WO2013051600A1 - Composition de résine durcissable, tablette de composition de résine durcissable, corps moulé, boîtier de semi-conducteurs, pièce semi-conductrice et diode électroluminescente - Google Patents

Composition de résine durcissable, tablette de composition de résine durcissable, corps moulé, boîtier de semi-conducteurs, pièce semi-conductrice et diode électroluminescente Download PDF

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WO2013051600A1
WO2013051600A1 PCT/JP2012/075633 JP2012075633W WO2013051600A1 WO 2013051600 A1 WO2013051600 A1 WO 2013051600A1 JP 2012075633 W JP2012075633 W JP 2012075633W WO 2013051600 A1 WO2013051600 A1 WO 2013051600A1
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component
resin composition
curable resin
composition according
group
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PCT/JP2012/075633
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English (en)
Japanese (ja)
Inventor
井手　正仁
直人 ▲高▼木
和章 金井
修平 尾崎
洋 大越
聡明 射場
平林　和彦
岩原　孝尚
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株式会社カネカ
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Priority to JP2013537530A priority Critical patent/JP6043292B2/ja
Priority to CN201280049280.4A priority patent/CN103842442B/zh
Publication of WO2013051600A1 publication Critical patent/WO2013051600A1/fr

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14639—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles for obtaining an insulating effect, e.g. for electrical components
    • B29C45/14655—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles for obtaining an insulating effect, e.g. for electrical components connected to or mounted on a carrier, e.g. lead frame
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/54—Nitrogen-containing linkages
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/14—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages

Definitions

  • the present invention relates to a curable resin composition, a curable resin composition tablet, a molded body, a semiconductor package, a semiconductor component, and a light emitting diode.
  • packages using curable resins of various shapes are applied to semiconductors.
  • Various metal materials are used for these packages in order to make electrical connection between the semiconductor and the outside of the package, to maintain the strength of the package, or to transfer heat generated from the semiconductor to the outside of the package.
  • Patent Documents 1 and 2 In that case, it is not possible to reduce the warp as described above, and the problem of warp becomes important.
  • an object of the present invention is to provide a curable resin composition having a low linear expansion coefficient and giving a tough cured product, and the warpage integrally formed with a metal using the composition is reduced. And a tough semiconductor package and a semiconductor manufactured using the same.
  • the present invention has the following configuration. (1). (A) a silicon compound having a molecular weight of less than 1000 and containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule; (B) a compound containing at least two SiH groups in one molecule; (C) a hydrosilylation catalyst, (D) a silicone compound containing at least one carbon-carbon double bond having reactivity with SiH group in one molecule and having a molecular weight of 1000 or more, and (E) inorganic filler, Is contained as an essential component. Curable resin composition characterized by the above-mentioned. (2).
  • the curable resin composition according to (1) further comprising (Z) an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule.
  • (3). The curable resin composition according to (1) or (2), wherein the component is a linear polysiloxane having a vinyl group at its terminal.
  • (4). The curable resin composition according to any one of (1) to (3), wherein the component has a weight average molecular weight of 2,000 or more and 1,000,000 or less.
  • (6). The curable resin composition according to any one of (1) to (5), further comprising (F) a white pigment. (7).
  • Tg of the cured product obtained by thermally curing the mixture of the components (A) to (C) and (Z) is in the range of 30 ° C. to 100 ° C.
  • the curable resin composition according to any one of the above. 24).
  • a cured product obtained by thermosetting the mixture of the components (A) to (C) and the (Z) component has a storage elastic modulus measured in a tensile mode at a frequency of 10 Hz at 150 ° C. within a range of 20 MPa to 100 MPa.
  • the curable resin composition according to (23). The curable resin composition according to (23).
  • a tablet comprising the curable resin composition according to any one of (6) to (26), wherein at least one of the component (A) and the component (B) has a viscosity at 23 ° C. of 50 Pa seconds or less.
  • the total content of component (E) and component (F) is 70 to 95% by weight,
  • grains of 12 micrometers or less to the sum total of (E) component and (F) component is 40 volume% or more,
  • the tablet characterized by the above-mentioned. (28).
  • a molded product obtained by curing the curable resin composition according to any one of (1) to (25), and having a light reflectance at a surface wavelength of 480 nm of 90% or more.
  • (34) A semiconductor component manufactured using the semiconductor package described in any one of (33).
  • (35) A light-emitting diode manufactured using the semiconductor package according to any one of (33) to (33).
  • curable resin composition of the present invention If used, a curable resin composition having a low linear expansion coefficient and giving a tough cured product can be obtained. A semiconductor package with reduced warpage and excellent toughness and a semiconductor manufactured using the same can be manufactured.
  • the curable resin composition of the present invention is (A) a silicon compound having a molecular weight of less than 1000 and containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule; (B) a compound containing at least two SiH groups in one molecule; (C) a hydrosilylation catalyst, (D) a silicone compound containing at least one carbon-carbon double bond having reactivity with a SiH group in one molecule and having a molecular weight of 1000 or more, and (E) A curable resin composition containing an inorganic filler as an essential component.
  • the component (A) can be used without particular limitation as long as it is a silicon compound having a molecular weight of less than 1000 and containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule.
  • the carbon-carbon double bond in component (A) preferably has a CH 2 ⁇ CH—Si type structure directly bonded to a silicon atom. This is because when the curable resin composition of the present invention is cured by a hydrosilylation reaction, the structure is highly active with respect to the hydrosilylation reaction, and no side reaction is involved. Is easy.
  • the component corresponding to the component (A) described in Patent Document 3 described above becomes a carbon-carbon double bond of a general organic compound not containing silicon, so that the isomerization reaction to an internal olefin is performed during hydrosilylation. Inevitable as a side reaction. Once the internal olefin is generated, the activity for hydrosilylation reaction is extremely reduced, and there are concerns about problems such as deterioration of mechanical properties and expression of surface tackiness associated with a decrease in reaction rate.
  • the proportion of Si—C bonds (bonding distance: 1.91 mm; C—C bond distance: 1.50 mm) constituting the crosslinked structure of the cured product obtained by curing the curable resin composition of the present invention is as described above. Since it increases compared with the hardened
  • the component (A) is preferably one containing 0.001 mol or more of carbon-carbon double bond having reactivity with the SiH group from 1 g of the component (A) from the viewpoint of further improving the heat resistance. Those containing 0.003 mol or more per gram are more preferable, and those containing 0.005 mol or more are more preferable.
  • the number of carbon-carbon double bonds having reactivity with the SiH group of component (A) should be at least 2 on average per molecule, but it should exceed 2 if it is desired to further improve the mechanical strength. It is preferable that the number is 3 or more. Conversely, when it is desired to give flexibility or toughness to the cured product, brittleness may appear when the number is 3 or more, and thus the number close to 2 on average is desirable.
  • the number of carbon-carbon double bonds having reactivity with the SiH group of component (A) is 1 or less per molecule, a crosslinked structure is obtained even if it reacts with component (B), resulting in a graft structure. Not.
  • the molecular weight of the component (A) is less than 1000.
  • the molecular weight is preferably less than 900, more preferably less than 700, and even more preferably less than 500.
  • the component (A) in order to obtain uniform mixing with other components and good workability, it is preferably a liquid at 23 ° C., and its viscosity is less than 1000 poise at 23 ° C. Preferably, those having 500 poises or less are more preferred, those having less than 300 poises are further preferred, and those having less than 30 poises are particularly preferred.
  • the viscosity can be measured with an E-type viscometer.
  • a part or all of the phenyl group may be replaced with the following aryl group.
  • aryl groups include naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2 -Propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 3-isobutyl Phenyl group, 4-isobutylphenyl group, 3-tbutylphenyl group, 4-tbutylphenyl group, 3-pentylphenyl group, 4-pentylphenylphenyl
  • (Mixing of component (A)) (A) component can be used individually or in mixture of 2 or more types.
  • the component (Z) is an organic compound containing at least two carbon-carbon double bonds having reactivity with the SiH group in one molecule, and is a compound different from the component (A).
  • the component (Z) may be used in combination with the component (A).
  • organic compound examples include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2-tetraallyloxyethane, Diallylidene pentaerythritol, triallyl cyanurate, triallyl isocyanurate, diallyl monoglycidyl isoanurate, diallyl monomethyl isocyanurate, 1,2,4-trivinylcyclohexane, divinylbenzenes (with a purity of 50 to 100%) , Preferably having a purity of 80 to 100%), divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and oligomers thereof,
  • Aliphatic chain polyene compounds such as butadiene, isoprene, octadiene and decadiene, aliphatic cyclic polyene compounds such as cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene and norbornadiene, vinylcyclopentene, vinylcyclohexene And substituted aliphatic cyclic olefin compound systems.
  • triallyl cyanurate, triallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monomethyl isocyanurate, 1,2,4-trivinylcyclohexane, divinylbenzenes (purity 50 to 100%, preferably 80 to 100%), preferably divinylbiphenyl is used
  • (A ) It is preferably in the range of 5 to 50 parts by weight, more preferably in the range of 10 to 45 parts by weight, and in the range of 15 to 40 parts by weight with respect to 100 parts by weight of the component. Further preferred.
  • the component (B) is a compound containing at least two SiH groups in one molecule.
  • the component (B) is not particularly limited as long as it is a compound containing at least two SiH groups in one molecule.
  • it is a compound described in WO 96/15194, and at least 2 in one molecule. Those having a single SiH group can be used.
  • R 1 represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10).
  • Cyclic organopolysiloxane having at least two SiH groups in one molecule Is preferred.
  • the substituent R 1 in the compound represented by the general formula (VI) is preferably composed of C, H and O, more preferably a hydrocarbon group, and a methyl group. Further preferred.
  • the compound represented by the general formula (VI) is preferably 1,3,5,7-tetramethylcyclotetrasiloxane from the viewpoint of availability.
  • the molecular weight of the component (B) is not particularly limited, and any one can be suitably used. However, the viewpoint that the fluidity is more easily expressed and the powder such as the component (E) and the component (F) is easily mixed uniformly. Are preferably those having a low molecular weight. In this case, the lower limit of the preferred molecular weight is 50, more preferably 100, still more preferably 150. The upper limit of the molecular weight is preferably 100,000, more preferably 5,000, still more preferably 2,000, and particularly preferably 1,500.
  • the component (B) in order to facilitate uniform mixing with other components, particularly powders such as the component (E) and the component (F), more specifically, heating above the melting point for uniform mixing.
  • the liquid is preferably liquid at 23 ° C., and its viscosity is preferably 50 Pa seconds or less at 23 ° C., more preferably 20 Pa seconds or less, and more preferably 5 Pa seconds or less. Further preferred. The viscosity can be measured with an E-type viscometer.
  • Component (B) can be used alone or in combination of two or more.
  • component (B) (B) From the viewpoint that the problem of outgas from the curable resin composition that can be reduced in volatility of the component is less likely to occur, and from the viewpoint of giving practical strength and toughness to the cured product obtained from the composition. It is more preferable than a compound composed of only a siloxane skeleton to have a component that is substantially non-functional and has a siloxane skeleton in addition to a skeleton derived from an organic compound.
  • the component (B) is composed of an organic compound ( ⁇ ) containing at least one carbon-carbon double bond having reactivity with the SiH group in one molecule and one molecule. It is preferable that the compound ( ⁇ ) having at least two SiH groups can be obtained by a hydrosilylation reaction.
  • the same component ( ⁇ 1) as the component (Z) that can be used in combination with the component (A) can be used.
  • the component ( ⁇ 1) is used, the resulting cured product has a high crosslink density and tends to be a cured product having high mechanical strength.
  • an organic compound ( ⁇ 2) containing one carbon-carbon double bond having reactivity with the SiH group in one molecule can also be used.
  • the ( ⁇ 2) component is used, the obtained cured product tends to have low elasticity.
  • the component ( ⁇ 2) is not particularly limited as long as it is an organic compound containing one carbon-carbon double bond having reactivity with the SiH group in one molecule.
  • the bonding position of the carbon-carbon double bond having reactivity with the SiH group of the ( ⁇ 2) component is not particularly limited and may be present anywhere in the molecule.
  • the ( ⁇ 2) component compound can be classified into a polymer compound and a monomer compound.
  • the polymer compound include polysiloxane, polyether, polyester, polyarylate, polycarbonate, saturated hydrocarbon, unsaturated hydrocarbon, polyacrylate ester, polyamide, phenol-formaldehyde ( Phenol resin type) and polyimide type compounds can be used.
  • monomer compounds include aromatic hydrocarbons such as phenols, bisphenols, benzene, and naphthalene: aliphatic hydrocarbons such as straight-chain and alicyclics: heterocyclic compounds, and silicon-based compounds. Examples thereof include compounds and mixtures thereof.
  • the carbon-carbon double bond having reactivity with the SiH group of the component ( ⁇ 2) is not particularly limited, but the following general formula (I)
  • a group represented by the formula (wherein R 1 represents a hydrogen atom or a methyl group) is preferred from the viewpoint of reactivity.
  • R 1 represents a hydrogen atom or a methyl group
  • An alicyclic group represented by the formula (wherein R 2 represents a hydrogen atom or a methyl group) is preferred from the viewpoint that the heat resistance of the cured product is high.
  • R 2 represents a hydrogen atom or a methyl group
  • the alicyclic group represented by is particularly preferable.
  • the carbon-carbon double bond having reactivity with the SiH group may be directly bonded to the skeleton portion of the ( ⁇ 2) component, or may be covalently bonded through a divalent or higher substituent.
  • the divalent or higher valent substituent is not particularly limited as long as it is a substituent having 0 to 10 carbon atoms. Examples of these substituents include
  • divalent or higher valent substituents may be connected by a covalent bond to constitute one divalent or higher valent substituent.
  • groups of the group covalently bonded to the skeleton as described above include vinyl group, allyl group, methallyl group, acrylic group, methacryl group, 2-hydroxy-3- (allyloxy) propyl group, 2-allylphenyl group, 3 -Allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) phenyl group, 2- (allyloxy) ethyl group, 2,2-bis (allyl) Oxymethyl) butyl group, 3-allyloxy-2,2-bis (allyloxymethyl) propyl group,
  • component ( ⁇ 2) examples include propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-undecene, Idemitsu Petrochemical Co., Ltd. linearene, 4,4-dimethyl-1-pentene, 2-methyl-1-hexene, 2,3,3-trimethyl-1-butene, 2,4,4-trimethyl-1-pentene, etc.
  • Chain aliphatic hydrocarbon compounds such as cyclohexene, methylcyclohexene, methylenecyclohexane, norbornylene, ethylidenecyclohexane, vinylcyclohexane, camphene, carene, ⁇ -pinene, ⁇ -pinene, etc.
  • Aromatic hydrocarbon compounds such as 4-phenyl-1-butene, allyl ethers such as alkyl allyl ether and allyl phenyl ether, glycerin monoallyl ether, ethylene glycol monoallyl ether, 4-vinyl-1,3- Aliphatic compounds such as dioxolan-2-one, aromatic compounds such as 1,2-dimethoxy-4-allylbenzene and o-allylphenol, monoallyl dibenzyl isocyanurate, monoallyl diglycidyl isocyanurate, etc.
  • Aromatic hydrocarbon compounds such as 4-phenyl-1-butene, allyl ethers such as alkyl allyl ether and allyl phenyl ether, glycerin monoallyl ether, ethylene glycol monoallyl ether, 4-vinyl-1,3- Aliphatic compounds such as dioxolan-2-one, aromatic compounds such as 1,2-dimethoxy-4-allylbenzene and o-ally
  • Substituted isocyanurates silicon compounds such as vinyltrimethylsilane, vinyltrimethoxysilane, and vinyltriphenylsilane.
  • polyether resins such as one-end allylated polyethylene oxide and one-end allylated polypropylene oxide
  • hydrocarbon resins such as one-end allylated polyisobutylene, one-end allylated polybutyl acrylate, one-end allylated polymethyl methacrylate
  • examples thereof also include polymers or oligomers having a vinyl group at one end, such as acrylic resins.
  • the structure of the ( ⁇ 2) component may be linear or branched, and the molecular weight is not particularly limited, and various types can be used.
  • the molecular weight distribution is not particularly limited, but the molecular weight distribution is preferably 3 or less, more preferably 2 or less, and more preferably 1.5 or less in that the viscosity of the mixture is low and the moldability is likely to be good. More preferably it is.
  • the glass transition temperature of the component ( ⁇ 2) there is no particular limitation on this, and various materials are used.
  • the glass point transfer temperature is 100 ° C. or lower in that the obtained cured product tends to be tough. It is preferable that it is 50 degrees C or less, and it is further more preferable that it is 0 degrees C or less.
  • examples of such ( ⁇ 2) component preferred resins include polybutyl acrylate resins.
  • the glass transition temperature is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, further preferably 150 ° C. or higher, in that the heat resistance of the cured product obtained is increased. Most preferably, it is 170 ° C. or higher.
  • the glass transition temperature can be determined as a temperature at which tan ⁇ exhibits a maximum in the dynamic viscoelasticity measurement.
  • the component ( ⁇ 2) is preferably a hydrocarbon compound in that the heat resistance of the resulting cured product is increased.
  • the preferable lower limit of the carbon number is 7, and the preferable upper limit of the carbon number is 10.
  • the component ( ⁇ 2) may have other reactive groups.
  • the reactive group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group.
  • an epoxy group is preferable from the viewpoint that the adhesiveness can be further increased.
  • Specific examples include monoallyl diglycidyl isocyanurate, allyl glycidyl ether, allyloxyethyl methacrylate, allyloxyethyl acrylate, vinyltrimethoxysilane, and the like.
  • ( ⁇ 1) component and / or ( ⁇ 2) component a single component may be used, or a plurality of components may be used in combination.
  • the component ( ⁇ ) is a compound having at least two SiH groups in one molecule, and chain and / or cyclic polyorganosiloxanes are also examples. Specifically, for example
  • R 1 represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10).
  • Cyclic polyorganosiloxane having at least 3 SiH groups in one molecule Is preferred.
  • the substituent R 1 in the compound represented by the general formula (VI) is preferably composed of C, H, and O, more preferably a hydrocarbon group, and a methyl group. Is more preferable.
  • the component ( ⁇ ) is preferably 1,3,5,7-tetramethylcyclotetrasiloxane.
  • ( ⁇ ) component examples include compounds having a SiH group such as bisdimethylsilylbenzene.
  • Various ( ⁇ ) components as described above can be used alone or in admixture of two or more.
  • the mixing ratio of the ( ⁇ ) component and the ( ⁇ ) component when the ( ⁇ ) component and the ( ⁇ ) component are subjected to a hydrosilylation reaction is not particularly limited, but the hydrosilylation of the obtained (B) component and (A) component is not limited.
  • the component (B) since it is preferable that the component (B) has more SiH groups, the total number of carbon-carbon double bonds having reactivity with SiH groups in the component ( ⁇ ) to be mixed (
  • the ratio of X) to the total number of SiH groups (Y) in the ( ⁇ ) component to be mixed is preferably Y / X ⁇ 2, and more preferably Y / X ⁇ 3.
  • an appropriate catalyst may be used.
  • chloroplatinic acid platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable from the viewpoint of catalytic activity.
  • these catalysts may be used independently and may be used together 2 or more types.
  • the addition amount of the catalyst is not particularly limited, the lower limit of the preferable addition amount is sufficient with respect to 1 mol of SiH groups of the ( ⁇ ) component in order to have sufficient curability and keep the cost of the curable resin composition relatively low. 10 -8 mol Te, more preferably 10 -6 mole, preferable amount of the upper limit is 10 -1 moles per mole of the SiH group (beta) component, more preferably 10 -2 moles.
  • a cocatalyst can be used in combination with the above catalyst.
  • examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl malate, 2-hydroxy-2-methyl-1 -Acetylene alcohol compounds such as butyne, sulfur compounds such as simple sulfur, and amine compounds such as triethylamine.
  • the addition amount of the cocatalyst is not particularly limited, but the lower limit of the preferable addition amount relative to 1 mol of the hydrosilylation catalyst is 10 ⁇ 2 mol, more preferably 10 ⁇ 1 mol, and the upper limit of the preferable addition amount is 10 2. Mol, more preferably 10 mol.
  • Various methods can be used for mixing the ( ⁇ ) component, the ( ⁇ ) component, and the catalyst in the reaction, and the ( ⁇ ) component mixed with the catalyst is mixed with the ( ⁇ ) component.
  • the method is preferred. If the catalyst is mixed with the mixture of the ( ⁇ ) component and the ( ⁇ ) component, it is difficult to control the reaction.
  • the method of mixing the ( ⁇ ) component with the mixture of the ( ⁇ ) component and the catalyst the ( ⁇ ) component is reactive in the presence of the catalyst and may be altered due to its reactivity with water. .
  • the reaction temperature can be variously set.
  • the lower limit of the preferable temperature range is 30 ° C., more preferably 50 ° C.
  • the upper limit of the preferable temperature range is 200 ° C., more preferably 150 ° C. If the reaction temperature is low, the reaction time for sufficiently reacting becomes long, and if the reaction temperature is high, it is not practical.
  • the reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. Various reaction times and pressures during the reaction can be set as required.
  • a solvent may be used during the hydrosilylation reaction.
  • Solvents that can be used are not particularly limited as long as they do not inhibit the hydrosilylation reaction. Specifically, hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1, Ether solvents such as 3-dioxolane and diethyl ether, ketone solvents such as acetone and methyl ethyl ketone, and halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane can be preferably used.
  • the solvent can also be used as a mixed solvent of two or more types.
  • solvent toluene, tetrahydrofuran, 1,3-dioxolane and chloroform are preferable.
  • the amount of solvent to be used can also be set as appropriate.
  • various additives may be used for the purpose of controlling reactivity.
  • the solvent or / and the unreacted ( ⁇ ) component or / and the ( ⁇ ) component can be removed.
  • the component (B) obtained does not have volatile components, so that the problem of voids and cracks due to volatilization of the volatile components hardly occurs in the case of curing with the component (A).
  • the removal method include treatment with activated carbon, aluminum silicate, silica gel and the like in addition to vacuum devolatilization.
  • the upper limit of the preferable temperature in this case is 100 ° C, more preferably 60 ° C.
  • Examples of the component (B) that is a reaction product of the components ( ⁇ ) and ( ⁇ ) as described above include a reaction product of bisphenol A diallyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane, Reaction product of vinylcyclohexene and 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of divinylbenzene and 1,3,5,7-tetramethylcyclotetrasiloxane, dicyclopentadiene and 1,3,5, Reaction product of 7-tetramethylcyclotetrasiloxane, reaction product of triallyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, diallyl monoglycidyl isocyanurate and 1,3,5,7-tetramethylcyclo Reactant of tetrasiloxane, allyl glycidyl ether and 1,3,5,7-tetramethylcyclotetrasilo A reaction product of
  • the mixing ratio of the component (A) and the component (B) is not particularly limited as long as the required strength is not lost, but the number of SiH groups in the component (B) (Y) is the carbon-carbon in the component (A).
  • the lower limit of the preferred range is Y / X ⁇ 0.3, more preferably Y / X ⁇ 0.5, and even more preferably Y / X ⁇ 0.7, which is preferable.
  • the upper limit of the range is 3 ⁇ Y / X, more preferably 2 ⁇ Y / X, and even more preferably 1.5 ⁇ Y / X.
  • the mixing ratio of the component (A) and the component (Z) and the component (B) is not particularly limited as long as the necessary strength is not lost.
  • the ratio of the number of SiH groups in the component (Y) to the sum (X) of the number of carbon-carbon double bonds in the components (A) and (Z) is preferably included in the above range.
  • ((C) component) Component (C) is a hydrosilylation catalyst.
  • the hydrosilylation catalyst is not particularly limited as long as it has a catalytic activity for the hydrosilylation reaction.
  • a platinum simple substance e.g Pt (CH 2 ⁇ CH 2 ) 2 (PPh 3 ) 2 , Pt (CH 2 ⁇ CH 2 ) 2 Cl 2 ), platinum-vinyl Siloxane complexes (eg, Pt (ViMe 2 SiOSiMe 2 Vi) n , Pt [(MeViSiO) 4 ] m ), platinum-phosphine complexes (eg, Pt (PPh 3 ) 4 , Pt (PBu 3 ) 4 ), platinum-phosphine complexes (eg, Pt (PPh 3 ) 4 , Pt (PBu 3 ) 4 ), platinum-phosphine complexes (eg, Pt (PPh 3 ) 4 , Pt (PBu 3
  • platinum chloride-olefin complexes described in Modic US Pat. No. 3,516,946 are also useful in the present invention.
  • catalysts other than platinum compounds include RhCl (PPh) 3 , RhCl 3 , RhAl 2 O 3 , RuCl 3 , IrCl 3 , FeCl 3 , AlCl 3 , PdCl 2 .2H 2 O, NiCl 2 , TiCl 4. , Etc.
  • chloroplatinic acid platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable from the viewpoint of catalytic activity.
  • these catalysts may be used independently and may be used together 2 or more types.
  • the addition amount of the catalyst is not particularly limited, but in order to have sufficient curability and keep the cost of the curable resin composition relatively low, a preferable lower limit of the addition amount is 1 mole of SiH group of component (B). 10 -8 mol for, more preferably 10 -6 mole, preferable amount of the upper limit is 10 -1 moles per mole of the SiH group (beta) component, more preferably 10 -2 moles.
  • a cocatalyst can be used in combination with the above catalyst.
  • examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl malate, 2-hydroxy-2-methyl-1 -Acetylene alcohol compounds such as butyne, sulfur compounds such as simple sulfur, and amine compounds such as triethylamine.
  • the addition amount of the cocatalyst is not particularly limited, but the lower limit of the preferable addition amount relative to 1 mol of the hydrosilylation catalyst is 10 ⁇ 2 mol, more preferably 10 ⁇ 1 mol, and the upper limit of the preferable addition amount is 10 2. Mol, more preferably 10 mol.
  • a cured product obtained by thermally curing a mixture of components (A) to (C) and (Z) In addition, from the viewpoint of achieving both the bending resistance and continuous moldability of the curable resin composition in the present invention, a cured product obtained by thermally curing a mixture of the components (A) to (C) and (Z).
  • the glass transition point (Tg) is preferably in the range of 30 ° C. to 100 ° C., more preferably in the range of 35 ° C. to 80 ° C., and further preferably in the range of 40 ° C. to 70 ° C. .
  • cured material is less than 30 degreeC, it may be inferior to continuous moldability, and when Tg exceeds 100 degreeC, the bending resistance of a molded object may be impaired.
  • a cured product obtained by thermally curing a mixture of the components (A) to (C) and (Z) has a storage elastic modulus of 20 MPa to 100 MPa measured at 150 ° C., a frequency of 10 Hz, and a tensile mode. Preferably, it is within the range of 25 MPa to 80 MPa, more preferably within the range of 30 MPa to 70 MPa.
  • the storage elastic modulus of the cured product is less than 20 MPa, the continuous moldability may deteriorate, and when the storage elastic modulus exceeds 100 MPa, the flexibility of the cured product may be impaired.
  • thermosetting a mixture of the above components (A) to (C) and (Z) for example, a dynamic viscoelasticity measuring apparatus (IT Measurement Control Co., Ltd.) DVA200 manufactured by company, tensile mode, measurement frequency 10 Hz).
  • the glass transition point is the peak temperature of loss tangent.
  • the component (D) is a silicone compound having a molecular weight of 1000 or more and containing at least one carbon-carbon double bond having reactivity with the SiH group in one molecule.
  • a silicone compound composed of a siloxane skeleton consisting essentially of Si—O—Si bonds By using a silicone compound composed of a siloxane skeleton consisting essentially of Si—O—Si bonds, a cured product having excellent heat resistance and light resistance can be obtained compared to the case of using a general organic polymer. be able to.
  • a curable resin composition that gives a cured product excellent in toughness while having a smaller linear expansion coefficient. Can do.
  • the silicone compound of component (D) is a compound whose skeleton is substantially formed of Si—O—Si bonds, and includes various compounds such as linear, cyclic, branched, and partial networks. Can be used.
  • examples of the substituent bonded to the skeleton include alkyl groups such as methyl group, ethyl group, propyl group, and octyl group, aryl groups such as phenyl group, 2-phenylethyl group, and 2-phenylpropyl group, methoxy group, Examples thereof include alkoxy groups such as ethoxy group and isopropoxy group, and groups such as hydroxyl group.
  • alkyl groups such as methyl group, ethyl group, propyl group, and octyl group
  • aryl groups such as phenyl group, 2-phenylethyl group, and 2-phenylpropyl group, methoxy group
  • alkoxy groups such as ethoxy group and isopropoxy group
  • groups such as hydroxyl group.
  • a methyl group, a phenyl group, a hydroxyl group, and a methoxy group are preferable, and a methyl group and a pheny
  • Examples of the substituent having a carbon-carbon double bond having reactivity with the SiH group include a vinyl group, an allyl group, an acryloxy group, a methacryloxy group, an acryloxypropyl group, and a methacryloxypropyl group.
  • a vinyl group is preferable in terms of good reactivity.
  • R n (CH 2 ⁇ CH) m SiO (4-n ⁇ m) / 2 wherein R is a group selected from a hydroxyl group, a methyl group or a phenyl group, and n and m are numbers satisfying 0 ⁇ n ⁇ 4, 0 ⁇ m ⁇ 4, and 0 ⁇ n + m ⁇ 4).
  • component (D) examples include polydimethylsiloxane, polydiphenylsiloxane, polymethylphenylsiloxane, and two or three random or block copolymers having vinyl groups as terminal groups or side groups. be able to.
  • component (D) a plurality of components may be mixed and used.
  • linear polysiloxanes having vinyl groups at the ends are preferable, linear polysiloxanes having vinyl groups at both ends are more preferable, and both ends are more preferable in that the effects of the present invention are more easily obtained. More preferred are linear polydimethyl-polydiphenylsiloxane or linear polymethylphenylsiloxane having vinyl groups at the ends, linear polydimethyl-polydiphenylsiloxane or linear polymethylphenylsiloxane having vinyl groups at both ends. And it is especially preferable that it is siloxane whose quantity of the phenyl group with respect to all the substituents is 10 mol% or more.
  • the weight average molecular weight (Mw) is 1,000 or more, preferably 2,000 or more, more preferably 5,000 or more, and 10,000 or more. More preferably. There exists a problem that toughness falls that it is less than 1,000.
  • the molecular weight of the component (D) is preferably 1,000,000 or less, and more preferably 100,000 or less. If it exceeds 1,000,000, it becomes difficult to obtain compatibility with the component (A) and the component (B).
  • the amount of the component (D) is preferably 30% by weight or more, more preferably 50% by weight or more based on the total weight of the component (A) and the component (B). 80% by weight or more is more preferable. If it is less than 30% by weight, the linear expansion coefficient may be difficult to decrease.
  • the mixing ratio of the component (A), the component (B), and the component (D) is not particularly limited as long as the required strength is not lost, but the component (A) having the number of SiH groups (Y) in the component (B). And (D) the ratio of the number of carbon-carbon double bonds having reactivity with SiH groups in the component (X) is preferably Y / X ⁇ 0.3, more preferably Y / X ⁇ 0.5, more preferably Y / X ⁇ 0.7, and the upper limit of the preferable range is 3 ⁇ Y / X, more preferably 2 ⁇ Y / X, still more preferably 1.5 ⁇ Y / X. When it deviates from the preferred range, sufficient strength may not be obtained or thermal deterioration may easily occur.
  • the component (E) is an inorganic filler.
  • the component (E) has an effect of increasing the strength and hardness of the obtained cured product and reducing the linear expansion coefficient.
  • silica-based materials such as quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, and ultrafine powder amorphous silica.
  • Inorganic filler alumina, zircon, titanium oxide, zinc oxide, silicon nitride, boron nitride, aluminum nitride, silicon carbide, glass fiber, alumina fiber, carbon fiber, mica, graphite, carbon black, graphite, diatomaceous earth, white clay, clay , Talc, aluminum hydroxide, calcium carbonate, magnesium carbonate, barium sulfate, barium titanate, potassium titanate, calcium silicate, inorganic balloons, conventional fillers such as epoxy, as well as silver powder Inorganic fillers that are generally used and / or proposed as fillers for That.
  • the inorganic filler is preferably low radiation from the viewpoint of hardly damaging the semiconductor element.
  • the inorganic filler may be appropriately surface treated.
  • the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, treatment with a coupling agent, and the like.
  • the coupling agent in this case examples include a silane coupling agent.
  • the silane coupling agent is not particularly limited as long as the compound has at least one functional group reactive with an organic group and at least one hydrolyzable silicon group in the molecule.
  • the group having reactivity with the organic group is preferably at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handleability. From the viewpoints of curability and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable.
  • As the hydrolyzable silicon group an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.
  • Preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) alkoxysilanes having an epoxy functional group such as ethyltriethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Methacrylic or acrylic groups such as triethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Alkoxysilanes having can be exemplified.
  • an inorganic filler is mentioned.
  • a hydrolyzable silane monomer or oligomer such as alkoxysilane, acyloxysilane or halogenated silane, or an alkoxide, acyloxide or halide of a metal such as titanium or aluminum is added to the curable resin composition of the present invention.
  • a method of reacting in a curable resin composition or a partial reaction product of the curable resin composition to produce an inorganic filler in the curable resin composition can also be mentioned.
  • a silica-based inorganic filler is preferable from the viewpoint that it is difficult to inhibit the curing reaction, has a large effect of reducing the linear expansion coefficient, and tends to have high adhesion to the lead frame.
  • fused silica is preferable in terms of a good balance of physical properties such as moldability and electrical characteristics
  • crystalline silica is preferable in terms of easy package thermal conductivity and high heat dissipation.
  • Alumina is preferable in that heat dissipation tends to be higher.
  • Titanium oxide is preferred in that the light reflectance of the package resin is high and the light extraction efficiency of the resulting light emitting diode tends to be high.
  • glass fiber, potassium titanate, and calcium silicate are preferable in that the reinforcing effect is high and the strength of the package tends to be high.
  • the average particle size and particle size distribution of the inorganic filler various types are used without particular limitation, including those used or / and proposed as fillers for conventional sealing materials such as epoxy type,
  • the lower limit of the commonly used average particle size is 0.1 ⁇ m, preferably 0.5 ⁇ m from the viewpoint that the fluidity tends to be good, and the upper limit of the commonly used average particle size is 120 ⁇ m, the fluidity. Is preferably 60 ⁇ m, more preferably 15 ⁇ m, from the viewpoint that it tends to be favorable.
  • the specific surface area of the inorganic filler can also be set in various ways including those used and / or proposed as fillers for conventional sealing materials such as epoxy.
  • the shape of the inorganic filler various types such as a crushed shape, a piece shape, a spherical shape, and a rod shape are used.
  • Various aspect ratios are used.
  • the aspect ratio of 10 or more is preferable in that the strength of the obtained cured product tends to increase.
  • a powder form is preferable to a fiber form.
  • the spherical thing is preferable at the point that the fluidity
  • the component (E) is preferably spherical silica. These inorganic fillers may be used alone or in combination of two or more.
  • the amount of the component (E) is not particularly limited, but the total amount of the component (E) in the entire curable resin composition is preferably 70% by weight or more, more preferably 80% by weight or more, More preferably, it is 90% by weight or more. If it is less than 70% by weight, it becomes difficult to obtain the effects of increasing the strength and hardness and reducing the linear expansion coefficient.
  • the component (A) A method of mixing the component (C) and the inorganic filler with the component (B) is preferable.
  • the component (B) is present in the presence and / or absence of the component (C).
  • (A) component, (B) component, (C) in that (A) component, (B) component, and (C) component which are reaction components are well mixed and a stable molded product is easily obtained. It is preferable to mix a mixture of components and an inorganic filler.
  • the inorganic filler of component (E) various means conventionally used and / or proposed for epoxy resins and the like can be used.
  • a two-roll or three-roll a planetary stirring and defoaming device, a stirrer such as a homogenizer, a dissolver and a planetary mixer, a melt kneader such as a plast mill, and the like can be mentioned.
  • a triple roll and a melt kneader are preferred in that sufficient dispersibility of the inorganic filler is easily obtained even with high filling.
  • the mixing of the inorganic filler may be performed at normal temperature or may be performed by heating.
  • the curable resin composition of the present invention preferably contains a white pigment (component (F)).
  • the component (F) is a white pigment and has an effect of increasing the light reflectance of the obtained cured product.
  • component (F) Various components can be used as the component (F), for example, titanium oxide, zinc oxide, magnesium oxide, antimony oxide, zirconia oxide, strontium oxide, niobium oxide, boron nitride, barium titanate, zinc sulfide, barium sulfate. , Magnesium carbonate, hollow glass particles, and the like.
  • titanium oxide or zinc oxide is preferable from the viewpoint of ease of handling, availability, and cost.
  • component (F) titanium oxide which may be anatase type or rutile type, but it is not photocatalytic and the curable resin composition is likely to be stable.
  • a rutile type is preferred.
  • an average particle diameter (number average particle diameter) of (F) component the viewpoint that the light reflectivity of the hardened
  • the average particle diameter can be measured using a laser diffraction / scattering particle size distribution analyzer.
  • the method for producing the component (F) titanium oxide those produced by any method such as sulfuric acid method and chlorine method can be used.
  • the component (F) may be subjected to surface treatment.
  • the surface of the component (F) is coated with at least one selected from an inorganic compound and an organic compound.
  • inorganic compounds include aluminum compounds, silicon compounds, zirconium compounds, tin compounds, titanium compounds, antimony compounds, and the like
  • organic compounds include polyhydric alcohols, alkanolamines or derivatives thereof, and organic siloxanes. Examples thereof include organosilicon compounds, higher fatty acids or metal salts thereof, and organometallic compounds.
  • a known method such as a wet method or a dry method is used, for example, when dry pulverizing titanium oxide, when slurrying, or when wet pulverizing. It can be carried out.
  • various methods such as a liquid phase method and a gas phase method.
  • cured material obtained is high and heat-resistant light resistance becomes favorable, it is preferable to process by the organosiloxane process.
  • the inclusion of an organosiloxane-treated titanium oxide is suitable for producing an excellent light-emitting diode that has high light extraction efficiency and does not decrease light extraction efficiency even when used for a long period of time.
  • various organic siloxane treating agents are used.
  • polysiloxanes such as polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrogensiloxane, or copolymers thereof, hexamethylcyclotrisiloxane, heptamethylcyclotetrasiloxane, 1,3,5,7-tetra Cyclosiloxanes such as methylcyclotetrasiloxane, chlorosilanes such as trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane and other silanes having an epoxy functional
  • These surface treatment agents preferably do not contain a carbon-carbon double bond, and if they contain a carbon-carbon double bond, the heat resistance tends to decrease. Further, a surface treatment other than the organic siloxane can be used in combination, and treatment with Al, Zr, Zn, or the like can also be performed.
  • the surface treatment with an inorganic compound is not particularly limited, and various surface treatments such as an aluminum compound, a silicon compound, and a zirconium compound are used.
  • titanium oxide surface treatment with an aluminum compound is preferable.
  • Titanium oxide may be surface-treated with an inorganic compound or an organic compound for the purpose of improving durability, improving affinity with the medium, or preventing the collapse of the particle shape, but the component (F) is inorganic. It is considered that the surface treatment with the compound improves the affinity with the component contained in the curable resin composition, improves the dispersibility of the component (F) in the curable resin composition, and improves the strength of the cured product. .
  • Various methods can be applied as the surface treatment method, and various methods such as a wet method, a dry method, a liquid phase method, and a gas phase method can be exemplified.
  • the amount of the component (F) is not particularly limited, but the amount of the component (F) in the entire curable resin composition is preferably 10% by weight or more, more preferably 15% by weight or more, More preferably, it is 20% by weight or more. If it is less than 10% by weight, the light reflectance of the resulting cured product may be lowered.
  • the component (F) is used when a white curable resin composition is prepared, but when applied to a black matrix of a display device, the black curable resin composition can be used. .
  • the black pigment that can be used in this case either an inorganic pigment or an organic pigment may be used, or a single pigment or a mixture of two or more pigments may be used.
  • the inorganic pigment include carbon black, graphite, iron black, titanium carbon, titanium black, manganese diacid value, and copper chromium manganese oxide. From the viewpoint of improving coloring power, carbon black or titanium black is preferable. Furthermore, titanium black is more preferable from the viewpoint of increasing the optical density and the electrical resistance value. Carbon black or titanium black whose surface is coated with a resin or the like can also be used. Aniline black, anthraquinone black pigment, perylene black pigment and the like can also be used.
  • the metal complex oxide black pigment contains copper-chromium-manganese complex oxide black pigment, copper oxide, manganese oxide, cobalt oxide and aluminum oxide.
  • the ratio of copper, manganese, cobalt and aluminum constituting the pigment is 5 to 30 mol% copper and 5 to 30 manganese when the total of these metals is 100 mol%.
  • Complex oxide black pigments with mol%, cobalt 15 to 40 mol%, and aluminum 25 to 50 mol% can also be used.
  • the total amount of the component (E) and the component (F) is not particularly limited, but the total amount of the component (E) and the component (F) in the entire curable resin composition is preferably 70% by weight or more. It is more preferably 85% by weight or more, and particularly preferably 90% by weight or more. Moreover, it is preferable that it is 97 weight% or less, and it is more preferable that it is 95 weight% or less. If it is less than 70% by weight, it becomes difficult to obtain the effects of increasing the strength and hardness and reducing the linear expansion coefficient. On the other hand, if it exceeds 97% by weight, the moldability may deteriorate.
  • the mixing order of the component (F) various methods can be used, but the preferred embodiment is the same as (E) described above. Moreover, you may add (F) component and (E) component simultaneously.
  • means for mixing the component (F) the same means as the means for mixing the component (E) can be used.
  • the curable resin composition of the present invention desirably contains a metal soap (component (G)).
  • component (G) A component is added in order to improve the moldability including the mold release property of a curable resin composition.
  • Examples of the component (G) include various conventionally used metal soaps.
  • the metal soap here is generally a combination of long-chain fatty acids and metal ions.
  • the nonpolar or low polarity part based on fatty acids and the polar part based on the metal binding part are combined in one molecule.
  • Examples of long-chain fatty acids include saturated fatty acids having 1 to 18 carbon atoms, unsaturated fatty acids having 3 to 18 carbon atoms, and aliphatic dicarboxylic acids. Among these, saturated fatty acids having 1 to 18 carbon atoms are preferable from the viewpoint of easy availability and high industrial feasibility, and further, from 6 to 18 carbon atoms from the viewpoint of high releasing effect. The saturated fatty acid is more preferable.
  • metal ions include zinc, cobalt, aluminum, strontium, and the like in addition to alkali metals and alkaline earth metals. More specific examples of metal soaps include lithium stearate, lithium 12-hydroxystearate, lithium laurate, lithium oleate, lithium 2-ethylhexanoate, sodium stearate, sodium 12-hydroxystearate, lauric acid Sodium, sodium oleate, sodium 2-ethylhexanoate, potassium stearate, potassium 12-hydroxystearate, potassium laurate, potassium oleate, potassium 2-ethylhexanoate, magnesium stearate, magnesium 12-hydroxystearate, Magnesium laurate, magnesium oleate, magnesium 2-ethylhexanoate, calcium stearate, calcium 12-hydroxystearate, calcium laurate , Calcium oleate, calcium 2-ethylhexanoate, barium stearate, barium 12-hydroxystearate, barium laurate, zinc stea
  • metal stearates are preferred from the viewpoint of easy availability, safety and industrial feasibility, and calcium stearate, magnesium stearate, stearin are particularly preferred from the viewpoint of economy. Most preferred is one or more selected from the group consisting of zinc acid and aluminum stearate.
  • the minimum of a preferable amount is 0.01 weight part (namely, 0.01 weight%) with respect to 100 weight part of the whole curable resin composition, More preferably, it is 0.00. 025 parts by weight, more preferably 0.05 parts by weight, and the upper limit of the preferred amount is 5 parts by weight (ie 5% by weight), more preferably 4 parts by weight, based on 100 parts by weight of the entire curable resin composition. .
  • the addition amount is too large, the physical properties of the cured product are deteriorated.
  • the addition amount is too small, mold releasability may not be obtained.
  • additives can be added to the curable resin composition of the present invention.
  • a curing retarder can be used for the purpose of improving the storage stability of the curable resin composition of the present invention or adjusting the reactivity of the hydrosilylation reaction during the production process.
  • the curing retarder include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin-based compound, and an organic peroxide, and these may be used in combination.
  • Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols such as 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne and 1-ethynyl-1-cyclohexanol. And maleic esters such as ene-yne compounds and dimethyl malate.
  • Examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite.
  • Examples of organic sulfur compounds include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide and the like.
  • nitrogen-containing compounds include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like.
  • tin compounds include stannous halide dihydrate and stannous carboxylate.
  • organic peroxide include di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.
  • benzothiazole thiazole, dimethylmalate, 3-hydroxy-3-methyl-1-butyne, 1-ethynyl-1- Cyclohexanol is preferred.
  • the addition amount of the curing retarder can be selected at various levels, the preferred amount of the lower limit is 10 -1 moles with respect to hydrosilylation catalyst 1mol used, more preferably 1 mol, the upper limit of the preferable amount is 10 3 mol, more preferably Is 50 moles.
  • these hardening retarders may be used independently and may be used together 2 or more types.
  • adhesion improver An adhesion improver can also be added to the curable resin composition of the present invention.
  • adhesives for example, various coupling agents, epoxy compounds, phenol resins, coumarone-indene resins, rosin ester resins, terpene-phenol resins, ⁇ -methylstyrene-vinyltoluene A copolymer, polyethylmethylstyrene, aromatic polyisocyanate, etc. can be mentioned.
  • Examples of coupling agents include silane coupling agents and titanate coupling agents. Examples and preferred examples of the coupling agent are the same as those described above.
  • the addition amount of the coupling agent can be variously set, but the lower limit of the preferable addition amount with respect to 100 parts by weight of [(A) component + (B) component] is 0.1 parts by weight, more preferably 0.5 parts by weight.
  • the upper limit of the preferable addition amount is 50 parts by weight, more preferably 25 parts by weight. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the physical properties of the cured product may be adversely affected.
  • epoxy compound examples include novolak phenol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, and 2,2′-bis (4-glycidyloxycyclohexyl).
  • the lower limit of the preferable addition amount with respect to 100 parts by weight of [(A) component + (B) component] is preferably 1 part by weight, more preferably 3 parts by weight.
  • the upper limit of the addition amount is 50 parts by weight, more preferably 25 parts by weight.
  • These coupling agents, silane coupling agents, epoxy compounds, etc. may be used alone or in combination of two or more.
  • a silanol condensation catalyst can be further used to enhance the effect of the coupling agent or the epoxy compound, and the adhesion can be improved and / or stabilized.
  • a silanol condensation catalyst is not particularly limited, but is preferably a boron compound or / and an aluminum compound or / and a titanium compound.
  • Examples of the aluminum compound used as a silanol condensation catalyst include aluminum alkoxides such as aluminum triisopropoxide, sec-butoxyaluminum diisoflopoxide, aluminum trisec-butoxide, ethyl acetoacetate aluminum diisopropoxide, aluminum tris (ethyl). Acetoacetate), aluminum chelate M (manufactured by Kawaken Fine Chemicals, alkyl acetoacetate aluminum diisopropoxide), aluminum tris (acetylacetonate), aluminum monoacetylacetonate bis (ethylacetoacetate) and other aluminum chelates Aluminum chelates are more preferable from the viewpoint of handleability.
  • aluminum alkoxides such as aluminum triisopropoxide, sec-butoxyaluminum diisoflopoxide, aluminum trisec-butoxide, ethyl acetoacetate aluminum diisopropoxide, aluminum tris (ethyl). Acetoacetate), aluminum chelate M (man
  • Titanium compounds that serve as silanol condensation catalysts include tetraalkoxy titaniums such as tetraisopropoxy titanium and tetrabutoxy titanium, titanium chelates such as titanium tetraacetylacetonate, and residues having residues such as oxyacetic acid and ethylene glycol. And titanate coupling agents.
  • Examples of the boron compound that serves as a silanol condensation catalyst include boric acid esters.
  • the borate ester those represented by the following general formulas (VII) and (VIII) can be preferably used.
  • boric acid esters include tri-2-ethylhexyl borate, normal trioctadecyl borate, trinormal octyl borate, triphenyl borate, trimethylene borate, tris (trimethylsilyl) borate, trinormal butyl borate, tri-sec-butyl borate, Tri-tert-butyl borate, triisopropyl borate, trinormalpropyl borate, triallyl borate, triethyl borate, trimethyl borate, and methoxymethoxy boronate can be preferably used. These borate esters may be used alone or in combination of two or more.
  • Trimethyl borate, triethyl borate, and trinormal butyl borate are preferable, and trimethyl borate is more preferable among them because it is easily available and has high industrial practicality.
  • normal trioctadecyl borate, tri-tert-butyl borate, triphenyl borate, and tributyl normal borate are more preferable. preferable.
  • trinormal butyl borate, triisopropyl borate and trinormal propyl borate are preferable, and trinormal butyl borate is more preferable.
  • trimethyl borate and triethyl borate are preferred, and trimethyl borate is more preferred.
  • the amount used in the case of using a silanol condensation catalyst can be variously set, but the lower limit of the preferred addition amount with respect to 100 parts by weight of the coupling agent and / or epoxy compound epoxy compound is 0.1 parts by weight, more preferably 1 part by weight.
  • the upper limit of the preferable addition amount is 50 parts by weight, more preferably 30 parts by weight.
  • silanol condensation catalysts may be used alone or in combination of two or more.
  • a silanol source compound can be further used in order to further enhance the effect of improving adhesiveness, and the adhesiveness can be improved and / or stabilized.
  • a silanol source include silanol compounds such as triphenylsilanol and diphenyldihydroxysilane, and alkoxysilanes such as diphenyldimethoxysilane, tetramethoxysilane, and methyltrimethoxysilane.
  • the amount used in the case of using a silanol source compound can be variously set, but the lower limit of the preferable addition amount with respect to 100 parts by weight of the coupling agent and / or epoxy compound is 0.1 parts by weight, more preferably 1 part by weight.
  • the upper limit of the preferable addition amount is 50 parts by weight, more preferably 30 parts by weight. If the addition amount is small, the effect of improving the adhesiveness does not appear, and if the addition amount is large, the cured product properties may be adversely affected. Moreover, these silanol source compounds may be used independently and may be used together 2 or more types.
  • carboxylic acids and / or acid anhydrides can be used to enhance the effect of the coupling agent or epoxy compound, and adhesion can be improved and / or stabilized.
  • Such carboxylic acids and acid anhydrides are not particularly limited,
  • carboxylic acids and / or acid anhydrides in terms of difficulty in impairing the physical properties of the cured product that has hydrosilylation reactivity and is less likely to exude from the cured product, Those having reactive carbon-carbon double bonds are preferred.
  • Preferred carboxylic acids and / or acid anhydrides include, for example,
  • Examples thereof include tetrahydrophthalic acid, methyltetrahydrophthalic acid, and single or complex acid anhydrides thereof.
  • the amount used in the case of using carboxylic acids or / and acid anhydrides can be variously set, but the lower limit of the preferred addition amount with respect to 100 parts by weight of the coupling agent or / and epoxy compound epoxy compound is 0.1 parts by weight, More preferably, it is 1 part by weight, and the upper limit of the preferable addition amount is 50 parts by weight, more preferably 10 parts by weight.
  • the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the physical properties of the cured product may be adversely affected.
  • carboxylic acids or / and acid anhydrides may be used alone or in combination of two or more.
  • the silane compound described above can be used in the curable resin composition of the present invention.
  • the silane compound contributes to improvement in adhesion to the lead and is effective in preventing moisture from entering from the interface between the package and the lead.
  • Illustrative examples include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, and the like, with dimethyldimethoxysilane being particularly preferred.
  • thermosetting resin a cured resin may be pulverized and mixed in a particle state.
  • the average particle diameter can be variously set, but the lower limit of the preferable average particle diameter is 10 nm, and the upper limit of the preferable average particle diameter is 10 ⁇ m.
  • the particle system may be distributed, and may be monodispersed or have a plurality of peak particle diameters. However, from the viewpoint that the viscosity of the curable resin composition is low and the moldability tends to be good.
  • the diameter variation coefficient is preferably 10% or less.
  • thermoplastic resin Various thermoplastic resins can be added to the curable resin composition of the present invention for the purpose of modifying the properties.
  • Various thermoplastic resins can be used.
  • a homopolymer of methyl methacrylate or a polymethyl methacrylate resin such as a random, block or graft polymer of methyl methacrylate and other monomers (for example, Hitachi Chemical) OPTRETZ etc.
  • acrylic resins represented by polybutyl acrylate resins such as butyl acrylate homopolymers or random, block or graft polymers of butyl acrylate and other monomers, bisphenol A,
  • a polycarbonate resin such as a polycarbonate resin containing 3,3,5-trimethylcyclohexylidene bisphenol or the like as a monomer structure (for example, APEC manufactured by Teijin Limited), norbornene derivative, vinyl monomer, etc.
  • a cycloolefin resin such as a copolymerized resin, a resin obtained by ring-opening metathesis polymerization of a norbornene derivative, or a hydrogenated product thereof (for example, APEL manufactured by Mitsui Chemicals, Inc., ZEONOR, ZEONEX manufactured by Nippon Zeon Co., Ltd., JSR shares) ARTON manufactured by the company), olefin-maleimide resins such as copolymers of ethylene and maleimide (eg TI-PAS manufactured by Tosoh Corporation), bisphenol A, bis (4- (2-hydroxyethoxy) phenyl) fluorene, etc.
  • a cycloolefin resin such as a copolymerized resin, a resin obtained by ring-opening metathesis polymerization of a norbornene derivative, or a hydrogenated product thereof (for example, APEL manufactured by Mitsui Chemicals, Inc., ZEONOR, ZEONEX manufactured by Nippo
  • Polyester resins such as polyesters (eg, O-PET manufactured by Kanebo Co., Ltd.) obtained by polycondensation of diols such as bisphenols and diethylene glycol with phthalic acids such as terephthalic acid and isophthalic acid, and aliphatic dicarboxylic acids.
  • the thermoplastic resin may have a carbon-carbon double bond or / and a SiH group having reactivity with the SiH group in the molecule.
  • the obtained cured product tends to be tougher, it has one or more carbon-carbon double bonds or / and SiH groups having reactivity with SiH groups in the molecule on average. Preferably it is.
  • the thermoplastic resin may have other crosslinkable groups.
  • the crosslinkable group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. From the viewpoint that the heat resistance of the obtained cured product tends to be high, it is preferable to have one or more crosslinkable groups in one molecule on average.
  • the molecular weight of the thermoplastic resin is not particularly limited, but the number average molecular weight is preferably 10,000 or less, in terms of easy compatibility with the component (A) or the component (B), and is preferably 5000 or less. It is more preferable that On the contrary, the number average molecular weight is preferably 10,000 or more, and more preferably 100,000 or more in that the obtained cured product tends to be tough.
  • the molecular weight distribution is not particularly limited, but the molecular weight distribution is preferably 3 or less, more preferably 2 or less, in that the viscosity of the mixture tends to be low and the moldability tends to be good. More preferably, it is as follows.
  • the blending amount of the thermoplastic resin is not particularly limited, but the lower limit of the preferable amount used is 5% by weight of the entire curable resin composition, more preferably 10% by weight, and the upper limit of the preferable amount used is the curable resin composition. 50% by weight of the product, more preferably 30% by weight.
  • the addition amount is small, the obtained cured product tends to be brittle, and when it is large, the heat resistance (elastic modulus at high temperature) tends to be low.
  • a single thermoplastic resin may be used, or a plurality of thermoplastic resins may be used in combination.
  • the thermoplastic resin may be dissolved in the component (A) or / and the component (B) and mixed in a uniform state, pulverized and mixed in a particle state, or dissolved in a solvent and mixed. It may be in a dispersed state. In the point that the obtained hardened
  • the average particle diameter can be variously set, but the lower limit of the preferable average particle diameter is 10 nm, and the upper limit of the preferable average particle diameter is 10 ⁇ m.
  • the particle system may be distributed, and may be monodispersed or have a plurality of peak particle diameters. However, from the viewpoint that the viscosity of the curable resin composition is low and the moldability tends to be good.
  • the diameter variation coefficient is preferably 10% or less.
  • An aging inhibitor may be added to the curable resin composition of the present invention.
  • the anti-aging agent include citric acid, phosphoric acid, sulfur-based anti-aging agent and the like in addition to the anti-aging agents generally used such as hindered phenol type.
  • antioxidants include mercaptans, mercaptan salts, sulfide carboxylic acid esters, sulfides including hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium Examples thereof include compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythioacids, thioamides, and sulfoxides.
  • these anti-aging agents may be used independently and may be used together 2 or more types.
  • radical inhibitor A radical inhibitor may be added to the curable resin composition of the present invention.
  • the radical inhibitor include 2,6-di-tert-butyl-3-methylphenol (BHT), 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), tetrakis (methylene- Phenol radical inhibitors such as 3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) methane, phenyl- ⁇ -naphthylamine, ⁇ -naphthylamine, N, N′-secondary butyl-p- Examples include amine radical inhibitors such as phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine. Moreover, these radical inhibitors may be used alone or in combination of two or more.
  • UV absorber An ultraviolet absorber may be added to the curable resin composition of the present invention.
  • examples of the ultraviolet absorber include 2 (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate and the like. Can be mentioned.
  • these ultraviolet absorbers may be used independently and may be used together 2 or more types.
  • the curable resin composition of the present invention can be used by dissolving in a solvent.
  • Solvents that can be used are not particularly limited, and specific examples include hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diethyl ether, and the like.
  • An ether solvent, a ketone solvent such as acetone, methyl ethyl ketone, and methyl isobutyl ketone
  • a halogen solvent such as chloroform, methylene chloride, and 1,2-dichloroethane can be preferably used.
  • As the solvent toluene, tetrahydrofuran, 1,3-dioxolane and chloroform are preferable.
  • the amount of solvent to be used can be set as appropriate, the lower limit of the preferable usage amount relative to 1 g of the curable resin composition to be used is 0.1 mL, and the upper limit of the preferable usage amount is 10 mL. If the amount used is small, it is difficult to obtain the effect of using a solvent such as a low viscosity, and if the amount used is large, the solvent tends to remain in the material, causing problems such as thermal cracks, and also from a cost standpoint. It is disadvantageous and the industrial utility value decreases. These solvents may be used alone or as a mixed solvent of two or more.
  • additives include phosphors such as yttrium, aluminum, and garnet phosphors activated with cerium that absorb light from the light emitting element to emit longer wavelength fluorescence, and blue that absorbs a specific wavelength.
  • Coloring agents such as ing agents, diffusion materials such as titanium oxide, aluminum oxide, melamine resin, CTU guanamine resin, benzoguanamine resin for diffusing light, metal oxides such as aluminosilicate, aluminum nitride, boron nitride, etc. Examples thereof include thermally conductive fillers such as metal nitrides.
  • the additive for improving the characteristics of the light emitting diode may be contained uniformly, or the content may be added with a gradient.
  • release agent Various releasing agents may be added to the curable resin composition of the present invention in order to improve the releasing property at the time of molding.
  • the release agent include the component (G) already described and waxes.
  • waxes include natural wax, synthetic wax, oxidized or non-oxidized polyolefin, and polyethylene wax.
  • the curable resin composition of the present invention includes other colorants, flame retardants, flame retardant aids, surfactants, antifoaming agents, emulsifiers, leveling agents, anti-fogging agents, ion trapping agents such as antimony-bismuth, Thixotropic agent, tackifier, storage stability improver, ozone degradation inhibitor, light stabilizer, thickener, plasticizer, reactive diluent, antioxidant, heat stabilizer, conductivity enhancer, Antistatic agents, radiation blocking agents, nucleating agents, phosphorus peroxide decomposing agents, lubricants, pigments, metal deactivators, thermal conductivity-imparting agents, physical property modifiers, and the like that do not impair the purpose and effect of the present invention Can be added.
  • the curable resin composition of the present invention may be used as it is by blending each component and additives, or may be used after being partially reacted (B-staged) by heating or the like. Viscosity can be adjusted by using B-stage, and transfer moldability can also be adjusted. In addition, there is an effect of further suppressing curing shrinkage.
  • the curable resin composition of the present invention has a temperature of 150 ° C. or less in terms of good moldability by transfer molding or the like. And those having fluidity are preferred.
  • the curability of the curable resin composition can be arbitrarily set, but the gelation time at 120 ° C. is preferably within 120 seconds, more preferably within 60 seconds in that the molding cycle can be shortened. preferable. Further, the gelation time at 150 ° C. is preferably within 60 seconds, and more preferably within 30 seconds. Further, the gelation time at 100 ° C. is preferably within 180 seconds, and more preferably within 120 seconds.
  • the gelation time in this case is examined as follows. An aluminum foil having a thickness of 50 ⁇ m is placed on a hot plate adjusted to a set temperature, and 100 mg of the curable resin composition is placed thereon, and the time until gelation is measured is defined as the gelation time.
  • the weight during the curing is from the viewpoint that the generation of voids in the curable resin composition and the process problems due to the outgas from the curable resin composition hardly occur.
  • the decrease is preferably 5% by weight or less, more preferably 3% by weight or less, and further preferably 1% or less.
  • the weight loss during curing is examined as follows. Using a thermogravimetric analyzer, 10 mg of the sealant is heated from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C./min, and can be determined as a ratio of the initial weight of the reduced weight.
  • the content of Si atoms in the volatile component in this case is 1% or less in that the problem of silicone contamination hardly occurs.
  • the curable resin composition of the present invention can be used for manufacturing a semiconductor package as described later.
  • the curable resin composition of the present invention is mixed in advance, and a part or all of SiH groups in the composition is cured by a hydrosilylation reaction with a carbon-carbon double bond having reactivity with SiH groups. be able to.
  • the required amount of each component may be mixed and reacted at one time, but after mixing and reacting partly, the remaining amount is mixed and further reacted, or after mixing as described above in the composition It is also possible to take a method in which only a part of the functional group is reacted (B-stage) and then subjected to a treatment such as molding and further cured. According to these methods, viscosity adjustment at the time of molding becomes easy.
  • the cured product obtained by curing the curable resin composition preferably has a Tg of 100 ° C. or higher, more preferably 150 ° C. or higher.
  • Tg is examined as follows. Dynamic measurement using a prismatic test piece of 3 mm ⁇ 5 mm ⁇ 30 mm in a tensile mode, a measurement frequency of 10 Hz, a strain of 0.1%, a static / power ratio of 1.5, and a temperature increase rate of 5 ° C./min.
  • the peak temperature of tan ⁇ in viscoelasticity measurement (using DVA-200 manufactured by IT Measurement Control Co., Ltd.) is defined as Tg.
  • the content of ions extracted from the cured product is preferably less than 10 ppm, more preferably less than 5 ppm, More preferably, it is less than 1 ppm.
  • the extracted ion content is examined as follows. 1 g of the cut cured product is sealed in a Teflon container (Teflon is a registered trademark) together with 50 ml of ultrapure water, and treated under conditions of 121 ° C., 2 atm and 20 hours.
  • the obtained extract was analyzed by ICP mass spectrometry (using HP-4500 manufactured by Yokogawa Analytical Systems Co., Ltd.), and the obtained Na and K content values were converted to the concentration in the cured product used. And ask.
  • the same extract was analyzed by ion chromatography (using DX-500 manufactured by Nippon Dionex Co., Ltd., column: AS12-SC), and the obtained Cl and Br content values were adjusted to the concentrations in the cured product used. Calculate by conversion. The contents of Na, K, Cl, and Br obtained as described above in the cured product are totaled to obtain the extracted ion content.
  • the linear expansion coefficient of the cured product is not particularly limited, but the average linear expansion coefficient from 23 ° C. to 150 ° C. is 30 ppm in that the adhesion to a metal such as a lead frame or ceramic is likely to be good. Or less, more preferably 20 ppm or less, and even more preferably 10 ppm or less.
  • the curable resin composition of the present invention preferably has a light reflectance of 80% or more at a wavelength of 480 nm on the surface of a molded product obtained by curing.
  • the light reflectivity R at 460 nm and 480 nm after curing is 80% or more, and the retention ratio of the light reflectivity after the heat test at 180 ° C. for 24 hours (the light reflectivity after the heat test / the initial light reflectivity).
  • X100 is desirably 90% or more.
  • the light reflectivity of the cured product is examined as follows.
  • the light reflectance at wavelengths of 400 nm to 700 nm (20 nm intervals) is measured using a micro surface spectral color difference meter (VSS400 manufactured by Nippon Denshoku Industries Co., Ltd.).
  • VSS400 micro surface spectral color difference meter manufactured by Nippon Denshoku Industries Co., Ltd.
  • the average value of the measurement values at any four locations (measurement area 0.1 mm ⁇ ) on the upper surface of the package is adopted as the measurement value at each wavelength.
  • the light reflectivity is preferably 75% or more in the wavelength band of 420 to 700 nm, and more preferably 80% or more from the viewpoint that the light extraction efficiency of the light emitting diode tends to be high.
  • the retention ratio of the light reflectance after the heat resistance test (for example, a test in which heating is performed in an oven at 180 ° C. for 24 hours) with respect to the initial light reflectance is obtained by the following calculation formula.
  • “Initial light reflectance” means light reflectance before the heat resistance test.
  • Retention rate (%) (light reflectance after heat test) / (initial light reflectance) ⁇ 100
  • the retention rate is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more in terms of high reliability when used as an electronic material.
  • the light reflectance of wavelength 480nm of a surface is 80% or more, It is more preferable that it is 90% or more, 95 % Or more, more preferably 97% or more, and particularly preferably 99% or more.
  • the bending strength of a flat plate (molded product) is 50 N / mm 2 or less. Is preferably 45 N / mm 2 or less, and more preferably 40 N / mm 2 or less. When the bending strength exceeds 50 N / mm 2 , sufficient flexibility may not be obtained.
  • problems such as cohesive failure of the molded body do not occur even if the molding is continuously performed a plurality of times.
  • the bending strength of the flat plate is preferably in the range of 20 to 50 N / mm 2 , more preferably in the range of 23 to 45 N / mm 2. Preferably, it is in the range of 25 to 40 mm 2 .
  • the continuous formability may be deteriorated.
  • the bending strength is more than 50 N / mm 2 , the flexibility of the molded body is impaired, and the bending resistance may be reduced. is there.
  • the bending strength of these flat plates is measured as follows. A test piece was cut out from the produced flat plate so that the two sides facing each other with a length of about 50 mm to 80 mm and a width of about 7 mm to 8 mm were parallel, and made by Stable Micro Systems, Texture Analyzer TA. A pressure wedge consisting of right-angled triangles made of glass with round corners with a width of 10 mm at plus, applying a load at a speed of 2.0 mm / sec to the center of the test piece, and the load when the test piece breaks (bending fracture) From the load N), the bending strength ⁇ b (N / mm 2 ) is calculated by the following equation.
  • the bending fracture load w (N), the fulcrum distance l (mm), the member cross section length h (mm), the member cross section width b (mm) is a bending moment
  • I is a cross section secondary moment
  • the tablet of the present invention comprises a curable resin composition containing components (A) to (F).
  • the curable resin composition tablet is a liquid in which at least one of the component (A) and the component (B) has a viscosity of 50 Pa seconds or less at 23 ° C., and the total content of the component (E) and the component (F) (Hereinafter referred to as filling factor) is 70 to 95% by weight, and the ratio of particles of 12 ⁇ m or less to the total of component (E) and component (F) is 40% by volume or more.
  • filling factor the total content of the component (E) and the component (F)
  • both the component (E) and the component (F) are powders.
  • At least one of the component (A) and the component (B) is a liquid having a viscosity at 23 ° C. of 50 Pa seconds or less.
  • the viscosity is preferably 40 Pa seconds or less, and more preferably 30 Pa seconds or less.
  • This curable resin composition tablet is capable of flowing the entire curable resin composition due to a decrease in viscosity of the component (A) and the component (B) at a high temperature. It can be formed into a shape.
  • the molding method is not particularly limited, and a molding method such as transfer molding or compression molding, which is generally used for molding a curable resin composition, can be used.
  • a molding method such as transfer molding or compression molding, which is generally used for molding a curable resin composition
  • the curable resin composition as a raw material is in the form of a paste or clay, it cannot maintain a constant shape and is attached, integrated, or deformed. Supply to the molding machine becomes very difficult.
  • the tablet shape makes it easy to measure, transport, and supply to a molding machine, and can be automated, greatly improving productivity.
  • a tablet means a solid that retains a constant shape at room temperature, has substantially no change in shape over time, and does not stick together or become integrated when brought into contact with each other. .
  • the shape of the tablet of the present invention is not particularly limited, and includes a columnar shape, a prismatic shape, a disk shape, a spherical shape, and the like, and a general columnar shape for transfer molding is preferable.
  • the total content of the component (E) and the component (F) in the tablet of the present invention is 70 to 95% by weight.
  • the total content is preferably 72% by weight or more, and more preferably 75% by weight or more. Moreover, it is preferable that it is 94 weight% or less, and it is more preferable that it is 90 weight% or less.
  • the distribution of the (E) component and the (F) component in the filling rate is not particularly limited and can be set freely. If the filling rate is less than 70% by weight, the thermal expansion coefficient of the resulting cured product will increase, causing dimensional change of the molded product, and the curable resin composition will become a hard paste or clay and become a tablet There is a problem that can not be. When the filling rate exceeds 95% by weight, there is a problem that the viscosity at high temperature becomes too high and the moldability is lowered, and the resulting tablet becomes too brittle.
  • the curable resin composition of the present invention when at least one of the component (A) and the component (B) is liquid at room temperature, it tends to be in the form of a paste or clay when the filling rate is low. In this case, the tablet does not become a tablet, but the moldability at high temperature tends to be good. On the other hand, when the filling rate is high, since there are few components to be flowed, it tends to be flaky or powdery. These can be compressed into a tablet shape by being compressed, but they tend to have poor fluidity at high temperatures and easily deteriorate moldability. Until now, it has been difficult to achieve both tableting and moldability by simply increasing the filling rate.
  • tableting and moldability can be achieved by setting the ratio of particles of 12 ⁇ m or less to the total of the (E) component and (F) component which are powders to 40% by volume or more. I found out that they can be compatible. Moreover, it is preferable that the ratio of the particle
  • a liquid resin comprising the components (A) to (D), for example, a porous filler or an oil-absorbing filler are preferably used alone or in combination.
  • the shape of the porous filler or oil-absorbing filler is not particularly limited, and for example, a spherical shape, a crushed shape, a disk shape, a rod shape, a fiber shape, or the like can be used. Considering the fluidity in the mold at the time of transfer molding, a spherical shape and a crushed shape are preferable.
  • spherical silica crushed silica, alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, barium carbonate, and zeolite. These may be used alone or in combination. Silica, alumina, or a mixture thereof is preferable from the viewpoint of thermal conductivity, light reflection characteristics, and moldability.
  • the surface of the porous filler or filler having oil absorbency may be subjected to a physical or chemical hydrophilization treatment or a hydrophobization treatment.
  • the surface is subjected to a hydrophobic treatment, and the oil absorption amount (specified amount according to JIS K5101) is preferably 50 ml / 100 g or more.
  • the apparent density of the porous filler or filler having oil absorbency is not particularly limited, but is preferably 0.4 g / cm 3 or more, and preferably 0.4 to 2.0 g / cm 3. More preferred.
  • the apparent density is a density in consideration of the density occupied by the raw material of the porous filler or the oil-absorbing filler and the space occupied by the fine pores (that is, the pore volume).
  • this apparent density is less than 0.4 g / cm 3 , the mechanical strength of the filler particles is small, and the particles may be destroyed at the time of melt-kneading that generates shearing force such as a mixing roll mill. is there.
  • the apparent density exceeds 2.0 g / cm 3 , the curable resin composition tends to adhere to the surface of the mortar mold and bowl mold during tablet molding.
  • the average particle size of the porous filler or oil-absorbing filler is preferably 0.1 to 100 ⁇ m, and more preferably in the range of 1 to 10 ⁇ m in view of packing efficiency with a white pigment. .
  • the average particle size is larger than 100 ⁇ m or smaller than 0.1 ⁇ m, the fluidity of the curable resin composition tends to be poor at the time of melting during transfer molding.
  • the specific surface area of the porous filler or oil-absorbing filler is preferably 100 to 1000 m 2 / g, more preferably 300 to 700 m 2 / g.
  • the specific surface area is smaller than 100 m 2 / g, the oil absorption amount of the resin by the filler is decreased, and the resin tends to adhere to the bowl at the time of tablet molding, and when the specific surface area is larger than 1000 m 2 / g, The fluidity of the curable resin composition tends to be poor at the time of melting during transfer molding.
  • the content of the porous filler or the oil-absorbing filler is not particularly limited, but is 0.1 volume% to 20 volume based on the total amount of (E) inorganic filler and (F) white pigment. % Is preferable. Considering the moldability of the resin composition at the time of melting, it is more preferably 1% by volume to 5% by volume. When this content is less than 0.1% by volume, a part of the curable resin composition tends to adhere to the surfaces of the mortar mold and the saddle mold, and when it is greater than 20% by volume, transfer is performed. The fluidity of the resin composition tends to decrease during melting during molding.
  • the semiconductor package of the present invention is obtained by molding the curable resin composition of the present invention, and is obtained, for example, by transfer molding.
  • the semiconductor package may be obtained by integrally molding a curable resin composition with a metal.
  • a curable resin composition and a lead frame are integrally formed by transfer molding, or one in which a resin is substantially molded on one side of a metal can be mentioned.
  • the semiconductor package referred to in the present invention is a member provided for supporting and / or protecting a semiconductor element or / and an external extraction electrode.
  • the semiconductor element may not be directly covered but may be one that supports and fixes an external extraction electrode or the like, or that forms the periphery or bottom surface of a semiconductor element such as a light-emitting diode reflector.
  • an integrated circuit such as an IC or LSI
  • an element such as a transistor, a diode, or a light emitting diode, or a light receiving element such as a CCD can be used.
  • the shape is not specified, the effect of the present invention is particularly easily obtained when the semiconductor package has a shape in which a resin is substantially molded on one side of a metal (MAP type).
  • MAP type a metal
  • the semiconductor package of the present invention does not directly cover the semiconductor element as described above, it can be further sealed with a sealing agent, for example, a conventionally used epoxy resin, silicone resin, A sealing resin such as an acrylic resin, a urea resin, or an imide resin can be used.
  • a sealing agent for example, a conventionally used epoxy resin, silicone resin, A sealing resin such as an acrylic resin, a urea resin, or an imide resin can be used.
  • a sealing agent for example, a conventionally used epoxy resin, silicone resin, A sealing resin such as an acrylic resin, a urea resin, or an imide resin can be used.
  • a sealing agent for example, a conventionally used epoxy resin, silicone resin, A sealing resin such as an acrylic resin, a urea resin, or an imide resin.
  • an aliphatic organic compound having at least two carbon-carbon double bonds having reactivity with a SiH group in one molecule A sealing agent comprising a compound having at least two SiH groups in one molecule and a
  • thermosetting resins such as thermoplastic resins, epoxy resins, and silicone resins
  • injection molding, transfer molding, RIM molding, casting molding, press molding, compression molding, and the like are used.
  • transfer molding is preferred in that the molding cycle is short and the moldability is good.
  • the molding conditions can be arbitrarily set, for example, the molding temperature is also arbitrary. However, in terms of fast curing and a short molding cycle, the moldability tends to be good, more preferably 100 ° C. or higher, more preferably 120 ° C. or higher. A temperature of 150 ° C. or higher is preferable.
  • post-curing After molding by the various methods as described above, post-curing (after-curing) is optional as required. Post-curing tends to increase the heat resistance.
  • Molding may be performed at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. It is preferable to carry out the reaction while raising the temperature in a multistage manner or continuously, as compared with the case where the temperature is constant, in that a uniform cured product without distortion can be easily obtained. Moreover, it is preferable to perform at a constant temperature in that the molding cycle can be shortened.
  • the pressure at the time of molding can be variously set as required, and the molding can be performed at normal pressure, high pressure, or reduced pressure. It is preferable to cure under reduced pressure in terms of suppressing the generation of voids, improving the filling property, and easily removing volatile components generated in some cases. In terms of preventing cracks in the molded body, it is preferable to cure under pressure.
  • the semiconductor component of the present invention is manufactured using the semiconductor package of the present invention.
  • the semiconductor component of the present invention can be used for various known applications. Specific examples include LSIs such as logic and memory, various sensors, light emitting and receiving devices, and the like.
  • the light emitting diode of the present invention is manufactured using the semiconductor package of the present invention.
  • the semiconductor is a light emitting diode, it can be used for various known applications. Specifically, for example, backlights such as liquid crystal display devices, illumination, sensor light sources, vehicle instrument light sources, signal lights, display lights, display devices, planar light source, display, decoration, various lights, etc. it can.
  • the warpage of the package is desirably ⁇ 1.0 mm or less.
  • the warpage in this case is measured based on the maximum warpage measuring method described in JIS C 6481. That is, the semiconductor package is suspended vertically at the center of one side, and a straight ruler is applied parallel to the side. The straight ruler is applied to the concave surface of the semiconductor package, and the maximum distance between the straight ruler and the base surface of the semiconductor package is measured to a unit of 1.0 mm with a metal straight scale.
  • the semiconductor package used for the measurement of warpage is manufactured by the method shown in the (Method for forming MAP product) of the example.
  • the total amount of unreacted 1,3,5,7-tetramethylcyclotetrasiloxane, toluene and allyl glycidyl ether by-products is 5,000 ppm or less in total.
  • the solution was distilled off under reduced pressure until a colorless and transparent liquid was obtained.
  • this product was obtained by reacting part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with allyl glycidyl ether and triallyl isocyanurate. It was found that
  • compositions 1 to 3 and Compositions A and B were prepared by blending each component according to the contents of Table 1.
  • compositions 1 to 3 A, B, and (D) listed in Table 1 was weighed into a cup-shaped container and mixed in advance (G) component, (F) component A mixed powder of (or carbon black) and (E) component was added little by little and kneaded with a plastic spatula.
  • the obtained curable resin composition was a slightly wet powder, but after it was stretched with a round bar-shaped jig and then folded and stretched again, it was gradually moistened and moistened flakes. To be uniform. However, those with a large amount of filler and those with a high proportion of fine powder were in the form of powder (somewhat wet) until the end. The following spherical silica was used.
  • MSR-3500, MSR-2212TN, MSR-SF650, MSR-SF630, and MSR-04 were manufactured by Tatsumori Co., Ltd., and Admafine SO-2C was manufactured by Admatechs Co., Ltd.
  • the white pigment zinc oxide (ZnO-1) manufactured by Sakai Chemical Co., Ltd. and titanium oxide (PC-3) manufactured by Ishihara Sangyo Co., Ltd. were used.
  • PC-3 is titanium oxide surface-treated with Al, Si, and organic matter.
  • As the carbon black dimethylpolysiloxane surface-treated acetylene black (product name: SI06-2 Denka Black granular) manufactured by Daito Kasei Kogyo Co., Ltd. was used.
  • the mold release agent calcium stearate was manufactured by Sakai Chemical Co., Ltd.
  • the produced curable resin composition was compressed into a tablet by a tablet production jig composed of a metal punch and mortar. Specifically, a predetermined amount of the composition was put into a 13 mm diameter mortar and compressed from the top with a spatula at a pressure of 100 kg / cm 2 for 5 seconds to obtain a tablet having a predetermined volume.
  • the curable resin composition of the present invention was compressed with a tablet manufacturing jig comprising a Teflon punch and mortar to produce a tablet having a diameter of 38 mm. Next, this tablet was placed in a pot of a transfer molding machine (model: ETA-20, plunger diameter: 40 mm) manufactured by Shindo Metal Industry Co., Ltd., and spiral flow data was measured.
  • the shape of the spiral flow mold was a semicircular shape having a width of 3 mm and a depth of 1.5 mm as a cross-sectional shape.
  • the molding conditions were a mold temperature: 170 ° C., a transfer pressure of 7 MPa, a curing time, and 120 seconds.
  • a molded MAP Mold Array Package: a type in which a semiconductor package has a shape in which a resin is substantially formed on one side of a metal) includes a total of 180 reflectors in 15 rows and 12 rows.
  • Each reflector has a top surface of 2.1 mm, a bottom surface of 1.8 mm (taper angle: 15 degrees), a height of 0.55 mm, a width of 0.20 mm from the right end along the transverse diameter, and a width of 0.20 mm.
  • the electrode slit which consists of a compound which hardened the conductive resin composition is provided vertically.
  • the interval between the reflectors is 1.1 mm in both the vertical and horizontal diameter directions.
  • the lead frame and the mold are not particularly limited as long as a reflector with a lead frame that satisfies the above requirements can be manufactured. This shape of the molded product is called a 3030 MAP type.
  • a conceptual diagram of the molded product is shown in FIG.
  • the transfer molding was performed using a G-Line manual press manufactured by Apic Yamada Co., Ltd. (clamping force 30 ton, injection pressure 8 MPa, injection speed 3 mm / s).
  • a white compound (5.0 g) was weighed, shaped into a cylindrical shape (tablet as described above), loaded into a cylinder, and molded.
  • the molding conditions were 170 ° C. and 150 seconds. After molding, it was post-cured (aftercured) at 180 ° C. for 1 hour in a hot air oven.
  • warp When the molded part is placed on a smooth surface with the molded part facing up, the warp is defined as a forward warp when the molded part is concave when viewed from the side, and the reverse warp is defined as a convex part.
  • degree of warpage a MAP product was placed on a smooth surface, and the value (mm) having the longest distance among the four sides away from the surface was quantified.
  • test piece is 50 mm to 80 mm in length, the width is about 7 mm to 8 mm, and the two sides facing each other are It cut out so that it might become parallel.
  • the test piece was installed between the metal fulcrums with rounded corners so that the shape formed between the fulcrums was rectangular.
  • three places of the test piece which enter between fulcrum were measured to 0.01 mm, and each average value was made into the measurement result. The area was calculated from the specimen width and thickness. Texture Microscope TA.
  • a pressure wedge consisting of right-angled triangles made of glass with round corners with a width of 10 mm at plus, applying a load at a speed of 2.0 mm / sec to the center of the test piece, and the load when the test piece breaks (bending fracture) Load N) and breaking displacement (deflection mm at break) were measured. The measurement results were averaged from the three measurements.
  • the bending fracture strength ⁇ b (N / mm 2 ) was calculated as follows.
  • the hardness was measured using a type D durometer based on JIS K 7125.
  • the test piece used was a stack of 6 or more flat plates produced by transfer molding having a thickness of 1 mm.
  • the cured product obtained from the curable resin composition of the present invention has a linear expansion of Cu used as a base material for LED package substrates and the like. It can be seen that a linear expansion coefficient equal to or lower than the coefficient can be realized.
  • the warpage is large in Comparative Example 1, the effect of using the component (D) in the present invention can be confirmed. That is, it can be seen that when the component (D) is added, a semiconductor package with a warp of 1.0 mm or less can be obtained.
  • Example 10 to 12 and Comparative Example 4 Based on the formulation examples based on Table 3, the curable resin compositions of Examples 10 to 12 and Comparative Example 4 shown in Table 4 were prepared, and the bending characteristics, bending strength, continuous moldability test, and (A The physical properties of cured products obtained by thermally curing a mixture of components (C) to (C) and (Z) were compared.
  • the continuous formability test will be described below.
  • the transfer molding is continuously performed 40 times in the same manner as the above-described (MAP product molding method), and the external appearance of the first-time molded MAP product and the 40th-time molded MAP product is visually observed.
  • ⁇ When the 40th MAP product has the same appearance as that of the 1st time, ⁇ , when there are 9 or less cohesive failure areas of 50 ⁇ m or more, ⁇ , when there are 10-20 places ⁇ , if over 20 locations, determined as x.

Abstract

L'invention concerne une composition de résine durcissable, laquelle possède un faible coefficient d'expansion linéaire et permet d'obtenir un objet durci résistant. Cette résine durcissable se caractérise en ce qu'elle contient en tant que composants essentiels: (A) un siliciure d'une masse moléculaire inférieure à 1000, lequel contient au moins deux doubles liaisons carbone - carbone présentant une réactivité avec un groupe SiH par molécule; (B) un composé contenant au moins deux groupes SiH par molécule; (C) un catalyseur d'hydrosilylation; (D) un composé de silicium contenant au moins une double liaison carbone - carbone présentant une réactivité avec un groupe SiH par molécule et dont la masse moléculaire est supérieure ou égale à 1000 et (E) une charge inorganique.
PCT/JP2012/075633 2011-10-04 2012-10-03 Composition de résine durcissable, tablette de composition de résine durcissable, corps moulé, boîtier de semi-conducteurs, pièce semi-conductrice et diode électroluminescente WO2013051600A1 (fr)

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CN201280049280.4A CN103842442B (zh) 2011-10-04 2012-10-03 固化性树脂组合物及其片状物、成形体、半导体的封装、半导体部件及发光二极管

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WO2014200110A1 (fr) * 2013-06-14 2014-12-18 東レ・ダウコーニング株式会社 Composition de silicium réactive, thermoplastique réactif, produit durci et dispositif semi-conducteur photoélectrique
WO2014200112A1 (fr) * 2013-06-14 2014-12-18 東レ・ダウコーニング株式会社 Composition de silicium réactive, thermoplastique réactif, produit durci et dispositif semi-conducteur photoélectrique
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KR20210108990A (ko) 2018-12-27 2021-09-03 다우 도레이 캄파니 리미티드 경화성 실리콘 조성물, 그의 경화물 및 그의 제조 방법
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