Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers

Definitions

• the present invention relates to a sealing material composition and an electronic component device.
• epoxy resins Conventionally, encapsulant compositions containing epoxy resins have been widely used in the field of encapsulating electronic components such as transistors and ICs (Integrated Circuits).
• the reason for this is that the epoxy resin has a well-balanced electrical property, moisture resistance, heat resistance, mechanical property, adhesiveness to the insert product, and the like.
• Transfer molding is generally used as a method for sealing electronic components using a sealing material composition.
• the molten sealant composition is pressurized to flow into the mold, and the flow may cause wire flow.
• techniques for increasing the fluidity of the sealing material composition have been investigated, but there is still a problem in suppressing the wire sweep.
• Compression molding is known as an alternative molding method to transfer molding.
• a sealing material composition is put into a cavity of a mold and melted, the mold is closed while the pressure is reduced, and the element is sealed by pressurizing the sealing material composition (for example, Patent Document 1 reference).
• the flow of the encapsulant composition in the plane direction of the element is suppressed, so the occurrence of wire sweep can be suppressed.
• Compression molding uses a granular encapsulant composition from the viewpoint of workability, so air is likely to be involved when the encapsulant composition melts. Therefore, as described in Patent Literature 1, the entrapped air is removed by reducing the pressure before sealing. However, the trapped air exists as closed cells in the encapsulant composition, and the closed cells do not open to the outside. The entire melted encapsulant composition may swell and leak out of the mold. If sealing is performed in a state where the sealing material composition has leaked out of the mold, the sealed electronic component will have a defective appearance.
• an object of the present disclosure is to provide a sealing material composition that can suppress foaming during degassing and suppress resin leakage from the mold.
• ⁇ 1> Contains an epoxy resin, a curing agent, an inorganic filler, and a silicone compound,
• the silicone compound is a chemical that appears at 3.0 ppm to 4.0 ppm when the integral value of chemical shift A that appears at ⁇ 0.3 ppm to 0.3 ppm is 300 in the measurement results of 1 H NMR in CDCl 3
• ⁇ 2> The encapsulant composition according to ⁇ 1>, wherein the silicone compound has a polyether moiety.
• ⁇ 3> The encapsulant composition according to ⁇ 1> or ⁇ 2>, wherein the content of the silicone compound is 5 parts by mass or less with respect to 100 parts by mass of the epoxy resin.
• ⁇ 4> Any one of ⁇ 1> to ⁇ 3>, wherein the integrated value of the chemical shift B appearing at 3.0 ppm to 4.0 ppm when the integrated value of the chemical shift A is 300 is 40 or more.
• ⁇ 4> The encapsulant composition according to any one of ⁇ 1> to ⁇ 4>, which is used for compression molding.
• An electronic component device comprising:
• a sealing material composition capable of suppressing foaming during degassing and suppressing leakage of resin from a mold, and an electronic component device provided with an element sealed by the composition. can do.
• 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.
• Particles corresponding to each component in the present disclosure may include a plurality of types. When multiple types of particles corresponding to each component are present in the composition, 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.
• the encapsulant composition of the present disclosure includes an epoxy resin, a curing agent, an inorganic filler, and a silicone compound, and the silicone compound has a 1 H NMR measurement result in CDCl 3 of ⁇ 0.3 ppm to 0 When the integrated value of chemical shift A appearing at 3 ppm is 300, the integrated value of chemical shift B appearing at 3.0 ppm to 4.0 ppm is 350 or less.
• the integral value of chemical shift A is 30 When the integrated value of the chemical shift B is within a specific range of 350 or less when relativized as 0, the hydrophobic organic portion and the hydrophilic organic portion in the silicone compound are balanced, and the silicone compound disappears. It is considered that the foam function is exhibited.
• the integrated value of the chemical shift B exceeds 350, the hydrophilic organic moiety in the silicone compound is too large, the compatibility with the resin component in the encapsulant composition is high, and the silicone compound is completely absorbed into the resin component. Dissolve. In this case, it is considered that the amount of the silicone compound exuding to the surface side such as the foam film is reduced, and the antifoaming function is less likely to be exhibited. In other words, it is presumed that when the silicone compound has appropriate compatibility with the resin component, a sufficient amount of the silicone compound enters the foam film and exhibits the defoaming function.
• foaming during degassing means that foaming subsides 3 seconds after starting pressure reduction for degassing.
• Components that may be included in the encapsulant composition of the present disclosure are described in detail below.
• Epoxy resin The encapsulant 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 esters of polyvalent carboxylic acid compounds such as phthalic acid, isophthalic
• biphenyl type epoxy resins biphenyl type epoxy resins, stilbene type epoxy resins, diphenylmethane type epoxy resins, sulfur atom-containing type epoxy resins, novolac type epoxy resins, and dicyclopentadiene type epoxy resins are selected from the viewpoint of the balance between reflow resistance and viscosity.
• triphenylmethane type epoxy resins, copolymer type epoxy resins and aralkyl type epoxy resins (these are referred to as "specific epoxy resins").
• the specific epoxy resins may be used singly or in combination of two or more.
• the total content is preferably 30% by mass or more, more preferably 50% by mass or more, of the entire epoxy resin. preferable.
• 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 viscosity, and dicyclopentadiene-type epoxy resin from the viewpoint of heat resistance.
• 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, ESLV-210 (Sumitomo Chemical Co., Ltd., trade name), etc., which is a mixture of one of which is a t-butyl group, the other R 9 is a hydrogen atom, and all of R 10 are hydrogen atoms. It is available as a commercial product.
• 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 such as a novolac-type phenolic resin of a compound having a triphenylmethane skeleton and a compound having a phenolic hydroxyl group is preferable, and is represented by the following general formula (VIII). epoxy resins are more preferred.
• 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.
• the definitions of i, j and k for R 19 to R 21 are the same as the definitions of i, j and k for R 19 to R 21 in formula (IX). is.
• 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 1 to 10, (n+m) is a number of 2 to 10, preferably 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 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.
• 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
• 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 6 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 encapsulant composition during melt molding decreases, resulting in poor filling and deformation of the bonding wire (gold wire connecting the element and the lead). etc. 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, reflow resistance and electrical reliability, the functional group equivalent weight of the epoxy resin is preferably 100 g/eq to 1000 g/eq, more preferably 150 g/eq to 500 g/eq. is more preferable.
• the epoxy equivalent of the epoxy resin is a value measured by a method according to JIS K 7236:2009.
• the temperature is preferably 40° C. to 180° C., and from the viewpoint of handleability during preparation of the encapsulant composition, it is more preferably 50° C. to 130° C.
• the melting point of the epoxy resin is a value measured by differential scanning calorimetry (DSC), and the softening point of the epoxy resin is JIS K 7234: A value measured by a method (ring and ball method) according to 1986.
• the content of the epoxy resin in the encapsulant composition is preferably 0.5% by mass to 50% by mass, more preferably 2% by mass to 30% by mass, from the viewpoint of strength, viscosity, heat resistance, moldability, etc. It is more preferable to have
• the curing agent is not particularly limited as long as it is generally used for encapsulant compositions. Specifically, it is selected from the group consisting of phenols such as phenol, cresol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol and aminophenol and/or naphthols such as ⁇ -naphthol, ⁇ -naphthol and dihydroxynaphthalene.
• phenols such as phenol, cresol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol and aminophenol and/or naphthols such as ⁇ -naphthol, ⁇ -naphthol and dihydroxynaphthalene.
• Novolac type phenol resin obtained by condensation or co-condensation of at least one compound having an aldehyde group such as formaldehyde, benzaldehyde, salicylaldehyde, etc.
• phenols and naphthols phenol-aralkyl resin synthesized from seeds and dimethoxy-para-xylene or bis(methoxymethyl)biphenyl
• aralkyl-type phenol resin such as naphthol-aralkyl resin
• dichlopentadiene type phenol resins such as naphthol novolak resins; terpene-modified phenol resins;
• a biphenyl-type phenol resin is preferable from the viewpoint of flame retardancy.
• Aralkyl-type phenolic resins are preferred from the viewpoint of reflow resistance and curability.
• a dicyclopentadiene type phenol resin is preferable from the viewpoint of low hygroscopicity.
• triphenylmethane type phenolic resin is preferable.
• a novolak type phenol resin is preferable from the viewpoint of curability. More preferably, the curing agent contains at least one selected from these phenol resins.
• biphenyl-type phenolic resins examples include phenolic resins represented by the following general formula (XI).
• R 1 to R 9 in the above formula (XI) are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group and an isobutyl group, a methoxy group; , alkoxyl groups having 1 to 10 carbon atoms such as ethoxy group, propoxy group and butoxy group; aryl groups having 6 to 10 carbon atoms such as phenyl group, tolyl group and xylyl group; or carbon numbers such as benzyl group and phenethyl group. Represents 6-10 aralkyl groups. Among them, a hydrogen atom and a methyl group are preferred. n represents an integer of 0-10.
• Examples of the biphenyl-type phenolic resin represented by the general formula (XI) include compounds in which all of R 1 to R 9 are hydrogen atoms. Mixtures of condensates containing more than % by mass are preferred. As such a compound, MEH-7851 (manufactured by Meiwa Kasei Co., Ltd., trade name) is commercially available.
• the content is preferably 30% by mass or more, more preferably 50% by mass or more, and more preferably 80% by mass or more with respect to the total amount of the curing agent in order to exhibit its performance. More preferred.
• aralkyl-type phenol resins include phenol-aralkyl resins and naphthol-aralkyl resins. Among them, phenol-aralkyl resins represented by the following general formula (XII) are preferable, and phenol-aralkyl resins in which R in general formula (XII) is a hydrogen atom and n has an average value of 0 to 8 are more preferable. Specific examples thereof include p-xylylene type phenol/aralkyl resins and m-xylylene type phenol/aralkyl resins. When these aralkyl-type phenolic resins are used, their content is preferably 30% by mass or more, more preferably 50% by mass or more, relative to the total amount of the curing agent in order to exhibit their performance.
• each R independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms.
• n represents an integer of 0-10.
• the substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms for R includes a methyl group and the like.
• dicyclopentadiene-type phenolic resins examples include phenolic resins represented by the following general formula (XIII).
• R 1 and R 2 each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms.
• Each R 2 independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms.
• n represents an integer of 0-10 and m represents an integer of 0-6.
• Examples of the substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms for R 1 and R 2 include methyl group and the like.
• a dicyclopentadiene type phenolic resin When a dicyclopentadiene type phenolic resin is used, its content is preferably 30% by mass or more, more preferably 50% by mass or more, relative to the total amount of the curing agent in order to exhibit its performance.
• triphenylmethane-type phenolic resins examples include phenolic resins represented by the following general formula (XIV).
• each R independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms.
• n represents an integer of 0-10.
• the substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms for R includes a methyl group and the like.
• a triphenylmethane-type phenolic resin When a triphenylmethane-type phenolic resin is used, its content is preferably 30% by mass or more, more preferably 50% by mass or more, relative to the total amount of the curing agent in order to exhibit its performance.
• novolac-type phenolic resin examples include phenolic novolak resin, cresol novolak resin, naphthol novolac resin, etc. Among them, phenolic novolac resin is preferable.
• a novolak-type phenol resin when used, its content is preferably 30% by mass or more, more preferably 50% by mass or more, relative to the total amount of the curing agent in order to exhibit its performance.
• any one of the biphenyl-type phenolic resin, aralkyl-type phenolic resin, dicyclopentadiene-type phenolic resin, triphenylmethane-type phenolic resin, and novolak-type phenolic resin may be used alone or in combination of two or more. good too.
• the inclusion of a biphenyl-type phenolic resin or an aralkyl-type phenolic resin is preferable because the contact angle can be reduced.
• the total content of each phenol resin is preferably 60% by mass or more, more preferably 80% by mass or more, based on the total amount of the curing agent.
• the equivalent ratio between (A) the epoxy resin and (B) the curing agent is, the ratio of the number of hydroxyl groups in the curing agent to the number of epoxy groups in the epoxy resin (number of hydroxyl groups in the curing agent/number of epoxy groups in the epoxy resin) is There are no restrictions. It is preferably set in the range of 0.5 to 2, more preferably 0.6 to 1.3, in order to suppress the unreacted amount of each. In order to obtain a solid sealing resin composition for compression molding which is excellent in moldability and reflow resistance, it is more preferably set in the range of 0.8 to 1.2.
• the encapsulant composition contains an inorganic filler.
• the sealing material composition when used as a sealing material for a semiconductor package, it preferably contains an inorganic filler.
• inorganic filler is not particularly limited. Specifically, fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite , titania, talc, clay, and mica.
• 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.
• fused silica is preferable from the viewpoint of reducing the coefficient of linear expansion
• 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 powders, beads obtained by spheroidizing powders, fibers, and the like.
• using a combination of two or more types of inorganic fillers means, for example, when using two or more types of inorganic fillers having the same component but different average particle sizes, inorganic fillers having the same average particle size but different components are used. Examples include the case of using two or more types and the case of using two or more types of inorganic fillers having different average particle sizes and types.
• the encapsulant composition contains an inorganic filler
• its content is not particularly limited. From the viewpoint of viscosity and strength, it is preferably 30% to 90% by volume, more preferably 35% to 88% by volume, and 40% to 85% by volume of the entire encapsulant composition. It is even more preferable to have
• the content of the inorganic filler is 30% by volume or more of the entire encapsulant composition, the properties of the cured product, such as coefficient of thermal expansion, thermal conductivity and elastic modulus, tend to be further improved.
• the content of the inorganic filler is 90% by volume or less of the entire encapsulant composition
• the increase in viscosity of the encapsulant composition is suppressed, and the viscosity tends to be further improved, resulting in better moldability. be.
• the content of the inorganic filler is 80% by mass to 95% by mass of the entire encapsulant composition from the viewpoint of reflow resistance and viscosity. It is preferably from 85% by mass to 94% by mass, and even more preferably from 88% by mass to 93% by mass.
• the content of the inorganic filler is 80% by mass or more of the entire encapsulant composition, there is a tendency that the reflow resistance is improved.
• the content of the inorganic filler is 95% by mass or less of the entire encapsulant composition, the viscosity tends to be excellent.
• the average particle size of the inorganic filler is not particularly limited.
• the volume average particle size is preferably 0.2 ⁇ m to 80 ⁇ m, more preferably 0.5 ⁇ m to 70 ⁇ m.
• the volume average particle size is 0.2 ⁇ m or more, the increase in viscosity of the encapsulant composition tends to be more suppressed.
• the volume average particle size is 80 ⁇ m or less, the filling property into narrow gaps tends to be further improved.
• 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 volume average particle size of the inorganic filler in the encapsulant composition or its cured product can be measured by a known method. For example, an organic solvent, nitric acid, aqua regia, or the like is used to extract the inorganic filler from the encapsulant composition or cured product, and the inorganic filler is sufficiently dispersed using an ultrasonic disperser or the like to prepare a dispersion. Using this dispersion, the volume average particle diameter of the inorganic filler can be measured from the volume-based particle size distribution measured by a laser diffraction scattering particle size distribution analyzer.
• the volume-average particle size of the inorganic filler can be measured from the volume-based particle size distribution obtained by embedding the cured product in a transparent epoxy resin or the like and polishing the resulting cross section with a scanning electron microscope. can be done. Furthermore, it is also possible to continuously observe a two-dimensional cross section of the cured product using an FIB device (focused ion beam SEM) or the like, and perform measurement by performing three-dimensional structural analysis.
• FIB device focused ion beam SEM
• the maximum particle size (also called cut point) of the inorganic filler is not particularly limited. From the viewpoint of filling narrow gaps, the maximum particle size of the inorganic filler is preferably 150 ⁇ m or less, more preferably 75 ⁇ m or less, and even more preferably 55 ⁇ m.
• 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 inorganic filler preferably contains alumina, and more preferably contains alumina as a main component.
• the average particle size of alumina when the inorganic filler contains alumina is not particularly limited.
• the volume average particle size of alumina is preferably 0.2 ⁇ m to 80 ⁇ m, more preferably 0.5 ⁇ m to 70 ⁇ m.
• the volume average particle size is 0.2 ⁇ m or more, the increase in viscosity of the encapsulant composition tends to be suppressed.
• the volume average particle size is 80 ⁇ m or less, the filling property into narrow gaps tends to be improved.
• the maximum particle size of alumina is not particularly limited. From the viewpoint of filling narrow gaps, the maximum particle size of alumina is preferably 150 ⁇ m or less, more preferably 75 ⁇ m or less, and even more preferably 55 ⁇ m or less.
• Alumina of more than 75 ⁇ m or less, preferably 5.0 ⁇ m to 55 ⁇ m, more preferably 8.0 ⁇ m to 20 ⁇ m may be used together.
• the shape of alumina is not particularly limited. From the viewpoint of kneadability of the encapsulant composition, the particle shape of alumina is preferably spherical.
• the content of alumina with respect to the total mass of the inorganic filler is preferably 90% by mass or more, more preferably 95% by mass or more, from the viewpoint of high thermal conductivity. , more preferably 98% by mass or more.
• the content of alumina with respect to the total mass of the inorganic filler is preferably 99.9% by mass or less, and is 99.8% by mass or less. is more preferable, and 99.7% by mass or less is even more preferable.
• the inorganic filler When the inorganic filler contains alumina, the inorganic filler preferably contains silica in addition to alumina. When the inorganic filler contains silica, the viscosity tends to decrease, and the kneadability and fluidity tend to be improved. In particular, the combined use of fine silica suppresses the generation of burrs when the cured product is made. tend to be In particular, the inorganic filler preferably contains finely divided silica, for example, silica having an average particle size of 0.01 ⁇ m to 2.0 ⁇ m, more preferably 0.1 ⁇ m to 1.5 ⁇ m, still more preferably 0.2 ⁇ m to 1.0 ⁇ m. .
• the inorganic filler preferably contains silica having a large particle size.
• large particle size silica include silica having a particle size of preferably more than 2.0 ⁇ m and 75 ⁇ m or less, more preferably 5.0 ⁇ m to 55 ⁇ m, and still more preferably 8.0 ⁇ m to 20 ⁇ m.
• the inorganic filler preferably contains silica, and may contain silica as a main component.
• the average particle size of silica when the inorganic filler contains silica is not particularly limited.
• the volume average particle size of silica is preferably 0.2 ⁇ m to 80 ⁇ m, more preferably 0.5 ⁇ m to 70 ⁇ m.
• the volume average particle size is 0.2 ⁇ m or more, the increase in viscosity of the encapsulant composition tends to be suppressed.
• the volume average particle size is 80 ⁇ m or less, the filling property into narrow gaps tends to be improved.
• the inorganic filler preferably contains finely divided silica, for example, silica having an average particle size of 0.01 ⁇ m to 2.0 ⁇ m, more preferably 0.1 ⁇ m to 1.5 ⁇ m, and still more preferably 0.2 ⁇ m to 1.0 ⁇ m. .
• silica having an average particle size of 0.01 ⁇ m to 2.0 ⁇ m, more preferably 0.1 ⁇ m to 1.5 ⁇ m, and still more preferably 0.2 ⁇ m to 1.0 ⁇ m.
• the maximum particle size of silica is not particularly limited. From the viewpoint of filling narrow gaps, the maximum particle size of silica is preferably 150 ⁇ m or less, more preferably 75 ⁇ m or less, and even more preferably 55 ⁇ m or less.
• the shape of silica is not particularly limited. From the viewpoint of the kneadability of the encapsulant composition, the particle shape of silica is preferably spherical.
• the silica content is not particularly limited, and may be 70% by mass to 100% by mass, or 80% by mass to 100% by mass with respect to the total mass of the inorganic filler. may be from 90% by mass to 100% by mass.
• the content of silica may be 0.1% by mass to 10% by mass, or 0.2% by mass to 5% by mass with respect to the total mass of the inorganic filler. It may be present, and may be 0.3% by mass to 2% by mass.
• the encapsulant composition contains a silicone compound.
• the silicone compound has a chemical shift appearing at 3.0 ppm to 4.0 ppm when the integral value of the chemical shift appearing at ⁇ 0.3 ppm to 0.3 ppm is 300 in the measurement results of 1 H NMR in CDCl 3 .
• the integral value is 350 or less.
• the chemical shift A appearing at ⁇ 0.3 ppm to 0.3 ppm is the chemical shift corresponding to the hydrophobic organic moiety in the silicone compound, specifically, the hydrogen atom on the carbon atom bonded to the silicon atom. , such as the hydrogen atom in the methyl group of ⁇ Si—CH 3 .
• the chemical shift B appearing at 3.0 ppm to 4.0 ppm is a chemical shift corresponding to a hydrophilic organic moiety in a silicone compound, specifically, a hydrogen atom on a carbon atom bonded to an etheric oxygen atom. are included, such as the chemical shifts corresponding to the hydrogen atoms in the methylene groups of —O—CH 2 —.
• the integrated value of chemical shift B When relative to the integrated value of chemical shift A as 300, the integrated value of chemical shift B is 350 or less, preferably 320 or less, more preferably 200 or less, and preferably 100 or less. More preferred. From the viewpoint of suppressing wire flow by suppressing the viscosity of the encapsulant composition, the integrated value of the chemical shift B is preferably 40 or more when relative to the integrated value of the chemical shift A of 300. It is more preferably 75 or more, and more preferably 75 or more from the viewpoint of suppressing foaming immediately after the start of depressurization.
• the integrated value of the chemical shift B is 40 or more, the hydrophobic organic portion in the silicone compound is moderately suppressed, the compatibility with the resin component in the encapsulant composition is moderately high, and the silicone compounds do not aggregate with each other. is suppressed. Therefore, since the silicone compound can uniformly seep out to the surface side such as the foam film, it is considered that the antifoaming function is less likely to be exhibited. Moreover, since the aggregation of the silicone compound is suppressed, the increase in viscosity of the encapsulant composition tends to be suppressed.
• the method for measuring 1 H NMR of silicone compounds 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 removing the silicone compound from the encapsulant composition is as follows. 20 g of the encapsulant composition was dissolved in 40 mL of acetone, and only the organic components of the supernatant were 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 to collect the silicone compound.
• RI differential refractive index detector
• the silicone compound preferably has a polyether moiety.
• examples of the structure of the polyether moiety 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 silicone 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.
• the silicone compound may be any of dimethylsilicone, diphenylsilicone, methylphenylsilicone, and the like. Also, the silicone compound may have other functional groups in addition to the polyether moiety. A hydroxyl group etc. are mentioned as another functional group.
• the content of the silicone compound is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less with respect to 100 parts by mass of the epoxy resin.
• the content of the silicone compound is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and 0.1 parts by mass or more with respect to 100 parts by mass of the epoxy resin. is more preferred.
• the encapsulant composition may 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 encapsulant composition, and the like.
• the curing accelerator preferably contains a phosphonium compound.
• phosphonium compounds include triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkyl/alkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiaryl Tertiary phosphines such as phosphine, maleic anhydride
• a compound represented by the following general formula (I-1) (hereinafter also referred to as a specific curing accelerator) is preferable.
• R 1 to R 3 are each independently a hydrocarbon group having 1 to 18 carbon atoms, and two or more of R 1 to R 3 are bonded to each other to form a cyclic structure.
• R 4 to R 7 each independently represent a hydrogen atom, a hydroxyl group, or a monovalent organic group having 1 to 18 carbon atoms, and two or more of R 4 to R 7 are bonded to each other A ring structure may be formed.
• the “hydrocarbon group having 1 to 18 carbon atoms” described as R 1 to R 3 in general formula (I-1) includes an aliphatic hydrocarbon group having 1 to 18 carbon atoms and an aliphatic hydrocarbon group having 6 to 18 carbon atoms. Contains some aromatic hydrocarbon groups.
• the aliphatic hydrocarbon group having 1 to 18 carbon atoms preferably has 1 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 4 to 6 carbon atoms.
• the aliphatic hydrocarbon group having 1 to 18 carbon atoms may be a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. good too. From the viewpoint of ease of production, it is preferably a straight-chain or branched aliphatic hydrocarbon group.
• linear or branched aliphatic hydrocarbon groups having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, Alkyl groups such as pentyl group, hexyl group, octyl group, decyl group and dodecyl group, allyl group, vinyl group and the like can be mentioned.
• a linear or branched aliphatic hydrocarbon group may or may not have a substituent.
• substituents include alkoxy groups such as methoxy group, ethoxy group, butoxy group and t-butoxy group, aryl groups such as phenyl group and naphthyl group, hydroxyl group, amino group and halogen atom.
• a straight-chain or branched aliphatic hydrocarbon group may have two or more substituents, which may be the same or different. When the linear or branched aliphatic hydrocarbon group has a substituent, the total number of carbon atoms contained in the aliphatic hydrocarbon group and the substituent is preferably 1-18.
• unsubstituted alkyl groups are preferred, and unsubstituted alkyl groups having 1 to 8 carbon atoms are more preferred, such as n-butyl, isobutyl, n-pentyl, n-hexyl and n-octyl. groups are more preferred.
• alicyclic hydrocarbons having 3 to 18 carbon atoms include cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cycloheptyl group, and cycloalkenyl groups such as cyclopentenyl group and cyclohexenyl group.
• the alicyclic hydrocarbon group may or may not have a substituent.
• substituents include alkyl groups such as methyl group, ethyl group, butyl group and tert-butyl group; alkoxy groups such as methoxy group, ethoxy group, butoxy group and t-butoxy group; and aryl groups such as phenyl group and naphthyl group.
• An alicyclic hydrocarbon group may have two or more substituents, in which case the substituents may be the same or different.
• the total number of carbon atoms contained in the alicyclic hydrocarbon group and the substituent is preferably 3-18.
• the position of the substituent is not particularly limited.
• an unsubstituted cycloalkyl group is preferable, an unsubstituted cycloalkyl group having 4 to 10 carbon atoms is more preferable, and a cyclohexyl group, a cyclopentyl group and a cycloheptyl group are more preferable.
• the aromatic hydrocarbon group having 6 to 18 carbon atoms preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms.
• the aromatic hydrocarbon group may or may not have a substituent.
• substituents include alkyl groups such as methyl group, ethyl group, butyl group and t-butyl group; alkoxy groups such as methoxy group, ethoxy group, butoxy group and t-butoxy group; and aryl groups such as phenyl group and naphthyl group. , a hydroxyl group, an amino group, a halogen atom, and the like.
• the aromatic hydrocarbon group may have two or more substituents, in which case the substituents may be the same or different.
• the aromatic hydrocarbon group has a substituent, the total number of carbon atoms contained in the aromatic hydrocarbon group and the substituent is preferably 6-18.
• the position of the substituent is not particularly limited.
• aromatic hydrocarbon groups having 6 to 18 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, tolyl, dimethylphenyl, ethylphenyl, butylphenyl and t-butyl.
• a phenyl group, a methoxyphenyl group, an ethoxyphenyl group, a butoxyphenyl group, and a t-butoxyphenyl group can be mentioned.
• the position of the substituent in these aromatic hydrocarbon groups may be any of the ortho position, meta position and para position.
• an unsubstituted aryl group having 6 to 12 carbon atoms or 6 to 12 carbon atoms including substituents is preferable, and an unsubstituted aryl group having 6 to 10 carbon atoms or including substituents is preferred.
• Aryl groups of 6 to 10 are more preferred, and phenyl, p-tolyl and p-methoxyphenyl groups are even more preferred.
• R 1 to R 3 may combine with each other to form a cyclic structure” described as R 1 to R 3 in general formula (I-1) means that R 1 to R 3 It means that two or three of them are combined to form one divalent or trivalent hydrocarbon group as a whole.
• R 1 to R 3 examples include alkylene groups such as ethylene, propylene, butylene, pentylene and hexylene which can form a cyclic structure by bonding with a phosphorus atom; alkenylene groups such as ethylene, propylene and butylenylene groups; Examples thereof include substituents capable of forming a ring structure by bonding with a phosphorus atom, such as aralkylene groups such as methylenephenylene groups, and arylene groups such as phenylene, naphthylene and anthracenylene groups. These substituents may be further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, halogen atoms and the like.
• the “monovalent organic group having 1 to 18 carbon atoms” described as R 4 to R 7 in general formula (I-1) above has 1 to 18 carbon atoms and is substituted or unsubstituted. It also includes aliphatic hydrocarbon groups, aromatic hydrocarbon groups, aliphatic hydrocarbon oxy groups, aromatic hydrocarbon oxy groups, acyl groups, hydrocarbon oxycarbonyl groups, and acyloxy groups.
• Examples of the above-mentioned aliphatic hydrocarbon groups and aromatic hydrocarbon groups include those mentioned above as examples of the aliphatic hydrocarbon groups and aromatic hydrocarbon groups represented by R 1 to R 3 .
• Examples of the aliphatic hydrocarbonoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a 2-butoxy group, a t-butoxy group, a cyclopropyloxy group, a cyclohexyloxy group, and a cyclopentyloxy group.
• an allyloxy group an oxy group having a structure in which an oxygen atom is bonded to the above-mentioned aliphatic hydrocarbon groups such as a vinyloxy group, and these aliphatic hydrocarbon oxy groups are further alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino and those substituted with groups, hydroxyl groups, halogen atoms, and the like.
• aromatic hydrocarbon oxy group examples include a phenoxy group, a methylphenoxy group, an ethylphenoxy group, a methoxyphenoxy group, a butoxyphenoxy group, a phenoxyphenoxy group having a structure in which an oxygen atom is bonded to the above aromatic hydrocarbon group, such as a phenoxyphenoxy group.
• acyl group examples include aliphatic hydrocarbon carbonyl groups such as formyl group, acetyl group, ethylcarbonyl group, butyryl group, cyclohexylcarbonyl group and allylcarbonyl group, and aromatic hydrocarbon carbonyl groups such as phenylcarbonyl group and methylphenylcarbonyl group. and the like, in which these aliphatic hydrocarbon carbonyl groups or aromatic hydrocarbon carbonyl groups are further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, or the like.
• hydrocarbon oxycarbonyl group examples include aliphatic hydrocarbon oxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, allyloxycarbonyl group and cyclohexyloxycarbonyl group, phenoxycarbonyl group, methylphenoxycarbonyl group and the like.
• aromatic hydrocarbon oxycarbonyl groups these aliphatic hydrocarbon carbonyloxy groups or aromatic hydrocarbon carbonyloxy groups further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, etc. things, etc.
• acyloxy group examples include aliphatic hydrocarbon carbonyloxy groups such as a methylcarbonyloxy group, an ethylcarbonyloxy group, a butylcarbonyloxy group, an allylcarbonyloxy group and a cyclohexylcarbonyloxy group, a phenylcarbonyloxy group and a methylphenylcarbonyloxy group. etc., these aliphatic hydrocarbon carbonyloxy groups or aromatic hydrocarbon carbonyloxy groups are further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, etc. and the like.
• R 4 to R 7 may combine with each other to form a cyclic structure” described for R 4 to R 7 in the general formula (I-1) means that 2 to 4 It means that R 4 to R 7 may combine to form one divalent to tetravalent organic group as a whole.
• R 4 to R 7 include alkylene groups such as ethylene, propylene, butylene, pentylene and hexylene; alkenylene groups such as ethylene, propylene, butyleneylene; aralkylene groups such as methylenephenylene; and arylene groups such as phenylene, naphthylene and anthracenylene.
• Substituents capable of forming a cyclic structure such as groups, their oxy groups or dioxy groups are included. These substituents may be further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, halogen atoms and the like.
• R 4 to R 7 in general formula (I-1) are not particularly limited.
• a hydrogen atom, a hydroxyl group, an aryl group substituted with at least one selected from the group consisting of an unsubstituted or alkyl group and an alkoxy group, or a chain or cyclic alkyl group preferable.
• Aryl groups that are unsubstituted or substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group include a phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, and the like. is mentioned.
• Chain or cyclic alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, t-butyl, octyl and cyclohexyl groups. From the viewpoint of curability, it is preferred that all of R 4 to R 7 are hydrogen atoms, or that at least one of R 4 to R 7 is a hydroxyl group and the rest are all hydrogen atoms.
• R 1 to R 3 in general formula (I-1) are alkyl groups having 1 to 18 carbon atoms or cycloalkyl groups having 3 to 18 carbon atoms
• R 4 to R 7 are All are hydrogen atoms, or at least one is a hydroxyl group and the rest are all hydrogen atoms.
• all of R 1 to R 3 are alkyl groups having 1 to 18 carbon atoms or cycloalkyl groups having 3 to 18 carbon atoms
• all of R 4 to R 7 are hydrogen atoms, or at least one is a hydroxyl group. and the rest are all hydrogen atoms.
• the specific curing accelerator is preferably a compound represented by the following general formula (I-2).
• R 1 to R 3 are each independently a hydrocarbon group having 1 to 18 carbon atoms, and two or more of R 1 to R 3 are bonded to each other to form a cyclic structure.
• R 4 to R 6 each independently represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and two or more of R 4 to R 6 are bonded together to form a cyclic structure may be formed.
• R 1 to R 6 in general formula (I-2) are the same as specific examples of R 1 to R 6 in general formula (I-1), and preferred ranges are also the same.
• the specific curing accelerator include an addition reaction product of triphenylphosphine and 1,4-benzoquinone, an addition reaction product of tri-n-butylphosphine and 1,4-benzoquinone, and tricyclohexylphosphine and 1,4-benzoquinone.
• addition reaction product of dicyclohexylphenylphosphine and 1,4-benzoquinone addition reaction product of cyclohexyldiphenylphosphine and 1,4-benzoquinone
• addition reaction product of triisobutylphosphine and 1,4-benzoquinone tricyclopentylphosphine and an addition reaction product of 1,4-benzoquinone.
• a specific curing accelerator can be obtained, for example, as an adduct of a tertiary phosphine compound and a quinone compound.
• the third phosphine compound include triphenylphosphine, tributylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, tris(4-methylphenyl)phosphine, and tris(4-ethylphenyl)phosphine.
• tris(4-propylphenyl)phosphine tris(4-butylphenyl)phosphine, tris(isopropylphenyl)phosphine, tris(t-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2, 6-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl) ) phosphine and the like. From the viewpoint of moldability, triphenylphosphine and tributylphosphine are preferred.
• quinone compounds include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, and anthraquinone. From the viewpoint of moisture resistance and storage stability, p-benzoquinone is preferred.
• the encapsulant composition may contain a curing accelerator other than the phosphonium compound.
• curing accelerators other than phosphonium compounds include 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU).
• Cyclic amidine compounds such as diazabicycloalkenes such as diazabicycloalkene, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; the cyclic amidine compounds or the Phenol novolak salts of derivatives; These compounds include maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3- quinone compounds such as dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, and phenyl-1,4-benzoquinone; and compounds with ⁇ bonds such as diazophenylmethane.
• diazabicycloalkenes such
• Cyclic amidiniums such as tetraphenylborate salt of DBU, tetraphenylborate salt of DBN, tetraphenylborate salt of 2-ethyl-4-methylimidazole, tetraphenylborate salt of N-methylmorpholine, etc.
• tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol; derivatives of the tertiary amine compounds; tetra-n-butylammonium acetate , tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, and ammonium salt compounds such as tetrapropylammonium hydroxide.
• the content of the specific curing accelerator is preferably 30% by mass or more, more preferably 50% by mass or more, of the total curing accelerator. More preferably, it is 70% by mass or more.
• the amount thereof is preferably 0.1 to 30 parts by mass, and 1 to 15 parts by mass with respect to 100 parts by mass of the resin component. is more preferred.
• the amount of the curing accelerator is 0.1 parts by mass or more with respect to 100 parts by mass of the resin component, there is a tendency for satisfactory curing in a short period of time.
• the amount of the curing accelerator is 30 parts by mass or less with respect to 100 parts by mass of the resin component, the curing speed is not too fast and a good molded article tends to be obtained.
• the encapsulant composition may contain antifoaming agents other than the above silicone compounds.
• Antifoaming agents are not particularly limited, and conventionally known ones can be used. Specific examples include ester-based antifoaming agents and polyalkylene-based antifoaming agents.
• An antifoaming agent may be used individually by 1 type, or may be used in combination of 2 or more types.
• the total amount of the antifoaming agents including the silicone compound is preferably 0.05 parts by mass to 5 parts by mass with respect to 100 parts by mass of the epoxy resin, and 0.1 parts by mass. parts to 3 parts by mass is more preferable.
• the encapsulant composition may contain various additives such as coupling agents, ion exchangers, release agents, flame retardants, colorants, stress relaxation agents, and the like, which are exemplified below.
• the encapsulant composition may contain various additives known in the art as necessary, in addition to the additives exemplified below.
• the encapsulant composition may contain a coupling agent in order to increase the adhesion between the resin component and the inorganic filler.
• Coupling agents include known coupling agents such as silane-based compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, and vinylsilane, titanium-based compounds, aluminum chelate compounds, and aluminum/zirconium-based compounds. .
• the amount of the coupling agent is preferably 0.05 parts by mass to 5 parts by mass with respect to 100 parts by mass of the inorganic filler, and 0.1 parts by mass to It is more preferably 2.5 parts by mass.
• the amount of the coupling agent is 0.05 parts by mass or more with respect to 100 parts by mass of the inorganic filler, the adhesion to the frame tends to be further improved.
• the amount of the coupling agent is 5 parts by mass or less with respect to 100 parts by mass of the inorganic filler, the moldability of the package tends to be further improved.
• the encapsulant composition may contain an ion exchanger.
• the encapsulant composition when used as a molding material for encapsulation, it preferably contains an ion exchanger from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of the electronic component device including the element to be encapsulated.
• the 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 sealant 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 15 parts by mass, based on 100 parts by mass of the resin component.
• the encapsulant composition 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 alone or in combination of two or more.
• the amount 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 resin component.
• the amount of the release agent is 0.01 parts by mass or more with respect to 100 parts by mass of the resin component, there is a tendency that sufficient releasability can be obtained.
• the amount is 15 parts by mass or less, better adhesion tends to be obtained.
• the encapsulant composition preferably contains a release agent, and the content of the release agent is more than 0% by mass and 2.0% by mass or less with respect to the total mass of the encapsulant composition, It is more preferably more than 0 mass % and 1.5 mass % or less, and more preferably more than 0 mass % and 1.2 mass % or less.
• the releasing agent at the above-mentioned content, it tends to be possible to suppress a significant decrease in appearance, adhesive strength, and laser marking properties, compared to the case where the release agent is contained in a larger amount than the above-mentioned content.
• the encapsulant composition of the present disclosure even when the content of the release agent is within the above range, there is a tendency that good releasability can be maintained.
• the encapsulant composition may also contain a flame retardant.
• 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 type.
• the encapsulant composition contains a flame retardant
• its amount 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 300 parts by mass, more preferably 2 parts by mass to 150 parts by mass, based on 100 parts by mass of the resin component.
• the encapsulant composition may further comprise a colorant.
• coloring agents include known coloring agents such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, and red iron oxide.
• the content of the coloring agent can be appropriately selected according to the purpose and the like.
• a coloring agent may be used individually by 1 type, or may be used in combination of 2 or more type.
• the encapsulant composition may contain a stress-relieving agent such as silicone rubber particles.
• a stress relaxation agent such as silicone rubber particles.
• the stress relaxation agent include commonly used known stress relaxation agents (flexible agents).
• a stress relaxation agent may be used individually by 1 type, or may be used in combination of 2 or more type.
• a method for preparing the encapsulant composition is not particularly limited.
• a general method there can be mentioned a method of thoroughly mixing components in predetermined amounts with a mixer or the like, melt-kneading the mixture with a mixing roll, an extruder or the like, cooling, and pulverizing. More specifically, for example, predetermined amounts of the above components are uniformly stirred and mixed, kneaded with a kneader, rolls, extruder, etc. preheated to 70° C. to 140° C., cooled, and pulverized. can be mentioned.
• the encapsulant composition is preferably solid at room temperature and normal pressure (eg, 25°C, atmospheric pressure).
• the shape is not particularly limited, and examples thereof include powder, granules, tablets, and the like.
• the encapsulant composition is in the form of a tablet, it is preferable from the standpoint of handleability that the dimensions and mass are such that they meet the molding conditions of the package.
• the minimum melt viscosity of the encapsulant composition at 140° C. is preferably 300 Pa s or less, more preferably 250 Pa s or less, and 160 Pa s or less, from the viewpoint of suppressing wire flow. is more preferred.
• the minimum melt viscosity at 140° C. of the encapsulant composition is measured by the method described in Examples.
• the encapsulant composition is preferably as small as possible, and in light of the recent demand for smaller and thinner semiconductor packages, it is desirable to make the encapsulant composition as small as possible.
• the particle size of the encapsulant composition may be 2 mm or less, 1.5 mm or less, or 1 mm or less.
• the size of the encapsulant composition is as large as possible.
• the particle size of the encapsulant composition may be 10 ⁇ m or more, 50 ⁇ m or more, or 100 ⁇ m or more. From the above viewpoints, it is preferable to appropriately design the particle size of the encapsulant composition according to the purpose.
• An electronic component device that is an embodiment of the present disclosure includes an element and a cured product of the sealing material composition described above that seals the element.
• elements active elements such as semiconductor chips, transistors, diodes, thyristors, capacitors, resistors, etc.
• passive elements such as coils, etc.
• a sealing material composition More specifically, a structure in which an element is fixed on a lead frame, terminal portions of the element such as bonding pads and lead portions are connected by wire bonding, bumps, or the like, and then sealed using a sealing material composition.
• TCP Transmission Carrier
• COB Chip On Board
• hybrid IC having a structure in which an element connected to a wiring formed on a support member by wire bonding, flip chip bonding, soldering, or the like is sealed with a sealing material composition
• Multi-chip module etc.: After mounting an element on the surface of a 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, composition of a sealing material BGAs (Ball Grid Grid
• sealing material composition 100 parts by mass of epoxy resin, 72.6 parts by mass of curing agent, 1.05 parts by mass of curing accelerator, 3 parts by mass of coupling agent, 1 part by mass of releasing agent, 2.44 parts by mass of coloring agent, 1 part by mass of ion trapping agent Part, an inorganic filler, and a silicone compound are mixed and kneaded using a twin-screw kneader at a kneading temperature of 100 ° C. to obtain the sealing material compositions of Examples 1 to 10 and Comparative Examples 1 and 2. were prepared respectively.
• the inorganic filler was blended so that the volume ratio of the spherical silica 1 and the spherical silica 2 was 9:1 (spherical silica 1:spherical silica 2), and the total amount was 75% by volume in the encapsulant composition. .
• the silicone compound was blended in the amount (parts by mass) shown in Table 1 below. In Comparative Example 1, no silicone compound was added.
• the raw materials used are as follows.
• Epoxy resin biphenyl aralkyl type epoxy resin with an epoxy equivalent of 272 g/eq
• Curing agent biphenyl aralkyl type phenolic resin with a hydroxyl equivalent of 203 g/eq and a softening point of 67° C.
• Curing accelerator addition reaction product of triphenylphosphine and 1,4-benzoquinone
• Spherical silica 1 average particle size 15 ⁇ m
• Spherical silica 2 average particle size 0.6 ⁇ m
• Coupling agent N-phenyl-3-aminopropyltrimethoxysilane Colorant: Carbon black Release agent: Ester wax (dropping point 79° C. to 83° C., acid value 15 mg KOH/g to 20 mg KOH/g, saponification value 140 mg KOH/g to 160 mg KOH/g)
• Ion trapping agent hydrotalcite compound, Mg4.3Al2 (OH) 12.6CO3.mH2O
• Silicone compound 1 Polyether-modified hydroxypolydimethylsiloxane Silicone compound 2: Alkyl polyether-modified branched polydimethylsiloxane Silicone compound 3: Side chain polyether-modified linear polydimethylsiloxane Silicone compound 4: Terminal polyether-modified Linear polydimethylsiloxane Silicone compound 5: Emulsion type siloxane Silicone compound 6: Both terminal epoxy-modified polydimethylsiloxane Silicone compound 7: Dimethylsiloxane-containing silicone
• Length H is less than 4 mm 2: Length H is 4 mm or more and less than 8 mm 3: Length H is 8 mm or more
• Epoxy resin 4.5 g (2:90 parts by mass)
• Epoxy resin 3 0.5 g (10 parts by mass)
• Curing agent 2 2.76 g (55.2 parts by mass)
• Foaming agent 0.01 g (0.2 parts by mass)
• Epoxy resin 2 Biphenyl-type epoxy resin with an epoxy equivalent of 192 g/eq
• Epoxy resin 3 Bisphenol F-type epoxy resin with an epoxy equivalent of 192 g/eq
• Curing agent 2 Novolac-type phenolic resin with a hydroxyl equivalent of 106 g/eq and a softening point of 83°C Foaming Agent: Organic modified silicone
• Length H is less than 2 mm
• Length H is 2 mm or more
• the encapsulant compositions of Examples suppressed foaming 3 seconds after the pressure was reduced, and in Examples 5 to 7, foaming was suppressed immediately after the pressure was reduced. It can be seen that the encapsulant compositions of Examples 1 to 9 have a suppressed increase in viscosity, and tend to further suppress wire flow. Further, in Examples 1 to 9, foaming was suppressed even with neat resin, and it can be seen that foaming is suppressed even when applied to a sealing material with a lower viscosity. Specifically, foaming tends to be suppressed even in the design of a sealing material that contains less filler, has a low viscosity, and is prone to foaming.
• Comparative Example 1 containing no silicone compound
• Comparative Example 2 using a silicone compound in which the integrated value of the chemical shift B appearing at 3.0 ppm to 4.0 ppm deviated from 350 or less, even after 3 seconds from decompression Foaming could not be suppressed.

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• Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
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• 2022
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