WO2020129249A1 - Composition de résine pour scellement et dispositif de composant électronique - Google Patents

Composition de résine pour scellement et dispositif de composant électronique Download PDF

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Publication number
WO2020129249A1
WO2020129249A1 PCT/JP2018/047311 JP2018047311W WO2020129249A1 WO 2020129249 A1 WO2020129249 A1 WO 2020129249A1 JP 2018047311 W JP2018047311 W JP 2018047311W WO 2020129249 A1 WO2020129249 A1 WO 2020129249A1
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Prior art keywords
epoxy resin
resin
mass
resin composition
curing agent
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PCT/JP2018/047311
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English (en)
Japanese (ja)
Inventor
高士 山本
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日立化成株式会社
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Priority to JP2020561127A priority Critical patent/JPWO2020129249A1/ja
Priority to PCT/JP2018/047311 priority patent/WO2020129249A1/fr
Publication of WO2020129249A1 publication Critical patent/WO2020129249A1/fr

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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
    • C08G59/20—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 epoxy compounds used
    • 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 invention relates to a sealing resin composition and an electronic component device.
  • the mounting density is increasing.
  • the mainstream of electronic component devices is changing from the conventional pin insertion type package to the surface mount type package.
  • the surface mount type package is different in mounting method from the conventional pin insertion type package. That is, when the pins are attached to the wiring board, the conventional pin insertion type package does not directly expose the package to high temperature because the pins are inserted into the wiring board and then soldering is performed from the back surface of the wiring board.
  • the surface mount type package since the entire electronic component device is processed by the solder bath, the reflow device, etc., the package is directly exposed to the soldering temperature (reflow temperature).
  • the package absorbs moisture, moisture due to moisture absorption expands rapidly during soldering, and the generated vapor pressure acts as peeling stress, causing peeling between the insert such as the element and lead frame and the sealing material. If they are generated, they may cause package cracks, poor electrical characteristics, and the like. Therefore, development of a sealing material having excellent solder heat resistance (reflow resistance) is desired.
  • epoxy resin which is the main material of the encapsulating material.
  • a method of using a biphenyl type epoxy resin or a naphthalene type epoxy resin as an epoxy resin has been studied (see, for example, JP-A-64-65116 and JP-A-2007-231159).
  • a mold underfill material (hereinafter also referred to as “MUF material”) used in a double side mold (Double Side Mold, hereinafter also referred to as “DSM”) method in which chips are mounted on both the upper surface and the lower surface of a substrate for high density mounting. Development is desired.
  • the encapsulating material used for the surface mount type package is required to have reflow resistance.
  • the reflow resistance is improved by reducing the water absorption rate, the elastic modulus at high temperature (for example, 260° C.), and the like.
  • it is also required to raise the glass transition temperature after curing the sealing material (for example, to 140° C. or higher).
  • the reflow resistance tends to be low, and it is difficult to achieve both the glass transition temperature and the reflow resistance.
  • the sealing material used for the surface mount type package is required to have fluidity.
  • the MUF material used in the DSM system package is required to have high fluidity so that a narrow gap can be filled.
  • the glass transition temperature tends to be low, and it is difficult to achieve both high fluidity and high glass transition temperature.
  • the present disclosure has been made in view of such circumstances, a cured product having both a low elastic modulus at high temperature and a high glass transition temperature is obtained, and the resin composition for sealing having high fluidity and An object is to provide an electronic component device using this.
  • Means for solving the above problems include the following embodiments.
  • a first epoxy resin having an epoxy equivalent of 300 g/eq or more and having a plurality of naphthalene skeletons in the molecule;
  • a second epoxy resin having a viscosity at 150° C. of 0.02 Pa ⁇ sec or less and a number average molecular weight of 1000 or less;
  • a curing agent A resin composition for encapsulation containing: ⁇ 2>
  • the encapsulating resin composition according to ⁇ 1> or ⁇ 2> which includes, as the curing agent, a curing agent having a viscosity of 0.5 Pa ⁇ sec or less at 150°C.
  • curing agent is a resin composition for sealing as described in ⁇ 4> containing at least 1 sort(s) selected from the group which consists of a phenol resin and a polyhydric phenol compound.
  • ⁇ 6> The encapsulating resin composition according to ⁇ 5>, wherein the phenolic resin includes at least one selected from the group consisting of novolac type phenolic resin and triphenylmethane type phenolic resin.
  • ⁇ 7> The encapsulating resin composition according to any one of ⁇ 4> to ⁇ 6>, further including, as the curing agent, a second curing agent having a functional group equivalent of 120 g/eq or more.
  • curing agent is a resin composition for closure as described in ⁇ 7> containing at least 1 sort(s) selected from the group which consists of a phenol resin and a polyhydric phenol compound.
  • ⁇ 9> The encapsulating resin composition according to ⁇ 8>, wherein the phenolic resin contains an aralkyl type phenolic resin.
  • ⁇ 10> The encapsulating resin composition according to any one of ⁇ 7> to ⁇ 9>, in which the second curing agent contains a compound having a biphenyl skeleton in the molecule.
  • ⁇ 11> The encapsulating resin composition according to any one of ⁇ 1> to ⁇ 10>, wherein the first epoxy resin further has a benzene skeleton in the molecule.
  • ⁇ 12> The encapsulating resin composition according to ⁇ 11>, wherein the first epoxy resin further has a methylene group directly bonded to the naphthalene skeleton and the benzene skeleton.
  • ⁇ 13> The encapsulating resin composition according to any one of ⁇ 1> to ⁇ 12>, in which the first epoxy resin has a glycidyloxy group directly bonded to the naphthalene skeleton.
  • ⁇ 14> The encapsulating resin composition according to any one of ⁇ 1> to ⁇ 13>, wherein the content of the second epoxy resin is 50 parts by mass to 150 parts by mass with respect to 100 parts by mass of the first epoxy resin. Stuff.
  • ⁇ 15> The encapsulating resin composition according to any one of ⁇ 1> to ⁇ 14>, further including a third epoxy resin that is an epoxy resin other than the first epoxy resin and the second epoxy resin.
  • ⁇ 16> The encapsulating resin composition according to ⁇ 15>, wherein the epoxy equivalent of the third epoxy resin is 200 g/eq or more.
  • ⁇ 17> The encapsulating resin composition according to ⁇ 15> or ⁇ 16>, in which the third epoxy resin contains a biphenyl skeleton.
  • ⁇ 18> The encapsulating resin composition according to any one of ⁇ 15> to ⁇ 17>, in which the third epoxy resin is an aralkyl type epoxy resin.
  • An electronic component device comprising an element and a cured product of the encapsulating resin composition according to any one of ⁇ 1> to ⁇ 18>, which encapsulates the element.
  • a cured product having both a low elastic modulus at a high temperature and a high glass transition temperature is obtained, and the fluidity of the encapsulating resin composition and an electronic component device using the same are high. Can be provided.
  • each component may include a plurality of types of corresponding substances. When a plurality of substances corresponding to each component are present in the composition, the content of each component means the total content of the plurality of substances present in the composition, unless otherwise specified.
  • the encapsulating resin composition according to the present disclosure (hereinafter, also simply referred to as “composition”) has an epoxy equivalent of 300 g/eq or more, a first epoxy resin having a plurality of naphthalene skeletons in the molecule, and 150 It contains a second epoxy resin having a viscosity of 0.02 Pa ⁇ sec or less at 0° C. and a number average molecular weight of 1000 or less, and a curing agent.
  • the above composition can provide a cured product that has both a low elastic modulus at high temperature (hereinafter also referred to as “high temperature low elastic modulus”) and a high glass transition temperature (hereinafter also referred to as “high Tg”), and , High liquidity.
  • high temperature low elastic modulus a low elastic modulus at high temperature
  • high Tg a high glass transition temperature
  • the encapsulating resin composition used for encapsulating the surface-mounting type package is required to have a high temperature and low elastic modulus of the cured product in order to improve the reflow resistance.
  • a high Tg of the cured product is required.
  • the encapsulating resin composition is also required to have high fluidity so that the composition itself can be injected into a narrow gap.
  • the encapsulating resin composition used for DSM is required to have the high temperature low elastic modulus, high Tg, and high fluidity at high levels.
  • the glass transition temperature of the cured product is likely to be high, but the elastic modulus at high temperature is also likely to be high. Not only lowers the glass transition temperature, but also tends to lower the glass transition temperature. It is also difficult to achieve both high Tg and high fluidity. Specifically, when a low-viscosity component is included in order to improve fluidity, the glass transition temperature of the cured product tends to be low.
  • the composition of the present disclosure includes a first epoxy resin having a plurality of naphthalene skeletons and an epoxy equivalent in the above range, and a second epoxy resin having a viscosity at 150° C. and a number average molecular weight in the above range. And a resin. Therefore, high fluidity can be obtained while achieving both high temperature low elastic modulus and high Tg of the cured product. Although the reason for this is not clear, a high Tg of the cured product can be obtained even if the first epoxy resin has a plurality of naphthalene skeletons and thus the epoxy equivalent is large, and the epoxy equivalent is within the above range. It is speculated that a high temperature low elastic modulus is obtained.
  • the glass in the case of combining with the second epoxy resin Small decrease in transition temperature. Therefore, it is presumed that high fluidity can be obtained while achieving both high temperature low elastic modulus and high Tg of the cured product.
  • the composition of the present disclosure contains the first epoxy resin and the second epoxy resin, a cured product having a low water absorption rate can be obtained.
  • the composition of the present disclosure contains at least a first epoxy resin and a second epoxy resin as an epoxy resin, and may further contain another epoxy resin as necessary.
  • the total content of the first epoxy resin and the second epoxy resin is preferably 50% by mass or more, and more preferably 65% by mass or more, based on all the epoxy resins contained in the composition. ..
  • the total content of the first epoxy resin and the second epoxy resin may be 90% by mass or more, 95% by mass or more, and 98% by mass or more.
  • the first epoxy resin is not particularly limited as long as it has an epoxy equivalent of 300 g/eq or more and has a plurality of naphthalene skeletons in the molecule.
  • the first epoxy resin may be used alone or in combination of two or more.
  • the epoxy equivalent of the first epoxy resin is preferably 300 g/eq to 500 g/eq, and preferably 300 g/eq to 400 g/eq, from the viewpoint of achieving both high temperature low elastic modulus and high Tg of the cured product. Is more preferable and 300 g/eq to 350 g/eq is even more preferable.
  • the epoxy equivalent is measured by dissolving the weighed epoxy resin in a solvent such as methyl ethyl ketone, adding acetic acid and a tetraethylammonium bromide acetic acid solution, and potentiometrically titrating with a perchloric acid acetic acid standard solution. An indicator may be used for this titration.
  • the number average molecular weight of the first epoxy resin is not particularly limited as long as the epoxy equivalent is in the above range, and may be in the range of 300 to 1500, preferably 300 to 1000 from the viewpoint of fluidity, It is more preferably 300 to 800.
  • the number average molecular weight is measured by gel permeation chromatography (GPC) by a usual method.
  • the softening point or melting point is not particularly limited. From the viewpoint of handleability during preparation of the encapsulating resin composition, the softening point or melting point is preferably 50° C. to 130° C., more preferably 60° C. to 110° C., and 70° C. It is more preferably 90°C.
  • the melting point of the epoxy resin is a value measured by differential scanning calorimetry (DSC), and the softening point of the epoxy resin is a value measured by a method (ring and ball method) according to JIS K 7234:1986.
  • the viscosity of the first epoxy resin at 150° C. is preferably 0.05 Pa ⁇ sec to 0.5 Pa ⁇ sec, and 0.1 Pa ⁇ sec to, from the viewpoint of achieving both fluidity and high Tg of the cured product. 0.4 Pa ⁇ sec is more preferable, and 0.2 Pa ⁇ sec to 0.3 Pa ⁇ sec is further preferable.
  • the viscosity at 150° C. is measured with a rheometer MCR301 (Anton Paar). Specifically, a temperature decreasing process of decreasing the temperature of the measurement target from 150° C. to 30° C. and a temperature increasing process of increasing the temperature of the measurement target from 30° C. to 150° C. are performed in this order, and in the temperature increasing process, The viscosity (Pa ⁇ sec) at 150° C. is measured.
  • the measurement conditions are as follows: frequency: 1 Hz, plate: ⁇ 12 mm, gap: 0.2 mm, temperature decrease rate during temperature decrease process: 2° C./min, temperature increase rate during temperature increase process: 2° C./min
  • the first epoxy resin may further have a connecting group between the plurality of naphthalene skeletons.
  • the linking group include a hydrocarbon group such as an alkylene group, a carbonyl group, and an oxygen atom.
  • the first epoxy resin preferably has an alkylene group, and more preferably has a methylene group.
  • the first epoxy resin may have a benzene skeleton in the molecule in addition to the plurality of naphthalene skeletons.
  • the naphthalene skeleton and the benzene skeleton of the first epoxy resin may be bonded via a linking group.
  • the linking group that connects the naphthalene skeleton and the benzene skeleton include a hydrocarbon group such as an alkylene group, a carbonyl group, an oxygen atom, and the like. Among them, an alkylene group is preferable, and a methylene group is more preferable. That is, the first epoxy resin preferably has in its molecule a methylene group that is directly bonded to the naphthalene skeleton and the benzene skeleton.
  • the first epoxy resin has at least two epoxy groups in one molecule.
  • the number of epoxy groups that the first epoxy resin has in one molecule is not particularly limited as long as the epoxy equivalent in the first epoxy resin is in the above range, and 2 to 5 can be mentioned, and 2 to 4 can be mentioned. It is preferably 2-3.
  • the epoxy group is preferably bound to the naphthalene skeleton.
  • the epoxy group is preferably bonded to at least one selected from the group consisting of a naphthalene skeleton and a benzene skeleton, and among them, bonded to the naphthalene skeleton.
  • the two or more epoxy groups are bonded to the naphthalene skeleton, they may be bonded to one naphthalene skeleton or different naphthalene skeletons, and it is preferable that they are bonded to different naphthalene skeletons.
  • the epoxy group When the epoxy group is bonded to the naphthalene skeleton, the epoxy group may be bonded directly to the naphthalene skeleton, or bonded via a linking group (hydrocarbon group such as alkylene group, carbonyl group, oxygen atom, etc.). Good. Among these, it is preferable that the epoxy group is bonded to the naphthalene skeleton via a linking group.
  • the epoxy group is bonded to the naphthalene skeleton through a linking group
  • glycidyl group, glycidyloxy group, glycidyloxycarbonyl group, epoxycycloalkyl group (epoxycyclopentyl group, epoxycyclohexyl group, epoxycyclooctyl group, etc.) etc.
  • the form in which at least one selected is directly bonded to the naphthalene skeleton is mentioned, and among them, the form in which the glycidyloxy group is directly bonded to the naphthalene skeleton is preferable.
  • the first epoxy resin may further have other substituents (alkyl group, alkoxy group, aryl group, aralkyl group, etc.).
  • Examples of the first epoxy resin include epoxy resins represented by the following general formula (I).
  • R 1 to R 5 each independently represent a monovalent organic group having 1 to 18 carbon atoms
  • a1 represents an integer of 0 to 4
  • a2 represents an integer of 0 to 3.
  • A3 is an integer of 0 to 4
  • a4 is an integer of 0 to 4
  • a5 is an integer of 0 to 2
  • a1+a2 is 6 or less
  • a4+a5 is 5 or less
  • m1 is 1 Indicates 4
  • Examples of the monovalent organic group having 1 to 18 carbon atoms represented by R 1 to R 5 in the general formula (I) include a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted Examples thereof include an aryl group and a substituted or unsubstituted aralkyl group.
  • a1 to a5 are preferably integers of 0 to 1, and more preferably 0.
  • M1 in the general formula (I) is preferably 1 to 2, and more preferably 1.
  • the content ratio of the first epoxy resin to the total epoxy resin contained in the composition is preferably 20% by mass to 90% by mass, more preferably 30% by mass to 80% by mass, and further preferably 35% by mass to 70% by mass. ..
  • the content of the first epoxy resin with respect to the total of the resin components contained in the composition is preferably 15% by mass to 70% by mass, more preferably 25% by mass to 60% by mass, and 30% by mass to 50% by mass. Is more preferable.
  • the content of the first epoxy resin in the entire composition is preferably 1.5% by mass to 10% by mass, more preferably 2.5% by mass to 8% by mass, and further preferably 3% by mass to 7% by mass. preferable.
  • the second epoxy resin is not particularly limited as long as it is an epoxy resin other than the first epoxy resin, has a viscosity at 150° C. of 0.02 Pa ⁇ sec or less and a number average molecular weight of 1000 or less. It is not something that will be done.
  • the 2nd epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the viscosity of the second epoxy resin at 150° C. is 0.02 Pa ⁇ sec or less, and from the viewpoint of fluidity and high Tg, it is preferably 0.0001 Pa ⁇ sec to 0.02 Pa ⁇ sec, and 0.001 Pa ⁇ sec. -Sec to 0.02 Pa-sec is more preferable, and 0.005 Pa-sec to 0.02 Pa-sec is further preferable.
  • the number average molecular weight of the second epoxy resin is 1,000 or less, and from the viewpoint of fluidity and high Tg, it is preferably 150 to 850, more preferably 200 to 700, and more preferably 300 to 600. Is more preferable.
  • the epoxy equivalent of the second epoxy resin is not particularly limited as long as the viscosity at 150° C. and the number average molecular weight are within the above ranges, and examples thereof include 150 g/eq to 300 g/eq, and 165 g/from the viewpoint of curability. eq to 275 g/eq is preferable, and 180 g/eq or more and less than 250 g/eq is more preferable.
  • the softening point or melting point is not particularly limited. From the viewpoint of handleability when preparing the encapsulating resin composition, the softening point or melting point is preferably 50° C. to 130° C., more preferably 75° C. to 125° C., and 100° C. More preferably, it is 120°C.
  • the second epoxy resin are selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A and bisphenol F, and naphthol compounds such as ⁇ -naphthol, ⁇ -naphthol and dihydroxynaphthalene.
  • phenol compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A and bisphenol F
  • naphthol compounds such as ⁇ -naphthol, ⁇ -naphthol and dihydroxynaphthalene.
  • a novolak type epoxy resin obtained by epoxidizing a novolak resin obtained by condensing or cocondensing at least one phenolic compound with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, or propionaldehyde under an acidic catalyst Phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, etc.
  • Triphenylmethane type phenol obtained by condensing or co-condensing the above phenolic compound with an aromatic aldehyde compound such as benzaldehyde and salicylaldehyde under an acidic catalyst.
  • Triphenylmethane type epoxy resin obtained by epoxidizing resin
  • Copolymer type epoxy obtained by epoxidizing novolak resin obtained by cocondensing the above-mentioned phenol compound and naphthol compound with an aldehyde compound under an acidic catalyst.
  • Diphenylmethane type epoxy resin which is diglycidyl ether of bisphenol A, bisphenol F, etc.
  • Biphenyl type epoxy resin which is diglycidyl ether of alkyl-substituted or unsubstituted biphenol
  • Stilbene type epoxy which is diglycidyl ether of stilbene phenol compound
  • Sulfur atom-containing epoxy resin which is a diglycidyl ether such as bisphenol S
  • Epoxy resin which is a glycidyl ether of alcohols such as butanediol, polyethylene glycol, polypropylene glycol
  • Phthalic acid isophthalic acid, tetrahydrophthalic acid, etc.
  • Glycidyl ester type epoxy resin which is a glycidyl ester of a carboxylic acid compound; glycidyl amine type epoxy resin, in which active hydrogen bonded to the nitrogen atom of aniline, diaminodiphenylmethane, isocyanuric acid, etc.
  • dicyclopentadiene Dicyclopentadiene-modified epoxy resin obtained by epoxidizing a co-condensation resin of a phenol compound; vinyl cyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxy obtained by epoxidizing an olefin bond in the molecule Cyclohexanecarboxylate, 2-(3,4-epoxy)cyclohex Alicyclic epoxy resins such as xyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane; glycidyl ethers of para-xylylene-modified phenolic resins, para-xylylene-modified epoxy resins, glycidyl ethers of meta-xylylene-modified phenolic resins Metaxylylene-modified epoxy resin; terpene-modified epoxy resin
  • the second epoxy resin is a biphenyl-type epoxy resin, a stilbene-type epoxy resin, a diphenylmethane-type epoxy resin, a sulfur atom-containing epoxy resin, a novolac-type epoxy resin, a dicyclopentadiene-modified, from the viewpoint of a balance between reflow resistance and fluidity.
  • Epoxy resin, triphenylmethane type epoxy resin, copolymer type epoxy resin, and aralkyl type epoxy resin are preferable, and from the viewpoint of fluidity, biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, and sulfur atom-containing Type epoxy resin is more preferable, biphenyl type epoxy resin, diphenylmethane type epoxy resin, and sulfur atom-containing type epoxy resin are further preferable, and among the biphenyl type epoxy resin and diphenylmethane type epoxy resin, bisphenol F type epoxy resin having a bisphenol F skeleton, Among the sulfur atom-containing epoxy resins, a bisphenol S epoxy resin having a bisphenol S skeleton is particularly preferable, and a biphenyl epoxy resin is extremely preferable.
  • the second epoxy resin is preferably an epoxy resin that does not have a plurality of naphthalene skeletons and an epoxy resin that has a plurality of naphthalene skeletons and does not have an ether bond connecting between naphthalene skeletons.
  • An epoxy resin having no or one naphthalene skeleton is more preferable, and an epoxy resin having no naphthalene skeleton is further preferable.
  • the biphenyl type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton.
  • an epoxy resin represented by the following general formula (II) is preferable.
  • 3,8',5' and 5'positions are methyl groups when the positions where oxygen atoms are substituted in R 8 are 4 and 4'positions.
  • YX-4000H (Mitsubishi Chemical Corporation, trade name) other R 8 is a hydrogen atom, all the R 8 are hydrogen atoms 4,4'-bis (2,3-epoxypropoxy) biphenyl, When all R 8 s are hydrogen atoms, and when the positions where oxygen atoms are substituted in R 8 s are 4 and 4'positions, the 3,3',5,5' positions are methyl groups and the other R When 8 is a hydrogen atom, YL-6121H (Mitsubishi Chemical Corporation, trade name), which is a mixed product, is available as a commercial product.
  • YL-6121H Mitsubishi Chemical Corporation, trade name
  • R 8 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aromatic group having 4 to 18 carbon atoms, and all of them may be the same or different.
  • n is an average value and represents a number of 0 to 2.
  • R 8 is preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.
  • n is preferably 0 or 1, and more preferably 0.
  • the stilbene type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton.
  • an epoxy resin represented by the following general formula (III) is preferable.
  • 3,3′,5,5′ positions are methyl groups when the positions where oxygen atoms are substituted in R 9 are 4 and 4′ positions.
  • R 9 is a hydrogen atom other than the above, and all of R 10 are hydrogen atoms, and three of the 3, 3′, 5, 5′ positions of R 9 are methyl groups, ESLV-210 (Sumitomo Chemical Co., Ltd., trade name), etc., which is a mixture of one of which is a t-butyl group, the other R 9 is a hydrogen atom, and all R 10 are hydrogen atoms, It is available as a commercial product.
  • R 9 and R 10 represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all may be the same or different.
  • n is an average value and represents a number of 0 to 2.
  • R 9 and R 10 are each independently a hydrogen atom or a carbon number of 1 to 5 Is preferably a monovalent organic group, and more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • n is preferably 0 or 1, and more preferably 0.
  • the diphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton, and among them, an epoxy resin represented by the following general formula (IV) is preferable, and a bisphenol F type epoxy which is an epoxy resin having a bisphenol F skeleton. Resins are more preferred.
  • R 11 are hydrogen atoms
  • R 12 is replaced with oxygen atoms at positions 4 and 4', 3,3
  • YSLV-80XY bisphenol F type epoxy resin, Nippon Steel Chemical & Material Co., Ltd., trade name
  • R 11 and R 12 represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different.
  • n is an average value and represents a number of 0 to 2.
  • R 11 and R 12 are each independently preferably a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. Further, in the formula (IV), n is preferably 0 or 1, and more preferably 0.
  • the sulfur atom-containing epoxy resin is not particularly limited as long as it is a sulfur atom-containing epoxy resin, and among them, an epoxy resin represented by the following general formula (V) is preferable, and a bisphenol S is an epoxy resin having a bisphenol S skeleton. S-type epoxy resin is more preferable.
  • the epoxy resins represented by the following general formula (V) when the position where the oxygen atom is substituted in R 13 is 4 and 4′ positions, the 3,3′ positions are t-butyl groups, YSLV-120TE (bisphenol S-type epoxy resin, Nippon Steel Chemical & Materials Co., Ltd., trade name) in which the 6,6′ position is a methyl group and the other R 13 is a hydrogen atom is commercially available. is there.
  • R 13 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different.
  • n is an average value and represents a number of 0 to 2.
  • R 13 's are preferably each independently a hydrogen atom or a monovalent organic group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • n is preferably 0 or 1, and more preferably 0.
  • the content of the second epoxy resin with respect to the total epoxy resin contained in the composition is preferably 10% by mass to 80% by mass, more preferably 15% by mass to 70% by mass, and further preferably 15% by mass to 65% by mass. , 20 mass% to 55 mass% are particularly preferable.
  • the content of the second epoxy resin with respect to 100 parts by mass of the first epoxy resin is preferably 15 parts by mass to 150 parts by mass, more preferably 35 parts by mass to 150 parts by mass, further preferably 50 parts by mass to 150 parts by mass. , 60 parts by mass to 140 parts by mass, particularly preferably 75 parts by mass to 125 parts by mass.
  • the content of the second epoxy resin with respect to the total of the resin components contained in the composition is preferably 10% by mass to 70% by mass, more preferably 15% by mass to 70% by mass, and 25% by mass to 60% by mass. Is more preferable, and 30% by mass to 50% by mass is particularly preferable.
  • the content of the second epoxy resin in the entire composition is preferably 1.0% by mass to 10% by mass, more preferably 1.5% by mass to 10% by mass, and 2.5% by mass to 8% by mass. Is more preferable, and 3% by mass to 7% by mass is particularly preferable.
  • the composition may optionally contain an epoxy resin other than the first epoxy resin and the second epoxy resin.
  • the other epoxy resin is not particularly limited as long as it is an epoxy resin other than the first epoxy resin and the second epoxy resin, a novolac type epoxy resin, a triphenylmethane type epoxy resin, a copolymerization type epoxy resin, Diphenylmethane type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, sulfur atom-containing epoxy resin, epoxy resin which is a glycidyl ether of alcohols, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, dicyclopentadiene modified epoxy resin , Alicyclic epoxy resin, paraxylylene modified epoxy resin, metaxylylene modified epoxy resin, terpene modified epoxy resin, dicyclopentadiene modified epoxy resin, cyclopentadiene modified epoxy resin, polycyclic aromatic ring modified epoxy resin, naphthalene type epoxy resin, halogen
  • an aralkyl type epoxy resin such as a biphenylene aralkyl type epoxy resin or a xylylene aralkyl type epoxy resin may be used as the third epoxy resin among other epoxy resins.
  • the third epoxy resin is preferably an aralkyl type epoxy resin, and among them, a biphenylene aralkyl type epoxy resin and a xylylene aralkyl type epoxy resin are more preferable.
  • the third epoxy resin preferably does not have a naphthalene skeleton.
  • the third epoxy resin preferably has a skeleton containing an aromatic ring other than the naphthalene ring, more preferably has a biphenyl skeleton, and is more preferably a biphenylene aralkyl type epoxy resin having a biphenyl skeleton. ..
  • the third epoxy resin which is an aralkyl type epoxy resin having a biphenyl skeleton include an epoxy resin represented by the following general formula (VI).
  • the xylylene aralkyl type epoxy resin include epoxy resins having a structure in which the biphenylene skeleton in the following general formula (VI) is replaced with a xylylene skeleton.
  • R 14 to R 17 each independently represent a monovalent organic group having 1 to 18 carbon atoms
  • a 6 to a 8 each independently represent an integer of 0 to 4
  • a9 represents an integer of 0 to 3
  • m2 represents 1 to 3.
  • Examples of the monovalent organic group having 1 to 18 carbon atoms represented by R 14 to R 17 in the general formula (VI) include a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted Examples thereof include an aryl group and a substituted or unsubstituted aralkyl group.
  • a6 to a9 are preferably integers of 0 to 1, and more preferably 0.
  • M2 in the general formula (VI) is preferably 1 to 2, and more preferably 1.
  • the viscosity of the third epoxy resin at 150° C. may be higher than 0.02 Pa ⁇ sec, and may be in the range of 0.02 Pa ⁇ sec to 0.1 Pa ⁇ sec. From the viewpoint of fluidity, 0.02 Pa ⁇ sec. It is preferably from sec to 0.08 Pa ⁇ sec, more preferably from 0.02 Pa ⁇ sec to 0.06 Pa ⁇ sec.
  • the number average molecular weight of the third epoxy resin is, for example, in the range of 200 to 1200. From the viewpoint of fluidity, it is preferably 250 to 700, and more preferably 300 to 600.
  • the epoxy equivalent in the third epoxy resin is in the range of 180 g/eq to 320 g/eq, preferably 200 g/eq to 300 g/eq, and more preferably 230 g/eq to 280 g/eq from the viewpoint of curability.
  • its softening point or melting point is not particularly limited and may be, for example, in the range of 40° C. to 130° C., from the viewpoint of handleability during preparation of the encapsulating resin composition. 50° C. to 130° C. is preferable, and 50° C. to 100° C. is more preferable.
  • the content of the third epoxy resin with respect to the total epoxy resin contained in the composition is in the range of 2% by mass to 60% by mass, and from the viewpoint of lowering the high temperature elastic modulus while maintaining the glass transition temperature and the fluidity. 10% by mass to 50% by mass is preferable, and 20% by mass to 40% by mass is more preferable.
  • the content of the third epoxy resin with respect to the total of the resin components contained in the composition is in the range of 5% by mass to 40% by mass, and the high temperature elastic modulus is low while maintaining the glass transition temperature and the fluidity. From this viewpoint, 10% by mass to 30% by mass is preferable, and 15% by mass to 25% by mass is more preferable.
  • the content of the third epoxy resin in the entire composition is in the range of 0.5% by mass to 7% by mass, preferably 1% by mass to 5% by mass, and 1.5% by mass to 4% by mass. Is more preferable.
  • the composition comprises at least one hardener.
  • the curing agent may be one generally used in encapsulating resin compositions containing an epoxy resin and is not particularly limited.
  • the curing agent include a phenol curing agent, an amine curing agent, an acid anhydride curing agent, a polymercaptan curing agent, a polyaminoamide curing agent, an isocyanate curing agent, and a blocked isocyanate curing agent.
  • the curing agent is preferably a phenol curing agent, an amine curing agent, and an acid anhydride curing agent, and more preferably a phenol curing agent.
  • the phenol curing agent examples include a phenol resin having two or more phenolic hydroxyl groups in one molecule and a polyhydric phenol compound.
  • polyhydric phenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, etc.
  • a phenol compound and at least one phenolic compound selected from the group consisting of naphthol compounds such as ⁇ -naphthol, ⁇ -naphthol, and dihydroxynaphthalene, and an aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst a novolak type phenol resin obtained by condensation or co-condensation; an aralkyl type phenol resin synthesized from the above phenolic compound and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, etc.
  • a triphenylmethane type phenolic resin a phenolic resin obtained by copolymerizing two or more of these.
  • These phenol resins and polyhydric phenol compounds may be used alone or in combination of two or more.
  • the phenol curing agent is preferably a novolac type phenol resin, an aralkyl type phenol resin, and a triphenylmethane type phenol resin.
  • the viscosity of the curing agent at 150° C. is preferably 0.02 Pa ⁇ sec to 0.5 Pa ⁇ sec, and 0.05 Pa ⁇ sec to 0.4 Pa from the viewpoint of achieving both fluidity and high Tg of the cured product. -Sec is more preferable, and 0.1 Pa-sec to 0.3 Pa-sec is further preferable.
  • the curing agent When the curing agent is solid, its softening point or melting point is not particularly limited. From the viewpoint of moldability and reflow resistance, it is preferably 40° C. to 180° C., and from the viewpoint of handleability during production of the encapsulating resin composition, the softening point or melting point is 50° C. to 130° C. Is more preferable, and 55° C. to 100° C. is further preferable.
  • the melting point or softening point of the curing agent is a value measured in the same manner as the melting point or softening point of the epoxy resin.
  • the number average molecular weight of the curing agent is not particularly limited and may be in the range of 100 to 5000. From the viewpoint of fluidity, it is preferably 100 to 2000, more preferably 100 to 1500.
  • the functional group equivalent of the curing agent is not particularly limited, and is preferably 70 g/eq to 1000 g/eq, more preferably 80 g/eq to 500 g/eq, from the viewpoint of a balance between high temperature low elastic modulus, high Tg, and fluidity. 85 g/eq to 300 g/eq is more preferable, and 90 g/eq to 200 g/eq is particularly preferable.
  • the functional group equivalent refers to a value measured according to JIS K0070:1992.
  • first curing agent a curing agent having a functional group equivalent of less than 120 g/eq (hereinafter, also referred to as “first curing agent”) is used from the viewpoint of a balance between high temperature low elastic modulus, high Tg, and fluidity.
  • first curing agent examples include a phenol curing agent (that is, a phenol resin and a polyphenol compound), and among them, a phenol resin is preferable, and a novolac type phenol resin, an aralkyl type phenol resin, and a triphenylmethane type phenol resin.
  • novolac type phenolic resins and triphenylmethane type phenolic resins are more preferred.
  • novolac type phenolic resins examples include phenolic resins represented by the following general formula (VII).
  • R 31 to R 33 each independently represent a monovalent organic group having 1 to 18 carbon atoms
  • b11 represents an integer of 0 to 4
  • b12 represents an integer of 0 to 3.
  • B13 is an integer of 0 to 4
  • n4 is 0 to 3.
  • Examples of the monovalent organic group having 1 to 18 carbon atoms represented by R 31 to R 33 in the general formula (VII) include a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted Examples thereof include an aryl group and a substituted or unsubstituted aralkyl group.
  • B11 to b13 in the general formula (VII) are preferably integers of 0 to 1, and more preferably 0.
  • N4 in the general formula (VII) is preferably 0 to 2, and more preferably 0 to 1.
  • triphenylmethane type phenol resin examples include a phenol resin represented by the following general formula (VIII).
  • R 26 to R 30 each independently represent a monovalent organic group having 1 to 18 carbon atoms
  • b 6 to b 7 each independently represent an integer of 0 to 4
  • b8 represents an integer of 0 to 3
  • b9 to b10 each independently represents an integer of 0 to 4
  • n3 represents 0 to 3.
  • Examples of the monovalent organic group having 1 to 18 carbon atoms represented by R 26 to R 30 in the general formula (VIII) include a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted Examples thereof include an aryl group and a substituted or unsubstituted aralkyl group.
  • b6 to b10 are preferably integers of 0 to 1, and more preferably 0.
  • N3 in the general formula (VIII) is preferably 1 to 2, and more preferably 1.
  • the composition contains a first curing agent
  • the composition has a functional group equivalent in addition to the first curing agent, from the viewpoint of further lowering the high temperature elastic modulus while maintaining the glass transition temperature and the fluidity as necessary.
  • the second curing agent include a phenol curing agent (that is, a phenol resin and a polyphenol compound), and among them, a phenol resin is preferable, and a novolac type phenol resin, an aralkyl type phenol, and a triphenylmethane type phenol resin are preferable.
  • the aralkyl-type phenol resin is more preferable, and the aralkyl-type phenol resin having a biphenyl skeleton is further preferable.
  • a preferable combination of the first curing agent and the second curing agent is a first curing agent which is a triphenylmethane type phenol resin.
  • a second curing agent which is an aralkyl-type phenol resin.
  • Examples of the aralkyl type phenol resin having a biphenyl skeleton include a phenol resin represented by the following general formula (IX).
  • R 21 to R 25 each independently represent a monovalent organic group having 1 to 18 carbon atoms
  • b 1 to b 3 each independently represent an integer of 0 to 4
  • b4 to b5 each independently represent an integer of 0 to 3
  • n1 represents 1 to 3
  • n2 represents 0 to 3.
  • the monovalent organic group having 1 to 18 carbon atoms represented by R 21 to R 25 in the general formula (IX) includes a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted Examples thereof include an aryl group and a substituted or unsubstituted aralkyl group.
  • b1 to b5 are preferably integers of 0 to 1, and more preferably 0.
  • N1 in the general formula (IX) is preferably 1 to 2, and more preferably 1.
  • N2 in the general formula (IX) is preferably 0 to 2, and more preferably 0-1.
  • the content of the entire curing agent is preferably 10 parts by mass to 50 parts by mass with respect to 100 parts by mass of all the epoxy resins (that is, the entire epoxy resin including the first epoxy resin and the second epoxy resin) contained in the composition, 15 to 40 parts by mass is more preferable, and 20 to 35 parts by mass is further preferable.
  • the content of the entire curing agent with respect to the total of the resin components contained in the composition is preferably 5.0% by mass to 35% by mass, more preferably 10% by mass to 30% by mass, and 15% by mass to 25% by mass. Is more preferable.
  • the content of the entire curing agent with respect to the entire composition is preferably 0.5% by mass to 5.0% by mass, more preferably 1.0% by mass to 3.0% by mass, and 1.5% by mass to 2% by mass. More preferably, it is 0.5% by mass.
  • the content of the second curing agent with respect to 100 parts by weight of the first curing agent is preferably 40 parts by mass to 100 parts by mass, and 50 parts by mass or more. 90 parts by mass is more preferable, and 55 parts by mass to 85 parts by mass is further preferable.
  • the mixing ratio of the epoxy resin and the curing agent is the ratio of the number of functional groups of the curing agent (phenolic hydroxyl group in the case of a phenol curing agent) to the number of epoxy groups of the epoxy resin from the viewpoint of suppressing the unreacted content of each.
  • (Functional group number of curing agent/Epoxy group number of epoxy resin) is preferably set within a range of 0.5 to 2.0, and set within a range of 0.6 to 1.3. Is more preferable, and it is still more preferable to set it in the range of 0.8 to 1.2.
  • the composition may further contain a curing accelerator if necessary.
  • the curing accelerator is not limited as long as it is a compound that accelerates the reaction between the epoxy resin contained in the composition and the curing agent.
  • 1,8-diaza-bicyclo(5,4,0)undecene-7,1,5-diaza-bicyclo(4,3,0)nonene, 5,6-dibutylamino-1,8 A cycloamidine compound such as diaza-bicyclo(5,4,0)undecene-7; maleic anhydride, a quinone compound (eg, 1,4-benzoquinone, 2,5-toluquinone, 1,4 -Naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, and phenyl-1, 4-benzoquinone), diazophenylmethane, a compound having an intramolecular polarization formed by adding a compound having a ⁇ bond such as phenol resin; benzyl
  • imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and the like; derivatives thereof; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris( 4-Methylphenyl)phosphine, diphenylphosphine, phenylphosphine, and other phosphine compounds; intramolecularly formed by adding a compound having a ⁇ bond such as maleic anhydride, the above quinone compound, diazophenylmethane, or phenol resin to the above phosphine compound Phosphorus compounds having polarization; Tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, tetraphenylboron salts such as
  • the content of the curing accelerator with respect to the entire composition is not particularly limited as long as the curing promoting effect is achieved, and is 0.005% by mass to 2% by mass. Is preferable, and 0.01% by mass to 0.5% by mass is more preferable.
  • the composition may optionally further comprise an inorganic filler.
  • the inorganic filler can be used, for example, for the purpose of hygroscopicity, reduction of linear expansion coefficient, improvement of thermal conductivity, and improvement of strength.
  • the type of inorganic filler is not particularly limited. Specifically, spherical silica (for example, fused silica), crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, Inorganic materials such as zirconia, zircon, fosterite, steatite, spinel, mullite, titania, talc, clay and mica can be mentioned. You may use the inorganic filler which has a flame retardant effect.
  • Examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, complex metal hydroxides such as complex hydroxide of magnesium and zinc, zinc borate, and zinc molybdate.
  • Examples of the shape of the inorganic filler include non-powder, spherical beads, fibers, and the like.
  • inorganic fillers may be used alone or in combination of two or more.
  • spherical silica is preferable from the viewpoint of filling property and reduction of linear expansion coefficient
  • alumina is preferable from the viewpoint of high thermal conductivity.
  • the shape of the inorganic filler is preferably spherical from the viewpoints of filling properties and mold abrasion properties.
  • the content of the inorganic filler with respect to the entire composition is 60% by mass from the viewpoint of flame retardancy, moldability, hygroscopicity, linear expansion coefficient reduction, strength improvement and reflow resistance.
  • the above is preferable, 60 mass% to 95 mass% is more preferable from the viewpoint of flame retardancy, and 70 mass% to 90 mass% is further preferable.
  • the composition may further contain a coupling agent, if necessary, in order to enhance the adhesiveness between the resin component and the inorganic filler.
  • the coupling agent is not particularly limited as long as it is generally used in a sealing resin composition containing an epoxy resin, and at least a primary amino group, a secondary amino group, and a tertiary amino group.
  • Examples include silane compounds having one kind, various silane compounds such as epoxysilane, mercaptosilane, alkylsilane, ureidosilane, and vinylsilane, titanium compounds, aluminum chelates, and aluminum/zirconium compounds. From the viewpoint of reflow resistance, it is preferable to use the above silane compound as a coupling agent, and it is more preferable to use a silane compound having a secondary amino group in the molecule.
  • the amount of the coupling agent is preferably 0.05 parts by mass to 5 parts by mass, and 0.1 parts by mass to 2.5 parts by mass with respect to 100 parts by mass of the inorganic filler. More preferably, it is parts by mass.
  • the amount of the coupling agent is 0.05 parts by mass or more with respect to 100 parts by mass of the inorganic filler, the adhesiveness with the frame tends to be further improved.
  • the amount of the coupling agent is 5 parts by mass or less with respect to 100 parts by mass of the inorganic filler, the moldability of the package tends to be further improved.
  • the composition may further contain a mold release agent, if necessary, from the viewpoint of obtaining good mold releasability from the mold during molding.
  • the release agent is not particularly limited, and conventionally known ones can be used. Specific examples of the release agent include carnauba wax, higher fatty acids such as montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid ester, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene. Can be mentioned.
  • the release agents may be used alone or in combination of two or more.
  • the amount of the releasing agent is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.1 parts by mass to 5 parts by mass with respect to 100 parts by mass of the resin component.
  • the amount of the release agent is 0.01 parts by mass or more with respect to 100 parts by mass of the resin component, the releasability tends to be sufficiently obtained.
  • it is 10 parts by mass or less, better adhesiveness tends to be obtained.
  • the composition may further contain a colorant, if desired.
  • a colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead and red iron oxide.
  • the content of the colorant can be appropriately selected according to the purpose and the like.
  • the colorants may be used alone or in combination of two or more.
  • the composition may optionally further comprise a stress relieving agent.
  • a stress relaxation agent By including the stress relaxation agent, the warp deformation of the package and the occurrence of package cracks can be further reduced.
  • the stress relaxation agent include known stress relaxation agents (flexible agents) generally used such as silicone oil and silicone rubber particles.
  • stress relaxation agents include thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based and polybutadiene-based thermoplastic elastomers, NR (natural rubber), NBR (acrylonitrile- (Butadiene rubber), acrylic rubber, urethane rubber, rubber particles such as silicone powder, methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer Rubber particles having a core-shell structure such as The stress relaxation agent may be used alone or in combination of two or more kinds.
  • thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based and polybutadiene-based thermoplastic
  • the composition may further contain other additives, if necessary.
  • Other additives include flame retardants, anion exchangers, adhesion promoters and the like. Further, various additives well known in the art may be added to the composition, if necessary.
  • the method for preparing the composition is not particularly limited.
  • a general method there can be mentioned a method in which predetermined amounts of components are sufficiently mixed with a mixer or the like, then melt-kneaded with a mixing roll, an extruder or the like, cooled, and pulverized. More specifically, for example, a method of uniformly agitating and mixing predetermined amounts of the above-mentioned components, kneading with a kneader, roll, extruder or the like preheated to 70° C. to 140° C., cooling, and pulverizing. Can be mentioned.
  • the composition is preferably solid at room temperature and atmospheric pressure (for example, 25° C. and atmospheric pressure).
  • the shape of the composition when it is a solid is not particularly limited, and examples thereof include powder, granules, and tablets. From the viewpoint of handleability, it is preferable that the size and weight of the curable resin composition when it is in the form of a tablet be such that it meets the molding conditions of the package.
  • the use of the composition is not particularly limited, and the composition can be used in various electronic component devices.
  • the composition of the present disclosure provides a cured product having a low elastic modulus at a high temperature and a high glass transition temperature, and has high fluidity. Therefore, the composition of the present disclosure is particularly suitable for use as a mold underfill material that fills a narrow gap of a DSM in which chips are mounted on both the top surface and the bottom surface of a substrate for high-density mounting.
  • An electronic component device includes an element and a cured product of the above sealing resin composition that seals the element.
  • elements semiconductor chips, transistors, diodes, active elements such as thyristors, active elements such as thyristors, capacitors, resistors
  • support members or mounting substrates such as lead frames, pre-wired tape carriers, wiring boards, glass, and silicon wafers.
  • Passive elements such as coils, etc. are mounted and necessary parts are sealed with the above-mentioned sealing resin composition.
  • the mounting substrate is not particularly limited, and specific examples include organic substrates, organic films, ceramic substrates, interposer substrates such as glass substrates, liquid crystal glass substrates, MCM (Multi Chip Module) substrates, and hybrid substrates. Examples include IC substrates.
  • a specific example of the electronic component device is, for example, a semiconductor device, and more specifically, an element such as a semiconductor chip is arranged on a lead frame (island, tab), and a terminal portion of the element such as a bonding pad is provided.
  • DIP Dual Inline Package
  • PLCC Plastic Leaded Chip Carrier
  • QFP QFP ( Quad Flat Package)
  • SOP Small Outline Package
  • SOJ Small Outline J-lead package
  • TSOP Thin Small Carrier Outer Package Package
  • TQFP Fluor Package
  • TQFP Fluor Package
  • TQFP Fluor Package
  • TCP Tepe Carrier Package obtained by encapsulating the semiconductor chip with the encapsulating resin composition; a semiconductor chip that is connected to wiring formed on a wiring board or glass by wire bonding, flip chip bonding, soldering, or the like.
  • Bare-chip mounted semiconductor devices such as COB (Chip On Board) and COG (Chip On Glass) sealed with the sealing resin composition; wire bonding, flip chip bonding, to wiring formed on a wiring board or glass,
  • a hybrid IC or MCM in which at least one of an active element (semiconductor chip, transistor, diode, thyristor, etc.) and a passive element (capacitor, resistor, coil, etc.) connected by solder or the like is encapsulated with the encapsulating resin composition.
  • a semiconductor chip is mounted on an interposer substrate on which terminals for connecting to a mother board are formed, and the semiconductor chip and wiring formed on the interposer substrate are connected by bumps or wire bonding, and then the semiconductor chip is formed by the resin composition for sealing.
  • BGA Bit Grid Array
  • CSP Chip Size Package
  • MCP Multi Chip Package
  • these semiconductor devices are stacked type packages in which two or more elements are mounted on a mounting substrate in a stacked manner, two or more elements can be sealed with the resin composition for encapsulation at one time. It may be a sealed one-piece mold type package.
  • these semiconductor devices may be a DSM (Double Side Mold) type package in which chips are mounted on both the upper surface and the lower surface of the substrate and are mounted at high density.
  • a method for obtaining an electronic component device such as a semiconductor device in which an element is encapsulated by using the encapsulating resin composition as an encapsulating material
  • a low-pressure transfer molding method an injection molding method, a compression molding method, or the like
  • a dispensing method a casting method, a printing method or the like may be used.
  • Epoxy resin 1-1 Epoxy resin represented by the general formula (I) (where a1 to a5 are all 0, m1 is 1 to 4), epoxy equivalent 320 g/eq, softening point 77° C., 150° C. Viscosity 0.25 Pa ⁇ sec, number average molecular weight 300, Nippon Steel Chemical & Materials Co., Ltd., trade name “ESN-475V”
  • Epoxy resin 2-1 Biphenyl type epoxy resin, epoxy equivalent 192 g/eq, softening point 107° C., viscosity at 150° C.
  • Epoxy resin 2-2 Bisphenol F type epoxy resin, epoxy equivalent 192 g/eq, melting point 66° C., viscosity at 150° C. 0.01 Pa ⁇ sec, number average molecular weight 384, Nippon Steel Chemical & Materials Co., Ltd., trade name “YSLV- 80XY” Epoxy resin 2-3: Bisphenol S type epoxy resin, epoxy equivalent 245 g/eq, melting point 111° C., viscosity at 150° C.
  • Epoxy resin 3-1 aralkyl type epoxy resin, epoxy resin represented by the general formula (VI) (where a6 to a9 are all 0, m2 is 1 to 3), epoxy equivalent 269 g/eq, softening point 52 .4° C., 150° C. viscosity 0.04 Pa ⁇ sec, number average molecular weight 450, Nippon Kayaku Co., Ltd., trade name “NC-3000 LLC”
  • Epoxy resin C-1 novolac type epoxy resin, epoxy equivalent 200 g/eq, softening point 60° C., viscosity at 150° C.
  • Epoxy resin C-2 triphenylmethane type epoxy resin, epoxy equivalent 167 g/eq, softening point 61° C., viscosity at 150° C. 0.11 Pa ⁇ sec, number average molecular weight 850, Nippon Kayaku Co., Ltd., trade name “EPPN- 501HY”
  • Curing agent 1 Novolak type phenolic resin represented by the above general formula (VII) (provided that b11 to b13 are all 0, n4 is 0 to 3), hydroxyl group equivalent 104 g/eq, softening point 71° C., 150° C.
  • Curing agent 2 triphenylmethane type phenolic resin represented by the above general formula (VIII) (however, b6 to b10 are all 0, n3 is 0 to 3), hydroxyl group equivalent 103 g/eq, softening point 83° C., 150 Viscosity at 0.10 Pa ⁇ sec, number average molecular weight 550, Meiwa Kasei Co., Ltd., trade name “MEH-7500-3S”
  • Hardener 3 Phenolic resin represented by the above general formula (IX) (provided that b1 to b5 are all 0, n1 is 1 to 3, n2 is 0 to 3), hydroxyl equivalent is 166 g/eq, softening point 66° C. , Viscosity at 150° C. 0.05 Pa ⁇ sec, number average molecular weight 1100, Mei
  • Curing accelerator 1 Imidazole curing accelerator, Hitachi Chemical Co., Ltd., trade name "HP-850NP”
  • Curing accelerator 2 Phosphorus curing accelerator, addition product of tributylphosphine and benzoquinone
  • Coupling agent 1 3-methacryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd., trade name "KBM-503”
  • Coupling agent 2 3-phenylaminopropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd., trade name "KBM-573” Release Agent: Hoechst Wax, Clariant, trade name "HW-E” Pigment: Carbon black, Mitsubishi Chemical Corporation, trade name “MA600”
  • the resin composition for encapsulation was molded into a disk having a diameter of 50 mm and a thickness of 3 mm under the above-mentioned molding conditions (molding temperature: 175° C.), and immediately after molding, a Shore D type hardness meter (Kobunshi Keiki Co., Ltd., Asker, type) The hardness at the time of heating was measured using a D durometer).
  • the encapsulating resin composition was molded under the above molding conditions (molding temperature: 175° C.) to prepare a test piece having a shape of 19 mm ⁇ 3 mm ⁇ 3 mm.
  • the glass transition temperature (hereinafter abbreviated as Tg) was determined from the bending point of the linear expansion curve measured on the test piece using a thermomechanical analyzer (TAS-100) of Rigaku Denki, under the condition of a temperature rising rate of 5° C./min. ..
  • Tg glass transition temperature
  • TAS-100 thermomechanical analyzer
  • the linear expansion coefficient hereinafter, the former is abbreviated as ⁇ 1 and the latter abbreviated as ⁇ 2) was obtained from the inclinations of Tg or less and the inclinations of Tg or more.
  • the encapsulating resin composition was molded under the above molding conditions (molding temperature: 175° C.) to prepare a test piece having a shape of 70 mm ⁇ 10 mm ⁇ 3 mm.
  • Molding temperature 175° C.
  • a three-point support type bending test according to JIS-K-6911 (2006) was conducted at 250° C. to obtain the high-temperature bending elastic modulus, high-temperature bending strength, and high-temperature elongation at break, respectively. It was The flexural modulus E is defined by the following formula.
  • E is a bending elastic modulus (MPa)
  • P is a load cell value (N)
  • y is a displacement amount (mm)
  • the bottom surface (adhesive surface) of the encapsulating resin composition has a circular shape with an area of 10 mm 2 , the upper surface has a circular shape of 8 mm 2 , and the truncated cone has a height of 4 mm. It was molded into a shape and post-cured at 180° C. for 90 seconds. After that, using a bond tester (Nordson Advanced Technology Co., Ltd., product name “Dage 4000”), the shear rate was set to 50 ⁇ m/s and the height was set to 100 ⁇ m while keeping the temperature of the copper plate at room temperature (25° C.). Then, the shear adhesive force (MPa) applied when the test piece fell off was determined as the adhesive strength.
  • MPa shear adhesive force
  • Resin composition for encapsulation of 80-pin flat package (QFP) (lead frame material: copper alloy, lead tip silver-plated product) with external dimensions of 20 mm ⁇ 14 mm ⁇ 2 mm mounted with 8 mm ⁇ 10 mm ⁇ 0.4 mm silicon chip.
  • QFP 80-pin flat package
  • the molded product was molded under the above molding conditions (molding temperature: 175° C.), and post-cured at 180° C. for 5 hours to prepare a test package.
  • the test package was humidified under the conditions of 85° C., 60% RH, and 168 hours, and reflow treatment was performed under the conditions of 260° C. for 10 seconds.
  • the presence or absence of peeling of the lead frame die paddle top portion was observed using an ultrasonic imaging device (SAT), and the number of peeling-generated packages was evaluated with respect to the total number of test packages (10). Further, with respect to the test packages after the reflow treatment, the presence or absence of cracks was observed with a microscope, and the number of cracked packages was evaluated with respect to the total number of test packages (10).
  • SAT ultrasonic imaging device
  • the glass transition temperature of the cured product was 140° C. or higher, the high temperature bending elastic modulus of the cured product was low, and a sealing composition having high fluidity was obtained.
  • the spiral flow (fluidity) is improved without significantly changing the glass transition temperature and the high temperature bending elastic modulus, as compared with Reference Example 1.
  • the glass transition temperature of Comparative Example B-1 is significantly lower than that of Comparative Example B-2. Further, it can be seen that the water absorption rate in this example is lower than that in the comparative example.

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

Abstract

L'invention concerne une composition de résine pour scellement, qui contient : une première résine époxy qui a un équivalent époxy de 300 g/éq ou plus, tout en ayant une pluralité de squelettes de naphtalène dans chaque molécule ; une seconde résine époxy qui a une viscosité à 150°C inférieure ou égale à 0,02 Pa·s et un poids moléculaire moyen en nombre inférieur ou égal 1000 ; et un agent de durcissement.
PCT/JP2018/047311 2018-12-21 2018-12-21 Composition de résine pour scellement et dispositif de composant électronique WO2020129249A1 (fr)

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JP2020561127A JPWO2020129249A1 (ja) 2018-12-21 2018-12-21 封止用樹脂組成物及び電子部品装置
PCT/JP2018/047311 WO2020129249A1 (fr) 2018-12-21 2018-12-21 Composition de résine pour scellement et dispositif de composant électronique

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021157623A1 (fr) * 2020-02-06 2021-08-12 昭和電工マテリアルズ株式会社 Composition de résine époxy pour un moulage par transfert, procédé de production s'y rapportant, composition de résine époxy pour un moulage par compression et dispositif à composant électronique

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07228663A (ja) * 1994-02-17 1995-08-29 Dai Ichi Kogyo Seiyaku Co Ltd エポキシ樹脂及びエポキシ樹脂組成物
JP2009108147A (ja) * 2007-10-29 2009-05-21 Nippon Kayaku Co Ltd フェノール樹脂、エポキシ樹脂、エポキシ樹脂組成物およびその硬化物
JP2015038197A (ja) * 2013-07-19 2015-02-26 味の素株式会社 樹脂組成物
JP2018152556A (ja) * 2017-03-10 2018-09-27 味の素株式会社 樹脂組成物層

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07228663A (ja) * 1994-02-17 1995-08-29 Dai Ichi Kogyo Seiyaku Co Ltd エポキシ樹脂及びエポキシ樹脂組成物
JP2009108147A (ja) * 2007-10-29 2009-05-21 Nippon Kayaku Co Ltd フェノール樹脂、エポキシ樹脂、エポキシ樹脂組成物およびその硬化物
JP2015038197A (ja) * 2013-07-19 2015-02-26 味の素株式会社 樹脂組成物
JP2018152556A (ja) * 2017-03-10 2018-09-27 味の素株式会社 樹脂組成物層

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021157623A1 (fr) * 2020-02-06 2021-08-12 昭和電工マテリアルズ株式会社 Composition de résine époxy pour un moulage par transfert, procédé de production s'y rapportant, composition de résine époxy pour un moulage par compression et dispositif à composant électronique

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