Classifications

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  • 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
  • C08K3/28—Nitrogen-containing compounds
• • C—CHEMISTRY; METALLURGY
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  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/14—Polycondensates modified by chemical after-treatment
  • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
  • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
  • C08G59/1444—Monoalcohols
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  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/14—Polycondensates modified by chemical after-treatment
  • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
  • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
  • C08G59/145—Compounds containing one epoxy group
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  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/223—Di-epoxy compounds together with monoepoxy compounds
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/24—Di-epoxy compounds carbocyclic
  • C08G59/245—Di-epoxy compounds carbocyclic aromatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
  • C08G59/5046—Amines heterocyclic
  • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
  • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
• • C—CHEMISTRY; METALLURGY
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  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/62—Alcohols or phenols
  • C08G59/621—Phenols
• • 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
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • 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
• • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
  • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
  • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins
  • H10W74/473—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins containing a filler
• • C—CHEMISTRY; METALLURGY
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  • 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
  • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
• • 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
  • C08K3/28—Nitrogen-containing compounds
  • C08K2003/282—Binary compounds of nitrogen with aluminium
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/005—Additives being defined by their particle size in general
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/011—Nanostructured additives

Definitions

• the present invention relates to epoxy resin compositions, liquid compression molding materials, glove top materials, and semiconductor devices.
• liquid curable resin compositions used for encapsulating semiconductor elements by compression molding are mainly solid resin compositions such as granules.
• liquid curable resin compositions are often used (hereinafter, such liquid curable resins used for sealing by compression molding
• the composition may be referred to as "liquid compression molding material” or “LCM (Lquid Compression Molding) material”).
• a liquid epoxy resin composition is often used as the liquid compression molding material from the viewpoint of a balance of properties such as electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness.
• WO2018/181737 WO2018/181600 Japanese Patent Application Laid-Open No. 2017-039802 JP 2011-079973 A JP 2016-023219 A JP 2005-248087 A Japanese Unexamined Patent Application Publication No. 2011-236118 JP 2014-005359 A JP 2017-195319 A JP 2017-110146 A
• the present invention has been made in view of the above circumstances. That is, the present invention provides an epoxy resin composition that is excellent in injectability and thermal conductivity of the cured product, and that can be used in the manufacture of semiconductor devices with high operational reliability, and a liquid compression molding material and a glove top material using the same. and a semiconductor device manufactured using these materials.
• the epoxy resin composition of the present invention is an epoxy resin composition containing (A) an epoxy resin, (B) a curing agent, (C) a curing catalyst, and (D) a filler.
• the (D) filler contains (D-1) an aluminum nitride filler, and the mixing ratio of the (D-1) aluminum nitride filler to the total amount of the (D) filler is It is characterized by being 70% by mass or more.
• (D-1) the average particle size of the aluminum nitride filler is 10.0 ⁇ m or less.
• (D-1) the uranium content of the aluminum nitride filler is 20 ppb or less.
• the ⁇ -ray dose of the cured product of the epoxy resin composition is 0.100 count/cm 2 ⁇ h or less.
• the ⁇ -ray dose of the cured product of the epoxy resin composition is 0.005 count/cm 2 ⁇ h or less.
• the cured epoxy resin composition preferably has a thermal conductivity of 1.5 W/m ⁇ K or more.
• the viscosity at 25°C is preferably 500.0 Pa ⁇ s or less.
• the average particle size of the (D-1) aluminum nitride filler is preferably 7.5 ⁇ m or less.
• the content of the (D) filler is 50.0 to 90.0 parts by mass with respect to 100 parts by mass of the total mass of the epoxy resin composition. is preferred.
• the (D) filler preferably further contains (D-2) silica filler.
• the average particle size of the (D-2) silica filler is 5 nm to 120 nm.
• (D-2) the uranium content of the silica filler is 20 ppb or less.
• the total mixing ratio of the (D-1) aluminum nitride filler and the (D-2) silica filler to the epoxy resin composition is from 60.0% by mass to It is preferably 85.0% by mass.
• the (D) filler preferably has an irregular shape.
• the (B) curing agent is any one selected from the group consisting of phenol-based curing agents, amine-based curing agents, and acid anhydride-based curing agents. Seeds or more are preferred.
• the curing agent (B) contains at least the phenolic curing agent, and the content ratio of the phenolic curing agent to the epoxy resin composition is 1. It is preferably from 5% by mass to 5% by mass.
• the liquid compression molding material of the present invention is characterized by containing the epoxy resin composition of the present invention.
• the glove top material of the present invention is characterized by containing the epoxy resin composition of the present invention.
• a semiconductor device of the first aspect of the present invention is characterized by comprising a sealing material made of a cured product of the liquid compression molding material of the present invention.
• a semiconductor device of the second aspect of the present invention is characterized by comprising a sealing material made of a cured glove top material of the present invention.
• an epoxy resin composition that is excellent in injectability and thermal conductivity of the cured product, and that can also be used in the manufacture of semiconductor devices with high operational reliability. Further, according to the present invention, it is possible to provide a liquid compression molding material and a glove top material using this epoxy resin. Furthermore, according to the present invention, it is possible to provide a semiconductor device manufactured using these materials.
• the epoxy resin composition of this embodiment is a resin composition containing (A) an epoxy resin, (B) a curing agent, (C) a curing catalyst, and (D) a filler.
• the (D) filler has (i) an average particle size of 10.0 ⁇ m or less and (ii) a uranium content of 20 ppb or less (D -1)
• An aluminum nitride filler is included, and the mixing ratio of (D-1) aluminum nitride filler to the total amount of (D) filler is 70% by mass or more.
• the aluminum nitride filler that satisfies the conditions (i) and (ii) may be simply abbreviated as "aluminum nitride filler".
• Aluminum nitride fillers that do not satisfy at least one of conditions (i) and (ii) are referred to as “other aluminum nitride fillers", and fillers made of materials other than aluminum nitride are referred to as "fillers made of other materials”.
• Fillers other than aluminum nitride fillers that satisfy the conditions (i) and (ii) in other words, both "other aluminum nitride fillers" and “fillers made of other materials” are collectively referred to as “other fillers”. .
• the aluminum nitride filler used as the filler has high thermal conductivity. Therefore, a cured product of the epoxy resin composition (ie, a sealing material for sealing a semiconductor element in a semiconductor device) has excellent thermal conductivity. Therefore, the semiconductor device is also excellent in heat dissipation.
• the aluminum nitride filler has an average particle size of 10.0 ⁇ m or less, the epoxy resin composition has excellent injectability.
• the content of uranium, which is the source of alpha rays is 20 ppb or less with respect to the total amount of aluminum nitride filler used as the filler.
• each component other than the filler does not substantially contain impurities such as uranium, which is a source of ⁇ -rays.
• the mixing ratio of the aluminum nitride filler having a uranium content of 20 ppb or less to the total amount of the filler is 70% by mass or more. That is, most of the filler is occupied by aluminum nitride filler with a small ⁇ -ray dose. As a result, the ⁇ -ray dose of the cured product of the epoxy resin composition of the present embodiment can be greatly reduced. Therefore, the semiconductor device manufactured using the epoxy resin composition of this embodiment has high operational reliability.
• the ⁇ -ray dose of the cured product can be very easily reduced to 0.100 count/cm 2 ⁇ h or less.
• the ⁇ -ray dose of the cured product is preferably 0.020 count/cm 2 ⁇ h or less, more preferably 0.010 count/cm 2 ⁇ h or less, and even more preferably 0.005 count/cm 2 ⁇ h or less.
• the ⁇ dose of the cured product should be as close to 0 count/cm 2 ⁇ h as possible.
• impurities such as uranium from the (D) filler blended in the epoxy resin composition. Therefore, the practical lower limit of the ⁇ -ray dose of the cured product may be 0.001 count/cm 2 ⁇ h or more.
• the mixing ratio of the aluminum nitride filler with a uranium content of 20 ppb or less relative to the total amount of the filler can be appropriately selected within the range of 70% by mass to 100% by mass.
• an aluminum nitride filler having a uranium content of 20 ppb or less and another filler are used in combination as the filler, the smaller the uranium content of the other filler, the better.
• the uranium content of other fillers is preferably 100 ppb or less, more preferably 20 ppb or less.
• Epoxy resin used in the epoxy resin composition of the present embodiment is not particularly limited as long as it is a variety of epoxy resins generally used for semiconductor encapsulation.
• the epoxy resin it is particularly preferable to use a polyfunctional type epoxy resin from the viewpoint of thermal cycle resistance and the like.
• the epoxy resin blended in the epoxy resin composition only one type of epoxy resin may be used, or two or more types of epoxy resins may be used in combination.
• one type of epoxy resin is used, the epoxy resin that is liquid at room temperature is used.
• each type of epoxy resin may be solid at normal temperature as long as the mixed state is liquid at normal temperature.
• epoxy resins include aliphatic epoxy resin compounds having at least one epoxy group in the molecule and no aromatic ring in the molecule, and compounds having at least one epoxy group in the molecule, and aromatic epoxy resin compounds having an aromatic ring in the molecule.
• the epoxy resin is not particularly limited as long as it is a variety of epoxy resins generally used for semiconductor encapsulation.
• the epoxy resin is not particularly limited as long as it is a variety of epoxy resins generally used for semiconductor encapsulation.
• Examples of aliphatic epoxy resin compounds include alkyl alcohol glycidyl ether [butyl glycidyl ether, 2-ethylhexyl glycidyl ether, etc.], alkenyl alcohol glycidyl ether [vinyl glycidyl ether, allyl glycidyl ether, etc.], etc., which have one epoxy group in the molecule.
• Bifunctional aliphatic epoxy resin compound having two epoxy groups in the molecule such as alkylene glycol diglycidyl ether, poly (alkylene glycol) diglycidyl ether, alkenylene glycol diglycidyl ether; Polyglycidyl ethers of trifunctional or higher alcohols such as methylolpropane, pentaerythritol, and dipentaerythritol [trimethylolpropane triglycidyl ether, pentaerythritol (tri- or tetra-)glycidyl ether, dipentaerythritol (tri-, tetra-, penta- or hexa) glycidyl ether, etc.] and polyfunctional aliphatic epoxy resin compounds having three or more epoxy groups in the molecule.
• bifunctional aliphatic epoxy resin compounds include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,3-propanediol diglycidyl ether, 2-methyl-1,3-propanediol diglycidyl ether, 2-butyl-2-ethyl-1,3-propanediol diglycidyl ether, 1,4-butanediol diglycidyl ether (tetramethylene glycol diglycidyl ether), neopentyl glycol diglycidyl ether, 3-methyl-2 ,4-pentanediol diglycidyl ether, 2,4-pentanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether (pentamethylene glycol diglycidyl ether), 3-methyl-1,5-pentanediol diglycidyl ether , 2-
• aromatic epoxy resin compounds include glycidyl ethers of phenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, catechol and resorcinol, glycidyl ether esters of hydroxycarboxylic acids such as p-hydroxybenzoic acid, Monoglycidyl esters or polyglycidyl esters of carboxylic acids such as benzoic acid, phthalic acid and terephthalic acid, glycidylamine types such as diglycidylaniline, diglycidyltoluidine, triglycidyl-p-aminophenol, tetraglycidyl-m-xylylenediamine Epoxy compounds having a naphthalene skeleton, such as epoxy compounds, naphthol glycidyl esters, and glycidyl ether esters such as ⁇ -hydroxynaphthoic acid.
• a novolac compound obtained by novolacifying phenols such
• the curing agent used in the epoxy resin composition of the present embodiment is not particularly limited as long as it is a commonly used various curing agent.
• curing agents include amine-based curing agents, acid anhydride-based curing agents, and phenol-based curing agents.
• a curing agent blended in the epoxy resin composition only one type of curing agent may be used, or two or more types of curing agents may be used in combination.
• the amount of the curing agent to be blended is preferably such that the stoichiometric equivalent ratio (curing agent equivalent/epoxy group equivalent) to the epoxy resin is 0.01 to 1.00.
• a more preferable equivalent ratio is an amount of 0.05 to 0.50.
• a more preferable equivalent ratio is an amount of 0.08 to 0.30.
• the blending ratio of the curing agent to the liquid component obtained by removing the filler (solid component) from the epoxy resin composition is preferably 1% by mass to 100% by mass, more preferably 5% by mass to 15% by mass.
• amine curing agents include aliphatic polyamines such as triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine and 2-methylpentamethylenediamine, isophoronediamine, 1,3- Alicyclic polyamines such as bisaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, N-aminoethylpiperazine, 1,4-bis(2-amino-2-methylpropyl ) piperazine-type polyamines such as piperazine, diethyltoluenediamine, dimethylthiotoluenediamine, 4,4′-diamino-3,3′-diethyldiphenylmethane, bis(methylthio)toluenediamine, diaminodiphenylmethane, m-phenyl
• acid anhydride curing agents include alkylated tetrahydrophthalic anhydrides such as methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, Examples thereof include methylhimic anhydride, alkenyl-substituted succinic anhydride, methylnadic anhydride, and glutaric anhydride.
• phenol-based curing agents include monomers, oligomers, and polymers in general having phenolic hydroxyl groups. ) resin, naphthol aralkyl resin, triphenolmethane resin, dicyclopentadiene type phenol resin, and the like.
• phenol-based curing agents are suitable.
• the content of the phenolic curing agent in the epoxy resin composition is preferably 1% by mass to 5% by mass. 5% by mass to 4% by mass is more preferable. If the content of the phenol-based curing agent is less than 1% by mass, the adhesion between the semiconductor element or substrate and the epoxy resin composition may easily deteriorate. Moreover, when the content of the phenol-based curing agent exceeds 5% by mass, the viscosity of the epoxy resin composition increases, and the injectability may easily deteriorate.
• the curing catalyst used in the epoxy resin composition of the present embodiment is not particularly limited as long as it is a commonly used various curing catalyst.
• curing catalysts include nitrogen-containing heterocyclic curing catalysts such as imidazole compounds (including those adducted or microencapsulated with epoxy resins or isocyanate resins), tertiary amine curing catalysts, and phosphorus compound curing catalysts. etc.
• a nitrogen-containing heterocyclic curing catalyst is preferable from the viewpoint of thermal cycle resistance.
• the curing catalyst blended in the epoxy resin composition only one curing catalyst may be used, or two or more curing catalysts may be used in combination. There are no particular restrictions.
• a preferable blending amount of the curing catalyst is 1% by mass to 15% by mass, and a more preferable blending amount is 2% by mass to 10% by mass, based on 100 parts by mass of the epoxy resin composition.
• nitrogen-containing heterocyclic curing catalysts include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl- 4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4 -imidazole, 2-phenylimidazole, 1-benzyl-2-phenylimidazole, benzimidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine, 2-phenyl- Examples include imidazole compounds such as 4,5-dihydroxymethylimidazole, 2,3-dihydro-1H-
• Nitrogen-containing heterocyclic curing catalysts other than imidazole compounds include diazabicycloundecene (DBU), DBU-phenol salt, DBU-octylate, DBU-p-toluenesulfonate, DBU-formate, DBU-orthophthalate, DBU-phenol novolak resin salt, DBU tetraphenylborate salt, diazabicyclononene (DBN), DBN-phenol novolac resin salt, diazabicyclooctane, pyrazole, oxazole, thiazole, imidazoline, pyrazine, Morpholine, thiazine, indole, isoindole, purine, quinoline, isoquinoline, quinoxaline, c
• imidazole compounds encapsulated imidazole called microcapsule imidazole or epoxy adduct imidazole can also be used. That is, an imidazole-based latent curing agent encapsulated by blocking the surface of an imidazole compound adducted with urea or an isocyanate compound with an isocyanate compound can be used. Alternatively, an imidazole-based latent curing agent encapsulated by blocking the surface of an imidazole compound adducted with an epoxy compound with an isocyanate compound can also be used.
• Novacure HX3941HP Novacure HXA3042HP
• Novacure HXA3922HP Novacure HXA3792
• Novacure HX3748 Novacure HX3721
• Novacure HX3722 Novacure HX3088
• Novacure HX3741 Novacure HX37 42
• Novacure HX3613 both manufactured by Asahi Kasei Chemicals, trade name
• Amicure PN-23J Amicure PN-40J (both manufactured by Ajinomoto Fine-Techno Co., Ltd., trade names)
• Fujicure FXR-1121 manufactured by Fuji Kasei Kogyo Co., Ltd., trade names
• the filler used in the epoxy resin composition of the present embodiment includes at least aluminum nitride having (i) an average particle size of 10.0 ⁇ m or less and (ii) a uranium content of 20 ppb or less.
• a filler is used.
• the filler only an aluminum nitride filler that satisfies the conditions (i) and (ii) may be used. However, if necessary, an aluminum nitride filler that satisfies conditions (i) and (ii) may be used in combination with other fillers.
• the mixing ratio of aluminum nitride filler to the total amount of filler is 70 mass. % to 99.9% by mass, more preferably 80% to 95% by mass.
• the content of the aluminum nitride filler in the epoxy resin composition of the present embodiment is determined from the viewpoint of reducing hygroscopicity and linear expansion coefficient, improving strength, and soldering heat resistance. It is preferably 50.0% by mass to 90% by mass, more preferably 52% by mass to 80% by mass, and even more preferably 55% by mass to 70% by mass, relative to the total amount of the composition.
• the aluminum nitride filler that satisfies the conditions (i) and (ii) used in the epoxy resin composition of the present embodiment is a commonly used material for other fillers (e.g., alumina, silicon carbide, It has a high thermal conductivity compared to fillers made of silicon nitride, silica, etc.). Therefore, by using an aluminum nitride filler that satisfies the conditions (i) and (ii) as the filler, excellent thermal conductivity of the cured product can be realized. As a result, in the semiconductor device manufactured by using the cured epoxy resin composition of the present embodiment as a sealing material, the heat dissipation of the sealed portion is improved and/or the thermal design of the semiconductor device is facilitated. is.
• the average particle size of the aluminum nitride filler used in the epoxy resin composition of the present embodiment is 10.0 ⁇ m or less. Therefore, the epoxy resin composition of this embodiment is also excellent in injectability. Therefore, when manufacturing a semiconductor device using the epoxy resin composition of the present embodiment, the injectability of the portion to be sealed is excellent.
• the average particle diameter of the aluminum nitride filler is preferably 7.5 ⁇ m or less, more preferably 6.0 ⁇ m or less.
• the lower limit of the average particle size is not particularly limited. However, from a practical viewpoint such as the availability of the aluminum nitride filler, the preferable lower limit of the average particle size is 0.1 ⁇ m or more.
• a more preferable lower limit of the average particle size is 0.5 ⁇ m or more.
• the average particle size is calculated using the particle size distribution obtained by the volume average particle size (D50) particle size measurement method. More specifically, the cumulative volume of the remaining particles obtained by subtracting the cumulative volume within the divided particle size range (channel) from the particle size distribution sequentially from the small particle size side is 50% of the cumulative volume of all particles. % (volume average particle diameter (D50)) is calculated. Average particle size is measured using a laser scattering diffraction method.
• particle size distribution analyzer manufactured by Beckman Coulter, LS13320
• flow rate 50 ml / sec
• measurement time 90 sec
• measurement number of times particle condition: designated optical model
• solvent pure water
• Average particle size is measured at solvent refractive index: 1.333.
• the aluminum nitride filler it is preferable to use a filler manufactured using metal aluminum or aluminum oxide as a raw material. Specifically, it is preferable to use an aluminum nitride filler produced by a direct nitriding method in which aluminum nitride is produced by subjecting metal aluminum, which is a raw material, to a nitriding reaction. Alternatively, it is also preferable to use an aluminum nitride filler produced by a reductive nitriding method in which aluminum nitride is produced by adding carbon powder to aluminum oxide as a raw material and then nitriding the aluminum oxide.
• the aluminum element constituting the aluminum nitride filler is derived from ore (bauxite) containing uranium as a minor component. Therefore, aluminum nitride fillers produced by various production methods also contain uranium as an unavoidable impurity. Therefore, alpha rays emitted from uranium may cause malfunction of a device using a semiconductor device (this point also applies to alumina filler). For this reason, the epoxy resin composition of the present embodiment uses an aluminum nitride filler in which the uranium content is reduced to 20 ppb or less. Therefore, by reducing the amount of ⁇ -rays from the cured product obtained by curing the epoxy resin composition of the present embodiment (that is, the sealing material in the semiconductor device), the operational reliability of the semiconductor device can be improved. .
• the uranium content in the aluminum nitride filler used in the epoxy resin composition of the present embodiment is more preferably 10 ppb or less, more preferably 7 ppb or less.
• the lower limit of the uranium content is not particularly limited. The ideally most preferred lower limit is 0 ppb. However, practically, the preferable lower limit is 0.5 ppb or more, and the more preferable lower limit is 0.8 ppb or more.
• the uranium content of the other fillers is preferably 20 ppb or less, more preferably 10 ppb or less, and even more preferably 7 ppb or less. .
• the lower limit of the uranium content of other fillers is not particularly limited.
• the ideally most preferred lower limit is 0 ppb, but practically the preferred lower limit is 0.5 ppb or more, and the more preferred lower limit is 0.8 ppb or more.
• the uranium content in the filler is measured using the ICP-MS method (inductively coupled plasma mass spectrometry).
• ICP-MS method inductively coupled plasma mass spectrometry
• 1 g of filler powder to be measured is weighed into a Teflon beaker.
• An aqueous solution is then prepared by adding 5 ml of nitric acid and 5 ml of hydrofluoric acid.
• a concentrated solution obtained by heating the aqueous solution with a hot plate is placed in the measurement container.
• This measurement container is set in an inductively coupled plasma mass spectrometer.
• the uranium content is determined.
• the other filler when a filler made of other material is used in addition to the aluminum nitride filler, the other filler includes an alumina filler, a silicon carbide filler, a silicon nitride filler, a silica filler, and the like. can be used one or more of known fillers. Among these, it is particularly preferable to use a silica filler having an average particle diameter of 5 nm to 120 nm and a uranium content of 20 ppb or less (hereinafter sometimes referred to as "nano-sized silica filler").
• the nano-sized silica filler has a smaller particle size than the aluminum nitride filler. Therefore, it is easy to fill the gaps between the large-diameter aluminum nitride fillers with the small-diameter nano-sized silica filler. As a result, it is easy to further improve the filling rate of the filler in the epoxy resin composition.
• the coefficient of thermal expansion of nano-sized silica fillers is much smaller than that of aluminum nitride fillers. Therefore, the thermal expansion coefficient of the cured product of the epoxy resin composition in which the aluminum nitride filler and the nano-sized silica filler are combined as fillers can be further reduced. As a result, it is easy to greatly improve the thermal cycle resistance of the cured product.
• the blending ratio of the nano-sized silica filler is With respect to the total amount of the epoxy resin composition, it is preferably 0.1% by mass to 25.0% by mass, more preferably 5.0% by mass to 25.0% by mass, and 10.0% by mass to 20% by mass. 0% by mass is more preferred.
• the blending ratio of the nano-sized silica filler is 0.1% by mass or more, it becomes easy to obtain the effects of reducing hygroscopicity, reducing the coefficient of linear expansion, improving strength, and improving solder heat resistance.
• the blending ratio to 25.0% by mass or less, it becomes easy to suppress excessive thickening of the epoxy resin composition.
• the particle size ratio (d2/d1) of the average particle size (d2) of the nano-sized silica filler to the average particle size (d1) of the aluminum nitride filler is preferably in the range of 1/200 to 1/5. It is more preferably in the range of /100 to 1/10, and more preferably in the range of 1/20 to 1/20.
• the blending ratio of the nano-sized silica filler is large, it becomes easy to suppress excessive thickening of the epoxy resin composition by setting the particle size ratio (d2/d1) to 1/200 or more. .
• the total mixing ratio of the aluminum nitride filler and the nano-sized silica filler with respect to the total amount of the epoxy resin composition is in the range of 60.0% by mass to 85.0% by mass. It is preferably within the range of 65.5% by mass to 80.5% by mass.
• the total blending ratio to 65.5% by mass or more, it becomes easier to further improve the thermal conductivity of the cured product, and by setting the total blending ratio to 80.5% by mass or less, it is possible to improve the epoxy resin composition. It becomes easy to suppress excessive thickening.
• the thermal conductivity of the aluminum nitride filler compounded in the epoxy resin composition of this embodiment is not particularly limited. However, from the viewpoint of obtaining a cured product with high thermal conductivity, it is preferably 145 W/m ⁇ K or more, more preferably 230 W/m ⁇ K or more. Moreover, the thermal conductivity of the nano-sized silica filler that is optionally blended in the epoxy resin composition of the present embodiment is not particularly limited. However, from the same viewpoint as above, 1.2 W/m ⁇ K or more is preferable.
• the shape of the filler used in the epoxy resin composition of this embodiment is not particularly limited.
• the shape of the filler may be spherical, irregular, scale-like, or the like. However, an irregular shape is preferable from the viewpoint of improving the thermal conductivity of the cured product. Examples of irregularly shaped fillers include fillers produced by a pulverization method.
• the epoxy resin composition of the present embodiment may optionally contain other components other than components (A) to (D).
• Other components are not particularly limited.
• Other components include, for example, coupling agents, ion trapping agents, leveling agents, antioxidants, antifoaming agents, flame retardants, coloring agents, reactive diluents, elastomers, and the like.
• the blending amount of other compounding agents is appropriately determined according to the purpose of use.
• the epoxy resin composition of the present embodiment is prepared by mixing and stirring each component that is a raw material.
• the method of mixing and stirring is not particularly limited. A known mixing and stirring method can be used. For example, a roll mill or the like can be used.
• the (A) epoxy resin used as a raw material is solid, it is preferable to mix the epoxy resin liquefied by performing heat processing etc. before mixing with other components.
• all the raw materials may be mixed at once.
• the rest of the components may be mixed with a primary mixture prepared by mixing some of the components selected from all raw materials. For example, if it is difficult to uniformly disperse (A) the epoxy resin and (D) the filler, for the primary mixture prepared by mixing the (A) epoxy resin and (D) the filler , may be mixed with each of the remaining ingredients.
• the epoxy resin composition of this embodiment has excellent injectability. Therefore, it is easy to lower the viscosity. Therefore, the viscosity at 25° C. of the epoxy resin composition of the present embodiment can easily be typically set to 500 Pa ⁇ s or less.
• the viscosity at 25° C. is preferably 400 Pa ⁇ s or less, more preferably 300 Pa ⁇ s or less.
• the lower limit of the viscosity at 25°C is not particularly limited. However, from the viewpoint of handling, it is preferably 10 Pa ⁇ s or more, more preferably 20 Pa ⁇ s or more, and even more preferably 40 Pa ⁇ s or more.
• the viscosity is measured at 25° C. and 20 rpm using a HB-DV type viscometer manufactured by Brookfield. At this time, an SC4-14 spindle is used. The measurement range is 50-500 Pa ⁇ s.
• the epoxy resin composition of this embodiment can be widely applied to resin encapsulation of various electronic components such as semiconductor elements or LED packages. Further, in the case of resin-sealing an electronic component using the epoxy resin composition of the present embodiment, (1) the space inside the mold and the A molding method (so-called transfer molding) in which the mold is filled with a liquid epoxy resin composition that is injected through a communicating resin supply channel (gate, runner, etc.), or (2) a mold A known molding method such as a molding method (so-called compression molding) in which the inside is filled with a liquid epoxy resin composition in advance, and a member to be resin-sealed is arranged, followed by press mold clamping can be used. Compression molding does not require a flow path for resin supply.
• compression molding is characterized by a usage efficiency of the epoxy resin composition that is close to 100%. Therefore, compression molding has been widely used in recent years.
• the epoxy resin composition of the present embodiment can be suitably used as a member (liquid compression mold material) used for compression molding. Moreover, the epoxy resin composition of the present embodiment can be suitably used as a glove top material.
• the epoxy resin composition of the present embodiment is suitably used for manufacturing semiconductor devices.
• the semiconductor device of this embodiment includes a sealing material made of a cured product of the epoxy resin composition of this embodiment. At least the semiconductor element is resin-sealed with the sealing material.
• Epoxy Resin Composition Raw materials were mixed and stirred using a roll mill so as to obtain the compounding ratios shown in Tables 1 to 4. Thus, epoxy resin compositions of Examples 1-16 and Comparative Examples 1-8 were prepared. The details of the components (A) to (D) used as raw materials are as follows.
• Epoxy resin/Epoxy resin 1 (Epogose PT (general grade), diglycidyl ether of polytetramethylene glycol, epoxy equivalent 440 g/eq, manufactured by Yokkaichi Gosei Co., Ltd.)
• Epoxy resin 2 (jER630, aminophenol type liquid epoxy resin, epoxy equivalent 98 g / eq, manufactured by Mitsubishi Chemical Corporation)
• Epoxy resin 3 (HP4032D, naphthalene type liquid epoxy resin, epoxy equivalent 140 g / eq, manufactured by DIC)
• Epoxy resin 4 (YDF8170, bisphenol F type liquid epoxy resin, epoxy equivalent 158 g / eq, manufactured by Nippon Steel Chemical & Materials Co., Ltd.)
• Epoxy resin 5 (RE410S, bisphenol A liquid epoxy resin, epoxy equivalent 178 g / eq, manufactured by Nippon Kayaku Co., Ltd.)
• Curing agent / Curing agent 1 (MEH-8005, phenolic curing agent, hydroxyl equivalent 139 to 143 g / eq, manufactured by Meiwa Kasei Co., Ltd.)
• Curing agent 2 (ETHACURE 100 PLUS, amine-based curing agent, manufactured by Albemarle)
• Curing agent 3 (HN-2200, acid anhydride curing agent, manufactured by Showa Denko Materials Co., Ltd.)
• Curing catalyst/curing catalyst 1 (2P4MZ, 2-phenyl-4-methylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.)
• Curing catalyst 2 (2MZA, 2,4-diamino-6-[2′-methylimidazolyl-(1′)]-ethyl-s-triazine, manufactured by Shikoku Chemical Industry Co., Ltd.)
• D Filler
• D-1 Aluminum nitride filler/filler AN1 (average particle size 1.0 ⁇ m, uranium content 1.0 ppb or less, pulverization method) ⁇ Filler AN2 (average particle size 5.0 ⁇ m, uranium content 5.0 ppb or less, thermal spraying method)
• D-2 Silica filler (silica nanofiller)
• ⁇ Filler S1 YA050C-SM1, average particle size 0.05 ⁇ m, manufactured by Admatechs, uranium content 3.0 ppb or less, wet method
• Filler S2 YA010C-SM1, average particle size 0.01 ⁇ m, manufactured by Admatechs, uranium content 3.0 ppb or less, wet method
• D3 YC100C-SM1, average particle size 0.10 ⁇ m, manufactured by Admatechs, uranium content 3.0 ppb or less, wet method
• D-3 Other fillers (alumina filler)
• viscosity The viscosity of the epoxy resin composition of each example and comparative example was measured using a Brookfield HB-DV viscometer (model number: HB-DV1) under the conditions of a liquid temperature of 25° C. and 20 rpm. was measured immediately after preparation.
• A The cured product can completely fill the half-diced portion without unevenness of the filler.
• B The cured product does not completely fill the half-diced portion, or even if the cured product completely fills the half-diced portion, the filler is unevenly distributed in the cured product.
• the thermal conductivity of the cured epoxy resin composition of each example and comparative example was measured by the following procedure. First, the epoxy resin composition was cured by heating at 150° C. for 60 minutes to obtain a cured product having a thickness of 0.7 mm. A measurement sample was prepared by cutting this cured product into a length of 10 mm and a width of 10 mm. Next, the thermal conductivity of this measurement sample was measured using a thermal conductivity measuring device (LFA447 nanoflash, manufactured by NETZSCH).
• peel test The peel test was carried out in the following procedure. First, on the surface of an FR-4 substrate (vertical and horizontal: 4 cm ⁇ 4 cm, thickness: 0.75 mm), within a region of vertical and horizontal: 3 cm ⁇ 3 cm, the coating thickness of Examples 1, 2, and 10 is 1 mm. , 17 epoxy resin compositions were each printed. After that, the epoxy resin composition was cured at 150° C. for 60 minutes. As a result, a cured product layer of the cured epoxy resin composition was formed on the FR-4 substrate. Next, the FR-4 substrate on which the cured product layer was formed was left in a constant temperature and humidity chamber for 192 hours under conditions of a temperature of 30° C. and a humidity of 60%.

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