WO2011125753A1 - 硬化性樹脂組成物、硬化性樹脂組成物タブレット、成形体、半導体のパッケージ、半導体部品及び発光ダイオード - Google Patents
硬化性樹脂組成物、硬化性樹脂組成物タブレット、成形体、半導体のパッケージ、半導体部品及び発光ダイオード Download PDFInfo
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- WO2011125753A1 WO2011125753A1 PCT/JP2011/058047 JP2011058047W WO2011125753A1 WO 2011125753 A1 WO2011125753 A1 WO 2011125753A1 JP 2011058047 W JP2011058047 W JP 2011058047W WO 2011125753 A1 WO2011125753 A1 WO 2011125753A1
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- 0 *N(C(N(*)C(N1*)=O)=O)C1=O Chemical compound *N(C(N(*)C(N1*)=O)=O)C1=O 0.000 description 4
- NFNRYAJDLKTJBP-UHFFFAOYSA-N C=CCN(C(N(CC(COCC=C)OCC=C)C(N1CC(COCC=C)OCC=C)=O)=O)C1=O Chemical compound C=CCN(C(N(CC(COCC=C)OCC=C)C(N1CC(COCC=C)OCC=C)=O)=O)C1=O NFNRYAJDLKTJBP-UHFFFAOYSA-N 0.000 description 1
- CZRZPVKMNCCXRR-UHFFFAOYSA-N C=CCN(C(N(c1ccccc1)C(N1CC=C)=O)O)C1=O Chemical compound C=CCN(C(N(c1ccccc1)C(N1CC=C)=O)O)C1=O CZRZPVKMNCCXRR-UHFFFAOYSA-N 0.000 description 1
- UCBVELLBUAKUNE-UHFFFAOYSA-N C=CCN(C(NC(N1CC=C)=O)=O)C1=O Chemical compound C=CCN(C(NC(N1CC=C)=O)=O)C1=O UCBVELLBUAKUNE-UHFFFAOYSA-N 0.000 description 1
- BDCBBKCMGCDEJN-UHFFFAOYSA-N CC(C(N(C(N(C(C(C)=C)=O)C(N1C(C(C)=C)=O)=O)=O)C1=O)=O)=C Chemical compound CC(C(N(C(N(C(C(C)=C)=O)C(N1C(C(C)=C)=O)=O)=O)C1=O)=O)=C BDCBBKCMGCDEJN-UHFFFAOYSA-N 0.000 description 1
- INEVSRHULFGDQT-UHFFFAOYSA-N CC(C)(C)CN(C(N(CC(C)=C)C(N1CC(C)=C)=O)=O)C1=O Chemical compound CC(C)(C)CN(C(N(CC(C)=C)C(N1CC(C)=C)=O)=O)C1=O INEVSRHULFGDQT-UHFFFAOYSA-N 0.000 description 1
- IRHRJBSDPLGJFG-UHFFFAOYSA-N CCCCNC(N(CC=C)C(N(CC=C)C(C)=O)=O)=O Chemical compound CCCCNC(N(CC=C)C(N(CC=C)C(C)=O)=O)=O IRHRJBSDPLGJFG-UHFFFAOYSA-N 0.000 description 1
- LQYCSLMMIDYBIS-UHFFFAOYSA-N CN(C(N(CC(COCC=C)OCC=C)C(N1CC=C)=O)=O)C1=O Chemical compound CN(C(N(CC(COCC=C)OCC=C)C(N1CC=C)=O)=O)C1=O LQYCSLMMIDYBIS-UHFFFAOYSA-N 0.000 description 1
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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
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- 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
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- 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
- H01L23/295—Organic, e.g. plastic containing a filler
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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
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
- H01L23/3157—Partial encapsulation or coating
- H01L23/3171—Partial encapsulation or coating the coating being directly applied to the semiconductor body, e.g. passivation layer
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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
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/495—Lead-frames or other flat leads
- H01L23/49579—Lead-frames or other flat leads characterised by the materials of the lead frames or layers thereon
- H01L23/49586—Insulating layers on lead frames
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- 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
- H01L33/58—Optical field-shaping elements
- H01L33/60—Reflective elements
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- 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
- H01L33/62—Arrangements for conducting electric current to or from the semiconductor body, e.g. lead-frames, wire-bonds or solder balls
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- 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
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.
- resins generally have a large coefficient of linear expansion, and the coefficient of linear expansion is generally difficult to match that of a metal material having a small coefficient of linear expansion, various types of heating during heat molding, post-curing, or in use as semiconductor components— Problems such as warpage, peeling, cracking, and damage to the semiconductor may occur in the process involving cooling.
- an object of the present invention is to provide a curable resin composition that provides a cured product having a low coefficient of linear expansion, and a semiconductor package with reduced warpage integrally formed with a metal using the same, and It is providing the semiconductor manufactured using this.
- the present inventors have intensively studied and (A) an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule, (B) 1 A compound containing at least two SiH groups in the molecule, (C) a hydrosilylation catalyst, (D) a silicone compound containing at least one carbon-carbon double bond reactive with the SiH group in one molecule, (E) It discovered that the said subject could be achieved by making a curable resin composition by making an inorganic filler into an essential component, and it came to this invention.
- the present invention has the following configuration. (1) (A) an organic compound containing at least two carbon-carbon double bonds reactive 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 reactive with a SiH group in one molecule; (E) inorganic filler, Is contained as an essential component. Curable resin composition characterized by the above-mentioned.
- component (F) is at least one selected from zinc oxide, zirconia oxide, strontium oxide, niobium oxide, boron nitride, barium titanate and barium sulfate. object.
- Spectral reflectance at 420 nm, 440 nm, and 460 nm after curing is 80 R% or more, and retention ratio of spectral reflectance after heat resistance test at 180 ° C. for 72 hours (spectral reflectance after heat resistance test / initial spectral reflectance
- the curable resin composition according to any one of (1) to (19), wherein the light reflectance at a wavelength of 470 nm on the surface of the molded product obtained by curing is 90% or more.
- (F) a tablet comprising a curable resin composition containing a white pigment as an essential component, 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 total content of component (E) and component (F) is 70 to 95% by weight, The ratio of the particle
- (25) A semiconductor package formed using the curable resin composition according to (22).
- (26) A semiconductor package, which is integrally formed with a metal using the curable resin composition according to (22).
- (27) The semiconductor package according to (25) or (26), wherein the curable resin composition and the lead frame are integrally formed by transfer molding.
- (28) The semiconductor package according to any one of (25) to (27), wherein the semiconductor package is a package formed by substantially molding a resin on one side of a metal.
- (29) A semiconductor package, which is transfer molded using the curable resin composition according to (22).
- the curable resin composition of the present invention it is possible to obtain a curable resin composition that gives a cured product having a low linear expansion coefficient. Therefore, a semiconductor that is integrally molded with a metal and that has a reduced warpage. Package and a semiconductor manufactured using the same package.
- the curable resin composition of the present invention is (A) an organic compound containing at least two carbon-carbon double bonds reactive 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 reactive with a SiH group in one molecule; (E) A curable resin composition containing an inorganic filler as an essential component.
- each component will be described.
- the component (A) is not particularly limited as long as it is an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule.
- Organic compounds do not contain siloxane units (Si-O-Si) like polysiloxane-organic block copolymers and polysiloxane-organic graft copolymers, but other than C, H, N, O, S and halogen as constituent elements A compound containing no element is more preferable. In the case of those containing siloxane units, there is a problem that the adhesiveness between the semiconductor package and the lead frame or the sealing resin tends to be low.
- the organic compound (A) can be classified into an organic polymer compound and an organic monomer compound.
- component (A) is a polymer
- component (A) of the organic polymer system for example, polyether-based, polyester-based, polyarylate-based, polycarbonate-based, saturated hydrocarbon-based, unsaturated hydrocarbon-based, polyacrylate ester-based, polyamide-based, phenol-formaldehyde
- examples thereof include those having a skeleton of a system (phenolic resin system) or a polyimide system.
- examples of the polyether polymer include polyoxyethylene, polyoxypropylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and the like. More specific examples:
- R 1 and R 2 are C, H, N, O, S, C 1 -C 6 divalent organic groups not containing any elements other than halogen as constituent elements, n, m, and l are 1 to Represents a number of 300.) Etc.
- Examples of other polymers include dibasic acids such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, and hexahydrophthalic acid, and glycols such as ethylene glycol, diethylene glycol, propylene glycol, tetramethylene glycol, and neopentyl glycol.
- dibasic acids such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, and hexahydrophthalic acid
- glycols such as ethylene glycol, diethylene glycol, propylene glycol, tetramethylene glycol, and neopentyl glycol.
- Polyester polymers obtained by condensation of lactones or ring-opening polymerization of lactones, ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene and butadiene, acrylonitrile, Copolymers with styrene, etc., polybutadiene, copolymers with butadiene and styrene, acrylonitrile, etc., polyisoprene, polybutadiene, isoprene or copolymers with butadiene and acrylonitrile, styrene, etc.
- Polyolefin (saturated hydrocarbon) polymers obtained by hydrogenating the body polyacrylates obtained by radical polymerization of monomers such as ethyl acrylate and butyl acrylate, acrylic esters such as ethyl acrylate and butyl acrylate, and Acrylate ester copolymer with vinyl acetate, acrylonitrile, methyl methacrylate, styrene, etc., graft polymer obtained by polymerizing vinyl monomer in the organic polymer, polysulfide polymer, ring opening of ⁇ -aminocaprolactam Nylon 6 by polymerization, Nylon 66 by polycondensation of hexamethylenediamine and adipic acid, Nylon 610 by polycondensation of hexamethylenediamine and sebacic acid, Nylon 11 by polycondensation of ⁇ -aminoundecanoic acid, ⁇ -aminolauracta Nylon 12 by ring-opening polymer
- An alkenyl group having a carbon-carbon double bond can be introduced into these polymer skeletons to obtain the component (A).
- the alkenyl group having a carbon-carbon double bond may be present anywhere in the molecule, but is preferably present in the side chain or the terminal from the viewpoint of reactivity.
- an organic polymer having a functional group such as a hydroxyl group, an alkoxide group, a carboxyl group, or an epoxy group at the terminal, main chain, or side chain is reactive with the functional group.
- An alkenyl group can be introduced into the terminal, main chain or side chain by reacting an organic compound having both an active group and an alkenyl group.
- organic compounds having both an active group and an alkenyl group reactive to the functional group include C3-C20 unsaturated groups such as acrylic acid, methacrylic acid, vinyl acetic acid, acrylic acid chloride, and acrylic acid bromide.
- Allyl chloride allyl bromide
- vinyl (chloromethyl) benzene allyl (chloromethyl)
- This method is a method of transesterifying an alcohol residue of an ester portion of a polyester resin or an acrylic resin with an alkenyl group-containing alcohol or an alkenyl group-containing phenol derivative using a transesterification catalyst.
- the alkenyl group-containing alcohol and alkenyl group-containing phenol derivative used for exchange with an alcohol residue may be any alcohol or phenol derivative having at least one alkenyl group and having at least one hydroxyl group. It is preferable to have it.
- a catalyst may or may not be used, but a titanium-based catalyst and a tin-based catalyst are preferable.
- Examples of the above compounds include vinyl alcohol, allyl alcohol, 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, 6-hepten-1-ol, and 7-octene-1. -Ol, 8-nonen-1-ol, 9-decen-1-ol, 2- (allyloxy) ethanol, neopentyl glycol monoallyl ether, glyceryl diallyl ether, trimethylolpropane triallyl ether, trimethylolethane triallyl ether Pentaerythritol tetraallyl ether, 1,2,6-hexanetriol triallyl ether, sorbitan triallyl ether,
- ester residue of the above-mentioned alcohol or phenol derivative such as acetate ester and the ester part of the polyester resin or acrylic resin are transesterified using a transesterification catalyst, and the alcohol residue of the ester part of the produced polyester resin or acrylic resin is changed.
- a method of introducing an alkenyl group by a method of distilling low molecular weight esterified products such as acetates out of the system by vacuum devolatilization or the like.
- an alkenyl group can also be introduce
- an alkenyl group during the polymerization for example, in the case of producing the organic polymer skeleton of the component (A) used in the present invention by radical polymerization, radical reactivity in the molecule of allyl methacrylate, allyl acrylate, etc.
- a vinyl monomer having a low alkenyl group or a radical chain transfer agent having a low alkenyl group such as allyl mercaptan
- an alkenyl group can be introduced into the side chain or terminal of the organic polymer skeleton. .
- the molecular weight is not particularly limited, but any of 100 to 100,000 can be suitably used, and an organic polymer containing an alkenyl group is particularly preferably 500 to 20,000.
- an organic polymer containing an alkenyl group is particularly preferably 500 to 20,000.
- the molecular weight is 500 or less, characteristics due to the use of an organic polymer such as imparting flexibility are hardly exhibited, and when the molecular weight is 100,000 or more, the effect of crosslinking due to the reaction between the alkenyl group and the SiH group is hardly exhibited.
- component (A) is a monomer
- organic monomer-based component (A) examples include, for example, aromatic hydrocarbons such as phenols, bisphenols, benzene, and naphthalene: aliphatic hydrocarbons such as linear and alicyclic: heterocyclic compounds And mixtures thereof.
- Carbon-carbon double bond of component (A) The bonding position of the carbon-carbon double bond having reactivity with the SiH group is not particularly limited, and may be present anywhere in the molecule.
- the carbon-carbon double bond having reactivity with the SiH group of the component (A) 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 of the component (A) 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. However, a constituent element containing no element other than C, H, N, O, S and halogen is preferable. 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.
- Examples 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 (A) Specific examples of component (A) in the organic polymer system include 1,2-polybutadiene (1,2 ratio of 10 to 100%, preferably 1,2 ratio of 50 to 100%), novolak phenol Allyl ether, allylated polyphenylene oxide,
- R 1 is H or CH 3
- R 2 , R 3 is a divalent organic group having 1 to 6 carbon atoms that does not contain elements other than C, H, N, O, S, and halogen as constituent elements
- X and Y are divalent substituents having 0 to 10 carbon atoms
- n, m, and l are numbers 1 to 300.
- R 1 is H or CH 3
- R 4 , R 5 is a divalent organic group having 1 to 6 carbon atoms
- X and Y are divalent substituents having 0 to 10 carbon atoms
- n, m, l represents a number from 1 to 300.
- R 1 is H or CH 3
- R 6 , R 7 is a divalent organic group having 1 to 20 carbon atoms
- X and Y are divalent substituents having 0 to 10 carbon atoms
- n, m, l represents a number from 1 to 300.
- R 1 is H or CH 3
- R 8 and R 9 are divalent organic groups having 1 to 6 carbon atoms
- X and Y are divalent substituents having 0 to 10 carbon atoms
- n, m, l represents a number from 1 to 300.
- R 1 is H or CH 3
- R 10 , R 11 , R 12 are divalent organic groups having 1 to 6 carbon atoms
- X and Y are divalent substituents having 0 to 10 carbon atoms
- n , M, l, and p represent numbers of 1 to 300).
- organic monomer type (A) component examples include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2 -Tetraallyloxyethane, diarylidenepentaerythritol, triallyl cyanurate, triallyl isocyanurate, 1,2,4-trivinylcyclohexane, divinylbenzenes (having a purity of 50 to 100%, preferably a purity of 80 to 100%), divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and oligomers thereof,
- low molecular weight compounds that are difficult to express separately as described above for the skeleton portion and the alkenyl group can also be used.
- these low molecular weight compounds include aliphatic chain polyene compound systems such as butadiene, isoprene, octadiene and decadiene, fats such as cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene and norbornadiene.
- examples thereof include aromatic cyclic polyene compound systems and substituted aliphatic cyclic olefin compound systems such as vinylcyclopentene and vinylcyclohexene.
- the component (A) preferably contains 0.001 mol or more of a carbon-carbon double bond having reactivity with the SiH group per 1 g of the component (A) from the viewpoint of further improving the heat resistance. What contains 0.005 mol or more per is more preferable, and what contains 0.008 mol or more is still more preferable.
- the number of carbon-carbon double bonds reactive with the SiH group of the component (A) should be on average at least 2 per molecule, but it may exceed 2 if it is desired to further improve the mechanical strength. Preferably, it is 3 or more. When the number of carbon-carbon double bonds reactive with the SiH group of component (A) is 1 or less per molecule, the reaction with component (B) only results in a graft structure and a crosslinked structure. Don't be.
- the component (A) From the viewpoint of good reactivity as the component (A), it is preferable that one or more vinyl groups are contained in one molecule, and two or more vinyl groups are contained in one molecule. Is more preferable. Further, from the viewpoint that the storage stability tends to be good, it is preferable that 6 or less vinyl groups are contained in one molecule, and it is more preferable that 4 or less vinyl groups are contained in one molecule.
- the viscosity is preferably less than 1000 poise at 23 ° C., more preferably less than 300 poise, More preferred is less than 30 poise.
- the viscosity can be measured with an E-type viscometer.
- those having a low content of a compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group are preferable from the viewpoint of higher light resistance.
- a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group is preferable. What does not contain the compound which has is preferable.
- the phenolic hydroxyl group means a hydroxyl group directly bonded to an aromatic hydrocarbon nucleus exemplified by a benzene ring, naphthalene ring, anthracene ring, etc.
- a phenolic hydroxyl group derivative means a hydrogen atom of the above-mentioned phenolic hydroxyl group.
- a group substituted by an alkyl group such as a methyl group or an ethyl group, an alkenyl group such as a vinyl group or an allyl group, an acyl group such as an acetoxy group, or the like.
- the weight ratio of the component (A) in the aromatic ring is preferably 50% by weight or less, more preferably 40% by weight or less, and more preferably 30% by weight. The following are more preferable. Most preferred are those that do not contain an aromatic hydrocarbon ring.
- the component (A) includes vinylcyclohexene, dicyclopentadiene, vinylnorbornene, triallyl isocyanurate, 2,2-bis (4-hydroxycyclohexyl).
- Preferred is diallyl ether of propane, 1,2,4-trivinylcyclohexane, particularly preferred is triallyl isocyanurate, diallyl ether of 2,2-bis (4-hydroxycyclohexyl) propane, and 1,2,4-trivinylcyclohexane. . *
- R 1 represents a monovalent organic group having 1 to 50 carbon atoms, and each R 1 may be different or the same).
- R 1 in the general formula (III) is preferably a monovalent organic group having 1 to 20 carbon atoms from the viewpoint that the heat resistance of the resulting cured product can be further increased. 10 monovalent organic groups are more preferable, and monovalent organic groups having 1 to 4 carbon atoms are more preferable. Examples of these preferable R 1 are methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group,
- the R 1 in the general formula (III) includes three R 1 from the viewpoint that the adhesiveness between the package and the lead frame or the sealing agent can be improved, or the mechanical strength of the obtained package can be increased.
- at least one of them is a monovalent organic group having 1 to 50 carbon atoms containing one or more epoxy groups,
- R 1 a monovalent organic group having 1 to 50 carbon atoms containing at least one epoxy group represented by the formula:
- R 1 examples include a glycidyl group
- R 1 in the general formula (III) is a carbon containing two or less oxygen atoms and containing only C, H, and O as constituent elements from the viewpoint that the heat resistance of the resulting cured product can be improved.
- a monovalent organic group having 1 to 50 carbon atoms is preferable, and a monovalent hydrocarbon group having 1 to 50 carbon atoms is more preferable.
- examples of these preferable R 1 are methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group,
- R 1 in the general formula (III) is at least one of three R 1 from the viewpoint of good reactivity.
- R 2 represents a hydrogen atom or a. Represents methyl group
- R 1 is a monovalent organic group of 1 to 50 carbon atoms containing a group represented by one or more at least of the three R 1 Two are the following general formula (V)
- R 3 represents a direct bond or a divalent organic group having 1 to 48 carbon atoms
- R 4 represents a hydrogen atom or a methyl group
- a plurality of R 3 and R 4 are More preferably, they may be the same or different.
- R 3 in the general formula (V) is a direct bond or a divalent organic group having 1 to 48 carbon atoms. From the viewpoint that the heat resistance of the resulting package can be further increased, the direct bond or the carbon number It is preferably a divalent organic group having 1 to 20, more preferably a direct bond or a divalent organic group having 1 to 10 carbon atoms, and a direct bond or a divalent organic group having 1 to 4 carbon atoms. More preferably. Examples of these preferred R 3 include
- R 3 in the general formula (V) from the viewpoint that the heat resistance of the resulting package can be improved, only C, H, or O is included as a constituent element including a direct bond or two or less oxygen atoms. It is preferably a divalent organic group having 1 to 48 carbon atoms, more preferably a direct bond or a divalent hydrocarbon group having 1 to 48 carbon atoms. Examples of these preferred R 3 include
- R 4 in the general formula (V) is a hydrogen atom or a methyl group, and a hydrogen atom is preferable from the viewpoint of good reactivity.
- the organic compound represented by the general formula (III) as described above it is necessary to contain at least two carbon-carbon double bonds having reactivity with the SiH group in one molecule. is there. From the viewpoint of further improving the heat resistance, it is more preferably an organic compound containing three or more carbon-carbon double bonds having reactivity with SiH groups in one molecule.
- organic compound represented by the above general formula (III) examples include triallyl isocyanurate,
- the component ( ⁇ ) is a compound having a SiH group, and a chain and / or cyclic polyorganosiloxane having a SiH group is an 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) preferably does not contain a constituent element other than C, H, and O, more preferably a hydrocarbon group, and a methyl group. Further preferred.
- ( ⁇ ) component examples include compounds having a SiH group such as bisdimethylsilylbenzene. *
- component (A) of the present invention an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule and ( ⁇ ) component are obtained by hydrosilylation reaction.
- the hydrosilylation reaction between an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule and the ( ⁇ ) component in the case of using a compound capable of reacting with SiH will be described.
- a hydrosilylation reaction of an organic compound containing at least two carbon-carbon double bonds reactive with a SiH group in one molecule and the ( ⁇ ) component results in a plurality of compounds containing the component (A) of the present invention.
- the curable resin composition of the present invention can also be prepared by using the mixture as it is without separating the component (A).
- Carbon-carbon double having reactivity with SiH group when hydrosilylation reaction of ( ⁇ ) component with organic compound containing at least two carbon-carbon double bonds reactive with SiH group in one molecule The mixing ratio of the organic compound containing at least two bonds in one molecule and the ( ⁇ ) component is not particularly limited, but generally is reactive with the SiH group to be mixed in that gelation during the reaction can be suppressed.
- an appropriate catalyst may be used.
- 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, 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 with respect 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 as a method of mixing an organic compound containing at least two carbon-carbon double bonds that are reactive with SiH groups in one molecule, a ( ⁇ ) component, and a catalyst.
- a method in which a catalyst is mixed with an organic compound containing at least two carbon-carbon double bonds reactive with an SiH group in one molecule is mixed with the ( ⁇ ) component. It is difficult to control the reaction by a method of mixing a catalyst with a mixture of an organic compound ( ⁇ ) component containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule.
- 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. *
- 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, 1,1,4-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.
- As the solvent toluene, tetrahydrofuran, 1,3-dioxolane and chloroform are preferable.
- the amount of solvent to be used can also be set as appropriate. *
- Examples of the component (A), which is a reaction product of the organic compound containing at least two carbon-carbon double bonds reactive with the SiH group in one molecule and the component ( ⁇ ), include bisphenol A reaction product of diallyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of vinylcyclohexene and 1,3,5,7-tetramethylcyclotetrasiloxane, divinylbenzene and 1,3,5, Reaction product of 7-tetramethylcyclotetrasiloxane, reaction product of dicyclopentadiene and 1,3,5,7-tetramethylcyclotetrasiloxane, triallyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane Reaction products of diallyl monoglycidyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane Applied Physics, mention may be made of reaction products of vinyl norbornene and bis dimethylsilyl
- (Other reactive groups of component (A)) (A) As a component, you may have another reactive group.
- 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.
- (Mixing of component (A)) (A) component can be used individually or in mixture of 2 or more types.
- 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.
- the compound described in International Publication WO 96/15194 is at least two SiH groups in one molecule. Those having a 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, and the upper limit of the preferred molecular weight is 100,000, more preferably 1,000, and still more preferably 700. *
- component (B) in order to facilitate uniform mixing with other components, particularly powders such as component (E) and 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) From the viewpoint of having good compatibility with the component (A), and from the viewpoint that the problem of outgas from the curable resin composition that can be reduced in volatility of the component (B) is less likely to occur, the component (B) An organic compound ( ⁇ ) containing at least one carbon-carbon double bond reactive with a SiH group in one molecule and a compound ( ⁇ ) having at least two SiH groups in one molecule are hydrosilylated. It is preferable that the compound is obtained by a chemical reaction.
- the component ( ⁇ ) used here is the same component ( ⁇ 1) as the component (A) described above, which is the same as the organic compound containing at least two carbon-carbon double bonds reactive with the SiH group in one molecule. Can do.
- 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 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, but the component (B) is compatible with the component (A).
- the compound does not contain a siloxane unit (Si—O—Si) such as polysiloxane-organic block copolymer or polysiloxane-organic graft copolymer, and C, H, N as constituent elements , O, S, and halogen are preferred.
- the bonding position of the carbon-carbon double bond reactive 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.
- polysiloxane examples 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.
- polysiloxane examples 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 ( ⁇ 2) component 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
- the carbon-carbon double bond having reactivity with the SiH group of the component ( ⁇ 2) is represented by the following general formula (II)
- 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.
- C Those containing only H, N, O, S and halogen are preferred. Examples of these substituents are:
- divalent or higher valent substituents may be connected by a covalent bond to constitute one divalent or higher valent substituent.
- Examples 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's 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 and the like, Styrene, ⁇ -methylstyrene, indene, phenylacetylene, 4-ethynyltoluene, allylbenzene, 4- Aromatic hydrocarbon compounds such as 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-dioxolane- Substitution of aliphatic compounds such as 2-one, aromatic compounds such as 1,2-dimethoxy-4-allylbenzene, o-allylphenol
- 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
- 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 tends 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. Preferably, it is 50 ° C. or lower, and more preferably 0 ° C. or lower. Examples of 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.
- ( ⁇ 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.
- 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.
- ( ⁇ ) component examples include compounds having a SiH group such as bisdimethylsilylbenzene. *
- 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.
- 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, 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 with respect 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.
- 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. *
- 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, 1,1,4-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.
- As the solvent toluene, tetrahydrofuran, 1,3-dioxolane and chloroform are preferable.
- the amount of solvent to be used can also be set as appropriate. *
- 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.
- 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 a support made of alumina, silica, carbon black or the like on which solid platinum is supported, chloroplatinic acid, platinum chloride Complexes of acids with alcohols, aldehydes, ketones, etc., platinum-olefin complexes (eg, 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-phos Fight complexes (e.g., Pt [P (OP
- 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, the lower limit of the preferable addition amount is sufficient with respect to 1 mol of SiH groups of the component (B) 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 with respect 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.
- the component (D) of the present invention is a silicone compound containing at least one carbon-carbon double bond having reactivity with the SiH group in one molecule.
- a curable resin composition that gives a cured product having a smaller linear expansion coefficient when mixed with the inorganic filler of the component (E) can be obtained.
- the silicone compound of component (D) is a compound whose skeleton is substantially formed of Si—O—Si bonds, and various compounds such as linear, cyclic, branched, and partial networks are available. 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 reactive with the SiH group include a vinyl group, an allyl group, an acryloxy group, a methacryloxy group, an acryloxypropyl group, and a methacryloxypropyl group. Of these, a vinyl group is preferred in terms of good reactivity.
- 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)
- the component (D) include polydimethylsiloxane having a vinyl group as a terminal group or side chain group, polydiphenylsiloxane, polymethylphenylsiloxane, and two or three kinds of random or block copolymers, 1, 3 -Divinyltetramethyldisiloxane, 1,3,5,7-tetravinylcyclotetrasiloxane and the like.
- 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.
- a linear polymethylphenylsiloxane having a vinyl group is more preferable, and a linear polymethylphenylsiloxane having a vinyl group at both ends, wherein the amount of phenyl groups with respect to all substituents is 20 mol% or more. It is particularly preferred that
- the weight average molecular weight (Mw) is preferably 1,000 or more, more preferably 5,000 or more, and further preferably 10,000 or more. When the molecular weight is high, the obtained cured product tends to have low stress. Further, the molecular weight of the component (D) is preferably 1,000,000 or less, and more preferably 100,000 or less. When the molecular weight is large, it becomes difficult to obtain compatibility with the component (A).
- 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.
- 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).
- the ratio of the number of carbon-carbon double bonds (X) having reactivity with SiH groups in component (D) is preferably Y / X ⁇ 0.3, more preferably Y / X ⁇ 0. 0.5, more preferably Y / X ⁇ 0.7, and the upper limit of the preferred range is 3 ⁇ Y / X, more preferably 2 ⁇ Y / X, and even 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 balloon, silver powder, and other conventional sealing materials such as epoxy 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.
- Examples of 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 it is a compound having at least one functional group reactive with an organic group and one hydrolyzable silicon group in the molecule.
- the group reactive 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.
- 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 which 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 average particle size usually used is 0.1 ⁇ m, preferably 0.5 ⁇ m from the viewpoint that the fluidity tends to be good, and the upper limit of the average particle size usually used is 120 ⁇ m, the fluidity tends to be good. From the viewpoint, it is preferably 60 ⁇ m, more preferably 15 ⁇ m.
- 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 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.
- the amount of the component (E) is small, it is 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.
- 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.
- (F) Although various things are used also as an average particle diameter of a component, 1.0 micrometer or less from a 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.
- the cured product obtained is preferably treated with an organic siloxane treatment because the light reflectance is high and the heat and light resistance is improved.
- 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 group, 3-methacryloxypropyltrimethyl Xy
- 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 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 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 85% by weight or more. More preferably, it is 90% by weight or more.
- the total amount of the component (E) and the component (F) is small, it is difficult to obtain the effects of increasing the strength and hardness and reducing the linear expansion coefficient.
- 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.
- the minimum of a preferable amount is 0.01 weight part with respect to 100 weight part of the whole curable resin composition, More preferably, it is 0.025 weight part, More preferably, it is 0.
- the upper limit of the preferable amount is 5 parts by weight, more preferably 4 parts by weight with respect to 100 parts by weight of the entire curable resin composition.
- 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.
- 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.
- 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.
- coupling agents include silane coupling agents and titanate coupling agents. *
- 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.
- 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.
- 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 the 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), etc.
- Aluminum chelates are more preferable from the viewpoint of handleability.
- Titanium compounds used as silanol condensation catalysts include tetraalkoxy titaniums such as tetraisopropoxy titanium and tetrabutoxy titanium: titanium chelates such as titanium tetraacetylacetonate: general 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.
- borate esters may be used alone or in combination of two or more. Mixing may be performed in advance or may be performed at the time of producing a cured product.
- 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 or / and 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.
- 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 react with SiH groups in that they have hydrosilylation reactivity and are unlikely to impair the physical properties of the resulting cured product with little possibility of seepage from the cured product. Those having a carbon-carbon double bond having properties are preferred.
- Preferred carboxylic acids and / or acid anhydrides include, for example,
- 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
- a polycarbonate resin such as a polycarbonate resin containing 3,5-trimethylcyclohexylidenebisphenol or the like as a monomer structure (for example, APEC manufactured by Teijin Limited), a norbornene derivative, a vinyl monomer, or the like is copolymerized.
- Cycloolefin resins such as resins obtained by ring-opening metathesis polymerization of fats and norbornene derivatives, or hydrogenated products thereof (for example, APEL manufactured by Mitsui Chemicals, ZEONOR, ZEONEX manufactured by Nippon Zeon, ARTON manufactured by JSR, etc.), ethylene and Olefin-maleimide resins such as maleimide copolymers (eg, TI-PAS manufactured by Tosoh Corporation), bisphenols such as bisphenol A and bis (4- (2-hydroxyethoxy) phenyl) fluorene, and diols such as diethylene glycol Polyester resins such as polyester obtained by polycondensation of phthalic acids and aliphatic dicarboxylic acids such as terephthalic acid and isophthalic acid (eg O-PET manufactured by Kanebo Co., Ltd.), polyethersulfone resins, polyarylate resins, polyvinyl acetal resins, Polyethylene resin Polypropy
- 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 molecule has one or more carbon-carbon double bonds or / and SiH groups having reactivity with SiH groups in the molecule on average. It is preferable.
- 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 that the compatibility with the component (A) or the component (B) tends to be good. The following is more preferable. 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 in 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.
- 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 As the hindered phenol-based anti-aging agent, various types such as Irganox 1010 available from Ciba Specialty Chemicals are used. *
- Sulfur-based 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. *
- anti-aging agents may be used independently and may be used together 2 or more types.
- 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.
- 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.
- 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 such as acetone, a ketone solvent such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and a halogen solvent such as chloroform, methylene chloride, and 1,2-dichloroethane can be preferably used.
- 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.
- 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.
- 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 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 viscoelasticity measurement using a 3 mm x 5 mm x 30 mm prismatic test piece under the conditions of tensile mode, measurement frequency 10 Hz, strain 0.1%, static / power ratio 1.5, temperature rising side 5 ° C / min ( Tg is a peak temperature of tan ⁇ of DVA-200 manufactured by IT Measurement & Control Co.). *
- 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 (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. Ask. On the other hand, the same extract was analyzed by ion chromatography (using DX-500 manufactured by Dionex, column: AS12-SC), and the obtained Cl and Br content values were converted to the concentrations in the cured product used. Ask. 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 has a spectral reflectance at 420 nm, 440 nm, and 460 nm after curing of 80 R% or more, and a spectral reflectance retention ratio after a heat test at 180 ° C. for 72 hours (after the heat test).
- Spectral reflectance / initial spectral reflectance ⁇ 100 is desirably 90% or more.
- the spectral reflectance of the cured product is examined as follows. Spectral reflectance at wavelengths of 400 nm to 700 nm (20 nm intervals) was measured using a micro-surface spectral color difference meter (VSS400 manufactured by Nippon Denshoku Industries Co., Ltd.).
- the spectral reflectance is preferably 75% or more and more preferably 80% or more in the wavelength band of 420 to 700 nm from the viewpoint that the light extraction efficiency of the light emitting diode tends to be high.
- the retention rate with respect to the initial spectral reflectance of the spectral reflectance after the heat resistance test was obtained by the following calculation formula.
- Retention rate (%) (spectral reflectance after heat test) / (initial spectral 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 at a surface wavelength of 470 nm is preferably 90% or more, more preferably 95% or more, 97 % Or more is more preferable, and 99% or more is particularly preferable.
- the light reflectance of the surface can be measured as follows. Using a PET film as a release film, a 0.5 mm-thick molded body without voids is prepared by press molding under a predetermined temperature condition. The obtained molded body is subjected to predetermined post-curing as necessary. It can obtain
- the curable resin composition of the present invention can be made into a curable resin composition tablet when it contains at least the component (F) in addition to the components (A) to (E). Specifically, at least one of the curable resin composition tablet cures the component (A) and the component (B), the component (A) and the component (B) that are liquids having a viscosity at 23 ° C. of 50 Pa seconds or less. (C) component, (E) component and (F) component which are both powder, Furthermore, (D) component is contained, It is characterized by the above-mentioned.
- 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 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 ratio of the component (E) and the component (F) in the curable resin composition tablet of the present invention (hereinafter sometimes referred to as a filling rate) is preferably 70 to 95% by weight.
- the distribution of the (E) component and the (F) component in the filling rate is not particularly limited and can be set freely.
- the filling rate is 70% by weight or less, the thermal expansion coefficient of the resulting cured product becomes large, causing a problem of dimensional change of the molded product, and the resulting curable resin composition becomes a hard paste or clay. There is a problem that can not be tableted.
- the filling rate is 95% by weight or more, the viscosity at high temperature becomes too high and the moldability may be lowered, and the resulting tablet may become 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.
- the proportion of particles of 12 ⁇ m or less in the total powder of the component (E) and the component (F) is 40% by volume or more, so that tableting and moldability are achieved. It was found that both can be achieved.
- 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.
- an aliphatic organic compound having at least two carbon-carbon double bonds having reactivity with SiH groups as proposed in Japanese Patent Application Laid-Open Nos. 2002-80733 and 2002-88244, 1
- a sealant made of a curable resin composition containing a compound having at least two SiH groups in the molecule and a hydrosilylation catalyst may be used. Adhesion with the package resin is better when this sealant is used. It is preferable in that it is highly effective and the effect of high transparency and high light resistance of the package of the present invention is remarkable. On the other
- a lens in the case of a light emitting diode or a light receiving element, a lens can be further applied, and a sealing agent can be molded into a lens shape to have a lens function.
- thermosetting resins such as thermoplastic resins, epoxy resins, and silicone resins
- injection 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 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. Also, when 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.
- 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 curable resin composition of the present invention desirably has a package warpage of ⁇ 1.0 mm or less when formed into a package by molding on one side of a lead frame for a light emitting diode.
- the warpage in this case is measured based on the maximum warpage measuring method described in JIS C 6481.
- a semiconductor package is suspended vertically at the center of one side, and a straight ruler is applied parallel to that side.
- the straight ruler is applied to the concave surface of the semiconductor package, and the maximum distance between the straight ruler and the substrate surface of the semiconductor package is measured to a unit of 1.0 mm with a metal straight scale.
- the resin is molded on the concave surface of the semiconductor package, measure the maximum distance between the straight ruler and the resin surface molded on the semiconductor package to a unit of 1.0 mm with a metal linear scale. The value obtained by subtracting the thickness is rounded off to the nearest 1.0 mm. The other sides are also measured sequentially, and the greatest gap is warped.
- the semiconductor package shown by the (molding method) of an Example was used for the semiconductor package used for measurement of curvature.
- 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.
- compositions A to D were prepared by blending each component according to the contents of Table 1.
- TMA thermomechanical analysis
- a tablet-like sample molded to a thickness of 20 ⁇ 20 ⁇ 4.0 mm is cut into a 20 ⁇ 10 ⁇ 4.0 mm with a diamond cutter, and the temperature is raised in a compression mode using a BRUKER burning thermal analyzer TMA4000SA in the 20 mm direction.
- the dimensional change was measured when changing to heating to 280 ° C. at a rate of 5 ° C./min, holding for 20 minutes, and cooling to room temperature.
- the point at which the inclination of the chart during heating changes was Tg, and the linear expansion coefficient ⁇ 1 of Tg or less and the linear expansion coefficient ⁇ 2 of Tg or more were obtained.
- a package (MAP type) having a shape in which a resin is molded on one side of a metal was obtained by transfer molding. Molding was performed under the following conditions. Molding temperature: 170 ° C Molding time: 180 seconds Molding pressure: 7.8 to 13.7 MPa Further, after the above molding, curing was performed at 180 ° C. for 1 hour.
- Table 4 shows the blending ratio of each component of the curable resin composition.
- the raw materials used for the component (D), the component (E), and the component (F) are as follows.
- Table 4 shows the final blending ratio of each component of the curable resin composition and the properties of the resin.
- a lead frame made of Cu with 50 mm in length, 55 mm in width, and 0.25 mm in thickness is prepared.
- the MAP after molding 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 white 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.
- a conceptual diagram of the molded product is shown in FIG.
- 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, formed into a cylindrical shape, loaded into a cylinder, and molded. The molding conditions were 150 ° C. and 5 minutes. After molding, it was post-cured (aftercured) in a hot air oven at 150 ° C. for 1 hour + 180 ° C. for 30 minutes.
- warpage The warpage was measured by the following method based on the method for measuring the maximum warpage described in JIS C 6481.
- the semiconductor package is suspended vertically at the center of one side, and a straight ruler is applied to the concave side of the semiconductor package so that it is parallel to that side, and the maximum gap between the straight ruler and the substrate surface of the semiconductor package is The scale was measured to a unit of 1.0 mm.
- the resin is molded on the concave surface of the semiconductor package, measure the maximum distance between the straight ruler and the resin surface molded on the semiconductor package to a unit of 1.0 mm with a metal linear scale.
- the value obtained by subtracting the thickness was rounded to the nearest 1.0 mm.
- the other sides were also measured sequentially, and the greatest gap was warped.
- Table 4 Comparing the example and the comparative example, it can be seen that when the component (D) is added, a semiconductor package having a warpage of 1.0 mm or less can be obtained.
- the curable resin composition shown in Table 4 is made of a PET film as a release film, a rectangular mold made of stainless steel (SUS304) having an inner dimension of 80 mm ⁇ 50 mm and a thickness of 0.5 mm, and a condition of 150 ° C./5 minutes. And press-molded.
- the produced rectangular plate-shaped press-molded body was post-cured in an oven at 150 ° C./1 hour and 180 ° C./0.5 hour.
- the resulting molded product was measured for light reflectance at a wavelength of 470 nm using a spectrophotometer (manufactured by JASCO Corporation, UV-visible spectrophotometer V-560) equipped with an integrating sphere.
- the reflectance was measured using a Spectralon plate manufactured by Labsphere as a standard plate. The measurement results are shown in Table 4.
- Table 5 shows the blending ratio of each component of the curable resin composition.
- Each raw material used is as follows.
- Table 6 shows the final proportions of the components (A), (B), (C), (D), (E), and (F).
- the curable resin composition shown in Table 5 is made of a PET film as a release film, a stainless steel (SUS304) rectangular mold having an internal dimension of 80 mm ⁇ 50 mm and a thickness of 0.5 mm, and a condition of 150 ° C./5 minutes. And press-molded.
- the produced rectangular plate-shaped press-molded body was post-cured in an oven at 150 ° C./1 hour and 180 ° C./0.5 hour to produce a flat plate.
- test piece was cut out so that 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. As shown in FIG. 4, the test piece was installed between the metal fulcrums with rounded corners so that the shape formed between the fulcrums was rectangular. About the test piece width and thickness, 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. Manufactured by Stable Micro Systems.
- a pressure wedge made of a right-angled triangle 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 (maximum load) ) was measured. The values of the five measurements were averaged to obtain a measurement result. The maximum stress was calculated by dividing the maximum load by the area. Table 6 shows the measurement results.
- titanium oxide surface-treated with an aluminum compound in addition to using surface treatment with an aluminum compound and a silica compound, titanium oxide that has been surface-treated with an organic silicon compound or an organic compound is the maximum. It can be seen that the load is large. It is considered that the reason why the surface treatment with the aluminum compound alone is better is the dispersibility of the titanium oxide as the component (D) in the curable resin composition.
- a lead frame made of Cu with 50 mm in length, 55 mm in width, and 0.25 mm in thickness is prepared.
- the MAP after molding 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 white 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.
- Transfer molding was performed using a G-Line manual press manufactured by Apic Yamada Co., Ltd.
- the values shown in Table 8 were set for the mold clamping force 30 ton, the injection pressure, and the injection speed.
- a white compound of 5.0 g is weighed, shaped into a cylindrical shape, loaded into a cylinder, and sprayed with a fluorine type mold release agent (Daikin Kogyo Co., Ltd .: Die Free GA-7500). did. Molding conditions are 170 ° C./3 minutes. After molding, it was post-cured at 180 ° C./1 h.
- the filling rate was determined by the ratio of the unfilled area when the compound resin was completely filled in the molded part as 100%.
- 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.
- the 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.
- Examples 19 to 22 Components shown in Table 9 were mixed to obtain a curable resin composition of the present invention.
- the obtained curable resin composition was pasty, it was kneaded with a stirring bar to make it uniform.
- clay In the case of clay, it was homogenized by repeating the work of stretching with a round bar-shaped jig and then folding and stretching again.
- flakes or powders In the case of flakes or powders, they were crushed with a mortar and made uniform.
- the curable resin composition shown in Table 9 is a condition of 170 ° C./3 minutes using a rectangular form made of stainless steel (SUS304) having a PET film as a release film, an internal dimension of 80 mm ⁇ 50 mm, and a thickness of 0.5 mm. And press-molded.
- the formed rectangular plate-shaped press-molded body was post-cured in an oven at 180 ° C./1 hour. This was cut into a size of 50 mm ⁇ 25 mm to obtain a sample for evaluation.
- the durability test a heat resistance test, a light resistance test, and a constant temperature and humidity test were performed by the following methods. Before the endurance test, the light reflectance of the sample at a wavelength of 470 nm was measured and used as the initial reflectance.
- the light reflectance at a wavelength of 470 nm was measured using a spectrophotometer (manufactured by JASCO Corporation, UV-visible spectrophotometer V-560) equipped with an integrating sphere. The reflectance was measured using a Spectralon plate manufactured by Labsphere as a standard plate. The measurement results are shown in Table 9.
Abstract
Description
しかし、樹脂は一般に線膨張係数が大きく、一般に小さな線膨張係数を有する金属材料と線膨張係数が整合しにくいことから、加熱成形時、後硬化時、あるいは半導体部品として使用中における種々の加熱-冷却を伴う工程において反り、剥離、割れ、半導体へのダメージなどといった問題を生ずる場合がある。
しかし、近年半導体から発生する熱量の増大により放熱性の高い設計が求められるようになっており、熱をパッケージの外へ有効に導くために、半導体素子を接着する金属がパッケージの底面を形成するようなパッケージ設計がなされるようになってきている(特許文献1、2)。
その場合、上記のような反りの低減化をとることができず、反りの問題が重要となってくる。
しかし、線膨張を低減させるために無機フィラーを大量に充填すると樹脂の成形時の流動性が低下して成型加工性を損なうため限界があり、また低弾性化すると樹脂の強度が低下して半導体素子を保護するというパッケージとしての主要機能を損なうことにもなる。
以上のことから、半導体のパッケージにおいて反りを低減化できる硬化性樹脂が求められている。
(1)(A)SiH基と反応性を有する炭素-炭素二重結合を1分子中に少なくとも2個含有する有機化合物、
(B)1分子中に少なくとも2個のSiH基を含有する化合物、
(C)ヒドロシリル化触媒、
(D)SiH基と反応性を有する炭素-炭素二重結合を1分子中に少なくとも1個含有するシリコーン化合物、
(E)無機充填材、
を必須成分として含有することを特徴とする硬化性樹脂組成物。
(3)(D)成分の重量平均分子量が1,000以上かつ1,000,000以下である(1)または(2)に記載の硬化性樹脂組成物。
(4)(E)成分が球状シリカである(1)~(3)のいずれかに記載の硬化性樹脂組成物。
(6)(F)成分の平均粒子径が1.0μm以下である(5)に記載の硬化性樹脂組成物。
(7)(F)成分が酸化チタンである(5)または(6)に記載の硬化性樹脂組成物。
(8)(F)成分が有機シロキサンにより表面処理された酸化チタンである(7)に記載の硬化性樹脂組成物。
(9)(F)成分が無機化合物で表面処理された酸化チタンである(7)に記載の硬化性樹脂組成物。
(10)(F)成分がアルミニウム化合物で表面処理されている(9)に記載の硬化性樹脂組成物。
(11)(F)成分が酸化亜鉛、酸化ジルコニア、酸化ストロンチウム、酸化ニオブ、窒化ホウ素、チタン酸バリウム及び硫酸バリウムから選ばれる少なくとも一種である(5)または(6)に記載の硬化性樹脂組成物。
(13)(G)成分がステアリン酸金属塩である(12)に記載の硬化性樹脂組成物。
(14)(G)成分がステアリン酸カルシウム、ステアリン酸マグネシウム、ステアリン酸亜鉛、ステアリン酸アルミニウムからなる群より選択される1つ以上である(13)に記載の硬化性樹脂組成物。
(16)硬化性樹脂組成物全体に占める(E)成分の合計の量が70重量%以上である(1)~(15)のいずれかに記載の硬化性樹脂組成物。
(17)硬化性樹脂組成物全体に占める(F)成分の含有量が10重量%以上である(5)~(16)のいずれかに記載の硬化性樹脂組成物。
(18)硬化性樹脂組成物全体に占める(G)成分の含有量が0.01~5重量%である(12)~(17)のいずれかに記載の硬化性樹脂組成物。
(20)硬化させてなる成形体の表面の波長470nmの光線反射率が90%以上である(1)~(19)のいずれかに記載の硬化性樹脂組成物。
(21)発光ダイオード用のリードフレームの片面に成形してパッケージとした場合の、パッケージの反りが±1.00mm以下である(1)~(20)のいずれかに記載の硬化性樹脂組成物。
(22)半導体のパッケージに用いられる(1)~(21)のいずれかに記載の硬化性樹脂組成物。
(A)成分および(B)成分の少なくとも一方が23℃における粘度が50Pa秒以下の液体であり、
(E)成分と(F)成分の合計の含有量が70~95重量%であり、
(E)成分と(F)成分の合計に占める12μm以下の粒子の割合が40体積%以上であることを特徴とする硬化性樹脂組成物タブレット。
(26)(22)に記載の硬化性樹脂組成物を用いて金属と一体成形したことを特徴とする半導体のパッケージ。
(27)硬化性樹脂組成物とリードフレームとをトランスファーモールドにより一体成形した(25)または(26)に記載の半導体のパッケージ。
(28)半導体のパッケージが実質的に金属の片面に樹脂が成形されてなるパッケージである、(25)~(27)のいずれかに記載の半導体のパッケージ。
(29)(22)に記載の硬化性樹脂組成物を用いてトランスファー成形されたことを特徴とする半導体のパッケージ。
(31)(25)~(29)のいずれかに記載の半導体のパッケージを用いて製造された発光ダイオード。
(A)SiH基と反応性を有する炭素-炭素二重結合を1分子中に少なくとも2個含有する有機化合物、
(B)1分子中に少なくとも2個のSiH基を含有する化合物、
(C)ヒドロシリル化触媒、
(D)SiH基と反応性を有する炭素-炭素二重結合を1分子中に少なくとも1個含有するシリコーン化合物、
(E)無機充填材、を必須成分として含有することを特徴とする硬化性樹脂組成物である。
以下、各成分について説明する。
(A)成分はSiH基と反応性を有する炭素-炭素二重結合を1分子中に少なくとも2個含有する有機化合物であれば特に限定されない。
有機化合物としてはポリシロキサン-有機ブロックコポリマーやポリシロキサン-有機グラフトコポリマーのようなシロキサン単位(Si-O-Si)を含むものではなく、構成元素としてC、H、N、O、S及びハロゲン以外の元素を含まない化合物がより好ましい。
シロキサン単位を含むものの場合は、半導体のパッケージとリードフレームや封止樹脂との接着性が低くなりやすいという問題がある。
((A)成分が重合体の場合の例)
有機重合体系の(A)成分としては、例えば、ポリエーテル系、ポリエステル系、ポリアリレート系、ポリカーボネート系、飽和炭化水素系、不飽和炭化水素系、ポリアクリル酸エステル系、ポリアミド系、フェノール-ホルムアルデヒド系(フェノール樹脂系)、ポリイミド系の骨格を有するものを挙げることができる。
等が挙げられる。
有機単量体系の(A)成分としては例えば、フェノール系、ビスフェノール系、ベンゼン、ナフタレン等の芳香族炭化水素系:直鎖系、脂環系等の脂肪族炭化水素系:複素環系の化合物およびこれらの混合物等が挙げられる。
SiH基と反応性を有する炭素-炭素二重結合の結合位置は特に限定されず、分子内のどこに存在してもよい。
SiH基と反応性を有する炭素-炭素二重結合は(A)成分の骨格部分に直接結合していてもよく、2価以上の置換基を介して共有結合していても良い。2価以上の置換基としては炭素数0~10の置換基であれば特に限定されないが、構成元素としてC、H、N、O、S、およびハロゲン以外の元素を含まないものが好ましい。これらの置換基の例としては、
有機重合体系の(A)成分の具体的な例としては、1,2-ポリブタジエン(1,2比率10~100%のもの、好ましくは1,2比率50~100%のもの)、ノボラックフェノールのアリルエーテル、アリル化ポリフェニレンオキサイド、
(A)成分としては、耐熱性をより向上し得るという観点からは、SiH基と反応性を有する炭素-炭素二重結合を(A)成分1gあたり0.001mol以上含有するものが好ましく、1gあたり0.005mol以上含有するものがより好ましく、0.008mol以上含有するものがさらに好ましい。
(A)成分としては、耐熱性および耐光性が特に高いという観点からは、下記一般式(III)
また、(B)成分と良好な相溶性を有するという観点、および(A)成分の揮発性が低くなり、得られるパッケージからのアウトガスの問題が生じ難いという観点からは、(A)成分の例として上記したような、SiH基と反応性を有する炭素-炭素二重結合を1分子中に少なくとも2個含有する有機化合物から選ばれた1種以上の化合物と、SiH基を有する化合物(β)との反応物も好ましい。
(β)成分は、SiH基を有する化合物であり、SiH基を有する鎖状及び/又は環状のポリオルガノシロキサンもその例である。
次に、本発明の(A)成分として、SiH基と反応性を有する炭素-炭素二重結合を1分子中に少なくとも2個含有する有機化合物と(β)成分をヒドロシリル化反応して得ることができる化合物を用いる場合の、SiH基と反応性を有する炭素-炭素二重結合を1分子中に少なくとも2個含有する有機化合物と(β)成分とのヒドロシリル化反応に関して説明する。
(A)成分としてはその他の反応性基を有していてもよい。この場合の反応性基としては、エポキシ基、アミノ基、ラジカル重合性不飽和基、カルボキシル基、イソシアネート基、ヒドロキシル基、アルコキシシリル基等が挙げられる。これらの官能基を有している場合には得られる硬化性樹脂組成物の接着性が高くなりやすく、得られる硬化物の強度が高くなりやすい。接着性がより高くなりうるという点からは、これらの官能基のうちエポキシ基が好ましい。また、得られる硬化物の耐熱性が高くなりやすいという点においては、反応性基を平均して1分子中に1個以上有していることが好ましい。
(A)成分は、単独もしくは2種以上のものを混合して用いることが可能である。
(B)成分は、1分子中に少なくとも2個のSiH基を含有する化合物である。
(A)成分と良好な相溶性を有するという観点、および(B)成分の揮発性が低くなり得られる硬化性樹脂組成物からのアウトガスの問題が生じ難いという観点からは、(B)成分は、SiH基と反応性を有する炭素-炭素二重結合を1分子中に1個以上含有する有機化合物(α)と、1分子中に少なくとも2個のSiH基を有する化合物(β)を、ヒドロシリル化反応して得ることができる化合物であることが好ましい。
ここで(α)成分は上記した(A)成分である、SiH基と反応性を有する炭素-炭素二重結合を1分子中に少なくとも2個含有する有機化合物と同じもの(α1)も用いることができる。(α1)成分を用いると得られる硬化物の架橋密度が高くなり力学強度が高い硬化物となりやすい。
(α2)成分としては、SiH基と反応性を有する炭素-炭素二重結合を1分子中に1個含有する有機化合物であれば特に限定されないが、(B)成分が(A)成分と相溶性がよくなるという点においては、化合物としてはポリシロキサン-有機ブロックコポリマーやポリシロキサン-有機グラフトコポリマーのようなシロキサン単位(Si-O-Si)を含むものではなく、構成元素としてC、H、N、O、S、およびハロゲンのみを含むものであることが好ましい。
(β)成分は、1分子中に少なくとも2個のSiH基を有する化合物であり、鎖状及び/又は環状のポリオルガノシロキサンもその例である。
次に、本発明の(B)成分として、(α)成分と(β)成分をヒドロシリル化反応して得ることができる化合物を用いる場合の、(α)成分と(β)成分とのヒドロシリル化反応に関して説明する。
(A)成分と(B)成分の組合せについては(A)成分の例として挙げたものおよびそれらの各種混合物/(B)成分の例として挙げたものおよびそれらの各種混合物、の各種組み合わせを挙げることができる。
(C)成分はヒドロシリル化触媒である。
本発明の(D)成分は、SiH基と反応性を有する炭素-炭素二重結合を1分子中に少なくとも1個含有するシリコーン化合物である。(D)成分を用いることにより(E)成分の無機充填材と混合した場合に、より小さな線膨張係数を有する硬化物を与える硬化性樹脂組成物とすることができる。
(式中、Rは水酸基、メチル基あるいはフェニル基から選ばれる基であり、n、mは0≦n<4、0<m≦4、0<n+m≦4を満たす数)
(D)成分の例としては、末端基あるいは側鎖基としてビニル基を有するポリジメチルシロキサン、ポリジフェニルシロキサン、ポリメチルフェニルシロキサンやこれら2種あるいは3種のランダムあるいはブロック共重合体、1,3-ジビニルテトラメチルジシロキサン、1,3,5,7-テトラビニルシクロテトラシロキサンなどを挙げることができる。(D)成分としては複数のものを混合して用いてもよい。
(E)成分は、得られる硬化物の強度や硬度を高くしたり、線膨張率を低減化したりする効果を有する。
本発明の硬化性樹脂組成物は、白色顔料((F)成分)を含有することが望ましい。
(F)成分は白色顔料であり、得られる硬化物の光線反射率を高める効果を有する。
(F)成分としては種々のものを用いることができ、例えば、酸化チタン、酸化亜鉛、酸化マグネシウム、酸化アンチモン、酸化ジルコニア、酸化ストロンチウム、酸化ニオブ、窒化ホウ素、チタン酸バリウム、硫化亜鉛、硫酸バリウム、炭酸マグネシウム、中空ガラス粒子、などが挙げられる。中でも、取り扱いの容易性や入手性、コストの観点から酸化チタンまたは酸化亜鉛が好ましい。
一方、硬化性樹脂組成物の流動性が高いという点では、0.05μm以上であることが好ましく、0.1μm以上であることがより好ましい。
平均粒径は、レーザー回折散乱式粒度分布計を用いて測定することができる。
(F)成分の表面処理では、(F)成分の表面に無機化合物、有機化合物から選ばれる少なくとも1種を被覆する。無機化合物としては、例えば、アルミニウム化合物、ケイ素化合物、ジルコニウム化合物、スズ化合物、チタニウム化合物、アンチモン化合物等が挙げられ、また、有機化合物としては、多価アルコール、アルカノールアミン又はその誘導体、有機シロキサン等の有機ケイ素化合物、高級脂肪酸又はその金属塩、有機金属化合物等が挙げられる。
(F)成分の表面に無機化合物や有機化合物を被覆する場合は、湿式法や乾式法の公知の方法を用いて、例えば酸化チタンの乾式粉砕の際、スラリー化した際あるいは湿式粉砕した際に行うことができる。他にも、液相法、気相法等、種々の方法が挙げられる。
その場合の有機シロキサン処理剤としては種々のものが適用される。例えば、ポリジメチルシロキサン、ポリメチルフェニルシロキサン、ポリメチルハイドロジェンシロキサン、あるいはそれらの共重合体などのポリシロキサン類、ヘキサメチルシクロトリシロキサン、ヘプタメチルシクロテトラシロキサン、1,3,5,7-テトラメチルシクロテトラシロキサン、などのシクロシロキサン類、トリメチルクロロシラン、ジメチルジクロロシラン、メチルトリクロロシランなどのクロロシラン類、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルトリエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリエトキシシラン等のエポキシ官能基を有するシラン類、3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルトリエトキシシラン、3-アクリロキシプロピルトリメトキシシラン、3-アクリロキシプロピルトリエトキシシラン、メタクリロキシメチルトリメトキシシラン、メタクリロキシメチルトリエトキシシラン、アクリロキシメチルトリメトキシシラン、アクリロキシメチルトリエトキシシラン等のメタクリル基あるいはアクリル基を有するシラン類、ビニルトリクロロシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス(β-メトキシエトキシ)シラン、ビニルトリアセトキシシラン等のビニル基を有するシラン類、γ-メルカプトプロピルトリメトキシシラン、γ-メルカプトプロピルメチルジメトキシシラン等のメルカプトシラン類、γ-アミノプロピルトリエトキシシラン、γ-[ビス(β-ヒドロキシエチル)]アミノプロピルトリエトキシシラン、N-β-(アミノエチル)-γ-アミノプロピルトリメトキシシラン、γ-(β-アミノエチル)アミノプロピルジメトキシメチルシラン、N-(トリメトキシシリルプロピル)エチレンジアミン、N-(ジメトキシメチルシリルイソプロピル)エチレンジアミン、N-β-(N-ビニルベンジルアミノエチル)-γ-アミノプロピルトリメトキシシラン等のアミノ基を有するシラン類、イソシアネートプロピルトリメトキシシラン、イソシアネートプロピルトリエトキシシラン等のイソシアネート基を有するシラン類、メチルトリメトキシシラン、メチルトリエトキシシラン、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、オクチルトリメトキシシラン、オクチルトリエトキシシラン等のアルキル基を有するシラン類、γ-クロロプロピルトリメトキシシラン、γ-アニリノプロピルトリメトキシシラン等のその他のシラン類等の各種シラン類で例示されるシランカップリング剤や、ヘキサメチルジシロキサン、ヘキサメチルジシラザンなどを挙げることができる。これらの表面処理剤としては炭素-炭素二重結合を含まないものであることが好ましく、炭素-炭素二重結合を含むと耐熱性が低下しやすくなる。また、有機シロキサン以外の表面処理を併用することも可能であり、Al、Zr、Zn等で処理することもできる。
無機化合物による表面処理について特に限定されず、アルミニウム化合物、ケイ素化合物、ジルコニウム化合物、等種々の表面処理が用いられる。酸化チタンは、耐久性向上、媒体との親和性向上のため、あるいは、粒子形状の崩れを防止するなどの目的で無機化合物、有機化合物で表面処理する場合があるが、(F)成分を無機化合物で表面処理することで、硬化性樹脂組成物に含まれる成分との親和性が向上し、(F)成分の硬化性樹脂組成物に対する分散性が良くなり硬化物の強度が向上すると考えられる。
(E)成分および(F)成分の合計量は特に限定されないが、硬化性樹脂組成物全体に占める(E)成分および(F)成分の合計の量が85重量%以上であることが好ましく、90重量%以上であることがより好ましい。
(E)成分および(F)成分の合計量が少ないと、強度や硬度を高くしたり、線膨張率を低減化するという効果が得られにくくなる。
本発明の硬化性樹脂組成物は、金属石鹸((G)成分)を含有することが望ましい。
(G)成分は、硬化性樹脂組成物の離型性をはじめとする成型性を改良するために添加される。
本発明の硬化性樹脂組成物には種々の添加剤を添加することができる。
本発明の硬化性樹脂組成物の保存安定性を改良する目的、あるいは製造過程でのヒドロシリル化反応の反応性を調整する目的で、硬化遅延剤を使用することができる。硬化遅延剤としては、脂肪族不飽和結合を含有する化合物、有機リン化合物、有機イオウ化合物、窒素含有化合物、スズ系化合物、有機過酸化物等が挙げられ、これらを併用してもかまわない。
本発明の硬化性樹脂組成物には、接着性改良剤を添加することもできる。接着性改良剤としては一般に用いられている接着剤の他、例えば種々のカップリング剤、エポキシ化合物、フェノール樹脂、クマロン-インデン樹脂、ロジンエステル樹脂、テルペン-フェノール樹脂、α-メチルスチレン-ビニルトルエン共重合体、ポリエチルメチルスチレン、芳香族ポリイソシアネート等を挙げることができる。
ほう酸エステルの具体例として、ほう酸トリ-2-エチルヘキシル、ほう酸ノルマルトリオクタデシル、ほう酸トリノルマルオクチル、ほう酸トリフェニル、トリメチレンボレート、トリス(トリメチルシリル)ボレート、ほう酸トリノルマルブチル、ほう酸トリ-sec-ブチル、ほう酸トリ-tert-ブチル、ほう酸トリイソプロピル、ほう酸トリノルマルプロピル、ほう酸トリアリル、ほう酸トリエチル、ほう酸トリメチル、ほう素メトキシエトキサイドを好適に用いることができる。
熱硬化樹脂は樹脂を硬化させたものを、粉砕して粒子状態で混合してもよい。熱硬化性樹脂を分散させて用いる場合は、平均粒子径は種々設定できるが、好ましい平均粒子径の下限は10nmであり、好ましい平均粒子径の上限は10μmである。粒子系の分布はあってもよく、単一分散であっても複数のピーク粒径を持っていてもよいが、硬化性樹脂組成物の粘度が低く成形性が良好となりやすいという観点からは粒子径の変動係数が10%以下であることが好ましい。
本発明の硬化性樹脂組成物には特性を改質する等の目的で、種々の熱可塑性樹脂を添加することも可能である。熱可塑性樹脂としては種々のものを用いることができるが、例えば、メチルメタクリレートの単独重合体あるいはメチルメタクリレートと他モノマーとのランダム、ブロック、あるいはグラフト重合体等のポリメチルメタクリレート系樹脂(例えば日立化成社製オプトレッツ等)、ブチルアクリレートの単独重合体あるいはブチルアクリレートと他モノマーとのランダム、ブロック、あるいはグラフト重合体等のポリブチルアクリレート系樹脂等に代表されるアクリル系樹脂、ビスフェノールA、3,3,5-トリメチルシクロヘキシリデンビスフェノール等をモノマー構造として含有するポリカーボネート樹脂等のポリカーボネート系樹脂(例えば帝人社製APEC等)、ノルボルネン誘導体、ビニルモノマー等を単独あるいは共重合した樹脂、ノルボルネン誘導体を開環メタセシス重合させた樹脂、あるいはその水素添加物等のシクロオレフィン系樹脂(例えば、三井化学社製APEL、日本ゼオン社製ZEONOR、ZEONEX、JSR社製ARTON等)、エチレンとマレイミドの共重合体等のオレフィン-マレイミド系樹脂(例えば東ソー社製TI-PAS等)、ビスフェノールA、ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレン等のビスフェノール類やジエチレングリコール等のジオール類とテレフタル酸、イソフタル酸、等のフタル酸類や脂肪族ジカルボン酸類を重縮合させたポリエステル等のポリエステル系樹脂(例えば鐘紡社製O-PET等)、ポリエーテルスルホン樹脂、ポリアリレート樹脂、ポリビニルアセタール樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、ポリスチレン樹脂、ポリアミド樹脂、シリコーン樹脂、フッ素樹脂等の他、天然ゴム、EPDMといったゴム状樹脂が例示されるがこれに限定されるものではない。
本発明の硬化性樹脂組成物には老化防止剤を添加してもよい。老化防止剤としては、ヒンダートフェノール系等一般に用いられている老化防止剤の他、クエン酸やリン酸、硫黄系老化防止剤等が挙げられる。
本発明の硬化性樹脂組成物にはラジカル禁止剤を添加してもよい。ラジカル禁止剤としては、例えば、2,6-ジ-tert-ブチル-3-メチルフェノール(BHT)、2,2’-メチレン-ビス(4-メチル-6-tert-ブチルフェノール)、テトラキス(メチレン-3(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート)メタン等のフェノール系ラジカル禁止剤や、フェニル-β-ナフチルアミン、α-ナフチルアミン、N,N’-第二ブチル-p-フェニレンジアミン、フェノチアジン、N,N’-ジフェニル-p-フェニレンジアミン等のアミン系ラジカル禁止剤等が挙げられる。
本発明の硬化性樹脂組成物には紫外線吸収剤を添加してもよい。紫外線吸収剤としては、例えば2(2’-ヒドロキシ-3’,5’-ジ-tert-ブチルフェニル)ベンゾトリアゾール、ビス(2,2,6,6-テトラメチル-4-ピペリジン)セバケート等が挙げられる。
本発明の硬化性樹脂組成物は溶剤に溶解して用いることも可能である。使用できる溶剤は特に限定されるものではなく、具体的に例示すれば、ベンゼン、トルエン、ヘキサン、ヘプタン等の炭化水素系溶媒、テトラヒドロフラン、1, 4-ジオキサン、1,3-ジオキソラン、ジエチルエーテル等のエーテル系溶媒、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶媒、クロロホルム、塩化メチレン、1, 2-ジクロロエタン等のハロゲン系溶媒を好適に用いることができる。
さらに、本発明の硬化性樹脂組成物には必要に応じて、種々の発光ダイオード特性改善のための添加剤を添加してもよい。添加剤としては例えば、発光素子からの光を吸収してより長波長の蛍光を出す、セリウムで付活されたイットリウム・アルミニウム・ガーネット系蛍光体等の蛍光体や、特定の波長を吸収するブルーイング剤等の着色剤、光を拡散させるための酸化チタン、酸化アルミニウム、メラミン樹脂、CTUグアナミン樹脂、ベンゾグアナミン樹脂等のような拡散材、アルミノシリケート等の金属酸化物、窒化アルミニウム、窒化ボロン等の金属窒化物等の熱伝導性充填材等を挙げることができる。
本発明の硬化性樹脂組成物には成形時の離型性を改良するために種々の離型剤を添加してもよい。
離型剤としては、既に説明した(G)成分や、ワックス類等が挙げられる。
ワックス類としては、天然ワックス、合成ワックス、酸化または非酸化のポリオレフィン、ポリエチレンワックス等が例示できる。
尚、離型剤を添加しなくても十分な離型性が得られる場合には離型剤は用いない方がよい。
本発明の硬化性樹脂組成物には、その他、着色剤、難燃剤、難燃助剤、界面活性剤、消泡剤、乳化剤、レベリング剤、はじき防止剤、アンチモン-ビスマス等のイオントラップ剤、チクソ性付与剤、粘着性付与剤、保存安定改良剤、オゾン劣化防止剤、光安定剤、増粘剤、可塑剤、反応性希釈剤、酸化防止剤、熱安定化剤、導電性付与剤、帯電防止剤、放射線遮断剤、核剤、リン系過酸化物分解剤、滑剤、顔料、金属不活性化剤、熱伝導性付与剤、物性調整剤等を本発明の目的および効果を損なわない範囲において添加することができる。
本発明の硬化性樹脂組成物は、各成分および添加剤等の配合物をそのまま用いてもよいし、加熱等により部分的に反応(Bステージ化)させてから使用してもよい。Bステージ化することにより粘度調整が可能であり、トランスファー成形性を調整することもできる。また、硬化収縮をより抑制する効果もある。
本発明の硬化性樹脂組成物としては上記したように各種組み合わせのものが使用できるが、トランスファー成形などによる成形性が良好であるという点においては、硬化性樹脂組成物としては150℃以下の温度で流動性を有するものが好ましい。
耐熱性が良好であるという観点からは、硬化性樹脂組成物を硬化させて得られる硬化物のTgが100℃以上となるものが好ましく、150℃以上となるものがより好ましい。
硬化物の分光反射率は以下のように調べられる。
微小面分光色差計(日本電色工業社製VSS400)を用いて波長400nm~700nm(20nm間隔)における分光反射率を測定した。ここで各波長における測定値は、パッケージ上面の任意の4箇所(測定面積0.1mmφ)の測定値の平均値を採用した。
分光反射率は、発光ダイオードの光取りだし効率が高くなりやすいという点においては、420~700nmの波長帯域において75%以上が好ましく、80%以上であることがより好ましい。
保持率(%)=(耐熱試験後の分光反射率)/(初期の分光反射率)×100
保持率は、電子材料として用いた場合に信頼性が高いといった点においては、80%以上であることが好ましく、85%以上であることがより好ましく、90%以上であることがさらに好ましい。
表面の光線反射率は以下のように測定することができる。
PETフィルムを離型フィルムとして用い、所定の温度条件でプレス成形にてボイドのない0.5mm厚の成形体を作成する。得られた成形体に必要に応じて所定の後硬化を実施する。得られた成形体について積分球を設置した分光光度計を用いて470nmの全反射を測定することにより求めることができる。
本発明の硬化性樹脂組成物は、(A)~(E)成分に加えて、少なくとも(F)成分を含有する場合は、硬化性樹脂組成物タブレットとすることができる。
具体的には、硬化性樹脂組成物タブレットは、少なくとも一方が23℃における粘度が50Pa秒以下の液体である(A)成分および(B)成分、(A)成分と(B)成分を硬化させるための(C)成分、共に粉体である(E)成分および(F)成分、更には、(D)成分を含有することを特徴とする。
この硬化性樹脂組成物タブレットは、高温で(A)成分および(B)成分が粘度低下することによって硬化性樹脂組成物全体が流動可能となり、さらに加熱を続けると硬化反応が進行して所望の形状に成形することが可能である。
本発明のタブレットの形状は、特に限定されず、円柱状、角柱状、円盤状、球状などの形状を含むが、トランスファー成形に一般的な円柱状が好ましい。
充填率が70重量%以下であると、得られる硬化物の熱膨張率が大きくなって成形体の寸法変化が問題となることや、得られる硬化性樹脂組成物が硬いペースト状や粘土状となりタブレット化ができなくなる問題がある。充填率が95重量%以上であると、高温での粘度が高くなりすぎて成形性が低下することや、得られるタブレットが脆くなりすぎることがある。
言い換えると、粒子中の小粒子の割合を増やすことで、硬化性樹脂組成物の高温での流動性を維持したまま、常温での状態を固くすることができることになる。このことは、常温で固体のエポキシ樹脂やシリコーン系樹脂を用いた文献(特開2008-112977号公報や、特開2009-155415号公報)、また、粒子の粒度分布まで言及せず平均粒径のみを記載している特許文献3からは想到できない。
本発明で言う半導体のパッケージとは、半導体素子あるいは/および外部取出し電極等を支持固定あるいは/および保護するために設けられた部材である。半導体素子を直接被覆せず、外部取り出し電極等を支持固定するものや発光ダイオードのリフレクターのような半導体素子の周囲や底面を形成するものであってもよい。
本発明で言う半導体パッケージの成形方法としては各種の方法が用いられる。例えば、射出成形、トランスファー成形、RIM成形、キャスティング成形、プレス成形、コンプレッション成形等、熱可塑性樹脂やエポキシ樹脂、シリコーン樹脂等の熱硬化性樹脂に一般に用いられる各種成形方法が用いられる。これらの内、成形サイクルが短く成形性が良好であるという点においてはトランスファー成形が好ましい。成形条件も任意に設定可能であり、例えば成形温度についても任意であるが、硬化が速く成形サイクルが短く成形性が良好になりやすいという点においては100℃以上、より好ましくは120℃以上、さらに好ましくは150℃以上の温度が好ましい。上記のような各種方法によって成形した後、必要に応じて後硬化(アフターキュア)することも任意である。後硬化した方が耐熱性が高くなり易い。
本発明の半導体は従来公知の各種の用途に用いることができる。具体的には、ロジック、メモリーなどのLSI、各種センサー、受発光デバイスなどをあげることができる。また、半導体が発光ダイオードの場合も従来公知の各種の用途に用いることができる。具体的には、例えば液晶表示装置等のバックライト、照明、センサー光源、車両用計器光源、信号灯、表示灯、表示装置、面状発光体の光源、ディスプレイ、装飾、各種ライト等を挙げることができる。
本発明の硬化性樹脂組成物は、発光ダイオード用のリードフレームの片面に成形してパッケージとした場合の、パッケージの反りが±1.0mm以下であることが望ましい。
この場合の反りはJIS C 6481に記載の最大反りの測定方法に基づき測定される。半導体パッケージを一辺の中央で垂直に吊り下げ、その辺に平行に直定規を当てる。直定規は半導体パッケージの凹面に当て、直定規と半導体パッケージの基材面との最大の隔たりを金属製直尺で1.0mmの単位まで測定する。半導体パッケージの凹面に樹脂が成形されている場合は、直定規と半導体パッケージに成形された樹脂面との最大の隔たりを金属製直尺で1.0mmの単位まで測定し、その値から樹脂の厚み分を引いた値を、1.0mmの単位に四捨五入する。
他の辺についても順次測定し、最も大きな隔たりを反りとする。尚、反りの測定に用いる半導体パッケージは、実施例の(成型方法)で示した半導体パッケージを用いた。
5Lの四つ口フラスコに、攪拌装置、滴下漏斗、冷却管をセットした。このフラスコにトルエン1800g、1,3,5,7-テトラメチルシクロテトラシロキサン1440gを入れ、120℃のオイルバス中で加熱、攪拌した。トリアリルイソシアヌレート200g、トルエン200g及び白金ビニルシロキサン錯体のキシレン溶液(白金として3wt%含有)1.44mlの混合液を50分かけて滴下した。得られた溶液をそのまま6時間加温、攪拌した後、未反応の1,3,5,7-テトラメチルシクロテトラシロキサン及びトルエンを減圧留去した。1H-NMRの測定によりこのものは1,3,5,7-テトラメチルシクロテトラシロキサンのSiH基の一部がトリアリルイソシアヌレートと反応した以下の構造を有するものであることがわかった。
2Lオートクレーブにトルエン720g、1,3,5,7-テトラメチルシクロテトラシロキサン240gを入れ、気相部を窒素で置換した後、ジャケット温50℃で加熱、攪拌した。アリルグリシジルエーテル171g、トルエン171g及び白金ビニルシロキサン錯体のキシレン溶液(白金として3wt%含有)0.049gの混合液を90分かけて滴下した。滴下終了後にジャケット温を60℃に上げて40分反応、1H-NMRでアリル基の反応率が95%以上であることを確認した。トリアリルイソシアヌレート17g、トルエン17gの混合液を滴下した後、ジャケット温を105℃に上げて、トリアリルイソシアヌレート66g、トルエン66g及び白金ビニルシロキサン錯体のキシレン溶液(白金として3wt%含有)0.033gの混合液を30分かけて滴下した。滴下終了から4時間後に1H-NMRでアリル基の反応率が95%以上であることを確認し、冷却により反応を終了した。1,3,5,7-テトラメチルシクロテトラシロキサンの未反応率は0.8%だった。未反応の1,3,5,7-テトラメチルシクロテトラシロキサンとトルエンとアリルグリシジルエーテルの副生物(アリルグリシジルエーテルのビニル基の内転移物(シス体およびトランス体))が合計5,000ppm以下となるまで減圧留去し、無色透明の液体を得た。1H-NMRの測定によりこのものは1,3,5,7-テトラメチルシクロテトラシロキサンのSiH基の一部がアリルグリシジルエーテル及びトリアリルイソシアヌレートと反応したものであり平均的に以下の構造を有するものであることがわかった。
表1の内容に従って各成分を配合して組成物A~Dを調製した。
表2の内容に従って各成分を混合して本発明の硬化性樹脂組成物とした。
硬化性樹脂組成物を150℃にてプレス成形し、得られた成形体をオーブン中で150℃/1時間、180℃/0.5時間の条件で後硬化させた。このサンプルについて熱機械分析(TMA)を用いて線膨張係数を測定した。TMAの測定方法は、下記の通りである。
成形温度:170℃
成形時間:180秒
成形圧力:7.8~13.7MPa
さらに上記成形後に、180℃で1時間のキュアを行った。
上記成形により得られた硬化性樹脂組成物のパッケージおよび比較例2~6のパッケージについて、微小面分光色差計(日本電色工業社製VSS400)を用いて波長400nm~700nm(20nm間隔)における分光反射率を測定した。ここで各波長における測定値は、パッケージ上面の任意の4箇所(測定面積0.1mmφ)の測定値の平均値を採用した。また、耐熱試験(180℃のオーブンで72時間加熱する試験)後の分光反射率の初期の分光反射率に対する保持率を下記計算式によって求めた。
保持率(%)=(耐熱試験後の分光反射率)/(初期の分光反射率)×100
分光反射率の結果を表3に示す。
表4に、硬化性樹脂組成物の各成分の配合割合を記載した。(D)成分、(E)成分、および、(F)成分に使用した各原料は以下の通りである。
PDV2331(Gelest製、両末端ビニルのジフェニルジメチルシリコーン)
((E)成分)
球状シリカ(龍森製MSR-3500、比重2.2、平均粒径36.5μm、12μm以下の粒子の割合:19%)
球状シリカ(龍森製MSR-2212-TN、比重2.2、平均粒径24.8μm、12μm以下の粒子の割合:28%)
球状シリカ(アドマテックス製アドマファインSO-C2、比重2.2、平均粒径0.5μm、12μm以下の粒子の割合:100%)
((F)成分)
酸化チタン(石原産業製タイペークPC-3、ルチル型、比重4.2、塩素法、表面有機:Al、Si、ポリメチルハイドロジェンシロキサン、平均粒径0.21μm、12μm以下の粒子の割合:100%)
別途作成した組成物A、B、および(D)成分の混合液に、あらかじめ混合しておいた(F)成分および(E)成分の混合粉体を少量ずつ加えて混練した。得られた硬化性樹脂組成物がペースト状の場合は、攪拌棒で混練して均一化した。粘土状の場合は、丸棒状の冶具にて押し延ばした後、折り重ねて再度押し延ばす作業を繰り返して均一化した。フレーク状や粉体状の場合は、乳鉢ですり潰して均一化した。
作製した硬化性樹脂組成物がフレーク状や粉体状の場合、金属製の杵と臼からなるタブレット製造冶具で圧縮してタブレットとした。
硬化性樹脂組成物の各成分の最終的な配合割合、および樹脂の性状を表4に示した。
発光ダイオード用のリードフレームの片面に、表4に示した実施例6~8及び比較例7~9の硬化性樹脂組成物を成形してMAPタイプ(半導体のパッケージが実質的に金属の片面に樹脂が成形されている形状を有するタイプ)の発光ダイオード用パッケージを作製した。
反りはJIS C 6481に記載の最大反りの測定方法に基づき次に述べる方法で測定した。半導体パッケージを一辺の中央で垂直に吊り下げ、その辺に平行となるように、半導体パッケージの凹面側に直定規を当て、直定規と半導体パッケージの基材面との最大の隔たりを金属製直尺で1.0mmの単位まで測定した。半導体パッケージの凹面に樹脂が成形されている場合は、直定規と半導体パッケージに成形された樹脂面との最大の隔たりを金属製直尺で1.0mmの単位まで測定し、その値から樹脂の厚み分を引いた値を、1.0mmの単位に四捨五入した。他の辺についても順次測定し、最も大きな隔たりを反りとした。測定結果を表4に示した。
実施例と比較例を比較すると、(D)成分を入れた場合、反りが1.0mm以下の半導体パッケージを得られることがわかる。
表4の硬化性樹脂組成物を、PETフィルムを離型フィルムとし、内寸法が80mmx50mmであり厚み0.5mmのステンレス鋼(SUS304)製の長方形型枠を用いて、150℃/5分の条件でプレス成形した。作成した長方形板状のプレス成形体をオーブン中で150℃/1時間、180℃/0.5時間の条件で後硬化させた。得られた成形体について積分球を設置した分光光度計(日本分光(株)製、紫外可視分光光度計V-560)を用いて波長470nmの光線反射率を測定した。反射率は、ラブスフェア製スペクトラロン板を標準板として測定した。測定結果を表4に示した。
表5に、硬化性樹脂組成物の各成分の配合割合を記載した。使用した各原料は以下の通りである。
PDV2331(Gelest製、両末端ビニルのジフェニルジメチルシリコーン)
((E)成分)
球状シリカ(龍森製MSR-3500、比重2.2、平均粒径36.5μm、12μm以下の粒子の割合:19%)
((F)成分)
酸化チタン(石原産業製タイペークCR-60、ルチル型、比重4.2、塩素法、表面処理:アルミニウム化合物、平均粒径0.21μm、12μm以下の粒子の割合:100%)
酸化チタン(石原産業製タイペークPC-3、ルチル型、比重4.2、塩素法、表面処理:アルミニウム化合物、ケイ素化合物、有機ケイ素化合物、平均粒径0.21μm、12μm以下の粒子の割合:100%)
酸化チタン(石原産業製タイペークPF690、ルチル型、比重4.2、塩素法、表面処理:アルミニウム化合物、ケイ素化合物、有機化合物、平均粒径0.21μm、12μm以下の粒子の割合:100%)
別途作成した組成物A、B、および(D)成分の混合液に、あらかじめ混合しておいた(F)成分および(E)成分の混合粉体を少量ずつ加えて混練した。得られた硬化性樹脂組成物を、丸棒状の冶具にて押し延ばした後、折り重ねて再度押し延ばす作業を繰り返して均一化した。フレーク状や粉体状の場合は、乳鉢ですり潰して均一化した。
表5の硬化性樹脂組成物を、PETフィルムを離型フィルムとし、内寸法が80mmx50mmであり厚み0.5mmのステンレス鋼(SUS304)製の長方形型枠を用いて、150℃/5分の条件でプレス成形した。作成した長方形板状のプレス成形体をオーブン中で150℃/1時間、180℃/0.5時間の条件で後硬化させて、平板を作製した。
作製された平板から、試験片を、長さ50mm以上80mm以下、幅が7mmから8mm程度で向かい合う2辺が平行となるように切り出した。図4に示すように、角が丸い直方体の金属製の支点間に、支点間に形成される形が長方形となるように試験片を設置した。試験片幅と厚さについて、支点間に入る試験片の3箇所を0.01mmまで測定し、それぞれの平均値を測定結果とした。試験片幅と厚さから面積を算出した。Stable Micro Systems社製、テクスチャーアナライザーTA.plusにて、幅10mmの角の丸いガラス製の直角三角形からなる加圧くさびで、試験片の中央に2.0mm/secの速度で荷重を加え、試験片が折れたときの荷重(最大荷重)を測定した。5回測定の値を平均して測定結果とした。最大荷重を面積で割ることで最大応力を算出した。
表6に測定結果を示す。アルミニウム化合物による表面処理をした酸化チタンを用いた場合の方が、アルミニウム化合物およびシリカ化合物による表面処理に加えて、有機ケイ素化合物あるいは有機化合物による表面処理をした酸化チタンを用いた場合よりも、最大荷重が大きいことがわかる。単にアルミニウム化合物による表面処理のみをした方が、(D)成分の酸化チタンの硬化性樹脂組成物に対する分散性が良いことが要因と考えられる。
作製された試験片について、積分球を設置した分光光度計(日本分光(株)製、紫外可視分光光度計V-560)を用いて波長470nmの光線反射率を測定した。反射率は、ラブスフェア製スペクトラロン板を標準板として測定した。測定結果を表6に示した。
表7、8の内容に従って各成分を混合して本発明の硬化性樹脂組成物とした。
PETフイルム(25x30x0.15mm)とポリイミドテープでマスキングした1枚のSUS304板(冷間圧延ステンレス鋼板:(株)太佑機材製;25x70x0.15mm)とL字型に加工しパンチ穴を開けたSUS304板(25x50x0.15mm)の間に、硬化性樹脂組成物0.5gを挟み、室温条件下、5MPaで10秒間プレスした。これを170℃のホットプレート上で5kg加重をかけながら5分間圧着硬化させた。得られた硬化物成形体を170℃のホットプレート上で、SUS板テストサンプルのSUS304板の一端を抑えながら、L字に曲げたSUS304板にプッシュプルゲージ(DS2-20N:IMADA)を用いて5mm/sの速度でSUS304板を剥がしたときの樹脂剥離強度を測定した。さらに、剥離面の状態を観察し、樹脂自身が破壊した状態を凝集破壊(CF)、樹脂とSUS板間できれいに剥離した場合を界面剥離(AF)と評価した。
表8に示した実施例14~18の硬化性樹脂組成物を用いて下記の方法に従いMAP状リードフレーム付リフレクターを作製した。
充填率はコンパウンド樹脂が成形部に完全に充填された状態を100%としたときの未充填面積の割合で決定した。
MAP品の反りは成形部を上にして平滑な面に置いたとき、成形部が真横から見た状態凹になっている場合を順反り、凸になっている場合を逆反りと定義した。反りの程度はMAP品を平滑な面に置き、面から離れている4辺のうちで最も距離がある値(mm)を数値化した。
表9に記載の成分をそれぞれ混合し本発明の硬化性樹脂組成物を得た。得られた硬化性樹脂組成物がペースト状の場合は、攪拌棒で混練して均一化した。粘土状の場合は、丸棒状の冶具にて押し延ばした後、折り重ねて再度押し延ばす作業を繰り返して均一化した。フレーク状や粉体状の場合は、乳鉢ですり潰して均一化した。
表9の硬化性樹脂組成物を、PETフィルムを離型フィルムとし、内寸法が80mmx50mmであり厚み0.5mmのステンレス鋼(SUS304)製の長方形型枠を用いて、170℃/3分の条件でプレス成形した。作成した長方形板状のプレス成形体をオーブン中で180℃/1時間の条件で後硬化させた。これを50mmx25mmのサイズにカットし、評価用サンプルとした。
上記の通り作成したサンプルを、180℃に温度設定した対流式オーブン内(空気中)で20時間養生した。その後、波長470nmの光線反射率を測定した。
スガ試験機(株)製、メタリングウェザーメーター(形式M6T)を用いた。上記の通り作成したサンプルを、ブラックパネル温度120℃、放射照度0.53kW/m2で、積算放射照度50MJ/m2まで照射し、その後、波長470nmの光線反射率を測定した。
NAGANO SCIENCE社製、低温恒温恒湿器(LH43-13M)を用いた。上記の通り作成したサンプルを、温度85℃、85%RHで90時間養生した。その後、波長470nmの光線反射率を測定した。
耐久試験前後のサンプルについて、積分球を設置した分光光度計(日本分光(株)製、紫外可視分光光度計V-560)を用いて波長470nmの光線反射率を測定した。反射率は、ラブスフェア製スペクトラロン板を標準板として測定した。測定結果を表9に示した。
Claims (31)
- (A)SiH基と反応性を有する炭素-炭素二重結合を1分子中に少なくとも2個含有する有機化合物、
(B)1分子中に少なくとも2個のSiH基を含有する化合物、
(C)ヒドロシリル化触媒、
(D)SiH基と反応性を有する炭素-炭素二重結合を1分子中に少なくとも1個含有するシリコーン化合物、
(E)無機充填材、
を必須成分として含有することを特徴とする硬化性樹脂組成物。 - (D)成分がビニル基を末端に有する直鎖状ポリシロキサンである請求項1に記載の硬化性樹脂組成物。
- (D)成分の重量平均分子量が1,000以上かつ1,000,000以下である請求項1または2に記載の硬化性樹脂組成物。
- (E)成分が球状シリカである請求項1~3のいずれか1項に記載の硬化性樹脂組成物。
- 更に(F)白色顔料を含有する請求項1~4のいずれか1項に記載の硬化性樹脂組成物。
- (F)成分の平均粒子径が1.0μm以下である請求項5に記載の硬化性樹脂組成物。
- (F)成分が酸化チタンである請求項5または6に記載の硬化性樹脂組成物。
- (F)成分が有機シロキサンにより表面処理された酸化チタンである請求項7に記載の硬化性樹脂組成物。
- (F)成分が無機化合物で表面処理された酸化チタンである請求項7に記載の硬化性樹脂組成物。
- (F)成分がアルミニウム化合物で表面処理されている請求項9に記載の硬化性樹脂組成物。
- (F)成分が酸化亜鉛、酸化ジルコニア、酸化ストロンチウム、酸化ニオブ、窒化ホウ素、チタン酸バリウム及び硫酸バリウムから選ばれる少なくとも一種である請求項5または6に記載の硬化性樹脂組成物。
- 更に、(G)金属石鹸を含有する請求項1~11のいずれか1項に記載の硬化性樹脂組成物。
- (G)成分がステアリン酸金属塩である請求項12に記載の硬化性樹脂組成物。
- (G)成分がステアリン酸カルシウム、ステアリン酸マグネシウム、ステアリン酸亜鉛、ステアリン酸アルミニウムからなる群より選択される1つ以上である請求項13に記載の硬化性樹脂組成物。
- (A)成分および(B)成分の合計の重量に対する(D)成分の重量が30重量%以上である請求項1~14のいずれか1項に記載の硬化性樹脂組成物。
- 硬化性樹脂組成物全体に占める(E)成分の合計の量が70重量%以上である請求項1~15のいずれか1項に記載の硬化性樹脂組成物。
- 硬化性樹脂組成物全体に占める(F)成分の含有量が10重量%以上である請求項5~16のいずれか1項に記載の硬化性樹脂組成物。
- 硬化性樹脂組成物全体に占める(G)成分の含有量が0.01~5重量%である請求項12~17のいずれか1項に記載の硬化性樹脂組成物。
- 硬化後の420nm、440nm、460nmにおける分光反射率が80R%以上であり、180℃72時間の耐熱試験後の分光反射率の保持率(耐熱試験後の分光反射率/初期の分光反射率×100)が90%以上である請求項1~18のいずれか1項に記載の硬化性樹脂組成物。
- 硬化させてなる成形体の表面の波長470nmの光線反射率が90%以上である請求項1~19のいずれか1項に記載の硬化性樹脂組成物。
- 発光ダイオード用のリードフレームの片面に成形してパッケージとした場合の、パッケージの反りが±1.0mm以下である請求項1~20のいずれか1項に記載の硬化性樹脂組成物。
- 半導体のパッケージに用いられる請求項1~21のいずれか1項に記載の硬化性樹脂組成物。
- 請求項1~22のいずれか1項に記載の硬化性樹脂組成物のうち、(F)白色顔料を必須成分として含有する硬化性樹脂組成物からなるタブレットであって、
(A)成分および(B)成分の少なくとも一方が23℃における粘度が50Pa秒以下の液体であり、
(E)成分と(F)成分の合計の含有量が70~95重量%であり、
(E)成分と(F)成分の合計に占める12μm以下の粒子の割合が40体積%以上であることを特徴とする硬化性樹脂組成物タブレット。 - 請求項1~21のいずれか1項に記載の硬化性樹脂組成物を硬化してなり、表面の波長470nmの光線反射率が90%以上であることを特徴とする成形体。
- 請求項22に記載の硬化性樹脂組成物を用いて成形したことを特徴とする半導体のパッケージ。
- 請求項22に記載の硬化性樹脂組成物を用いて金属と一体成形したことを特徴とする半導体のパッケージ。
- 硬化性樹脂組成物とリードフレームとをトランスファーモールドにより一体成形した請求項25または26に記載の半導体のパッケージ。
- 半導体のパッケージが実質的に金属の片面に樹脂が成形されてなるパッケージである、請求項25~27のいずれか1項に記載の半導体のパッケージ。
- 請求項22に記載の硬化性樹脂組成物を用いてトランスファー成形されたことを特徴とする半導体のパッケージ。
- 請求項25~29のいずれか1項に記載の半導体のパッケージを用いて製造された半導体部品。
- 請求項25~29のいずれか1項に記載の半導体のパッケージを用いて製造された発光ダイオード。
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TW201200563A (en) | 2012-01-01 |
US9496468B2 (en) | 2016-11-15 |
TWI593758B (zh) | 2017-08-01 |
JPWO2011125753A1 (ja) | 2013-07-08 |
US20150188008A1 (en) | 2015-07-02 |
CN102844383B (zh) | 2016-01-20 |
CN102844383A (zh) | 2012-12-26 |
US9178120B2 (en) | 2015-11-03 |
US20130082369A1 (en) | 2013-04-04 |
JP5844252B2 (ja) | 2016-01-13 |
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