WO2023120739A1 - Composition de résine époxyde et dispositif à composants électroniques - Google Patents

Composition de résine époxyde et dispositif à composants électroniques Download PDF

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WO2023120739A1
WO2023120739A1 PCT/JP2022/048051 JP2022048051W WO2023120739A1 WO 2023120739 A1 WO2023120739 A1 WO 2023120739A1 JP 2022048051 W JP2022048051 W JP 2022048051W WO 2023120739 A1 WO2023120739 A1 WO 2023120739A1
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epoxy resin
resin composition
compound
viscosity
silicone
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PCT/JP2022/048051
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English (en)
Japanese (ja)
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東哲 姜
智博 池田
真志 白神
千嘉 内山
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株式会社レゾナック
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Publication of WO2023120739A1 publication Critical patent/WO2023120739A1/fr

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    • 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
    • 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

Definitions

  • the present disclosure relates to epoxy resin compositions and electronic component devices.
  • epoxy resin compositions containing epoxy resins and the like have been widely used in the fields of molding materials, laminated plate materials, adhesive materials and the like.
  • Epoxy resin-based compositions are widely used in the field of encapsulation technology for electronic components such as transistors and integrated circuits (ICs). The reason for this is that the epoxy resin composition has well-balanced properties such as moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness to inserts.
  • Epoxy resin compositions are sometimes required to be fast-curing from the viewpoint of improving productivity. Therefore, compounds that accelerate the curing reaction of epoxy resins, that is, curing accelerators are generally used (see, for example, Patent Documents 1 to 3).
  • molding is sometimes used in which a resin encapsulant made of an epoxy resin composition is molded with a mold.
  • transfer molding may be used in which a pellet-shaped resin sealing material is melted and poured into a mold for sealing.
  • a melted resin sealing material is poured into the mold, so when sealing a large area, unfilled portions may occur. Therefore, in recent years, compression molding, in which molding is performed after supplying a resin sealing material to a mold or an object to be sealed in advance, has begun to be used.
  • compression molding since the resin sealing material is directly supplied to the mold or the object to be sealed, there is an advantage that unfilled portions are less likely to occur even when sealing a large area.
  • the present disclosure has been made in view of the following conventional circumstances, and one aspect of the present disclosure is an epoxy resin composition that suppresses an increase in impurities such as chloride ions and foaming during degassing under reduced pressure, and An object of the present invention is to provide an electronic component device using this epoxy resin composition.
  • An epoxy resin composition containing an epoxy resin, a curing agent, an inorganic filler, and a silicone compound The silicone-based compound has a viscosity A at 175° C. of the epoxy resin composition when the silicone-based compound is added in an amount of 0.0015% by mass or more based on the total solid content of the epoxy resin composition, and the epoxy An epoxy resin composition having the following relationship between the viscosity B at 175° C. of a composition obtained by removing the silicone compound from the resin composition.
  • Viscosity A ⁇ Viscosity B ⁇ 2> The epoxy resin composition according to ⁇ 1>, wherein the silicone compound has a ratio of the viscosity A to the viscosity B (viscosity A/viscosity B) of 0.60 or more and less than 1.
  • the silicone-based compound has a gel time A at 175° C. of the epoxy resin composition when the silicone-based compound is added in an amount of 0.0015% by mass or more based on the total solid content of the epoxy resin composition.
  • the epoxy resin composition according to ⁇ 1> or ⁇ 2>, wherein the gel time B at 175° C. for the composition obtained by removing the silicone compound from the epoxy resin composition has the following relationship.
  • gel time A ⁇ gel time B ⁇ 4>
  • ⁇ 5> The epoxy resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the silicone compound comprises a polyether-modified polysiloxane compound.
  • An electronic component device comprising an element and the cured epoxy resin composition according to any one of ⁇ 1> to ⁇ 5> for encapsulating the element.
  • an epoxy resin composition that suppresses an increase in impurities such as chloride ions and foaming during degassing under reduced pressure, and an electronic component device using this epoxy resin composition. be able to.
  • the term "process” includes a process that is independent of other processes, and even if the purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
  • the numerical range indicated using "-" includes the numerical values before and after "-" as the minimum and maximum values, respectively.
  • the upper limit or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described step by step.
  • the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
  • each component may contain multiple types of applicable substances.
  • the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition unless otherwise specified. means quantity.
  • the particles corresponding to each component may include multiple types of particles.
  • the particle size of each component means a value for a mixture of the multiple types of particles present in the composition, unless otherwise specified.
  • An epoxy resin composition of the present disclosure is an epoxy resin composition containing an epoxy resin, a curing agent, an inorganic filler, and a silicone-based compound, wherein the silicone-based compound converts the silicone-based compound into the epoxy Viscosity A at 175° C. of the epoxy resin composition when added in an amount of 0.0015% by mass or more based on the total solid content of the resin composition, and a composition obtained by removing the silicone compound from the epoxy resin composition and the viscosity B at 175° C. for the following relationship. Viscosity A ⁇ Viscosity B
  • the specific silicone compound is the viscosity A at 175° C. of the epoxy resin composition when 0.0015% by mass to 0.6% by mass of the silicone compound is added to the total solid content of the epoxy resin composition.
  • the viscosity B at 175° C. of the composition obtained by removing the silicone compound from the epoxy resin composition may be in the relationship of “viscosity A ⁇ viscosity B”.
  • the gel time of the epoxy resin composition is shortened to improve moldability.
  • the viscosity of the epoxy resin composition usually increases.
  • the epoxy resin composition of the present disclosure tends to achieve a reduction in viscosity while increasing the strength of the cured product. Therefore, the epoxy resin composition of the present disclosure can be said to be most suitable for encapsulation of packages such as ultra-thin packages that are fragile and require filling properties in narrow passages.
  • the epoxy resin composition of the present disclosure contains an epoxy resin, a curing agent, an inorganic filler, and a specific silicone compound, and may contain other components as necessary. Each component contained in the epoxy resin composition of the present disclosure will be described in detail below.
  • Epoxy resin The epoxy resin composition of the present disclosure contains an epoxy resin.
  • the type of epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule.
  • at least one phenol selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A and bisphenol F, and naphthol compounds such as ⁇ -naphthol, ⁇ -naphthol and dihydroxynaphthalene.
  • a novolak type epoxy resin (phenol novolac type epoxy resin, ortho-cresol novolak-type epoxy resins, etc.); epoxidized triphenylmethane-type phenolic resins obtained by condensation or co-condensation of the above phenolic compounds and aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde in the presence of an acidic catalyst.
  • a triphenylmethane type epoxy resin a copolymer type epoxy resin obtained by epoxidizing a novolak resin obtained by co-condensing the above phenol compound and naphthol compound with an aldehyde compound in the presence of an acidic catalyst; bisphenol A, bisphenol diphenylmethane-type epoxy resins that are diglycidyl ethers such as F; biphenyl-type epoxy resins that are diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene-type epoxy resins that are diglycidyl ethers of stilbene-based phenol compounds; Sulfur atom-containing epoxy resins that are diglycidyl ethers; Epoxy resins that are glycidyl ethers of alcohols such as butanediol, polyethylene glycol and polypropylene glycol; Glycidyl polyvalent carboxylic acid compounds such as phthalic acid, isophthalic acid and
  • biphenyl type epoxy resins stilbene type epoxy resins, diphenylmethane type epoxy resins, sulfur atom-containing type epoxy resins, novolak type epoxy resins, and dicyclopentadiene type epoxy resins are selected from the viewpoint of the balance between heat resistance and fluidity.
  • triphenylmethane type epoxy resins, copolymer type epoxy resins and aralkyl type epoxy resins (these are referred to as "specific epoxy resins").
  • the specific epoxy resin may be used singly or in combination of two or more.
  • the content is preferably 30% by mass or more, more preferably 50% by mass or more, of the entire epoxy resin from the viewpoint of exhibiting the performance of the specific epoxy resin. .
  • biphenyl-type epoxy resin, stilbene-type epoxy resin, diphenylmethane-type epoxy resin or sulfur atom-containing epoxy resin is more preferable from the viewpoint of fluidity, and dicyclopentadiene-type epoxy resin is more preferable from the viewpoint of heat resistance.
  • Resins, triphenylmethane type epoxy resins or aralkyl type epoxy resins are preferred. Specific examples of preferred epoxy resins are shown below.
  • the biphenyl-type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton.
  • an epoxy resin represented by the following general formula (II) is preferred.
  • the 3, 3', 5, and 5' positions are methyl groups when the positions where the oxygen atoms are substituted in R 8 are the 4 and 4' positions.
  • R 8 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aromatic group having 4 to 18 carbon atoms, all of which may be the same or different.
  • n is the average value and represents a number from 0 to 10.
  • the stilbene-type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton.
  • an epoxy resin represented by the following general formula (III) is preferred.
  • the 3,3',5,5' positions when the positions where the oxygen atoms are substituted in R 9 are the 4 and 4' positions are methyl groups and three of the 3,3′,5,5′ positions of R 9 are methyl groups,
  • a mixed product in which one is a t-butyl group, the other R 9 is a hydrogen atom, and all of the R 10 are hydrogen atoms can be mentioned.
  • R 9 and R 10 each represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different.
  • n is the average value and represents a number from 0 to 10.
  • the diphenylmethane-type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton.
  • an epoxy resin represented by the following general formula (IV) is preferred.
  • all of R 11 are hydrogen atoms, and 3,3 when the positions of R 12 substituted with oxygen atoms are 4 and 4′.
  • YSLV-80XY (Nippon Steel Chemical & Materials Co., Ltd., trade name), which has methyl groups at the ', 5, 5' positions and hydrogen atoms at the other R 12 , is available as a commercial product.
  • R 11 and R 12 each represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different.
  • n is the average value and represents a number from 0 to 10.
  • the sulfur atom-containing type epoxy resin is not particularly limited as long as it is an epoxy resin containing a sulfur atom.
  • examples thereof include epoxy resins represented by the following general formula (V).
  • the epoxy resins represented by the following general formula (V) t-butyl groups are at the 3 and 3′ positions when the positions substituted with oxygen atoms in R 13 are the 4 and 4′ positions, YSLV-120TE (Nippon Steel Chemical & Materials Co., Ltd., trade name) having methyl groups at the 6 and 6′ positions and a hydrogen atom at the other R 13 is available as a commercial product.
  • R 13 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different.
  • n is the average value and represents a number from 0 to 10.
  • the novolak type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolak type phenol resin.
  • an epoxy resin obtained by epoxidizing a novolak-type phenolic resin such as a phenol novolak resin, a cresol novolak resin, or a naphthol novolak resin using a technique such as glycidyl etherification is preferable, and an epoxy represented by the following general formula (VI) Resin is more preferred.
  • R 14 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different.
  • R 15 represents a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different.
  • i each independently represents an integer of 0 to 3;
  • n is the average value and represents a number from 0 to 10.
  • the dicyclopentadiene type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a compound having a dicyclopentadiene skeleton as a raw material.
  • an epoxy resin represented by the following general formula (VII) is preferred.
  • R 16 represents a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different.
  • i each independently represents an integer of 0 to 3;
  • n is the average value and represents a number from 0 to 10.
  • the triphenylmethane-type epoxy resin is not particularly limited as long as it is an epoxy resin made from a compound having a triphenylmethane skeleton.
  • an epoxy resin obtained by glycidyl-etherifying a triphenylmethane-type phenolic resin obtained from an aromatic aldehyde compound and a phenolic compound is preferable, and an epoxy resin represented by the following general formula (VIII) is more preferable.
  • the epoxy resins represented by the following general formula (VIII) 1032H60 (Mitsubishi Chemical Co., Ltd., trade name) in which i is 0 and k is 0, EPPN-502H (Nippon Kayaku Co., Ltd., trade name) etc. are commercially available.
  • R 17 and R 18 each represent a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different.
  • Each i independently represents an integer of 0 to 3
  • each k independently represents an integer of 0 to 4.
  • n is the average value and represents a number from 0 to 10.
  • the copolymer type epoxy resin obtained by epoxidizing a novolac resin obtained from a naphthol compound, a phenolic compound, and an aldehyde compound is not particularly limited as long as it is an epoxy resin made from a compound having a naphthol skeleton and a compound having a phenolic skeleton.
  • an epoxy resin obtained by glycidyl-etherifying a novolac-type phenol resin using a compound having a naphthol skeleton and a compound having a phenol skeleton is preferable, and an epoxy resin represented by the following general formula (IX) is more preferable.
  • the epoxy resins represented by the following general formula (IX) NC-7300 (Nippon Kayaku Co., Ltd., trade name ) and the like are available as commercial products.
  • R 19 to R 21 represent monovalent organic groups having 1 to 18 carbon atoms, and may be the same or different.
  • Each i independently represents an integer of 0 to 3
  • each j independently represents an integer of 0 to 2
  • each k independently represents an integer of 0 to 4.
  • l and m are average values, numbers from 0 to 10, and (l+m) shows numbers from 0 to 10.
  • the terminal of the epoxy resin represented by formula (IX) is either one of formula (IX-1) or (IX-2) below.
  • Definitions of R 19 to R 21 , i, j and k in formulas (IX-1) and (IX-2) are the same as definitions of R 19 to R 21 , i, j and k in formula (IX).
  • n is 1 (when linked via a methylene group) or 0 (when not linked via a methylene group).
  • Examples of the epoxy resin represented by the general formula (IX) include random copolymers containing l structural units and m structural units at random, alternating copolymers containing alternately, and copolymers containing regularly , block copolymers containing in block form, and the like. Any one of these may be used alone, or two or more may be used in combination.
  • n and m are each an average value and a number of 0 to 10
  • (n+m) is a number of 0 to 10
  • n and m are each an average value and 1 to 9 and (n+m) represents a number from 2 to 10.
  • the aralkyl-type epoxy resin is composed of at least one selected from the group consisting of phenol compounds such as phenol and cresol, and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis(methoxymethyl)biphenyl or derivatives thereof.
  • phenol compounds such as phenol and cresol
  • naphthol compounds such as naphthol and dimethylnaphthol
  • dimethoxyparaxylene bis(methoxymethyl)biphenyl or derivatives thereof.
  • a phenolic resin synthesized from at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis(methoxymethyl)biphenyl or derivatives thereof is preferably an epoxy resin obtained by glycidyl etherification, and more preferably an epoxy resin represented by the following general formulas (X) and (XI).
  • epoxy resins represented by the following general formula (X) i is 0 and R 38 is a hydrogen atom, NC-3000S (Nippon Kayaku Co., Ltd., trade name), i is 0 and R 38 CER-3000 (Nippon Kayaku Co., Ltd., trade name), etc., which is a mixture of an epoxy resin in which is a hydrogen atom and an epoxy resin in which all R 8 in the general formula (II) are hydrogen atoms at a mass ratio of 80:20. available as a commodity.
  • ESN-175 Nippon Steel Chemical & Materials Co., Ltd., trade name
  • l j is 0, and k is 0, etc.
  • R 38 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different.
  • R 37 , R 39 to R 41 each represent a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different.
  • i is each independently an integer of 0 to 3
  • j is each independently an integer of 0 to 2
  • k is each independently an integer of 0 to 4
  • l is each independently an integer of 0 to 4 show.
  • n is an average value, each independently a number from 0 to 10.
  • R 8 to R 21 and R 37 to R 41 in general formulas (II) to (XI) above “all of which may be the same or different” means, for example, 8 to R 41 in formula (II). It means that all 88 R 8 may be the same or different.
  • Other R 9 to R 21 and R 37 to R 41 also mean that the respective numbers contained in the formula may all be the same or different.
  • R 8 to R 21 and R 37 to R 41 may be the same or different.
  • all of R 9 and R 10 may be the same or different.
  • the monovalent organic group having 1 to 18 carbon atoms in general formulas (III) to (XI) is preferably an alkyl group or an aryl group.
  • n in the above general formulas (II) to (XI) is an average value, and each independently preferably ranges from 0 to 10.
  • n is 10 or less, the melt viscosity of the resin component does not become too high, and the viscosity of the epoxy resin composition during melt molding decreases, resulting in poor filling, deformation of the bonding wire (gold wire that connects the element and the lead), and the like. tend to be suppressed.
  • n is set in the range of 0-4.
  • the epoxy equivalent of the epoxy resin is not particularly limited. From the viewpoint of the balance of various properties such as moldability, heat resistance and electrical reliability, the epoxy equivalent of the epoxy resin is preferably 60 g/eq to 1000 g/eq, more preferably 80 g/eq to 500 g/eq. is more preferred.
  • Epoxy resins may be liquid or solid. If the epoxy resin is solid, the softening point or melting point of the epoxy resin is not particularly limited. From the viewpoint of moldability and heat resistance, the temperature is preferably 40° C. to 180° C., and from the viewpoint of handleability during preparation of the epoxy resin composition, it is more preferably 50° C. to 130° C.
  • softening point refers to a value measured by the ring and ball method of JIS K 7234:1986.
  • melting point refers to a value measured according to the visual observation method of JIS K 0064:1992.
  • the content of the epoxy resin in the epoxy resin composition is preferably 0.5% by mass to 60% by mass, more preferably 2% by mass to 50% by mass, from the viewpoint of strength, fluidity, heat resistance, moldability, etc. It is more preferable to have
  • the epoxy resin composition may contain thermosetting resins other than the epoxy resin.
  • the type of thermosetting resin is not particularly limited, and examples thereof include phenol resins, thiol resins, urea resins, melamine resins, urethane resins, silicone resins, maleimide resins, unsaturated polyester resins, and the like.
  • thermosetting resins includes those that exhibit both thermoplastic and thermosetting properties, such as acrylic resins containing epoxy groups.
  • the thermosetting resin may be solid or liquid at normal temperature and normal pressure (eg, 25° C., atmospheric pressure), and is preferably solid. Thermosetting resins may be used singly or in combination of two or more.
  • the ratio of the epoxy resin to the total of the epoxy resin and the other thermosetting resin is preferably 30% by mass to 85% by mass, and 40% by mass to 80% by mass. % by mass is more preferred, and 50% by mass to 75% by mass is even more preferred.
  • the epoxy resin composition of the present disclosure contains a curing agent.
  • the type of curing agent is not particularly limited as long as it is a compound that undergoes a curing reaction with the epoxy resin used in combination.
  • curing agents used in combination with epoxy resins include phenol-based curing agents, amine-based curing agents, acid anhydride-based curing agents, polymercaptan-based curing agents, polyaminoamide-based curing agents, isocyanate-based curing agents, and blocked isocyanate-based curing agents. agents and the like.
  • the curing agent may be used singly or in combination of two or more.
  • the curing agent may be solid or liquid at normal temperature and normal pressure (for example, 25° C., atmospheric pressure), and is preferably solid. From the viewpoint of heat resistance, the curing agent is preferably a phenol-based curing agent or an amine-based curing agent.
  • Phenolic curing agents include, for example, phenol resins and polyhydric phenol compounds having two or more phenolic hydroxyl groups in one molecule. Specifically, polyhydric phenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, etc.
  • At least one phenolic compound selected from the group consisting of phenol compounds and naphthol compounds such as ⁇ -naphthol, ⁇ -naphthol, and dihydroxynaphthalene, and aldehyde compounds such as formaldehyde, acetaldehyde, and propionaldehyde are condensed under an acidic catalyst or Novolak-type phenolic resins obtained by cocondensation; phenol-aralkyl-type phenolic resins such as phenol aralkyl resins and naphthol-aralkyl resins synthesized from the above phenolic compounds and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, etc.; para-xylylene-modified phenols Resin; meta-xylylene-modified phenolic resin; melamine-modified phenolic resin; terpene-modified phenolic resin; Modified phenolic resin; polycyclic aromatic ring-modified
  • the phenol-based curing agent also includes a monohydric phenol compound having one phenolic hydroxyl group in one molecule. These phenol-based curing agents may be used singly or in combination of two or more.
  • the aralkyl-type phenol resin may be further copolymerized with another phenol resin.
  • Copolymerized aralkyl-type phenolic resins include copolymerized phenolic resins of triphenylmethane-type phenolic resin and aralkyl-type phenolic resin, copolymerized phenolic resins of salicylaldehyde-type phenolic resin and aralkyl-type phenolic resin, and novolac-type phenolic resin.
  • a copolymer type phenol resin of a resin and an aralkyl type phenol resin can be used.
  • phenolic curing agents from the viewpoint of heat resistance, aralkyl-type phenolic resin, dicyclopentadiene-type phenolic resin, triphenylmethane-type phenolic resin, and copolymer type phenolic resin of triphenylmethane-type phenolic resin and aralkyl-type phenolic resin. and at least one selected from the group consisting of novolac type phenolic resins (these are referred to as "specific phenolic curing agents").
  • the specific phenol-based curing agent may be used alone or in combination of two or more.
  • the content of the specific phenolic curing agent is preferably 30% by mass or more of the total phenolic curing agent from the viewpoint of sufficiently exhibiting their performance. It is more preferably 50% by mass or more.
  • the aralkyl-type phenolic resin is not particularly limited as long as it is a phenolic resin synthesized from at least one selected from the group consisting of phenolic compounds and naphthol compounds and dimethoxyparaxylene, bis(methoxymethyl)biphenyl or derivatives thereof.
  • phenol resins represented by the following general formulas (XII) to (XIV) are preferred.
  • R 23 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different.
  • R 22 , R 24 , R 25 and R 28 each represent a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different.
  • R 26 and R 27 each represent a hydroxyl group or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different.
  • i is each independently an integer of 0 to 3
  • j is each independently an integer of 0 to 2
  • k is each independently an integer of 0 to 4
  • n is an average value, each independently a number from 0 to 10.
  • phenolic resins represented by the general formula (XII), MEH-7851 (Meiwa Kasei Co., Ltd., trade name) in which i is 0 and all R 23 are hydrogen atoms is available as a commercial product. .
  • phenolic resins represented by the general formula (XIII) i is 0 and k is 0 XL-225, XLC (Mitsui Chemicals, Inc., trade name), MEH-7800 (Meiwa Kasei Co., Ltd., (trade name) and the like are available as commercial products.
  • phenolic resins represented by the general formula (XIV) j is 0, k is 0, and p is 0 SN-170 (Nippon Steel Chemical & Materials Co., Ltd., trade name), j is 0, k is 1, R 27 is a hydroxyl group, and p is 0, such as SN-395 (manufactured by Nippon Steel Chemical & Materials Co., Ltd., trade name), etc. are commercially available.
  • the dicyclopentadiene-type phenolic resin is not particularly limited as long as it is a phenolic resin obtained using a compound having a dicyclopentadiene skeleton as a raw material.
  • a phenol resin represented by the following general formula (XV) is preferred.
  • phenolic resins represented by the following general formula (XV) phenolic resins in which i is 0 are commercially available.
  • R 29 represents a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different.
  • i each independently represents an integer of 0 to 3;
  • n is the average value and represents a number from 0 to 10.
  • the triphenylmethane-type phenolic resin is not particularly limited as long as it is a phenolic resin obtained using an aromatic aldehyde compound as a raw material.
  • a phenol resin represented by the following general formula (XVI) is preferred.
  • phenolic resins represented by the following general formula (XVI), MEH-7500 (Meiwa Kasei Co., Ltd., trade name) in which i is 0 and k is 0 is commercially available.
  • R 30 and R 31 each represent a monovalent organic group having 1 to 18 carbon atoms and may be the same or different.
  • Each i is independently an integer of 0 to 3
  • each k is independently an integer of 0 to 4.
  • n is the average value and is a number from 0 to 10.
  • the copolymerized phenolic resin of triphenylmethane-type phenolic resin and aralkyl-type phenolic resin is not particularly limited as long as it is a copolymerized-type phenolic resin of phenolic resin and aralkyl-type phenolic resin obtained by using a compound having a benzaldehyde skeleton as a raw material. .
  • a phenol resin represented by the following general formula (XVII) is preferred.
  • phenol resins represented by the following general formula (XVII) i is 0, k is 0, q is 0 HE-510 (Air Water Chemical Co., Ltd., trade name), etc. are commercially available. available as a commodity.
  • R 32 to R 34 each represent a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different.
  • Each i is independently an integer of 0 to 3
  • each k is independently an integer of 0 to 4
  • each q is independently an integer of 0 to 5.
  • Each l and m is an average value and each independently represents a number from 0 to 11. However, the sum of l and m is a number from 1 to 11.
  • the novolak-type phenolic resin is not particularly limited as long as it is a phenolic resin obtained by condensation or co-condensation of at least one phenolic compound selected from the group consisting of phenolic compounds and naphthol compounds and an aldehyde compound in the presence of an acidic catalyst.
  • a phenol resin represented by the following general formula (XVIII) is preferred.
  • phenolic resins represented by the following general formula (XVIII) i is 0 and R 35 is all hydrogen atoms Tamanol 758, 759 (Arakawa Chemical Industries, Ltd., trade name), H-4 (Meiwa Kasei Co., Ltd., trade name) and the like are available as commercial products.
  • R 35 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different.
  • R 36 represents a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different.
  • i each independently represents an integer of 0 to 3;
  • n is the average value and represents a number from 0 to 10.
  • R 22 to R 36 in the general formulas (XII) to (XVIII) means, for example, that all i R 22 in formula (XII) are the same However, it means that they may be different from each other.
  • Other R 23 to R 36 also mean that the respective numbers contained in the formula may all be the same or different from each other.
  • R 22 to R 36 may be the same or different.
  • all of R 22 and R 23 may be the same or different
  • all of R 30 and R 31 may be the same or different.
  • n in the general formulas (XII) to (XVIII) is preferably in the range of 0 to 10. If it is 10 or less, the melt viscosity of the resin component does not become too high, and the viscosity of the epoxy resin composition during melt molding becomes low, causing poor filling and deformation of the bonding wire (gold wire connecting the element and the lead). becomes difficult.
  • the average n in one molecule is preferably set in the range of 0-4.
  • Examples of monohydric phenol compounds include “Tinuvin405”, “Tinuvin900”, “Tinuvin99-2”, “Tinuvin326”, “Tinuvin384-2”, “Tinuvin928” and the like (all of which are manufactured by BASF).
  • the proportion of the monohydric phenol compound in the total phenol-based curing agent is preferably 5% by mass to 20% by mass, more preferably 10% by mass to 19% by mass, more preferably 12% by mass to 12% by mass. More preferably, it is 18% by mass. In a certain aspect, it may be 5% by mass or less, 2% by mass or less, 1% by mass or less, or 0% by mass.
  • amine curing agents include aliphatic amine compounds such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4′-diamino-dicyclohexylmethane, Aromatic amine compounds such as diethyltoluenediamine, 3,3'-diethyl-4,4'-diaminodiphenylmethane, dimethylthiotoluenediamine, and 2-methylaniline; imidazoline compounds such as imidazoline, 2-methylimidazoline, and 2-ethylimidazoline; etc.
  • aliphatic amine compounds such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4′-diamino-dicyclohexylmethane
  • Aromatic amine compounds such as die
  • aromatic amine compounds are preferred, and diethyltoluenediamine, 3,3'-diethyl-4,4'-diaminodiphenylmethane and dimethylthiotoluenediamine are more preferred.
  • the functional group equivalent weight of the curing agent (hydroxyl group equivalent weight in the case of a phenol curing agent and active hydrogen equivalent weight in the case of an amine curing agent) is not particularly limited. From the viewpoint of the balance of various properties such as moldability, heat resistance and electrical reliability, it is preferably 10 g/eq to 1000 g/eq, more preferably 30 g/eq to 500 g/eq.
  • the hydroxyl equivalent in the case of a phenol curing agent is a value calculated based on the hydroxyl value measured according to JIS K0070:1992.
  • the active hydrogen equivalent in the case of an amine-based curing agent is a value calculated based on the amine value measured according to JIS K7237:1995.
  • the softening point or melting point when the curing agent is solid is not particularly limited. From the viewpoint of moldability and heat resistance, the temperature is preferably 40° C. to 180° C., and from the viewpoint of handleability during production of the epoxy resin composition, it is more preferably 50° C. to 130° C.
  • the equivalent ratio between the epoxy resin and the curing agent (the number of moles of epoxy groups in the resin/the number of moles of active hydrogen in the curing agent) is not particularly limited. .7 to 1.6 is preferred, 0.8 to 1.4 is more preferred, and 0.9 to 1.2 is even more preferred.
  • the epoxy resin composition of the present disclosure contains an inorganic filler.
  • the type of inorganic filler is not particularly limited. Specifically, silica such as spherical silica and crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, aluminum nitride, boehmite, beryllia, magnesium oxide, zirconia, Inorganic materials such as zircon, forsterite, steatite, spinel, mullite, titania, talc, clay, mica, and titanates. Inorganic fillers having a flame retardant effect may also be used.
  • Inorganic fillers having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as composite hydroxides of magnesium and zinc, and zinc borate. Among them, spherical silica is preferable from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferable from the viewpoint of high thermal conductivity.
  • An inorganic filler may be used individually by 1 type, or may be used in combination of 2 or more types. Examples of the state of the inorganic filler include powder, beads obtained by spheroidizing powder, and fibers.
  • the average particle size of the inorganic filler is not particularly limited.
  • the volume average particle size is preferably 30 ⁇ m or less, more preferably 0.1 ⁇ m to 30 ⁇ m, even more preferably 0.2 ⁇ m to 25 ⁇ m, particularly preferably 0.5 ⁇ m to 20 ⁇ m. .
  • the volume average particle size is 30 ⁇ m or less, the filling property into narrow gaps tends to be improved.
  • the volume average particle size is 0.1 ⁇ m or more, the increase in the viscosity of the epoxy resin composition tends to be more suppressed.
  • the volume-average particle size of the inorganic filler can be measured as the volume-average particle size (D50) with a particle size distribution analyzer using a laser diffraction scattering method.
  • the particle shape of the inorganic filler is preferably spherical rather than square, and the particle size distribution of the inorganic filler is preferably distributed over a wide range.
  • the content of the inorganic filler in the epoxy resin composition is not particularly limited. From the viewpoint of fluidity and strength, the total solid content of the epoxy resin composition is preferably 60% by volume or more, more preferably 60% to 90% by volume, and 62% to 88% by volume. It is even more preferable to have When the content of the inorganic filler is 60% by volume or more of the total solid content of the epoxy resin composition, the properties of the cured product, such as coefficient of thermal expansion, thermal conductivity and elastic modulus, tend to be further improved. When the content of the inorganic filler is 90% by volume or less of the total solid content of the epoxy resin composition, the increase in viscosity of the epoxy resin composition is suppressed, the fluidity is further improved, and the moldability is further improved. There is a tendency.
  • the epoxy resin composition of the present disclosure contains a specific silicone compound.
  • the specific silicone compound is not particularly limited as long as the viscosity A and the viscosity B are in the relationship of "viscosity A ⁇ viscosity B".
  • the specific silicone compound preferably has a ratio of viscosity A to viscosity B (viscosity A/viscosity B) of 0.60 or more and less than 1, more preferably 0.61 to 0.99.
  • the viscosity at 175° C. of the epoxy resin composition and the composition from which the silicone compound is removed from the epoxy resin composition refers to the value measured using a Koka-type flow tester.
  • the specific silicone compound may be a compound that is liquid at 25°C.
  • the specific silicone-based compound is the gel time A at 175° C. of the epoxy resin composition when the silicone-based compound is added in an amount of 0.0015% by mass or more based on the total solid content of the epoxy resin composition, and the epoxy resin composition. It is preferable that the gel time B at 175° C. of the composition excluding the silicone-based compound from the above is in the relationship of “gel time A ⁇ gel time B”.
  • the specific silicone-based compound is the gel time A at 175° C. of the epoxy resin composition when 0.0015% by mass to 0.6% by mass of the silicone-based compound is added to the total solid content of the epoxy resin composition. , and the gel time B at 175° C.
  • the ratio of gel time A to gel time B is preferably 0.80 or more and less than 1, more preferably 0.81 to 0.99. More preferably 82 to 0.98.
  • the gel time at 175° C. for the epoxy resin composition and the composition excluding the silicone compound from the epoxy resin composition refers to a value measured using a JSR Trading Co., Ltd. curelastometer. 3 g of the measurement sample is measured at 175° C. using a cureastometer manufactured by JSR Trading Co., Ltd.
  • the gel time (seconds) is defined as the time until the torque curve rises.
  • the chemical shift A appearing at ⁇ 0.3 ppm to 0.3 ppm is a chemical shift corresponding to a hydrophobic organic moiety in a specific silicone compound, and specifically corresponds to a hydrogen atom on a carbon atom bonded to a silicon atom.
  • the chemical shift corresponding to the hydrogen atom in the methyl group of ⁇ Si—CH 3 is a chemical shift corresponding to the hydrophilic organic portion in the specific silicone compound, specifically, on the carbon atom bonded to the etheric oxygen atom
  • Chemical shifts corresponding to hydrogen atoms are included, such as chemical shifts corresponding to hydrogen atoms in the methylene group of —O—CH 2 —.
  • the integrated value of the chemical shift B is preferably 35 to 100, more preferably 40 to 80, even more preferably 45 to 60 when relative to the integrated value of the chemical shift A as 300. .
  • a method for measuring 1 H NMR of a specific silicone-based compound in CDCl 3 is as follows. 10 mg of the sample was dissolved in 0.7 mL of CDCl 3 (not containing tetramethylsilane (TMS)), and subjected to a resonance frequency of 400 MHz and a temperature of 25 using a superconducting Fourier transform nuclear magnetic resonance apparatus (eg, Bruker's "AVANCE3 HD 400 Nanobay”). °C, 16 integration times, and 1 second relaxation time.
  • TMS tetramethylsilane
  • the method for extracting the specific silicone compound from the epoxy resin composition is as follows. 20 g of the epoxy resin composition is dissolved in 40 mL of acetone, and only the organic component of the supernatant is extracted using a centrifuge. After that, the extracted organic matter was subjected to GPC: LC pump LC-20AR (manufactured by Shimadzu Corporation), degasser: DGU-20A3R (manufactured by Shimadzu Corporation), columns: GL-R450, GL-R440, GL-R400, Solvent: acetone, Column temperature: Room temperature (25 ° C.), Flow rate: 4.0 mL / min, Detector: Differential refractive index detector (RI) RID-20A (manufactured by Shimadzu Corporation) is used for fractionation, and the silicone compound is Take out.
  • RI Differential refractive index detector
  • the specific silicone compound preferably has a polyether moiety, more preferably a polyether-modified polysiloxane compound.
  • a polyether moiety examples include a polyethyleneoxy group, a polypropyleneoxy group, and the like.
  • the structure of the polyether portion may be of one type alone or a combination of two or more types.
  • the arrangement position of the polyether portion in the specific silicone-based compound may be any of the side chain, the main chain, and the end.
  • the structure of the polyether portion may be a structure represented by the following formula (1).
  • the C2H4O and C3H6O may be included in a random, alternating or block order .
  • R 1 represents an alkylene group
  • R 2 represents an alkyl group
  • x represents 0 or 1
  • y and z each independently represent 0-40.
  • the alkylene group represented by R 1 may have 1 to 15 carbon atoms
  • the alkyl group represented by R 2 may have 1 to 15 carbon atoms.
  • the structure of the polyether portion may be the structure represented by the following formula (2).
  • R 1 , x, y and z in formula (2) are synonymous with R 1 , x, y and z in formula (1), respectively.
  • Two R 1s included in formula (2) may be the same or different.
  • the specific silicone compound may have other functional groups in addition to the polyether moiety.
  • a hydroxyl group etc. are mentioned as another functional group.
  • a curing accelerator is usually used to improve the curability of the epoxy resin composition.
  • impurities such as chloride ions in the epoxy resin composition tend to increase as the amount of the curing accelerator increases.
  • the viscosity of the epoxy resin composition tends to increase.
  • a polyether-modified polysiloxane compound is used as the specific silicone-based compound, the gel time of the epoxy resin composition becomes shorter as the amount added increases, and impurities such as chloride ions decrease accordingly, and the viscosity increases.
  • the polyether-modified polysiloxane compound used as the specific silicone compound functions as a curing accelerator or its auxiliary agent.
  • the reason why the polyether-modified polysiloxane compound used as the specific silicone-based compound functions as a curing accelerator or its auxiliary agent is considered to be that the pH of the water extracted from the epoxy resin composition is made acidic. It is believed that the polyether-modified polysiloxane compound used as the specific silicone compound does not deteriorate the solubility of the epoxy resin composition during compression molding, and also functions as a curing accelerator or its auxiliary agent.
  • the "solubility" of an epoxy resin composition means the ease with which an epoxy resin composition melts.
  • the content of the specific silicone-based compound in the epoxy resin composition is preferably 0.0010% by mass to 5% by mass, more preferably 0.0012% by mass to 1% by mass, from the viewpoint of exhibiting further antifoaming properties. more preferably 0.0015% by mass to 0.7% by mass.
  • the epoxy resin composition of the present disclosure may contain other silicone-based compounds other than the specific silicone-based compound.
  • Other silicone compounds include conventionally known liquid silicone antifoaming agents.
  • the content of other silicone compounds is preferably from 0.010% by mass to 1% by mass, more preferably from 0.012% by mass to 0.8% by mass, and from 0.015% by mass to More preferably, it is 0.5% by mass.
  • the other silicone-based compounds may be included in the composition excluding the specific silicone-based compound from the epoxy resin composition.
  • the epoxy resin composition of the present disclosure when the curing agent contains a phenolic curing agent, the epoxy resin composition of the present disclosure may or may not contain a curing accelerator.
  • the type of curing accelerator is not particularly limited, and can be selected according to the type of epoxy resin, desired properties of the epoxy resin composition, and the like.
  • diazabicycloalkenes such as 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU); -cyclic amidine compounds such as methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole; derivative of the compound; phenol novolak salt of the cyclic amidine compound or its derivative; ,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, quinone compounds such as phenyl-1,4-benzoquinone, diazophenylmethane, etc.
  • DBN 1,5-diazabicyclo[4.3.0]n
  • a compound having intramolecular polarization obtained by adding a compound having a ⁇ bond DBU tetraphenylborate salt, DBN tetraphenylborate salt, 2-ethyl-4-methylimidazole tetraphenylborate salt, N-methyl cyclic amidinium compounds such as tetraphenylborate salts of morpholine; tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; the tertiary amine compounds derivatives; ammonium salt compounds such as tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, tetrapropyl
  • primary phosphine dimethylphosphine, secondary phosphine such as diphenylphosphine, triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkylalkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine , dialkylarylphosphine, alkyldiarylphosphine, trinaphthylphosphine, tris(benzyl)phosphin
  • curing accelerators capable of low-temperature curing include adducts of tributylphosphine and 1,4-benzoquinone, dimethylaminopyridine, 2-ethyl-4-methylimidazole, 2-methylimidazole, 1-benzyl-2-methyl imidazole and the like.
  • a hardening accelerator may be used individually by 1 type, or may be used in combination of 2 or more types.
  • the content of the curing accelerator is, in one aspect, 0.1% by mass to 8% by mass with respect to the total amount of the epoxy resin and the curing agent. is preferred, more preferably 0.3% by mass to 6% by mass, and even more preferably 0.5% by mass to 5% by mass.
  • the content of the curing accelerator is preferably 0.1% by mass to 4% by mass, and 0.3% by mass to 3% by mass, based on the total amount of the epoxy resin and the curing agent. % by mass is more preferred, and 0.5% by mass to 1% by mass is even more preferred.
  • the epoxy resin composition of the present disclosure may contain colorants.
  • the coloring agent include known coloring agents such as carbon black, black titanium oxide, organic dyes, organic pigments, red lead, and red iron oxide.
  • the content of the coloring agent can be appropriately selected depending on the purpose.
  • the colorants may be used singly or in combination of two or more.
  • the content is preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 3% by mass.
  • the epoxy resin composition of the present disclosure may contain an ion exchanger.
  • an ion exchanger is not particularly limited, and conventionally known ones can be used. Specific examples include hydrotalcite compounds and hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth.
  • the ion exchangers may be used singly or in combination of two or more. Among them, hydrotalcite represented by the following general formula (A) is preferable.
  • the epoxy resin composition contains an ion exchanger
  • its content is not particularly limited as long as it is sufficient to trap ions such as halogen ions.
  • it is preferably 0.1 to 30 parts by mass, more preferably 1 to 5 parts by mass, with respect to 100 parts by mass of the epoxy resin.
  • the epoxy resin composition of the present disclosure may contain a mold release agent from the viewpoint of obtaining good releasability from the mold during molding.
  • the release agent is not particularly limited, and conventionally known agents can be used. Specific examples include carnauba wax, higher fatty acids such as montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene.
  • the release agent may be used singly or in combination of two or more.
  • the content thereof is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the epoxy resin.
  • the amount of the release agent is 0.01 parts by mass or more with respect to 100 parts by mass of the epoxy resin, there is a tendency that sufficient releasability can be obtained.
  • the amount of release agent is 15 parts by mass or less with respect to 100 parts by mass of the epoxy resin, there is a tendency that better adhesion is obtained.
  • the epoxy resin composition of the present disclosure may contain flame retardants.
  • the flame retardant is not particularly limited, and conventionally known ones can be used. Specific examples include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms or phosphorus atoms, and metal hydroxides.
  • a flame retardant may be used individually by 1 type, or may be used in combination of 2 or more types.
  • the epoxy resin composition contains a flame retardant
  • its content is not particularly limited as long as it is sufficient to obtain the desired flame retardant effect.
  • it is preferably 1 part by mass to 30 parts by mass, more preferably 2 parts by mass to 20 parts by mass with respect to 100 parts by mass of the epoxy resin.
  • the epoxy resin composition of the present disclosure may contain stress relieving agents such as silicone rubber particles.
  • stress relaxation agent By including a stress relaxation agent in the epoxy resin composition, it is possible to further reduce the warpage deformation of the package and the occurrence of package cracks.
  • the stress relaxation agent include commonly used known stress relaxation agents (flexible agents).
  • thermoplastic elastomers such as silicone, styrene, olefin, urethane, polyester, polyether, polyamide, and polybutadiene that may be epoxy-modified, NR (natural rubber), NBR ( acrylonitrile-butadiene rubber), acrylic rubber, urethane rubber, rubber particles such as silicone powder, methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer rubber particles having a core-shell structure such as polymers; A polymer etc. are mentioned.
  • a stress relaxation agent may be used individually by 1 type, or may be used in combination of 2 or more types.
  • the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 25 parts by mass with respect to 100 parts by mass of the epoxy resin. is more preferable.
  • the epoxy resin composition of the present disclosure may contain a coupling agent.
  • the type of coupling agent is not particularly limited, and known coupling agents can be used. Examples of coupling agents include silane coupling agents and titanium coupling agents.
  • a coupling agent may be used individually by 1 type, or may use 2 or more types together.
  • silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxy Propylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane , 3-(2-aminoethyl)aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane , 3-ureido
  • Titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tris(dioctylpyrophosphate) titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, tetraoctylbis(ditridecylphosphite) titanate, tetra(2, 2-diallyloxymethyl-1-butyl)bis(ditridecylphosphite)titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate, isopropyltrioctanoyltitanate, isopropyldimethacrylisostearoyltitanate , isopropyltridodecylbenzenesulfonyltitanate, isopropylisostearoyldiacryl
  • the content of the coupling agent is 0.001 with respect to 100 parts by mass of the inorganic filler, from the viewpoint of adhesion at the interface between the epoxy resin and the inorganic filler. It is preferably from 0.01 to 8 parts by mass, even more preferably from 0.05 to 5 parts by mass.
  • the epoxy resin composition of the present disclosure may contain a solvent.
  • the solvent contained in the epoxy resin composition may or may not dissolve either the epoxy resin or the curing agent.
  • the boiling point of the solvent at normal pressure is preferably from 50°C to 180°C, more preferably from 60°C to 170°C, even more preferably from 70°C to 160°C, and at 70°C to 140°C. is particularly preferred, and 70°C to 120°C is most preferred.
  • a solvent may be used individually by 1 type, or may be used in combination of 2 or more types. When two or more solvents are used in combination, the boiling point at normal pressure of the solvent with the highest boiling point is preferably within the above range.
  • solvents include methyl ethyl ketone, methyl isobutyl ketone, toluene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclohexanone.
  • methyl isobutyl ketone and methyl ethyl ketone are preferred.
  • the content of the solvent in the entire epoxy resin composition is preferably 0.1% by mass to 2% by mass, more preferably 0.1% by mass to 0.5% by mass. is more preferable.
  • the content of the solvent in the entire epoxy resin composition is 2% by mass or less, blocking of the epoxy resin composition is less likely to occur, and the supply of the epoxy resin composition to a molding machine such as a press tends to become easier. It is in.
  • the content of the solvent in the entire epoxy resin composition is 0.1% by mass or more, the fluidity during molding tends to be further improved.
  • the solvent content is calculated based on the change in mass before and after heating the epoxy resin composition at 175° C. for 1 hour.
  • the viscosity of the epoxy resin composition is not particularly limited. It is preferable to adjust the desired viscosity according to the molding method, the composition of the epoxy resin composition, and the like.
  • the viscosity of the epoxy resin composition at 175° C. is preferably 200 Pa s or less, preferably 180 Pa s or less, from the viewpoint of reducing wire flow. It is more preferably 150 Pa ⁇ s or less.
  • the lower limit of the viscosity of the epoxy resin composition is not particularly limited.
  • the epoxy resin composition of the present disclosure may be produced through any process.
  • a general method for producing an epoxy resin composition after thoroughly mixing components in predetermined amounts with a mixer or the like to form a mixture, the mixture is melt-kneaded with a mixing roll, an extruder, or the like, and cooled.
  • a method of crushing can be mentioned. More specifically, for example, predetermined amounts of the above components are uniformly stirred and mixed, kneaded in a kneading device preheated to 70° C. to 140° C., cooled, and pulverized. .
  • the epoxy resin composition obtained through kneading may be cooled and pulverized to obtain a powdery epoxy resin composition. Further, the epoxy resin composition obtained through kneading may be molded into a granular, tablet, pellet or granule (cylindrical granules, etc.).
  • the pulverization method or molding method of the epoxy resin composition is not particularly limited, and conventionally known methods can be used.
  • the epoxy resin composition of the present disclosure is not particularly limited, and for example, it can be used as a resin sealing material for electronic component devices in various mounting techniques.
  • the epoxy resin composition of the present disclosure is used for resin moldings for various modules, resin moldings for motors, vehicle-mounted resin moldings, sealing materials for electronic circuit protective materials, etc. It can be used in various applications where it is desirable to have properties.
  • foaming tends to be suppressed during heating under reduced pressure and degassing.
  • the epoxy resin composition of the present disclosure is used as a resin encapsulant and molded by a transfer molding method, the occurrence of voids after molding tends to be suppressed.
  • An electronic component device of the present disclosure includes an element and a cured product of the epoxy resin composition of the present disclosure that seals the element.
  • elements active elements such as semiconductor chips, transistors, diodes, thyristors, capacitors, resistors, etc.
  • passive elements such as coils, etc.
  • the element is fixed on a lead frame, and the terminal portion of the element such as a bonding pad and the lead portion are connected by wire bonding, bumps, or the like, and then transfer molding or compression molding is performed using an epoxy resin composition.
  • DIP Dual Inline Package
  • PLCC Plastic Leaded Chip Carrier
  • QFP Quadad Flat Package
  • SOP Small Outline Package
  • SOJ Small Outline J-lead pack
  • TCP Tepe Carrier Package having a structure in which an element connected to a tape carrier with bumps is sealed with an epoxy resin composition
  • COB Chip On Board
  • COB Chip On Board
  • hybrid ICs hybrid ICs, multi-chip modules, etc.
  • an epoxy resin composition After mounting the element on the surface of the support member on which terminals for wiring board connection are formed on the back surface, and connecting the element and the wiring formed on the support member by bumps or wire bonding, the element is sealed with an epoxy resin composition.
  • BGA All Grid Array
  • CSP Chip Size Package
  • MCP Multi Chip Package
  • SiP System In a Package
  • the epoxy resin composition can be suitably used in printed wiring boards.
  • Methods for sealing electronic component devices using epoxy resin compositions include transfer molding, injection molding, and compression molding. Among these, the transfer molding method or the compression molding method is preferable, and the compression molding method is more preferable.
  • Examples 1 to 15 and Comparative Examples 1 to 16 The components shown in Tables 1 to 5 were mixed in the amounts (parts by mass) shown in Tables 1 to 5 to prepare epoxy resin compositions. Specifically, after mixing the materials, they were kneaded by a twin-screw extruder whose internal temperature was adjusted to 70° C. to 140° C., cooled and pulverized to obtain an epoxy resin composition. Details of each component are as follows.
  • Epoxy resin 1 biphenyl type epoxy resin (epoxy equivalent: 196 g / eq) ⁇ Epoxy resin 2 ... biphenyl type epoxy resin (epoxy equivalent: 192 g / eq) ⁇ Epoxy resin 3 ... triphenylmethane type epoxy resin (epoxy equivalent: 165 g / eq) ⁇ Epoxy resin 4 ... aralkyl type epoxy resin (epoxy equivalent: 275 g / eq) ⁇ Epoxy resin 5 ... copolymer type epoxy resin (epoxy equivalent: 250 g / eq) ⁇ Curing agent 1 ...
  • novolac type phenol resin (hydroxyl equivalent: 103 g / eq to 107 g / eq g / eq) ⁇ Curing agent 2 ... aralkyl-type phenolic resin (hydroxyl equivalent: 201 g / eq to 205 g / eq g / eq) ⁇ Curing agent 3: triphenylmethane type phenolic resin (hydroxyl equivalent: 103 g/eq) ⁇ Curing agent 4 ...
  • aralkyl-type phenol resin (hydroxyl equivalent: 167 g / eq to 179 g / eq g / eq)
  • Curing agent 6 aralkyl-type phenolic resin (hydroxyl group equivalent: 175 g/eqg/eq) ⁇ Curing agent 6 ...
  • Example 8 is compared with Comparative Example 4, Examples 9 and 10 are compared with Comparative Example 5, Example 11 is compared with Comparative Example 6, and Examples 12 to 14 are comparative examples. 7, Example 15 is compared with Comparative Example 8, Comparative Examples 9 to 15 are compared with Comparative Example 1, and Comparative Example 1 is compared with Comparative Example 16 to determine the viscosity ratio. rice field.
  • the gel time (GT) of the epoxy resin composition was measured using a cureastometer manufactured by JSR Trading Co., Ltd. 3 g of the epoxy resin composition was measured at 175° C. using a cureastometer manufactured by JSR Trading Co., Ltd. The gel time (seconds) was defined as the time until the torque curve rises. Based on the gel time measured as described above, the gel time ratio (ratio (gel time A/gel time B)) for each example and comparative example was obtained. The results obtained are shown in Tables 6 to 10. Incidentally, Examples 1 to 3 are compared with Comparative Example 1, Examples 4 and 5 are compared with Comparative Example 2, Example 6 is compared with Comparative Example 3, and Examples 7 and 3 are compared.
  • Example 8 is compared with Comparative Example 4, Examples 9 and 10 are compared with Comparative Example 5, Example 11 is compared with Comparative Example 6, and Examples 12 to 14 are comparative examples. 7, Example 15 is compared with Comparative Example 8, Comparative Examples 9 to 15 are compared with Comparative Example 1, and Comparative Example 1 is compared with Comparative Example 16 to determine the gel time ratio. rice field.
  • rheometer viscosity (rheometer viscosity) Using a HAAKE RheoStressTM6000 manufactured by Thermo Fisher Scientific, the rheometer viscosity was measured under the conditions of a sample amount of about 1.0 g, a measurement temperature of 140° C., a rotation frequency of 5 rad/sec, and a gap of 0.5 mm.
  • the starting point of the viscosity measurement using the rheometer is the time when the sample is set on the rheometer plate when the temperature reaches 140°C. was taken as the rheometer viscosity. The results are shown in Tables 6-10.
  • the epoxy resin composition was molded using a transfer molding machine at a molding temperature of 175° C., a molding pressure of 6.9 MPa, and a molding time of 120 seconds. Then, post-curing was performed at 175° C. for 5 hours. Thus, a test piece having a length of 130 mm, a width of 13 mm and a thickness of 4 mm was prepared. Using this test piece, using a viscoelasticity measuring device RSA-3 (TA Instruments), the elastic modulus and bending at 25 ° C. and 210 ° C. under the conditions of a temperature increase rate of 10 ° C./min and a frequency of 1 Hz in 3-point bending mode. asked for strength. The elastic modulus and strength at 25° C. were defined as room temperature elastic modulus and room temperature strength. The elastic modulus and strength at 210° C. were defined as high temperature elastic modulus and high temperature strength. The results are shown in Tables 6-10.
  • the epoxy resin composition was molded using a transfer molding machine at a molding temperature of 175° C., a molding pressure of 6.9 MPa, and a molding time of 120 seconds. Then, the molded product obtained was pulverized with an alumina ball mill. 5 g of the obtained pulverized powder was put into a pressure container together with 50 g of ion-exchanged water, left at 121° C. under 2 atmospheres for 20 hours, the pulverized powder and extracted water were filtered, and the obtained extracted water was heated at 25° C. pH was measured using a pH meter. The results are shown in Tables 6-10.
  • the epoxy resin composition was molded using a transfer molding machine at a molding temperature of 175° C., a molding pressure of 6.9 MPa, and a molding time of 120 seconds. Then, the molded product obtained was pulverized with an alumina ball mill. 5 g of the obtained pulverized powder was put into a pressure vessel together with 50 g of ion-exchanged water, left at 121 ° C. under 2 atmospheres for 20 hours, and then filtered. ppm) was determined using ion chromatography. The results are shown in Tables 6-10.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

Une composition de résine époxyde selon la présente invention contient une résine époxyde, un agent de durcissement, une charge inorganique et un composé de silicone ; et le composé de silicone est conçu de façon à satisfaire l'expression relationnelle (viscosité A) < (viscosité B), dans laquelle (viscosité A) est la viscosité à 175 °C de la composition de résine époxyde dans laquelle au moins 0,0015 % en masse du composé de silicone est ajouté par rapport à la teneur totale en solides de la composition de résine époxyde et (viscosité B) est la viscosité à 175 °C d'une composition qui est obtenue par élimination du composé de silicone de la composition de résine époxyde.
PCT/JP2022/048051 2021-12-24 2022-12-26 Composition de résine époxyde et dispositif à composants électroniques WO2023120739A1 (fr)

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CN117467243A (zh) * 2023-12-05 2024-01-30 昆山兴凯半导体材料有限公司 一种高导热、高绝缘性的环氧组合物及其应用

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JPH08176269A (ja) * 1994-12-27 1996-07-09 Matsushita Electric Works Ltd 封止用エポキシ樹脂組成物
JPH10158361A (ja) * 1996-11-29 1998-06-16 Sumitomo Bakelite Co Ltd 半導体封止用エポキシ樹脂組成物
JPH10231355A (ja) * 1997-02-20 1998-09-02 Sumitomo Bakelite Co Ltd 半導体封止用エポキシ樹脂組成物
JP2000007900A (ja) * 1998-04-23 2000-01-11 Matsushita Electric Works Ltd 封止用のエポキシ樹脂組成物および半導体装置
JP2000327883A (ja) * 1999-05-20 2000-11-28 Sumitomo Bakelite Co Ltd エポキシ樹脂組成物及び半導体装置
WO2018135558A1 (fr) * 2017-01-23 2018-07-26 株式会社ダイセル Composition de résine durcissable destinée à réfléchir la lumière, produit durci obtenu à partir de ladite composition, et dispositif semi-conducteur optique
JP2021123647A (ja) * 2020-02-05 2021-08-30 味の素株式会社 樹脂組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08176269A (ja) * 1994-12-27 1996-07-09 Matsushita Electric Works Ltd 封止用エポキシ樹脂組成物
JPH10158361A (ja) * 1996-11-29 1998-06-16 Sumitomo Bakelite Co Ltd 半導体封止用エポキシ樹脂組成物
JPH10231355A (ja) * 1997-02-20 1998-09-02 Sumitomo Bakelite Co Ltd 半導体封止用エポキシ樹脂組成物
JP2000007900A (ja) * 1998-04-23 2000-01-11 Matsushita Electric Works Ltd 封止用のエポキシ樹脂組成物および半導体装置
JP2000327883A (ja) * 1999-05-20 2000-11-28 Sumitomo Bakelite Co Ltd エポキシ樹脂組成物及び半導体装置
WO2018135558A1 (fr) * 2017-01-23 2018-07-26 株式会社ダイセル Composition de résine durcissable destinée à réfléchir la lumière, produit durci obtenu à partir de ladite composition, et dispositif semi-conducteur optique
JP2021123647A (ja) * 2020-02-05 2021-08-30 味の素株式会社 樹脂組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117467243A (zh) * 2023-12-05 2024-01-30 昆山兴凯半导体材料有限公司 一种高导热、高绝缘性的环氧组合物及其应用
CN117467243B (zh) * 2023-12-05 2024-04-09 昆山兴凯半导体材料有限公司 一种高导热、高绝缘性的环氧组合物及其应用

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