WO2020080369A1 - Additif pour composition de résine durcissable, composition de résine durcissable, et dispositif de composant électronique - Google Patents

Additif pour composition de résine durcissable, composition de résine durcissable, et dispositif de composant électronique Download PDF

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Publication number
WO2020080369A1
WO2020080369A1 PCT/JP2019/040521 JP2019040521W WO2020080369A1 WO 2020080369 A1 WO2020080369 A1 WO 2020080369A1 JP 2019040521 W JP2019040521 W JP 2019040521W WO 2020080369 A1 WO2020080369 A1 WO 2020080369A1
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group
curable resin
resin composition
carbon atoms
epoxy resin
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PCT/JP2019/040521
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English (en)
Japanese (ja)
Inventor
中村　真也
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日立化成株式会社
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Priority to CN201980063220.XA priority Critical patent/CN112771122B/zh
Publication of WO2020080369A1 publication Critical patent/WO2020080369A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/132—Phenols containing keto groups, e.g. benzophenones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape

Definitions

  • the present invention relates to an additive for a curable resin composition, a curable resin composition, and an electronic component device.
  • the surface mount type package has a different mounting method from the conventional pin insertion type package. That is, when the pins are attached to the wiring board, the conventional pin insertion type package does not directly expose the package to high temperature because the pins are inserted into the wiring board and then soldering is performed from the back surface of the wiring board.
  • the entire electronic component device is processed by the solder bath, the reflow device, and the like, so that the package is directly exposed to the soldering temperature (reflow temperature).
  • reflow temperature soldering temperature
  • the package absorbs moisture
  • the moisture due to moisture absorption expands rapidly during soldering, and the generated vapor pressure acts as peeling stress, causing peeling between the insert such as the element and lead frame and the sealing material. If they are generated, they may cause package cracks, defective electrical characteristics, and the like. Therefore, it is desired to develop a sealing material that has excellent adhesiveness to the insert and, by extension, excellent solder heat resistance (reflow resistance).
  • silane coupling agents as a modifier for the inorganic filler contained in the encapsulant is being considered.
  • the use of an epoxy group-containing silane coupling agent or an amino group-containing silane coupling agent is being studied.
  • Means for solving the above problems include the following embodiments.
  • An additive for a curable resin composition which contains a hydroxybenzophenone compound having an aliphatic hydrocarbon group having 6 to 12 carbon atoms or an aliphatic hydrocarbon oxy group having 6 to 12 carbon atoms.
  • a curable resin composition comprising the curable resin composition additive according to any one of ⁇ 1> to ⁇ 3> and a curable resin component.
  • An electronic component device comprising a ⁇ 7> element and a cured product of the curable resin composition according to any one of ⁇ 4> to ⁇ 6>, which seals the element.
  • an additive for a curable resin composition capable of improving the reflow resistance of a sealing structure, a curable resin composition using the same, and an electronic component device are provided.
  • the term “process” includes not only a process independent of other processes but also the process even if the process is not clearly distinguishable from other processes as long as the purpose of the process is achieved.
  • the numerical range indicated by using “to” includes the numerical values before and after “to” as the minimum value and the maximum value, respectively.
  • the upper limit or the lower limit described in one numerical range may be replaced with the upper limit or the lower limit of the numerical range described in other stages.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
  • the content rate or content of each component in the composition means that when there are a plurality of substances corresponding to each component in the composition, the plurality of substances present in the composition unless otherwise specified. Means the total content rate or content.
  • the particle size of each component in the composition is a plurality of types of particles corresponding to each component in the composition, unless otherwise specified, with respect to a mixture of the plurality of types of particles present in the composition. Means the value of.
  • the additive for curable resin composition of the present disclosure is a hydroxybenzophenone compound having an aliphatic hydrocarbon group having 6 to 12 carbon atoms or an aliphatic hydrocarbon oxy group having 6 to 12 carbon atoms (hereinafter, also referred to as a specific hydroxybenzophenone compound. Include).
  • a curable resin composition containing a specific hydroxybenzophenone compound as an additive has excellent reflow resistance of a sealing structure produced using this.
  • the aliphatic hydrocarbon group having 6 to 12 carbon atoms or the aliphatic hydrocarbon oxy group having 6 to 12 carbon atoms which the specific hydroxybenzophenone compound has is used as the lead frame and the curable resin composition. It is considered that the reflow resistance is improved as a result of the reduction of elastic modulus and the reduction of water absorption occurring near the interface of the cured product.
  • the curable resin composition containing the specific hydroxybenzophenone compound as an additive is particularly suitable as a sealing material for a package including at least a lead frame whose surface material is silver.
  • the “specific hydroxybenzophenone compound” is a compound (hydroxybenzophenone compound) having a benzophenone skeleton and a hydroxy group bonded to at least one of two aromatic rings forming the benzophenone skeleton, and having a carbon number of Means having 6 to 12 aliphatic hydrocarbon groups or aliphatic hydrocarbon oxy groups.
  • the position of the hydroxy group in the specific hydroxybenzophenone compound is not particularly limited, and may be any of the second position, the third position, and the fourth position with respect to the bonding position with the carbonyl group of the aromatic ring, but the second position. Is preferred.
  • the number of hydroxy groups contained in the specific hydroxybenzophenone compound is not particularly limited, but is preferably 1 or 2, and more preferably 1.
  • Specific examples of the specific hydroxybenzophenone compound include 2-hydroxybenzophenone, 3-hydroxybenzophenone, 4-hydroxybenzophenone, 2,2′-dihydroxybenzophenone, 3,3′-dihydroxybenzophenone and 4,4′-dihydroxybenzophenone.
  • Examples thereof include compounds in which an aliphatic hydrocarbon group having 6 to 12 carbon atoms or an aliphatic hydrocarbon oxy group is bonded to a hydroxybenzophenone compound.
  • 2-hydroxybenzophenone, 3-hydroxybenzophenone and 4-hydroxybenzophenone having an aliphatic hydrocarbon group having 6 to 12 carbon atoms or an aliphatic hydrocarbon oxy group bonded thereto are preferable, and 2-hydroxybenzophenone has carbon atoms. It is more preferable that an aliphatic hydrocarbon group having 6 to 12 carbon atoms or an aliphatic hydrocarbon oxy group having 6 to 12 carbon atoms be bonded.
  • the number of the aliphatic hydrocarbon group having 6 to 12 carbon atoms or the aliphatic hydrocarbon oxy group having 6 to 12 carbon atoms in the specific hydroxybenzophenone compound is not particularly limited, but is preferably 2 or less, and preferably 1. More preferable.
  • the position of the aliphatic hydrocarbon group having 6 to 12 carbon atoms or the aliphatic hydrocarbon oxy group having 6 to 12 carbon atoms is not particularly limited, but is preferably bonded to the aromatic ring to which the hydroxy group is bonded.
  • the specific hydroxybenzophenone compound is an aliphatic hydrocarbon group having 6 to 12 carbon atoms or an aliphatic hydrocarbon oxy group having 6 to 12 carbon atoms in the aromatic ring to which the hydroxy group of 2-hydroxybenzophenone is bonded.
  • the carbon number of the aliphatic hydrocarbon group having 6 to 12 carbon atoms or the aliphatic hydrocarbon oxy group having 6 to 12 carbon atoms which the specific hydroxybenzophenone compound has may be 8 to 10 or 8 .
  • the aliphatic hydrocarbon group having 6 to 12 carbon atoms or the aliphatic hydrocarbon oxy group having 6 to 12 carbon atoms which the specific hydroxybenzophenone compound has may or may not have an unsaturated double bond. Preferably has no unsaturated double bond.
  • the aliphatic hydrocarbon group having 6 to 12 carbon atoms or the aliphatic hydrocarbon oxy group having 6 to 12 carbon atoms which the specific hydroxybenzophenone compound has may be branched or unbranched, but is not branched. It is preferable.
  • the curable resin composition of the present disclosure contains the curable resin composition additive described above and a curable resin component.
  • the curable resin component is not particularly limited as long as it forms a three-dimensional crosslinked structure by reaction, and may be thermosetting or photocurable. From the viewpoint of mass productivity, it is preferably thermosetting.
  • the curable resin component may be one that is cured by self-polymerization or one that is cured by a reaction with a curing agent, a crosslinking agent or the like.
  • the functional group that causes the reaction of the curable resin component is not particularly limited, and examples thereof include an epoxy group, a cyclic ether group such as an oxetanyl group, a hydroxyl group, a carboxy group, an amino group, an acryloyl group, an isocyanate group, a maleimide group, and an alkenyl group.
  • a curable resin component containing a cyclic ether group is preferable
  • a curable resin component containing an epoxy group (epoxy resin) is more preferable
  • a combination of an epoxy resin and a curing agent is used. Is more preferable.
  • the type of the 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, resorcin, catechol, bisphenol A and bisphenol F, and naphthol compounds such as ⁇ -naphthol, ⁇ -naphthol and dihydroxynaphthalene.
  • Type compound formaldehyde, acetaldehyde, a novolak type epoxy resin obtained by epoxidizing a novolak resin obtained by condensation or co-condensation of an aliphatic aldehyde compound such as propionaldehyde under an acidic catalyst (phenol novolak type epoxy resin, Orthocresol novolac type epoxy resin, etc.); obtained by condensing or co-condensing the above-mentioned phenolic compound with an aromatic aldehyde compound such as benzaldehyde, salicylaldehyde under an acidic catalyst.
  • phenol novolak type epoxy resin obtained by condensation or co-condensation of an aliphatic aldehyde compound such as propionaldehyde under an acidic catalyst
  • an aromatic aldehyde compound such as benzaldehyde, salicylaldehyde under an acidic catalyst.
  • Triphenylmethane type epoxy resin obtained by epoxidizing a triphenylmethane type phenolic resin; epoxidized novolak resin obtained by co-condensing the above phenol compound and naphthol compound with an aldehyde compound under an acidic catalyst
  • a copolymer type epoxy resin a diphenylmethane type epoxy resin which is a diglycidyl ether of bisphenol A, bisphenol F, etc .
  • a biphenyl type epoxy resin which is a diglycidyl ether of an alkyl-substituted or unsubstituted biphenol; a diglycidyl stilbene phenol compound Stilbene type epoxy resin which is ether; sulfur atom-containing epoxy resin which is diglycidyl ether such as bisphenol S; butanediol, polyethylene glycol, polypropylene glycol and the like
  • Epoxy resin which is glycidyl ether of coal
  • biphenyl type epoxy resin from the viewpoint of balance between reflow resistance and fluidity, biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom-containing type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy.
  • An epoxy resin selected from the group consisting of a resin, a triphenylmethane type epoxy resin, a copolymerization type epoxy resin and an aralkyl type epoxy resin (these are referred to as “specific epoxy resin”) is preferable.
  • the specific epoxy resins may be used alone or in combination of two or more.
  • the content thereof is preferably 30% by mass or more, and more preferably 50% by mass or more, from the viewpoint of exhibiting the performance of the specific epoxy resin. .
  • a biphenyl type epoxy resin, a stilbene type epoxy resin, a diphenylmethane type epoxy resin or a sulfur atom-containing type epoxy resin is more preferable from the viewpoint of fluidity, and a dicyclopentadiene type epoxy from the viewpoint of heat resistance.
  • Resins, triphenylmethane type epoxy resins or aralkyl type epoxy resins are preferred. Specific examples of preferable 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 preferable.
  • 3,8 ', 5' and 5'positions are methyl groups when the positions where oxygen atoms are substituted in R 8 are 4 and 4'positions.
  • YX-4000H (Mitsubishi Chemical Corporation, trade name) other R 8 is a hydrogen atom, all the R 8 are hydrogen atoms 4,4'-bis (2,3-epoxypropoxy) biphenyl, When all the R 8 s are hydrogen atoms, or when the positions of the R 8 s substituted by oxygen atoms are the 4 and 4'positions, the 3,3 ', 5,5' positions are methyl groups and the other R's are not.
  • YL-6121H (Mitsubishi Chemical Co., Ltd., trade name), which is a mixed product in which 8 is a hydrogen atom, is commercially available.
  • 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, and all of them may be the same or different.
  • n is an 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 preferable.
  • 3,3 ′, 5,5 ′ positions are methyl groups when the oxygen atom-substituted position of R 9 is 4 and 4 ′ positions.
  • R 9 is a hydrogen atom other than the above, all of R 10 are hydrogen atoms, and three of the 3,3 ′, 5,5 ′ positions of R 9 are methyl groups, ESLV-210 (Sumitomo Chemical Co., Ltd., trade name), which is a mixed product in which one is a t-butyl group, the other R 9 is a hydrogen atom, and all R 10 are hydrogen atoms, It is available as a commercial product.
  • ESLV-210 Suditomo Chemical Co., Ltd., trade name
  • R 9 and R 10 represent 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 an 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 preferable.
  • all of R 11 are hydrogen atoms, and 3,3 when the positions of R 12 substituted with oxygen atoms are 4 and 4 ′ positions.
  • YSLV-80XY (Nippon Steel & Sumikin Chemical Co., Ltd., trade name) in which the ', 5, 5'position is a methyl group and the other R 12 is a hydrogen atom is commercially available.
  • R 11 and R 12 represent 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 an average value and represents a number from 0 to 10.
  • the sulfur atom-containing epoxy resin is not particularly limited as long as it is an epoxy resin containing a sulfur atom.
  • an epoxy resin represented by the following general formula (V) may be mentioned.
  • 3,3'-position is a t-butyl group when the position where the oxygen atom is substituted in R 13 is 4 and 4'-positions
  • YSLV-120TE Nippon Steel & Sumikin Chemical Co., Ltd., trade name
  • 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 an average value and represents a number from 0 to 10.
  • the novolac type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolac type phenol resin.
  • an epoxy resin obtained by epoxidizing a novolac type phenol resin such as a phenol novolac resin, a cresol novolac resin, or a naphthol novolac resin using a method such as glycidyl etherification is preferable, and is represented by the following general formula (VI).
  • Epoxy resins are more preferred.
  • R 14 are hydrogen atoms
  • 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, and all of them may be the same or different.
  • i independently represents an integer of 0 to 3.
  • n is an 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 preferable.
  • R 16 represents a monovalent organic group having 1 to 18 carbon atoms, and all may be the same or different.
  • i independently represents an integer of 0 to 3.
  • n is an 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 of a compound having a triphenylmethane skeleton as a raw material.
  • an epoxy resin obtained by glycidyl etherifying a triphenylmethane type phenolic resin such as a novolak 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).
  • the epoxy resin used is more preferable.
  • epoxy resins represented by the following general formula (VIII) i is 0 and k is 0, 1032H60 (Mitsubishi Chemical Co., Ltd., trade name), EPPN-502H (Nippon Kayaku Co., Ltd., trade name) Etc. are commercially available.
  • R 17 and R 18 represent a monovalent organic group having 1 to 18 carbon atoms, and all may be the same or different.
  • i is independently an integer of 0 to 3
  • k is independently an integer of 0 to 4.
  • n is an average value and represents a number from 0 to 10.
  • Copolymerization type epoxy resin obtained by epoxidizing a novolac resin obtained from a naphthol compound and a phenol compound, and an aldehyde compound is not particularly limited as long as it is an epoxy resin using a compound having a naphthol skeleton and a compound having a phenol skeleton as raw materials.
  • an epoxy resin obtained by glycidyl etherification of 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.
  • R 19 to R 21 each represent a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different.
  • i is independently an integer of 0 to 3
  • j is an integer of 0 to 2 independently
  • k is an integer of 0 to 4 independently.
  • Each of 1 and m is an average value and is a number of 0 to 10
  • (l + m) is a number of 0 to 10.
  • the terminal of the epoxy resin represented by the formula (IX) is one of the following formulas (IX-1) and (IX-2).
  • R 19 to R 21 have the same definitions of i, j and k as R 19 to R 21 in formula (IX) have the same definition as i, j and k.
  • Is. n is 1 (when binding via a methylene group) or 0 (when not binding via a methylene group).
  • epoxy resin represented by the general formula (IX) a random copolymer containing 1 constitutional unit and m constitutional units at random, an alternating copolymer containing them alternately, a copolymer containing them regularly , Block copolymers contained in blocks, and the like. Any one of these may be used alone or in combination of two or more.
  • the copolymer type epoxy resin is a methoxynaphthalene / cresol formaldehyde cocondensation type epoxy resin containing the following two types of structural units in a random, alternating or block order, which is represented by the following general formula, Epiclon HP-5000 ( DIC Corporation, trade name) is also preferred.
  • n and m are average values and are numbers from 0 to 10
  • (n + m) is a number from 0 to 10
  • preferably n and m are average values and are from 1 to 9
  • And (n + m) is 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. It is not particularly limited as long as it is an epoxy resin made from a phenol resin as a raw material.
  • the epoxy resin obtained by glycidyl etherification is preferable, and the epoxy resins represented by the following general formulas (X) and (XI) are more preferable.
  • R 38 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 37 and R 39 to R 41 represent a monovalent organic group having 1 to 18 carbon atoms, and all 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.
  • n is an average value and is a number of 0 to 10 independently.
  • R 8 to R 21 and R 37 to R 41 in the above general formulas (II) to (XI) “all may be the same or different” means, for example, 8 to R in the formula (II). It means that all of 88 R 8 's may be the same or different. It also means that all other R 9 to R 21 and R 37 to R 41 may be the same or different in terms of the respective numbers included in the formula. Further, R 8 to R 21 and R 37 to R 41 may be the same or different. For example, R 9 and R 10 may all be the same or different. Further, the organic group having 1 to 18 carbon atoms in the 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 it is preferable that n is independently in the range of 0 to 10.
  • n is 10 or less, the melt viscosity of the resin component does not become too high, the viscosity of the curable resin composition during melt molding decreases, the filling failure occurs, and the bonding wire (gold wire connecting the element and the lead) deforms. Occurrence of such a phenomenon tends to be suppressed. More preferably, n is set in the range of 0-4.
  • the functional group equivalent of the curable resin (epoxy equivalent in the case of epoxy resin) is not particularly limited. From the viewpoint of the balance of various characteristics such as moldability, reflow resistance and electrical reliability, the functional group equivalent of the curable resin is preferably 100 g / eq to 1000 g / eq, and 150 g / eq to 500 g / eq. More preferably.
  • the softening point or melting point of the curable resin is not particularly limited. From the viewpoint of moldability and reflow resistance, it is preferably 40 ° C to 180 ° C, and more preferably 50 ° C to 130 ° C from the viewpoint of handleability during preparation of the curable resin composition.
  • the content of the curable resin in the curable resin composition is preferably 0.5% by mass to 50% by mass, from the viewpoint of strength, fluidity, heat resistance, moldability, etc., and 2% by mass to 30% by mass. % Is more preferable.
  • the curable resin composition may include a curing agent as the curable resin component.
  • the type of curing agent is not particularly limited, and can be selected according to the type of curable resin component, desired properties of the curable resin composition, and the like.
  • the curing agent when the curable resin component contains an epoxy resin, a phenol curing agent, an amine curing agent, an acid anhydride curing agent, a polymercaptan curing agent, a polyaminoamide curing agent, an isocyanate curing agent, a blocked isocyanate curing agent, etc. Can be mentioned.
  • At least one selected from the group consisting of phenol curing agents, amine curing agents and acid anhydride curing agents is preferable, and phenol curing agents are more preferable from the viewpoint of electrical reliability. preferable.
  • phenol curing agents include phenol resins and polyhydric phenol compounds having two or more phenolic hydroxyl groups in one molecule.
  • 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.
  • 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, propionaldehyde, benzaldehyde, salicylaldehyde, etc.
  • Novolac type phenolic resin obtained by condensation or co-condensation under a catalyst the above phenolic compound, dimethoxyparaxylene, bis (methoxy) Aralkyl-type phenol resin such as phenol aralkyl resin and naphthol aralkyl resin synthesized from methyl) biphenyl and the like; paraxylylene and / or metaxylylene modified phenol resin; melamine modified phenol resin; terpene modified phenol resin; Dicyclopentadiene type phenol resin and dicyclopentadiene type naphthol resin synthesized by copolymerization with pentadiene; cyclopentadiene modified phenol resin; polycyclic aromatic ring modified phenol resin; biphenyl type phenol resin; the above phenolic compound and benzaldehyde, Triphenylmethane type phenolic resin obtained by condensation or co-condensation with an aromatic aldehyde compound such as salicylaldehyde
  • phenol curing agents from the viewpoint of reflow resistance, aralkyl type phenol resin, dicyclopentadiene type phenol resin, triphenylmethane type phenol resin, copolymer type phenol resin of benzaldehyde type phenol resin and aralkyl type phenol resin, and At least one selected from the group consisting of novolac type phenol resins (these are referred to as "specific phenol curing agents”) is preferable.
  • the specific phenol curing agents may be used alone or in combination of two or more.
  • the content of the specific phenol curing agent is preferably 30% by mass or more, and 50% by mass or more, based on the total amount of the curing agent, from the viewpoint of sufficiently exhibiting the performance thereof. Is more preferable.
  • aralkyl-type phenol resin examples include a phenol aralkyl resin synthesized from a phenolic compound and dimethoxyparaxylene, bis (methoxymethyl) biphenyl, naphthol aralkyl resin, and the like.
  • the aralkyl type phenol resin may be further copolymerized with another phenol resin.
  • a copolymer-type phenol resin of a benzaldehyde-type phenol resin and an aralkyl-type phenol resin examples thereof include a copolymer type phenol resin with an aralkyl type phenol resin.
  • the aralkyl type phenol resin is not particularly limited as long as it is a phenol resin synthesized from at least one selected from the group consisting of a phenol compound and a naphthol compound and dimethoxyparaxylene, bis (methoxymethyl) biphenyl or a derivative thereof.
  • phenol resins represented by the following general formulas (XII) to (XIV) are preferable.
  • R 23 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 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 represent a hydroxyl group or a monovalent organic group having 1 to 18 carbon atoms, and all 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
  • p is each independently an integer of 0 to 4. is there.
  • n is an average value and is a number of 0 to 10 independently.
  • phenolic resins represented by the general formula (XII), MEH-7851 (Meiwa Kasei Co., Ltd., trade name) in which i is 0 and R 23 are all hydrogen atoms is commercially available. .
  • phenolic resins represented by the above general formula (XIII) XL-225 in which i is 0 and k is 0, XLC (Mitsui Chemicals, Inc., trade name), MEH-7800 (Meiwa Kasei Co., Ltd., Trade name) etc. are available as commercial products.
  • phenolic resins represented by the above general formula (XIV) SN-170 (Nippon Steel & Sumikin Chemical Co., Ltd., trade name) in which j is 0, k is 0 and p is 0, j is 0 SN-395 (Nippon Steel & Sumikin Chemical Co., Ltd., trade name) in which k is 1, R 27 is a hydroxyl group, and p is 0 is commercially available.
  • the dicyclopentadiene type phenol resin is not particularly limited as long as it is a phenol resin obtained from a compound having a dicyclopentadiene skeleton as a raw material.
  • a phenol resin represented by the following general formula (XV) is preferable.
  • R 29 represents a monovalent organic group having 1 to 18 carbon atoms, and all may be the same or different.
  • i independently represents an integer of 0 to 3.
  • n is an average value and represents a number from 0 to 10.
  • the triphenylmethane type phenol resin is not particularly limited as long as it is a phenol resin obtained from a compound having a triphenylmethane skeleton as a raw material.
  • a phenol resin represented by the following general formula (XVI) is preferable.
  • R 30 and R 31 represent a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different.
  • i is independently an integer of 0 to 3
  • k is independently an integer of 0 to 4.
  • n is an average value and is a number from 0 to 10.
  • the copolymerization type phenol resin of a benzaldehyde type phenol resin and an aralkyl type phenol resin is not particularly limited as long as it is a copolymerization type phenol resin of a phenol resin obtained from a compound having a benzaldehyde skeleton as a raw material and an aralkyl type phenol resin.
  • a phenol resin represented by the following general formula (XVII) is preferable.
  • R 32 to R 34 each represents 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
  • k is each independently an integer of 0 to 4
  • q is each independently an integer of 0 to 5.
  • l and m are average values, and are numbers 0 to 11 each independently. However, the sum of 1 and m is a number from 1 to 11.
  • the novolac type phenol resin is not particularly limited as long as it is a phenol resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of a phenol compound and a naphthol compound with an aldehyde compound under an acidic catalyst.
  • a phenol resin represented by the following general formula (XVIII) is preferable.
  • phenolic resins represented by the following general formula (XVIII), Tamanor 758, 759 (Arakawa Chemical Industry Co., Ltd., trade name) in which i is 0 and R 35 are all hydrogen atoms, HP-850N (Hitachi Chemical Co., Ltd.) Co., Ltd., product name) etc. are available as commercial products.
  • R 35 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 36 represents a monovalent organic group having 1 to 18 carbon atoms, and all may be the same or different.
  • i independently represents an integer of 0 to 3.
  • n is an average value and represents a number from 0 to 10.
  • R 22 to R 36 in the general formulas (XII) to (XVIII) means that, for example, all i R 22 's in the formula (XII) are the same. However, it means that they may be different from each other.
  • the other R 23 to R 36 also mean that the respective numbers included in the formula may all be the same or different from each other.
  • R 22 to R 36 may be the same or different. For example, all of R 22 and R 23 may be the same or different, and all of R 30 and R 31 may be the same or different.
  • n is preferably in the range of 0 to 10.
  • the melt viscosity of the resin component does not become too high, the viscosity of the curable resin composition at the time of melt molding also becomes low, and unfilling failure and deformation of the bonding wire (gold wire connecting the element and the lead) are prevented. Less likely to occur.
  • the average n in one molecule is preferably set in the range of 0 to 4.
  • the functional group equivalent of the curing agent is not particularly limited. From the viewpoint of various characteristics balance such as moldability, reflow resistance, electrical reliability, etc., it is preferably 70 g / eq to 1000 g / eq, more preferably 80 g / eq to 500 g / eq. ⁇
  • the softening point or melting point of the curing agent is not particularly limited. From the viewpoint of moldability and reflow resistance, it is preferably 40 ° C. to 180 ° C., and from the viewpoint of handleability during production of the curable resin composition, more preferably 50 ° C. to 130 ° C. ⁇
  • the equivalent ratio of the curable resin and the curing agent that is, the ratio of the number of functional groups in the curing agent to the number of functional groups in the curable resin (the number of functional groups in the curing agent / the number of functional groups in the curable resin) is not particularly limited.
  • the range of 0.5 to 2.0 is preferable, and the range of 0.6 to 1.3 is more preferable. From the viewpoints of moldability and reflow resistance, it is more preferable to set it in the range of 0.8 to 1.2.
  • the curable resin composition may include a curing accelerator.
  • the type of curing accelerator is not particularly limited and can be selected according to the type of curable resin, desired properties of the curable resin composition, and the like.
  • the curing accelerator preferably contains a phosphonium compound.
  • the phosphonium compound include 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, alkyldiaryl Tertiary phosphines such as phos
  • a compound having a ⁇ bond such as
  • Compound having an intramolecular polarization obtained by reacting the halogenated phenol compound of 1. with a dehydrohalogenation step; bound to a tetra-substituted phosphonium such as tetraphenylphosphonium or a boron atom such as tetra-p-tolylborate A phenyl group-free tetra-substituted phosphonium and a tetra-substituted borate; a salt of a tetra-substituted phosphonium with an anion whose proton is eliminated from a phenol compound, a salt of a tetra-substituted phosphonium and an anion whose proton is eliminated from a carboxylic acid compound, etc. Can be mentioned.
  • the 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 are each independently a hydrogen atom, a hydroxyl group or an organic group having 1 to 18 carbon atoms, and two or more of R 4 to R 7 are bonded to each other to form a cyclic structure. You may form.
  • the “hydrocarbon group having 1 to 18 carbon atoms” described as R 1 to R 3 in the general formula (I-1) is an aliphatic hydrocarbon group having 1 to 18 carbon atoms and 6 to 18 carbon atoms. Contains certain 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 further 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. From the viewpoint of ease of production, a linear or branched aliphatic hydrocarbon group is preferred.
  • linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, Examples thereof include an alkyl group such as a pentyl group, a hexyl group, an octyl group, a decyl group and a dodecyl group, an allyl group and a vinyl group.
  • the linear or branched aliphatic hydrocarbon group may or may not have a substituent.
  • substituents examples include an alkoxy group such as a methoxy group, an ethoxy group, a butoxy group and a t-butoxy group, an aryl group such as a phenyl group and a naphthyl group, a hydroxyl group, an amino group and a halogen atom.
  • the linear or branched aliphatic 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 aliphatic hydrocarbon group and the substituent is preferably 1-18.
  • an unsubstituted alkyl group is preferable, an unsubstituted alkyl group having 1 to 8 carbon atoms is more preferable, and an n-butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group and an n-octyl group. More preferred are groups.
  • alicyclic hydrocarbon having 3 to 18 carbon atoms include cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cycloheptyl group, cycloalkenyl groups such as cyclopentenyl group and cyclohexenyl group.
  • the alicyclic hydrocarbon group may or may not have a substituent.
  • substituents examples include an alkyl group such as a methyl group, an ethyl group, a butyl group, and a tert-butyl group, an alkoxy group such as a methoxy group, an ethoxy group, a butoxy group, and a t-butoxy group, and an aryl group such as a phenyl group and a naphthyl group.
  • alkyl group such as a methyl group, an ethyl group, a butyl group, and a tert-butyl group
  • alkoxy group such as a methoxy group, an ethoxy group, a butoxy group, and a t-butoxy group
  • aryl group such as a phenyl group and a naphthyl group.
  • the alicyclic hydrocarbon group may have two or more substituents, in which case the
  • 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. From the viewpoint of curability, 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 further preferable.
  • the aromatic hydrocarbon group having 6 to 18 carbon atoms preferably has 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms.
  • the aromatic hydrocarbon group may or may not have a substituent.
  • the substituent include an alkyl group such as a methyl group, an ethyl group, a butyl group, and a t-butyl group, an alkoxy group such as a methoxy group, an ethoxy group, a butoxy group, and a t-butoxy group, and an aryl group such as a phenyl group and a naphthyl group.
  • the aromatic 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 aromatic hydrocarbon group and the substituent is preferably 6-18.
  • the position of the substituent is not particularly limited.
  • aromatic hydrocarbon group having 6 to 18 carbon atoms include phenyl group, 1-naphthyl group, 2-naphthyl group, tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group and t-butyl. Examples thereof include a phenyl group, a methoxyphenyl group, an ethoxyphenyl group, a butoxyphenyl group and a t-butoxyphenyl group.
  • the position of the substituent in these aromatic hydrocarbon groups may be any of the ortho position, the meta position and the para position.
  • an unsubstituted aryl group having 6 to 12 carbon atoms or 6 to 12 carbon atoms including a substituent is preferable, and an unsubstituted aryl group having 6 to 10 carbon atoms or a carbon atom including a substituent.
  • Aryl groups of the formulas 6 to 10 are more preferable, and phenyl group, p-tolyl group and p-methoxyphenyl group are even more preferable.
  • R 1 to R 3 may combine with each other to form a cyclic structure” described as R 1 to R 3 in the general formula (I-1) means that R 1 to R 3 It means a case where two or three of them are combined to form one divalent or trivalent hydrocarbon group as a whole.
  • R 1 to R 3 in this case include an alkylene group such as ethylene, propylene, butylene, pentylene, and hexylene which can be bonded to a phosphorus atom to form a cyclic structure, an alkenylene group such as ethylenylene, propylenylene, butyrenylene group, and the like.
  • substituents examples include an aralkylene group such as a methylenephenylene group, an arylene group such as phenylene, naphthylene, and anthracenylene, and the like, which can bond to a phosphorus atom to form a cyclic structure.
  • substituents may be further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen atom or the like.
  • the “organic group having 1 to 18 carbon atoms” described as R 4 to R 7 in the general formula (I-1) has 1 to 18 carbon atoms and may be substituted or unsubstituted. It is meant to include a group hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbon oxy group, an aromatic hydrocarbon oxy group, an acyl group, a hydrocarbon oxycarbonyl group, and an acyloxy group.
  • Examples of the above aliphatic hydrocarbon group and aromatic hydrocarbon group include those mentioned above as examples of the aliphatic hydrocarbon group and aromatic hydrocarbon group represented by R 1 to R 3 .
  • Examples of the aliphatic hydrocarbon oxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, 2-butoxy group, t-butoxy group, cyclopropyloxy group, cyclohexyloxy group, cyclopentyloxy group.
  • aromatic hydrocarbon oxy group a phenoxy group, a methylphenoxy group, an ethylphenoxy group, a methoxyphenoxy group, a butoxyphenoxy group, an oxy having a structure in which an oxygen atom is bonded to the above aromatic hydrocarbon group such as a phenoxyphenoxy group.
  • aromatic hydrocarbonoxy groups those in which these aromatic hydrocarbonoxy groups are further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, and the like.
  • acyl group examples include an aliphatic hydrocarbon carbonyl group such as a formyl group, an acetyl group, an ethylcarbonyl group, a butyryl group, a cyclohexylcarbonyl group and an allylcarbonyl group, an aromatic hydrocarbon carbonyl group such as a phenylcarbonyl group and a methylphenylcarbonyl group.
  • hydrocarbon oxycarbonyl group examples include an methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, an allyloxycarbonyl group, an aliphatic hydrocarbon oxycarbonyl group such as a cyclohexyloxycarbonyl group, a phenoxycarbonyl group, and a methylphenoxycarbonyl group.
  • Aromatic hydrocarbon oxycarbonyl groups, 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. Things are included.
  • acyloxy group examples include an aliphatic hydrocarbon carbonyloxy group such as a methylcarbonyloxy group, an ethylcarbonyloxy group, a butylcarbonyloxy group, an allylcarbonyloxy group and a cyclohexylcarbonyloxy group, a phenylcarbonyloxy group, a methylphenylcarbonyloxy group.
  • aromatic hydrocarbon carbonyloxy groups, and 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. Some of them have been made.
  • R 4 to R 7 may be bonded to each other to form a cyclic structure” described as R 4 to R 7 in the above general formula (I-1) means 2 to 4 It means that R 4 to R 7 may be combined to form one divalent to tetravalent organic group as a whole.
  • R 4 to R 7 are alkylene groups such as ethylene, propylene, butylene, pentylene and hexylene, alkenylene groups such as ethylenylene, propylenylene and butyrenylene, aralkylene groups such as methylenephenylene, arylene such as phenylene, naphthylene and anthracenylene.
  • substituents examples include a substituent capable of forming a cyclic structure such as a group, and an oxy group or a dioxy group thereof. These substituents may be further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen atom or the like.
  • R 4 to R 7 in the general formula (I-1) are not particularly limited.
  • each may be independently selected from a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group.
  • a hydrogen atom, a hydroxyl group, an unsubstituted or substituted aryl group with at least one selected from the group consisting of an alkyl group and an alkoxy group, or a chain or cyclic alkyl group is preferable.
  • Examples of the aryl group which is unsubstituted or substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group include phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group and the like. Is mentioned.
  • Examples of the chain or cyclic alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-butyl group, a t-butyl group, an octyl group and a cyclohexyl group. From the viewpoint of curability, it is preferable that R 4 to R 7 are all 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 are an alkyl group having 1 to 18 carbon atoms or a cycloalkyl group 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.
  • R 1 to R 3 are all alkyl groups having 1 to 18 carbon atoms or cycloalkyl groups having 3 to 18 carbon atoms
  • R 4 to R 7 are all hydrogen atoms, or at least one is a hydroxyl group.
  • 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 are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, and two or more of R 4 to R 6 are bonded to each other to form a cyclic structure. May be.
  • R 1 ⁇ R 6 in the formula (I-2) is the same as specific examples of R 1 ⁇ R 6, respectively, in formula (I-1), and preferred ranges are also the same.
  • Specific examples of the specific curing accelerator include addition reaction products of triphenylphosphine and 1,4-benzoquinone, addition reaction products of tri-n-butylphosphine and 1,4-benzoquinone, tricyclohexylphosphine and 1,4-benzoquinone.
  • an addition reaction product of 1,4-benzoquinone isofurylphosphine and 1,4-benzoquinone.
  • the 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, tris (4-ethylphenyl) phosphine.
  • the quinone compound examples include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone and anthraquinone. From the viewpoint of moisture resistance and storage stability, p-benzoquinone is preferable.
  • the curable resin composition may contain a curing accelerator other than the phosphonium compound.
  • a curing accelerator other than the phosphonium compound 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 diazabicycloalkene, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; Derivatives of the cyclic amidine compounds; Phenolic novolac salts of derivatives; maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-to these compounds Dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1, -Quinone compounds such as benzoquinone and phenyl-1,4-benzoquinone, compounds having an intramolecular polarization formed by adding a compound having a ⁇ bond such as diazophenylmethane; DBU tetraphenylborate salt, DBN
  • the content rate of the specific curing accelerator is preferably 30% by mass or more and more preferably 50% by mass or more based on the entire curing accelerator. More preferably, it is more preferably 70% by mass or more.
  • the amount thereof is preferably 0.1 parts by mass to 30 parts by mass and preferably 1 part by mass to 15 parts by mass with respect to 100 parts by mass of the resin component. Is more preferable.
  • 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, the curing tends to be excellently performed in a short time. If 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 will not be too fast, and a good molded article will tend to be obtained.
  • the curable resin composition may include an inorganic filler.
  • an inorganic filler when the curable resin composition is used as a sealing material for semiconductor packages, it is preferable to include an inorganic filler.
  • the type of 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. Inorganic materials such as titania, talc, clay and mica can be mentioned. You may use the inorganic filler which has a flame retardant effect. Examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, complex metal hydroxides such as complex hydroxide of magnesium and zinc, zinc borate and the like.
  • fused silica is preferable from the viewpoint of reducing the linear expansion coefficient
  • alumina is preferable from the viewpoint of high thermal conductivity.
  • the inorganic fillers may be used alone or in combination of two or more. Examples of the state of the inorganic filler include non-powder, spherical beads, fibers and the like.
  • the curable resin composition contains an inorganic filler
  • its content is not particularly limited. From the viewpoint of fluidity and strength, 30% by volume to 90% by volume of the entire curable resin composition is preferable, 35% by volume to 80% by volume is more preferable, and 40% by volume to 70% by volume. Is more preferable.
  • the content of the inorganic filler is 30% by volume or more of the entire curable resin composition, properties such as the thermal expansion coefficient, thermal conductivity and elastic modulus of the cured product tend to be further improved.
  • the content of the inorganic filler is 90% by volume or less of the entire curable resin composition, the increase in viscosity of the curable resin composition is suppressed, the fluidity is further improved, and the moldability tends to be better. It is in.
  • the average particle size of the inorganic filler is not particularly limited.
  • the volume average particle diameter is preferably 0.2 ⁇ m to 10 ⁇ m, more preferably 0.5 ⁇ m to 5 ⁇ m.
  • the volume average particle diameter is 0.2 ⁇ m or more, increase in viscosity of the resin composition for mold underfill tends to be further suppressed.
  • the volume average particle diameter is 10 ⁇ m or less, the filling property into a narrow gap tends to be further improved.
  • the volume average particle diameter of the inorganic filler can be measured as a volume average particle diameter (D50) by a laser diffraction scattering method particle size distribution measuring device.
  • the volume average particle size of the inorganic filler in the curable resin composition or the cured product thereof can be measured by a known method.
  • the inorganic filler is extracted from the curable resin composition or the cured product using an organic solvent, nitric acid, aqua regia, or the like, and sufficiently dispersed with an ultrasonic disperser to prepare a dispersion liquid.
  • the volume average particle size of the inorganic filler can be measured from the volume-based particle size distribution measured by a laser diffraction / scattering particle size distribution analyzer.
  • measure the volume average particle size of the inorganic filler from the volume-based particle size distribution obtained by observing the cross section obtained by embedding the cured product in a transparent epoxy resin, etc. and polishing and observing with a scanning electron microscope.
  • FIB device focused ion beam SEM
  • the particle shape of the inorganic filler is preferably spherical rather than prismatic, and the particle size distribution of the inorganic filler is preferably widely distributed.
  • the curable resin composition may contain various additives such as a coupling agent, an ion exchanger, a release agent, a flame retardant, a colorant, and a stress relaxation agent, which are exemplified below, in addition to the above components.
  • the curable resin composition may contain various additives well known in the art, if necessary, in addition to the additives exemplified below.
  • a coupling agent may be included in order to enhance the adhesiveness between the resin component and the inorganic filler.
  • the coupling agent include known coupling agents such as silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane and vinylsilane, titanium compounds, aluminum chelate compounds, aluminum / zirconium compounds. .
  • the amount of the coupling agent is preferably 0.05 parts by mass to 5 parts by mass, and 0.1 parts by mass to 100 parts by mass of the inorganic filler. 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 adhesiveness with 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 curable resin composition may include an ion exchanger.
  • an ion exchanger when the curable resin composition is used as a molding material for encapsulation, it is preferable to include an ion exchanger from the viewpoint of improving the moisture resistance and high-temperature storage property of an electronic component device including an 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 alone or in combination of two or more. Among them, hydrotalcite represented by the following general formula (A) is preferable.
  • the content is not particularly limited as long as it is an amount sufficient to trap ions such as halogen ions.
  • it is preferably 0.1 part by mass to 30 parts by mass, more preferably 1 part by mass to 15 parts by mass, relative to 100 parts by mass of the resin component.
  • the curable resin composition may contain a mold release agent from the viewpoint of obtaining good mold releasability from the mold during molding.
  • the release agent is not particularly limited, and conventionally known ones can be used. Specific examples thereof include higher fatty acids such as carnauba wax, montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid ester, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene.
  • the release agents may be used alone or in combination of two or more.
  • the amount thereof is preferably 0.01 part by mass to 15 parts by mass, more preferably 0.1 part by mass to 10 parts by mass, relative to 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, the mold releasability tends to be sufficiently obtained.
  • it is 15 parts by mass or less, better adhesiveness tends to be obtained.
  • the curable resin composition may include 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, metal hydroxides and the like.
  • the flame retardants may be used alone or in combination of two or more.
  • the amount thereof is not particularly limited as long as it is an amount sufficient to obtain a 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, relative to 100 parts by mass of the resin component.
  • the curable resin composition may further include a colorant.
  • a colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead and red iron oxide.
  • the content of the colorant can be appropriately selected according to the purpose and the like.
  • the colorants may be used alone or in combination of two or more.
  • the curable resin composition may contain a stress relaxation agent such as silicone oil or silicone rubber particles.
  • a stress relaxation agent such as silicone oil or silicone rubber particles.
  • the stress relaxation agent By including the stress relaxation agent, it is possible to further reduce the warp deformation of the package and the occurrence of package cracks.
  • the stress relaxation agent include known stress relaxation agents (flexible agents) that are generally used.
  • thermoplastic elastomers such as silicone type, styrene type, olefin type, urethane type, polyester type, polyether type, polyamide type, polybutadiene type, NR (natural rubber), NBR (acrylonitrile-butadiene rubber), acrylic Rubber particles such as rubber, urethane rubber and silicone powder, core-shell such as methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer Examples thereof include rubber particles having a structure.
  • the stress relaxation agent may be used alone or in combination of two or more. Of these, a silicone-based stress relaxation agent is preferable. Examples of the silicone-based stress relaxation agent include those having an epoxy group, those having an amino group, those modified with polyether, and the like.
  • the method for preparing the curable resin composition is not particularly limited.
  • a general method there can be mentioned a method in which components having a predetermined blending amount are sufficiently mixed with a mixer or the like, and then melt-kneaded with a mixing roll, an extruder or the like, cooled, and pulverized. More specifically, for example, a method of uniformly stirring and mixing predetermined amounts of the above-mentioned components, kneading with a kneader, roll, extruder or the like preheated to 70 ° C to 140 ° C, cooling, and pulverizing. Can be mentioned.
  • the curable resin composition is preferably solid at room temperature and atmospheric pressure (for example, 25 ° C. and atmospheric pressure).
  • the shape of the curable resin composition when it is solid is not particularly limited, and examples thereof include powder, granules, and tablets. From the viewpoint of handleability, it is preferable that the size and weight of the curable resin composition in the form of a tablet be such that it meets the molding conditions of the package.
  • An electronic component device includes an element and a cured product of the curable resin composition that seals the element.
  • Examples of electronic component devices include lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers, organic substrates, and other supporting members, elements (semiconductor chips, transistors, diodes, active elements such as thyristors, capacitors, resistors). , A passive element such as a coil) and an element portion obtained by mounting it with a curable resin composition.
  • the element is fixed on a lead frame, the terminal portion of the element such as a bonding pad and the lead portion are connected by wire bonding, bumps, etc., and then transfer molding or the like using a curable resin composition.
  • DIP Dual Inline Package
  • PLCC Physical Leaded Chip Carrier
  • QFP Quad Flat Package
  • SOP Small Outline Package
  • SOJ Small Outlet Line
  • SOJ Small Outlet Line
  • General resin encapsulation type IC such as Package), TQFP (Thin Quad Flat Package), etc .
  • TCP Tepe Carrier Package having a structure sealed with a composition
  • a curable resin composition A COB (Chip On Board) module, a hybrid IC, a multi-chip module, etc .; an element is mounted on the surface of a supporting member having terminals for connecting a wiring board formed on the back surface, and the element and the supporting member are formed by bumping or wire bonding BGA (Ball Grid Array), CSP (Chip Size Package), MCP (Multi Chip Package), etc., which have a structure in which an element is sealed with a curable resin composition after connecting to the formed wiring. Further, the curable resin composition can also be suitably used in a printed wiring board.
  • a low-pressure transfer molding method As a method of sealing the electronic component device using the curable resin composition, a low-pressure transfer molding method, an injection molding method, a compression molding method and the like can be mentioned. Among these, the low pressure transfer molding method is general.
  • Epoxy resin 1 Biphenyl type epoxy resin having an epoxy equivalent of 196 g / eq and a melting point of 106 ° C.
  • Epoxy resin 2 Styrene-modified phenol novolac type epoxy resin having an epoxy equivalent of 282 g / eq and a softening point of 59 ° C.
  • Epoxy resin 3 methoxynaphthalene / cresol formaldehyde co-condensation type epoxy resin having an epoxy equivalent of 250 g / eq and a softening point of 58 ° C.
  • Epoxy resin 4 aralkyl type epoxy resin containing a biphenylene skeleton having an epoxy equivalent of 282 g / eq and a softening point of 56 ° C.
  • Epoxy resin 5 Orthocresol novolac type epoxy resin having an epoxy equivalent of 197 g / eq (Chang Chun Plastics Co., Ltd., trade name "CNE-195LLB”)
  • Curing agent 1 Phenol aralkyl resin having a hydroxyl equivalent of 176 g / eq and a softening point of 70 ° C. (Meiwa Kasei Co., Ltd., trade name “MEH-7800”)
  • Curing agent 2 Biphenyl skeleton type phenol aralkyl resin having a hydroxyl equivalent of 199 g / eq and a softening point of 89 ° C. (Meiwa Kasei Co., Ltd., trade name “MEH-7851”)
  • Curing agent 3 Orthocresol novolac resin having a hydroxyl equivalent of 116 g / eq and a softening point of 64 ° C. (Meiwa Kasei Co., Ltd., trade name “MEH-5100-5S”)
  • Hydroxybenzophenone compound 1 2-hydroxy-4-n-octyloxybenzophenone (Kemipro Chemicals Co., Ltd., trade name “Kemisorb 12") Hydroxybenzophenone compound A: 2,4-dihydroxybenzophenone (Kemipro Kasei Co., Ltd., trade name "Kemisorb 10") Hydroxybenzophenone compound B: 2-hydroxy-4-methoxybenzophenone (Kemipro Kasei Co., Ltd., trade name "Kemisorb 11”) Hydroxybenzophenone compound C: 2,2′-dihydroxy-4-methoxybenzophenone (Kemipro Kasei Co., Ltd., trade name “Kemisorb 111”)
  • Curing accelerator addition reaction product of triphenylphosphine and 1,4-benzoquinone (inorganic filler) Spherical fused silica (volume average particle diameter 17.5 ⁇ m, specific surface area 3.8 m 2 / g) (Coupling agent) Epoxy silane ( ⁇ -glycidoxypropyltrimethoxysilane) (Colorant) Carbon black (Mitsubishi Chemical Corporation, trade name "MA-100”) (Release agent) Carnauba wax
  • Examples 1 to 12 containing the hydroxybenzophenone compound 1 corresponding to the specific hydroxybenzophenone compound had a larger reflow resistance than Comparative Examples 1 to 9 containing no hydroxybenzophenone compound. Improved. Comparative Examples 10 to 12 containing the hydroxybenzophenone compounds A, B and C which do not correspond to the specific hydroxybenzophenone compound are larger in reflow resistance than Example 2 having the same composition except that the hydroxybenzophenone compound 1 is contained. There was no improvement.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Power Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
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  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un additif pour composition de résine durcissable qui contient un composé hydroxybenzophénone possédant un groupe hydrocarbure aliphatique de 6 à 12 atomes de carbone ou un groupe hydrocarbure-oxy aliphatique de 6 à 12 atomes de carbone.
PCT/JP2019/040521 2018-10-17 2019-10-15 Additif pour composition de résine durcissable, composition de résine durcissable, et dispositif de composant électronique WO2020080369A1 (fr)

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CN117858915A (zh) * 2021-08-30 2024-04-09 株式会社力森诺科 硬化性树脂组合物及电子零件装置

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JPH01167359A (ja) * 1987-12-24 1989-07-03 Sumitomo Bakelite Co Ltd エポキシ樹脂組成物
JP2005239912A (ja) * 2004-02-27 2005-09-08 Sumitomo Bakelite Co Ltd 光半導体封止用エポキシ樹脂組成物及び光半導体装置
JP2005272543A (ja) * 2004-03-23 2005-10-06 Sumitomo Bakelite Co Ltd 光半導体封止用エポキシ樹脂組成物及び光半導体装置
JP2012140566A (ja) * 2011-01-06 2012-07-26 Hitachi Chemical Co Ltd 封止用エポキシ樹脂成形材料および電子部品装置

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JP3508289B2 (ja) * 1995-05-02 2004-03-22 住友化学工業株式会社 エポキシ樹脂組成物および樹脂封止型半導体装置
JPH11147939A (ja) * 1997-11-14 1999-06-02 Toshiba Chem Corp エポキシ樹脂組成物および半導体封止装置
JP5400267B2 (ja) * 2005-12-13 2014-01-29 日立化成株式会社 封止用エポキシ樹脂組成物及び電子部品装置
WO2012147874A1 (fr) * 2011-04-28 2012-11-01 日立化成工業株式会社 Composition de résine pour composant électronique et dispositif à composant électronique
JP6690355B2 (ja) * 2016-03-28 2020-04-28 味の素株式会社 樹脂組成物

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
JPH01167359A (ja) * 1987-12-24 1989-07-03 Sumitomo Bakelite Co Ltd エポキシ樹脂組成物
JP2005239912A (ja) * 2004-02-27 2005-09-08 Sumitomo Bakelite Co Ltd 光半導体封止用エポキシ樹脂組成物及び光半導体装置
JP2005272543A (ja) * 2004-03-23 2005-10-06 Sumitomo Bakelite Co Ltd 光半導体封止用エポキシ樹脂組成物及び光半導体装置
JP2012140566A (ja) * 2011-01-06 2012-07-26 Hitachi Chemical Co Ltd 封止用エポキシ樹脂成形材料および電子部品装置

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