WO2022210384A1 - 封止用樹脂組成物およびこれを用いた電子装置 - Google Patents
封止用樹脂組成物およびこれを用いた電子装置 Download PDFInfo
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- WO2022210384A1 WO2022210384A1 PCT/JP2022/014525 JP2022014525W WO2022210384A1 WO 2022210384 A1 WO2022210384 A1 WO 2022210384A1 JP 2022014525 W JP2022014525 W JP 2022014525W WO 2022210384 A1 WO2022210384 A1 WO 2022210384A1
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- resin composition
- epoxy
- sealing
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- resin
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- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- YOTZYFSGUCFUKA-UHFFFAOYSA-N dimethylphosphine Chemical compound CPC YOTZYFSGUCFUKA-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- JLHMVTORNNQCRM-UHFFFAOYSA-N ethylphosphine Chemical compound CCP JLHMVTORNNQCRM-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- YKIKLXKZLFKIJB-UHFFFAOYSA-J magnesium;zinc;tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mg+2].[Zn+2] YKIKLXKZLFKIJB-UHFFFAOYSA-J 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/562—Protection against mechanical damage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G59/20—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
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3218—Carbocyclic compounds
-
- 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
- C08G59/621—Phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- 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
- H01L23/293—Organic, e.g. plastic
- H01L23/295—Organic, e.g. plastic containing a filler
Definitions
- the present invention relates to a sealing resin composition and an electronic device using the same. More particularly, the present invention relates to resin compositions for encapsulating electronic components such as semiconductors, and devices comprising electronic components encapsulated with such resin compositions.
- SiC/GaN power semiconductor devices equipped with elements using SiC (silicon carbide) or GaN (gallium nitride) have attracted attention from the viewpoint of effective utilization of electric energy (see, for example, Patent Document 1). .
- Such devices not only have significantly reduced power loss compared to conventional devices using Si, but can also operate at higher voltages, larger currents, and at temperatures above 200°C. Since it is possible, it is expected to develop into applications that were difficult to apply to conventional Si power semiconductor devices.
- elements that can operate under severe conditions represented by elements (semiconductor elements) using SiC/GaN, are not suitable for semiconductor encapsulants provided in semiconductor devices to protect these elements.
- elements semiconductor elements
- a sealing material containing a cured epoxy resin composition as a main material is used as a semiconductor sealing material from the viewpoint of adhesiveness, electrical stability, and the like.
- the glass transition temperature (Tg) is generally used as an index representing the heat resistance of a cured product of such a resin composition. This is because the encapsulating resin composition (cured product) becomes rubber-like in a temperature range of Tg or higher, which reduces its strength and adhesive strength. Therefore, as a method for increasing Tg, the epoxy group equivalent of the epoxy resin contained in the resin composition or the hydroxyl group equivalent of the curing agent (phenolic resin curing agent) is lowered to increase the crosslink density, or (Epoxy group and hydroxyl group) A technique such as making the structure connecting between them rigid.
- the resin skeleton formed by the epoxy resin and the curing agent and the density of the functional groups should be designed under optimal conditions to have a high Tg, adhesion and high temperature resistance. Realization of a resin composition designed to be excellent in reliability is desired.
- the present invention provides a resin composition capable of forming a semiconductor encapsulant that has a high glass transition temperature and is excellent in adhesion and high-temperature reliability.
- the present invention also provides an electronic device obtained by encapsulating an electronic component with such a resin composition.
- the epoxy resin contains an epoxy resin having 2 or more and 6 or less epoxy groups in the molecule
- the curing agent contains a compound having two or more active hydrogens in the molecule
- the equivalent ratio which is the ratio of the epoxy equivalent of the epoxy resin to the active hydrogen equivalent of the curing agent, is 1.4 or more and 2.0 or less.
- an electronic device comprising an electronic component encapsulated with the encapsulating resin composition.
- a sealing resin composition and an electronic device having an excellent balance of high Tg, adhesion and high-temperature reliability are provided.
- the resin composition of the present embodiment contains an epoxy resin, a curing agent and an inorganic filler, the epoxy resin contains an epoxy resin having 2 or more and 6 or less epoxy groups in the molecule, and the curing agent contains contains a compound having two or more active hydrogens, and the lower limit of the equivalent ratio, which is the ratio of the epoxy equivalent of the epoxy resin to the active hydrogen equivalent of the curing agent, is preferably 1.4 or more, more preferably 1 0.5 or more, more preferably 1.6 or more. Also, the upper limit of the equivalent ratio is preferably 2.0 or less, more preferably 1.85, still more preferably 1.75.
- the amount of epoxy groups in the epoxy resin within the above range, the cross-linking density between the epoxy resin and the curing agent is improved, which is preferable. This has the effect of inhibiting the movement and reaction of free ions contained in the resin composition and preventing deterioration of the resin.
- the amount of epoxy groups in the epoxy resin within the above range, the residual amount of unreacted curing agent can be reduced, and the influence of polarization of unreacted curing agent can be reduced.
- the amount of active hydrogen in the curing agent within the above range, the cross-linking density between the epoxy resin and the curing agent is improved, which is preferable. This has the effect of inhibiting the movement and reaction of free ions contained in the resin composition and preventing deterioration of the resin.
- the equivalent ratio to the above lower limit or more, the residual amount of unreacted curing agent can be reduced, and the influence of polarization of the unreacted curing agent can be reduced.
- Crosslinking density improves and it becomes suitable. This has the effect of inhibiting movement and reaction of free ions contained in the resin composition, preventing deterioration of the resin, and improving high-temperature reliability of the resin composition.
- the equivalent ratio equal to or less than the upper limit, the fluidity of the resin composition is made more suitable. And the adhesion to the lead frame or substrate can be improved.
- the epoxy equivalent of the epoxy resin can be measured according to JIS K7236, and is the mass of the resin containing one equivalent of epoxy groups. Further, in the present embodiment, when a plurality of types of epoxy resins are mixed and used, the epoxy equivalent is the number of equivalents after mixing the plurality of types of epoxy resins.
- the above active hydrogen equivalent means a functional group having an active hydrogen reactive with an epoxy group (hereinafter referred to as an active hydrogen group.
- active hydrogen groups include acid anhydride groups, carboxyl groups, amino groups, and phenolic hydroxyl groups.
- carboxyl group (--COOH) and phenolic hydroxyl group (--OH) are calculated as 1 mol, and amino group (--NH 2 ) as 2 mol.
- the active hydrogen equivalent can be determined by measurement. For example, by reacting a monoepoxy resin with a known epoxy equivalent such as phenyl glycidyl ether with a curing agent with an unknown active hydrogen equivalent and measuring the amount of monoepoxy resin consumed, the active hydrogen equivalent of the curing agent used can be asked for.
- the active hydrogen equivalent is the number of equivalents after mixing the plurality of types of curing agents.
- epoxy resin preferably contains a monomer represented by the following general formula (1).
- n and n indicate the number of epoxy groups on the naphthalene ring, each independently representing an integer of 1 to 3.
- the epoxy resins that can be used in the present embodiment include known epoxy resins that are generally used in epoxy resin compositions for sealing. be done.
- known epoxy resins include phenols such as phenol novolac type epoxy resins and ortho-cresol novolac type epoxy resins, phenols such as cresol, xylenol, resorcinol, catechol, bisphenol A and bisphenol F, and/or ⁇ -naphthol, ⁇ - Epoxidized novolak resins obtained by condensation or co-condensation of naphthols such as naphthol and dihydroxynaphthalene and compounds having aldehyde groups such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde under an acidic catalyst; Diglycidyl ethers such as bisphenol A, bisphenol F, bisphenol S, and bisphenol A/D; biphenyl ethers such as bisphenol A, bisphenol F
- the epoxy resin containing the monomer represented by the general formula (1) may be used alone, or the known epoxy resin other than the monomer represented by the general formula (1) may be used.
- the epoxy resin may be used alone, or one or more epoxy resins selected from the known epoxy resins described above and an epoxy resin containing a monomer represented by the general formula (1) may be mixed. may be used.
- the epoxy resin is a mixture of an epoxy resin containing the monomer represented by the general formula (1) and one or more epoxy resins different from the monomer.
- the content of the total epoxy resin in the encapsulating resin composition is set to It is preferably 5% by mass or more, more preferably 6% by mass or more, and still more preferably 7% by mass or more based on the entire product.
- the content of the total epoxy resin in the encapsulating resin composition is It is preferably 15% by mass or less, more preferably 14% by mass or less, and still more preferably 13% by mass or less based on the entire composition.
- the resin composition does not contain ionic impurities such as Na ions, Cl ions, and S ions as much as possible.
- the epoxy equivalent weight of all the epoxy resins in the encapsulating resin composition is preferably 100 g/g from the viewpoint of realizing excellent fluidity and improving filling properties and adhesion during molding. eq or more, more preferably 120 g/eq or more, and still more preferably 150 g/eq or more.
- the epoxy equivalent of all the epoxy resins in the encapsulating resin composition is preferably 500 g/ eq or less, more preferably 480 g/eq or less, and still more preferably 450 g/eq or less.
- Curing agent Curing agent
- Curing agents that can be used in this embodiment include known curing agents that are generally used in epoxy resin compositions for sealing. Specific examples of known curing agents include phenol-based curing agents and amine-based curing agents (curing agents having an amino group).
- phenol-based curing agents examples include phenols such as phenol, cresol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol and aminophenol, and/or naphthols such as ⁇ -naphthol, ⁇ -naphthol and dihydroxynaphthalene, and formaldehyde.
- Polyfunctional phenols such as novolac type phenolic resins, triphenylmethane type phenolic resins and biphenylene skeleton-containing polyfunctional phenolic resins obtained by condensing or co-condensing compounds having an aldehyde group such as benzaldehyde and salicylaldehyde in the presence of an acidic catalyst.
- Phenol aralkyl-type phenol resins such as biphenylene skeleton-containing polyfunctional phenol resins synthesized from resins, phenols and/or naphthols and dimethoxyparaxylene or bis(methoxymethyl)biphenyl, dicyclopentadiene-type phenol resins, terpene-modified phenol resins is mentioned.
- Amine-based curing agents include linear aliphatic diamines having 2 to 20 carbon atoms such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, metaphenylenediamine, paraphenylenediamine, paraxylenediamine, 4,4' -diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodicyclohexane, bis(4-aminophenyl)phenylmethane, 1 ,5-diaminonaphthalene, metaxylenediamine, paraxylenediamine, 1,1-bis(4-aminophenyl)cyclohexane, dicyanodiamide and the like.
- curing agents include polyoxystyrenes such as polyparaoxystyrene; alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA); trimellitic anhydride (TMA); Acid anhydrides including aromatic acid anhydrides such as pyromellitic acid (PMDA) and benzophenonetetracarboxylic acid (BTDA); polymercaptan compounds such as polysulfide, thioesters and thioethers; isocyanates such as isocyanate prepolymers and blocked isocyanates Compounds; organic acids such as carboxylic acid-containing polyester resins and the like can be mentioned.
- polyoxystyrenes such as polyparaoxystyrene
- alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA); trimellitic anhydr
- the curing agent used in the resin composition for semiconductor encapsulation preferably contains one or two of polyfunctional phenol resins and phenol aralkyl phenol resins from the viewpoint of adhesion and high-temperature reliability. More preferably, it contains a triphenylmethane-type phenolic resin or a biphenylene skeleton-containing polyfunctional phenolic resin. These may be used alone or in combination of two or more.
- the content of the curing agent in the encapsulating resin composition is adjusted from the viewpoint of achieving excellent fluidity during molding and improving filling properties and adhesion. It is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more based on the whole.
- the content of the curing agent in the encapsulating resin composition It is preferably 25% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less based on the entire product.
- the inorganic filler has the function of reducing the increase in moisture absorption and the decrease in strength associated with curing of the resin composition, and inorganic fillers commonly used in the field can be used.
- inorganic fillers include fused silica, spherical silica, crystalline silica, alumina, silicon nitride and aluminum nitride, and these inorganic fillers may be used singly or in combination.
- the average particle diameter D50 of the inorganic filler can be, for example, 0.01 ⁇ m or more and 150 ⁇ m or less.
- the lower limit of the amount of the inorganic filler in the resin composition is preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass, relative to the total mass of the resin composition. That's it.
- the lower limit is within the above range, it is possible to more effectively reduce the increase in moisture absorption and the decrease in strength accompanying curing of the obtained resin composition, and therefore the solder crack resistance of the cured product can be further improved. can be improved.
- the upper limit of the amount of the inorganic filler in the resin composition is preferably 93% by mass or less, more preferably 91% by mass or less, and still more preferably 90% by mass, relative to the total mass of the resin composition. % by mass or less. When the upper limit is within the above range, the obtained resin composition has good fluidity and good moldability.
- inorganic flame retardants such as zinc borate, zinc molybdate, and antimony trioxide, which will be described later, these inorganic flame retardants and the above
- the total amount of inorganic fillers is preferably within the above range.
- the resin composition of the present invention may contain the components shown below in addition to the curing agent, epoxy resin and inorganic filler.
- the curing accelerator has a function of accelerating the reaction between the epoxy group of the epoxy resin and the reactive group of the curing agent, and curing accelerators commonly used in the field are used.
- curing accelerators include phosphorus atom-containing compounds such as organic phosphines, tetrasubstituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds; -Diazabicyclo(5,4,0)undecene-7, benzyldimethylamine, 2-methylimidazole, etc.
- Examples include amidines and tertiary amines, and nitrogen atom-containing compounds such as quaternary salts of the above amidines and amines. One or more of these can be used in combination.
- phosphorus atom-containing compounds are preferred from the viewpoint of curability, and phosphobetaine compounds and adducts of phosphine compounds and quinone compounds are particularly preferred from the viewpoint of solder resistance and fluidity.
- Phosphorus atom-containing compounds such as tetra-substituted phosphonium compounds and adducts of phosphonium compounds and silane compounds are particularly preferable in that the contamination of the silane compound is mild.
- the coupling agent has a function of improving the adhesion between the epoxy resin and the inorganic filler when the resin composition contains the inorganic filler.
- a silane coupling agent is used.
- silane coupling agents can be used, but it is preferable to use aminosilane. This can improve the fluidity and solder resistance of the resin composition.
- aminosilane examples include, but are not limited to, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropylmethyldimethoxysilane, N-phenyl ⁇ -aminopropyltriethoxysilane, N-phenyl ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltriethoxysilane, N-6-(amino hexyl)3-aminopropyltrimethoxysilane, N-(3-(trimethoxysilylpropyl)-1,3-benzenedimethanamine, and the like.
- the lower limit of the mixing ratio of the coupling agent such as the silane coupling agent is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass in the total resin composition. That's it. If the lower limit of the mixing ratio of the coupling agent such as the silane coupling agent is within the above range, the interfacial strength between the epoxy resin and the inorganic filler does not decrease, and good solder crack resistance in electronic devices can be achieved. Obtainable.
- the upper limit of the mixing ratio of the coupling agent such as the silane coupling agent is preferably 1% by mass or less, more preferably 0.8% by mass or less, and particularly preferably 0.6% by mass in the total resin composition. It is below.
- the mixing ratio of the coupling agent such as the silane coupling agent is within the above range, the interfacial strength between the epoxy resin and the inorganic filler does not decrease, and good solder crack resistance in the device can be obtained. be able to. Further, when the mixing ratio of the coupling agent such as the silane coupling agent is within the above range, the water absorption of the cured product of the resin composition does not increase, and good solder crack resistance in electronic devices can be obtained. can be done.
- the inorganic flame retardant has a function of improving the flame retardancy of the resin composition, and generally used inorganic flame retardants are used.
- metal hydroxides that inhibit the combustion reaction by dehydrating and absorbing heat during combustion and composite metal hydroxides that can shorten the combustion time are preferably used.
- metal hydroxides examples include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, and zirconia hydroxide.
- the composite metal hydroxide is a hydrotalcite compound containing two or more metal elements, wherein at least one metal element is magnesium, and the other metal elements are calcium, aluminum, tin, titanium, and iron. , cobalt, nickel, copper, or zinc.
- a magnesium hydroxide-zinc solid solution is commercially available and readily available.
- aluminum hydroxide and magnesium hydroxide/zinc solid solution are preferable from the viewpoint of the balance between adhesion and high-temperature reliability.
- the inorganic flame retardants may be used alone or in combination of two or more. Further, for the purpose of reducing the influence on adhesion, the surface may be treated with a silicon compound such as a silane coupling agent or an aliphatic compound such as wax before use.
- a silicon compound such as a silane coupling agent or an aliphatic compound such as wax before use.
- the inorganic flame retardant may be used, but preferably the inorganic flame retardant is dried at 125 ° C. for 20 hours, and the weight after cooling in a desiccator is taken as the initial weight, and the high temperature of 200 ° C. is used.
- the inorganic flame retardant is put into a tank, heat-treated for 1000 hours, and the weight after cooling in a desiccator is defined as the weight after treatment.
- the epoxy resin contains an epoxy resin having 2 to 6 epoxy groups in the molecule
- the curing agent contains a compound having 2 or more active hydrogens in the molecule
- the curing agent Since the equivalent ratio, which is the ratio of the epoxy equivalent of the epoxy resin to the active hydrogen equivalent of the epoxy resin, is 1.4 or more and 2.0 or less, it has high flame retardancy and also functions as a flame retardant. Therefore, even if the addition of a metal hydroxide-based flame retardant, which may release water at a high temperature of 200 ° C. or higher and result in an increase in the weight loss rate of the cured product, is omitted, the flame retardant is added. It is possible to impart the same properties to the resin composition as in the case of
- Colorants such as carbon black, red iron oxide, and titanium oxide; ion scavengers; natural waxes such as carnauba wax, synthetic waxes such as polyethylene wax, and higher fatty acids such as stearic acid and zinc stearate and metal salts thereof or release agents such as paraffin; and low-stress additives such as silicone oil and silicone rubber.
- the resin composition of the present invention can be obtained by mixing the above curing agent and epoxy resin, and, if necessary, the above other components by a method commonly used in the field.
- the glass transition temperature (Tg ) is preferably 190°C, more preferably 200°C, and still more preferably 210°C.
- the measurement start temperature is not particularly limited, it is 25° C., for example.
- Tg is at least the above lower limit, for example, when an electronic component is sealed using the resin composition of the present embodiment, the strength of the cured product of the resin composition during high temperature treatment such as reflow treatment, and the resin A decrease in adhesive strength between the composition and the lead frame or substrate can be prevented, and high-temperature reliability can be improved.
- the upper limit of the glass transition temperature (Tg) of the sealing resin composition is preferably 330°C, more preferably 290°C, and still more preferably 250°C.
- Tg glass transition temperature
- the lower limit of the water absorption of the resin composition measured according to JIS K 7209 is preferably 0%, more preferably 0.1%, still more preferably 0 .28%.
- the resin composition of the present embodiment is used for encapsulation of an electronic component, for example, when the water absorption is equal to or higher than the above lower limit, the adhesiveness between the resin composition and the lead frame or substrate is excellent.
- the upper limit of the water absorption rate is preferably 0.6%, more preferably 0.4%, and still more preferably 0.32%. When the water absorption rate is equal to or less than the above upper limit, for example, when the resin composition of the present embodiment is used for sealing electronic components, it is possible to obtain excellent high-temperature reliability and good solder crack resistance in devices. can.
- the resin composition is heat-treated at 175° C. for 120 seconds and then treated at 200° C. for 4 hours to obtain a cured product having a viscosity of 300 when measured using a dynamic viscoelasticity measuring instrument.
- the lower limit of the ratio E'300 / E'350 of the storage elastic modulus E'300 at °C and the storage elastic modulus E'350 at 350 °C is preferably 1.4, more preferably 1.45, and further Preferably it is 1.5.
- the ratio E' 300 /E' 350 is equal to or higher than the above lower limit, for example, when the resin composition of the present embodiment is used for encapsulating an electronic component, the adhesion between the resin composition and the lead frame or substrate Excellent in nature.
- the upper limit of E' 300 /E' 350 is preferably 2.0, more preferably 1.95, still more preferably 1.9.
- the ratio E' 300 /E' 350 is equal to or less than the above upper limit value, for example, when the resin composition of the present embodiment is used for sealing electronic components, excellent high temperature reliability and good solder resistance in the device can be obtained. Crack resistance can be obtained.
- the resin composition is heat-treated at 175° C. for 120 seconds and then treated at 200° C. for 4 hours to obtain a cured product having a viscosity of 350 when measured using a dynamic viscoelasticity measuring instrument.
- the lower limit of the ratio E'350 / E'400 between the storage modulus E'350 at °C and the storage modulus E'400 at 400 °C is preferably 1.4, more preferably 1.5, and further Preferably it is 1.6.
- the ratio E' 350 /E' 400 is equal to or higher than the above lower limit, for example, when the resin composition of the present embodiment is used for encapsulating electronic components, the adhesion between the resin composition and the lead frame or substrate Excellent in nature.
- the upper limit of E' 350 /E' 400 is preferably 2.0, more preferably 1.9, still more preferably 1.8.
- the ratio E' 350 /E' 400 is equal to or less than the above upper limit value, for example, when the resin composition of the present embodiment is used for sealing electronic components, excellent high temperature reliability and good solder resistance in the device can be obtained. Crack resistance can be obtained.
- the vertical axis is tan ⁇ measured using a dynamic viscoelasticity measuring instrument at a temperature increase rate of 5 ° C./min, frequency: 10 Hz, measurement mode: compression, and the horizontal axis is temperature (° C. ),
- the inflection point at which the value of tan ⁇ changes from decreasing to increasing is preferably at the glass transition temperature or higher, more preferably at 310° C. or higher, further preferably at 320° C. or higher.
- the inflection point is preferably 400° C.
- the equivalent ratio which is the ratio of the epoxy equivalent of the epoxy resin to the active hydrogen equivalent of the curing agent, is higher than in the past, and the form is epoxy-rich. It is thought that a conventional resin composition does not become a rubber-like elastic body even in the temperature range that is in the rubber-like elastic region, and tan ⁇ increases.
- the shape of the encapsulating resin composition will be described.
- the shape of the encapsulating resin composition can be selected according to the molding method of the encapsulating resin composition. is mentioned.
- the respective components described above are mixed by known means, further melt-kneaded with a kneader such as a roll, kneader or extruder, cooled and then pulverized. method.
- a kneader such as a roll, kneader or extruder
- molding may be performed to obtain a particulate or sheet-like encapsulating resin composition.
- a particulate encapsulating resin composition may be obtained by compression molding into a tablet.
- a sheet-like encapsulating resin composition may be obtained by, for example, a vacuum extruder.
- the degree of dispersion, fluidity, etc. of the resulting encapsulating resin composition may be appropriately adjusted.
- the encapsulating resin composition obtained in the present embodiment has a high glass transition temperature, it has excellent adhesion to metal members. More specifically, according to the present embodiment, it is also possible to improve the adhesion between the sealing material and the member made of Ag, Ni, Cu, or an alloy containing one or more of these. Moreover, by using the encapsulating resin composition obtained in the present embodiment, a semiconductor device having excellent high-temperature reliability can be obtained.
- an electronic component can be sealed with the sealing resin composition to form an electronic device.
- the electronic device it can be applied to any known electronic device, but it is preferably used for a semiconductor package in which a semiconductor chip is sealed, for example.
- a preferred embodiment of the semiconductor chip is a semiconductor chip using silicon carbide (SiC) and gallium nitride (GaN).
- the electronic device of the present invention can be applied to various known forms of semiconductor packages, such as dual in-line package (DIP), plastic leaded chip carrier (PLCC), quad flat Package (QFP), Low Profile Quad Flat Package (LQFP), Small Outline Package (SOP), Small Outline J-Lead Package (SOJ), Thin Small Outline Package (TSOP), Thin Quad Flat Package (TQFP), Tape Carrier Package (TCP), Ball Grid Array (BGA), Chip Size Package (CSP), Matrix Array Package Ball Grid Array (MAPBGA) ), not only packages applied to memory and logic devices such as chip stacked chip size packages, but also to packages such as TO-220 that mount power devices such as power transistors. can.
- DIP dual in-line package
- PLCC plastic leaded chip carrier
- QFP Quad flat Package
- LQFP Low Profile Quad Flat Package
- SOP Small Outline Package
- SOJ Small Outline J-Lead Package
- TSOP Small Outline J-Lead Package
- TQFP Thin
- the resin composition of the present invention may contain any component that can exhibit similar functions.
- each part of the electronic device of the present invention can be replaced with an arbitrary one that can exhibit similar functions, or an arbitrary configuration can be added.
- a sealing resin composition was prepared as follows. First, each component shown in Table 1 was mixed with a mixer. Next, the obtained mixture was roll-kneaded, cooled and pulverized to obtain a sealing resin composition in the form of granules. Details of each component in Table 1 are as follows. In addition, the blending ratio of each component shown in Table 1 indicates the blending ratio (% by mass) with respect to the entire resin composition.
- Inorganic filler 1 fused silica (FB-560, manufactured by Denka, average particle size: 30 ⁇ m)
- Inorganic filler 2 fused silica (FB-105, manufactured by Denka, average particle size: 10 ⁇ m)
- Coloring agent 1 carbon black (carbon #5, manufactured by Mitsubishi Chemical Corporation)
- Silane coupling agent 1 Silane coupling agent 1: phenylaminopropyltrimethoxysilane (CF4083, Dow Corning Toray Co., Ltd.)
- Epoxy resin 1 polyfunctional epoxy resin (YL6677, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 163 g/eq)
- Curing agent 1 triphenylmethane type phenolic resin (HE910-20, manufactured by Air Water, active hydrogen equivalent: 101)
- Curing agent 2 Biphenylene skeleton-containing polyfunctional phenolic resin represented by formula (2) below (active hydrogen equivalent: 135)
- two Y each independently represent a hydroxyphenyl group represented by the following formula (2-1) or the following formula (2-2), and X represents the following formula (2- 3) or represents a hydroxyphenylene group represented by the following formula (2-4).
- n represents an integer of 0 or more and 10 or less.
- the curing agent 2 was synthesized by the following method.
- a separable flask was equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet, and 1,3-dihydroxybenzene (manufactured by Tokyo Chemical Industry Co., Ltd., "Resorcinol", melting point 111 ° C., molecular weight 110, purity 99.4%).
- 1,3-dihydroxybenzene manufactured by Tokyo Chemical Industry Co., Ltd., "Resorcinol", melting point 111 ° C., molecular weight 110, purity 99.4%).
- 291 parts by mass of phenol Karlo Kagaku Co., Ltd.
- the system was reacted for 3 hours while maintaining the temperature in the system within the range of 110-130°C, then heated and reacted for 3 hours while maintaining the temperature within the range of 140-160°C.
- the hydrochloric acid gas generated in the system by the above reaction was discharged out of the system by a nitrogen stream.
- Curing accelerator 1 4-hydroxy-2-(triphenylphosphonium) phenolate
- Release agent 1 carnauba wax (TOWAX-132, manufactured by Toagosei Co., Ltd.)
- Ion scavenger 1 ion scavenger (DHT-4H, manufactured by Kyowa Chemical Industry Co., Ltd.)
- Low stress agent 1 silicone oil (FZ-3730, manufactured by Dow Corning Toray)
- Glass transition temperature (Tg), TMA The glass transition temperature of the resin composition of each example and each comparative example was measured according to JIS K 6911. That is, for the resin composition of each example and each comparative example, a test piece of 80 mm ⁇ 10 mm ⁇ 4 mm was molded using a transfer molding machine at a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 90 seconds. Then, after curing at 175° C. for 2 hours, the thermal expansion coefficient of the test piece obtained at a heating rate of 5° C./min was measured using a thermomechanical analyzer (manufactured by Seiko Instruments Inc., TMA/SS6000). . Next, based on the obtained measurement results, the glass transition temperature (Tg) of the cured product was calculated from the inflection point of the coefficient of thermal expansion.
- the storage elastic modulus E' of the resin composition of each example and each comparative example was measured by the following method. That is, for the resin composition of each example and each comparative example, a test piece of 80 mm ⁇ 10 mm ⁇ 4 mm was molded using a transfer molding machine at a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 120 seconds. Then, after curing at 200 ° C.
- the resin composition was injection molded under the conditions of a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, and a curing time of 120 seconds, and the length was 80 mm. , 10 mm wide and 4 mm thick.
- the obtained molding was subjected to heat treatment at 200° C. for 4 hours as post-curing, and a test piece was used. .
- evaluation samples were prepared by the following method, and the reliability of the obtained samples was evaluated by the following method.
Abstract
Description
エポキシ樹脂、硬化剤および無機充填材を含み、
上記エポキシ樹脂が、分子内に2以上6以下のエポキシ基を有するエポキシ樹脂を含み、
上記硬化剤が、分子内に2以上の活性水素を有する化合物を含み、
上記硬化剤の活性水素当量に対する上記エポキシ樹脂のエポキシ当量の比である当量比が、1.4以上2.0以下である、封止用樹脂組成物が提供される。
上記封止用樹脂組成物で封止された電子部品を備える、電子装置が提供される。
まず、本実施形態の樹脂組成物について説明する。
ほかにも、上記エポキシ樹脂のエポキシ基の量を上記範囲内とすることにより、未反応の硬化剤の残存量を減少させ、未反応の硬化剤の分極による影響を低下させることができる。
本実施形態においては、エポキシ樹脂として、下記一般式(1)に示されるモノマーを含むことが望ましい。
ェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂をはじめとするフェノール、クレゾール、キシレノール、レゾルシン、カテコール、ビスフェノールA、ビスフェノールF等のフェノール類及び/又はα-ナフトール、β-ナフトール、ジヒドロキシナフタレン等のナフトール類とホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ベンズアルデヒド、サリチルアルデヒド等のアルデヒド基を有する化合物とを酸性触媒下で縮合又は共縮合させて得られるノボラック樹脂をエポキシ化したもの;例えばビスフェノールA、ビスフェノールF、ビスフェノールS、ビスフェノールA/D等のジグリシジルエーテル;アルキル置換又は非置換のビフェノールのジグリシジルエーテルであるビフェニル型エポキシ樹脂;フェノール類とジメトキシパラキシレン又はビス(メトキシメチル)ビフェニルから合成されるフェノールアラルキル型樹脂やビフェニレン骨格フェノールアラルキル型樹脂、ナフトールアラルキル型樹脂等アラルキル型樹脂のエポキシ化物;スチルベン型エポキシ樹脂;ハイドロキノン型エポキシ樹脂;フタル酸、ダイマー酸等の多塩基酸とエピクロルヒドリンの反応により得られるグリシジルエステル型エポキシ樹脂;ジアミノジフェニルメタン、イソシアヌル酸等のポリアミンとエピクロルヒドリンの反応により得られるグリシジルアミン型エポキシ樹脂;ジシクロペンタジエンとフェノール類の共縮合樹脂のエポキシ化物であるジシクロペンタジエン型エポキシ樹脂;トリフェノールメタン型エポキシ樹脂、トリメチロールプロパン型エポキシ樹脂;テルペン変性エポキシ樹脂;オレフィン結合を過酢酸等の過酸で酸化して得られる線状脂肪族エポキシ樹脂;脂環族エポキシ樹脂;及びこれらのエポキシ樹脂をシリコーン、アクリロニトリル、ブタジエン、イソプレン系ゴム、ポリアミド系樹脂等により変性したエポキシ樹脂などが挙げられる。
また、封止用樹脂組成物を用いて得られる半導体装置について、高温信頼性や耐リフロー性を向上させる観点から、封止用樹脂組成物中の全エポキシ樹脂の含有量は、封止用樹脂組成物全体に対して好ましくは15質量%以下であり、より好ましくは14質量%以下、さらに好ましくは13質量%以下である。
また、封止用樹脂組成物を用いて得られる半導体装置について、高温信頼性や耐リフロー性を向上させる観点から、封止用樹脂組成物中の全エポキシ樹脂のエポキシ当量は、好ましくは500g/eq以下であり、より好ましくは480g/eq以下であり、さらに好ましくは450g/eq以下である。
本実施形態に用いることができる硬化剤としては、一般的に封止用のエポキシ樹脂組成物に使用される公知の硬化剤が挙げられる。公知の硬化剤として具体的には、フェノール系硬化剤、アミン系硬化剤(アミノ基を有する硬化剤)などを挙げることができる。
これらは単独で用いてもよいし、2種以上を混合して用いてもよい。
また、封止用樹脂組成物を用いて得られる半導体装置について、高温信頼性や耐リフロー性を向上させる観点から、封止用樹脂組成物中の硬化剤の含有量は、封止用樹脂組成物全体に対して好ましくは25質量%以下であり、より好ましくは15質量%以下、さらに好ましくは10質量%以下である。
無機充填材は、樹脂組成物の硬化に伴う吸湿量の増加や、強度の低下を低減する機能を有するものであり、当該分野で一般的に用いられる無機充填材を使用することができる。
本発明の樹脂組成物は、硬化剤、エポキシ樹脂および無機充填材に加え、以下に示す成分を含み得る。
硬化促進剤は、エポキシ樹脂のエポキシ基と硬化剤の反応基との反応を促進する機能を有するものであり、当該分野で一般に使用される硬化促進剤が用いられる。
カップリング剤は、樹脂組成物中に無機充填材が含まれる場合に、エポキシ樹脂と無機充填材との密着性を向上させる機能を有するものであり、例えば、シランカップリング剤等が用いられる。
無機難燃剤は、樹脂組成物の難燃性を向上させる機能を有するものであり、一般に使用される無機難燃剤が用いられる。
Tgが上記下限値以上であることにより、例えば本実施形態における樹脂組成物を用いて電子部品を封止した場合、リフロー処理のような高温処理時における樹脂組成物の硬化物の強度や、樹脂組成物とリードフレームもしくは基板との接着強度の低下を防止でき、高温信頼性に向上させることができる。
吸水率が上記下限値以上であることにより、例えば本実施形態における樹脂組成物を電子部品の封止に用いた場合において、上記樹脂組成物およびリードフレームもしくは基板との密着性に優れる。
また、上記吸水率の上限値は、好ましくは0.6%であり、より好ましくは0.4%であり、さらに好ましくは0.32%である。
吸水率が上記上限値以下であることにより、例えば本実施形態における樹脂組成物を電子部品の封止に用いた場合において、高温信頼性に優れ、装置における良好な耐半田クラック性を得ることができる。
また上記E'300/E'350の上限値は、好ましくは2.0であり、より好ましくは1.95であり、さらに好ましくは1.9である。比E'300/E'350が上記上限値以下であることにより、例えば本実施形態における樹脂組成物を電子部品の封止に用いた場合において、高温信頼性に優れ、装置における良好な耐半田クラック性を得ることができる。
また上記E'350/E'400の上限値は、好ましくは2.0であり、より好ましくは1.9であり、さらに好ましくは1.8である。比E'350/E'400が上記上限値以下であることにより、例えば本実施形態における樹脂組成物を電子部品の封止に用いた場合において、高温信頼性に優れ、装置における良好な耐半田クラック性を得ることができる。
また、上記変曲点を好ましくは400℃以下、より好ましくは390℃以下、さらに好ましくは380℃以下で有する。上記の特徴を有することにより、例えば本実施形態における樹脂組成物を電子部品の封止に用いた場合において、高温信頼性に優れ、装置における良好な耐半田クラック性を得ることができる。
本実施形態において、封止用樹脂組成物の形状は、封止用樹脂組成物の成形方法等に応じて選択することができ、たとえばタブレット状、粉末状、顆粒状等の粒子状;シート状が挙げられる。
また、本実施形態において得られる封止用樹脂組成物を用いることにより、高温信頼性に優れる半導体装置を得ることができる。
(封止用樹脂組成物の調製)
各実施例および各比較例のそれぞれについて、以下のように封止用樹脂組成物を調製した。
まず、表1に示す各成分をミキサーにより混合した。次いで、得られた混合物を、ロール混練した後、冷却、粉砕して粉粒体である封止用樹脂組成物を得た。
表1中の各成分の詳細は下記のとおりである。また、表1中に示す各成分の配合割合は、樹脂組成物全体に対する配合割合(質量%)を示している。
(原料)
(無機充填材)
無機充填材1:溶融シリカ(FB-560、デンカ社製、平均粒径:30μm)
無機充填材2:溶融シリカ(FB-105、デンカ社製、平均粒径:10μm)
着色剤1:カーボンブラック(カーボン#5、三菱ケミカル社製)
シランカップリング剤1:フェニルアミノプロピルトリメトキシシラン(CF4083、東レ・ダウコーニング社製)
エポキシ樹脂1:多官能エポキシ樹脂(YL6677、三菱ケミカル社製、エポキシ当量:163g/eq)
エポキシ樹脂2:多官能エポキシ樹脂(HP-4700-RC、DIC社製、エポキシ当量:156g/eq、一般式(1)(m=n=2)で表されるモノマーを含むエポキシ樹脂)
硬化剤1:トリフェニルメタン型フェノール樹脂(HE910-20、エア・ウォーター社製、活性水素当量:101)
硬化剤2:以下式(2)で示すビフェニレン骨格含有多官能フェノール樹脂(活性水素当量:135)
セパラブルフラスコに撹拌装置、温度計、還流冷却器、窒素導入口を装着し、1,3-ジヒドロキシベンゼン(東京化成工業社製、「レゾルシノール」、融点111℃、分子量110、純度99.4%)291質量部、フェノール(関東化学社製特級試薬、「フェノール」、融点41℃、分子量94、純度99.3%)235質量部、あらかじめ粒状に砕いた4,4'-ビスクロロメチルビフェニル(和光純薬工業社製、「4,4'-ビスクロロメチルビフェニル」、融点126℃、純度95%、分子量251)125質量部を、セパラブルフラスコに秤量し、窒素置換しながら加熱し、フェノールの溶融の開始に併せて攪拌を開始した。
なお、この硬化剤2における水酸基当量は135であった。
硬化促進剤1:4-ヒドロキシ-2-(トリフェニルホスホニウム)フェノラート
離型剤1:カルナバワックス(TOWAX-132、東亜合成社製)
イオン捕捉剤1:イオン捕捉剤(DHT-4H、協和化学工業社製)
(低応力剤)
低応力剤1:シリコーンオイル(FZ-3730、東レ・ダウコーニング社製)
各例で得られた樹脂組成物の各物性を、以下の方法で評価した。
低圧トランスファー成形機(コータキ精機株式会社製、「KTS-15」)を用いて、ANSI/ASTM D 3123-72に準じたスパイラルフロー測定用金型に、175℃、注入圧力6.9MPa、保圧時間120秒の条件で、各実施例および各比較例の樹脂組成物を注入し、流動長を測定し、これをスパイラルフローとした。また、注入開始から樹脂組成物が硬化し流動しなくなるまでの時間を測定し、ゲルタイムとした。
なお、スパイラルフローは、流動性のパラメータであり、数値が大きい方が、流動性が良好である。
各実施例および各比較例の樹脂組成物のガラス転移温度は、JIS K 6911に準じて測定した。すなわち、各実施例および各比較例の樹脂組成物について、トランスファー成形機を用いて、金型温度175℃、注入圧力6.9MPa、硬化時間90秒で、80mm×10mm×4mmの試験片を成形し、175℃2時間で後硬化し、熱機械分析装置(セイコーインスツルメンツ社製、TMA/SS6000)を用いて、5℃/分の昇温速度で得られた試験片の熱膨張率を測定した。次いで、得られた測定結果に基づき、熱膨張率の変曲点から硬化物のガラス転移温度(Tg)を算出した。
各実施例および各比較例の樹脂組成物の貯蔵弾性率E'は、以下の方法で測定した。すなわち、各実施例および各比較例の樹脂組成物について、トランスファー成形機を用いて、金型温度175℃、注入圧力6.9MPa、硬化時間120秒で、80mm×10mm×4mmの試験片を成形し、200℃4時間で後硬化し、動的粘弾性測定器(エーアンドディ社製、「DDV-25GP」)を用いて貯蔵弾性率およびtanδを測定した(昇温速度:5℃/分、周波数:10Hz、荷重:800g)。
各実施例においては、縦軸に測定したtanδ、横軸に温度(℃)を取ったグラフにおいて、tanδの値が減少から上昇に転じる変曲点をガラス転移温度以上400℃以下で有していた。一方、各比較例においては上記変曲点を有していなかった。
低圧トランスファー成形機(コータキ精機株式会社製、KTS-30)を用いて、金型温度175℃、注入圧力9.8MPa、硬化時間120秒の条件で、樹脂組成物を注入成形し、長さ80mm、幅10mm、厚さ4mmの成形物を得た。得られた成形物を、後硬化として200℃で4時間加熱処理したものを試験片とし、曲げ弾性率および曲げ強さをJIS K 6911に準じて25℃および260℃の雰囲気温度下で測定した。
低圧トランスファー成形機(コータキ精機株式会社製、KTS-30)を用いて、金型温度175℃、注入圧力7.4MP、硬化時間120秒の条件で、樹脂組成物を注入成形して直径50mm、厚さ3mmの試験片を作製し、200℃で4時間後硬化した。その後、得られた試験片を煮沸環境下で24時間加湿処理し、加湿処理前後の重量変化を測定し吸水率を求めた。
各例で得られた樹脂組成物を用いて以下の方法で評価用試料を作製し、得られた試料の信頼性を以下の方法で評価した。
各例で得られた封止用樹脂組成物について、低圧トランスファー成形機(アピックヤマダ社製「MSL-06M」)を用いて、金型温度175℃、注入圧力10MPa、硬化時間180秒で16pSOP(Cuワイヤー)を成形し、200℃で4時間硬化させることでテスト用の半導体装置を作製した。封止したテスト用半導体装置を、温度:130℃、湿度:85%RH、電圧:20Vの環境下に静置し、40h毎に240hまで抵抗値を測定した。抵抗値が初期値の1.2倍以上を不合格とし、200h以上合格した場合を〇、200hより前に不合格となった場合を×とした。
Claims (11)
- エポキシ樹脂、硬化剤および無機充填材を含み、
前記エポキシ樹脂が、分子内に2以上6以下のエポキシ基を有するエポキシ樹脂を含み、
前記硬化剤が、分子内に2以上の活性水素を有する化合物を含み、
前記硬化剤の活性水素当量に対する前記エポキシ樹脂のエポキシ当量の比である当量比が、1.4以上2.0以下である、封止用樹脂組成物。 - 請求項2に記載の封止用樹脂組成物であって、
前記エポキシ樹脂が、前記一般式(1)で表されるモノマーを含むエポキシ樹脂と前記モノマーとは異なる1種類または2種類以上のエポキシ樹脂との混合物である、封止用樹脂組成物。 - 請求項1~3のいずれか1項に記載の封止用樹脂組成物であって、
前記硬化剤が、多官能型フェノール樹脂、フェノールアラルキル型フェノール樹脂のうち1種または2種を含む、封止用樹脂組成物。 - 請求項1~4のいずれか1項に記載の封止用樹脂組成物であって、
前記硬化剤が、トリフェニルメタン型フェノール樹脂またはビフェニレン骨格含有多官能フェノール樹脂を含む、封止用樹脂組成物。 - 請求項1~5のいずれか1項に記載の封止用樹脂組成物であって、
熱機械分析(TMA)において、昇温速度:5℃/minの条件下で測定される当該封止用樹脂組成物のガラス転移温度が190℃以上330℃以下である、封止用樹脂組成物。 - 請求項1~6のいずれか1項に記載の封止用樹脂組成物であって、
JIS K 7209に基づいて測定された吸水率が0.6%以下である、封止用樹脂組成物。 - 請求項1~7のいずれか1項に記載の封止用樹脂組成物であって、
当該封止用樹脂組成物を175℃で120秒間熱処理した後、200℃で4時間処理して得られる硬化物の、動的粘弾性測定器を用いて測定した300℃における貯蔵弾性率E'300と350℃における貯蔵弾性率E'350の比E'300/E'350が1.4以上2.0以下である、封止用樹脂組成物。 - 請求項1~8のいずれか1項に記載の封止用樹脂組成物であって、
当該封止用樹脂組成物を175℃で120秒間熱処理した後、200℃で4時間処理して得られる硬化物の、動的粘弾性測定器を用いて測定した350℃における貯蔵弾性率E'350と400℃における貯蔵弾性率E'400の比E'350/E'400が1.4以上2.0以下である、封止用樹脂組成物。 - 請求項1~9のいずれか1項に記載の封止用樹脂組成物であって、
縦軸が動的粘弾性測定器を用いて昇温速度:5℃/分、周波数:10Hz、測定モード:圧縮の条件で測定したtanδ、横軸が温度(℃)のグラフにおいて、tanδの値が減少から上昇に転じる変曲点をガラス転移温度以上400℃以下の温度域で有する、封止用樹脂組成物。 - 請求項1~10のいずれか1項に記載の封止用樹脂組成物で封止された電子部品を備える、電子装置。
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