WO2023032861A1 - Curable resin composition and electronic component device - Google Patents

Curable resin composition and electronic component device Download PDF

Info

Publication number
WO2023032861A1
WO2023032861A1 PCT/JP2022/032272 JP2022032272W WO2023032861A1 WO 2023032861 A1 WO2023032861 A1 WO 2023032861A1 JP 2022032272 W JP2022032272 W JP 2022032272W WO 2023032861 A1 WO2023032861 A1 WO 2023032861A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
resin composition
curable resin
mass
epoxy resin
Prior art date
Application number
PCT/JP2022/032272
Other languages
French (fr)
Japanese (ja)
Inventor
東哲 姜
恵一 畠山
智雄 西山
貴耶 山本
貴和 金
亜唯 横倉
Original Assignee
株式会社レゾナック
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社レゾナック filed Critical 株式会社レゾナック
Priority to CN202280058018.XA priority Critical patent/CN117858915A/en
Publication of WO2023032861A1 publication Critical patent/WO2023032861A1/en

Links

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
    • C08G59/62—Alcohols or phenols
    • 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 disclosure relates to curable resin compositions and electronic component devices.
  • these packages are mounted differently than pin insertion packages. That is, in the pin-insertion type package, the pins are inserted into the wiring board and then soldered from the rear surface of the wiring board, so the package is not directly exposed to high temperatures.
  • surface-mounted ICs are temporarily fixed to the surface of the wiring board and processed by a solder bath, a reflow device, or the like, so the package is directly exposed to the soldering temperature (reflow temperature).
  • reflow temperature soldering temperature
  • the package absorbs moisture
  • the absorbed moisture evaporates during reflow, and the generated vapor pressure acts as peeling stress, causing peeling between the sealing material and the supporting member such as the element or lead frame.
  • the occurrence of package cracks, poor electrical characteristics, and the like Therefore, there is a demand for the development of a sealing material that is excellent in adhesion to a supporting member and, in turn, excellent in solder heat resistance (reflow resistance).
  • a curable resin composition containing an epoxy resin and a phenol-based curing agent is known as a sealing material.
  • Patent Document 1 There is room for further improvement in the reflow resistance of the curable resin composition proposed in Patent Document 1.
  • the present disclosure has been made in view of the above situation, and the problem to be solved is to provide a curable resin composition having excellent reflow resistance and an element sealed with this curable resin composition.
  • An object of the present invention is to provide an electronic component device.
  • the epoxy resin comprises a copolymerized epoxy resin having an alkylphenol-derived structural unit and an alkoxynaphthalene-derived structural unit.
  • the content of the copolymer type epoxy resin relative to the total mass of the epoxy resin is 50% by mass to 90% by mass.
  • ⁇ 4> The curable resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the epoxy resin contains a biphenyl-type epoxy resin.
  • the phenolic curing agent contains one or more phenolic curing agents selected from the group consisting of aralkyl-type phenolic resins and novolac-type phenolic resins.
  • the curable resin composition according to . ⁇ 6> The above ⁇ 1, wherein the phenol-based curing agent contains an aralkyl-type phenol resin, and the content of the aralkyl-type phenol resin with respect to the total mass of the phenol-based curing agent is 60% by mass to 95% by mass.
  • An electronic component device comprising an element and a resin cured product of the curable resin composition according to any one of ⁇ 1> to ⁇ 7> for sealing the element.
  • an electronic component device including a curable resin composition having excellent reflow resistance and an element sealed with this curable resin composition.
  • the numerical range indicated using “-" includes the numerical values before and after "-" as the minimum and maximum values, respectively.
  • the upper limit or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described step by step.
  • the upper or lower limits of the numerical ranges may be replaced with the values shown in Synthetic Examples.
  • each component may contain multiple types of applicable compounds. When there are multiple types of substances corresponding to each component in the composition, 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.
  • Plural types of particles corresponding to each component in the present disclosure may be contained.
  • 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 term "laminate" refers to stacking layers, and two or more layers may be bonded or two or more layers may be detachable.
  • the notation without describing substitution and unsubstitution includes not only those not having substituents but also those having substituents.
  • the number of structural units represents an integer value for a single molecule, but represents a rational number which is an average value for an aggregate of multiple types of molecules.
  • the number of carbon atoms means the total number of carbon atoms contained in a group as a whole, and when the group does not have a substituent, it represents the number of carbon atoms forming the skeleton of the group. When has a substituent, it represents the total sum of the number of carbon atoms forming the skeleton of the group plus the number of carbon atoms in the substituent.
  • the equivalent ratio of the phenolic hydroxyl group (active hydrogen) of the phenolic curing agent to the epoxy group of the epoxy resin is the curability 1 H-NMR of the resin composition is measured, and it can be determined from the integral ratio of the protons of the epoxy group and the protons of the phenolic hydroxyl group. 1 H-NMR of the curable resin composition is measured under the following conditions.
  • the dynamic viscoelasticity measurement of the resin cured product of the curable resin composition can be performed using a dynamic viscoelasticity measuring device (for example, DMA8000 manufactured by PerkinElmer).
  • a dynamic viscoelasticity measuring device for example, DMA8000 manufactured by PerkinElmer.
  • test mode 3-point bending mode
  • measurement temperature 25 ° C. to 330 ° C.
  • temperature increase rate 10 ° C./min
  • Test frequency Perform dynamic viscoelasticity measurement under the condition of 1 Hz, and specify the value of storage viscoelasticity, the peak value of tan ⁇ , the glass transition temperature, etc. from the obtained chart (vertical axis: tan ⁇ , horizontal axis: temperature) be able to.
  • the resin cured product was produced by molding the curable resin composition using a transfer molding machine under the conditions of a mold temperature of 175°C, a molding pressure of 8.3 MPa, and a curing time of 120 seconds. By carrying out curing.
  • the coefficient of thermal expansion (CTE) of the cured resin of the curable resin composition is measured using a thermomechanical analyzer, for example, on a cured resin of ⁇ 4 mm ⁇ 20 mm. .
  • the production of the resin cured product is as described above.
  • the measurement conditions are a load of 15 g, a measurement temperature of ⁇ 50° C. to 220° C., and a heating rate of 5° C./min.
  • TMA/SS6100 manufactured by Seiko Instruments Inc. can be used.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) are measured using the following GPC measurement device under the following measurement conditions, and converted using a standard polystyrene calibration curve.
  • a calibration curve was prepared using a set of 5 samples (“PStQuick MP-H” and “PStQuick B”, manufactured by Tosoh Corporation) as standard polystyrene.
  • PStQuick MP-H and “PStQuick B”, manufactured by Tosoh Corporation
  • the molecular weight determined from the chemical structure of the compound is adopted as the Mw or Mn of the compound.
  • GPC measuring device GPC device: High-speed GPC device "HCL-8320GPC", detector is differential refractometer or UV, column manufactured by Tosoh Corporation: column TSKgel SuperMultipore HZ-H (column length: 15 cm, column inner diameter: 4.6 mm), Tosoh stock Company made (measurement conditions) Solvent: Tetrahydrofuran (THF) Measurement temperature: 40°C Flow rate: 0.35 mL/min Sample concentration: 10 mg/THF5 mL Injection volume: 20 ⁇ L
  • the curable resin composition of the present disclosure contains an epoxy resin and a phenolic curing agent at an equivalent ratio of the phenolic hydroxyl group of the phenolic curing agent to the epoxy group of the epoxy resin of 0.5 or more and less than 1.0. .
  • the curable resin composition of the present disclosure has excellent reflow resistance.
  • the curable resin composition of the present disclosure achieves the above effects is not clear, but is presumed as follows.
  • the curable resin composition of the present disclosure contains an epoxy resin and a phenolic curing agent at an equivalent ratio of the phenolic hydroxyl group of the phenolic curing agent to the epoxy group of the epoxy resin of 0.5 or more and less than 1.0.
  • the tan ⁇ value near the reflow temperature can be increased, and the internal stress of the cured resin tends to be relaxed during reflow.
  • the adhesiveness between the cured resin of the curable resin composition and the supporting member is improved, so that it is presumed to have excellent reflow resistance.
  • MSL Moisture Sensitive Level
  • JEDEC Joint Electron Device Engineers Council
  • the temperature at which tan ⁇ becomes maximum is preferably less than 120°C, more preferably less than 110°C.
  • a glass transition temperature of less than 120° C. tends to improve the reflow resistance of the curable resin composition of the present disclosure.
  • the lower limit of the glass transition temperature is not particularly limited, it can be, for example, 50° C. or higher.
  • tan ⁇ at the glass transition temperature is preferably over 0.400, more preferably over 0.410.
  • the upper limit of tan ⁇ at the glass transition temperature is not particularly limited, it can be, for example, 1.0 or less.
  • the value of tan ⁇ at the glass transition temperature is 100
  • the value of tan ⁇ at at least one temperature of -10 ° C. is more than 60. more preferably greater than 63, and even more preferably greater than 65.
  • the sum of tan ⁇ values at each temperature of 220°C, 230°C, 240°C and 250°C is preferably more than 0.400.
  • the upper limit of the sum of tan ⁇ values at temperatures of 220° C., 230° C., 240° C. and 250° C. is not particularly limited, but can be, for example, 2.0 or less.
  • the total value of tan ⁇ at each temperature of 70 ° C., 80 ° C. and 90 ° C. is preferably more than 0.600, and more than 0.700 It is more preferable to have
  • the upper limit of the sum of tan ⁇ values at temperatures of 70° C., 80° C. and 90° C. is not particularly limited, but can be, for example, 2.0 or less.
  • the storage viscoelasticity at 260 ° C. obtained by performing dynamic viscoelasticity measurement on the resin cured product of the curable resin composition is preferably 450 MPa or less, and is 435 MPa or less. is more preferably 420 MPa or less.
  • the lower limit of the storage modulus is not particularly limited, it can be, for example, 150 MPa or more.
  • the thermal expansion coefficient (CTE1) below the glass transition temperature of the resin cured product of the curable resin composition of the present disclosure obtained by thermomechanical analysis is preferably 15 ppm / ° C. or less from the viewpoint of followability to the support member. 13 ppm/°C or less is more preferable, and 10 ppm/°C or less is even more preferable.
  • the lower limit of the coefficient of thermal expansion is not particularly limited, it can be set to 3 ppm/°C, for example.
  • the coefficient of thermal expansion (CTE2) above the glass transition temperature is preferably 10 ppm/° C. to 45 ppm/° C., more preferably 12 ppm/° C. to 40 ppm/° C., more preferably 15 ppm/° C. to 38 ppm/° C. °C is more preferred.
  • epoxy resin The curable resin composition of the present disclosure contains an epoxy resin.
  • the type of epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule.
  • the linear polysiloxane compound is not included in the epoxy resin. Specific examples of epoxy resins are described below, but are not limited thereto.
  • At least one phenol selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A and bisphenol F, and naphthol compounds such as ⁇ -naphthol, ⁇ -naphthol and dihydroxynaphthalene.
  • a novolak type epoxy resin phenol novolac type epoxy resin, ortho-cresol novolak-type epoxy resins, etc.
  • epoxidized triphenylmethane-type phenolic resins obtained by condensation or co-condensation of the above phenolic compounds and aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde in the presence of an acidic catalyst.
  • a triphenylmethane type epoxy resin a copolymer type epoxy resin obtained by epoxidizing a novolak resin obtained by co-condensing the above phenol compound and naphthol compound with an aldehyde compound in the presence of an acidic catalyst; bisphenol A, bisphenol diphenylmethane-type epoxy resins that are diglycidyl ethers such as F; biphenyl-type epoxy resins that are diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene-type epoxy resins that are diglycidyl ethers of stilbene-based phenol compounds; Sulfur atom-containing epoxy resins that are diglycidyl ethers; Epoxy resins that are glycidyl ethers of alcohols such as butanediol, polyethylene glycol and polypropylene glycol; Glycidyl polyvalent carboxylic acid compounds such as phthalic acid, isophthalic acid and
  • co-condensation resins of dicyclopentadiene and phenol compounds Dicyclopentadiene type epoxy resin which is obtained by epoxidizing the; vinylcyclohexene diepoxide obtained by epoxidizing the olefin bond in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 2- (3,4-epoxy)cyclohexyl-5,5-spiro(3 ,4-epoxy)cyclohexane-m-dioxane and other alicyclic epoxy resins; para-xylylene-modified epoxy resins that are glycidyl ethers of para-xylylene-modified phenol resins; meta-xylylene-modified epoxy resins that are glycidyl ethers of meta-xylylene-modified phenol resins; terpene-modified phenol
  • 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.
  • 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 an average value and represents an integer of 0-10.
  • 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.
  • 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 an average value and represents an integer of 0-10.
  • 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.
  • 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 an average value and represents an integer of 0-10.
  • the sulfur atom-containing type epoxy resin is not particularly limited as long as it is an epoxy resin containing sulfur atoms.
  • examples thereof include epoxy resins represented by the following general formula (V).
  • 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 an integer of 0-10.
  • 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.
  • 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 an average value and represents an integer of 0-10.
  • 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.
  • 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 an average value and represents an integer of 0-10.
  • 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.
  • 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 an average value and represents an integer of 0-10.
  • 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.
  • R 19 to R 21 represent monovalent organic groups having 1 to 18 carbon atoms, and may be the same or different.
  • Each i independently represents an integer of 0 to 3
  • each j independently represents an integer of 0 to 2
  • each k independently represents an integer of 0 to 4.
  • l and m are average values, numbers from 0 to 10, and (l+m) shows numbers from 0 to 10.
  • the terminal of the epoxy resin represented by formula (IX) is either one of formula (IX-1) or (IX-2) below.
  • Definitions of R 19 to R 21 , i, j and k in formulas (IX-1) and (IX-2) are the same as definitions of R 19 to R 21 , i, j and k in formula (IX).
  • n is 1 (when linked via a methylene group) or 0 (when not linked via a methylene group).
  • the epoxy resin represented by the general formula (IX) includes a random copolymer having l structural units and m structural units at random, an alternating copolymer having alternating structural units, and a copolymer having regularly , a block copolymer having a block shape, and the like. Any one of these may be used alone, or two or more may be used in combination.
  • the aralkyl-type epoxy resin is composed of at least one selected from the group consisting of phenol compounds such as phenol and cresol, and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis(methoxymethyl)biphenyl or derivatives thereof.
  • phenol compounds such as phenol and cresol
  • naphthol compounds such as naphthol and dimethylnaphthol
  • dimethoxyparaxylene bis(methoxymethyl)biphenyl or derivatives thereof.
  • a phenolic resin synthesized from at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis(methoxymethyl)biphenyl or derivatives thereof is preferably an epoxy resin obtained by glycidyl etherification, and more preferably an epoxy resin represented by the following general formulas (X) and (XI).
  • R 38 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different.
  • R 37 , R 39 to R 41 each represent a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different.
  • i is each independently an integer of 0 to 3
  • j is each independently an integer of 0 to 2
  • k is each independently an integer of 0 to 4
  • l is each independently an integer of 0 to 4 show.
  • n is an average value, each independently an integer of 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. If n is 10 or less, the melt viscosity of the resin component does not become too high, and the viscosity of the curable resin composition during melt molding decreases, resulting in insufficient filling and deformation of the bonding wire (gold wire that connects the element and the lead). etc. tend to be suppressed. More preferably, n is set in the range of 0-4.
  • the epoxy resin is a copolymerized epoxy resin having a structural unit derived from alkylphenol and a structural unit derived from alkoxynaphthalene (hereinafter referred to as a specific copolymerized epoxy resin). is preferably included.
  • Structural units derived from alkylphenols include structural units (a) below.
  • each R 1 A independently represents a monovalent alkyl group having 1 to 18 carbon atoms, preferably a monovalent alkyl group having 1 to 6 carbon atoms.
  • X represents an integer of 1-3.
  • Structural units derived from alkoxynaphthalene include the following structural units (b).
  • each R 2 B independently represents a monovalent alkoxy group having 1 to 18 carbon atoms, preferably a monovalent alkoxy group having 1 to 6 carbon atoms.
  • y represents an integer of 1-6.
  • the two bonding sites in the structural unit (b) may exist in the same naphthalene ring or may exist in each of the two naphthalene rings.
  • the specific copolymerization type epoxy resin can have the following structural unit (c).
  • n is an integer of 1-10, preferably an integer of 2-8.
  • the two bonding sites of the naphthalene ring in the structural unit (c) may exist in the same naphthalene ring or may exist in each of the two naphthalene rings.
  • Structural units satisfying the above structural unit (c) include, for example, the following structural unit (d).
  • the epoxy resin preferably contains a specific copolymerization type epoxy resin. Moreover, from the viewpoint of reflow resistance, the epoxy resin preferably contains a biphenyl-type epoxy resin.
  • the epoxy equivalent of the epoxy resin is not particularly limited. From the viewpoint of the balance of various properties such as moldability, heat resistance and electrical reliability, the epoxy equivalent of the epoxy resin is preferably 40 g/eq to 1000 g/eq, more preferably 45 g/eq to 500 g/eq, and 50 g/eq. eq to 350 g/eq is more preferred. Let the epoxy equivalent of an epoxy resin be the value measured by the method according to JISK7236:2009.
  • the epoxy resin may be solid or liquid at 25°C. If the epoxy resin is solid at 25°C, the softening point or melting point of the epoxy resin is not particularly limited. From the viewpoint of the balance between moldability and heat resistance, the softening point or melting point of the epoxy resin is preferably 40°C to 180°C. Also, from the viewpoint of handleability during production of the curable resin composition, the softening point or melting point of the epoxy resin is preferably 50°C to 130°C. In the present disclosure, softening point refers to a value measured by the ring and ball method of JIS K 7234:1986. In the present disclosure, melting point refers to a value measured according to the visual observation method of JIS K 0064:1992.
  • the Mw of the epoxy resin is preferably 550-1050, more preferably 650-950.
  • the Mn of the epoxy resin is preferably 250 to 800, more preferably 350 to 600.
  • the content of the epoxy resin with respect to the total mass of the curable resin composition is preferably 0.5% by mass to 60% by mass, and 2% by mass. It is more preferably 50% by mass, and even more preferably 3% by mass to 45% by mass.
  • the epoxy resin contains a specific copolymerization type epoxy resin
  • the content of the specific copolymerization type epoxy resin with respect to the total weight of the epoxy resin is 50% by mass or more. It is preferably 90% by mass, more preferably 55% to 80% by mass, even more preferably 60% to 75% by mass.
  • the content of the biphenyl-type epoxy resin with respect to the total weight of the epoxy resin is 5% to 40% by weight. preferably 7% by mass to 35% by mass, and even more preferably 10% by mass to 30% by mass.
  • the curable resin composition of the present disclosure contains a phenolic curing agent.
  • the type of phenol-based curing agent is not particularly limited, and can be selected from those commonly used as components of curable resin compositions.
  • the phenol-based curing agents may be used singly or in combination of two or more.
  • Phenolic curing agents include, for example, phenol resins and polyhydric phenol compounds having two or more phenolic hydroxyl groups in one molecule. Specific examples of the phenol-based curing agent are described below, but are not limited to these. Phenolic curing agents include 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, amino At least one phenolic compound selected from the group consisting of phenol compounds such as phenol and naphthol compounds such as ⁇ -naphthol, ⁇ -naphthol and dihydroxynaphthalene, and aldehyde compounds such as formaldehyde, acetaldehyde and propionaldehyde under an acidic catalyst.
  • phenol-based curing agent include polyhydric phenol compounds
  • Novolac-type phenolic resins obtained by condensation or co-condensation Phenolic aralkyl resins synthesized from the above phenolic compounds and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, etc., aralkyl-type phenolic resins such as naphthol aralkyl resins; Para-xylylene and / or metaxylylene-modified phenolic resin; melamine-modified phenolic resin; terpene-modified phenolic resin; Pentadiene-modified phenolic resin; Polycyclic aromatic ring-modified phenolic resin; Biphenyl-type phenolic resin; Triphenyl obtained by condensation or co-condensation of the above phenolic compound with an aromatic aldehyde compound such as benzaldehyde and salicylaldehyde in the presence of an acidic catalyst.
  • Methane-type phenolic resin 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1 triazine-type phenolic resins such as , 3,5-triazine; and phenolic resins obtained by copolymerizing two or more of these.
  • the phenolic curing agent may contain one or more phenolic curing agents selected from the group consisting of aralkyl-type phenolic resins and novolac-type phenolic resins. Preferably, both are included.
  • the phenol-based curing agent will be described in more detail below, but it is not limited to these.
  • the aralkyl-type phenolic resin is not particularly limited, and a phenol synthesized from at least one selected from the group consisting of phenolic compounds and naphthol compounds and dimethoxyparaxylene, bis(methoxymethyl)biphenyl or derivatives thereof. resin.
  • aralkyl-type phenol resins include phenol resins represented by the following general formulas (XII) to (XIV).
  • R 23 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different.
  • R 22 , R 24 , R 25 and R 28 each represent a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different.
  • R 26 and R 27 each represent a hydroxyl group or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different.
  • i is each independently an integer of 0 to 3
  • j is each independently an integer of 0 to 2
  • k is each independently an integer of 0 to 4
  • p is each independently an integer of 0 to 4 be.
  • n is an average value, each independently an integer of 0 to 10; “All may be the same or different" described for R 22 etc. in the above general formula means, for example, all i R 22 in general formula (XII) may be the same or different means that Further, R 22 to R 37 may be the same or different. For example, all of R 22 and R 23 may be the same or different.
  • the aralkyl-type phenol resin is preferably a phenol resin represented by general formula (XIII).
  • i and k are preferably 0 in general formula (XIII).
  • the aralkyl-type phenolic resin may be a copolymerized phenolic resin with other phenolic resins.
  • Copolymerized phenolic resins include copolymerized phenolic resins of triphenylmethane-type phenolic resin and aralkyl-type phenolic resin, copolymerized phenolic resins of salicylaldehyde-type phenolic resin and aralkyl-type phenolic resin, and novolac-type phenolic resin.
  • a copolymer type phenol resin with an aralkyl type phenol resin and the like can be mentioned.
  • the dicyclopentadiene-type phenolic resin is not particularly limited as long as it is a phenolic resin obtained using a compound having a dicyclopentadiene skeleton as a raw material.
  • a phenol resin represented by the following general formula (XV) is preferred.
  • R 29 represents a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different.
  • i each independently represents an integer of 0 to 3;
  • n is an average value and represents an integer of 0-10.
  • the triphenylmethane-type phenolic resin is not particularly limited as long as it is a phenolic resin obtained using an aromatic aldehyde compound as a raw material.
  • a phenol resin represented by the following general formula (XVI) is preferred.
  • R 30 and R 31 each represent a monovalent organic group having 1 to 18 carbon atoms and may be the same or different.
  • Each i is independently an integer of 0 to 3
  • each k is independently an integer of 0 to 4.
  • n is an average value and is an integer from 0 to 10;
  • the copolymerized phenolic resin of triphenylmethane-type phenolic resin and aralkyl-type phenolic resin is not particularly limited as long as it is a copolymerized-type phenolic resin of phenolic resin obtained using a compound having a benzaldehyde skeleton as a raw material and aralkyl-type phenolic resin. .
  • a phenol resin represented by the following general formula (XVII) is preferred.
  • R 32 to R 34 each represent a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different.
  • Each i is independently an integer of 0 to 3
  • each k is independently an integer of 0 to 4
  • each q is independently an integer of 0 to 5.
  • l and m are average values and independently integers from 0 to 11. However, the sum of l and m is an integer of 1-11.
  • the novolak-type phenolic resin is not particularly limited as long as it is a phenolic resin obtained by condensation or co-condensation of at least one phenolic compound selected from the group consisting of phenolic compounds and naphthol compounds and an aldehyde compound in the presence of an acidic catalyst.
  • a phenol resin represented by the following general formula (XVIII) is preferred.
  • R 35 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different.
  • R 36 represents a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different.
  • i each independently represents an integer of 0 to 3;
  • n is an average value and represents an integer of 0-10.
  • R 22 to R 36 in the general formulas (XII) to (XVIII) means, for example, that all i R 22 in formula (XII) are the same However, it means that they may be different from each other.
  • Other R 23 to R 36 also mean that the respective numbers contained in the formula may all be the same or different from each other.
  • R 22 to R 36 may be the same or different.
  • all of R 22 and R 23 may be the same or different
  • all of R 30 and R 31 may be the same or different.
  • n in the above general formulas (XII) to (XVIII) is preferably an integer of 0 to 10. If it is 10 or less, the melt viscosity of the resin component does not become too high, and the viscosity of the curable resin during melt molding becomes low, resulting in defective filling and deformation of the bonding wire (gold wire that connects the element and the lead). it gets harder.
  • the average n in one molecule is preferably set in the range of 0-4.
  • the hydroxyl equivalent of the phenolic curing agent is not particularly limited. From the viewpoint of the balance of various properties such as reflow resistance, moldability, and electrical reliability, it is preferably 10 g/eq to 1000 g/eq, more preferably 30 g/eq to 500 g/eq.
  • the hydroxyl equivalent refers to a value calculated based on the hydroxyl value measured according to JIS K 0070:1992.
  • the softening point or melting point of the phenolic curing agent is not particularly limited. From the viewpoint of moldability and heat resistance, the softening point or melting point of the phenolic curing agent is preferably 40°C to 180°C. Also, from the viewpoint of handleability during production of the curable resin composition, the softening point or melting point of the phenolic curing agent is preferably 50°C to 130°C.
  • the content of the phenolic curing agent with respect to the total mass of the curable resin composition is preferably 0.5% by mass to 40% by mass. It is more preferably from 2% by mass to 30% by mass, and even more preferably from 2% by mass to 20% by mass.
  • the content of the aralkyl-type phenol resin with respect to the total mass of the phenol-based curing agent is 60% by mass to It is preferably 95% by mass, more preferably 65% to 90% by mass.
  • the content of the novolac-type phenolic resin with respect to the total mass of the phenolic curing agent is 5% by mass to It is preferably 40% by mass, more preferably 10% to 30% by mass.
  • the curable resin composition of the present disclosure includes a curing accelerator, an inorganic filler, a coupling agent, a stress relaxation agent, a mold release agent, a coloring agent, a flame retardant, an ion exchanger, other than an epoxy resin. It may also contain various additives such as a resin and a curing agent other than a phenol-based curing agent.
  • the curable resin composition may contain various additives known in the art as necessary, in addition to the additives exemplified below.
  • the curable resin composition of the present disclosure 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 curable resin 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, 1,
  • the phosphonium compound preferably contains a compound represented by the following general formula (I-1) (hereinafter also referred to as a specific curing accelerator).
  • 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 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. 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, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, Alkyl groups such as t-butyl group, 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, n-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 hydrocarbon groups 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, n-butyl group and t-butyl group, alkoxy groups such as methoxy group, ethoxy group, n-butoxy group and t-butoxy group, 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, n-butyl group and t-butyl group, alkoxy groups such as methoxy group, ethoxy group, n-butoxy group and t-butoxy group, phenyl group and naphthyl group. aryl groups, hydroxyl groups, amino groups, halogen atoms, 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 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. phenyl group, methoxyphenyl group, ethoxyphenyl group, n-butoxyphenyl group, t-butoxyphenyl group and the like.
  • 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 carbon atoms including substituents
  • An aryl group of numbers 6 to 10 is more preferred, and a phenyl group, p-tolyl group and p-methoxyphenyl group 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; Substituents capable of forming a cyclic 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, can be mentioned. These substituents may be further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, halogen atoms and the like.
  • alkylene groups such as ethylene, propylene, butylene, pentylene and hexylene which can form a cyclic structure by bonding with a phosphorus atom
  • the “organic group having 1 to 18 carbon atoms” described as R 4 to R 7 in general formula (I-1) above is an aliphatic group having 1 to 18 carbon atoms which may or may not be substituted. It is meant to include aromatic hydrocarbon groups, aromatic hydrocarbon groups, aliphatic hydrocarbon oxy groups, aromatic hydrocarbon oxy groups, acyl groups, hydrocarbon oxycarbonyl groups, and acyloxy groups.
  • Examples of the 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 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 as R 4 to R 7 in the general formula (I-1) means that two to four may be combined 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, n-propyl, isopropyl, n-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 preferably contains 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 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.
  • 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.
  • 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-n-propylphenyl)phosphine tris(4-n-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 1,2-benzoquinone, 1,4-benzoquinone, diphenoquinone, 1,4-naphthoquinone, and anthraquinone. From the viewpoint of moisture resistance and storage stability, 1,4-benzoquinone is preferred.
  • 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.
  • the curable resin 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 with respect to the total mass of the curing accelerator is preferably 30% by mass or more, and is 50% by mass or more. is more preferable, and 70% by mass or more is even more preferable.
  • the content of the curing accelerator with respect to the total mass of the resin component is It is preferably 0.1% by mass to 30% by mass, more preferably 1% by mass to 15% by mass.
  • the content of the curing accelerator with respect to the total mass of the resin component is 0.1% by mass or more, the curable resin composition tends to cure satisfactorily in a short time.
  • the content of the curing accelerator with respect to the total mass of the resin component is 30% by mass or less, the curing rate of the curable resin composition is not too fast, and good molded articles tend to be obtained.
  • the curable resin composition of the present disclosure may contain inorganic fillers.
  • the curable resin composition contains an inorganic filler, the hygroscopicity of the curable resin composition tends to decrease, and the strength in the cured state tends to improve.
  • the curable resin composition is used as a sealing material for semiconductor packages, it preferably contains an inorganic filler.
  • inorganic filler is not particularly limited. Specifically, silica such as spherical silica and crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, Inorganic materials such as 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.
  • 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.
  • An inorganic filler may be used individually by 1 type, or may be used in combination of 2 or more types.
  • the shape of the inorganic filler is not particularly limited, and examples include powdery, spherical, and fibrous shapes. From the viewpoints of fluidity during molding of the curable resin composition and resistance to mold wear, it is preferably spherical.
  • the average particle size of the inorganic filler is not particularly limited. From the viewpoint of the balance between the viscosity of the curable resin composition and the filling property, etc., the volume average particle size of the inorganic filler is preferably 0.1 ⁇ m to 50 ⁇ m, more preferably 0.3 ⁇ m to 30 ⁇ m. , 0.5 ⁇ m to 25 ⁇ m.
  • the average particle size of the inorganic filler can be measured as the volume average particle size (D50) with a laser diffraction scattering method particle size distribution analyzer. A volume average particle diameter can be measured by a known method.
  • an inorganic filler is extracted from a curable resin composition or cured resin using an organic solvent, nitric acid, aqua regia, etc., and sufficiently dispersed using an ultrasonic disperser or the like to prepare a 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 is measured from the volume-based particle size distribution obtained by embedding the cured resin in a transparent epoxy resin or the like and polishing the resulting cross-section with a scanning electron microscope. be able to.
  • FIB device focused ion beam SEM
  • the curable resin composition contains an inorganic filler
  • its content is not particularly limited.
  • the content of the inorganic filler with respect to the total mass of the curable resin composition is preferably 30% by mass to 90% by mass, more preferably 35% by mass to 80% by mass, and 40% by mass to 70% by mass. % is more preferred.
  • the properties of the cured resin such as coefficient of thermal expansion, thermal conductivity and elastic modulus, tend to be further improved.
  • the content of the inorganic filler with respect to the total mass of the curable resin composition is 90% by mass or less, the increase in viscosity of the curable resin composition is suppressed, the fluidity is further improved, and the moldability is better. tend to become
  • the curable resin composition of the present disclosure may contain a coupling agent.
  • the type of coupling agent is not particularly limited, and known coupling agents can be used. Examples of coupling agents include silane coupling agents and titanium coupling agents.
  • a coupling agent may be used individually by 1 type, or may use 2 or more types together.
  • the silane coupling agent is not particularly limited as long as it is a compound other than the linear polysiloxane compound described above. sidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)amino propyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercapto propyltriethoxysilane, 3-ureidopropyltriethoxysilane, octenyltrimethoxysilane, gly
  • Titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tris(dioctylpyrophosphate) titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, tetraoctylbis(ditridecylphosphite) titanate, tetra(2, 2-diallyloxymethyl-1-butyl)bis(ditridecylphosphite)titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate, isopropyltrioctanoyltitanate, isopropyldimethacrylisostearoyltitanate , isopropyltridodecylbenzenesulfonyltitanate, isopropylisostearoyldiacryl
  • the curable resin composition of the present disclosure may contain at least one of 3-aminopropyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane. preferable.
  • the ratio of the coupling agent to the total mass of the inorganic filler contained in the curable resin composition is The content is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 8% by mass, and even more preferably 0.05% by mass to 5% by mass. .
  • the curable resin composition of the present disclosure may contain stress relaxation agents such as silicone oil and silicone rubber particles.
  • stress relaxation agents such as silicone oil and silicone rubber particles.
  • the stress relaxation agent include commonly used known stress relaxation agents (flexible agents).
  • stress relaxation agents include thermoplastic elastomers such as silicone, styrene, olefin, urethane, polyester, polyether, polyamide, and polybutadiene, natural rubber (NR), and acrylonitrile-butadiene.
  • NBR Non-acrylate-styrene-butadiene copolymer
  • MVS methyl methacrylate-silicone copolymer
  • methacrylate-butyl acrylate examples include rubber particles having a core-shell structure such as copolymers.
  • a stress relaxation agent may be used individually by 1 type, or may be used in combination of 2 or more types. Among them, a silicone-based stress relieving agent is preferable. Examples of silicone-based stress relieving agents include those having epoxy groups, those having amino groups, and those modified with polyethers.
  • the content of the stress relaxation agent with respect to the total weight of the epoxy resin contained in the curable resin composition is 0.1% by mass to 30% by mass. It is preferably 1% by mass to 5% by mass.
  • the curable resin composition of the present disclosure may contain a mold release agent from the viewpoint of releasability from the mold when using a mold for molding.
  • the release agent is not particularly limited, and conventionally known agents can be used. Examples of release agents include carnauba wax, higher fatty acids such as montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene.
  • the release agent may be used singly or in combination of two or more.
  • the content of the release agent with respect to the total mass of the epoxy resin contained in the curable resin composition is 0.01% by mass to 15% by mass. preferably 0.1% by mass to 10% by mass.
  • the content of the release agent with respect to the total mass of the epoxy resin contained in the curable resin composition is 0.01% by mass or more, the release property tends to be sufficiently obtained.
  • the content of the release agent with respect to the total mass of the epoxy resin contained in the curable resin composition is 15% by mass or less, better releasability tends to be obtained.
  • the curable resin composition of the present disclosure may contain 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.
  • the colorants may be used singly or in combination of two or more.
  • the content of the coloring agent with respect to the total weight of the curable resin composition is preferably 0.01% by mass to 5% by mass, and 0.05% by mass to It is more preferably 3% by mass, and even more preferably 0.01% by mass to 1% by mass.
  • the curable resin composition of the present disclosure may contain flame retardants.
  • the flame retardant is not particularly limited, and conventionally known ones can be used. Flame retardants include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms or phosphorus atoms, metal hydroxides, and the like. A flame retardant may be used individually by 1 type, or may be used in combination of 2 or more types.
  • the curable resin composition of the present disclosure contains a flame retardant
  • its content is not particularly limited as long as it is sufficient to obtain the desired flame retardant effect.
  • the content of the flame retardant with respect to the total mass of the epoxy resin contained in the curable resin composition is preferably 1% by mass to 300% by mass, more preferably 2% by mass to 150% by mass.
  • the curable resin composition of the present disclosure may contain an ion exchanger.
  • an ion exchanger When the curable resin composition is used as a sealing material for a semiconductor package, 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 sealed.
  • 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.
  • the ion exchanger includes hydrotalcite represented by the following general formula (A).
  • the curable resin composition of the present disclosure contains an ion exchanger
  • its content is not particularly limited as long as it is sufficient to capture ions such as halogen ions.
  • the content of the ion exchanger relative to the total weight of the epoxy resin contained in the curable resin composition is preferably 0.1% by mass to 30% by mass, more preferably 1% by mass to 5% by mass. preferable.
  • the curable resin composition of the present disclosure may contain resins other than epoxy resins.
  • the type of resin other than the epoxy resin is not particularly limited, and can be selected from those commonly used as components of curable resin compositions. Resins other than epoxy resins may be used singly or in combination of two or more.
  • Resins other than epoxy resins include thiol resins, urea resins, melamine resins, urethane resins, silicone resins, maleimide resins, Saturated polyester resin and the like can be mentioned.
  • the curable resin composition of the present disclosure may contain curing agents other than phenolic curing agents.
  • the type of curing agent other than the phenol-based curing agent is not particularly limited, and can be selected from those commonly used as components of curable resin compositions. Curing agents other than phenol-based curing agents may be used alone or in combination of two or more.
  • Curing agents other than phenolic curing agents include amine curing agents, acid anhydride curing agents, poly Mercaptan-based curing agents, polyaminoamide-based curing agents, isocyanate-based curing agents, blocked isocyanate-based curing agents, and the like are included.
  • the active hydrogen equivalent of the amine-based curing agent is not particularly limited. From the viewpoint of the balance of various properties such as reflow resistance, moldability, and electrical reliability, it is preferably 10 g/eq to 1000 g/eq, more preferably 30 g/eq to 500 g/eq.
  • the active hydrogen equivalent of the amine curing agent is a value calculated based on the amine value measured according to JIS K 7237:1995.
  • the content of the curing agent other than the phenolic curing agent with respect to the total mass of the curable resin composition is not particularly limited. It is preferably 2% by mass to 35% by mass, more preferably 5% by mass to 30% by mass.
  • the method for producing the curable resin 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 components described above are uniformly stirred and mixed, kneaded with a kneader, roll, extruder, or the like preheated to 70° C. to 140° C., cooled, and pulverized. can be mentioned.
  • the curable resin composition is preferably solid at 25°C.
  • the shape of the curable resin composition is not particularly limited, and examples thereof include powder, granules, tablets, and the like.
  • the curable resin 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.
  • curable resin composition of the present disclosure is not particularly limited, and it can be used in various mounting techniques, for example, as a sealing material for electronic component devices.
  • the curable resin composition of the present disclosure is used for resin moldings for various modules, resin moldings for motors, vehicle-mounted resin moldings, sealing materials for protective materials for electronic circuits, etc.
  • the resin composition has good fluidity. And it can be used for various applications where it is desirable to have curability.
  • An electronic component device of the present disclosure includes an element and a cured product of the curable resin composition that seals the element.
  • the electronic component device can further include a support member on which the element is mounted.
  • supporting members include lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers, organic substrates, and the like.
  • a lead frame is preferable from the viewpoint of adhesion to the cured product of the curable resin composition.
  • the lead frame may or may not have a roughened surface, but from the viewpoint of manufacturing cost, a non-roughened lead frame is preferable, and from the viewpoint of adhesiveness, a roughened lead frame is preferred. Planarized leadframes are preferred.
  • the roughening method is not particularly limited, and includes alkali treatment, silane coupling treatment, sand mat treatment, plasma treatment, corona discharge treatment and the like.
  • the lead frame can have a plated layer containing at least one of Au, Pd and Ni on at least part of the surface. Further, the plated layer may be a single layer or multiple layers.
  • the multi-layer plating layer a plating layer having a three-layer configuration in which a Ni plating layer, a Pd plating layer, and an Au plating layer are laminated from the lead frame side, or the like can be used.
  • the three-layer lead frame include a lead frame called PPF (Pre Plating Lead Frame), which is a copper lead frame plated with Ni--Pd--Au.
  • the thickness of the plating layer is not particularly limited, and is preferably 5 ⁇ m or less, more preferably 4 ⁇ m or less, and even more preferably 3 ⁇ m or less.
  • elements included in electronic component devices include active elements such as silicon chips, transistors, diodes, and thyristors, and passive elements such as capacitors, resistors, and coils.
  • Specific configurations of the electronic component device include, but are not limited to, the following configurations.
  • TCP Tape Carrier Package having a structure in which an element connected to a tape carrier using bumps is sealed with a curable resin composition
  • a COB (Chip On Board) module having a structure in which an element connected to wiring formed on a support member by wire bonding, flip chip bonding, soldering, or the like is sealed with
  • a curable resin composition is formed.
  • BGA Bit Grid Array
  • CSP Chip Size Package
  • MCP Multi Chip Package
  • SiP System in a Package
  • the method of sealing the element using the curable resin composition is not particularly limited, and known methods can be applied.
  • a sealing method for example, low-pressure transfer molding is generally used, but injection molding, compression molding, cast molding, or the like may also be used.
  • Examples 1 to 7 and Comparative Examples 1 to 3 After pre-mixing (dry blending) the materials of the formulation shown in Table 1, they are kneaded for about 15 minutes with a biaxial roll (roll surface temperature: about 80 ° C.), cooled, and pulverized to obtain a powdery curable resin composition. manufactured.
  • Epoxy resin A copolymer type epoxy resin having the following structural units, epoxy equivalent of 250 g/eq, melt viscosity at 150° C. of 0.7 dPa s, Mn of 350 to 600
  • Epoxy resin B biphenyl type epoxy resin, epoxy equivalent 196 g / eq, softening point 106 ° C., manufactured by Mitsubishi Chemical Corporation, trade name "YX-4000H", Mn350 ⁇ Epoxy resin C: biphenyl aralkyl type epoxy resin, epoxy equivalent 284 g / eq
  • Phenol-based curing agent A aralkyl-type phenolic resin, hydroxyl equivalent of 106 g/eq ⁇ Phenolic curing agent B: triphenylmethane type phenol resin, hydroxyl equivalent 95 g / eq - Phenol-based curing agent C: aralkyl-type phenolic resin, hydroxyl equivalent 203 g/eq - Phenol-based curing agent D: melamine-modified phenolic resin, hydroxyl equivalent 120 g/eq, softening point: 90°C Phenolic curing agent E: triazine-type phenolic resin, 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2, 4-dimethylphenyl)-1,3,5-triazine, BASF, trade name "Tinuvin (registered trademark) 405" - Phenolic curing
  • Coupling agent A 3-aminopropyltrimethoxysilane ⁇
  • Coupling agent B 3-glycidoxypropyltrimethoxysilane ⁇
  • Coupling agent C linear polysiloxane, melting point: -70 ° C., epoxy equivalent 120 g / eq ⁇ 150g/eq
  • Coupling agent D tetrasulfide ditriethoxysilane
  • ⁇ Stress relaxation agent A Epoxy-modified silicone resin
  • ⁇ Stress relaxation agent B Indene-containing copolymer
  • ⁇ Stress relaxation agent C Phenyl group-containing silicone resin
  • ⁇ Inorganic filler A silica filler with an average particle size of 19.4 ⁇ m
  • ⁇ Inorganic filler B silica filler with an average particle size of 0.6 ⁇ m
  • ⁇ Inorganic filler C silica filler with an average particle size of 50 nm or less
  • ⁇ Inorganic filler D Metal hydroxide containing magnesium and zinc with an average particle size of 1.2 ⁇ m
  • the temperature at which tan ⁇ becomes maximum glass transition temperature
  • the value of tan ⁇ at the glass transition temperature is set to 100, the glass transition
  • the tan ⁇ value at a temperature 10 degrees lower than the temperature described as tan ⁇ ratio in Table 1
  • the resin cured product was a cured product having a rectangular shape with a short side of 5.1 mm, a long side of 20 mm and a thickness of 2 mm. Then, the cured resin was allowed to stand for 168 hours under conditions of a temperature of 85° C. and a relative humidity of 85%. The mass (g) of the cured resin material after standing was measured, and the rate of increase (%) from the mass (g) of the cured resin material before standing was determined. The results are summarized in Table 1.

Abstract

A curable resin composition containing an epoxy resin and a phenolic curing agent, the equivalent ratio of phenolic hydroxyl groups of the phenolic curing agent to the epoxy groups of the epoxy resin ranging from 0.5 to less than 1.0.

Description

硬化性樹脂組成物及び電子部品装置Curable resin composition and electronic component device
　本開示は、硬化性樹脂組成物及び電子部品装置に関する。 The present disclosure relates to curable resin compositions and electronic component devices.
　近年、半導体素子の高密度実装化が進んでいる。これに伴い、樹脂封止型半導体装置は従来のピン挿入型のパッケージから面実装型のパッケージが主流になっている。面実装型のＩＣ（Ｉｎｔｅｇｒａｔｅｄ　Ｃｉｒｃｕｉｔ）、ＬＳＩ（Ｌａｒｇｅ　Ｓｃａｌｅ　Ｉｎｔｅｇｒａｔｉｏｎ）等は、実装密度を高くし、実装高さを低くするために薄型且つ小型のパッケージになっている。そのため、素子のパッケージに対する占有面積が大きくなり、パッケージの厚さは非常に薄くなってきている。 In recent years, high-density mounting of semiconductor elements is progressing. Along with this, resin-encapsulated semiconductor devices are shifting from conventional pin-insertion type packages to surface-mount type packages. Surface-mounted ICs (Integrated Circuits), LSIs (Large Scale Integration), and the like have thin and small packages in order to increase the mounting density and reduce the mounting height. As a result, the area occupied by the device with respect to the package has increased, and the thickness of the package has become extremely thin.
　さらに、これらのパッケージはピン挿入型パッケージとは実装方法が異なっている。すなわち、ピン挿入型パッケージはピンを配線板に挿入した後、配線板の裏面からはんだ付けを行うため、パッケージが直接高温に曝されることはなかった。
　しかし、面実装型ＩＣは配線板表面に仮止めを行い、はんだバス、リフロー装置等で処理されるため、直接はんだ付け温度（リフロー温度）にパッケージが曝される。この結果、パッケージが吸湿している場合、リフロー時に吸湿水分が気化して、発生した蒸気圧が剥離応力として働き、素子、リードフレーム等の支持部材と封止材との間における剥離が発生し、パッケージクラックの発生、電気的特性不良等の原因となる。そのため、支持部材との接着性に優れ、ひいては、はんだ耐熱性（耐リフロー性）に優れる封止材料の開発が望まれている。 In addition, these packages are mounted differently than pin insertion packages. That is, in the pin-insertion type package, the pins are inserted into the wiring board and then soldered from the rear surface of the wiring board, so the package is not directly exposed to high temperatures.
However, surface-mounted ICs are temporarily fixed to the surface of the wiring board and processed by a solder bath, a reflow device, or the like, so the package is directly exposed to the soldering temperature (reflow temperature). As a result, when the package absorbs moisture, the absorbed moisture evaporates during reflow, and the generated vapor pressure acts as peeling stress, causing peeling between the sealing material and the supporting member such as the element or lead frame. , the occurrence of package cracks, poor electrical characteristics, and the like. Therefore, there is a demand for the development of a sealing material that is excellent in adhesion to a supporting member and, in turn, excellent in solder heat resistance (reflow resistance).
　封止材料として、エポキシ樹脂及びフェノール系硬化剤を含有する硬化性樹脂組成物が知られている。 A curable resin composition containing an epoxy resin and a phenol-based curing agent is known as a sealing material.
　特許文献１において提案される硬化性樹脂組成物の耐リフロー性には、さらなる改善の余地があった。
　本開示は上記状況に鑑みてなされたものであり、その解決しようとする課題は、優れた耐リフロー性を有する、硬化性樹脂組成物及びこの硬化性樹脂組成物により封止される素子を備える電子部品装置を提供しようとするものである。 There is room for further improvement in the reflow resistance of the curable resin composition proposed in Patent Document 1.
The present disclosure has been made in view of the above situation, and the problem to be solved is to provide a curable resin composition having excellent reflow resistance and an element sealed with this curable resin composition. An object of the present invention is to provide an electronic component device.
　上記課題を達成するための具体的手段は以下の通りである。
＜１＞　エポキシ樹脂と、フェノール系硬化剤とを、上記エポキシ樹脂のエポキシ基に対する上記フェノール系硬化剤のフェノール性水酸基の当量比０．５以上、１．０未満で含有する、硬化性樹脂組成物。
＜２＞　上記エポキシ樹脂が、アルキルフェノール由来の構造単位及びアルコキシナフタレン由来の構造単位を有する共重合型エポキシ樹脂を含む、上記＜１＞に記載の硬化性樹脂組成物。
＜３＞　上記エポキシ樹脂の全質量に対する上記共重合型エポキシ樹脂の含有率が、５０質量％～９０質量％である、上記＜２＞に記載の硬化性樹脂組成物。
＜４＞　上記エポキシ樹脂が、ビフェニル型エポキシ樹脂を含む、上記＜１＞～＜３＞のいずれか１つに記載の硬化性樹脂組成物。
＜５＞　上記フェノール系硬化剤が、アラルキル型フェノール樹脂及びノボラック型フェノール樹脂からなる群より選択される１つ以上のフェノール系硬化剤を含む、上記＜１＞～＜４＞のいずれか１つに記載の硬化性樹脂組成物。
＜６＞　上記フェノール系硬化剤が、アラルキル型フェノール樹脂を含み、且つ
　上記フェノール系硬化剤の全質量に対する上記アラルキル型フェノール樹脂の含有率が、６０質量％～９５質量％である、上記＜１＞～＜５＞のいずれか１つに記載の硬化性樹脂組成物。
＜７＞　第三ホスフィン化合物とキノン化合物との付加物を含む硬化促進剤をさらに含有する、上記＜１＞～＜６＞のいずれか１つに記載の硬化性樹脂組成物。
＜８＞　素子と、上記素子を封止する上記＜１＞～＜７＞のいずれか１つに記載の硬化性樹脂組成物の樹脂硬化物とを備える、電子部品装置。
＜９＞　上記素子を一方の面に搭載する支持部材をさらに備える、上記＜８＞に記載の電子部品装置。 Concrete means for achieving the above object are as follows.
<1> A curable resin composition containing an epoxy resin and a phenolic curing agent at an equivalent ratio of the phenolic hydroxyl group of the phenolic curing agent to the epoxy group of the epoxy resin of 0.5 or more and less than 1.0. thing.
<2> The curable resin composition according to <1> above, wherein the epoxy resin comprises a copolymerized epoxy resin having an alkylphenol-derived structural unit and an alkoxynaphthalene-derived structural unit.
<3> The curable resin composition according to <2> above, wherein the content of the copolymer type epoxy resin relative to the total mass of the epoxy resin is 50% by mass to 90% by mass.
<4> The curable resin composition according to any one of <1> to <3>, wherein the epoxy resin contains a biphenyl-type epoxy resin.
<5> Any one of <1> to <4> above, wherein the phenolic curing agent contains one or more phenolic curing agents selected from the group consisting of aralkyl-type phenolic resins and novolac-type phenolic resins. The curable resin composition according to .
<6> The above <1, wherein the phenol-based curing agent contains an aralkyl-type phenol resin, and the content of the aralkyl-type phenol resin with respect to the total mass of the phenol-based curing agent is 60% by mass to 95% by mass. > The curable resin composition according to any one of <5>.
<7> The curable resin composition according to any one of <1> to <6> above, further comprising a curing accelerator containing an adduct of a tertiary phosphine compound and a quinone compound.
<8> An electronic component device comprising an element and a resin cured product of the curable resin composition according to any one of <1> to <7> for sealing the element.
<9> The electronic component device according to <8> above, further comprising a support member for mounting the element on one surface thereof.
　本開示によれば、優れた耐リフロー性を有する、硬化性樹脂組成物及びこの硬化性樹脂組成物により封止される素子を備える電子部品装置を提供することができる。 According to the present disclosure, it is possible to provide an electronic component device including a curable resin composition having excellent reflow resistance and an element sealed with this curable resin composition.
　以下、本開示を実施するための形態について詳細に説明する。但し、本開示は以下の実施形態に限定されない。以下の実施形態において、その構成要素（要素ステップ等も含む）は、特に明表した場合を除き、必須ではない。数値及びその範囲についても同様であり、本開示を制限するものではない。 A detailed description will be given below of the embodiment for implementing the present disclosure. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and their ranges, which do not limit the present disclosure.
　本開示において「～」を用いて示された数値範囲には、「～」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。
　本開示中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、合成例に示されている値に置き換えてもよい。
　本開示において各成分は該当する化合物を複数種含有していてもよい。組成物中に各成分に該当する物質が複数種存在する場合、各成分の含有率又は含有量は、特に断らない限り、組成物中に存在する当該複数種の物質の合計の含有率又は含有量を意味する。
　本開示において各成分に該当する粒子は複数種含有していてもよい。組成物中に各成分に該当する粒子が複数種存在する場合、各成分の粒子径は、特に断らない限り、組成物中に存在する当該複数種の粒子の混合物についての値を意味する。
　本開示において「積層」との語は、層を積み重ねることを表し、二以上の層が結合されていてもよく、二以上の層が着脱可能であってもよい。
　本開示の基（原子団）の表記において、置換及び非置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。
　本開示において構造単位数は、単一の分子については整数値を表すが、複数種の分子の集合体としては平均値である有理数を表す。
　本開示において、炭素数とは、ある基全体に含まれる炭素原子の総数を意味し、該基が置換基を有さない場合は当該基の骨格を形成する炭素原子の数を表し、該基が置換基を有する場合は当該基の骨格を形成する炭素原子の数に置換基中の炭素原子の数を加えた総数を表す。 In the present disclosure, the numerical range indicated using "-" includes the numerical values before and after "-" as the minimum and maximum values, respectively.
In the numerical ranges described step by step in the present disclosure, the upper limit or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described step by step. . In addition, in the numerical ranges described in the present disclosure, the upper or lower limits of the numerical ranges may be replaced with the values shown in Synthetic Examples.
In the present disclosure, each component may contain multiple types of applicable compounds. When there are multiple types of substances corresponding to each component in the composition, 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.
Plural types of particles corresponding to each component in the present disclosure may be contained. 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.
In the present disclosure, the term "laminate" refers to stacking layers, and two or more layers may be bonded or two or more layers may be detachable.
In the notation of a group (atomic group) of the present disclosure, the notation without describing substitution and unsubstitution includes not only those not having substituents but also those having substituents.
In the present disclosure, the number of structural units represents an integer value for a single molecule, but represents a rational number which is an average value for an aggregate of multiple types of molecules.
In the present disclosure, the number of carbon atoms means the total number of carbon atoms contained in a group as a whole, and when the group does not have a substituent, it represents the number of carbon atoms forming the skeleton of the group. When has a substituent, it represents the total sum of the number of carbon atoms forming the skeleton of the group plus the number of carbon atoms in the substituent.
　本開示において、エポキシ樹脂のエポキシ基に対するフェノール系硬化剤のフェノール性水酸基（活性水素）の当量比（フェノール系硬化剤の活性水素のモル数／エポキシ樹脂のエポキシ基のモル数）は、硬化性樹脂組成物の１Ｈ－ＮＭＲを測定し、エポキシ基のプロトンと、フェノール性水酸基のプロトンとの積分比から求めることができる。なお、硬化性樹脂組成物の１Ｈ－ＮＭＲは、以下の条件で測定する。
（測定条件）
・測定装置：Ｂｒｕｋｅｒ社製、ＡＶＡＮＣＥ３　ＨＤ　４００　Ｎａｎｏｂａｙ
・測定溶媒：ＤＭＳＯ－ｄ６（０．７ｍｌ）
・測定温度：２５℃
・１Ｈ共鳴周波数：４００ＭＨｚ
・測定モード：ＮＰＲＯＴＯＮ
・積算回数：１６回
・緩和時間：１秒 In the present disclosure, the equivalent ratio of the phenolic hydroxyl group (active hydrogen) of the phenolic curing agent to the epoxy group of the epoxy resin (number of moles of active hydrogen of the phenolic curing agent/number of moles of epoxy groups of the epoxy resin) is the curability 1 H-NMR of the resin composition is measured, and it can be determined from the integral ratio of the protons of the epoxy group and the protons of the phenolic hydroxyl group. 1 H-NMR of the curable resin composition is measured under the following conditions.
(Measurement condition)
・ Measuring device: AVANCE3 HD 400 Nanobay manufactured by Bruker
・Measurement solvent: DMSO-d6 (0.7 ml)
・Measurement temperature: 25°C
・1 H resonance frequency: 400 MHz
・Measurement mode: NPROTON
・Accumulated times: 16 times ・Relaxation time: 1 second
　本開示において、硬化性樹脂組成物の樹脂硬化物に対する動的粘弾性測定は、動的粘弾性測定装置（例えば、ＰｅｒｋｉｎＥｌｍｅｒ社製、ＤＭＡ８０００）を用いて実施することができる。例えば、短辺５ｍｍ×長辺５０ｍｍ×厚さ２ｍｍの長方形形状の樹脂硬化物に対して、試験モード：３点曲げモード、測定温度：２５℃～３３０℃、昇温速度：１０℃／分、試験周波数：１Ｈｚの条件で動的粘弾性測定を実施し、得られたチャート（縦軸：ｔａｎδ、横軸：温度）から貯蔵粘弾性の値、ｔａｎδのピーク値、ガラス転移温度等を特定することができる。
　なお、樹脂硬化物の作製は、トランスファ成形機により、金型温度１７５℃、成形圧力８．３ＭＰａ、硬化時間１２０秒の条件で硬化性樹脂組成物を成形し、次いで、１７５℃５時間の後硬化を実施することにより行う。 In the present disclosure, the dynamic viscoelasticity measurement of the resin cured product of the curable resin composition can be performed using a dynamic viscoelasticity measuring device (for example, DMA8000 manufactured by PerkinElmer). For example, for a rectangular resin cured product of short side 5 mm x long side 50 mm x thickness 2 mm, test mode: 3-point bending mode, measurement temperature: 25 ° C. to 330 ° C., temperature increase rate: 10 ° C./min, Test frequency: Perform dynamic viscoelasticity measurement under the condition of 1 Hz, and specify the value of storage viscoelasticity, the peak value of tan δ, the glass transition temperature, etc. from the obtained chart (vertical axis: tan δ, horizontal axis: temperature) be able to.
The resin cured product was produced by molding the curable resin composition using a transfer molding machine under the conditions of a mold temperature of 175°C, a molding pressure of 8.3 MPa, and a curing time of 120 seconds. By carrying out curing.
　本開示において、硬化性樹脂組成物の樹脂硬化物の熱膨張係数（ＣＴＥ：Ｃｏｅｆｆｉｃｉｅｎｔ　ｏｆ　Ｔｈｅｒｍａｌ　Ｅｘｐａｎｓｉｏｎ）の測定は、例えば、φ４ｍｍ×２０ｍｍの樹脂硬化物に対して、熱機械分析装置を用いて行う。なお、樹脂硬化物の作製については、上記した通りである。
　測定条件は、荷重１５ｇ、測定温度－５０℃～２２０℃、昇温速度５℃／分とする。
　熱機械分析装置としては、セイコーインスツルメンツ株式会社製ＴＭＡ／ＳＳ６１００を用いることができる。 In the present disclosure, the coefficient of thermal expansion (CTE) of the cured resin of the curable resin composition is measured using a thermomechanical analyzer, for example, on a cured resin of φ4 mm × 20 mm. . The production of the resin cured product is as described above.
The measurement conditions are a load of 15 g, a measurement temperature of −50° C. to 220° C., and a heating rate of 5° C./min.
As a thermomechanical analyzer, TMA/SS6100 manufactured by Seiko Instruments Inc. can be used.
　本開示において、重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、下記測定条件において、下記ＧＰＣ測定装置を使用して測定し、標準ポリスチレンの検量線を使用して換算した値である。また、検量線の作成は、標準ポリスチレンとして５サンプルセット（「ＰＳｔＱｕｉｃｋ　ＭＰ－Ｈ」及び「ＰＳｔＱｕｉｃｋ　Ｂ」、東ソー株式会社製）を用いた。
　但し、分子量が小さいためにＧＰＣでは正確なＭｗ又はＭｎを測定できない化合物については、化合物の化学構造から求められる分子量を、その化合物のＭｗ又はＭｎとして採用する。
（ＧＰＣ測定装置）
ＧＰＣ装置　：高速ＧＰＣ装置「ＨＣＬ－８３２０ＧＰＣ」、検出器は示差屈折計又はＵＶ、東ソー株式会社製
カラム　　　：カラムＴＳＫｇｅｌ　ＳｕｐｅｒＭｕｌｔｉｐｏｒｅ　ＨＺ－Ｈ（カラム長さ：１５ｃｍ、カラム内径：４．６ｍｍ）、東ソー株式会社製
（測定条件）
溶媒　　　　：テトラヒドロフラン（ＴＨＦ）
測定温度　　：４０℃
流量　　　　：０．３５ｍＬ／分
試料濃度　　：１０ｍｇ／ＴＨＦ５ｍＬ
注入量　　　：２０μＬ In the present disclosure, the weight average molecular weight (Mw) and number average molecular weight (Mn) are measured using the following GPC measurement device under the following measurement conditions, and converted using a standard polystyrene calibration curve. In addition, a calibration curve was prepared using a set of 5 samples (“PStQuick MP-H” and “PStQuick B”, manufactured by Tosoh Corporation) as standard polystyrene.
However, for a compound whose molecular weight is too small to accurately measure Mw or Mn by GPC, the molecular weight determined from the chemical structure of the compound is adopted as the Mw or Mn of the compound.
(GPC measuring device)
GPC device: High-speed GPC device "HCL-8320GPC", detector is differential refractometer or UV, column manufactured by Tosoh Corporation: column TSKgel SuperMultipore HZ-H (column length: 15 cm, column inner diameter: 4.6 mm), Tosoh stock Company made (measurement conditions)
Solvent: Tetrahydrofuran (THF)
Measurement temperature: 40°C
Flow rate: 0.35 mL/min Sample concentration: 10 mg/THF5 mL
Injection volume: 20 μL
＜硬化性樹脂組成物＞
　本開示の硬化性樹脂組成物は、エポキシ樹脂と、フェノール系硬化剤とを、エポキシ樹脂のエポキシ基に対するフェノール系硬化剤のフェノール性水酸基の当量比０．５以上、１．０未満で含有する。 <Curable resin composition>
The curable resin composition of the present disclosure contains an epoxy resin and a phenolic curing agent at an equivalent ratio of the phenolic hydroxyl group of the phenolic curing agent to the epoxy group of the epoxy resin of 0.5 or more and less than 1.0. .
　本開示の硬化性樹脂組成物は、優れた耐リフロー性を有する。 The curable resin composition of the present disclosure has excellent reflow resistance.
　本開示の硬化性樹脂組成物により上記効果が奏される理由は明らかではないが以下のように推察される。
　本開示の硬化性樹脂組成物が、エポキシ樹脂と、フェノール系硬化剤とを、エポキシ樹脂のエポキシ基に対するフェノール系硬化剤のフェノール性水酸基の当量比０．５以上、１．０未満で含有することにより、リフロー温度付近のｔａｎδの値を増大することができ、リフロー時における樹脂硬化物の内部応力が緩和される傾向にある。その結果、硬化性樹脂組成物の樹脂硬化物と支持部材との接着性が向上するため、優れた耐リフロー性を有すると推察される。
　耐リフロー性を評価するための試験として、ＪＥＤＥＣ（Ｊｏｉｎｔ　Ｅｌｅｃｔｒｏｎ　Ｄｅｖｉｃｅ　Ｅｎｇｉｎｅｅｒ　Ｃｏｕｎｃｉｌ）規格であるＭＳＬ（Ｍｏｉｓｔｕｒｅ　Ｓｅｎｓｉｔｉｖｅ　Ｌｅｖｅｌ）試験が知られる。
　本開示の硬化性樹脂組成物によれば、温度８５℃、相対湿度８５％、１６８時間の条件（ＭＳＬレベル１に相当）による加熱加湿後であっても、優れた耐リフロー性を示し、これは驚くべきものである。 The reason why the curable resin composition of the present disclosure achieves the above effects is not clear, but is presumed as follows.
The curable resin composition of the present disclosure contains an epoxy resin and a phenolic curing agent at an equivalent ratio of the phenolic hydroxyl group of the phenolic curing agent to the epoxy group of the epoxy resin of 0.5 or more and less than 1.0. As a result, the tan δ value near the reflow temperature can be increased, and the internal stress of the cured resin tends to be relaxed during reflow. As a result, the adhesiveness between the cured resin of the curable resin composition and the supporting member is improved, so that it is presumed to have excellent reflow resistance.
As a test for evaluating reflow resistance, an MSL (Moisture Sensitive Level) test, which is a JEDEC (Joint Electron Device Engineers Council) standard, is known.
According to the curable resin composition of the present disclosure, even after heating and humidifying under the conditions of 85 ° C. temperature, 85% relative humidity, and 168 hours (corresponding to MSL level 1), it exhibits excellent reflow resistance. is amazing.
　本開示の硬化性樹脂組成物の樹脂硬化物に対して動的粘弾性測定を行うことにより得られる縦軸をｔａｎδ及び横軸を温度とするチャートにおいて、ｔａｎδが最大となる温度（いわゆるガラス転移温度）が、１２０℃未満であることが好ましく、１１０℃未満であることがより好ましい。ガラス転移温度が１２０℃未満であることにより、本開示の硬化性樹脂組成物の耐リフロー性を向上することができる傾向にある。ガラス転移温度の下限値は特に限定されるものではないが、例えば、５０℃以上とすることができる。 In a chart with tan δ on the vertical axis and temperature on the horizontal axis obtained by performing dynamic viscoelasticity measurement on the resin cured product of the curable resin composition of the present disclosure, the temperature at which tan δ becomes maximum (so-called glass transition temperature) is preferably less than 120°C, more preferably less than 110°C. A glass transition temperature of less than 120° C. tends to improve the reflow resistance of the curable resin composition of the present disclosure. Although the lower limit of the glass transition temperature is not particularly limited, it can be, for example, 50° C. or higher.
　本開示の硬化性樹脂組成物の耐リフロー性の観点から、ガラス転移温度におけるｔａｎδは、０．４００超であることが好ましく、０．４１０超であることがより好ましい。ガラス転移温度におけるｔａｎδの上限値は特に限定されるものではないが、例えば、１．０以下とすることができる。 From the viewpoint of reflow resistance of the curable resin composition of the present disclosure, tan δ at the glass transition temperature is preferably over 0.400, more preferably over 0.410. Although the upper limit of tan δ at the glass transition temperature is not particularly limited, it can be, for example, 1.0 or less.
　本開示の硬化性樹脂組成物の耐リフロー性の観点から、ガラス転移温度におけるｔａｎδの値を１００としたとき、ガラス転移温度－１０℃の少なくともいずれかの温度におけるｔａｎδの値が６０超であることが好ましく、６３超であることがより好ましく、６５超であることがさらに好ましい。 From the viewpoint of reflow resistance of the curable resin composition of the present disclosure, when the value of tan δ at the glass transition temperature is 100, the value of tan δ at at least one temperature of -10 ° C. is more than 60. more preferably greater than 63, and even more preferably greater than 65.
　本開示の硬化性樹脂組成物の耐リフロー性の観点から、２２０℃、２３０℃、２４０℃及び２５０℃の各温度におけるｔａｎδの値の合計が、０．４００超であることが好ましい。２２０℃、２３０℃、２４０℃及び２５０℃の各温度におけるｔａｎδの値の合計の上限値は特に限定されるものではないが、例えば、２．０以下とすることができる。 From the viewpoint of reflow resistance of the curable resin composition of the present disclosure, the sum of tan δ values at each temperature of 220°C, 230°C, 240°C and 250°C is preferably more than 0.400. The upper limit of the sum of tan δ values at temperatures of 220° C., 230° C., 240° C. and 250° C. is not particularly limited, but can be, for example, 2.0 or less.
　本開示の硬化性樹脂組成物の耐リフロー性の観点から、７０℃、８０℃及び９０℃の各温度におけるｔａｎδの値の合計が、０．６００超であることが好ましく、０．７００超であることがより好ましい。７０℃、８０℃及び９０℃の各温度におけるｔａｎδの値の合計の上限値は特に限定されるものではないが、例えば、２．０以下とすることができる。 From the viewpoint of reflow resistance of the curable resin composition of the present disclosure, the total value of tan δ at each temperature of 70 ° C., 80 ° C. and 90 ° C. is preferably more than 0.600, and more than 0.700 It is more preferable to have The upper limit of the sum of tan δ values at temperatures of 70° C., 80° C. and 90° C. is not particularly limited, but can be, for example, 2.0 or less.
　耐リフロー性の観点から、硬化性樹脂組成物の樹脂硬化物に対して動的粘弾性測定を行うことにより求められる２６０℃における貯蔵粘弾性が、４５０ＭＰａ以下であることが好ましく、４３５ＭＰａ以下であることがより好ましく、４２０ＭＰａ以下であることがさらに好ましい。
　貯蔵弾性率の下限値は、特に限定されるものではないが、例えば、１５０ＭＰａ以上とすることができる。 From the viewpoint of reflow resistance, the storage viscoelasticity at 260 ° C. obtained by performing dynamic viscoelasticity measurement on the resin cured product of the curable resin composition is preferably 450 MPa or less, and is 435 MPa or less. is more preferably 420 MPa or less.
Although the lower limit of the storage modulus is not particularly limited, it can be, for example, 150 MPa or more.
　熱機械分析測定により求められる本開示の硬化性樹脂組成物の樹脂硬化物のガラス転移温度未満の熱膨張係数（ＣＴＥ１）は、支持部材への追従性の観点から、１５ｐｐｍ／℃以下が好ましく、１３ｐｐｍ／℃以下がより好ましく、１０ｐｐｍ／℃以下がさらに好ましい。熱膨張係数の下限値は、特に限定されるものではないが、例えば、３ｐｐｍ／℃とすることができる。
　支持部材との接着性の観点から、ガラス転移温度以上の熱膨張係数（ＣＴＥ２）は、１０ｐｐｍ／℃～４５ｐｐｍ／℃が好ましく、１２ｐｐｍ／℃～４０ｐｐｍ／℃がより好ましく、１５ｐｐｍ／℃～３８ｐｐｍ／℃がさらに好ましい。 The thermal expansion coefficient (CTE1) below the glass transition temperature of the resin cured product of the curable resin composition of the present disclosure obtained by thermomechanical analysis is preferably 15 ppm / ° C. or less from the viewpoint of followability to the support member. 13 ppm/°C or less is more preferable, and 10 ppm/°C or less is even more preferable. Although the lower limit of the coefficient of thermal expansion is not particularly limited, it can be set to 3 ppm/°C, for example.
From the viewpoint of adhesion to the support member, the coefficient of thermal expansion (CTE2) above the glass transition temperature is preferably 10 ppm/° C. to 45 ppm/° C., more preferably 12 ppm/° C. to 40 ppm/° C., more preferably 15 ppm/° C. to 38 ppm/° C. °C is more preferred.
　以下、硬化性樹脂組成物が含有しうる各種材料について説明する。 Various materials that can be contained in the curable resin composition are described below.
（エポキシ樹脂）
　本開示の硬化性樹脂組成物は、エポキシ樹脂を含有する。エポキシ樹脂は１分子中に２個以上のエポキシ基を有するものであればその種類は特に制限されない。なお、本開示において、上記直鎖状ポリシロキサン化合物は、エポキシ樹脂には含めないものとする。
　エポキシ樹脂の具体例を以下に記載するが、これらに限定されるものではない。 (Epoxy resin)
The curable resin composition of the present disclosure contains an epoxy resin. The type of epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule. In addition, in the present disclosure, the linear polysiloxane compound is not included in the epoxy resin.
Specific examples of epoxy resins are described below, but are not limited thereto.
　具体的には、フェノール、クレゾール、キシレノール、レゾルシン、カテコール、ビスフェノールＡ、ビスフェノールＦ等のフェノール化合物及びα－ナフトール、β－ナフトール、ジヒドロキシナフタレン等のナフトール化合物からなる群より選ばれる少なくとも１種のフェノール性化合物と、ホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド等の脂肪族アルデヒド化合物とを酸性触媒下で縮合又は共縮合させて得られるノボラック樹脂をエポキシ化したものであるノボラック型エポキシ樹脂（フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂等）；上記フェノール性化合物と、ベンズアルデヒド、サリチルアルデヒド等の芳香族アルデヒド化合物とを酸性触媒下で縮合又は共縮合させて得られるトリフェニルメタン型フェノール樹脂をエポキシ化したものであるトリフェニルメタン型エポキシ樹脂；上記フェノール化合物及びナフトール化合物と、アルデヒド化合物とを酸性触媒下で共縮合させて得られるノボラック樹脂をエポキシ化したものである共重合型エポキシ樹脂；ビスフェノールＡ、ビスフェノールＦ等のジグリシジルエーテルであるジフェニルメタン型エポキシ樹脂；アルキル置換又は非置換のビフェノールのジグリシジルエーテルであるビフェニル型エポキシ樹脂；スチルベン系フェノール化合物のジグリシジルエーテルであるスチルベン型エポキシ樹脂；ビスフェノールＳ等のジグリシジルエーテルである硫黄原子含有型エポキシ樹脂；ブタンジオール、ポリエチレングリコール、ポリプロピレングリコール等のアルコール類のグリシジルエーテルであるエポキシ樹脂；フタル酸、イソフタル酸、テトラヒドロフタル酸等の多価カルボン酸化合物のグリシジルエステルであるグリシジルエステル型エポキシ樹脂；アニリン、ジアミノジフェニルメタン、イソシアヌル酸等の窒素原子に結合した活性水素をグリシジル基で置換したものであるグリシジルアミン型エポキシ樹脂；ジシクロペンタジエンとフェノール化合物の共縮合樹脂をエポキシ化したものであるジシクロペンタジエン型エポキシ樹脂；分子内のオレフィン結合をエポキシ化したものであるビニルシクロヘキセンジエポキシド、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、２－（３，４－エポキシ）シクロヘキシル－５，５－スピロ（３，４－エポキシ）シクロヘキサン－ｍ－ジオキサン等の脂環型エポキシ樹脂；パラキシリレン変性フェノール樹脂のグリシジルエーテルであるパラキシリレン変性エポキシ樹脂；メタキシリレン変性フェノール樹脂のグリシジルエーテルであるメタキシリレン変性エポキシ樹脂；テルペン変性フェノール樹脂のグリシジルエーテルであるテルペン変性エポキシ樹脂；ジシクロペンタジエン変性フェノール樹脂のグリシジルエーテルであるジシクロペンタジエン変性エポキシ樹脂；シクロペンタジエン変性フェノール樹脂のグリシジルエーテルであるシクロペンタジエン変性エポキシ樹脂；多環芳香環変性フェノール樹脂のグリシジルエーテルである多環芳香環変性エポキシ樹脂；ナフタレン環含有フェノール樹脂のグリシジルエーテルであるナフタレン型エポキシ樹脂；ハロゲン化フェノールノボラック型エポキシ樹脂；ハイドロキノン型エポキシ樹脂；トリメチロールプロパン型エポキシ樹脂；オレフィン結合を過酢酸等の過酸で酸化して得られる線状脂肪族エポキシ樹脂；フェノールアラルキル樹脂、ナフトールアラルキル樹脂等のアラルキル型フェノール樹脂をエポキシ化したものであるアラルキル型エポキシ樹脂；などが挙げられる。さらにはアミノフェノールのグリシジルエーテルであるアミノフェノール型エポキシ樹脂等もエポキシ樹脂として挙げられる。これらのエポキシ樹脂は、１種類を単独で用いても２種類以上を組み合わせて用いてもよい。 Specifically, 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 α-naphthol, β-naphthol and dihydroxynaphthalene. A novolak type epoxy resin (phenol novolac type epoxy resin, ortho-cresol novolak-type epoxy resins, etc.); epoxidized triphenylmethane-type phenolic resins obtained by condensation or co-condensation of the above phenolic compounds and aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde in the presence of an acidic catalyst. A triphenylmethane type epoxy resin; a copolymer type epoxy resin obtained by epoxidizing a novolak resin obtained by co-condensing the above phenol compound and naphthol compound with an aldehyde compound in the presence of an acidic catalyst; bisphenol A, bisphenol diphenylmethane-type epoxy resins that are diglycidyl ethers such as F; biphenyl-type epoxy resins that are diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene-type epoxy resins that are diglycidyl ethers of stilbene-based phenol compounds; Sulfur atom-containing epoxy resins that are diglycidyl ethers; Epoxy resins that are glycidyl ethers of alcohols such as butanediol, polyethylene glycol and polypropylene glycol; Glycidyl polyvalent carboxylic acid compounds such as phthalic acid, isophthalic acid and tetrahydrophthalic acid Glycidyl ester-type epoxy resins that are esters; glycidylamine-type epoxy resins in which active hydrogens bonded to nitrogen atoms of aniline, diaminodiphenylmethane, isocyanuric acid, etc. are substituted with glycidyl groups; co-condensation resins of dicyclopentadiene and phenol compounds Dicyclopentadiene type epoxy resin which is obtained by epoxidizing the; vinylcyclohexene diepoxide obtained by epoxidizing the olefin bond in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 2- (3,4-epoxy)cyclohexyl-5,5-spiro(3 ,4-epoxy)cyclohexane-m-dioxane and other alicyclic epoxy resins; para-xylylene-modified epoxy resins that are glycidyl ethers of para-xylylene-modified phenol resins; meta-xylylene-modified epoxy resins that are glycidyl ethers of meta-xylylene-modified phenol resins; terpene-modified phenol resins a terpene-modified epoxy resin that is a glycidyl ether of dicyclopentadiene-modified phenol resin; a dicyclopentadiene-modified epoxy resin that is a glycidyl ether of a cyclopentadiene-modified phenol resin; Polycyclic aromatic ring-modified epoxy resins that are glycidyl ethers of resins; naphthalene type epoxy resins that are glycidyl ethers of naphthalene ring-containing phenol resins; halogenated phenol novolac type epoxy resins; hydroquinone type epoxy resins; trimethylolpropane type epoxy resins; linear aliphatic epoxy resin obtained by oxidizing the bond with peracid such as peracetic acid; aralkyl-type epoxy resin obtained by epoxidizing aralkyl-type phenol resin such as phenol aralkyl resin and naphthol aralkyl resin; . Further examples of epoxy resins include aminophenol-type epoxy resins, which are glycidyl ethers of aminophenol. These epoxy resins may be used singly or in combination of two or more.
　ビフェニル型エポキシ樹脂は、ビフェニル骨格を有するエポキシ樹脂であれば特に限定されない。例えば、下記一般式（ＩＩ）で表されるエポキシ樹脂が好ましい。 The biphenyl-type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton. For example, an epoxy resin represented by the following general formula (II) is preferred.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　式（ＩＩ）中、Ｒ８は水素原子、炭素数１～１２のアルキル基又は炭素数４～１８の芳香族基を示し、それぞれ全てが同一でも異なっていてもよい。ｎは平均値であり、０～１０の整数を示す。 In formula (II), 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 an average value and represents an integer of 0-10.
　スチルベン型エポキシ樹脂は、スチルベン骨格を有するエポキシ樹脂であれば特に限定されない。例えば、下記一般式（ＩＩＩ）で表されるエポキシ樹脂が好ましい。 The stilbene-type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton. For example, an epoxy resin represented by the following general formula (III) is preferred.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　式（ＩＩＩ）中、Ｒ９及びＲ１０は水素原子又は炭素数１～１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｎは平均値であり、０～１０の整数を示す。 In formula (III), 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 an average value and represents an integer of 0-10.
　ジフェニルメタン型エポキシ樹脂は、ジフェニルメタン骨格を有するエポキシ樹脂であれば特に限定されない。例えば、下記一般式（ＩＶ）で表されるエポキシ樹脂が好ましい。 The diphenylmethane-type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton. For example, an epoxy resin represented by the following general formula (IV) is preferred.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　式（ＩＶ）中、Ｒ１１及びＲ１２は水素原子又は炭素数１～１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｎは平均値であり、０～１０の整数を示す。 In formula (IV), 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 an average value and represents an integer of 0-10.
　硫黄原子含有型エポキシ樹脂は、硫黄原子を含有するエポキシ樹脂であれば特に限定されない。例えば、下記一般式（Ｖ）で表されるエポキシ樹脂が挙げられる。 The sulfur atom-containing type epoxy resin is not particularly limited as long as it is an epoxy resin containing sulfur atoms. Examples thereof include epoxy resins represented by the following general formula (V).
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　式（Ｖ）中、Ｒ１３は水素原子又は炭素数１～１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｎは平均値であり、０～１０の整数を示す。 In formula (V), 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 an integer of 0-10.
　ノボラック型エポキシ樹脂は、ノボラック型フェノール樹脂をエポキシ化して得られるエポキシ樹脂であれば、特に限定されない。 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.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　式（ＶＩ）中、Ｒ１４は水素原子又は炭素数１～１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。Ｒ１５は炭素数１～１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｉは各々独立に０～３の整数を示す。ｎは平均値であり、０～１０の整数を示す。 In formula (VI), 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 an average value and represents an integer of 0-10.
　ジシクロペンタジエン型エポキシ樹脂は、ジシクロペンタジエン骨格を有する化合物を原料としてエポキシ化して得られるエポキシ樹脂であれば特に限定されない。 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.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　式（ＶＩＩ）中、Ｒ１６は炭素数１～１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｉは各々独立に０～３の整数を示す。ｎは平均値であり、０～１０の整数を示す。 In formula (VII), 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 an average value and represents an integer of 0-10.
　トリフェニルメタン型エポキシ樹脂は、トリフェニルメタン骨格を持つ化合物を原料とするエポキシ樹脂であれば特に制限されない。 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.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　式（ＶＩＩＩ）中、Ｒ１７及びＲ１８は炭素数１～１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｉは各々独立に０～３の整数、ｋは各々独立に０～４の整数を示す。ｎは平均値であり、０～１０の整数を示す。 In formula (VIII), 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, and each k independently represents an integer of 0 to 4. n is an average value and represents an integer of 0-10.
　ナフトール化合物及びフェノール化合物と、アルデヒド化合物とから得られるノボラック樹脂をエポキシ化した共重合型エポキシ樹脂は、ナフトール骨格を有する化合物及びフェノール骨格を有する化合物を原料とするエポキシ樹脂であれば、特に限定されない。
　例えば、ナフトール骨格を有する化合物及びフェノール骨格を有する化合物を用いたノボラック型フェノール樹脂をグリシジルエーテル化して得られるエポキシ樹脂が好ましく、下記一般式（ＩＸ）で表されるエポキシ樹脂がより好ましい。 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. .
For example, 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.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　式（ＩＸ）中、Ｒ１９～Ｒ２１は炭素数１～１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｉは各々独立に０～３の整数、ｊは各々独立に０～２の整数、ｋは各々独立に０～４の整数を示す。ｌ及びｍはそれぞれ平均値であり、０～１０の数であり、（ｌ＋ｍ）は０～１０の数を示す。式（ＩＸ）で表されるエポキシ樹脂の末端は、下記式（ＩＸ－１）又は（ＩＸ－２）のいずれか一方である。式（ＩＸ－１）及び（ＩＸ－２）において、Ｒ１９～Ｒ２１、ｉ、ｊ及びｋの定義は式（ＩＸ）におけるＲ１９～Ｒ２１、ｉ、ｊ及びｋの定義と同じである。ｎは１（メチレン基を介して結合する場合）又は０（メチレン基を介して結合しない場合）である。 In formula (IX), 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, and each k independently represents an integer of 0 to 4. l and m are average values, numbers from 0 to 10, and (l+m) shows numbers from 0 to 10. The terminal of the epoxy resin represented by formula (IX) is either one of formula (IX-1) or (IX-2) below. Definitions of R 19 to R 21 , i, j and k in formulas (IX-1) and (IX-2) are the same as definitions of R 19 to R 21 , i, j and k in formula (IX). . n is 1 (when linked via a methylene group) or 0 (when not linked via a methylene group).
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　上記一般式（ＩＸ）で表されるエポキシ樹脂としては、ｌ個の構造単位及びｍ個の構造単位をランダムに有するランダム共重合体、交互に有する交互共重合体、規則的に有する共重合体、ブロック状に有するブロック共重合体等が挙げられる。これらのいずれか１種類を単独で用いても２種類以上を組み合わせて用いてもよい。 The epoxy resin represented by the general formula (IX) includes a random copolymer having l structural units and m structural units at random, an alternating copolymer having alternating structural units, and a copolymer having regularly , a block copolymer having a block shape, and the like. Any one of these may be used alone, or two or more may be used in combination.
　アラルキル型エポキシ樹脂は、フェノール、クレゾール等のフェノール化合物及びナフトール、ジメチルナフトール等のナフトール化合物からなる群より選ばれる少なくとも１種と、ジメトキシパラキシレン、ビス（メトキシメチル）ビフェニル又はこれらの誘導体と、から合成されるフェノール樹脂を原料とするエポキシ樹脂であれば、特に限定されない。例えば、フェノール、クレゾール等のフェノール化合物及びナフトール、ジメチルナフトール等のナフトール化合物からなる群より選ばれる少なくとも１種と、ジメトキシパラキシレン、ビス（メトキシメチル）ビフェニル又はこれらの誘導体とから合成されるフェノール樹脂をグリシジルエーテル化して得られるエポキシ樹脂が好ましく、下記一般式（Ｘ）及び（ＸＩ）で表されるエポキシ樹脂がより好ましい。 The aralkyl-type epoxy resin is composed of at least one selected from the group consisting of phenol compounds such as phenol and cresol, and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis(methoxymethyl)biphenyl or derivatives thereof. There is no particular limitation as long as it is an epoxy resin made from a synthesized phenol resin. For example, 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).
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　式（Ｘ）及び（ＸＩ）において、Ｒ３８は水素原子又は炭素数１～１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。Ｒ３７、Ｒ３９～Ｒ４１は炭素数１～１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｉは各々独立に０～３の整数であり、ｊは各々独立に０～２の整数であり、ｋは各々独立に０～４の整数であり、ｌは各々独立に０～４の整数を示す。ｎは平均値であり、各々独立に０～１０の整数である。 In formulas (X) and (XI), R 38 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different. R 37 , R 39 to R 41 each represent a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. i is each independently an integer of 0 to 3, j is each independently an integer of 0 to 2, k is each independently an integer of 0 to 4, l is each independently an integer of 0 to 4 show. n is an average value, each independently an integer of 0 to 10;
　上記一般式（ＩＩ）～（ＸＩ）中のＲ８～Ｒ２１及びＲ３７～Ｒ４１について、「それぞれ全てが同一でも異なっていてもよい」とは、例えば、式（ＩＩ）中の８～８８個のＲ８の全てが同一でも異なっていてもよいことを意味している。他のＲ９～Ｒ２１及びＲ３７～Ｒ４１についても、式中に含まれるそれぞれの個数について全てが同一でも異なっていてもよいことを意味している。また、Ｒ８～Ｒ２１及びＲ３７～Ｒ４１はそれぞれが同一でも異なっていてもよい。例えば、Ｒ９とＲ１０の全てについて同一でも異なっていてもよい。
　また、一般式（ＩＩＩ）～（ＸＩ）における炭素数１～１８の１価の有機基はアルキル基又はアリール基であることが好ましい。 Regarding 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. Also, R 8 to R 21 and R 37 to R 41 may be the same or different. For example, all of R 9 and R 10 may be the same or different.
Further, 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.
　上記一般式（ＩＩ）～（ＸＩ）中のｎは、平均値であり、各々独立に０～１０の範囲であることが好ましい。ｎが１０以下であると樹脂成分の溶融粘度が高くなりすぎず、硬化性樹脂組成物の溶融成形時の粘度が低下し、充填不良、ボンディングワイヤ（素子とリードを接続する金線）の変形等の発生が抑制される傾向にある。ｎは０～４の範囲に設定されることがより好ましい。 n in the above general formulas (II) to (XI) is an average value, and each independently preferably ranges from 0 to 10. If n is 10 or less, the melt viscosity of the resin component does not become too high, and the viscosity of the curable resin composition during melt molding decreases, resulting in insufficient filling and deformation of the bonding wire (gold wire that connects the element and the lead). etc. tend to be suppressed. More preferably, n is set in the range of 0-4.
　本開示の硬化性樹脂組成物の耐リフロー性の観点から、エポキシ樹脂は、アルキルフェノール由来の構造単位及びアルコキシナフタレン由来の構造単位を有する共重合型エポキシ樹脂（以下、特定共重合型エポキシ樹脂という）を含むことが好ましい。アルキルフェノール由来の構造単位としては、下記構造単位（ａ）が挙げられる。 From the viewpoint of reflow resistance of the curable resin composition of the present disclosure, the epoxy resin is a copolymerized epoxy resin having a structural unit derived from alkylphenol and a structural unit derived from alkoxynaphthalene (hereinafter referred to as a specific copolymerized epoxy resin). is preferably included. Structural units derived from alkylphenols include structural units (a) below.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　上記構造単位中、ＲＡは、各々独立に、炭素数１～１８の１価のアルキル基を示し、好ましくは、炭素数１～６の１価のアルキル基を示す。Ｘは、１～３の整数を示す。 In the above structural units, each R 1 A independently represents a monovalent alkyl group having 1 to 18 carbon atoms, preferably a monovalent alkyl group having 1 to 6 carbon atoms. X represents an integer of 1-3.
　アルコキシナフタレン由来の構造単位としては、以下の構造単位（ｂ）が挙げられる。 Structural units derived from alkoxynaphthalene include the following structural units (b).
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　上記構造単位中、ＲＢは、各々独立に炭素数１～１８の１価のアルコキシ基を示し、好ましくは、炭素数１～６の１価のアルコキシ基を示す。ｙは、１～６の整数を示す。
　なお、上記構造単位（ｂ）における２つの結合部位は、ナフタレン環の同一環に存在してもよく、ナフタレン環の２つの環それぞれに存在してもよい。 In the above structural unit, each R 2 B independently represents a monovalent alkoxy group having 1 to 18 carbon atoms, preferably a monovalent alkoxy group having 1 to 6 carbon atoms. y represents an integer of 1-6.
The two bonding sites in the structural unit (b) may exist in the same naphthalene ring or may exist in each of the two naphthalene rings.
　特定共重合型エポキシ樹脂は、下記構造単位（ｃ）を有することができる。
　下記構造単位では、ｎは、１～１０の整数であり、２～８の整数であることが好ましい。
　なお、上記構造単位（ｃ）におけるナフタレン環が有する２つの結合部位は、ナフタレン環の同一環に存在してもよく、ナフタレン環の２つの環それぞれに存在してもよい。 The specific copolymerization type epoxy resin can have the following structural unit (c).
In the following structural units, n is an integer of 1-10, preferably an integer of 2-8.
The two bonding sites of the naphthalene ring in the structural unit (c) may exist in the same naphthalene ring or may exist in each of the two naphthalene rings.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　上記構造単位（ｃ）を満たす構造単位としては、例えば、下記構造単位（ｄ）が挙げられる。 Structural units satisfying the above structural unit (c) include, for example, the following structural unit (d).
Figure JPOXMLDOC01-appb-C000014
 
 
Figure JPOXMLDOC01-appb-C000014
 
 
　上記エポキシ樹脂の中でも、本開示の硬化性樹脂組成物の耐リフロー性の観点からは、エポキシ樹脂は、特定共重合型エポキシ樹脂を含むことが好ましい。
　また、耐リフロー性の観点から、エポキシ樹脂は、ビフェニル型エポキシ樹脂を含むことが好ましい。 Among the above epoxy resins, from the viewpoint of reflow resistance of the curable resin composition of the present disclosure, the epoxy resin preferably contains a specific copolymerization type epoxy resin.
Moreover, from the viewpoint of reflow resistance, the epoxy resin preferably contains a biphenyl-type epoxy resin.
　エポキシ樹脂のエポキシ当量は特に制限されない。成形性、耐熱性及び電気的信頼性等の各種特性バランスの観点からは、エポキシ樹脂のエポキシ当量は、４０ｇ／ｅｑ～１０００ｇ／ｅｑが好ましく、４５ｇ／ｅｑ～５００ｇ／ｅｑがより好ましく、５０ｇ／ｅｑ～３５０ｇ／ｅｑがさらに好ましい。
　エポキシ樹脂のエポキシ当量は、ＪＩＳ　Ｋ　７２３６：２００９に準じた方法で測定される値とする。 The epoxy equivalent of the epoxy resin is not particularly limited. From the viewpoint of the balance of various properties such as moldability, heat resistance and electrical reliability, the epoxy equivalent of the epoxy resin is preferably 40 g/eq to 1000 g/eq, more preferably 45 g/eq to 500 g/eq, and 50 g/eq. eq to 350 g/eq is more preferred.
Let the epoxy equivalent of an epoxy resin be the value measured by the method according to JISK7236:2009.
　エポキシ樹脂は、２５℃において、固体であってもよく、液体であってもよい。２５℃においてエポキシ樹脂が固体である場合、エポキシ樹脂の軟化点又は融点は特に制限されない。
　成形性と耐熱性とのバランスの観点からは、エポキシ樹脂の軟化点又は融点は、４０℃～１８０℃であることが好ましい。また、硬化性樹脂組成物の製造の際の取扱い性の観点からは、エポキシ樹脂の軟化点又は融点は、５０℃～１３０℃であることが好ましい。
　本開示において、軟化点は、ＪＩＳ　Ｋ　７２３４：１９８６の環球法により測定された値をいう。
　本開示において、融点は、ＪＩＳ　Ｋ　００６４：１９９２の目視による方法に則って測定された値をいう。 The epoxy resin may be solid or liquid at 25°C. If the epoxy resin is solid at 25°C, the softening point or melting point of the epoxy resin is not particularly limited.
From the viewpoint of the balance between moldability and heat resistance, the softening point or melting point of the epoxy resin is preferably 40°C to 180°C. Also, from the viewpoint of handleability during production of the curable resin composition, the softening point or melting point of the epoxy resin is preferably 50°C to 130°C.
In the present disclosure, softening point refers to a value measured by the ring and ball method of JIS K 7234:1986.
In the present disclosure, melting point refers to a value measured according to the visual observation method of JIS K 0064:1992.
　耐リフロー性、成形性、耐熱性等の観点から、エポキシ樹脂のＭｗは、５５０～１０５０であることが好ましく、６５０～９５０であることがより好ましい。
　また、耐リフロー性、成形性、耐熱性等の観点から、エポキシ樹脂のＭｎは、２５０～８００であることが好ましく、３５０～６００であることがより好ましい。 From the viewpoint of reflow resistance, moldability, heat resistance, etc., the Mw of the epoxy resin is preferably 550-1050, more preferably 650-950.
From the viewpoint of reflow resistance, moldability, heat resistance, etc., the Mn of the epoxy resin is preferably 250 to 800, more preferably 350 to 600.
　耐リフロー性、強度、流動性、成形性等の観点から、硬化性樹脂組成物の全質量に対するエポキシ樹脂の含有率は、０．５質量％～６０質量％であることが好ましく、２質量％～５０質量％であることがより好ましく、３質量％～４５質量％であることがさらに好ましい。 From the viewpoint of reflow resistance, strength, fluidity, moldability, etc., the content of the epoxy resin with respect to the total mass of the curable resin composition is preferably 0.5% by mass to 60% by mass, and 2% by mass. It is more preferably 50% by mass, and even more preferably 3% by mass to 45% by mass.
　本開示の硬化性樹脂組成物の耐リフロー性の観点から、エポキシ樹脂が特定共重合型エポキシ樹脂を含む場合、エポキシ樹脂の全質量に対する特定共重合型エポキシ樹脂の含有率は、５０質量％～９０質量％であることが好ましく、５５質量％～８０質量％であることがより好ましく、６０質量％～７５質量％であることがさらに好ましい。 From the viewpoint of reflow resistance of the curable resin composition of the present disclosure, when the epoxy resin contains a specific copolymerization type epoxy resin, the content of the specific copolymerization type epoxy resin with respect to the total weight of the epoxy resin is 50% by mass or more. It is preferably 90% by mass, more preferably 55% to 80% by mass, even more preferably 60% to 75% by mass.
　本開示の硬化性樹脂組成物の耐リフロー性の観点から、エポキシ樹脂がビフェニル型エポキシ樹脂を含む場合、エポキシ樹脂の全質量に対するビフェニル型エポキシ樹脂の含有率は、５質量％～４０質量％であることが好ましく、７質量％～３５質量％であることがより好ましく、１０質量％～３０質量％であることがさらに好ましい。 From the viewpoint of reflow resistance of the curable resin composition of the present disclosure, when the epoxy resin contains a biphenyl-type epoxy resin, the content of the biphenyl-type epoxy resin with respect to the total weight of the epoxy resin is 5% to 40% by weight. preferably 7% by mass to 35% by mass, and even more preferably 10% by mass to 30% by mass.
（フェノール系硬化剤）
　本開示の硬化性樹脂組成物は、フェノール系硬化剤を含有する。フェノール系硬化剤の種類は特に制限されず、硬化性樹脂組成物の成分として一般に使用されているものから選択できる。フェノール系硬化剤は、１種類を単独で用いても２種類以上を組み合わせて用いてもよい。 (Phenolic curing agent)
The curable resin composition of the present disclosure contains a phenolic curing agent. The type of phenol-based curing agent is not particularly limited, and can be selected from those commonly used as components of curable resin compositions. The phenol-based curing agents may be used singly or in combination of two or more.
　フェノール系硬化剤としては、例えば、１分子中に２個以上のフェノール性水酸基を有するフェノール樹脂及び多価フェノール化合物が挙げられる。
　フェノール系硬化剤の具体例を以下に記載するが、これらに限定されるものではない。
　フェノール系硬化剤としては、レゾルシン、カテコール、ビスフェノールＡ、ビスフェノールＦ、置換又は非置換のビフェノール等の多価フェノール化合物；フェノール、クレゾール、キシレノール、レゾルシン、カテコール、ビスフェノールＡ、ビスフェノールＦ、フェニルフェノール、アミノフェノール等のフェノール化合物及びα－ナフトール、β－ナフトール、ジヒドロキシナフタレン等のナフトール化合物からなる群より選ばれる少なくとも一種のフェノール性化合物と、ホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド等のアルデヒド化合物とを酸性触媒下で縮合又は共縮合させて得られるノボラック型フェノール樹脂；上記フェノール性化合物と、ジメトキシパラキシレン、ビス（メトキシメチル）ビフェニル等とから合成されるフェノールアラルキル樹脂、ナフトールアラルキル樹脂等のアラルキル型フェノール樹脂；パラキシリレン及び／又はメタキシリレン変性フェノール樹脂；メラミン変性フェノール樹脂；テルペン変性フェノール樹脂；上記フェノール性化合物と、ジシクロペンタジエンとから共重合により合成されるジシクロペンタジエン型フェノール樹脂及びジシクロペンタジエン型ナフトール樹脂；シクロペンタジエン変性フェノール樹脂；多環芳香環変性フェノール樹脂；ビフェニル型フェノール樹脂；上記フェノール性化合物と、ベンズアルデヒド、サリチルアルデヒド等の芳香族アルデヒド化合物とを酸性触媒下で縮合又は共縮合させて得られるトリフェニルメタン型フェノール樹脂；２－［４－［（２－ヒドロキシ－３－（２’－エチル）ヘキシル）オキシ］－２－ヒドロキシフェニル］－４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン等のトリアジン型フェノール樹脂；これら２種以上を共重合して得たフェノール樹脂などが挙げられる。 Phenolic curing agents include, for example, phenol resins and polyhydric phenol compounds having two or more phenolic hydroxyl groups in one molecule.
Specific examples of the phenol-based curing agent are described below, but are not limited to these.
Phenolic curing agents include 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, amino At least one phenolic compound selected from the group consisting of phenol compounds such as phenol and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene, and aldehyde compounds such as formaldehyde, acetaldehyde and propionaldehyde under an acidic catalyst. Novolac-type phenolic resins obtained by condensation or co-condensation; Phenolic aralkyl resins synthesized from the above phenolic compounds and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, etc., aralkyl-type phenolic resins such as naphthol aralkyl resins; Para-xylylene and / or metaxylylene-modified phenolic resin; melamine-modified phenolic resin; terpene-modified phenolic resin; Pentadiene-modified phenolic resin; Polycyclic aromatic ring-modified phenolic resin; Biphenyl-type phenolic resin; Triphenyl obtained by condensation or co-condensation of the above phenolic compound with an aromatic aldehyde compound such as benzaldehyde and salicylaldehyde in the presence of an acidic catalyst. Methane-type phenolic resin; 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1 triazine-type phenolic resins such as , 3,5-triazine; and phenolic resins obtained by copolymerizing two or more of these.
　本開示の硬化性樹脂組成物の耐リフロー性の観点から、フェノール系硬化剤は、アラルキル型フェノール樹脂及びノボラック型フェノール樹脂からなる群より選択される１つ以上のフェノール系硬化剤を含むことが好ましく、共に含むことがより好ましい。以下に、フェノール系硬化剤についてより具体的に説明するがこれらに限定されるものではない。 From the viewpoint of reflow resistance of the curable resin composition of the present disclosure, the phenolic curing agent may contain one or more phenolic curing agents selected from the group consisting of aralkyl-type phenolic resins and novolac-type phenolic resins. Preferably, both are included. The phenol-based curing agent will be described in more detail below, but it is not limited to these.
　アラルキル型フェノール樹脂は、特に限定されるものではなく、フェノール化合物及びナフトール化合物からなる群より選ばれる少なくとも１種と、ジメトキシパラキシレン、ビス（メトキシメチル）ビフェニル又はこれらの誘導体とから合成されるフェノール樹脂が挙げられる。
　アラルキル型フェノール樹脂の具体例としては、下記一般式（ＸＩＩ）～（ＸＩＶ）で表されるフェノール樹脂が挙げられる。
　式（ＸＩＩ）～（ＸＩＶ）において、Ｒ２３は水素原子又は炭素数１～１８の１価の有機基を表し、それぞれ全てが同一でも異なっていてもよい。Ｒ２２、Ｒ２４、Ｒ２５及びＲ２８は炭素数１～１８の１価の有機基を表し、それぞれ全てが同一でも異なっていてもよい。Ｒ２６及びＲ２７は水酸基又は炭素数１～１８の１価の有機基を表し、それぞれ全てが同一でも異なっていてもよい。ｉは各々独立に０～３の整数であり、ｊは各々独立に０～２の整数であり、ｋは各々独立に０～４の整数であり、ｐは各々独立に０～４の整数である。ｎは平均値であり、各々独立に０～１０の整数である。
　上記一般式におけるＲ２２等ついて記載した「それぞれ全てが同一でも異なっていてもよい」は、例えば、一般式（ＸＩＩ）中のｉ個のＲ２２の全てが同一でも相互に異なっていてもよいことを意味している。また、Ｒ２２～Ｒ３７は、それぞれが同一でも異なっていてもよい。例えば、Ｒ２２及びＲ２３の全てについて同一でも異なっていてもよい。 The aralkyl-type phenolic resin is not particularly limited, and a phenol synthesized from at least one selected from the group consisting of phenolic compounds and naphthol compounds and dimethoxyparaxylene, bis(methoxymethyl)biphenyl or derivatives thereof. resin.
Specific examples of aralkyl-type phenol resins include phenol resins represented by the following general formulas (XII) to (XIV).
In formulas (XII) to (XIV), R 23 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different. R 22 , R 24 , R 25 and R 28 each represent a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. R 26 and R 27 each represent a hydroxyl group or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. i is each independently an integer of 0 to 3, j is each independently an integer of 0 to 2, k is each independently an integer of 0 to 4, p is each independently an integer of 0 to 4 be. n is an average value, each independently an integer of 0 to 10;
"All may be the same or different" described for R 22 etc. in the above general formula means, for example, all i R 22 in general formula (XII) may be the same or different means that Further, R 22 to R 37 may be the same or different. For example, all of R 22 and R 23 may be the same or different.
　本開示の硬化性樹脂組成物の耐リフロー性の観点から、アラルキル型フェノール樹脂は、一般式（ＸＩＩＩ）で表されるフェノール樹脂が好ましい。
　本開示の硬化性樹脂組成物の耐リフロー性の観点から、また、一般式（ＸＩＩＩ）中、ｉ及びｋは共に０であることが好ましい。 From the viewpoint of reflow resistance of the curable resin composition of the present disclosure, the aralkyl-type phenol resin is preferably a phenol resin represented by general formula (XIII).
From the viewpoint of reflow resistance of the curable resin composition of the present disclosure, both i and k are preferably 0 in general formula (XIII).
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　アラルキル型フェノール樹脂はその他のフェノール樹脂との共重合型フェノール樹脂であってもよい。共重合型フェノール樹脂としては、トリフェニルメタン型フェノール樹脂とアラルキル型フェノール樹脂との共重合型フェノール樹脂、サリチルアルデヒド型フェノール樹脂とアラルキル型フェノール樹脂との共重合型フェノール樹脂、ノボラック型フェノール樹脂とアラルキル型フェノール樹脂との共重合型フェノール樹脂等が挙げられる。 The aralkyl-type phenolic resin may be a copolymerized phenolic resin with other phenolic resins. Copolymerized phenolic resins include copolymerized phenolic resins of triphenylmethane-type phenolic resin and aralkyl-type phenolic resin, copolymerized phenolic resins of salicylaldehyde-type phenolic resin and aralkyl-type phenolic resin, and novolac-type phenolic resin. A copolymer type phenol resin with an aralkyl type phenol resin and the like can be mentioned.
　ジシクロペンタジエン型フェノール樹脂は、ジシクロペンタジエン骨格を有する化合物を原料として得られるフェノール樹脂であれば特に限定されない。例えば、下記一般式（ＸＶ）で表されるフェノール樹脂が好ましい。 The dicyclopentadiene-type phenolic resin is not particularly limited as long as it is a phenolic resin obtained using a compound having a dicyclopentadiene skeleton as a raw material. For example, a phenol resin represented by the following general formula (XV) is preferred.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　式（ＸＶ）中、Ｒ２９は炭素数１～１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｉは各々独立に０～３の整数を示す。ｎは平均値であり、０～１０の整数を示す。 In formula (XV), R 29 represents a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. i each independently represents an integer of 0 to 3; n is an average value and represents an integer of 0-10.
　トリフェニルメタン型フェノール樹脂は、芳香族アルデヒド化合物を原料として得られるフェノール樹脂であれば特に限定されない。例えば、下記一般式（ＸＶＩ）で表されるフェノール樹脂が好ましい。 The triphenylmethane-type phenolic resin is not particularly limited as long as it is a phenolic resin obtained using an aromatic aldehyde compound as a raw material. For example, a phenol resin represented by the following general formula (XVI) is preferred.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　式（ＸＶＩ）中、Ｒ３０及びＲ３１は炭素数１～１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｉはそれぞれ独立に０～３の整数であり、ｋはそれぞれ独立に０～４の整数である。ｎは平均値であり、０～１０の整数である。 In formula (XVI), R 30 and R 31 each represent a monovalent organic group having 1 to 18 carbon atoms and may be the same or different. Each i is independently an integer of 0 to 3, and each k is independently an integer of 0 to 4. n is an average value and is an integer from 0 to 10;
　トリフェニルメタン型フェノール樹脂とアラルキル型フェノール樹脂との共重合型フェノール樹脂は、ベンズアルデヒド骨格を有する化合物を原料として得られるフェノール樹脂とアラルキル型フェノール樹脂との共重合型フェノール樹脂であれば特に限定されない。例えば、下記一般式（ＸＶＩＩ）で表されるフェノール樹脂が好ましい。 The copolymerized phenolic resin of triphenylmethane-type phenolic resin and aralkyl-type phenolic resin is not particularly limited as long as it is a copolymerized-type phenolic resin of phenolic resin obtained using a compound having a benzaldehyde skeleton as a raw material and aralkyl-type phenolic resin. . For example, a phenol resin represented by the following general formula (XVII) is preferred.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　式（ＸＶＩＩ）中、Ｒ３２～Ｒ３４は炭素数１～１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｉはそれぞれ独立に０～３の整数であり、ｋはそれぞれ独立に０～４の整数であり、ｑはそれぞれ独立に０～５の整数である。ｌ及びｍはそれぞれ平均値であり、それぞれ独立に０～１１の整数である。ただし、ｌとｍの合計は１～１１の整数である。 In formula (XVII), R 32 to R 34 each represent a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. Each i is independently an integer of 0 to 3, each k is independently an integer of 0 to 4, and each q is independently an integer of 0 to 5. l and m are average values and independently integers from 0 to 11. However, the sum of l and m is an integer of 1-11.
　ノボラック型フェノール樹脂は、フェノール化合物及びナフトール化合物からなる群より選ばれる少なくとも１種のフェノール性化合物と、アルデヒド化合物とを酸性触媒下で縮合又は共縮合させて得られるフェノール樹脂であれば特に限定されない。例えば、下記一般式（ＸＶＩＩＩ）で表されるフェノール樹脂が好ましい。 The novolak-type phenolic resin is not particularly limited as long as it is a phenolic resin obtained by condensation or co-condensation of at least one phenolic compound selected from the group consisting of phenolic compounds and naphthol compounds and an aldehyde compound in the presence of an acidic catalyst. . For example, a phenol resin represented by the following general formula (XVIII) is preferred.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　式（ＸＶＩＩＩ）中、Ｒ３５は水素原子又は炭素数１～１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。Ｒ３６は炭素数１～１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｉは各々独立に０～３の整数を示す。ｎは平均値であり、０～１０の整数を示す。 In formula (XVIII), R 35 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different. R 36 represents a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different. i each independently represents an integer of 0 to 3; n is an average value and represents an integer of 0-10.
　上記一般式（ＸＩＩ）～（ＸＶＩＩＩ）におけるＲ２２～Ｒ３６について記載した「それぞれ全てが同一でも異なっていてもよい」は、例えば、式（ＸＩＩ）中のｉ個のＲ２２の全てが同一でも相互に異なっていてもよいことを意味している。他のＲ２３～Ｒ３６についても、式中に含まれるそれぞれの個数について全てが同一でも相互に異なっていてもよいことを意味している。また、Ｒ２２～Ｒ３６は、それぞれが同一でも異なっていてもよい。例えば、Ｒ２２及びＲ２３の全てについて同一でも異なっていてもよく、Ｒ３０及びＲ３１の全てについて同一でも異なっていてもよい。 "All of which may be the same or different" described for R 22 to R 36 in the general formulas (XII) to (XVIII) means, for example, that all i R 22 in formula (XII) are the same However, it means that they may be different from each other. Other R 23 to R 36 also mean that the respective numbers contained in the formula may all be the same or different from each other. Also, 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.
　上記一般式（ＸＩＩ）～（ＸＶＩＩＩ）におけるｎは、０～１０の整数であることが好ましい。１０以下であると樹脂成分の溶融粘度が高くなりすぎず、硬化性樹脂の溶融成形時の粘度も低くなり、充填不良、ボンディングワイヤ（素子とリードを接続する金線）の変形等が発生し難くなる。１分子中の平均ｎは０～４の範囲に設定されることが好ましい。 n in the above general formulas (XII) to (XVIII) is preferably an integer of 0 to 10. If it is 10 or less, the melt viscosity of the resin component does not become too high, and the viscosity of the curable resin during melt molding becomes low, resulting in defective filling and deformation of the bonding wire (gold wire that connects the element and the lead). it gets harder. The average n in one molecule is preferably set in the range of 0-4.
　フェノール系硬化剤の水酸基当量は、特に制限されない。耐リフロー性、成形性、電気的信頼性等の各種特性バランスの観点からは、１０ｇ／ｅｑ～１０００ｇ／ｅｑであることが好ましく、３０ｇ／ｅｑ～５００ｇ／ｅｑであることがより好ましい。
　水酸基当量は、ＪＩＳ　Ｋ　００７０：１９９２に準拠して測定された水酸基価に基づいて算出された値をいう。 The hydroxyl equivalent of the phenolic curing agent is not particularly limited. From the viewpoint of the balance of various properties such as reflow resistance, moldability, and electrical reliability, it is preferably 10 g/eq to 1000 g/eq, more preferably 30 g/eq to 500 g/eq.
The hydroxyl equivalent refers to a value calculated based on the hydroxyl value measured according to JIS K 0070:1992.
　２５℃においてフェノール系硬化剤が固体である場合、その軟化点又は融点は、特に制限されない。成形性と耐熱性の観点からは、フェノール系硬化剤の軟化点又は融点は、４０℃～１８０℃であることが好ましい。また、硬化性樹脂組成物の製造時における取扱い性の観点からは、フェノール系硬化剤の軟化点又は融点は、５０℃～１３０℃であることが好ましい。 When the phenolic curing agent is solid at 25°C, its softening point or melting point is not particularly limited. From the viewpoint of moldability and heat resistance, the softening point or melting point of the phenolic curing agent is preferably 40°C to 180°C. Also, from the viewpoint of handleability during production of the curable resin composition, the softening point or melting point of the phenolic curing agent is preferably 50°C to 130°C.
　本開示の硬化性樹脂組成物の耐リフロー性の観点から、硬化性樹脂組成物の全質量に対するフェノール系硬化剤の含有率は、０．５質量％～４０質量％であることが好ましく、１質量％～３０質量％であることがより好ましく、２質量％～２０質量％であることがさらに好ましい。 From the viewpoint of reflow resistance of the curable resin composition of the present disclosure, the content of the phenolic curing agent with respect to the total mass of the curable resin composition is preferably 0.5% by mass to 40% by mass. It is more preferably from 2% by mass to 30% by mass, and even more preferably from 2% by mass to 20% by mass.
　本開示の硬化性樹脂組成物の耐リフロー性の観点から、フェノール系硬化剤がアラルキル型フェノール樹脂を含む場合、フェノール系硬化剤の全質量に対するアラルキル型フェノール樹脂の含有率は、６０質量％～９５質量％であることが好ましく、６５質量％～９０質量％であることがより好ましい。 From the viewpoint of reflow resistance of the curable resin composition of the present disclosure, when the phenol-based curing agent contains an aralkyl-type phenol resin, the content of the aralkyl-type phenol resin with respect to the total mass of the phenol-based curing agent is 60% by mass to It is preferably 95% by mass, more preferably 65% to 90% by mass.
　本開示の硬化性樹脂組成物の耐リフロー性の観点から、フェノール系硬化剤がノボラック型フェノール樹脂を含む場合、フェノール系硬化剤の全質量に対するノボラック型フェノール樹脂の含有率は、５質量％～４０質量％であることが好ましく、１０質量％～３０質量％であることがより好ましい。 From the viewpoint of reflow resistance of the curable resin composition of the present disclosure, when the phenolic curing agent contains a novolak-type phenolic resin, the content of the novolac-type phenolic resin with respect to the total mass of the phenolic curing agent is 5% by mass to It is preferably 40% by mass, more preferably 10% to 30% by mass.
（各種添加材）
　本開示の硬化性樹脂組成物は、上述の成分に加えて、硬化促進剤、無機充填剤、カップリング剤、応力緩和剤、離型剤、着色剤、難燃剤、イオン交換体、エポキシ樹脂以外の樹脂、フェノール系硬化剤以外の硬化剤等の各種添加材を含有していてもよい。硬化性樹脂組成物は、以下に例表する添加材以外にも必要に応じて当技術分野で周知の各種添加材を含有していてもよい。 (Various additives)
In addition to the components described above, the curable resin composition of the present disclosure includes a curing accelerator, an inorganic filler, a coupling agent, a stress relaxation agent, a mold release agent, a coloring agent, a flame retardant, an ion exchanger, other than an epoxy resin. It may also contain various additives such as a resin and a curing agent other than a phenol-based curing agent. The curable resin composition may contain various additives known in the art as necessary, in addition to the additives exemplified below.
（硬化促進剤）
　本開示の硬化性樹脂組成物は、硬化促進剤を含有してもよい。硬化促進剤の種類は特に制限されず、エポキシ樹脂の種類、硬化性樹脂組成物の所望の特性等に応じて選択できる。 (Curing accelerator)
The curable resin composition of the present disclosure 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 curable resin composition, and the like.
　硬化性及び流動性の観点からは、硬化促進剤はホスホニウム化合物を含むことが好ましい。ホスホニウム化合物として具体的には、トリフェニルホスフィン、ジフェニル（ｐ－トリル）ホスフィン、トリス（アルキルフェニル）ホスフィン、トリス（アルコキシフェニル）ホスフィン、トリス（アルキル・アルコキシフェニル）ホスフィン、トリス（ジアルキルフェニル）ホスフィン、トリス（トリアルキルフェニル）ホスフィン、トリス（テトラアルキルフェニル）ホスフィン、トリス（ジアルコキシフェニル）ホスフィン、トリス（トリアルコキシフェニル）ホスフィン、トリス（テトラアルコキシフェニル）ホスフィン、トリアルキルホスフィン、ジアルキルアリールホスフィン、アルキルジアリールホスフィン等の三級ホスフィンと、無水マレイン酸、１，４－ベンゾキノン、２，５－トルキノン、１，４－ナフトキノン、２，３－ジメチルベンゾキノン、２，６－ジメチルベンゾキノン、２，３－ジメトキシ－５－メチル－１，４－ベンゾキノン、２，３－ジメトキシ－１，４－ベンゾキノン、フェニル－１，４－ベンゾキノン等のキノン化合物、ジアゾフェニルメタンなどの、π結合をもつ化合物を付加してなる分子内分極を有する化合物；三級ホスフィンと４－ブロモフェノール、３－ブロモフェノール、２－ブロモフェノール、４－クロロフェノール、３－クロロフェノール、２－クロロフェノール、４－ヨウ化フェノール、３－ヨウ化フェノール、２－ヨウ化フェノール、４－ブロモ－２－メチルフェノール、４－ブロモ－３－メチルフェノール、４－ブロモ－２，６－ジメチルフェノール、４－ブロモ－３，５－ジメチルフェノール、４－ブロモ－２，６－ジ－ｔｅｒｔ－ブチルフェノール、４－クロロ－１－ナフトール、１－ブロモ－２－ナフトール、６－ブロモ－２－ナフトール、４－ブロモ－４’－ヒドロキシビフェニル等のハロゲン化フェノール化合物を反応させた後に、脱ハロゲン化水素の工程を経て得られる、分子内分極を有する化合物；テトラフェニルホスホニウム等のテトラ置換ホスホニウムとテトラ－ｐ－トリルボレート等のテトラ置換ボレートとの塩；テトラ置換ホスホニウムとフェノール化合物からプロトンが脱離したアニオンとの塩、テトラ置換ホスホニウムとカルボン酸化合物からプロトンが脱離したアニオンとの塩、などが挙げられる。 From the viewpoint of curability and fluidity, the curing accelerator preferably contains a phosphonium compound. Specific examples of 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, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy- quinone compounds such as 5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, and compounds having a π bond such as diazophenylmethane Compounds with intramolecular polarization; tertiary phosphines and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodinated phenol, 3-iodine phenol, 2-iodinated phenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4 Halogenation of -bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl, etc. A compound having intramolecular polarization obtained through a step of dehydrohalogenation after reacting a phenolic compound; a salt of a tetra-substituted phosphonium such as tetraphenylphosphonium and a tetra-substituted borate such as tetra-p-tolylborate; A salt of a tetra-substituted phosphonium and an anion resulting from deprotonation from a phenol compound, a salt of a tetra-substituted phosphonium and an anion resulting from deprotonation from a carboxylic acid compound, and the like.
　上記ホスホニウム化合物は、下記一般式（Ｉ－１）で表される化合物（以下、特定硬化促進剤とも称する）を含むことが好ましい。 The phosphonium compound preferably contains a compound represented by the following general formula (I-1) (hereinafter also referred to as a specific curing accelerator).
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　式（Ｉ－１）中、Ｒ１～Ｒ３は、各々独立して、炭素数１～１８の炭化水素基であり、Ｒ１～Ｒ３のうち２以上が互いに結合して環状構造を形成してもよく、Ｒ４～Ｒ７は、各々独立して、水素原子、水酸基又は炭素数１～１８の有機基であり、Ｒ４～Ｒ７のうち２以上が互いに結合して環状構造を形成してもよい。 In formula (I-1), 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 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. may be formed.
　一般式（Ｉ－１）のＲ１～Ｒ３として記載した「炭素数１～１８の炭化水素基」は、炭素数が１～１８である脂肪族炭化水素基及び炭素数が６～１８である芳香族炭化水素基を含む。 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.
　流動性の観点からは、炭素数１～１８の脂肪族炭化水素基は炭素数１～８であることが好ましく、２～６であることがより好ましく、４～６であることがさらに好ましい。 From the viewpoint of fluidity, 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.
　炭素数１～１８の脂肪族炭化水素基は、炭素数１～１８の直鎖又は分岐状の脂肪族炭化水素基であっても、炭素数３～１８の脂環式炭化水素基であってもよい。製造しやすさの観点からは、直鎖又は分岐状の脂肪族炭化水素基であることが好ましい。 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.
　炭素数１～１８の直鎖又は分岐状の脂肪族炭化水素基として具体的には、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔ－ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基等のアルキル基、アリル基、ビニル基などが挙げられる。直鎖又は分岐状の脂肪族炭化水素基は、置換基を有していても有していなくてもよい。置換基としては、メトキシ基、エトキシ基、ｎ－ブトキシ基、ｔ－ブトキシ基等のアルコキシ基、フェニル基、ナフチル基等のアリール基、水酸基、アミノ基、ハロゲン原子などが挙げられる。直鎖又は分岐状の脂肪族炭化水素基は２以上の置換基を有してもよく、その場合の置換基は同じでも異なっていてもよい。直鎖又は分岐状の脂肪族炭化水素基が置換基を有する場合、脂肪族炭化水素基と置換基に含まれる炭素数の合計が１～１８であることが好ましい。硬化性の観点からは無置換のアルキル基が好ましく、炭素数１～８の無置換のアルキル基がより好ましく、ｎ－ブチル基、イソブチル基、ｎ－ペンチル基、ｎ－ヘキシル基及びｎ－オクチル基がさらに好ましい。 Specific examples of linear or branched aliphatic hydrocarbon groups having 1 to 18 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, Alkyl groups such as t-butyl group, 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. Examples of substituents include alkoxy groups such as methoxy group, ethoxy group, n-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. From the viewpoint of curability, 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.
　炭素数３～１８の脂環式炭化水素基として具体的には、シクロペンチル基、シクロヘキシル基、シクロヘプチル基等のシクロアルキル基、シクロペンテニル基、シクロヘキセニル基等のシクロアルケニル基などが挙げられる。脂環式炭化水素基は、置換基を有していても有していなくてもよい。置換基としては、メチル基、エチル基、ｎ－ブチル基、ｔ－ブチル基等のアルキル基、メトキシ基、エトキシ基、ｎ－ブトキシ基、ｔ－ブトキシ基等のアルコキシ基、フェニル基、ナフチル基等のアリール基、水酸基、アミノ基、ハロゲン原子などが挙げられる。脂環式炭化水素基は２以上の置換基を有してもよく、その場合の置換基は同じでも異なっていてもよい。脂環式炭化水素基が置換基を有する場合、脂環式炭化水素基と置換基に含まれる炭素数の合計が３～１８であることが好ましい。脂環式炭化水素基が置換基を有する場合、置換基の位置は特に限定されない。硬化性の観点からは無置換のシクロアルキル基が好ましく、炭素数４～１０の無置換のシクロアルキル基がより好ましく、シクロヘキシル基、シクロペンチル基及びシクロヘプチル基がさらに好ましい。 Specific examples of alicyclic hydrocarbon groups 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. Examples of substituents include alkyl groups such as methyl group, ethyl group, n-butyl group and t-butyl group, alkoxy groups such as methoxy group, ethoxy group, n-butoxy group and t-butoxy group, phenyl group and naphthyl group. aryl groups, hydroxyl groups, amino groups, halogen atoms, and the like. An alicyclic hydrocarbon group may have two or more substituents, in which case the substituents may be the same or different. When the alicyclic hydrocarbon group has a substituent, the total number of carbon atoms contained in the alicyclic hydrocarbon group and the substituent is preferably 3-18. When the alicyclic hydrocarbon group has a substituent, 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 more preferable.
　炭素数が６～１８である芳香族炭化水素基は炭素数６～１４であることが好ましく、６～１０であることがより好ましい。芳香族炭化水素基は置換基を有していても、有していなくてもよい。置換基としては、メチル基、エチル基、ｎ－ブチル基、ｔ－ブチル基等のアルキル基、メトキシ基、エトキシ基、ｎ－ブトキシ基、ｔ－ブトキシ基等のアルコキシ基、フェニル基、ナフチル基等のアリール基、水酸基、アミノ基、ハロゲン原子などが挙げられる。芳香族炭化水素基は２以上の置換基を有してもよく、その場合の置換基は同じでも異なっていてもよい。芳香族炭化水素基が置換基を有する場合、芳香族炭化水素基と置換基に含まれる炭素数の合計が６～１８であることが好ましい。芳香族炭化水素基が置換基を有する場合、置換基の位置は特に限定されない。 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. Examples of substituents include alkyl groups such as methyl group, ethyl group, n-butyl group and t-butyl group, alkoxy groups such as methoxy group, ethoxy group, n-butoxy group and t-butoxy group, phenyl group and naphthyl group. aryl groups, hydroxyl groups, amino groups, halogen atoms, and the like. The aromatic hydrocarbon group may have two or more substituents, in which case the substituents may be the same or different. When 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. When the aromatic hydrocarbon group has a substituent, the position of the substituent is not particularly limited.
　炭素数が６～１８である芳香族炭化水素基として具体的には、フェニル基、１－ナフチル基、２－ナフチル基、トリル基、ジメチルフェニル基、エチルフェニル基、ブチルフェニル基、ｔ－ブチルフェニル基、メトキシフェニル基、エトキシフェニル基、ｎ－ブトキシフェニル基、ｔ－ブトキシフェニル基等が挙げられる。これらの芳香族炭化水素基における置換基の位置はオルト位、メタ位及びパラ位のうちいずれでもよい。流動性の観点からは、無置換で炭素数が６～１２又は置換基を含めた炭素数が６～１２のアリール基が好ましく、無置換で炭素数が６～１０又は置換基を含めた炭素数６～１０のアリール基がより好ましく、フェニル基、ｐ－トリル基及びｐ－メトキシフェニル基がさらに好ましい。 Specific examples of aromatic hydrocarbon groups having 6 to 18 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, tolyl, dimethylphenyl, ethylphenyl, butylphenyl and t-butyl. phenyl group, methoxyphenyl group, ethoxyphenyl group, n-butoxyphenyl group, t-butoxyphenyl group and the like. The position of the substituent in these aromatic hydrocarbon groups may be any of the ortho position, meta position and para position. From the viewpoint of fluidity, 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 carbon atoms including substituents An aryl group of numbers 6 to 10 is more preferred, and a phenyl group, p-tolyl group and p-methoxyphenyl group are even more preferred.
　一般式（Ｉ－１）のＲ１～Ｒ３として記載した用語「Ｒ１～Ｒ３のうち２以上が互いに結合して環状構造を形成してもよい」とは、Ｒ１～Ｒ３のうち２個又は３個が結合し、全体としてひとつの２価又は３価の炭化水素基となる場合を意味する。この場合のＲ１～Ｒ３の例としては、リン原子と結合して環状構造を形成し得るエチレン、プロピレン、ブチレン、ペンチレン、ヘキシレン等のアルキレン基、エチレニレン、プロピレニレン、ブチレニレン基等のアルケニレン基、メチレンフェニレン基等のアラルキレン基、フェニレン、ナフチレン、アントラセニレン等のアリーレン基などの、リン原子と結合して環状構造を形成しうる置換基が挙げられる。これらの置換基はさらにアルキル基、アルコキシ基、アリール基、アリールオキシ基、アミノ基、水酸基、ハロゲン原子等で置換されていてもよい。 The term “two or more of 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. Examples of R 1 to R 3 in this case 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; Substituents capable of forming a cyclic 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, can be mentioned. These substituents may be further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, halogen atoms and the like.
　上記一般式（Ｉ－１）のＲ４～Ｒ７として記載した「炭素数１～１８の有機基」は、炭素数１～１８であり、かつ置換されても置換されていなくてもよい脂肪族炭化水素基、芳香族炭化水素基、脂肪族炭化水素オキシ基、芳香族炭化水素オキシ基、アシル基、炭化水素オキシカルボニル基、及びアシルオキシ基を含むことを意味する。 The “organic group having 1 to 18 carbon atoms” described as R 4 to R 7 in general formula (I-1) above is an aliphatic group having 1 to 18 carbon atoms which may or may not be substituted. It is meant to include aromatic hydrocarbon groups, aromatic hydrocarbon groups, aliphatic hydrocarbon oxy groups, aromatic hydrocarbon oxy groups, acyl groups, hydrocarbon oxycarbonyl groups, and acyloxy groups.
　上記脂肪族炭化水素基及び芳香族炭化水素基の例としては、Ｒ１～Ｒ３で表される脂肪族炭化水素基及び芳香族炭化水素基の例として上述したものが挙げられる。 Examples of the 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 .
　上記脂肪族炭化水素オキシ基としては、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基、２－ブトキシ基、ｔ－ブトキシ基、シクロプロピルオキシ基、シクロヘキシルオキシ基、シクロペンチルオキシ基、アリルオキシ基、ビニルオキシ基等の上述の脂肪族炭化水素基に酸素原子が結合した構造のオキシ基、これらの脂肪族炭化水素オキシ基がさらにアルキル基、アルコキシ基、アリール基、アリールオキシ基、アミノ基、水酸基、ハロゲン原子等で置換されたものなどが挙げられる。 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.
　上記芳香族炭化水素オキシ基としては、フェノキシ基、メチルフェノキシ基、エチルフェノキシ基、メトキシフェノキシ基、ブトキシフェノキシ基、フェノキシフェノキシ基等の上述の芳香族炭化水素基に酸素原子が結合した構造のオキシ基、これらの芳香族炭化水素オキシ基がさらにアルキル基、アルコキシ基、アリール基、アリールオキシ基、アミノ基、ハロゲン原子等で置換されたものなどが挙げられる。 Examples of the aromatic hydrocarbon oxy group 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. groups, and those in which these aromatic hydrocarbon oxy groups are further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, and the like.
　上記アシル基としては、ホルミル基、アセチル基、エチルカルボニル基、ブチリル基、シクロヘキシルカルボニル基、アリルカルボニル等の脂肪族炭化水素カルボニル基、フェニルカルボニル基、メチルフェニルカルボニル基等の芳香族炭化水素カルボニル基等、これらの脂肪族炭化水素カルボニル基又は芳香族炭化水素カルボニル基がさらにアルキル基、アルコキシ基、アリール基、アリールオキシ基、アミノ基、ハロゲン原子等で置換されたものなどが挙げられる。 Examples of the acyl group 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.
　上記炭化水素オキシカルボニル基としては、メトキシカルボニル基、エトキシカルボニル基、ブトキシカルボニル基、アリルオキシカルボニル基、シクロヘキシルオキシカルボニル基等の脂肪族炭化水素オキシカルボニル基、フェノキシカルボニル基、メチルフェノキシカルボニル基等の芳香族炭化水素オキシカルボニル基、これらの脂肪族炭化水素カルボニルオキシ基又は芳香族炭化水素カルボニルオキシ基がさらにアルキル基、アルコキシ基、アリール基、アリールオキシ基、アミノ基、ハロゲン原子等で置換されたものなどが挙げられる。 Examples of the hydrocarbon oxycarbonyl group 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.
　上記アシルオキシ基としては、メチルカルボニルオキシ基、エチルカルボニルオキシ基、ブチルカルボニルオキシ基、アリルカルボニルオキシ基、シクロヘキシルカルボニルオキシ基等の脂肪族炭化水素カルボニルオキシ基、フェニルカルボニルオキシ基、メチルフェニルカルボニルオキシ基等の芳香族炭化水素カルボニルオキシ基、これらの脂肪族炭化水素カルボニルオキシ基又は芳香族炭化水素カルボニルオキシ基がさらにアルキル基、アルコキシ基、アリール基、アリールオキシ基、アミノ基、ハロゲン原子等で置換されたものなどが挙げられる。 Examples of the acyloxy group 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.
　上記一般式（Ｉ－１）のＲ４～Ｒ７として記載した用語「Ｒ４～Ｒ７のうち２以上が互いに結合して環状構造を形成してもよい」とは、２個～４個のＲ４～Ｒ７が結合し、全体としてひとつの２価～４価の有機基を形成してもよいことを意味する。この場合のＲ４～Ｒ７としては、エチレン、プロピレン、ブチレン、ペンチレン、ヘキシレン等のアルキレン基、エチレニレン、プロピレニレン、ブチレニレン等のアルケニレン基、メチレンフェニレン等のアラルキレン基、フェニレン、ナフチレン、アントラセニレン等のアリーレン基などの環状構造を形成しうる置換基、これらのオキシ基又はジオキシ基などが挙げられる。これらの置換基はさらにアルキル基、アルコキシ基、アリール基、アリールオキシ基、アミノ基、水酸基、ハロゲン原子等で置換されていてもよい。 The term “two or more of R 4 to R 7 may combine with each other to form a cyclic structure” described as R 4 to R 7 in the general formula (I-1) means that two to four may be combined to form one divalent to tetravalent organic group as a whole. In this case, 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.
　上記一般式（Ｉ－１）のＲ４～Ｒ７としては、特に限定されるものではない。例えば、各々独立に、水素原子、水酸基、置換又は非置換のアルキル基、置換又は非置換のアリール基、置換又は非置換のアルコキシ基、又は置換又は非置換のアリールオキシ基から選択されることが好ましい。中でも原料の入手しやすさの観点からは、水素原子、水酸基、非置換若しくはアルキル基及びアルコキシ基からなる群より選ばれる少なくとも１つで置換されたアリール基、又は鎖状若しくは環状のアルキル基が好ましい。非置換又はアルキル基及びアルコキシ基からなる群より選ばれる少なくとも１つで置換されたアリール基としては、フェニル基、ｐ－トリル基、ｍ－トリル基、ｏ－トリル基、ｐ－メトキシフェニル基等が挙げられる。鎖状又は環状のアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、２－ブチル基、ｔ－ブチル基、オクチル基、シクロヘキシル基等が挙げられる。硬化性の観点からは、Ｒ４～Ｒ７はすべて水素原子である場合か、又はＲ４～Ｒ７の少なくとも一つが水酸基であり、残りがすべて水素原子である場合が好ましい。 R 4 to R 7 in general formula (I-1) are not particularly limited. For example, each 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. preferable. Among them, from the viewpoint of availability of raw materials, 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, n-propyl, isopropyl, n-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.
　一般式（Ｉ－１）においてより好ましくは、Ｒ１～Ｒ３のうち２個以上が炭素数１～１８のアルキル基又は炭素数３～１８のシクロアルキル基であり、Ｒ４～Ｒ７がすべて水素原子であるか、少なくとも一つが水酸基であり残りがすべて水素原子である。さらに好ましくは、Ｒ１～Ｒ３のすべてが炭素数１～１８のアルキル基又は炭素数３～１８のシクロアルキル基であり、Ｒ４～Ｒ７がすべて水素原子であるか、少なくとも一つが水酸基であり残りがすべて水素原子である。 More preferably, two or more of 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, and 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. More preferably, 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, and 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.
　速硬化性の観点からは、特定硬化促進剤は、下記一般式（Ｉ－２）で表される化合物を含むことが好ましい。 From the viewpoint of rapid curing, the specific curing accelerator preferably contains a compound represented by the following general formula (I-2).
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　式（Ｉ－２）中、Ｒ１～Ｒ３は、各々独立して、炭素数１～１８の炭化水素基であり、Ｒ１～Ｒ３のうち２以上が互いに結合して環状構造を形成してもよく、Ｒ４～Ｒ６は、各々独立して、水素原子又は炭素数１～１８の有機基であり、Ｒ４～Ｒ６のうち２以上が互いに結合して環状構造を形成してもよい。 In 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 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
　一般式（Ｉ－２）におけるＲ１～Ｒ６の具体例はそれぞれ一般式（Ｉ－１）におけるＲ１～Ｒ６の具体例と同様であり、好ましい範囲も同様である。 Specific examples of 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.
　特定硬化促進剤は、例えば、第三ホスフィン化合物とキノン化合物との付加物として得ることができる。
　第三ホスフィン化合物として具体的には、トリフェニルホスフィン、トリブチルホスフィン、ジブチルフェニルホスフィン、ブチルジフェニルホスフィン、エチルジフェニルホスフィン、トリフェニルホスフィン、トリス（４－メチルフェニル）ホスフィン、トリス（４－エチルフェニル）ホスフィン、トリス（４－ｎ－プロピルフェニル）ホスフィン、トリス（４－ｎ－ブチルフェニル）ホスフィン、トリス（イソプロピルフェニル）ホスフィン、トリス（ｔ－ブチルフェニル）ホスフィン、トリス（２，４－ジメチルフェニル）ホスフィン、トリス（２，６－ジメチルフェニル）ホスフィン、トリス（２，４，６－トリメチルフェニル）ホスフィン、トリス（２，６－ジメチル－４－エトキシフェニル）ホスフィン、トリス（４－メトキシフェニル）ホスフィン、トリス（４－エトキシフェニル）ホスフィン等が挙げられる。成形性の観点からは、トリフェニルホスフィン及びトリブチルホスフィンが好ましい。 A specific curing accelerator can be obtained, for example, as an adduct of a tertiary phosphine compound and a quinone compound.
Specific examples of the third phosphine compound include triphenylphosphine, tributylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, tris(4-methylphenyl)phosphine, and tris(4-ethylphenyl)phosphine. , tris(4-n-propylphenyl)phosphine, tris(4-n-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.
　キノン化合物として具体的には、１，２－ベンゾキノン、１，４－ベンゾキノン、ジフェノキノン、１，４－ナフトキノン、アントラキノン等が挙げられる。耐湿性と保存安定性の観点からは、１，４－ベンゾキノンが好ましい。 Specific examples of quinone compounds include 1,2-benzoquinone, 1,4-benzoquinone, diphenoquinone, 1,4-naphthoquinone, and anthraquinone. From the viewpoint of moisture resistance and storage stability, 1,4-benzoquinone is preferred.
　特定硬化促進剤の具体例としては、トリフェニルホスフィンと１，４－ベンゾキノンの付加反応物、トリ－ｎ－ブチルホスフィンと１，４－ベンゾキノンの付加反応物、トリシクロヘキシルホスフィンと１，４－ベンゾキノンの付加反応物、ジシクロヘキシルフェニルホスフィンと１，４－ベンゾキノンの付加反応物、シクロヘキシルジフェニルホスフィンと１，４－ベンゾキノンの付加反応物、トリイソブチルホスフィンと１，４－ベンゾキノンの付加反応物、トリシクロペンチルホスフィンと１，４－ベンゾキノンの付加反応物等が挙げられる。 Specific examples of 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.
　硬化性樹脂組成物は、ホスホニウム化合物以外の硬化促進剤を含有してもよい。
　ホスホニウム化合物以外の硬化促進剤として具体的には、１，５－ジアザビシクロ［４．３．０］ノネン－５（ＤＢＮ）、１，８－ジアザビシクロ［５．４．０］ウンデセン－７（ＤＢＵ）等のジアザビシクロアルケン、２－メチルイミダゾール、２－フェニルイミダゾール、２－フェニル－４－メチルイミダゾール、２－ヘプタデシルイミダゾール等の環状アミジン化合物；前記環状アミジン化合物の誘導体；前記環状アミジン化合物又はその誘導体のフェノールノボラック塩；これらの化合物に無水マレイン酸、１，４－ベンゾキノン、２，５－トルキノン、１，４－ナフトキノン、２，３－ジメチルベンゾキノン、２，６－ジメチルベンゾキノン、２，３－ジメトキシ－５－メチル－１，４－ベンゾキノン、２，３－ジメトキシ－１，４－ベンゾキノン、フェニル－１，４－ベンゾキノン等のキノン化合物、ジアゾフェニルメタンなどの、π結合をもつ化合物を付加してなる分子内分極を有する化合物；ＤＢＵのテトラフェニルボレート塩、ＤＢＮのテトラフェニルボレート塩、２－エチル－４－メチルイミダゾールのテトラフェニルボレート塩、Ｎ－メチルモルホリンのテトラフェニルボレート塩等の環状アミジニウム化合物；ピリジン、トリエチルアミン、トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス（ジメチルアミノメチル）フェノール等の三級アミン化合物；前記三級アミン化合物の誘導体；酢酸テトラ－ｎ－ブチルアンモニウム、リン酸テトラ－ｎ－ブチルアンモニウム、酢酸テトラエチルアンモニウム、安息香酸テトラ－ｎ－ヘキシルアンモニウム、水酸化テトラプロピルアンモニウム等のアンモニウム塩化合物などが挙げられる。 The curable resin composition may contain a curing accelerator other than the phosphonium compound.
Specific examples of 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 π bonds such as diazophenylmethane. 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. Compounds; 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.
　硬化性樹脂組成物が硬化促進剤として特定硬化促進剤を含む場合、硬化促進剤の全質量に対する特定硬化促進剤の含有率は、３０質量％以上であることが好ましく、５０質量％以上であることがより好ましく、７０質量％以上であることがさらに好ましい。 When the curable resin composition contains a specific curing accelerator as a curing accelerator, the content of the specific curing accelerator with respect to the total mass of the curing accelerator is preferably 30% by mass or more, and is 50% by mass or more. is more preferable, and 70% by mass or more is even more preferable.
　硬化性樹脂組成物が硬化促進剤を含有する場合、樹脂成分の全質量に対する硬化促進剤の含有率は、
０．１質量％～３０質量％であることが好ましく、１質量％～１５質量％であることがより好ましい。樹脂成分の全質量に対する硬化促進剤の含有率が０．１質量％以上であると、硬化性樹脂組成物が、短時間で良好に硬化する傾向にある。樹脂成分の全質量に対する硬化促進剤の含有率が３０質量％以下であると、硬化性樹脂組成物の硬化速度が速すぎず良好な成形品が得られる傾向にある。 When the curable resin composition contains a curing accelerator, the content of the curing accelerator with respect to the total mass of the resin component is
It is preferably 0.1% by mass to 30% by mass, more preferably 1% by mass to 15% by mass. When the content of the curing accelerator with respect to the total mass of the resin component is 0.1% by mass or more, the curable resin composition tends to cure satisfactorily in a short time. When the content of the curing accelerator with respect to the total mass of the resin component is 30% by mass or less, the curing rate of the curable resin composition is not too fast, and good molded articles tend to be obtained.
（無機充填材）
　本開示の硬化性樹脂組成物は、無機充填材を含有してもよい。硬化性樹脂組成物が無機充填材を含有することで、硬化性樹脂組成物の吸湿性が低減し、硬化状態での強度が向上する傾向にある。硬化性樹脂組成物を半導体パッケージの封止材として用いる場合には、無機充填材を含有することが好ましい。 (Inorganic filler)
The curable resin composition of the present disclosure may contain inorganic fillers. When the curable resin composition contains an inorganic filler, the hygroscopicity of the curable resin composition tends to decrease, and the strength in the cured state tends to improve. When the curable resin composition is used as a sealing material for semiconductor packages, it preferably contains an inorganic filler.
　無機充填材の種類は、特に制限されない。具体的には、球状シリカ、結晶シリカ等のシリカ、ガラス、アルミナ、炭酸カルシウム、ケイ酸ジルコニウム、ケイ酸カルシウム、窒化珪素、窒化アルミ、窒化ホウ素、ベリリア、ジルコニア、ジルコン、フォステライト、ステアタイト、スピネル、ムライト、チタニア、タルク、クレー、マイカなどの無機材料が挙げられる。難燃効果を有する無機充填材を用いてもよい。難燃効果を有する無機充填材としては、水酸化アルミニウム、水酸化マグネシウム、マグネシウムと亜鉛の複合水酸化物等の複合金属水酸化物、硼酸亜鉛などが挙げられる。中でも、線膨張係数低減の観点からは球状シリカが好ましく、高熱伝導性の観点からはアルミナが好ましい。無機充填材は１種類を単独で用いても２種類以上を組み合わせて用いてもよい。無機充填材の状態としては粉未、粉末を球形化したビーズ、繊維等が挙げられる。
　無機充填材は１種類を単独で用いても２種類以上を組み合わせて用いてもよい。 The type of inorganic filler is not particularly limited. Specifically, silica such as spherical silica and crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, Inorganic materials such as 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. Among them, spherical silica is preferable from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferable from the viewpoint of high thermal conductivity. An inorganic filler may be used individually by 1 type, or may be used in combination of 2 or more types. Examples of the state of the inorganic filler include powders, beads obtained by spheroidizing powders, fibers, and the like.
An inorganic filler may be used individually by 1 type, or may be used in combination of 2 or more types.
　無機充填材の形状は特に制限されず、粉状、球状、繊維状等の形状が挙げられる。硬化性樹脂組成物の成形時の流動性及び金型摩耗性の点からは、球状であることが好ましい。 The shape of the inorganic filler is not particularly limited, and examples include powdery, spherical, and fibrous shapes. From the viewpoints of fluidity during molding of the curable resin composition and resistance to mold wear, it is preferably spherical.
　無機充填材の平均粒子径は、特に制限されない。硬化性樹脂組成物の粘度、充填性等のバランスの観点からは、無機充填材の体積平均粒子径は、０．１μｍ～５０μｍであることが好ましく、０．３μｍ～３０μｍであることがより好ましく、０．５μｍ～２５μｍであることがさらに好ましい。
　無機充填材の平均粒子径は、レーザー回折散乱法粒度分布測定装置により、体積平均粒子径（Ｄ５０）として測定することができる。
　体積平均粒子径は、公知の方法によって測定することができる。一例として、有機溶剤、硝酸、王水等を用いて、硬化性樹脂組成物又は樹脂硬化物から無機充填材を抽出し、超音波分散機等で充分に分散して分散液を調製する。この分散液を用いて、レーザー回折散乱法粒度分布測定装置により測定される体積基準の粒度分布から、無機充填材の体積平均粒子径を測定することができる。あるいは、樹脂硬化物を透明なエポキシ樹脂等に埋め込み、研磨して得られる断面を走査型電子顕微鏡にて観察して得られる体積基準の粒度分布から、無機充填材の体積平均粒子径を測定することができる。さらには、ＦＩＢ装置（集束イオンビームＳＥＭ）等を用いて、樹脂硬化物の二次元の断面観察を連続的に行い、三次元構造解析を行なうことで測定することもできる。 The average particle size of the inorganic filler is not particularly limited. From the viewpoint of the balance between the viscosity of the curable resin composition and the filling property, etc., the volume average particle size of the inorganic filler is preferably 0.1 μm to 50 μm, more preferably 0.3 μm to 30 μm. , 0.5 μm to 25 μm.
The average particle size of the inorganic filler can be measured as the volume average particle size (D50) with a laser diffraction scattering method particle size distribution analyzer.
A volume average particle diameter can be measured by a known method. As an example, an inorganic filler is extracted from a curable resin composition or cured resin using an organic solvent, nitric acid, aqua regia, etc., and 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. Alternatively, the volume-average particle size of the inorganic filler is measured from the volume-based particle size distribution obtained by embedding the cured resin in a transparent epoxy resin or the like and polishing the resulting cross-section with a scanning electron microscope. be able to. Furthermore, it is also possible to continuously observe a two-dimensional cross-section of the cured resin material using an FIB device (focused ion beam SEM) or the like, and perform measurement by performing three-dimensional structural analysis.
　硬化性樹脂組成物が無機充填材を含有する場合、その含有率は特に制限されない。硬化性樹脂組成物の全質量に対する無機充填剤の含有率は、３０質量％～９０質量％であることが好ましく、３５質量％～８０質量％であることがより好ましく、４０質量％～７０質量％であることがさらに好ましい。
　硬化性樹脂組成物の全質量に対する無機充填材の含有率が３０質量％以上であると、樹脂硬化物の熱膨張係数、熱伝導率、弾性率等の特性がより向上する傾向にある。
　硬化性樹脂組成物の全質量に対する無機充填材の含有率が９０質量％以下であると、硬化性樹脂組成物の粘度の上昇が抑制され、流動性がより向上して成形性がより良好になる傾向にある。 When the curable resin composition contains an inorganic filler, its content is not particularly limited. The content of the inorganic filler with respect to the total mass of the curable resin composition is preferably 30% by mass to 90% by mass, more preferably 35% by mass to 80% by mass, and 40% by mass to 70% by mass. % is more preferred.
When the content of the inorganic filler with respect to the total mass of the curable resin composition is 30% by mass or more, the properties of the cured resin, such as coefficient of thermal expansion, thermal conductivity and elastic modulus, tend to be further improved.
When the content of the inorganic filler with respect to the total mass of the curable resin composition is 90% by mass or less, the increase in viscosity of the curable resin composition is suppressed, the fluidity is further improved, and the moldability is better. tend to become
（カップリング剤）
　本開示の硬化性樹脂組成物は、カップリング剤を含有してもよい。カップリング剤の種類は特に制限されず、公知のカップリング剤を使用することができる。カップリング剤としては、シランカップリング剤、チタンカップリング剤等が挙げられる。カップリング剤は、１種類を単独で使用しても、２種類以上を併用してもよい。 (coupling agent)
The curable resin composition of the present disclosure may contain a coupling agent. The type of coupling agent is not particularly limited, and known coupling agents can be used. Examples of coupling agents include silane coupling agents and titanium coupling agents. A coupling agent may be used individually by 1 type, or may use 2 or more types together.
　シランカップリング剤は、上記直鎖状ポリシロキサン化合物以外の化合物であれば特に限定されるものではなく、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－（２－アミノエチル）アミノプロピルトリメトキシシラン、３－（２－アミノエチル）アミノプロピルトリエトキシシラン、３－アミノプロピルトリメトキシシラン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－メルカプトプロピルトリエトキシシラン、３－ウレイドプロピルトリエトキシシラン、オクテニルトリメトキシシラン、グリシドキシオクチルトリメトキシシラン、メタクリロキシオクチルトリメトキシシラン等が挙げられる。 The silane coupling agent is not particularly limited as long as it is a compound other than the linear polysiloxane compound described above. sidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)amino propyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercapto propyltriethoxysilane, 3-ureidopropyltriethoxysilane, octenyltrimethoxysilane, glycidoxyoctyltrimethoxysilane, methacryloxyoctyltrimethoxysilane and the like.
　チタンカップリング剤としては、イソプロピルトリイソステアロイルチタネート、イソプロピルトリス（ジオクチルパイロホスフェート）チタネート、イソプロピルトリ（Ｎ－アミノエチル－アミノエチル）チタネート、テトラオクチルビス（ジトリデシルホスファイト）チタネート、テトラ（２，２－ジアリルオキシメチル－１－ブチル）ビス（ジトリデシルホスファイト）チタネート、ビス（ジオクチルパイロホスフェート）オキシアセテートチタネート、ビス（ジオクチルパイロホスフェート）エチレンチタネート、イソプロピルトリオクタノイルチタネート、イソプロピルジメタクリルイソステアロイルチタネート、イソプロピルトリドデシルベンゼンスルホニルチタネート、イソプロピルイソステアロイルジアクリルチタネート、イソプロピルトリ（ジオクチルホスフェート）チタネート、イソプロピルトリクミルフェニルチタネート、テトライソプロピルビス（ジオクチルホスファイト）チタネート等が挙げられる。 Titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tris(dioctylpyrophosphate) titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, tetraoctylbis(ditridecylphosphite) titanate, tetra(2, 2-diallyloxymethyl-1-butyl)bis(ditridecylphosphite)titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate, isopropyltrioctanoyltitanate, isopropyldimethacrylisostearoyltitanate , isopropyltridodecylbenzenesulfonyltitanate, isopropylisostearoyldiacryltitanate, isopropyltri(dioctylphosphate)titanate, isopropyltricumylphenyltitanate, tetraisopropylbis(dioctylphosphite)titanate and the like.
　上記したカップリング剤の中でも、耐リフロー性の観点から、本開示の硬化性樹脂組成物は、３－アミノプロピルトリメトキシシラン及び３－グリシドキシプロピルトリメトキシシランの少なくとも一方を含有することが好ましい。 Among the above coupling agents, from the viewpoint of reflow resistance, the curable resin composition of the present disclosure may contain at least one of 3-aminopropyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane. preferable.
　硬化性樹脂組成物がカップリング剤を含有する場合、エポキシ樹脂と無機充填材との界面の接着性の観点から、硬化性樹脂組成物に含有される無機充填材の全質量に対するカップリング剤の含有率は、０．００１質量％～１０質量％であることが好ましく、０．０１質量％～８質量％であることがより好ましく、０．０５質量％～５質量％であることがさらに好ましい。 When the curable resin composition contains a coupling agent, from the viewpoint of adhesiveness at the interface between the epoxy resin and the inorganic filler, the ratio of the coupling agent to the total mass of the inorganic filler contained in the curable resin composition is The content is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 8% by mass, and even more preferably 0.05% by mass to 5% by mass. .
（応力緩和剤）
　本開示の硬化性樹脂組成物は、シリコーンオイル、シリコーンゴム粒子等の応力緩和剤を含有してもよい。硬化性樹脂組成物が応力緩和剤を含有することにより、パッケージの反り変形及びパッケージクラックの発生をより低減させることができる。応力緩和剤としては、一般に使用されている公知の応力緩和剤（可とう剤）が挙げられる。具体的には、応力緩和剤としては、シリコーン系、スチレン系、オレフィン系、ウレタン系、ポリエステル系、ポリエーテル系、ポリアミド系、ポリブタジエン系等の熱可塑性エラストマー、天然ゴム（ＮＲ）、アクリロニトリル－ブタジエン共重合体（ＮＢＲ）、アクリルゴム、ウレタンゴム、シリコーンパウダー等のゴム粒子、メタクリル酸メチル－スチレン－ブタジエン共重合体（ＭＢＳ）、メタクリル酸メチル－シリコーン共重合体、メタクリル酸メチル－アクリル酸ブチル共重合体等のコア－シェル構造を有するゴム粒子などが挙げられる。応力緩和剤は、１種類を単独で用いても２種類以上を組み合わせて用いてもよい。中でも、シリコーン系応力緩和剤が好ましい。シリコーン系応力緩和剤としては、エポキシ基を有するもの、アミノ基を有するもの、これらをポリエーテル変性したもの等が挙げられる。 (Stress relaxation agent)
The curable resin composition of the present disclosure may contain stress relaxation agents such as silicone oil and silicone rubber particles. By including a stress relaxation agent in the curable resin composition, it is possible to further reduce the warpage deformation of the package and the occurrence of package cracks. Examples of the stress relaxation agent include commonly used known stress relaxation agents (flexible agents). Specifically, stress relaxation agents include thermoplastic elastomers such as silicone, styrene, olefin, urethane, polyester, polyether, polyamide, and polybutadiene, natural rubber (NR), and acrylonitrile-butadiene. Copolymer (NBR), acrylic rubber, urethane rubber, rubber particles such as silicone powder, methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate Examples include rubber particles having a core-shell structure such as copolymers. A stress relaxation agent may be used individually by 1 type, or may be used in combination of 2 or more types. Among them, a silicone-based stress relieving agent is preferable. Examples of silicone-based stress relieving agents include those having epoxy groups, those having amino groups, and those modified with polyethers.
　硬化性樹脂組成物が応力緩和剤を含有する場合、硬化性樹脂組成物に含有されるエポキシ樹脂の全質量に対する応力緩和剤の含有率は、０．１質量％～３０質量％であることが好ましく、１質量％～５質量％であることがより好ましい。 When the curable resin composition contains a stress relaxation agent, the content of the stress relaxation agent with respect to the total weight of the epoxy resin contained in the curable resin composition is 0.1% by mass to 30% by mass. It is preferably 1% by mass to 5% by mass.
（離型剤）
　本開示の硬化性樹脂組成物は、成形時における金型を使用する場合、金型との離型性の観点から、離型剤を含有してもよい。離型剤は特に制限されず、従来公知のものを用いることができる。離型剤としては、カルナバワックス、モンタン酸、ステアリン酸等の高級脂肪酸、高級脂肪酸金属塩、モンタン酸エステル等のエステル系ワックス、酸化ポリエチレン、非酸化ポリエチレン等のポリオレフィン系ワックスなどが挙げられる。離型剤は、１種類を単独で用いても２種類以上を組み合わせて用いてもよい。 (Release agent)
The curable resin composition of the present disclosure may contain a mold release agent from the viewpoint of releasability from the mold when using a mold for molding. The release agent is not particularly limited, and conventionally known agents can be used. Examples of release agents include carnauba wax, higher fatty acids such as montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene. The release agent may be used singly or in combination of two or more.
　本開示の硬化性樹脂組成物が離型剤を含有する場合、硬化性樹脂組成物に含有されるエポキシ樹脂の全質量に対する離型剤の含有率は、０．０１質量％～１５質量％であることが好ましく、０．１質量％～１０質量％であることがより好ましい。硬化性樹脂組成物に含有されるエポキシ樹脂の全質量に対する離型剤の含有率が０．０１質量％以上であると、離型性が充分に得られる傾向にある。硬化性樹脂組成物に含有されるエポキシ樹脂の全質量に対する離型剤の含有率が１５質量％以下であると、より良好な離型性が得られる傾向にある。 When the curable resin composition of the present disclosure contains a release agent, the content of the release agent with respect to the total mass of the epoxy resin contained in the curable resin composition is 0.01% by mass to 15% by mass. preferably 0.1% by mass to 10% by mass. When the content of the release agent with respect to the total mass of the epoxy resin contained in the curable resin composition is 0.01% by mass or more, the release property tends to be sufficiently obtained. When the content of the release agent with respect to the total mass of the epoxy resin contained in the curable resin composition is 15% by mass or less, better releasability tends to be obtained.
（着色剤）
　本開示の硬化性樹脂組成物は、着色剤を含有してもよい。着色剤としてはカーボンブラック、有機染料、有機顔料、酸化チタン、鉛丹、ベンガラ等の公知の着色剤を挙げることができる。着色剤の含有量は目的等に応じて適宜選択できる。着色剤は、１種類を単独で用いても２種類以上を組み合わせて用いてもよい。 (coloring agent)
The curable resin composition of the present disclosure may contain a colorant. Examples of 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. The colorants may be used singly or in combination of two or more.
　硬化性樹脂組成物が着色剤を含有する場合、硬化性樹脂組成物の全質量に対する着色剤の含有率は、０．０１質量％～５質量％であることが好ましく、０．０５質量％～３質量％であることがより好ましく、０．０１質量％～１質量％であることがさらに好ましい。 When the curable resin composition contains a coloring agent, the content of the coloring agent with respect to the total weight of the curable resin composition is preferably 0.01% by mass to 5% by mass, and 0.05% by mass to It is more preferably 3% by mass, and even more preferably 0.01% by mass to 1% by mass.
（難燃剤）
　本開示の硬化性樹脂組成物は、難燃剤を含有してもよい。難燃剤は特に制限されず、従来公知のものを用いることができる。難燃剤としては、ハロゲン原子、アンチモン原子、窒素原子又はリン原子を含む有機又は無機の化合物、金属水酸化物等が挙げられる。難燃剤は、１種類を単独で用いても２種類以上を組み合わせて用いてもよい。 (Flame retardants)
The curable resin composition of the present disclosure may contain flame retardants. The flame retardant is not particularly limited, and conventionally known ones can be used. Flame retardants include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms or phosphorus atoms, metal hydroxides, and the like. A flame retardant may be used individually by 1 type, or may be used in combination of 2 or more types.
　本開示の硬化性樹脂組成物が難燃剤を含有する場合、その含有量は、所望の難燃効果を得るのに充分な量であれば特に制限されない。硬化性樹脂組成物に含有されるエポキシ樹脂の全質量に対する難燃剤の含有率は、１質量％～３００質量％であることが好ましく、２質量％～１５０質量％であることがより好ましい。 When the curable resin composition of the present disclosure contains a flame retardant, its content is not particularly limited as long as it is sufficient to obtain the desired flame retardant effect. The content of the flame retardant with respect to the total mass of the epoxy resin contained in the curable resin composition is preferably 1% by mass to 300% by mass, more preferably 2% by mass to 150% by mass.
（イオン交換体）
　本開示の硬化性樹脂組成物は、イオン交換体を含有してもよい。硬化性樹脂組成物を半導体パッケージの封止材として用いる場合には、封止される素子を備える電子部品装置の耐湿性及び高温放置特性を向上させる観点から、イオン交換体を含有することが好ましい。
　イオン交換体は特に制限されず、従来公知のものを用いることができる。具体的には、ハイドロタルサイト化合物、並びに、マグネシウム、アルミニウム、チタン、ジルコニウム及びビスマスからなる群より選ばれる少なくとも１種の元素の含水酸化物等が挙げられる。イオン交換体は、１種類を単独で用いても２種類以上を組み合わせて用いてもよい。
具体的には、イオン交換体としては、下記一般式（Ａ）で表されるハイドロタルサイトが挙げられる。 (Ion exchanger)
The curable resin composition of the present disclosure may contain an ion exchanger. When the curable resin composition is used as a sealing material for a semiconductor package, 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 sealed. .
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.
Specifically, the ion exchanger includes hydrotalcite represented by the following general formula (A).
　Ｍｇ（１－Ｘ）ＡｌＸ（ＯＨ）２（ＣＯ３）Ｘ／２・ｍＨ２Ｏ　・・・（Ａ）
　（０＜Ｘ≦０．５、ｍは正の数） Mg (1-X) Al X (OH) 2 (CO 3 ) X/2 ·mH 2 O (A)
(0<X≤0.5, m is a positive number)
　本開示の硬化性樹脂組成物がイオン交換体を含有する場合、その含有量は、ハロゲンイオン等のイオンを捕捉するのに充分な量であれば特に制限はない。硬化性樹脂組成物に含有されるエポキシ樹脂の全質量に対するイオン交換体の含有率は、０．１質量％～３０質量％であることが好ましく、１質量％～５質量％であることがより好ましい。 When the curable resin composition of the present disclosure contains an ion exchanger, its content is not particularly limited as long as it is sufficient to capture ions such as halogen ions. The content of the ion exchanger relative to the total weight of the epoxy resin contained in the curable resin composition is preferably 0.1% by mass to 30% by mass, more preferably 1% by mass to 5% by mass. preferable.
（エポキシ樹脂以外の樹脂）
　本開示の硬化性樹脂組成物は、エポキシ樹脂以外の樹脂を含有してもよい。エポキシ樹脂以外の樹脂の種類は特に制限されず、硬化性樹脂組成物の成分として一般に使用されているものから選択できる。エポキシ樹脂以外の樹脂は、１種類を単独で用いても２種類以上を組み合わせて用いてもよい。 (Resins other than epoxy resins)
The curable resin composition of the present disclosure may contain resins other than epoxy resins. The type of resin other than the epoxy resin is not particularly limited, and can be selected from those commonly used as components of curable resin compositions. Resins other than epoxy resins may be used singly or in combination of two or more.
　エポキシ樹脂以外の樹脂の具体例を以下に記載するが、これらに限定されるものではない
　エポキシ樹脂以外の樹脂としては、チオール樹脂、ユリア樹脂、メラミン樹脂、ウレタン樹脂、シリコーン樹脂、マレイミド樹脂、不飽和ポリエステル樹脂等が挙げられる。 Specific examples of resins other than epoxy resins are described below, but are not limited thereto. Resins other than epoxy resins include thiol resins, urea resins, melamine resins, urethane resins, silicone resins, maleimide resins, Saturated polyester resin and the like can be mentioned.
（フェノール系硬化剤以外の硬化剤）
　本開示の硬化性樹脂組成物は、フェノール系硬化剤以外の硬化剤を含有してもよい。フェノール系硬化剤以外の硬化剤の種類は特に制限されず、硬化性樹脂組成物の成分として一般に使用されているものから選択できる。フェノール系硬化剤以外の硬化剤は、１種類を単独で用いても２種類以上を組み合わせて用いてもよい。 (Curing agent other than phenolic curing agent)
The curable resin composition of the present disclosure may contain curing agents other than phenolic curing agents. The type of curing agent other than the phenol-based curing agent is not particularly limited, and can be selected from those commonly used as components of curable resin compositions. Curing agents other than phenol-based curing agents may be used alone or in combination of two or more.
　フェノール系硬化剤以外の硬化剤の具体例を以下に記載するが、これらに限定されるものではない
　フェノール系硬化剤以外の硬化剤としては、アミン系硬化剤、酸無水物系硬化剤、ポリメルカプタン系硬化剤、ポリアミノアミド系硬化剤、イソシアネート系硬化剤、ブロックイソシアネート系硬化剤等が挙げられる。 Specific examples of curing agents other than phenolic curing agents are described below, but are not limited to these. Curing agents other than phenolic curing agents include amine curing agents, acid anhydride curing agents, poly Mercaptan-based curing agents, polyaminoamide-based curing agents, isocyanate-based curing agents, blocked isocyanate-based curing agents, and the like are included.
　フェノール系硬化剤以外の硬化剤がアミン系硬化剤を含む場合、アミン系硬化剤の活性水素当量は、特に制限されない。耐リフロー性、成形性、電気的信頼性等の各種特性バランスの観点からは、１０ｇ／ｅｑ～１０００ｇ／ｅｑであることが好ましく、３０ｇ／ｅｑ～５００ｇ／ｅｑであることがより好ましい。
　アミン系硬化剤の活性水素当量は、ＪＩＳ　Ｋ　７２３７：１９９５に準拠して測定されたアミン価に基づいて算出された値をいう。 When the curing agent other than the phenol-based curing agent contains an amine-based curing agent, the active hydrogen equivalent of the amine-based curing agent is not particularly limited. From the viewpoint of the balance of various properties such as reflow resistance, moldability, and electrical reliability, it is preferably 10 g/eq to 1000 g/eq, more preferably 30 g/eq to 500 g/eq.
The active hydrogen equivalent of the amine curing agent is a value calculated based on the amine value measured according to JIS K 7237:1995.
　本開示の硬化性樹脂組成物が、フェノール系硬化剤以外の硬化剤を含有する場合、硬化性樹脂組成物の全質量に対するフェノール系硬化剤以外の硬化剤の含有率は特に限定されるものではなく、２質量％～３５質量％であることが好ましく、５質量％～３０質量％であることがより好ましい。 When the curable resin composition of the present disclosure contains a curing agent other than a phenolic curing agent, the content of the curing agent other than the phenolic curing agent with respect to the total mass of the curable resin composition is not particularly limited. It is preferably 2% by mass to 35% by mass, more preferably 5% by mass to 30% by mass.
（硬化性樹脂組成物の製造方法）
　硬化性樹脂組成物の製造方法は、特に制限されない。一般的な手法としては、所定の配合量の成分をミキサー等によって十分混合した後、ミキシングロール、押出機等によって溶融混練し、冷却し、粉砕する方法を挙げることができる。より具体的には、例えば、上述した成分の所定量を均一に攪拌及び混合し、予め７０℃～１４０℃に加熱してあるニーダー、ロール、エクストルーダー等で混練し、冷却し、粉砕する方法を挙げることができる。 (Method for producing curable resin composition)
The method for producing the curable resin composition is not particularly limited. As 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 components described above are uniformly stirred and mixed, kneaded with a kneader, roll, extruder, or the like preheated to 70° C. to 140° C., cooled, and pulverized. can be mentioned.
　硬化性樹脂組成物は、２５℃において固体であることが好ましい。２５℃において硬化性樹脂組成物が固体である場合、硬化性樹脂組成物の形状は特に制限されず、粉状、粒状、タブレット状等が挙げられる。硬化性樹脂組成物がタブレット状である場合の寸法及び質量は、パッケージの成形条件に合うような寸法及び質量となるようにすることが取り扱い性の観点から好ましい。 The curable resin composition is preferably solid at 25°C. When the curable resin composition is solid at 25° C., the shape of the curable resin composition is not particularly limited, and examples thereof include powder, granules, tablets, and the like. When the curable resin 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.
（硬化性樹脂組成物の用途）
　本開示の硬化性樹脂組成物の用途は特に制限されず、例えば電子部品装置の封止材として種々の実装技術に用いることができる。また、本開示の硬化性樹脂組成物は、各種モジュール用樹脂成形体、モーター用樹脂成形体、車載用樹脂成形体、電子回路用保護材用封止材等、樹脂組成物が良好な流動性及び硬化性を有することが望ましい種々の用途に用いることができる。 (Use of curable resin composition)
Applications of the curable resin composition of the present disclosure are not particularly limited, and it can be used in various mounting techniques, for example, as a sealing material for electronic component devices. In addition, the curable resin composition of the present disclosure is used for resin moldings for various modules, resin moldings for motors, vehicle-mounted resin moldings, sealing materials for protective materials for electronic circuits, etc. The resin composition has good fluidity. And it can be used for various applications where it is desirable to have curability.
＜電子部品装置＞
　本開示の電子部品装置は、素子と、素子を封止する上記硬化性樹脂組成物の硬化物とを備える。 <Electronic parts equipment>
An electronic component device of the present disclosure includes an element and a cured product of the curable resin composition that seals the element.
　電子部品装置は、素子を搭載する支持部材をさらに備えることができる。
　支持部材としては、リードフレーム、配線済みのテープキャリア、配線板、ガラス、シリコンウエハ、有機基板等が挙げられる。上記支持部材の中でも、上記硬化性樹脂組成物の硬化物との接着性の観点からリードフレームが好ましい。 The electronic component device can further include a support member on which the element is mounted.
Examples of supporting members include lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers, organic substrates, and the like. Among the supporting members, a lead frame is preferable from the viewpoint of adhesion to the cured product of the curable resin composition.
　リードフレームは、表面が粗面化されていてもよく、粗面化されていなくてもよいが、製造コストの観点からは、非粗面化リードフレームが好ましく、接着性の観点からは、粗面化リードフレームが好ましい。
　粗面化方法は、特に限定されるものではなく、アルカリ処理、シランカップリング処理、サンドマット処理、プラズマ処理、コロナ放電処理等が挙げられる。 The lead frame may or may not have a roughened surface, but from the viewpoint of manufacturing cost, a non-roughened lead frame is preferable, and from the viewpoint of adhesiveness, a roughened lead frame is preferred. Planarized leadframes are preferred.
The roughening method is not particularly limited, and includes alkali treatment, silane coupling treatment, sand mat treatment, plasma treatment, corona discharge treatment and the like.
　リードフレームは、Ａｕ、Ｐｄ及びＮｉの少なくとも１つを含むめっき層を表面の少なくとも一部に備えることができる。
　また、上記めっき層は、単層であっても、多層であってもよい。多層のめっき層としては、リードフレーム側から、Ｎｉめっき層、Ｐｄめっき層及びＡｕめっき層が積層された３層構成のめっき層等が挙げられる。
　上記３層構成のリードフレームとしては、例えば、ＰＰＦ（Ｐｒｅ　Ｐｌａｔｉｎｇ　Ｌｅａｄ　Ｆｌａｍｅ）と呼ばれる銅リードフレームにＮｉ－Ｐｄ－Ａｕめっきを施したリードフレームが挙げられる。 The lead frame can have a plated layer containing at least one of Au, Pd and Ni on at least part of the surface.
Further, the plated layer may be a single layer or multiple layers. As the multi-layer plating layer, a plating layer having a three-layer configuration in which a Ni plating layer, a Pd plating layer, and an Au plating layer are laminated from the lead frame side, or the like can be used.
Examples of the three-layer lead frame include a lead frame called PPF (Pre Plating Lead Frame), which is a copper lead frame plated with Ni--Pd--Au.
　めっき層の厚さは特に限定されるものではなく、５μｍ以下であることが好ましく、４μｍ以下であることがより好ましく、３μｍ以下であることがさらに好ましい。 The thickness of the plating layer is not particularly limited, and is preferably 5 μm or less, more preferably 4 μm or less, and even more preferably 3 μm or less.
　電子部品装置が備える素子としては、例えば、シリコンチップ、トランジスタ、ダイオード、サイリスタ等の能動素子、コンデンサ、抵抗体、コイル等の受動素子などが挙げられる。 Examples of elements included in electronic component devices include active elements such as silicon chips, transistors, diodes, and thyristors, and passive elements such as capacitors, resistors, and coils.
　電子部品装置の具体的な構成としては、以下の構成が挙げられるが、これらに限定されるものではない。
（１）リードフレーム上に素子を固定し、ボンディングパッド等の素子の端子部とリード部とをワイヤボンディング、バンプ等を用いて接続した後、硬化性樹脂組成物を用いて封止した構造を有するＤＩＰ（Ｄｕａｌ　Ｉｎｌｉｎｅ　Ｐａｃｋａｇｅ）、ＰＬＣＣ（Ｐｌａｓｔｉｃ　Ｌｅａｄｅｄ　Ｃｈｉｐ　Ｃａｒｒｉｅｒ）、ＱＦＰ（Ｑｕａｄ　Ｆｌａｔ　Ｐａｃｋａｇｅ）、ＳＯＰ（Ｓｍａｌｌ　Ｏｕｔｌｉｎｅ　Ｐａｃｋａｇｅ）、ＳＯＪ（Ｓｍａｌｌ　Ｏｕｔｌｉｎｅ　Ｊ－ｌｅａｄ　Ｐａｃｋａｇｅ）、ＴＳＯＰ（Ｔｈｉｎ　Ｓｍａｌｌ　Ｏｕｔｌｉｎｅ　Ｐａｃｋａｇｅ）、ＴＱＦＰ（Ｔｈｉｎ　Ｑｕａｄ　Ｆｌａｔ　Ｐａｃｋａｇｅ）等の一般的な樹脂封止型ＩＣ；
（２）テープキャリアにバンプを用いて接続した素子を、硬化性樹脂組成物を用いて封止した構造を有するＴＣＰ（Ｔａｐｅ　Ｃａｒｒｉｅｒ　Ｐａｃｋａｇｅ）；
（３）支持部材上に形成した配線に、ワイヤボンディング、フリップチップボンディング、はんだ等を用いて接続した素子を、硬化性樹脂組成物を用いて封止した構造を有するＣＯＢ（Ｃｈｉｐ　Ｏｎ　Ｂｏａｒｄ）モジュール、ハイブリッドＩＣ、マルチチップモジュール等；
（４）裏面に配線板接続用の端子を形成した支持部材の表面に素子を搭載し、バンプ又はワイヤボンディングを用いて素子と支持部材に形成された配線とを接続した後、硬化性樹脂組成物を用いて素子を封止した構造を有するＢＧＡ（Ｂａｌｌ　Ｇｒｉｄ　Ａｒｒａｙ）、ＣＳＰ（Ｃｈｉｐ　Ｓｉｚｅ　Ｐａｃｋａｇｅ）、ＭＣＰ（Ｍｕｌｔｉ　Ｃｈｉｐ　Ｐａｃｋａｇｅ）、ＳｉＰ（Ｓｙｓｔｅｍ　ｉｎ　ａ　Ｐａｃｋａｇｅ）等 Specific configurations of the electronic component device include, but are not limited to, the following configurations.
(1) 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 using wire bonding, bumps, or the like, and then sealed using a curable resin composition.有するＤＩＰ（Ｄｕａｌ Ｉｎｌｉｎｅ Ｐａｃｋａｇｅ）、ＰＬＣＣ（Ｐｌａｓｔｉｃ Ｌｅａｄｅｄ Ｃｈｉｐ Ｃａｒｒｉｅｒ）、ＱＦＰ（Ｑｕａｄ Ｆｌａｔ Ｐａｃｋａｇｅ）、ＳＯＰ（Ｓｍａｌｌ Ｏｕｔｌｉｎｅ Ｐａｃｋａｇｅ）、ＳＯＪ（Ｓｍａｌｌ Ｏｕｔｌｉｎｅ Ｊ－ｌｅａｄ Ｐａｃｋａｇｅ）、ＴＳＯＰ（Ｔｈｉｎ Ｓｍａｌｌ Ｏｕｔｌｉｎｅ Ｐａｃｋａｇｅ）、ＴＱＦＰ（ general resin-encapsulated IC such as Thin Quad Flat Package;
(2) TCP (Tape Carrier Package) having a structure in which an element connected to a tape carrier using bumps is sealed with a curable resin composition;
(3) A COB (Chip On Board) module having a structure in which an element connected to wiring formed on a support member by wire bonding, flip chip bonding, soldering, or the like is sealed with a curable resin composition. , hybrid ICs, multi-chip modules, etc.;
(4) After mounting an element on the surface of a support member having wiring board connection terminals formed on the back surface and connecting the element and the wiring formed on the support member using bumps or wire bonding, a curable resin composition is formed. BGA (Ball Grid Array), CSP (Chip Size Package), MCP (Multi Chip Package), SiP (System in a Package), etc., which have a structure in which elements are sealed using materials
　硬化性樹脂組成物を用いて素子を封止する方法は特に限定されず、公知の方法を適用することが可能である。封止方法としては、例えば、低圧トランスファ成形が一般的であるが、インジェクション成形、圧縮成形、注型等を用いてもよい。 The method of sealing the element using the curable resin composition is not particularly limited, and known methods can be applied. As a sealing method, for example, low-pressure transfer molding is generally used, but injection molding, compression molding, cast molding, or the like may also be used.
　以下に、本開示を実施例により具体的に説明するが、本開示はこれらの実施例に限定されるものではない。また、表中の数値は特に断りのない限り「質量部」を意味する。 Although the present disclosure will be specifically described below with reference to examples, the present disclosure is not limited to these examples. Numerical values in the table mean "mass parts" unless otherwise specified.
（実施例１～７及び比較例１～３）
　表１に示す配合の材料を予備混合（ドライブレンド）した後、二軸ロール（ロール表面温度：約８０℃）で約１５分間混練し、冷却し、粉砕して粉末状の硬化性樹脂組成物を製造した。 (Examples 1 to 7 and Comparative Examples 1 to 3)
After pre-mixing (dry blending) the materials of the formulation shown in Table 1, they are kneaded for about 15 minutes with a biaxial roll (roll surface temperature: about 80 ° C.), cooled, and pulverized to obtain a powdery curable resin composition. manufactured.
　表１中における材料の詳細は以下の通りである。なお、表１におけるエポキシ樹脂のエポキシ基に対するフェノール系硬化剤のフェノール性水酸基の当量比は上記方法により求めた。 The details of the materials in Table 1 are as follows. The equivalent ratio of the phenolic hydroxyl group of the phenolic curing agent to the epoxy group of the epoxy resin in Table 1 was determined by the above method.
・エポキシ樹脂Ａ：下記構造単位を有する共重合型エポキシ樹脂、エポキシ当量２５０ｇ／ｅｑ、１５０℃での溶融粘度０．７ｄＰａ・ｓ、Ｍｎ３５０～６００ Epoxy resin A: copolymer type epoxy resin having the following structural units, epoxy equivalent of 250 g/eq, melt viscosity at 150° C. of 0.7 dPa s, Mn of 350 to 600
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
・エポキシ樹脂Ｂ：ビフェニル型エポキシ樹脂、エポキシ当量１９６ｇ／ｅｑ、軟化点１０６℃、三菱ケミカル株式会社製、商品名「ＹＸ－４０００Ｈ」、Ｍｎ３５０
・エポキシ樹脂Ｃ：ビフェニルアラルキル型エポキシ樹脂、エポキシ当量２８４ｇ／ｅｑ ・ Epoxy resin B: biphenyl type epoxy resin, epoxy equivalent 196 g / eq, softening point 106 ° C., manufactured by Mitsubishi Chemical Corporation, trade name "YX-4000H", Mn350
· Epoxy resin C: biphenyl aralkyl type epoxy resin, epoxy equivalent 284 g / eq
・フェノール系硬化剤Ａ：アラルキル型フェノール樹脂、水酸基当量１０６ｇ／ｅｑ
・フェノール系硬化剤Ｂ：トリフェニルメタン型フェノール樹脂、水酸基当量９５ｇ／ｅｑ
・フェノール系硬化剤Ｃ：アラルキル型フェノール樹脂、水酸基当量２０３ｇ／ｅｑ
・フェノール系硬化剤Ｄ：メラミン変性フェノール樹脂、水酸基当量１２０ｇ／ｅｑ、軟化点：９０℃
・フェノール系硬化剤Ｅ：トリアジン型フェノール樹脂、２－［４－［（２－ヒドロキシ－３－（２’－エチル）ヘキシル）オキシ］－２－ヒドロキシフェニル］－４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン、ＢＡＳＦ社、商品名「Ｔｉｎｕｖｉｎ（登録商標）４０５」
・フェノール系硬化剤Ｆ：ノボラック型フェノール樹脂、水酸基当量２２３ｇ／ｅｑ
・フェノール系硬化剤Ｇ：ノボラック型フェノール樹脂、水酸基当量１５６ｇ／ｅｑ - Phenol-based curing agent A: aralkyl-type phenolic resin, hydroxyl equivalent of 106 g/eq
· Phenolic curing agent B: triphenylmethane type phenol resin, hydroxyl equivalent 95 g / eq
- Phenol-based curing agent C: aralkyl-type phenolic resin, hydroxyl equivalent 203 g/eq
- Phenol-based curing agent D: melamine-modified phenolic resin, hydroxyl equivalent 120 g/eq, softening point: 90°C
Phenolic curing agent E: triazine-type phenolic resin, 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2, 4-dimethylphenyl)-1,3,5-triazine, BASF, trade name "Tinuvin (registered trademark) 405"
- Phenolic curing agent F: Novolac type phenolic resin, hydroxyl equivalent 223g/eq
- Phenolic curing agent G: Novolac type phenolic resin, hydroxyl equivalent 156g/eq
・硬化促進剤：トリフェニルホスフィンと１，４－ベンゾキノンとの付加反応物 ・Curing accelerator: addition reaction product of triphenylphosphine and 1,4-benzoquinone
・カップリング剤Ａ：３－アミノプロピルトリメトキシシラン
・カップリング剤Ｂ：３－グリシドキシプロピルトリメトキシシラン
・カップリング剤Ｃ：直鎖状ポリシロキサン、融点：－７０℃、エポキシ当量１２０ｇ／ｅｑ～１５０ｇ／ｅｑ
・カップリング剤Ｄ：テトラスルフィドジトリエトキシシラン · Coupling agent A: 3-aminopropyltrimethoxysilane · Coupling agent B: 3-glycidoxypropyltrimethoxysilane · Coupling agent C: linear polysiloxane, melting point: -70 ° C., epoxy equivalent 120 g / eq~150g/eq
Coupling agent D: tetrasulfide ditriethoxysilane
・応力緩和剤Ａ：エポキシ変性シリコーンレジン
・応力緩和剤Ｂ：インデン含有共重合体
・応力緩和剤Ｃ：フェニル基含有シリコーンレジン ・Stress relaxation agent A: Epoxy-modified silicone resin ・Stress relaxation agent B: Indene-containing copolymer ・Stress relaxation agent C: Phenyl group-containing silicone resin
・無機充填剤Ａ：平均粒子径１９．４μｍのシリカフィラー
・無機充填剤Ｂ：平均粒子径０．６μｍのシリカフィラー
・無機充填剤Ｃ：平均粒子径５０ｎｍ以下のシリカフィラー
・無機充填剤Ｄ：平均粒子径１．２μｍのマグネシウム及び亜鉛を含む金属水酸化物 ・Inorganic filler A: silica filler with an average particle size of 19.4 µm ・Inorganic filler B: silica filler with an average particle size of 0.6 µm ・Inorganic filler C: silica filler with an average particle size of 50 nm or less ・Inorganic filler D: Metal hydroxide containing magnesium and zinc with an average particle size of 1.2 μm
＜＜硬化性樹脂組成物の評価＞＞
　実施例及び比較例において製造した硬化性樹脂組成物の特性を次の特性試験により評価した。評価結果を表１に示す。
　なお、硬化性樹脂組成物を用いた樹脂硬化物の作製は、明記しない限りトランスファ成形機により、金型温度１７５℃、成形圧力８．３ＭＰａ、硬化時間１２０秒の条件で成形した後、１７５℃で５時間の条件で後硬化を行うことにより行った。 <<Evaluation of curable resin composition>>
The properties of the curable resin compositions produced in Examples and Comparative Examples were evaluated by the following property tests. Table 1 shows the evaluation results.
In addition, unless otherwise specified, the resin cured product using the curable resin composition was produced by molding under the conditions of a mold temperature of 175 ° C., a molding pressure of 8.3 MPa, and a curing time of 120 seconds. and post-curing for 5 hours at .
＜耐リフロー性評価＞
　３．２ｍｍ×２．２ｍｍ×０．３７ｍｍのシリコンチップを５．２ｍｍ×４．１ｍｍのダイパッドに搭載した２８ピンのＳＯ（Ｓｍａｌｌ　Ｏｕｔｌｉｎｅ）パッケージ（リードフレーム材質：銅合金、Ｎｉ－Ｐｄ－Ａｕメッキ処理品）を、硬化性樹脂組成物を用いて成形し、次いで１７５℃で５時間の条件で後硬化した。
　得られた成形品の外部のクラックなきことを目視で、内部の剥離発生のなきことを超音波探傷装置（株式会社日立製作所製、ＦＳ－２００）でそれぞれ確認した。成形品を１２５℃で１２時間乾燥後、温度８５℃、相対湿度８５％の条件で１６８時間加湿した。
　その後、ＪＥＤＥＣの規定に準拠し、温度条件を２６０℃に設定し、同一温度で３回リフロー処理を行い、パッケージ外部のクラック有無を目視で、パッケージ内部の剥離発生の有無を超音波探傷装置でそれぞれ観察した。試験パッケージ数に対する、クラック及び剥離のいずれかが発生したパッケージ数の割合で耐リフロー性を評価した。評価結果を表１にまとめた。
（評価基準）
Ａ：クラック及び剥離の発生が０％
Ｂ：クラック及び剥離の発生が０％超、６０％未満
Ｃ：クラック及び剥離の発生が６０％以上、１００％未満
Ｄ：クラック及び剥離の発生が１００％ <Reflow resistance evaluation>
28-pin SO (Small Outline) package with a 3.2 mm x 2.2 mm x 0.37 mm silicon chip mounted on a 5.2 mm x 4.1 mm die pad (lead frame material: copper alloy, Ni-Pd-Au plating Treated product) was molded using the curable resin composition and then post-cured at 175° C. for 5 hours.
It was visually confirmed that there were no cracks on the outside of the molded product obtained, and it was confirmed by an ultrasonic flaw detector (manufactured by Hitachi, Ltd., FS-200) that there was no peeling inside. After drying the molded product at 125° C. for 12 hours, it was humidified for 168 hours under conditions of a temperature of 85° C. and a relative humidity of 85%.
After that, in accordance with JEDEC regulations, the temperature condition is set to 260°C, and reflow treatment is performed three times at the same temperature. observed each. The reflow resistance was evaluated by the ratio of the number of packages in which either cracks or peeling occurred to the number of test packages. The evaluation results are summarized in Table 1.
(Evaluation criteria)
A: Occurrence of cracks and peeling is 0%
B: Occurrence of cracks and peeling is more than 0% and less than 60% C: Occurrence of cracks and peeling is 60% or more and less than 100% D: Occurrence of cracks and peeling is 100%
＜ｔａｎδ及び貯蔵弾性率の測定＞
　上記条件に基づいて、上記実施例及び比較例において得られた硬化性樹脂組成物の樹脂硬化物を作製した。樹脂硬化物は、短辺５ｍｍ、長辺５０ｍｍ、厚さ２ｍｍの長方形形状を有する樹脂硬化物とした。
　上記樹脂硬化物に対し、試験モード：３点曲げモード、測定温度：２５℃～３３０℃、昇温速度：１０℃／分、試験周波数：１Ｈｚの条件で動的粘弾性測定を実施し、得られたチャート（縦軸：ｔａｎδ、横軸：温度）から貯蔵粘弾性の値を求め、表１にまとめた。
　また、上記チャートから、（１）ｔａｎδが最大となる温度（ガラス転移温度）、（２）ガラス転移温度におけるｔａｎδの値、（３）ガラス転移温度におけるｔａｎδの値を１００としたとき、ガラス転移温度より１０度低い温度におけるｔａｎδの値（表１中では、ｔａｎδ比と記載）、（４）２２０℃、２３０℃、２４０℃及び２５０℃の各温度におけるｔａｎδの値の合計（表１中では、ｔａｎδ合計１と記載）、（５）７０℃、８０℃及び９０℃の各温度におけるｔａｎδの値の合計（表１中では、ｔａｎδ合計２と記載）を求め、表１にまとめた。 <Measurement of tan δ and storage modulus>
Based on the above conditions, resin cured products of the curable resin compositions obtained in the above examples and comparative examples were produced. The cured resin product was a rectangular shape having a short side of 5 mm, a long side of 50 mm and a thickness of 2 mm.
Dynamic viscoelasticity measurement was performed on the cured resin under the conditions of test mode: 3-point bending mode, measurement temperature: 25 ° C. to 330 ° C., temperature increase rate: 10 ° C./min, test frequency: 1 Hz. The storage viscoelasticity values were obtained from the obtained chart (vertical axis: tan δ, horizontal axis: temperature) and summarized in Table 1.
Further, from the above chart, (1) the temperature at which tan δ becomes maximum (glass transition temperature), (2) the value of tan δ at the glass transition temperature, and (3) the value of tan δ at the glass transition temperature is set to 100, the glass transition The tan δ value at a temperature 10 degrees lower than the temperature (described as tan δ ratio in Table 1), (4) the sum of tan δ values at each temperature of 220 ° C., 230 ° C., 240 ° C. and 250 ° C. , tan δ total 1);
＜熱膨張係数（ＣＴＥ１）の測定＞
　上記条件に基づいて、上記実施例及び比較例において得られた硬化性樹脂組成物の樹脂硬化物を作製した。樹脂硬化物は、φ４ｍｍ×２０ｍｍの樹脂硬化物とした。
　次いで、ＪＩＳ　Ｋ　７１９７：２０１２に基づいて熱機械分析法により、樹脂硬化物の歪みを温度に対してプロットした場合の接線の傾きを、１０℃～３０℃の範囲において求めた。測定結果を表１にまとめた。
　なお、試験荷重は１５ｇ、昇温速度は５℃／分として測定した。
　また、線膨張率の測定には、セイコーインスルツメンツ株式会社製のＴＭＡ高精度二試
料熱分析装置（装置名ＳＳ６１００）を使用した。 <Measurement of coefficient of thermal expansion (CTE1)>
Based on the above conditions, resin cured products of the curable resin compositions obtained in the above examples and comparative examples were produced. A cured resin material of φ4 mm×20 mm was used as the cured resin material.
Then, the slope of the tangential line when the strain of the cured resin was plotted against temperature was determined in the range of 10°C to 30°C by thermomechanical analysis based on JIS K 7197:2012. Table 1 summarizes the measurement results.
The test load was 15 g, and the temperature increase rate was 5° C./min.
A TMA high-precision two-sample thermal analyzer (device name SS6100) manufactured by Seiko Instruments Inc. was used for the measurement of the coefficient of linear expansion.
＜吸水率の測定＞
　上記条件に基づいて、上記実施例及び比較例において得られた硬化性樹脂組成物の樹脂硬化物を作製した。樹脂硬化物は、短辺５．１ｍｍ、長辺２０ｍｍ、厚さ２ｍｍの長方形形状を有する硬化物とした。
　次いで、温度８５℃、相対湿度８５％の条件下に、上記樹脂硬化物を１６８時間静置した。
　静置後の樹脂硬化物の質量（ｇ）を測定し、静置前の樹脂硬化物の質量（ｇ）からの増加率（％）を求めた。結果を表１にまとめた。 <Measurement of water absorption>
Based on the above conditions, resin cured products of the curable resin compositions obtained in the above examples and comparative examples were produced. The resin cured product was a cured product having a rectangular shape with a short side of 5.1 mm, a long side of 20 mm and a thickness of 2 mm.
Then, the cured resin was allowed to stand for 168 hours under conditions of a temperature of 85° C. and a relative humidity of 85%.
The mass (g) of the cured resin material after standing was measured, and the rate of increase (%) from the mass (g) of the cured resin material before standing was determined. The results are summarized in Table 1.
＜流動性評価（スパイラルフロー）＞
　ＥＭＭＩ－１－６６に準じたスパイラルフロー測定用金型を用いて、実施例及び比較例において得られた硬化性樹脂組成物を金型温度１８０℃、成形圧力６．９ＭＰａ、硬化時間９０秒の条件で成形し、流動距離（ｃｍ）を求めた。測定結果を表１にまとめた。 <Fluidity evaluation (spiral flow)>
Using a spiral flow measurement mold according to EMMI-1-66, the curable resin compositions obtained in Examples and Comparative Examples were cured at a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Molding was carried out under these conditions, and the flow distance (cm) was determined. Table 1 summarizes the measurement results.
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000023
　表１にまとめた結果から、実施例において得られた硬化性樹脂組成物は、比較例において得られた硬化性樹脂組成物に比べ、耐リフロー性に優れることがわかる。 From the results summarized in Table 1, it can be seen that the curable resin compositions obtained in Examples are superior in reflow resistance to the curable resin compositions obtained in Comparative Examples.
　２０２１年８月３０日に出願された日本国特許出願２０２１－１４０４０８号の開示は、その全体が参照により本明細書に取り込まれる。本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記載された場合と同程度に、本明細書に参照により取り込まれる。 The disclosure of Japanese Patent Application No. 2021-140408 filed on August 30, 2021 is incorporated herein by reference in its entirety. All publications, patent applications and technical standards mentioned herein are to the same extent as if each individual publication, patent application and technical standard were specifically and individually indicated to be incorporated by reference. incorporated herein by reference.

Claims (9)

  1. 　エポキシ樹脂と、フェノール系硬化剤とを、前記エポキシ樹脂のエポキシ基に対する前記フェノール系硬化剤のフェノール性水酸基の当量比０．５以上、１．０未満で含有する、硬化性樹脂組成物。 A curable resin composition containing an epoxy resin and a phenolic curing agent such that the equivalent ratio of the phenolic hydroxyl group of the phenolic curing agent to the epoxy group of the epoxy resin is 0.5 or more and less than 1.0.
  2. 　前記エポキシ樹脂が、アルキルフェノール由来の構造単位及びアルコキシナフタレン由来の構造単位を有する共重合型エポキシ樹脂を含む、請求項１に記載の硬化性樹脂組成物。 The curable resin composition according to claim 1, wherein the epoxy resin comprises a copolymerized epoxy resin having an alkylphenol-derived structural unit and an alkoxynaphthalene-derived structural unit.
  3. 　前記エポキシ樹脂の全質量に対する前記共重合型エポキシ樹脂の含有率が、５０質量％～９０質量％である、請求項２に記載の硬化性樹脂組成物。 The curable resin composition according to claim 2, wherein the content of said copolymer type epoxy resin with respect to the total mass of said epoxy resin is 50% by mass to 90% by mass.
  4. 　前記エポキシ樹脂が、ビフェニル型エポキシ樹脂を含む、請求項１～請求項３のいずれか一項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 3, wherein the epoxy resin contains a biphenyl type epoxy resin.
  5. 　前記フェノール系硬化剤が、アラルキル型フェノール樹脂及びノボラック型フェノール樹脂からなる群より選択される１つ以上のフェノール系硬化剤を含む、請求項１～請求項４のいずれか一項に記載の硬化性樹脂組成物。 Curing according to any one of claims 1 to 4, wherein the phenolic curing agent comprises one or more phenolic curing agents selected from the group consisting of aralkyl-type phenolic resins and novolac-type phenolic resins. elastic resin composition.
  6. 　前記フェノール系硬化剤が、アラルキル型フェノール樹脂を含み、且つ
    　前記フェノール系硬化剤の全質量に対する前記アラルキル型フェノール樹脂の含有率が、６０質量％～９５質量％である、請求項１～請求項５のいずれか一項に記載の硬化性樹脂組成物。     Claims 1 to 3, wherein the phenol-based curing agent contains an aralkyl-type phenol resin, and the content of the aralkyl-type phenol resin with respect to the total mass of the phenol-based curing agent is 60% by mass to 95% by mass. 6. The curable resin composition according to any one of 5.
  7. 　第三ホスフィン化合物とキノン化合物との付加物を含む硬化促進剤をさらに含有する、請求項１～請求項６のいずれか一項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 6, further comprising a curing accelerator containing an adduct of a tertiary phosphine compound and a quinone compound.
  8. 　素子と、前記素子を封止する請求項１～請求項７のいずれか一項に記載の硬化性樹脂組成物の樹脂硬化物とを備える、電子部品装置。 An electronic component device comprising an element and a resin cured product of the curable resin composition according to any one of claims 1 to 7, which seals the element.
  9. 　前記素子を一方の面に搭載する支持部材をさらに備える、請求項８に記載の電子部品装置。 The electronic component device according to claim 8, further comprising a support member for mounting the element on one surface.
PCT/JP2022/032272 2021-08-30 2022-08-26 Curable resin composition and electronic component device WO2023032861A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202280058018.XA CN117858915A (en) 2021-08-30 2022-08-26 Curable resin composition and electronic component device

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021140408 2021-08-30
JP2021-140408 2021-08-30

Publications (1)

Publication Number Publication Date
WO2023032861A1 true WO2023032861A1 (en) 2023-03-09

Family

ID=85412725

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/032272 WO2023032861A1 (en) 2021-08-30 2022-08-26 Curable resin composition and electronic component device

Country Status (3)

Country Link
CN (1) CN117858915A (en)
TW (1) TW202309190A (en)
WO (1) WO2023032861A1 (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018104603A (en) * 2016-12-27 2018-07-05 日立化成株式会社 Curable resin composition and electronic component device
JP2020063366A (en) * 2018-10-17 2020-04-23 日立化成株式会社 Additive for curable resin composition, curable resin composition and electronic component device

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018104603A (en) * 2016-12-27 2018-07-05 日立化成株式会社 Curable resin composition and electronic component device
JP2020063366A (en) * 2018-10-17 2020-04-23 日立化成株式会社 Additive for curable resin composition, curable resin composition and electronic component device

Also Published As

Publication number Publication date
TW202309190A (en) 2023-03-01
CN117858915A (en) 2024-04-09

Similar Documents

Publication Publication Date Title
JP7302598B2 (en) Curable resin composition and electronic component device
JP6435708B2 (en) Resin composition for mold underfill and electronic component device
KR100893022B1 (en) Curing accelerator, curable resin composition, and electronic part/device
JP2023068032A (en) Additive for curable resin composition, curable resin composition and electronic component device
TWI824034B (en) Curable resin composition and electronic component device
JP7269579B2 (en) Epoxy resin composition and electronic component device
WO2021075207A1 (en) Epoxy resin composition, electronic component equipment, and method for producing electronic component equipment
JP7322368B2 (en) Curable resin composition and electronic component device
WO2023120739A1 (en) Epoxy resin composition and electronic component device
CN111094450A (en) Epoxy resin composition and electronic component device
JP7119823B2 (en) Epoxy resin composition for encapsulation and electronic component device
JP6705487B2 (en) Resin composition for mold underfill and electronic component device
WO2023032861A1 (en) Curable resin composition and electronic component device
WO2023032860A1 (en) Curable resin composition and electronic component device
JP7484081B2 (en) Curable resin composition and electronic component device
JP6708242B2 (en) Resin composition for mold underfill and electronic component device
WO2022186361A1 (en) Curable resin composition and electronic component device
JP2023034255A (en) Resin cured product and electronic component device
WO2023032971A1 (en) Epoxy resin composition for compression molding and electronic component device
WO2023120738A1 (en) Sealing material composition and electronic component device
JP2023034256A (en) Thermosetting resin composition and semiconductor device
TW202235510A (en) Thermosetting resin composition and electronic component device

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22864445

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023545533

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE