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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials

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. This may cause 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.
• ⁇ 2> In a chart obtained by performing dynamic viscoelasticity measurement on the resin cured product of the curable resin composition, the vertical axis is tan ⁇ and the horizontal axis is the temperature of 30 ° C. to 260 ° C., 70 ° C., 80 A curable resin composition, wherein the sum of tan ⁇ values at each temperature of °C and 90 °C is more than 0.600.
• the maximum value of tan ⁇ in the above chart is 100
• the value of tan ⁇ at at least one of ⁇ 10° C. at which tan ⁇ is maximum is greater than 60, according to the above ⁇ 1> or ⁇ 2> A curable resin composition as described.
• ⁇ 4> Any of the above ⁇ 1> to ⁇ 3>, wherein the storage viscoelasticity at 260 ° C. obtained by performing dynamic viscoelasticity measurement on the resin cured product of the curable resin composition is 450 MPa or less. 1.
• the curable resin composition according to one. ⁇ 5> The above ⁇ 1 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 > The curable resin composition according to any one of ⁇ 4>.
• ⁇ 6> An electronic component device comprising an element and a resin cured product of the curable resin composition according to any one of ⁇ 1> to ⁇ 5> 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.
• a plurality of 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 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.
• 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.
• GPS measuring device high-speed GPC device “HCL-8320GPC”, detector is differential refractometer or UV, manufactured by Tosoh Corporation ⁇ Column: column TSKgel SuperMultipore HZ-H (column length: 15 cm, column inner diameter: 4.6 mm), Manufactured by Tosoh Corporation (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 according to the first aspect is obtained by performing dynamic viscoelasticity measurement on the resin cured product of the curable resin composition.
• the temperature at which tan ⁇ is maximum is less than 120 ° C.
• the maximum value of tan ⁇ is greater than 0.400
• 220 The sum of the tan ⁇ values at each temperature of °C, 230 °C, 240 °C and 250 °C is greater than 0.400.
• the curable resin composition according to the first aspect has excellent reflow resistance.
• the vertical axis is tan ⁇ and the horizontal axis is the temperature of 30 ° C. to 260 ° C.
• tan ⁇ is the maximum
• the maximum value of tan ⁇ is greater than 0.400
• the temperatures of 220°C, 230°C, 240°C and 250°C According to the curable resin composition according to the first aspect, in which the sum of the tan ⁇ values in is more than 0.400, the internal stress of the cured resin that occurs during reflow tends to be relaxed.
• the temperature at which tan ⁇ becomes maximum is preferably less than 110°C.
• the lower limit of the temperature at which tan ⁇ is maximized is not particularly limited, it can be, for example, 50° C. or higher.
• the maximum value of tan ⁇ is preferably more than 0.410.
• the upper limit of the maximum value of tan ⁇ is not particularly limited, it can be, for example, 1.0 or less.
• the upper limit of the total tan ⁇ at each temperature of 220°C, 230°C, 240°C and 250°C is not particularly limited. can be, for example, 2.0 or less.
• the value of tan ⁇ at at least any temperature of -10 ° C. at which tan ⁇ becomes maximum is 60 It is preferably greater than, more preferably greater than 63, and even more preferably greater than 65.
• the sum of tan ⁇ values at each temperature of 70°C, 80°C and 90°C is preferably more than 0.600. More preferably above 700.
• 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 It is preferably 450 MPa or less, more preferably 435 MPa or less, and even 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 according to the first aspect obtained by thermomechanical analysis measurement is 15 ppm / ° C. or less from the viewpoint of followability to the support member. is preferred, 13 ppm/°C or less is more preferred, and 10 ppm/°C or less is even more preferred.
• 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.
• the curable resin composition according to the first aspect contains 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. It is preferably contained at 5 or more and less than 1.0.
• 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 curable resin composition according to the first aspect can contain 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.
• an epoxy resin made from a synthesized phenol resin.
• 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.
• n is 10 or less, the melt viscosity of the resin component does not become too high, and the viscosity decreases during melt molding of the curable resin composition, resulting in poor filling and bonding wires (gold wires that connect elements and leads). There is a tendency that the occurrence of deformation, etc., is suppressed.
• 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 content of the specific copolymerization type epoxy resin with respect to the total mass of the epoxy resin is 50. It is preferably 90% by mass, more preferably 55% by mass to 80% by mass, and even more preferably 60% by mass to 75% by mass.
• the content of the biphenyl-type epoxy resin with respect to the total weight of the epoxy resin is 5% by mass to 40% by mass. % by mass is preferable, 7% by mass to 35% by mass is more preferable, and 10% by mass to 30% by mass is even more preferable.
• the curable resin composition according to the first aspect can contain a phenol-based 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 includes one or more phenolic curing agents selected from the group consisting of aralkyl-type phenolic resins and novolac-type phenolic resins. It is preferably included, more preferably included together.
• 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 phenolic resin is preferably a phenolic 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 becomes low when the curable resin is melt-molded, resulting in poor filling, deformation of the bonding wire (gold wire that connects the element and the lead), and the like. less likely to occur.
• 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 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 phenol-based 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 0.5% by mass to 40% by mass. It is preferably from 1% 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. It is preferably from 65% to 90% by mass, more preferably from 65% by mass to 95% by mass.
• the content of the novolak-type phenolic resin with respect to the total mass of the phenolic curing agent is 5. It is preferably from 10% by mass to 40% by mass, more preferably from 10% by mass to 30% by mass.
• the curable resin composition according to the first aspect includes, in addition to the components described above, a curing accelerator, an inorganic filler, a coupling agent, a stress relaxation agent, a release agent, a coloring agent, a flame retardant, an ion exchanger, Various additives such as resins other than epoxy resins and curing agents other than phenolic curing agents may be contained.
• 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 according to the first aspect 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 thermosetting resin composition may contain curing accelerators 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.
• thermosetting resin composition contains a specific curing accelerator as a curing accelerator
• the content of the specific curing accelerator is preferably 30% by mass or more of the total curing accelerator, and is 50% by mass or more. is more preferable, and 70% by mass or more is even more preferable.
• the amount thereof is preferably 0.1 parts by mass to 30 parts by mass with respect to 100 parts by mass of the resin component, and 1 part by mass to 15 parts by mass. It is more preferable to have When the amount of the curing accelerator is 0.1 parts by mass or more with respect to 100 parts by mass of the resin component, there is a tendency for satisfactory curing in a short period of time. When the amount of the curing accelerator is 30 parts by mass or less with respect to 100 parts by mass of the resin component, the curing speed is not too fast and a good molded article tends to be obtained.
• the curable resin composition according to the first aspect may contain an inorganic filler.
• 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.
• a spherical shape is preferable from the viewpoint of fluidity during molding of the curable resin composition and resistance to mold wear.
• 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. It is preferably 30% by mass to 90% by mass, more preferably 35% by mass to 80% by mass, and even more preferably 40% by mass to 70% by mass of the total curable resin composition.
• the content of the inorganic filler is 30% by mass or more of the entire curable resin composition, 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 is 90% by mass or less of the entire curable resin composition, the increase in viscosity of the curable resin composition is suppressed, the fluidity is further improved, and the moldability tends to be better. It is in.
• the curable resin composition according to the first aspect 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 according to the first aspect contains at least one of 3-aminopropyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane. preferably.
• the content of the coupling agent should be the same as the inorganic filler contained in the curable resin composition, from the viewpoint of the adhesiveness of the interface between the epoxy resin and the inorganic filler.
• 100 parts by mass it is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 8 parts by mass, and 0.05 to 5 parts by mass. is more preferred.
• the curable resin composition according to the first aspect 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 is preferably 0.1 parts by mass to 30 parts by mass with respect to 100 parts by mass of the epoxy resin contained in the curable resin composition. , more preferably 1 to 5 parts by mass.
• the curable resin composition according to the first aspect may contain a release agent from the viewpoint of releasability from the mold.
• 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 is 0.01 parts by mass with respect to 100 parts by mass of the epoxy resin contained in the curable resin composition. It is preferably from 0.1 to 10 parts by mass, more preferably from 0.1 to 10 parts by mass.
• the amount of the release agent is 0.01 parts by mass or more with respect to 100 parts by mass of the resin component, there is a tendency that sufficient releasability can be obtained.
• it is 15 parts by mass or less, there is a tendency that better releasability can be obtained.
• the curable resin composition according to the first aspect 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 curable resin composition contains a colorant
• its content is preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 3% by mass, and 0 More preferably, it is 0.01% by mass to 1% by mass.
• the curable resin composition according to the first aspect may contain a flame retardant.
• 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 according to the first aspect 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 is preferably 1 part by mass to 300 parts by mass, more preferably 2 parts by mass to 150 parts by mass with respect to 100 parts by mass of the epoxy resin contained in the curable resin composition. .
• the curable resin composition according to the first aspect 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 according to the first aspect contains an ion exchanger
• its content is not particularly limited as long as it is sufficient to trap ions such as halogen ions.
• the content of the ion exchanger is preferably 0.1 to 30 parts by mass, more preferably 1 to 5 parts by mass, with respect to 100 parts by mass of the epoxy resin contained in the curable resin composition. is more preferred.
• the curable resin composition according to the first aspect 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 according to the first aspect may contain a curing agent other than the phenolic curing agent.
• 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 from 5% by mass to 35% by mass, more preferably from 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 according to the second aspect is obtained by performing dynamic viscoelasticity measurement on the resin cured product of the curable resin composition.
• the sum of the tan ⁇ values at each temperature of 70°C, 80°C and 90°C is over 0.600.
• the curable resin composition according to the second aspect has excellent reflow resistance.
• the vertical axis is tan ⁇ and the horizontal axis is the temperature from 30 ° C. to 260 ° C., 70 ° C., 80 ° C. and 90 ° C.
• the curable resin composition according to the second aspect in which the total value of tan ⁇ at each temperature of ° C. exceeds 0.600, the internal stress of the cured resin that occurs during reflow tends to be relaxed. It is in.
• 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.
• 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.
• the sum of tan ⁇ values at each temperature of 70°C, 80°C and 90°C is preferably more than 0.700.
• 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 temperature at which tan ⁇ becomes maximum is preferably less than 120°C, more preferably less than 110°C.
• the lower limit of the temperature at which tan ⁇ is maximized is not particularly limited, it can be, for example, 50° C. or higher.
• the maximum value of tan ⁇ is preferably over 0.400, more preferably over 0.410.
• the upper limit of the maximum value of tan ⁇ is not particularly limited, it can be, for example, 1.0 or less.
• the sum of tan ⁇ values at each temperature of 20°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 20° C., 230° C., 240° C. and 250° C. is not particularly limited, but can be, for example, 2.0 or less.
• the value of tan ⁇ at at least any temperature of -10 ° C. at which tan ⁇ becomes maximum is 60 It is preferably greater than, more preferably greater than 63, and even more preferably greater than 65.
• 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 according to the second aspect obtained by thermomechanical analysis is 15 ppm / ° C. or less from the viewpoint of followability to the support member. is preferred, 13 ppm/°C or less is more preferred, and 10 ppm/°C or less is even more preferred.
• 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.
• the curable resin composition according to the second aspect contains the epoxy resin and the phenolic curing agent in such a manner 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. It is preferably contained at 5 or more and less than 1.0.
• curable resin composition Applications of the curable resin composition according to the first aspect and the curable resin composition according to the second aspect are not particularly limited, and can be used in various mounting techniques, for example, as sealing materials for electronic component devices.
• the curable resin composition 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 curability. can be used in a variety of applications where it is desirable to have
• An electronic component device of the present disclosure includes an element and a resin cured product of the curable resin composition according to the first aspect or the curable resin composition according to the second aspect for sealing the element.
• the electronic component device can have 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 adhesiveness to the resin 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 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.

Landscapes

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

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=85412723

Family Applications (1)

Country Status (4)

Citations (8)

• 2022
  • 2022-08-26 CN CN202280057840.4A patent/CN117858924A/zh active Pending
  • 2022-08-26 JP JP2023545532A patent/JPWO2023032860A1/ja active Pending
  • 2022-08-26 WO PCT/JP2022/032271 patent/WO2023032860A1/ja not_active Ceased
  • 2022-08-26 TW TW111132328A patent/TW202313838A/zh unknown

Patent Citations (9)

Also Published As

Similar Documents

Legal Events