Classifications

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  • 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
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
  • C08L91/06—Waxes
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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
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
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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
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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
  • C08G59/68—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 catalysts used
  • C08G59/688—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 catalysts used containing phosphorus
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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
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
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  • 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
  • C08L63/04—Epoxynovolacs
• • 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
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  • 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
  • H10W74/111—Encapsulations, e.g. protective coatings characterised by their shape or disposition the semiconductor body being completely enclosed
  • H10W74/114—Encapsulations, e.g. protective coatings characterised by their shape or disposition the semiconductor body being completely enclosed by a substrate and the encapsulations
• • 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
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  • 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
• • 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
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3472—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/20—Applications use in electrical or conductive gadgets
  • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/851—Dispositions of multiple connectors or interconnections
  • H10W72/874—On different surfaces
  • H10W72/884—Die-attach connectors and bond wires
• • H—ELECTRICITY
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  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
• • 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
  • H10W74/15—Encapsulations, e.g. protective coatings characterised by their shape or disposition on active surfaces of flip-chip devices, e.g. underfills
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  • H10W74/00—Encapsulations, e.g. protective coatings
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  • 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
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  • H10W90/00—Package configurations
  • H10W90/701—Package configurations characterised by the relative positions of pads or connectors relative to package parts
  • H10W90/721—Package configurations characterised by the relative positions of pads or connectors relative to package parts of bump connectors
  • H10W90/724—Package configurations characterised by the relative positions of pads or connectors relative to package parts of bump connectors between a chip and a stacked insulating package substrate, interposer or RDL
• • 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
  • H10W90/00—Package configurations
  • H10W90/701—Package configurations characterised by the relative positions of pads or connectors relative to package parts
  • H10W90/731—Package configurations characterised by the relative positions of pads or connectors relative to package parts of die-attach connectors
  • H10W90/734—Package configurations characterised by the relative positions of pads or connectors relative to package parts of die-attach connectors between a chip and a stacked insulating package substrate, interposer or RDL
• • 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
  • H10W90/00—Package configurations
  • H10W90/701—Package configurations characterised by the relative positions of pads or connectors relative to package parts
  • H10W90/751—Package configurations characterised by the relative positions of pads or connectors relative to package parts of bond wires
  • H10W90/754—Package configurations characterised by the relative positions of pads or connectors relative to package parts of bond wires between a chip and a stacked insulating package substrate, interposer or RDL

Definitions

• the present invention relates to a sealing resin composition and a method for producing a single-sided sealed structure using the same. More specifically, the present invention relates to a sealing resin composition used for manufacturing a structure having an electronic component mounted on a substrate sealed with resin, and a method for manufacturing the structure.
• the electronic control device is a single-sided sealed module
• single-sided sealing is performed in which only the top surface of the substrate, that is, the side on which electronic components are mounted, is sealed with resin.
• the entire substrate is warped after molding. This warpage occurs due to the difference in balance between the thickness of the substrate and the thickness of the resin sealing, and the warpage occurs due to the stronger contraction force of the substrate after molding and the contraction force of the sealing resin.
• the module warps toward the resin side after molding.
• the present invention has been made in view of the above circumstances, and provides a sealing resin composition with reduced mold shrinkage during molding, and a single-sided sealed structure with reduced warpage produced using the same.
• the purpose is to provide a method for manufacturing the body.
• the present inventor has discovered that by having a specific formulation, a sealing resin composition with a reduced mold shrinkage rate can be obtained, and the warpage of a single-sided sealed structure manufactured using the same can be reduced. They discovered this and completed the present invention.
• a sealing resin composition used for manufacturing a single-sided sealed structure by sealing one side of a motherboard on which at least one electronic device is mounted comprising:
• the sealing resin composition contains a trifunctional or higher functional epoxy resin, a curing agent, a curing accelerator, an inorganic filler, and a wax
• the present invention provides a sealing resin composition in which the molding shrinkage rate of the sealing resin composition is 0.1% or less.
• a method for manufacturing a single-sided sealed structure comprising:
• the sealing resin composition contains a trifunctional or higher functional epoxy resin, a curing agent, a curing accelerator, an inorganic filler, and a wax,
• the resin composition for sealing has a molding shrinkage rate of 0.1% or less.
• a sealing resin composition with a reduced molding shrinkage rate during molding and a method for producing a single-sided sealed structure with reduced warpage produced using the same.
• the sealing resin composition of the present embodiment seals only the upper surface of the motherboard on which at least one electronic device is mounted, that is, the surface on which the electronic device is mounted, thereby forming a single-sided sealed structure. used for manufacturing.
• the sealing resin composition of the present embodiment contains a trifunctional or higher functional epoxy resin, a curing agent, a curing accelerator, an inorganic filler, and a wax, and the molding shrinkage rate of the resin composition is 0.1% or less. It is.
• the encapsulating resin composition of this embodiment has a molding shrinkage rate of 0.1% or less by containing a combination of the above-mentioned specific components.
• a single-sided sealed structure obtained by using a sealing resin composition having such a molding shrinkage rate as a sealing material has reduced warpage, especially warpage toward the sealing resin side, and therefore has excellent reliability.
• a single-sided sealed structure is obtained.
• the trifunctional or higher functional epoxy resin used in the sealing resin composition of the present embodiment refers to a compound having three or more epoxy groups in one molecule. By using a trifunctional or higher functional epoxy resin, the heat resistance of the cured product obtained by curing the resin can be improved.
• the valence of the epoxy resin is preferably 3 to 20.
• the bifunctional or higher functional epoxy resin used in this embodiment includes bisphenol A epoxy resin, bisphenol F epoxy resin, tetramethylbisphenol F epoxy resin, hydroquinone epoxy resin, biphenyl epoxy resin, and bisphenol fluorene epoxy resin.
• bisphenol S type epoxy resin bisthioether type epoxy resin, resorcinol type epoxy resin, biphenylaralkyl type epoxy resin, naphthalene diol type epoxy resin, phenol novolac type epoxy resin, aromatic modified phenol novolac type epoxy resin, cresol novolak type epoxy resin , alkyl novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, ⁇ -naphthol aralkyl type epoxy resin, dinaphthol aralkyl type epoxy resin, ⁇ -naphthol aralkyl type epoxy resin, trisphenylmethane type epoxy resin, alkylene Examples include, but are not limited to, glycol type epoxy resins, aliphatic cyclic epoxy resins, diaminodiphenylmethane tetraglycidylamine, aminophenol type epoxy resins, urethane-modified epoxy resins, and oxazolidone ring-containing epoxy
• naphthalene diol type epoxy resin phenol novolac type epoxy resin, aromatic modified phenol novolac type epoxy resin, cresol novolac type epoxy resin, ⁇ -naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin , oxazolidone ring-containing epoxy resins, etc. are preferred. These may be used alone or in combination of two or more.
• the content of the epoxy resin is preferably 5% by mass or more and 40% by mass or less, more preferably 10% by mass or more and 20% by mass or less, based on the entire sealing resin composition.
• the sealing resin composition of this embodiment contains a curing agent to three-dimensionally crosslink the epoxy resin.
• a phenolic resin curing agent is preferably used.
• the phenolic resin curing agent include novolac type resins such as phenol novolac resin, cresol novolac resin, and naphthol novolac resin; polyfunctional phenol resins such as triphenolmethane type phenol resin; terpene-modified phenol resin, and dicyclopentadiene-modified resin.
• Modified phenolic resins such as phenol resins; phenol aralkyl resins having a phenylene skeleton and/or biphenylene skeleton; aralkyl type resins such as naphthol aralkyl resins having a phenylene and/or biphenylene skeleton; bisphenol compounds such as bisphenol A and bisphenol F; It will be done. These may be used alone or in combination of two or more.
• a phenolic resin curing agent provides a good balance of flame resistance, moisture resistance, electrical properties, curability, storage stability, etc.
• the hydroxyl equivalent of the phenolic resin curing agent can be set to 90 g/eq or more and 250 g/eq or less.
• phenolic resin curing agent for example, a polyaddition type curing agent, a catalyst type curing agent, a condensation type curing agent, etc. may be used.
• polyaddition type curing agents include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylene diamine (MXDA), diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), and diaminodiamine.
• DETA diethylenetriamine
• TETA triethylenetetramine
• MXDA metaxylene diamine
• DDM diaminodiphenylmethane
• MPDA m-phenylenediamine
• aromatic polyamines such as diphenyl sulfone (DDS), polyamine compounds including dicyandiamide (DICY) and organic acid dihydralazide; alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA) Acid anhydrides, including aromatic acid anhydrides such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), and benzophenone tetracarboxylic acid (BTDA); polyphenolic compounds such as novolak-type phenolic resins and phenolic polymers Polymercaptan compounds such as polysulfide, thioester, and thioether; Isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; Organic acids such as carboxylic acid-containing polyester resins.
• DDS diphenyl sulfone
• DIY dicyandiamide
• catalytic curing agents examples include tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol (DMP-30); 2-methylimidazole, 2-ethyl-4 - Imidazole compounds such as methylimidazole (EMI24); Lewis acids such as BF 3 complex, and the like.
• BDMA benzyldimethylamine
• DMP-30 2,4,6-trisdimethylaminomethylphenol
• 2-methylimidazole, 2-ethyl-4 - Imidazole compounds such as methylimidazole (EMI24)
• Lewis acids such as BF 3 complex, and the like.
• condensation type curing agent examples include resol resins, urea resins such as methylol group-containing urea resins, and melamine resins such as methylol group-containing melamine resins.
• the lower limit of the content of the phenolic resin curing agent should be 20% by mass or more based on the total curing agent.
• the content is preferably 30% by mass or more, more preferably 30% by mass or more, and particularly preferably 50% by mass or more.
• the upper limit of the content of the phenolic resin curing agent is not particularly limited, but it is preferably 100% by mass or less based on the total curing agent.
• the lower limit of the total content of curing agents in the encapsulating resin composition according to the present invention is not particularly limited, but is 0.8% by mass based on the entire encapsulating resin composition. It is preferably at least 1.5% by mass, more preferably at least 1.5% by mass. When the lower limit of the blending ratio is within the above range, good curability can be obtained. Furthermore, the upper limit of the total content of curing agents in the encapsulating resin composition is not particularly limited, but it must be 12% by mass or less based on the entire encapsulating resin composition. is preferable, and more preferably 10% by mass or less.
• the phenol resin as a curing agent and the above-mentioned polyfunctional epoxy resin are based on the equivalent ratio ( It is preferable to mix so that EP)/(OH) is 0.8 or more and 1.3 or less. When the equivalent ratio is within the above range, sufficient curing characteristics can be obtained when molding the resulting sealing resin composition. However, if a resin other than the phenol resin that can react with the epoxy resin is used in combination, the equivalent ratio may be adjusted as appropriate.
• imidazoles As the curing accelerator used in the sealing resin composition of this embodiment, it is preferable to use imidazoles.
• imidazoles include imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4 -Methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2- Imidazole compounds such as undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4,5-dihydroxydimethylimidazole, and 2-phenyl-4-methyl-5-
• the content of imidazoles is preferably 0.01% by mass or more, and preferably 0.03% by mass or more based on the entire sealing resin composition. More preferably, the content is particularly preferably 0.05% by mass or more.
• the content of imidazoles is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and 0.5% by mass based on the entire sealing resin composition. The following is particularly preferable.
• curing accelerators include phosphorus atom-containing compounds such as organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds; It may further contain one or more selected from amine-based curing accelerators other than imidazoles, such as 1,8-diazabicyclo(5,4,0)undecene.
• Examples of the tetra-substituted phosphonium compound that can be used in the sealing resin composition include a compound represented by the following general formula (4).
• P represents a phosphorus atom.
• R 4 , R 5 , R 6 and R 7 represent an aromatic group or an alkyl group.
• A represents an anion of an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group in its aromatic ring.
• AH represents an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group in an aromatic ring.
• x and y are numbers from 1 to 3
• z is a number from 0 to 3
• x y.
• the compound represented by general formula (4) can be obtained, for example, as follows, but is not limited thereto. First, a tetra-substituted phosphonium halide, an aromatic organic acid, and a base are mixed uniformly in an organic solvent, and an aromatic organic acid anion is generated in the solution system. Then, by adding water, the compound represented by general formula (4) can be precipitated.
• R 4 , R 5 , R 6 and R 7 bonded to the phosphorus atom are phenyl groups
• AH is a compound having a hydroxyl group in the aromatic ring, that is, a phenol.
• A is preferably an anion of the phenol.
• phenols include monocyclic phenols such as phenol, cresol, resorcinol, and catechol; condensed polycyclic phenols such as naphthol, dihydroxynaphthalene, and anthraquinol; and bisphenols such as bisphenol A, bisphenol F, and bisphenol S; Examples include polycyclic phenols such as phenylphenol and biphenol.
• Examples of the phosphobetaine compound used as a curing accelerator include a compound represented by the following general formula (5).
• R 8 represents an alkyl group having 1 to 3 carbon atoms
• R 9 represents a hydroxyl group.
• f is a number from 0 to 5
• g is a number from 0 to 3.
• the compound represented by general formula (5) can be obtained, for example, as follows. First, a triaromatic substituted phosphine, which is a tertiary phosphine, is brought into contact with a diazonium salt, and the diazonium group of the triaromatic substituted phosphine and the diazonium salt is substituted. However, it is not limited to this.
• Examples of the adduct of a phosphine compound and a quinone compound used as a curing accelerator include a compound represented by the following general formula (6).
• P represents a phosphorus atom.
• R 10 , R 11 and R 12 represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and may be the same or different from each other.
• R 13 , R 14 and R 15 represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and may be the same or different from each other, and R 14 and R 15 are bonded to form a cyclic structure. It's okay.
• Examples of phosphine compounds used in the adduct of a phosphine compound and a quinone compound include triphenylphosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, trinaphthylphosphine, tris(benzyl)phosphine, etc. It is preferable that the substituent is substituted or has a substituent such as an alkyl group or an alkoxyl group, and examples of the substituent such as an alkyl group or an alkoxyl group include those having 1 to 6 carbon atoms. Triphenylphosphine is preferred from the viewpoint of availability.
• examples of the quinone compound used in the adduct of a phosphine compound and a quinone compound include benzoquinone and anthraquinones, and among them, p-benzoquinone is preferred from the viewpoint of storage stability.
• the adduct can be obtained by contacting and mixing both the organic tertiary phosphine and the benzoquinone in a solvent that can dissolve them.
• the solvent is preferably a ketone such as acetone or methyl ethyl ketone, which has low solubility in the adduct.
• ketone such as acetone or methyl ethyl ketone
• R 10 , R 11 and R 12 bonded to the phosphorus atom are phenyl groups, and R 13 , R 14 and R 15 are hydrogen atoms, that is, 1,
• a compound to which 4-benzoquinone and triphenylphosphine are added is preferred in that it lowers the thermal modulus of the cured product of the sealing resin composition.
• Examples of the adduct of a phosphonium compound and a silane compound used as a curing accelerator include a compound represented by the following general formula (7).
• P represents a phosphorus atom
• Si represents a silicon atom
• R 16 , R 17 , R 18 and R 19 each represent an organic group having an aromatic ring or a heterocycle, or an aliphatic group, and may be the same or different from each other.
• R 20 is an organic group bonded to the groups Y 2 and Y 3 .
• R 21 is an organic group bonded to groups Y 4 and Y 5 .
• Y 2 and Y 3 represent a group formed by a proton-donating group releasing a proton, and the groups Y 2 and Y 3 in the same molecule bond to a silicon atom to form a chelate structure.
• Y 4 and Y 5 represent a group formed by a proton-donating group releasing a proton, and the groups Y 4 and Y 5 in the same molecule bond to a silicon atom to form a chelate structure.
• R 20 and R 21 may be the same or different from each other, and Y 2 , Y 3 , Y 4 and Y 5 may be the same or different from each other.
• Z 1 is an organic group having an aromatic ring or a heterocycle, or an aliphatic group.
• R 16 , R 17 , R 18 and R 19 are, for example, phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, naphthyl group, hydroxynaphthyl group, benzyl group, methyl group. , ethyl group, n-butyl group, n-octyl group, cyclohexyl group, etc.
• alkyl groups such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, hydroxynaphthyl group, and alkoxy groups
• an aromatic group having a substituent such as a hydroxyl group, or an unsubstituted aromatic group is more preferable.
• R 20 is an organic group bonded to Y 2 and Y 3 .
• R 21 is an organic group that is bonded to groups Y 4 and Y 5 .
• Y 2 and Y 3 are groups formed by a proton-donating group releasing protons, and the groups Y 2 and Y 3 in the same molecule bond to a silicon atom to form a chelate structure.
• Y 4 and Y 5 are groups formed by a proton-donating group releasing protons, and the groups Y 4 and Y 5 in the same molecule combine with a silicon atom to form a chelate structure.
• the groups R 20 and R 21 may be the same or different from each other, and the groups Y 2 , Y 3 , Y 4 and Y 5 may be the same or different from each other.
• the groups represented by -Y 2 -R 20 -Y 3 - and -Y 4 -R 21 -Y 5 - in general formula (7) are such that the proton donor releases two protons.
• a proton donor an organic acid having at least two carboxyl groups or hydroxyl groups in the molecule is preferable, and furthermore, it is preferable to use an organic acid having at least two carboxyl groups or hydroxyl groups in the molecule.
• An aromatic compound having at least two hydroxyl groups is preferable, and an aromatic compound having at least two hydroxyl groups on adjacent carbons constituting an aromatic ring is more preferable, such as catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3- Dihydroxynaphthalene, 2,2'-biphenol, 1,1'-bi-2-naphthol, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxy Examples include benzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol, and glycerin, but among these, catechol, 1,2-dihydroxynaphthalene, and 2,3-dihydroxynaphthalene are more preferred.
• Z 1 in the general formula (7) represents an organic group or aliphatic group having an aromatic ring or a heterocycle, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, Aliphatic hydrocarbon groups such as hexyl and octyl groups, aromatic hydrocarbon groups such as phenyl, benzyl, naphthyl and biphenyl groups, and glycidyloxy groups such as glycidyloxypropyl, mercaptopropyl and aminopropyl groups. , a mercapto group, an alkyl group having an amino group, and a vinyl group.
• methyl group, ethyl group, phenyl group, naphthyl group, and biphenyl group are preferable from the viewpoint of thermal stability. , more preferred.
• a silane compound such as phenyltrimethoxysilane and a proton donor such as 2,3-dihydroxynaphthalene are added to a flask containing methanol, dissolved, and then heated at room temperature.
• a sodium methoxide-methanol solution is added dropwise while stirring.
• crystals are precipitated.
• the precipitated crystals are filtered, washed with water, and dried under vacuum, an adduct of a phosphonium compound and a silane compound is obtained.
• the content of the curing accelerator is preferably 0.05% by mass or more, more preferably 0.08% by mass or more, and 0.10% by mass or more based on the entire sealing resin composition. It is particularly preferable that there be.
• the content of the curing accelerator is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and 0.5% by mass based on the entire sealing resin composition. % or less is particularly preferable.
• inorganic filler examples include fused silica such as fused crushed silica and fused spherical silica, crystalline silica, alumina, kaolin, talc, clay, mica, rock wool, and water.
• Lastite glass powder, glass flakes, glass beads, glass fiber, silicon carbide, silicon nitride, aluminum nitride, carbon black, graphite, titanium dioxide, calcium carbonate, calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate, Examples include pulverized powder obtained by pulverizing cured products of cellulose, aramid, wood, phenolic resin molding materials, and epoxy resin molding materials. Among these, silica such as fused crushed silica, fused spherical silica, and crystalline silica is preferred, and fused spherical silica is more preferred. Moreover, among these, calcium carbonate is preferable in terms of cost.
• the inorganic fillers may be used alone or in combination of two or more.
• the average particle diameter D 50 of the inorganic filler is preferably 0.01 ⁇ m or more and 75 ⁇ m or less, more preferably 0.05 ⁇ m or more and 50 ⁇ m or less.
• the average particle diameter D 50 was defined as the average particle diameter in terms of volume using a laser diffraction measuring device RODOS SR type (SYMPATEC HEROS & RODOS).
• the inorganic filler can include two or more types of spherical silica having different average particle diameters D50 . This can improve fluidity and filling properties during transfer molding.
• the content of the inorganic filler is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 65% by mass or more, and particularly preferably is 75% by mass or more.
• the amount of the inorganic filler is preferably 93% by mass or less, more preferably 91% by mass or less, and even more preferably 90% by mass or less, based on the entire sealing resin composition.
• the upper limit is within the above range, the resulting encapsulating resin composition has good fluidity and good moldability. Therefore, the manufacturing stability of the sealed structure is increased, and a structure with an excellent balance between yield and durability can be obtained.
• the content of silica is preferably 40% by mass or more based on the entire sealing resin composition. , more preferably 60% by mass or more.
• the lower limit is within the above range, the fluidity and thermal expansion coefficient of the sealing resin composition during transfer molding will be well balanced.
• an inorganic filler when used in combination with a metal hydroxide such as aluminum hydroxide or magnesium hydroxide, or an inorganic flame retardant such as zinc borate, zinc molybdate, or antimony trioxide, as described below, the total amount of these inorganic flame retardants and the above-mentioned inorganic filler is desirably within the range of the content of the above-mentioned inorganic filler.
• a metal hydroxide such as aluminum hydroxide or magnesium hydroxide
• an inorganic flame retardant such as zinc borate, zinc molybdate, or antimony trioxide
• the sealing resin composition according to this embodiment contains wax.
• the molding shrinkage rate of the sealing resin composition of this embodiment is reduced to 0.1% or less by containing wax.
• a wax having a melting point of 30°C to 90°C is preferably used.
• the sealing resin composition has good meltability under the temperature applied in transfer molding, and thus improves fluidity during sealing and improves filling properties. It is possible.
• Such waxes include natural waxes such as carnauba wax, synthetic waxes such as montan acid ester wax and oxidized polyethylene wax, higher fatty acids such as zinc stearate, and metal salts thereof.
• the amount of wax blended is, for example, 0.05% by mass or more and 5.0% by mass or less based on the entire sealing resin composition.
• the lower limit of the amount of wax blended is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, based on the entire sealing resin composition.
• the upper limit of the amount of wax blended is preferably 4.5% by mass or less, more preferably 4.0% by mass or less, based on the entire sealing resin composition.
• the encapsulating resin composition of the present embodiment may further contain other additives such as a coupling agent, an adhesion aid, a coloring agent, an ion scavenger, a flame retardant, and an antioxidant, if necessary. may include.
• the sealing resin composition according to the present invention may contain a coupling agent such as a silane coupling agent in order to improve the adhesion between the epoxy resin and the inorganic filler.
• a coupling agent such as a silane coupling agent
• Examples of coupling agents include epoxysilane, aminosilane, ureidosilane, and mercaptosilane.
• epoxysilane examples include ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, and ⁇ -(3,4epoxycyclohexyl)ethyltrimethoxysilane. etc.
• aminosilane examples include ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyl Methyldimethoxysilane, N-phenyl ⁇ -aminopropyltriethoxysilane, N-phenyl ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltriethoxysilane, N-6-(aminohexyl)3 -aminopropyltrimethoxysilane, N-(3-(trimethoxysilylpropyl)-1,3-benzenedimethanane), etc.
• ureidosilane examples include ⁇ -ureidopropyltriethoxysilane, hexa Examples include methyldisilazane.It may also be used as a latent aminosilane coupling agent in which the primary amino site of aminosilane is protected by reacting with a ketone or aldehyde.Also, as aminosilane, it may be used as a coupling agent having a secondary amino group and protected by reacting with a ketone or aldehyde.
• Examples of mercaptosilane include ⁇ -mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl) )
• Examples include silane coupling agents such as disulfide that exhibit the same functions as mercaptosilane coupling agents when thermally decomposed.Also, these silane coupling agents may be compounded with those that have been subjected to a hydrolysis reaction in advance. These silane coupling agents may be used alone or in combination of two or more.
• mercaptosilane is preferred, from the viewpoint of fluidity, aminosilane is preferred, and from the viewpoint of adhesiveness, epoxysilane is preferred.
• the lower limit of the content of a coupling agent such as a silane coupling agent that can be used in the encapsulating resin composition according to the present invention is 0.01% by mass or more based on the entire encapsulating resin composition. is preferable, more preferably 0.05% by mass or more, particularly preferably 0.1% by mass or more. If the lower limit of the content of the coupling agent such as a silane coupling agent is within the above range, the interfacial strength between the epoxy resin and the inorganic filler will not decrease, and good vibration resistance can be obtained. .
• the upper limit of the content of a coupling agent such as a silane coupling agent is preferably 1% by mass or less, more preferably 0.8% by mass or less, particularly preferably 0.8% by mass or less based on the entire sealing resin composition. is 0.6% by mass or less. If the upper limit of the content of the coupling agent such as the silane coupling agent is within the above range, the interfacial strength between the epoxy resin and the inorganic filler will not decrease and good vibration resistance can be obtained. . Moreover, if the content of the coupling agent such as a silane coupling agent is within the above range, the water absorption of the cured product of the sealing resin composition is prevented from increasing.
• the sealing resin composition according to the present invention may contain an adhesion aid in order to improve the adhesion between the sealing portion obtained by curing the resin composition and the substrate.
• adhesion aids include triazole compounds, and examples of the triazole compounds include compounds having a 1,2,4-triazole ring and compounds having a 1,2,3-triazole ring.
• Specific compounds include, for example, 3-amino-1,2,4-triazole, 4-amino-1,2,3-triazole, 3-amino-1,2,4-triazole-5-carboxylic acid, 3-mercapto-1,2,4-triazole, 4-mercapto-1,2,3-triazole, 3,5-diamino-1,2,4-triazole, 3,5-dimercapto-1,2,4- Triazole, 4,5-dimercapto-1,2,3-triazole, 3-amino-5-mercapto-1,2,4-triazole, 4-amino-5-mercapto-1,2,3-triazole, 3- Examples include hydrazino-4-amino-5-mercapto-1,2,4-triazole and 5-mercapto-1,2,4-triazole-3-methanol, and one or more of these may be used in combination. It can be used as Among these, compounds having at least one mercapto group are preferred.
• the content of the adhesion aid in the encapsulating resin composition is preferably 0.01 to 2% by mass, and preferably 0.03 to 1% by mass, based on the total mass of the encapsulating resin composition. It is more preferable that there be. By setting the content of the adhesion aid within this range, the above-mentioned effects can be exhibited more markedly.
• coloring agent examples include carbon black, red iron oxide, titanium oxide, phthalocyanine, perylene black, and the like.
• the ion trapping agent used in the sealing resin composition of the present embodiment examples include hydrotalcites; hydrous oxides of elements selected from magnesium, aluminum, bismuth, titanium, and zirconium.
• the content of the ion scavenger in the encapsulating resin composition is preferably 0.03% by mass or more based on the entire encapsulating resin composition, and more It is preferably 0.05% by mass or more, preferably 2.0% by mass or less, and more preferably 1.0% by mass or less.
• flame retardants examples include brominated epoxy resin, antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, and phosphazene.
• antioxidant examples include hindered phenol compounds, hindered amine compounds, and thioether compounds.
• the encapsulating resin composition of this embodiment is prepared by uniformly mixing the above-mentioned components and additives used as necessary in a mixer or blender such as a tumbler mixer or a Henschel mixer to a predetermined content. It can be produced by kneading while heating in a kneader, roll, disper, ajihomo mixer, planetary mixer, etc.
• the temperature during kneading must be within a temperature range in which no curing reaction occurs, and it is preferable to melt and knead at a temperature of about 70 to 150°C, although it depends on the composition of the epoxy resin and curing agent.
• the mixture may be cooled and solidified, and the kneaded product may be processed into powder, granules, tablets, or sheets.
• Examples of methods for obtaining a powdery resin composition include a method of pulverizing a kneaded material using a pulverizer.
• the kneaded material may be formed into a sheet and then pulverized.
• the crushing device for example, a hammer mill, a stone mill type crusher, or a roll crusher can be used.
• a die having a small diameter is installed at the outlet of a kneading device, and the molten kneaded material discharged from the die is cut into a predetermined length with a cutter or the like. It is also possible to use a granulation method typified by the hot cut method. In this case, after obtaining a granular or powdery resin composition by a granulation method such as a hot-cut method, it is preferable to perform deaeration before the temperature of the resin composition drops too much.
• the above-mentioned powder-like resin composition is supplied to an extruder equipped with a screw and a die provided at the tip of the screw, and the resin composition is heated.
• a method is used in which the molten resin composition is melted and then extruded from this die by rotating a screw, and the extruded resin composition is cut into a predetermined length to obtain a tablet-shaped resin composition. be able to.
• the sealing resin composition of this embodiment containing the above components in predetermined amounts has a molding shrinkage rate of 0.1% or less.
• the molding shrinkage rate is measured by a method based on JIS K6911 of the cured product of the encapsulating resin composition.
• the molding shrinkage rate of the sealing resin composition is preferably 0.09% or less, more preferably 0.08% or less.
• the sealing resin composition of the present embodiment containing the above components in predetermined amounts has a cured product having a glass transition temperature of, for example, 150°C to 250°C, preferably 180 to 220°C.
• the sealing resin composition of the present embodiment containing the above components in a predetermined amount has a linear expansion coefficient of the cured product from 40°C to 80°C of, for example, 9 ppm/K or more and 13 ppm/K or less, preferably , 9 ppm/K or more and 12 ppm/K or less. Since the sealing resin composition of the present embodiment has a suppressed coefficient of thermal expansion when heated, it is possible to suppress deformation (thermal expansion, thermal contraction) that occurs during heating and cooling during the curing process of the resin. As a result, the warpage of the resulting single-sided sealed structure toward the sealing resin side is reduced, and a highly reliable single-sided sealed structure is thus obtained.
• the sealing resin composition of this embodiment is used to manufacture a single-sided sealed structure. More specifically, the single-sided sealed structure of this embodiment has an electronic device mounted on one side of a motherboard, and the surface of the motherboard on which this electronic device is mounted is sealed with the resin composition of this embodiment.
• the method for manufacturing a single-sided sealed structure of the present embodiment includes a step of collectively sealing a relatively large-area motherboard on which an electronic device is mounted using the sealing resin composition of the present embodiment. More specifically, first, a motherboard mounted with an electronic device is placed in a mold at a predetermined temperature (for example, 150 to 190° C.). Next, the sealing resin composition of this embodiment is injected into the mold (filling space) using a plunger at a predetermined molding pressure (for example, 3 to 10 MPa), and the resin composition is sealed for 90 to 180 seconds. Perform stop forming. Thereafter, post-curing is performed at a predetermined curing temperature and curing time (for example, 150 to 190° C., 2 to 6 hours) as necessary. This results in a single-sided sealed structure.
• a predetermined temperature for example, 150 to 190° C.
• a predetermined molding pressure for example, 3 to 10 MPa
• the large-area motherboard used in the manufacturing method of the single-sided sealed structure of this embodiment refers to a substrate having a diameter of 150 mm or more, or a rectangular size of 150 mm or more in length and 150 mm or more in width.
• a substrate with a length of 150 to 400 mm and a width of 150 to 400 mm is used.
• the thickness of the substrate may be as long as it has a support function during molding, and is preferably 30 ⁇ m to 5,000 ⁇ m, more preferably 50 ⁇ m to 3,000 ⁇ m.
• motherboard materials include copper or aluminum substrates with insulated surfaces, glass epoxy substrates, BT (bismaleimide triazine) resin substrates, FRP (fiber reinforced plastic) substrates, and in particular, glass epoxy substrates and BT resin substrates.
• a ceramic substrate is preferably used.
• the thickness of the sealing resin can be adjusted as appropriate depending on the dimensions of the electronic device mounted on the motherboard, and may be, for example, 0.1 to 10 mm.
• the thickness is preferably 0.2 to 8 mm.
• the single-sided sealed structure obtained by the method of the present embodiment can be installed in a vehicle such as a hybrid vehicle, a fuel cell vehicle, or an electric vehicle.
• Epoxy resin Triphenylmethane type epoxy resin (manufactured by Mitsubishi Chemical Corporation, E-1032H60)
• Epoxy resin 2 Biphenyl type epoxy resin (manufactured by Mitsubishi Chemical Corporation, YX4000K)
• Epoxy resin 3 Biphenylaralkyl epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-3000)
• Epoxy resin 4 Bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, YL6810)
• Curing agent 1 Trisphenylmethane type phenol novolac resin (manufactured by Meiwa Kasei Co., Ltd., MEH-7500)
• Curing agent 2 Biphenylaralkyl phenol resin (MEH-7851SS, manufactured by Meiwa Kasei Co., Ltd.)
• Hardening agent 3 Novolac type phenolic resin (manufactured by Sumitomo Bakelite Co., Ltd., PR-HF-3)
• Curing accelerator 1 Tetraphenylphosphonium 4,4-sulfonyl diphenolate
• Curing accelerator 2 Triphenylphosphine (manufactured by K.I. Kasei Co., Ltd., PP-360)
• Curing accelerator 3 Tetraphenylphosphonium 2,3-dihydroxynaphthalate
• Inorganic filler - Inorganic filler 1: Silica filler (manufactured by Admatex, SO-25R, average diameter 0.5 ⁇ m) - Inorganic filler 2: Silica filler (manufactured by Denka, FB-105, average diameter 11 ⁇ m) - Inorganic filler 3: Silica filler (manufactured by Denka, FB-950, average diameter 23 ⁇ m)
• Wax (wax) - Wax 1: Carnauba wax (manufactured by Toagosei Co., Ltd., TOWAX-132) - Wax 2: Diethanolamine dimontanoic acid ester (ITOHWAX TP NC-133, manufactured by Ito Oil Co., Ltd.) - Wax 3: Stearic acid (manufactured by NOF Corporation, SR-Sakura)
• Coupled agent -Coupling agent 1: N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Dow Corning Toray Co., Ltd., CF-4083)
• Coupling agent 2 3-glycidoxypropyltrimethoxysilane (manufactured by JNC Corporation, GPS-M)
• -Coupling agent 3 ⁇ -mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803P)
• Adhesion aid Adhesion aid 1: 3-amino-5-mercapto-1,2,4-triazole (coloring agent)
• Colorant 1 Carbon black (manufactured by Mitsubishi Chemical Corporation, carbon #5) (hardening inhibitor)
• Curing inhibitor 1 2,3-dihydroxynaphthalene (ion scavenger)
• Ion scavenger 1 Hydrotalcite
• each component was mixed at 15 to 28°C using a mixer so as to have the composition (parts by mass) shown in Table 1. Next, the resulting mixtures were roll-kneaded at 70 to 100°C, cooled, and pulverized to obtain each sealing resin composition.
• the molding shrinkage rate of the cured product of the sealing resin composition obtained in each example was measured as follows. Using a low-pressure transfer molding machine (manufactured by Kotaki Seiki Co., Ltd., KTS-30), each resin composition was injection molded under the conditions of a mold temperature of 175°C, an injection pressure of 6.9 MPa, and a curing time of 120 seconds. A molded article with a thickness of 5 mm was obtained. Next, the obtained molded products were post-cured at 175° C. for 4 hours to obtain test pieces made of cured products of each resin composition. Next, the molding shrinkage rate of the test piece obtained by a method based on JIS K6911 was measured. Note that the unit of molding shrinkage rate is %.
• the glass transition temperature of the cured product of the sealing resin composition obtained in each example was measured as follows. First, the resin composition was injection molded using a low-pressure transfer molding machine (manufactured by Kotaki Seiki Co., Ltd., "KTS-15") at a mold temperature of 175°C, an injection pressure of 6.9 MPa, and a curing time of 120 seconds. A 4 mm test piece was obtained. Next, the obtained test piece was post-cured at 175°C for 4 hours, and then measured using a thermomechanical analyzer (TMA100, manufactured by Seiko Electronics Co., Ltd.) at a temperature range of 0°C to 320°C and a heating rate of 5°C. Measurements were carried out under conditions of /min. Then, the glass transition temperature (°C) was calculated from this measurement result.
• TMA100 thermomechanical analyzer
• thermomechanical analyzer TMA100, manufactured by Seiko Instruments Inc.
• the measurement was carried out.
• the measurement data was analyzed to determine the average coefficient of linear expansion in the temperature range from 40°C to 80°C.
• the unit of the average linear expansion coefficient is [ppm/K].
• sealed substrates were produced using sealing resin compositions as described below, and the warpage of the sealed substrates was evaluated.
• Board (6 layers 200mm x 100mm x 1.6mm thick, copper remaining rate 60-70% PCB board, equipped with a connector for external connection, Tg 150°C or higher, elastic modulus 24.3GPa, CTE 14ppm/K, Poisson's ratio 0.
• a sealing resin composition was transfer-molded on only the circuit surface of 3) under the conditions of a mold temperature of 175°C, a molding pressure of 6 MPa, and a curing time of 5 minutes so that the molding resin thickness was 4 mm, and the sealed board I got it.
• the obtained sealed substrate was post-cured at 175° C. for 4 hours, and then the sealed substrate was left standing so as to be convex upward, and the difference in height between the highest position and the lowest position was measured. This difference was defined as the amount of warpage of the sealed substrate.
• the substrate manufactured using the resin composition of the example as a sealing material had a reduced amount of warpage. Therefore, it can be suitably used to manufacture a single-sided sealed structure with excellent reliability.

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• 2023
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