydrolysis polycondensate.
  • the second step a small amount of water may be contained in the reaction solution, but when a large amount of water is contained, silica is generated in the reaction process, and the desired second hydrolysis polycondensate is formed. It may not be obtained.
  • the content of water is not particularly limited as long as the desired second hydrolysis polycondensate can be obtained, and is preferably 1% by mass or less, preferably 0.001% by mass with respect to tetraalkoxysilane [5].
  • the water content includes water that may be contained in strong acids such as nitric acid and hydrochloric acid.
  • the reaction can be carried out even under solvent-free conditions, but a reaction solvent can also be used and is preferably used.
  • the kind of the reaction solvent is not particularly limited as long as the reaction for obtaining the second hydrolyzed polycondensate is not inhibited.
  • hydrophilic organic solvents such as alcohols are preferable.
  • Specific examples of the alcohols include methanol, ethanol, normal propanol, isopropanol, and butanol, but are not limited thereto.
  • the amount of the reaction solvent used is preferably 0.1 to 1000% by mass, particularly preferably 1 to 300% by mass, based on the total amount of the first hydrolysis condensate and tetraalkoxysilane [5].
  • alcohols generated from the alkoxysilane compound as a reaction raw material in the reaction process function as a reaction solvent, it may not always be necessary to add.
  • the strong acid used is preferably an acid having an acid dissociation constant pKa of 3 or less.
  • Specific examples include nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, trifluoromethanesulfonic acid, tosylic acid, and trifluoroacetic acid. Of these, nitric acid, sulfuric acid, hydrochloric acid, and hydrofluoric acid are preferred, and nitric acid is more preferred because acid removal treatment after the reaction is easy.
  • the amount of the strong acid used is preferably from 0.0001 to 5% by mass, particularly preferably from 0.001 to 1%, based on the total amount of the first hydrolysis polycondensate, tetraalkoxysilane [5] and the reaction solvent. % By mass.
  • the reaction time and reaction temperature are not particularly limited.
  • the reaction time is usually 1 to 48 hours.
  • the reaction temperature is usually 60 to 120 ° C, preferably 80 to 100 ° C.
  • the second hydrolysis polycondensate may be separated from the reaction system and purified.
  • This separation method is not particularly limited. Examples of the separation method include the same methods as those described in the first step, and the second hydrolysis polycondensate can be separated and purified in the same manner as in the first step.
  • the second hydrolyzed polycondensate and the silane compound represented by the general formula [6], [7] or [8] are reacted under strong acid conditions to obtain the component (A).
  • This second hydrolyzed polycondensate may be separated from the reaction system in the second step and subjected to the reaction, or may be directly subjected to the reaction without being separated from the reaction system.
  • the second hydrolysis polycondensate the silane compound represented by the general formula [6], the silane compound represented by the general formula [7] or the silane compound represented by the general formula [8], and a desired
  • a strong acid is added as a catalyst for advancing the condensation reaction to obtain a reaction solution.
  • the order of addition at this time is not limited to this, and the reaction liquid can be supplied in any order, but the catalyst is preferably added last.
  • the component (A) can be obtained by advancing the reaction at a predetermined temperature for a predetermined time while stirring the reaction liquid.
  • the reaction vessel is preferably equipped with a reflux device.
  • the amount of the second hydrolyzed polycondensate and the silane compound represented by the general formula [6], the silane compound represented by the general formula [7] or the silane compound represented by the general formula [8] Is not particularly limited.
  • the silane compound represented by the general formula [6], the silane compound represented by the general formula [7], and the general formula [8] are used for 1 g of the second hydrolyzed polycondensate. It is preferable that the total amount of H—Si groups in the silane compound represented by the formula is 0.2 to 10 mmol.
  • the strong acid used in the third step is preferably an acid having an acid dissociation constant pKa of 3 or less.
  • Specific examples include nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, trifluoromethanesulfonic acid, tosylic acid, and trifluoroacetic acid. Of these, nitric acid, sulfuric acid, hydrochloric acid, and hydrofluoric acid are preferred, and nitric acid is more preferred because acid removal treatment after the reaction is easy.
  • the amount of strong acid used is preferably from 0.0001 to 10 mmol%, particularly preferably from 0.005 to 5 mmol%, based on 1 g of the second hydrolyzed polycondensate.
  • the type thereof is not particularly limited as long as the reaction for obtaining the component (A) is not inhibited.
  • a water-soluble organic solvent or a water-insoluble organic solvent can be used as the reaction solvent used in the third step.
  • the viscosity of the reaction solution can be reduced.
  • a water-soluble organic solvent is preferable.
  • the viscosity of the reaction solution can be reduced, and the second hydrolysis polycondensate and the strong acid used in the third step can be uniformly dispersed in the reaction system. .
  • the water-soluble organic solvent include alcohols, and more specifically, methanol, ethanol, normal propanol, isopropanol, butanol, and the like can be exemplified, but are not limited thereto.
  • Specific examples of the water-insoluble organic solvent include aromatic hydrocarbons, ethers and the like, and more specifically, toluene, diethyl ether, tetrahydrofuran, diisopropyl ether and the like can be exemplified, but are not limited thereto.
  • the amount of the reaction solvent used in the third step is preferably more than 0% by mass and 1000% by mass or less, particularly preferably 50 to 500% by mass, with respect to 1 g of the second hydrolyzed polycondensate.
  • the presence or absence of the use of this reaction solvent is not particularly limited.
  • the total amount with the reaction solvent used in the second step is preferably more than 0% by mass and less than 1000% by mass with respect to 1 g of the second hydrolysis polycondensate.
  • the amount is preferably 10 to 500% by mass.
  • reaction solvent in the third step is optional, and the target component (A) can be obtained even when not used.
  • the method for terminating the reaction in the third step is not particularly limited.
  • the reaction is terminated by adding water (preferably ion-exchanged water) to the reaction system.
  • water preferably ion-exchanged water
  • This separation method is not particularly limited.
  • an extraction method may be mentioned.
  • the organic layer is separated from the solution after the reaction described above.
  • the organic layer is washed with water (preferably ion-exchanged water), and an acid scavenger and a desiccant are added to remove the acid and water dissolved in the system.
  • the acid scavenger and the desiccant are removed from the organic layer, and the water-insoluble organic solvent is removed under reduced pressure, whereby the component (A) can be separated with high purity.
  • water may be removed simultaneously in the process of removing the water-insoluble organic solvent without using a desiccant. It is preferable to further remove the water contained in the component (A) by heating the separated component (A) without solvent and under reduced pressure.
  • the heating temperature is not particularly limited, but is usually 100 to 190 ° C.
  • a water-insoluble organic solvent can be used as the extraction solvent.
  • the type of this insoluble aqueous organic solvent is not particularly limited. Examples thereof include aromatic hydrocarbons and ethers. Specific examples include toluene, diethyl ether, isopropyl ether, dibutyl ether, and the like, but are not limited thereto.
  • the type of the acid scavenger is not particularly limited as long as a strong acid can be removed from the system.
  • a solid acid scavenger is preferably used.
  • a commercially available acid scavenger can be used as needed.
  • Kyowa Chemical Industry Co., Ltd. Kyoward 500 etc. are mentioned, However, It is not limited to this.
  • the desiccant is not particularly limited as long as it can remove water from the system.
  • a solid desiccant is preferably used.
  • magnesium sulfate etc. are mentioned, it is not limited to this.
  • the component (B) can be produced by a method including at least the following fourth step.
  • Fourth step: (B) component is obtained by reacting the second hydrolysis polycondensate with the silane compound represented by the following general formula [9], [10] or [11] under strong acid conditions.
  • R 9 represents an alkyl group having 1 to 3 carbon atoms.
  • the reaction conditions and the separation operation of the component (B) can be applied to the reaction conditions and the separation operation of the third step. That is, the silane compound represented by the general formula [6], the silane compound represented by the general formula [7], the silane compound represented by the general formula [8], the H—Si group, and the component (A) in the third step, By replacing with the silane compound represented by the general formula [9], the silane compound represented by the general formula [10], the silane compound represented by the general formula [11], the Vi—Si group, and the component (B), The process can be explained.
  • a cured product of the curable silicone resin composition of the present invention (hereinafter sometimes referred to as “cured product of the present invention”) is obtained by heating the composition of the present invention.
  • the cured product of the present invention can be used as a sealing material for semiconductor devices, and is particularly suitable as a sealing material for optical semiconductor devices and power semiconductor devices.
  • a sealing material for optical semiconductor devices it can be suitably used as a sealing material for LED optical members, a sealing material for optical members for semiconductor lasers, etc., among others, as a sealing material for LED optical members. Particularly preferred.
  • optical semiconductor devices have their light extraction efficiency enhanced by various technologies.
  • the transparency of the sealing material of the optical semiconductor element is low, the sealing material absorbs light.
  • the light extraction efficiency of the optical semiconductor device used decreases. As a result, it tends to be difficult to obtain a high-brightness optical semiconductor device product.
  • the energy corresponding to the decrease in light extraction efficiency is changed to heat, which causes thermal deterioration of the optical semiconductor device, which is not preferable.
  • the cured product of the present invention is excellent in transparency. Specifically, the cured product of the present invention has a good light transmittance at a wavelength in the range of usually 300 nm or more, preferably 350 nm or more, and usually 900 nm or less, preferably 500 nm or less. Therefore, it is preferable to use the cured product of the present invention as the sealing material in an optical semiconductor device having an emission wavelength in this region because a high-luminance optical semiconductor device can be obtained. In addition, this does not prevent using the hardened
  • the light transmittance can be measured by measuring transmittance with an ultraviolet / visible spectrophotometer.
  • the method for curing the composition of the present invention is not particularly limited.
  • the composition of the present invention is sealed like an LED by a method such as injection, dripping, casting, casting, extrusion from a container, or by integral molding by transfer molding or injection molding.
  • the composition can be cured to form a cured product, and the object to be sealed can be sealed.
  • the heating temperature is 45 ° C. or higher, stickiness is hardly observed in the obtained cured product, and if it is 300 ° C. or lower, foaming is hardly observed in the obtained cured product, which is practical.
  • the heating time is not particularly limited. Usually about 0.5 to 12 hours, preferably about 1 to 10 hours. If the heating time is 0.5 hours or longer, curing proceeds sufficiently, but if accuracy is required, such as for LED sealing, it is preferable to lengthen the curing time.
  • the cured product of the present invention can be used as a sealing material for semiconductor devices, and is particularly suitable as a sealing material for optical semiconductor devices and power semiconductor devices.
  • the sealing material made of the cured product of the present invention is excellent in transparency as described above. Moreover, it is excellent in heat resistance, cold resistance, and electrical insulation similarly to the cured
  • the optical semiconductor device of the present invention is an optical semiconductor device including at least an optical semiconductor element, and the optical semiconductor element is sealed at least by the cured product of the present invention.
  • Other configurations of the optical semiconductor device of the present invention are not particularly limited, and members other than the optical semiconductor element may be provided. Examples of such members include a base substrate, lead-out wiring, wire wiring, control element, insulating substrate, reflecting material, heat sink, conductive member, die bonding material, bonding pad, and the like. Further, in addition to the optical semiconductor element, a part or all of the members may be sealed with the cured product of the present invention.
  • optical semiconductor device of the present invention include, but are not limited to, a light emitting diode (LED) device, a semiconductor laser device, and a photocoupler.
  • the optical semiconductor device of the present invention includes, for example, a backlight such as a liquid crystal display, a light source such as illumination, various sensors, a printer and a copier, a measurement light source for a vehicle, a signal light, a display light, a display device, and a light source for a planar light emitter. It is suitably used for displays, decorations, various lights and switching elements.
  • the optical semiconductor device 10 includes at least a sealing material 1, an optical semiconductor element 2, and a bonding wire 3 on an optical semiconductor substrate 6.
  • the optical semiconductor substrate 6 has a recess composed of a bottom surface made of the lead frame 5 and an inner peripheral side surface made of the reflector 4.
  • the optical semiconductor element 2 is connected to the lead frame 5 using a die bond material (not shown).
  • a bonding pad (not shown) provided in the optical semiconductor element 2 and the lead frame 5 are electrically connected by a bonding wire 3.
  • the reflective material 4 has a function of reflecting light from the optical semiconductor element 2 in a predetermined direction.
  • a sealing material 1 is filled in the region of the concave portion of the optical semiconductor substrate 6 so as to at least seal the optical semiconductor element 2. At this time, the sealing material 1 may be filled so as to also seal the bonding wire 3.
  • the sealing material 1 consists of the hardened
  • the phosphor (not shown) may be included in the sealing material 1.
  • the sealing material 1 can protect the optical semiconductor element 2 from moisture, dust, and the like, and can maintain reliability over a long period of time. Furthermore, since the sealing material 1 also seals the bonding wire 3, it is possible to prevent electrical problems caused by the bonding wire 3 being disconnected, cut, or short-circuited at the same time.
  • the cured product of the present invention can be used as an adhesive for semiconductors as described later. Therefore, it can also be employed as the above-described die bond material.
  • the optical semiconductor element 2 sealed with the sealing material 1 made of the cured product of the present invention for example, an LED, a semiconductor laser, a photodiode, a phototransistor, a solar cell, a CCD (charge coupled device). Etc.
  • the structure shown in FIG. 1 is only an example of the optical semiconductor device of the present invention, and the structure of the reflector, the structure of the lead frame, the mounting structure of the optical semiconductor element, and the like can be modified as appropriate.
  • the method for manufacturing the optical semiconductor device 10 shown in FIG. 1 is not particularly limited.
  • the optical semiconductor element 2 is die-bonded to a lead frame 5 provided with a reflective material 4, the optical semiconductor element 2 and the lead frame 5 are wire-bonded by a bonding wire 3, and then provided around the optical semiconductor element.
  • An example is a method in which the composition of the present invention is filled on the inner side of the reflecting material (the recess made of the lead frame and the reflecting material), and then cured by heating at 50 to 250 ° C. to obtain the sealing material 1.
  • the composition of the present invention Since the composition of the present invention has good adhesion, it can be used as an adhesive for semiconductor devices. Specifically, for example, when bonding a semiconductor element and a package, when bonding a semiconductor element and a submount, when bonding package components, when bonding a semiconductor device and an external optical member, etc.
  • the composition of the invention can be used by coating, printing, potting and the like.
  • a (peak (a) area + peak (b) area) / sum of total peak areas
  • b (peak (c) area + peak (d) area + peak (e) area) / total peak area
  • c (peak (f) area + peak (g) area + peak (h) area + peak (i) area) / total peak area
  • d sum of peak (j) area / total peak area.
  • e (peak (a) area + peak (b) area) / sum of total peak areas
  • f (peak (c) area + peak (d) area + peak (e) area) / total peak area
  • g (peak (f) area + peak (g) area + peak (h) area + peak (i) area) / total peak area
  • h sum of peak (k) area / total peak area.
  • Mass average molecular weight (Mw) measurement The mass average molecular weight (Mw) of the silicone resin was calculated by creating a calibration curve using polystyrene as a reference material by the gel permeation chromatography (abbreviation: GPC) method under the following conditions: Device: manufactured by Tosoh Corporation, product name: HLC-8320GPC, Column: manufactured by Tosoh Corporation, product name: TSK Gel Super HZ 2000x4, 3000x2, Eluent: tetrahydrofuran.
  • GPC gel permeation chromatography
  • the refractive index of the silicone resin was measured using a refractometer (Kyoto Electronics Industry Co., Ltd., model: RA-600).
  • Viscosity measurement The viscosity of the silicone resin is determined according to JIS Z8803 (2011), “Viscosity measurement method using a cone-plate type rotational viscometer” (manufactured by ANTON PAAR, product name: PHYSICA MCR51, measurement range 200 to 1,000,000 cP). And a temperature control unit (manufactured by ANTON PAAR, product name: P-PTD200), measured at a shear rate of 30 [1 / s] in a standard state (25 ° C., 1 atm), and obtained 1 minute after the start of measurement. Values were adopted. When the viscosity was less than the measurement range, it was expressed as “ ⁇ 200”.
  • the yield of the silicone resin (I) is 1388.0G, weight average molecular weight (Mw) of 900, composition ratio was 0.51 (Me 2 SiO 2/2) 0.49 (PhSiO 3/2), HO-Si The content of the group was 7.2 mmol / g (12% by mass).
  • reaction solution was transferred to a separatory funnel, and 50 mL of toluene and 80 mL of water were added for extraction, and then the organic layer was recovered. Further, 80 mL of water and 20 mL of 2-propanol were added, extraction operation was performed, and the organic layer was recovered. The organic layer was washed by repeating this same operation three times.
  • an acid scavenger manufactured by Kyowa Chemical Industry Co., Ltd., product name: KYOWARD 500
  • PORE SIZE fluororesin filter paper
  • the yield of the silicone resin (A1) is 28.58 g, the weight average molecular weight (Mw) is 1400, the viscosity is less than 200 cP, and the composition ratio is (H—SiMe 2 O 1/2 ) 0.18 (Me 2 SiO 2 / 2 ) 0.32 (PhSiO 3/2 ) 0.43 (SiO 4/2 ) 0.07 , the H—Si group content is 1.36 mmol / g, and the HO—Si group content is 4.8 mmol / g. (8.2% by mass).
  • reaction solution was transferred to a separatory funnel, and 80 mL of toluene, 50 mL of water and 40 mL of 2-propanol were added to perform extraction, and then the organic layer was recovered. Further, 80 mL of water and 20 mL of 2-propanol were added, extraction operation was performed, and the organic layer was recovered. The organic layer was washed by repeating this same operation three times. Thereafter, 1 g of an acid scavenger (manufactured by Kyowa Chemical Industry Co., Ltd., product name: KYOWARD 500) was added to the organic layer and stirred, followed by filtration with a fluororesin filter paper (PORE SIZE; 1 ⁇ m) after 1 hour.
  • an acid scavenger manufactured by Kyowa Chemical Industry Co., Ltd., product name: KYOWARD 500
  • the yield of the silicone resin (B1) is 29.67 g, the mass average molecular weight (Mw) is 2000, the viscosity is 410 cP, and the composition ratio is (Vi-SiMe 2 O 1/2 ) 0.25 (Me 2 SiO 2 / 2 ) 0.25 (PhSiO 3/2 ) 0.32 (SiO 4/2 ) 0.18 , Vi-Si group content is 2.23 mmol / g, and HO-Si group content is 3.1 mmol / g ( 5.3 mass%).
  • the yield of the silicone resin (II) is 132.01 g, the mass average molecular weight (Mw) is 1600, the viscosity is less than 200 cP, and the composition ratio is (Me 2 SiO 2/2 ) 0.40 (PhSiO 3/2 ) 0.51 (SiO 4/2 ) 0.09 , and the content of HO—Si groups was 7.36 mmol / g (13 mass%).
  • the yield of the silicone resin (A2) is 16.05 g, the mass average molecular weight (Mw) is 1500, the viscosity is less than 200 cP, and the composition ratio is (H—SiMe 2 O 1/2 ) 0.24 (Me 2 SiO 2/2 ) 0.30 (PhSiO 3/2 ) 0.45 (SiO 4/2 ) 0.01 , the H—Si group content is 2.19 mmol / g, and the HO—Si group content is 2.9 mmol / g. g (4.9% by mass).
  • the yield of the silicone resin (B2) is 19.38 g, the mass average molecular weight (Mw) is 1500, the viscosity is 210 cP, and the composition ratio is (Vi-SiMe 2 O 1/2 ) 0.32 (Me 2 SiO 2 / 2 ) 0.25 (PhSiO 3/2 ) 0.33 (SiO 4/2 ) 0.10 , the Vi—Si group content is 2.19 mmol / g, and the HO—Si group content is 3.2 mmol / g. (3.0% by mass).
  • Comparative Synthesis Example 5-1 Synthesis of Silicone Resin (PI) In addition to 96.16 g (0.8 mol) of Me 2 Si (OMe) 2 and 158.64 g (0.8 mol) of PhSi (OMe) 3 , Further, hydrolysis and condensation reactions were performed in the same manner as in Comparative Synthesis Example 1 except that 52.08 g (0.25 mol) of Si (OEt) 4 was collected. Thereafter, the reaction solution was returned to room temperature, transferred to a 2 L separatory funnel, 400 mL of toluene and 400 mL of water were added, and after performing a liquid separation operation, the aqueous layer was removed. Next, the organic layer was washed twice with 400 mL of water.
  • a silicone resin (PI) was obtained as a colorless viscous liquid.
  • the yield of the silicone resin (PI) is 288.82 g
  • the mass average molecular weight (Mw) is 1200
  • the composition ratio is (Me 2 SiO 2/2 ) 0.36 (PhSiO 3/2 ) 0.48 (SiO 4/2 ).
  • the HO—Si group content was 8.4 mmol / g (14% by mass).
  • a silicone resin (PA1) was obtained as a colorless and transparent viscous liquid.
  • the yield of the silicone resin (PA1) is 159.76 g
  • the weight average molecular weight (Mw) is 2400
  • the viscosity is 42000 cP
  • the composition ratio is (H—SiMe 2 O 1/2 ) 0.23 (Me 2 SiO 2 / 2 ) 0.14 (PhSiO 3/2 ) 0.52 (SiO 4/2 ) 0.11
  • the H—Si group content is 2.1 mmol / g
  • the HO—Si group content is 3.2 mmol / g. (6% by mass).
  • a silicone resin (PB1) was obtained as a colorless and transparent viscous liquid.
  • the yield of the silicone resin (PB1) is 92.52 g
  • the mass average molecular weight (Mw) is 1700
  • the viscosity is 11000 cP
  • the composition ratio is (Vi-SiMe 2 O 1/2 ) 0.22 (Me 2 SiO 2/2 ) 0.21 (PhSiO 3/2 ) 0.44 (SiO 4/2 ) 0.13
  • Vi—Si group content is 2.0 mmol / g
  • HO—Si group content is 2.1 mmol / g (4 Mass%).
  • the yield of the silicone resin (QI) is 143.4 g, the mass average molecular weight (Mw) is 1,100, and the composition ratio is (Me 2 SiO 2/2 ) 0.36 (PhSiO 3/2 ) 0.50 (SiO 4 / 2 ) It was 0.14 , and the content of HO—Si group was 7.9 mmol / g (14 mass%).
  • a silicone resin (QA1) was obtained as a colorless and transparent viscous liquid.
  • the yield of the silicone resin (QA1) is 165.7 g
  • the mass average molecular weight (Mw) is 3300
  • the viscosity is 94000 cP
  • the composition ratio is (H-SiMe 2 O 1/2 ) 0.24 (Me 2 SiO 2 / 2 ) 0.15 (PhSiO 3/2 ) 0.48 (SiO 4/2 ) 0.13
  • the H—Si group content is 2.3 mmol / g
  • the HO—Si group content is 3.1 mmol / g. (5% by mass).
  • a silicone resin (QB1) was obtained as a colorless and transparent viscous liquid.
  • the yield of the silicone resin (QB1) is 99.2 g
  • the mass average molecular weight (Mw) is 1900
  • the viscosity is 9600 cP
  • the composition ratio is (Vi-SiMe 2 O 1/2 ) 0.23 (Me 2 SiO 2 / 2 ) 0.19 (PhSiO 3/2 ) 0.43 (SiO 4/2 ) 0.15
  • the Vi—Si group content is 2.2 mmol / g
  • the HO—Si group content is 1.7 mmol / g (3 Mass%).
  • a silicone resin (RA1) was obtained as a colorless and transparent viscous liquid.
  • the yield of the silicone resin (RA1) is 42.5 g
  • the weight average molecular weight (Mw) is 1900
  • the viscosity is 200 cP
  • the composition ratio is (H—SiMe 2 O 1/2 ) 0.27 (Me 2 SiO 2 / 2 ) 0.31 (PhSiO 3/2 ) 0.42
  • the H—Si group content is 2.8 mmol / g
  • the HO—Si group content is 2.0 mmol / g (3.4 mass%).
  • a silicone resin (RB1) was obtained as a colorless and transparent viscous liquid.
  • the yield of the silicone resin (RB1) is 20.6 g
  • the weight average molecular weight (Mw) is 1800
  • the viscosity is 350 cP
  • the composition ratio is (Vi-SiMe 2 O 1/2 ) 0.23 (Me 2 SiO 2 / 2 ) 0.32 (PhSiO 3/2 ) 0.45
  • the Vi—Si group content is 2.3 mmol / g
  • the HO—Si group content is 2.1 mmol / g (3.6% by mass).
  • composition ratios and physical properties of the synthesized silicone resins (A1), (B1), (A2), (B2), (PA1), (PB1), (QA1), (QB1), (RA1), and (RB1)
  • the values (HO—Si group content, H—Si group or Vi—Si group content, mass average molecular weight, viscosity, refractive index, and transparency) are shown in Table 2.
  • the silicone resins (A1), (B1), (A2), and (B2) obtained in the raw material synthesis examples are all silicone resins (PA1) and (PB1) obtained in the comparative synthesis examples. ), (QA1), and (QB1) showed extremely low viscosity. Further, the viscosity is comparable or low even when compared with the silicone resins (RA1) and (RB1), which are silicone resins having no structural unit represented by (SiO 4/2 ) obtained in the comparative synthesis example. showed that.
  • the platinum catalyst a platinum-divinyltetramethyldisiloxane complex was used so that the content of platinum atoms was 0.03 ppm in mass units with respect to the total amount of the composition.
  • the compositions of the prepared compositions 1 to 5 are shown in Table 3.
  • the viscosity of the prepared composition was determined according to “Viscosity measurement method using a cone-plate type rotational viscometer” in JIS Z8803 (2011) (product name: PHYSICA MCR51, product name: PHYSICA MCR51, measurement range: 200 to 1,000). , 000 cP) and a temperature control unit (manufactured by ANTON PAAR, product name: P-PTD200), measured at a shear rate of 30 [1 / s] in a standard state (25 ° C., 1 atm), 1 minute from the start of measurement The value obtained later was adopted. In the case of a low-viscosity liquid less than the measurement range, “ ⁇ 200” was indicated.
  • the prepared composition was poured into a mold (25 mm ⁇ ), heated in air at 90 ° C. for 1 hour, and further heated at 150 ° C. for 4 hours to produce a cured product having a thickness of 4 to 5 mm.
  • the hardness of Shore A or Shore D of the cured product is determined according to JIS K 7215 “Plastic Durometer Hardness Test Method” using a durometer (manufactured by TECLOCK Co., Ltd., model: GS-719R, GS-720R). It was measured by.
  • the prepared composition was poured into a mold (22 mm ⁇ ), heated in air at 90 ° C. for 1 hour, and further heated at 150 ° C. for 4 hours to produce a cured product having a thickness of 22 mm ⁇ and 2 mm.
  • the cured product was heated at 200 ° C. for 100 hours, and then the transmittance in the wavelength region of 405 nm and 365 nm was measured using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, model number: UV-3150).
  • [Appearance of cured product] 1 g of the prepared composition was spread on a glass mold (22 mm ⁇ ), heated in air at 90 ° C. for 1 hour, and further heated at 150 ° C. for 4 hours to prepare a cured product having a thickness of 22 mm ⁇ and 2 mm. Three test bodies were prepared, and the appearance of the test bodies was visually confirmed. In all the test bodies, a state in which generation of bubbles and cracks in the cured product was not observed was defined as “good”. In other cases, it was determined as “bad”.
  • the compositions 1-2 prepared in Examples 1-2 have extremely low viscosities compared to the compositions 3-4 prepared in Comparative Examples 1-2. Further, the cured products obtained from the compositions 1 and 2 exhibit good appearance and punching moldability, and have the same physical properties in terms of adhesion and transparency. Moreover, when compared with the cured product obtained from the low-viscosity composition 5 as in Comparative Example 3, it has excellent physical properties in terms of adhesion and resin strength.
  • compositions 1 and 2 prepared in Examples 1 and 2 within the scope of the present invention have extremely low viscosity, and the cured product has good physical properties.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Medicinal Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Polymers (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

La composition de résine de silicone durcissable selon la présente invention contient au moins un composant (A), un composant (B) et un composant (C). Composant (A) : une résine de silicone prédéterminée représentée par la formule [1] et ayant une viscosité de 10 000 cP ou moins. Composant (B) : une résine de silicone prédéterminée représentée par la formule [2] et ayant une viscosité de 10 000 cP ou moins. Composant (C) : un catalyseur hydrosilylé. (H-SiMe2O1/2)a(Me2SiO2/2)b(PhSiO3/2)c(SiO4/2)d [1] (Vi-SiMe2O1/2)e(Me2SiO2/2)f(PhSiO3/2)g(SiO4/2)h [2] La composition de résine de silicone durcissable présente une faible viscosité et une durabilité suffisante, et est utile en tant que matériau d'étanchéité pour éléments semi-conducteurs dans un dispositif semi-conducteur optique.
PCT/JP2016/083317 2016-01-19 2016-11-10 Composition de résine de silicone durcissable et son produit durci, et dispositif semi-conducteur optique l'utilisant Ceased WO2017126199A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2016-007512 2016-01-19
JP2016007512 2016-01-19
JP2016200588A JP2017128707A (ja) 2016-01-19 2016-10-12 硬化性シリコーン樹脂組成物およびその硬化物、並びにこれらを用いた光半導体装置
JP2016-200588 2016-10-12

Publications (1)

Publication Number Publication Date
WO2017126199A1 true WO2017126199A1 (fr) 2017-07-27

Family

ID=59362695

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/083317 Ceased WO2017126199A1 (fr) 2016-01-19 2016-11-10 Composition de résine de silicone durcissable et son produit durci, et dispositif semi-conducteur optique l'utilisant

Country Status (1)

Country Link
WO (1) WO2017126199A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005105217A (ja) * 2003-10-01 2005-04-21 Dow Corning Toray Silicone Co Ltd 硬化性オルガノポリシロキサン組成物および半導体装置
JP2009215420A (ja) * 2008-03-10 2009-09-24 Shin Etsu Chem Co Ltd 高硬度シリコーンゴムを与える組成物およびそれを封止材として用いた半導体装置
JP2010106223A (ja) * 2008-10-31 2010-05-13 Dow Corning Toray Co Ltd 電気・電子部品用封止・充填剤および電気・電子部品
WO2012029538A1 (fr) * 2010-08-31 2012-03-08 東レ・ダウコーニング株式会社 Composition de polysiloxane et produit durci de ladite composition
JP2012082300A (ja) * 2010-10-08 2012-04-26 Shin-Etsu Chemical Co Ltd 付加硬化型シリコーン組成物、及び該組成物の硬化物により半導体素子が被覆された半導体装置
JP2012144617A (ja) * 2011-01-11 2012-08-02 Sekisui Chem Co Ltd 光半導体装置用ダイボンド材及びそれを用いた光半導体装置
JP2013067683A (ja) * 2011-09-21 2013-04-18 Dow Corning Toray Co Ltd 光半導体素子封止用硬化性シリコーン組成物、樹脂封止光半導体素子の製造方法、および樹脂封止光半導体素子
JP2013147659A (ja) * 2007-11-19 2013-08-01 Toagosei Co Ltd ポリシロキサンおよびその硬化物の製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005105217A (ja) * 2003-10-01 2005-04-21 Dow Corning Toray Silicone Co Ltd 硬化性オルガノポリシロキサン組成物および半導体装置
JP2013147659A (ja) * 2007-11-19 2013-08-01 Toagosei Co Ltd ポリシロキサンおよびその硬化物の製造方法
JP2009215420A (ja) * 2008-03-10 2009-09-24 Shin Etsu Chem Co Ltd 高硬度シリコーンゴムを与える組成物およびそれを封止材として用いた半導体装置
JP2010106223A (ja) * 2008-10-31 2010-05-13 Dow Corning Toray Co Ltd 電気・電子部品用封止・充填剤および電気・電子部品
WO2012029538A1 (fr) * 2010-08-31 2012-03-08 東レ・ダウコーニング株式会社 Composition de polysiloxane et produit durci de ladite composition
JP2012082300A (ja) * 2010-10-08 2012-04-26 Shin-Etsu Chemical Co Ltd 付加硬化型シリコーン組成物、及び該組成物の硬化物により半導体素子が被覆された半導体装置
JP2012144617A (ja) * 2011-01-11 2012-08-02 Sekisui Chem Co Ltd 光半導体装置用ダイボンド材及びそれを用いた光半導体装置
JP2013067683A (ja) * 2011-09-21 2013-04-18 Dow Corning Toray Co Ltd 光半導体素子封止用硬化性シリコーン組成物、樹脂封止光半導体素子の製造方法、および樹脂封止光半導体素子

Similar Documents

Publication Publication Date Title
JP5526823B2 (ja) シリコーン樹脂で封止された光半導体装置
CN104245847B (zh) 固化性树脂组合物及其固化物
TWI516547B (zh) Low gas permeable silicone resin composition and optical semiconductor device
KR102338110B1 (ko) 부가 경화형 실리콘 조성물
KR101836962B1 (ko) 신규 유기 규소 화합물, 상기 유기 규소 화합물을 포함하는 열경화성 수지 조성물, 경화 수지 및 광 반도체용 봉지 재료
CN106459102B (zh) 有机硅氧烷、固化性有机硅组合物及半导体装置
WO2017010327A1 (fr) Composition de résine de polyborosiloxane durcissable, objet durci obtenu à partir de celle-ci et dispositif à semi-conducteur optique obtenu à l'aide de ladite composition ou comprenant ledit objet durci
CN102449034A (zh) 有机硅化合物、含有该有机硅化合物的热硬化性组成物及光半导体用密封材料
JP7562201B2 (ja) ホットメルト性硬化性シリコーン組成物、封止剤、フィルム、光半導体素子
CN102834465A (zh) 光半导体装置用密封剂及使用其的光半导体装置
CN106574118A (zh) 固化性有机硅树脂组合物和其固化物，以及使用它们的光半导体装置
TWI653295B (zh) 硬化性聚矽氧組合物、其硬化物及光半導體裝置
TW201431960A (zh) 可硬化性聚矽氧組合物、其硬化製品及光半導體裝置
WO2018047633A1 (fr) Composition de résine durcissable, produit durci associé, et dispositif semi-conducteur
JP5871413B2 (ja) 硬化性組成物
JP6502658B2 (ja) 硬化性シリコーン樹脂組成物及びその硬化物
JP5885368B2 (ja) 硬化性組成物
JP2017020005A (ja) 硬化性ポリボロシロキサン樹脂組成物およびその硬化物、並びにこれらを用いた光半導体装置
TWI579339B (zh) 硬化性樹脂組成物
WO2017164265A1 (fr) Composition de résine durcissable, son produit durci, et dispositif semi-conducteur
JP2017128707A (ja) 硬化性シリコーン樹脂組成物およびその硬化物、並びにこれらを用いた光半導体装置
JP5893212B2 (ja) 硬化性組成物
JP2018111783A (ja) 硬化性シリコーン樹脂組成物およびその硬化物、並びにこれらを用いた半導体装置
WO2014004969A1 (fr) Polyorganométallosiloxane, compositions polymères durcissables, leur produit durci, et dispositif optique semi-conducteur
TWI540182B (zh) A hardened silicone resin composition and a hardened product thereof, and a light-cured semiconductor device

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16886438

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16886438

Country of ref document: EP

Kind code of ref document: A1