CN104419121A - Resin composition for sealing semiconductor, semiconductor device with the cured product thereof and method for manufacturing semiconductor device - Google Patents

Resin composition for sealing semiconductor, semiconductor device with the cured product thereof and method for manufacturing semiconductor device Download PDF

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CN104419121A
CN104419121A CN201410427482.9A CN201410427482A CN104419121A CN 104419121 A CN104419121 A CN 104419121A CN 201410427482 A CN201410427482 A CN 201410427482A CN 104419121 A CN104419121 A CN 104419121A
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hydrogen atom
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CN104419121B (en
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长田将一
萩原健司
横田竜平
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Shin Etsu Chemical Co Ltd
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Priority claimed from JP2013181314A external-priority patent/JP5943487B2/en
Priority claimed from JP2013182126A external-priority patent/JP5943488B2/en
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Abstract

The invention provides a resin composition for sealing a semiconductor, a semiconductor device with the cured product thereof and a method for manufacturing the semiconductor device. The resin composition for sealing a semiconductor contains (A) a cyanate ester compound with one molecule containing more than two cyanate oxygroups, (B) a phenol compound containing more than two phenol hydroxyls in one molecule, represented by the formula (2) and having a specific structure, (C) an inorganic filler, and (D) an epoxy resin having a specific structure and represented by the formula (3) or the formula (4), wherein the molar ratio of the phenol hydroxyls in the (B) phenol compound to the cyanate oxygroups in the (A) cyanate ester compound is 0.2-0.4, and the molar ratio of the epoxy groups in the (D) epoxy resin to the cyanate oxygroups in the (A) cyanate ester compound is 0.04-0.25.

Description

Resin composition for encapsulating semiconductor and there is the semiconductor device of its hardening thing and the manufacture method of semiconductor device
Technical field
The present invention relates to a kind of resin composition for encapsulating semiconductor.Specifically, relate to a kind of with copper (Cu) lead frame (Lead Frame, LF) or the composition of the adhesion excellence of silver-plated (Ag) and can to form at high temperature long-term thermal stability excellent and can at hot and humid lower maintenance and the adhesion of metal substrate, the resin combination of hardening thing excellent in reliability and the semiconductor device of hardening thing with described composition.
In addition, the present invention relates to a kind of be provided in hot and humid under there is long-term excellent thermostability, corrosion or the migration of Cu lead frame (LF), plating Ag or Cu line are few, the resin combination of semiconductor device excellent in reliability and have the semiconductor device of hardening thing of described composition.
And, the present invention relates to a kind of can be provided in hot and humid under there is long-term excellent thermostability and have and Cu lead frame (LF) or adhesion, the hardening thing excellent in reliability of excellence plating Ag, and the semiconductor device of the composition that has excellent formability of metaideophone (transfer) and the hardening thing with described composition.
Background technology
In recent years, semiconductor device welcomes eye-catching technical renovation.Silicon path (through silicon via, TSV) technology is used, Large Copacity information can be processed at high speed in portable information terminal, the communication terminals such as smart mobile phone (smartphone), panel computer (tablet).In described technology, first semiconductor element is carried out multilayer connection, and in the silicon media layer (silicon interposer) of 8 inches or 12 inches, carry out flip-chip (flip chip) connect.Then, together with the media layer being equipped with multiple semiconductor element through multilayer connection, seal by thermosetting resin.After unwanted hardening resin on semiconductor element is ground, carry out being separated and can obtain slim, small-sized, multi-functional and can the semiconductor device of high speed processing.But, when whole coated heat hardening resin on the thin silicon media layer of 8 inches or 12 inches seals, due to the difference of the thermal expansivity of silicon and thermosetting resin, and produce large warpage.If warpage is large, then cannot be applied to grinding steps thereafter or separating step, and becomes large technical task.
In addition, in recent years, as global warming countermeasure, the environmental cure from the earth level such as energy transformation of fossil oil makes progress.Therefore, the production number of units of hybrid electric vehicle or electromobile increases.In addition, in the household electric appliances of the emerging nations such as China or India, carry the machine of inverter motor (inverter motor) as strategy of Saving Energy also in increase.
In hybrid electric vehicle or electromobile, inverter motor, give play to and having changed direct current into by exchanging, direct current being changed into the power semiconductor of the effect exchanging or voltage is carried out transformation and become important.But, be used as silicon (Si) the proximity energy limit of semi-conductor all the year round, be difficult to expect that tremendous performance improves.Therefore, next die power semiconductor of the materials such as silicon carbide (SiC), gan (GaN), diamond is used to receive publicity.Such as, in order to reduce loss during electric power conversion, and the low resistance of power metal-oxide-semiconductor field effect transistor (Metal-Oxide-Semiconductor Field Effect Transistor, MOSFET) is required.But in the Si-MOSFET of current main-stream, be difficult to realize significantly low resistance.Therefore, the exploitation of the low wasted power MOSFET of the SiC of the semi-conductor of band gap length (broad-band gap) is used as to make progress.
SiC or GaN has band gap and is about 3 times of Si, destroys the characteristic that strength of electric field is the excellence of more than 10 times.In addition, the feature such as hot operation (there is the report of 650 DEG C of work in SiC), high thermal conductivity (SiC and Cu is arranged side by side), large saturated electron drift velocity is also had.Consequently, if use SiC or GaN, then can reduce the connection resistance of power semiconductor, and significantly cut down the power loss of power conversion circuit.
Power semiconductor is usually by utilizing the metaideophone of epoxy resin to be shaped (transfer molding), utilizing the perfusion of silicone gel sealing to protect.Recently, from small-sized, light-weighted viewpoint (particularly mobile applications), utilizing the metaideophone of epoxy resin to be shaped becomes main flow gradually.But, epoxy resin is about plasticity, achieves the thermosetting resin of excellent balance with the adhesion of base material, physical strength, but at the temperature more than 200 DEG C, the thermolysis of cross-linking set can be carried out, and worry under the Working environment of the high temperature that SiC, GaN are expected, do not play the effect (non-patent literature 1) as sealing material.
Therefore, as heat-resistant quality excellence material and studying the thermosetting resin composition comprising cyanate ester resin always.Such as, record in patent documentation 1 and epoxy resin is formed oxazole ring by the reaction of multivalence cyanate and epoxy resin in the hardening thing of phenol resol resins, thus obtain stable thermotolerance.Record 1 epoxy equivalent (weight) relative to epoxy resin in patent documentation 1, and the hydroxyl equivalent of phenol resol resins is 0.4 ~ 1.0, the cyanate equivalent of multivalence cyanate is 0.1 ~ 0.6, can provide the hardening thing of thermotolerance and excellent water resistance by this.In addition, record the thermosetting resin composition comprising cyanate esters, phenolic compound and the inorganic filler with ad hoc structure in patent documentation 2, and record the excellent heat resistance of described resin combination, and there is high physical strength.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese Patent Laid-fair 6-15603 publication
[patent documentation 2] Japanese Patent Laid-Open 2013-53218 publication
[non-patent literature]
[non-patent literature 1] " Industrial materials " in November, 2011 number (vol 59 No.11)
Summary of the invention
[inventing problem to be solved]
But, need high temperature when the composition described in patent documentation 1 forms oxazole ring in the reaction by epoxy and cyanato-and long heat embrittlement, and there is the problem of production difference.In addition, the composition described in patent documentation 2 due to wet fastness insufficient, therefore there is following problem: if in hot and humid lower long-term placement, then CuLF or plating Ag and the adhesion of hardening thing reduce and are peeling or crackle.Therefore, the present invention is in view of described situation, object is to provide a kind of resin combination excellent in reliability, even if its to provide more than 200 DEG C, under the high temperature of such as 200 DEG C ~ 250 DEG C long-term placement and thermolysis (weight minimizings) even if also less and under hot and humid environment with the hardening thing of CuLF or the adhesion also excellence of plating Ag.
And, the present invention is in view of described situation, object is to provide a kind of resin combination, even if it can be formed more than 200 DEG C, under the high temperature of such as 200 DEG C ~ 250 DEG C long-term placement and thermolysis (weight minimizing) even if also less and under hot and humid environment with CuLF or the hardening thing of adhesion excellence plating Ag, and metaideophone has excellent formability.
[means of dealing with problems]
The described problem of solution that present inventor etc. are artificial and make great efforts research, found that, by in the composition containing cyanate esters and inorganic filler, allotment has the phenolic compound of ad hoc structure, and epoxy resin, and phenolic compound is set in specific scope relative to the allotment amount of cyanate esters and epoxy resin relative to the allotment amount of cyanate esters, and the hardening thing with excellent thermostability can be obtained, even if under described hardening thing is chronically exposed to hot and humid Working environment, thermolysis (weight minimizing) is also few, and can maintain and CuLF or the adhesion of excellence of plating Ag, thus complete the present invention.
That is, the first invention of the present invention is a kind of composition, comprises:
(A) there is in 1 molecule the cyanate esters of more than 2 cyanato-s;
(B) phenolic compound shown in following general formula (2),
[changing 1]
(in formula, R 5and R 6be the alkyl of hydrogen atom or carbon number 1 ~ 4 independently of each other, R 7be independently of each other following any one,
[changing 2]
R 4be hydrogen atom or methyl independently of each other, m is the integer of 0 ~ 10);
(C) inorganic filler; And
(D) following general formula (3) or the epoxy resin shown in general formula (4),
[changing 3]
[changing 4]
(in described formula (3) and formula (4), k and p is the integer of more than 0, less than 10 independently of each other, and j is the integer of 1 ~ 6, R 10be the alkyl of hydrogen atom or carbon number 1 ~ 4 independently of each other, R 11and R 12be independently of each other following any one); And
[changing 5]
(B) phenolic hydroxyl group in phenolic compound is 0.2 ~ 0.4 relative to the mol ratio of the cyanato-in (A) cyanate esters, and the epoxy group(ing) in (D) epoxy resin is 0.04 ~ 0.25 relative to the mol ratio of the cyanato-in (A) cyanate esters.
And the people such as present inventor find, by the alkoxysilane compound containing trialkylsilyl group in molecular structure of allotment containing mercaptopropyi in described first composition, and the adhesion of metal substrate and hardening thing can be improved significantly.But there is following problem: if described composition is at high temperature placed for a long time, then the alkoxysilane compound containing trialkylsilyl group in molecular structure oxidation containing mercaptopropyi can be produced sulfate ion, therefore metal substrate corrodes and variable color.
Therefore, the described problem of solution that present inventor etc. are artificial and make great efforts further research, found that, by having allocated in the composition of the alkoxysilane compound containing trialkylsilyl group in molecular structure containing mercaptopropyi in described first composition, allocate the material being carried with molybdic acid metal-salt on inorganic carrier and houghite compound (hydrotalcite-like compound) further in the lump, and the corrosion of the metal substrate produced when at high temperature placing for a long time can be suppressed, and the adhesion of hardening thing for the excellence of metal substrate can be maintained, thus complete the present invention.
That is, the second invention of the present invention is a kind of composition, and it comprises:
(A) there is in 1 molecule the cyanate esters of more than 2 cyanato-s;
(B) phenolic compound shown in following general formula (2),
[changing 6]
(in formula (2), R 5and R 6be the alkyl of hydrogen atom or carbon number 1 ~ 4 independently of each other, R 7be independently of each other following any one,
[changing 7]
R 4be hydrogen atom or methyl independently of each other, m is the integer of 0 ~ 10);
(C) inorganic filler;
(D) following general formula (3) or the epoxy resin shown in general formula (4),
[changing 8]
[changing 9]
(in described formula (3) and formula (4), k and p is the integer of more than 0, less than 10 independently of each other, and j is the integer of 1 ~ 6, R 10be the alkyl of hydrogen atom or carbon number 1 ~ 4 independently of each other, R 11and R 12be independently of each other following any one)
[changing 10]
(E) compound shown in following general formula (5),
[changing 11]
R 8 d(R 9O) (3-d)Si-C 3H 6-SH (5)
(in formula (5), R 8and R 9be the alkyl of carbon number 1 ~ 3 independently of each other, d is the integer of 0 ~ 2);
(F) on inorganic carrier, hold the material of molybdic acid metal-salt; And
(G) calcined material of houghite compound and/or houghite compound; And
(B) phenolic hydroxyl group in phenolic compound is 0.2 ~ 0.4 relative to the mol ratio of the cyanato-in (A) cyanate esters, and the epoxy group(ing) in (D) epoxy resin is 0.04 ~ 0.25 relative to the mol ratio of the cyanato-in (A) cyanate esters.
And, the people such as present inventor are studied the continuous molding improving described first composition, found that, by in described first composition further allotment acid number be less than 30 and saponification value be the releasing agent of less than 150 (wherein, when acid number is less than 5, saponification value is more than 80, less than 150, when saponification value is less than 5, acid number is more than 20, less than 30), and the continuous molding of resin combination can be improved, thus complete the present invention.
That is, the 3rd invention of the present invention is a kind of composition, and it comprises:
(A) there is in 1 molecule the cyanate esters of more than 2 cyanato-s;
(B) phenolic compound shown in following general formula (2),
[changing 12]
(in formula (2), R 5and R 6be the alkyl of hydrogen atom or carbon number 1 ~ 4 independently of each other, R 7be independently of each other following any one,
[changing 13]
R 4be hydrogen atom or methyl independently of each other, m is the integer of 0 ~ 10);
(C) inorganic filler;
(D) following general formula (3) or the epoxy resin shown in general formula (4),
[changing 14]
[changing 15]
(in described formula (3) and formula (4), k and p is the integer of more than 0, less than 10 independently of each other, and j is the integer of 1 ~ 6, R 10be the alkyl of hydrogen atom or carbon number 1 ~ 4 independently of each other, R 11and R 12be the group shown in following formula independently of each other)
[changing 16]
and
(H) acid number be less than 30 and saponification value be less than 150 releasing agent (wherein, when acid number is less than 5, saponification value is more than 80, less than 150, and when saponification value is less than 5, acid number is more than 20, less than 30); And
(B) phenolic hydroxyl group in phenolic compound is 0.2 ~ 0.4 relative to the mol ratio of the cyanato-in (A) cyanate esters, and the epoxy group(ing) in (D) epoxy resin is 0.04 ~ 0.25 relative to the mol ratio of the cyanato-in (A) cyanate esters.
[effect of invention]
Even if the first composition of the present invention can provide more than 200 DEG C, under the high temperature of particularly 200 DEG C ~ 250 DEG C long-term placement and thermolysis (weight minimizings) even if also less under hot and humid environment with CuLF or the adhesion also excellence and there is the hardening thing of high insulativity of plating Ag.Therefore, the semiconductor device being undertaken sealing by the hardening thing of composition of the present invention has long-term reliability under hot and humid.
Second composition of the present invention can suppress more than 200 DEG C, the variable color of long-term metal substrate when placing under the high temperature of particularly 200 DEG C ~ 250 DEG C, even and if under hot and humid environment long-term placement also can maintain CuLF or plate the adhesion of excellence of Ag and hardening thing.Therefore, the semiconductor device being undertaken sealing by the hardening thing of composition of the present invention has long-term reliability under hot and humid.
Even if the 3rd composition of the present invention can to provide under hot and humid condition long-term placement and thermolysis (weight minimizings) also less, with CuLF after plate Ag the hardening thing of adhesion also excellence.Therefore, the semiconductor device being undertaken sealing by the hardening thing of composition of the present invention has the long-term reliability under hot and humid.In addition, the 3rd composition of the present invention, due to continuous molding excellence, therefore can be suitable for being used as metaideophone molding material.
Embodiment
Below, the present invention will be described in more detail.
(A) cyanate esters
In first composition of the present invention, the second composition and the 3rd composition, (A) composition is the cyanate esters in 1 molecule with more than 2 cyanato-s.As long as the cyanate esters in the present invention has more than 2 cyanato-s in 1 molecule, generally well-known cyanate esters can be used.Described cyanate esters such as can be represented by following general formula (1).
[changing 17]
(in formula (1), R 1and R 2be the alkyl of hydrogen atom or carbon number 1 ~ 4 independently of each other, R 3be independently of each other following any one.
[changing 18]
R 4for hydrogen atom or methyl, n is the integer of 0 ~ 10)
Cyanate esters of the present invention such as can be enumerated: two (4-cyanato-phenyl) methane, two (3-methyl-4-cyanato-phenyl) methane, two (3-ethyl-4-cyanato-phenyl) methane, two (3,5-dimethyl-4-cyanato-phenyl) methane, two (the 4-cyanato-phenyl) ethane of 1,1-, two (the 4-cyanato-phenyl) propane of 2,2-, two (4-cyanato-phenyl)-1,1,1,3,3, the 3-HFC-236fa of 2,2-, 1,3-bis-cyanato-benzene and Isosorbide-5-Nitrae-two cyanato-benzene, the 2-tertiary butyl-Isosorbide-5-Nitrae-two cyanato-benzene, 2,4-dimethyl-1,3-bis-cyanato-benzene, 2,5-, bis--tertiary butyl-Isosorbide-5-Nitrae-two cyanato-benzene, tetramethyl--Isosorbide-5-Nitrae-two cyanato-benzene, 1,3,5-tri-cyanato-benzene, 2,2 '-two cyanato-biphenyl or 4,4 '-two cyanato-biphenyl, 3,3 ', 5,5 '-tetramethyl--4,4 '-two cyanato-biphenyl, 1,3-bis-cyanato-naphthalene, Isosorbide-5-Nitrae-two cyanato-naphthalene, 1,5-bis-cyanato-naphthalene, 1,6-bis-cyanato-naphthalene, 1,8-bis-cyanato-naphthalene, 2,6-bis-cyanato-naphthalene, or 2,7-bis-cyanato-naphthalene, 1,3,6-tri-cyanato-naphthalene, 1,1,1-tri-(4-cyanato-phenyl) ethane, two (4-cyanato-phenyl) ether, 4,4 '-(1,3-phenylenediisopropylidene) phenylbenzene cyanate, two (4-cyanato-phenyl) thioether, two (4-cyanato-phenyl) sulfone, three (4-cyanato--phenyl) phosphine, three (4-cyanato-phenyl) phosphoric acid ester, phenol novolak type cyanate, cresol novolak type cyanate, dicyclopentadiene novolac type cyanate, phenyl aralkyl-type cyanate, biphenyl aralkyl-type cyanate and naphthalene aralkyl-type cyanate etc.Described cyanate esters can be used alone a kind or mix two or more and use.
Described cyanate esters reacts by making phenols and mauguinite and obtains under alkalescence.Described cyanate esters can according to its structure from softening temperature be 106 DEG C solid cyanate esters to normal temperature for having in the cyanate esters of broad characteristic aqueous cyanate esters, suitably select according to purposes.Such as when manufacturing liquid epoxy resin composition, being aqueous compound under preferably using normal temperature, when making varnish being dissolved in solvent, preferably selecting according to solvability or soltion viscosity.In addition, when being shaped for power semiconductor seal applications by metaideophone, preferably selection is the compound of solid at normal temperatures.
In addition, little, that namely between functional group, molecular weight the is little composition of the equivalent of cyanato-, can obtain the little and hardening thing of low-thermal-expansion, high Tg of curing shrinkage.The composition that cyanato-equivalent is large, Tg is in a slight decrease, but triazine crosslinked interval becomes flexibility, can expect low elasticity, high highly malleablized, low water suction.In cyanate esters, bond or remaining chlorine are suitably below 50ppm, are more preferably below 20ppm.If the amount of chlorine is more than 50ppm, then the chlorine free because of thermolysis or chlorion when at high temperature placing for a long time, by the Cu framework through being oxidized or Cu line, plate Ag corrosion, and likely cause the stripping of hardening thing or electrically bad.In addition, the insulativity of resin is likely also reduced.
(B) phenolic compound
In first composition of the present invention, the second composition and the 3rd composition, (B) phenolic compound is the phenolic compound having more than 2 phenolic hydroxyl group and represented by following general formula (2) in 1 molecule.
[changing 19]
In described formula, R 5and R 6be the alkyl of hydrogen atom or carbon number 1 ~ 4 independently of each other, m is the integer of 0 ~ 10.
In described formula, R 7be independently of each other following any one.
[changing 20]
(in described formula, R 4be hydrogen atom or methyl independently of each other)
In first composition of the present invention, phenolic compound does not comprise R in described formula (2) 7for CH 2phenolic compound (such as phenol resol resins).R 7for CH 2phenolic compound there is following worry: easily cause thermolysis when at high temperature placing for a long time, and be peeling or crackle at the interface of copper lead frame and hardening thing.
Phenolic compound shown in described formula (2) can be enumerated: bisphenol F type resin, bisphenol A type resin, phenol aralkyl type resin, biphenyl aralkyl-type resin, naphthalene aralkyl-type resin.Describedly to can be used alone or two or more kinds may be used.
In second composition of the present invention and the 3rd composition, R in described formula (2) can be comprised 7for CH 2compound (such as phenol resol resins).But described composition exist poor heat resistance worry or because of the too fast and worry of plasticity difference of the reactivity of cyanate esters and described compound.Therefore, particularly preferably in R in the second composition of the present invention and the 3rd composition 7also be CH 2in addition.
In the past, the hardening catalyst of cyanate esters used metal-salt, metal complex etc. (Japanese Patent Laid-Open No. Sho 64-43527 publication, Japanese Patent Laid-Open 11-106480 publication, Japanese Patent spy table 2005-506422 publication).But can be used as metal-salt, metal complex be transition metal, transition metal-type has the worry of the oxidative degradation at high temperature promoting organic resin.In the present compositions, described phenolic compound has given play to the function of the catalyzer of the cyclization as cyanate esters.Therefore, metal-salt and metal complex need not be used.The long-term keeping stability under high temperature can be improved by this further.
In addition, the phenolic compound in a part with more than at least 2 hydroxyls can expect the linking agent as being connected by triazine ring.Phenolic compound is different from epoxy compounds or amine compound, by with cyanate esters bond, and the structure shown in-C-O-Ar-can be formed.Described structure is similar with the triazine ring structure formed when being hardened separately by cyanate esters, therefore can expect the thermotolerance of the hardening thing improving gained further.
In addition, the phenolic compound that hydroxyl equivalent is little, such as hydroxyl equivalent are the phenolic compound of less than 110, high with the reactivity of cyanato-.Therefore there is following situation: when composition melting being mixed below 120 DEG C, carry out sclerous reaction, and obvious damage mobility, not preferred for metaideophone is shaped.Therefore, phenolic compound particularly preferably hydroxyl equivalent be more than 111.
In the present invention, the allotment amount of phenolic compound is cyanato-1 mole relative to cyanate esters and hydroxyl is the amount of 0.2 mole ~ 0.4 mole.If the amount of phenolic compound is less than described lower value, then the reaction of cyanato-is insufficient, and remaining unreacted cyanato-.Remaining cyanato-can be hydrolyzed under high humidity environment.Therefore, if in hot and humid lower placement, then can cause the reduction of physical strength or reduce with the contiguity power of base material.In addition, if the amount of phenolic compound is more than described higher limit, then sclerous reaction is carried out from low temperature.Therefore, the mobility of composition can be damaged, and plasticity is deteriorated.In addition, the halogens in described phenolic compound or basic metal etc., 120 DEG C, extraction under 2 air pressure time, be desirably 10ppm, be desirably below 5ppm especially.
(C) inorganic filler
In first composition of the present invention, the second composition and the 3rd composition, there is no particular restriction for the kind of inorganic filler, and the inorganic filler of resin composition for encapsulating semiconductor can use known inorganic filler.Such as can enumerate: fused silica, crystallinity silicon-dioxide, crystobalite (cristobalite) etc. are silica-based, aluminum oxide, silicon nitride, aluminium nitride, boron nitride, titanium oxide, glass fibre, magnesium oxide and zinc oxide etc.As long as the median size of described inorganic filler or shape carry out selecting according to purposes.Wherein, in order to obtain the thermal expansivity close to silicon, preferred molten silicon-dioxide, shape is suitably spherical.The median size of inorganic filler is preferably 0.1 μm ~ 40 μm, is more preferably 0.5 μm ~ 15 μm.Described median size such as can be obtained as weighed average (or intermediate value footpath) by laser diffractometry etc. etc.
In inorganic filler, as at 120 DEG C, the impurity that extracts under the extraction conditions of sample 5g/ water 50g under 2.1 air pressure, chlorion is suitably below 10ppm, and sodium ion is suitably below 10ppm.If more than 10ppm, then there is the situation that the resistance to moisture performance by the semiconductor device of composition sealing reduces.
In the present invention, the allotment amount of inorganic filler can be set to 60 overall quality % ~ 94 quality % of composition, is preferably set to 70 quality % ~ 92 quality %, is more preferably set to 75 quality % ~ 90 quality %.
In order to strengthen the bond intensity of resin and inorganic filler, inorganic filler is preferably allocated: carry out surface-treated inorganic filler in advance by couplers such as silane coupling agent, titanic acid ester couplers.This kind of coupler preferably uses: γ-glycidoxypropyltrimewasxysilane, γ-glycidoxypropyl diethoxy silane, β-(3, 4-epoxycyclohexyl) epoxy silane such as ethyl trimethoxy silane, N-β (amino-ethyl)-gamma-amino propyl trimethoxy silicane, the reactant of imidazoles and γ-glycidoxypropyltrimewasxysilane, γ aminopropyltriethoxy silane, the aminosilanes such as N-phenyl-gamma-amino propyl trimethoxy silicane, γ-hydrosulphonyl silane, the silane coupling agents such as hydrosulphonyl silane such as γ-epithio oxygen base propyl trimethoxy silicane (γ-episulfidoxypropyltrimethoxysilane).But in the second composition of the present invention, can use and carry out surface-treated inorganic filler by hydrosulphonyl silanes such as γ-hydrosulphonyl silane, γ-epithio oxygen base propyl trimethoxy silicanes, but not too preferred.Herein, for the allotment amount of surface-treated coupler and surface treatment method, there is no particular restriction.
(D) epoxy resin
(D) composition is the epoxy resin shown in following formula (3) or formula (4).
[changing 21]
[changing 22]
In described formula (3) and formula (4), k and p is the integer of more than 0, less than 10 independently of each other, and j is the integer of 1 ~ 6, R 10be the alkyl of hydrogen atom or carbon number 1 ~ 4 independently of each other, R 11and R 12be independently of each other following any one.
[changing 23]
Described epoxy resin such as can be enumerated: phenol aralkyl type epoxy resin, biphenyl aralkyl-type epoxy resin, naphthalene type aralkyl epoxy resin etc.Epoxy resin and cyanate ester resin form oxazole ring, but compared with being formed with the triazine ring of cyanato-, reactive slow.In addition, if the ratio of epoxy group(ing) is many, then setting time is elongated and be unfavorable for that metaideophone is shaped., also there is the example used as the tertiary amine of triethylamine herein, but the worry having keeping quality to be deteriorated.
Described epoxy resin and cyanate esters react and form oxazole ring.In the present invention, relative to the cyanato-1 mole of cyanate esters, the addition of epoxy resin compound is the amount that epoxide equivalent becomes 0.04 mole ~ 0.25 mole.If the amount of epoxy resin is less than described lower value, then the moisture absorption quantitative change of hardening thing is many, and is peeling between lead frame and hardening thing under high-temperature high-humidity.In addition, if the amount of epoxy resin is more than described higher limit, then sclerosis becomes insufficient, and causes the reduction of the reduction of the glass transition temperature of hardening thing or hot and humid keeping characteristic.
In composition of the present invention, except the triazine ring of the cyclization by cyanate esters is formed, also carry out: the reaction (formation of oxazole ring) of epoxy compounds and cyanate esters, phenolic compound and the reaction of cyanate esters and the reaction of epoxy compounds and phenolic compound.Composition of the present invention causes described reaction by under the basis of described specific allotment ratio, and can provide the hardening thing that hot and humid patience is extremely excellent.
First composition
First form of the present invention is the resin combination comprising described (A) composition ~ (D) composition.In first sealing resin composition of the present invention except described (A) composition ~ (D) composition, can allocate further as required: the various additive such as releasing agent, fire retardant, ion capturing agent, antioxidant, bonding imparting agent, low-stress agent.In addition, adhesion imparting agent can use described coupler.In order to improve the adhesion with metal frame, sulfydryl system silane coupling agent Te Do is suitable for.
There is no particular restriction for releasing agent, can use known releasing agent.Such as can enumerate: carnauba wax (carnauba wax), rice bran wax (rice wax), bear ground lira wax (candelilla wax), polyethylene, oxidic polyethylene, polypropylene, montanic acid (montanic acid), the ester cpds of montanic acid and saturated alcohol, 2-(2-Hydroxy-ethylamino)-ethanol, ethylene glycol, glycerine etc. and montanic acid wax, stearic acid, stearate, stearic amide, ethylenebis stearic amide, the multipolymer etc. of ethene and vinyl-acetic ester.Describedly can be used alone a kind or combine two or more and use.
There is no particular restriction for fire retardant, can use known whole fire retardant.Such as can enumerate: phosphonitrile (phosphazene) compound, silicone compounds, zinc molybdate hold talcum, zinc molybdate holds zinc oxide, aluminium hydroxide, magnesium hydroxide, molybdenum oxide and ANTIMONY TRIOXIDE SB 203 99.8 PCT.
There is no particular restriction for ion capturing agent, can use known ion capturing agent.Such as can enumerate: hydrotalcite, bismuth hydroxide compound, rare-earth oxide etc.
Second composition
Second form of the present invention is the resin combination also comprising following (E) composition ~ (G) composition except described (A) composition ~ (D) composition further.
(E) alkoxysilane compound containing trialkylsilyl group in molecular structure containing mercaptopropyi
(E) composition is the compound shown in following general formula (5).
[changing 24]
R 8 d(R 9O) (3-d)Si-C 3H 6-SH (5)
In described formula (5), R 8and R 9be the alkyl of carbon number 1 ~ 3 independently of each other, d is the integer of 0 ~ 2.The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing mercaptopropyi such as can be enumerated: 3-mercaptopropyi Trimethoxy silane, 3-Mercaptopropyltriethoxysilane, 3-mercaptopropyi methyl dimethoxysilane and 3-mercaptopropyi methyldiethoxysilane etc.
Second composition of the present invention by containing shown in described formula (5) containing the alkoxysilane compound containing trialkylsilyl group in molecular structure of mercaptopropyi, and improve the adhesion of the metal substrates such as Cu alloy lead frames, plating Ag, gold-plated (Au) and nickel plating porpezite (NiPdAu) and hardening thing significantly.Relative to total 100 weight part of (A) composition and (B) composition, the allotment amount of (E) composition is 0.3 weight part ~ 1.0 weight part, is preferably 0.4 weight part ~ 0.8 weight part.If (E) amount of composition is less than described lower value, then there is the possibility of the adhesion deficiency of metal substrate and hardening thing.In addition, even if the amount of (E) composition exceedes described higher limit, adhesion also can not improve further, therefore not preferred economically.
(F) molybdic acid metal-salt holds material
(F) composition is the material holding molybdic acid metal-salt on inorganic carrier.(F) composition has: the pH value of composition is become the effect of partial neutral from acidity and suppresses or catch the free effect of Cu ion or the Ag ion being derived from lead frame or plating.Second composition of the present invention: (F) composition is allocated together with following described (G) composition.By this, the corrosion of the metal frame produced when the device sealed by the hardening thing by sealing resin composition can be suppressed at high temperature to place for a long time, and at high temperature can maintain the adhesion of the excellence of hardening thing and metal frame.
The inorganic carrier holding molybdic acid metal-salt can use: the inorganic carrier enumerated as described (C) inorganic filler.Such as can enumerate: fused silica, crystallinity silicon-dioxide etc. are silica-based, talcum, zinc oxide, aluminum oxide, silicon hydride, aluminum hydride, hydroborons, titanium oxide, glass fibre etc.Described inorganic carrier can be identical with described (C) composition, also can be different.Be particularly preferably silicon-dioxide, talcum, zinc oxide.
Molybdic acid metal-salt can use: zinc molybdate, calcium molybdate, strontium molybdate, barium molybdate or described mixture.In addition, the oxide compound of the metals such as zinc, calcium, strontium, barium can be combined in molybdic acid metal-salt.Be preferably zinc molybdate.The material that inorganic carrier holds zinc molybdate such as can be enumerated: Kai Mujiade (KEMGARD) series of Xuan Wei (SHERWIN-WILLIAMS) company.
Relative to the total amount of inorganic carrier, the amount of the molybdic acid metal-salt that inorganic carrier holds is preferably 5 quality % ~ 40 quality %, is particularly preferably 10 quality % ~ 30 quality %.If the content of molybdic acid metal-salt is very few, then there is the situation that cannot obtain sufficient effect, in addition, if the content of molybdic acid metal-salt is too much, then the situation that mobility when having a shaping, hardening reduce.
Relative to total 100 weight part of (A) composition and (B) composition, the addition of (F) composition is preferably set to 3 weight part ~ 30 weight parts, is more preferably set to 5 weight part ~ 20 weight parts.When the amount of (F) composition is less than described lower value, fully effect cannot be obtained.In addition, when the amount of adding (F) composition exceedes described higher limit, the situation causing mobility to reduce is had.
(G) houghite compound
(G) composition is the calcined material of houghite compound and/or houghite compound.So-called houghite compound, such as, be the layered double-hydroxide shown in following composition formula, given play to the function as anion ion exchange body.
[M 2+ 1-xM 3+ x(OH) 2] x+[(A n- x/n)·mH 2O] x-
In described formula, M 2+for Mg 2+, Ca 2+, Zn 2+, Co 2+, Ni 2+, Cu 2+, Mn 2+deng divalent metal ion, M 3+for Al 3+, Fe 3+, Cr 3+deng 3 valence metal ions, A n-for OH -, Cl -, CO 3 2-, SO 4 2-deng n valency negatively charged ion.X be greater than 0 number, particularly 0.10 ~ 0.50, especially 0.20 ~ 0.33, m be 0 or be greater than 0 number, particularly 0 ~ 10, especially 0 ~ 4.The calcined material of houghite compound is such as can by formula M 2+ 1-xm 3+ xo 1+x/2the double oxide that (x is positive number) represents.In addition, (G) composition of the present invention also can use: Mg 3znAl 2(OH) 12cO 3wH 2o, Mg 3znAl 2(OH) 12cO 3deng zinc modification hydrotalcite based compound (w is real number).
The calcined material of houghite compound and houghite compound has anionresin function.Therefore there is following effect: the sulfate ion produced by the oxidation of (D) composition can be caught, prevent sulfuration or the corrosion of Cu lead frame or plating Ag by this.In addition, as mentioned above, use together with (F) composition by by (G) composition, and can effectively prevent the problems such as the corrosion of Cu, Ag or migration in pole.
(G) of the present invention composition is preferably the calcined material of the hydrotalcite compound shown in following general formula (6) and/or described hydrotalcite compound.
Mg aAl b(OH) cCO 3·nH 2O (6)
In described formula (6), a, b and c be meet 2a+3b-c=2 be greater than 0 number, n is the number of satisfied 0≤n≤4.
Hydrotalcite compound shown in described formula (6) such as can be enumerated: Mg 4.5al 2(OH) 13cO 33.5H 2o, Mg 4.5al 2(OH) 13cO 3, Mg 4al 2(OH) 12cO 33.5H 2o, Mg 6al 2(OH) 16cO 34H 2o, Mg 5al 2(OH) 14cO 34H 2o, Mg 3al 2(OH) 10cO 31.7H 2o etc.Commercially available product can be enumerated: trade(brand)name " DHT-4A ", " DHT-6 ", " DHT-4A-2 " (being consonance chemical industrial company to manufacture) etc.
Relative to total 100 weight part of (A) composition and (B) composition, the allotment amount of (F) composition is preferably set to 1 weight part ~ 10 weight part, is more preferably set to 2 weight part ~ 8 weight parts.If (F) amount of composition is less than described lower value, then fully cannot obtain effect.In addition, when the addition of (F) composition exceedes described higher limit, there is the situation causing hardening or adhesion to reduce.
In second sealing resin composition of the present invention, can allocate further as required: the various additives such as the coupler beyond releasing agent, fire retardant, antioxidant, bonding imparting agent, low-stress agent, (E) composition.
There is no particular restriction for releasing agent, can use known releasing agent.Such as can enumerate: carnauba wax, rice bran wax, may ground lira wax, polyethylene, oxidic polyethylene, polypropylene, montanic acid, montanic acid and saturated alcohol, 2-(2-Hydroxy-ethylamino) ester cpds of-ethanol, ethylene glycol, glycerine etc. and the multipolymer etc. of montanic acid wax, stearic acid, stearate, stearic amide, ethylenebis stearic amide, ethene and vinyl-acetic ester.Describedly can be used alone a kind or combine two or more and use.
(E) coupler beyond composition can be by: γ-glycidoxypropyltrimewasxysilane, γ-glycidoxypropyl diethoxy silane, β-(3, 4-epoxycyclohexyl) epoxy silane such as ethyl trimethoxy silane, N-β (amino-ethyl)-gamma-amino propyl trimethoxy silicane, the reactant of imidazoles and γ-glycidoxypropyltrimewasxysilane, γ aminopropyltriethoxy silane, the silane coupling agents such as aminosilane such as N-phenyl-gamma-amino propyl trimethoxy silicane are used alone a kind, or combine two or more and use.
There is no particular restriction for fire retardant, can use known fire retardant.Such as can enumerate: phosphazene compound, silicone compounds, aluminium hydroxide, magnesium hydroxide, molybdenum oxide and ANTIMONY TRIOXIDE SB 203 99.8 PCT.
3rd composition
3rd form of the present invention is the resin combination also comprising following (H) composition except described (A) composition ~ (D) composition further.
(H) releasing agent
(H) composition used in 3rd composition of the present invention is that acid number is less than 30 and saponification value is the releasing agent of less than 150.Acid number is preferably 10 ~ 25.In addition, saponification value is preferably 70 ~ 140, is more preferably 70 ~ 100.Any one of acid number and saponification value can be 0.But need when acid number is less than 5, saponification value is more than 80, less than 150, be preferably more than 100, less than 150, when saponification value is less than 5, acid number is more than 20, less than 30, is preferably more than 25, less than 30.The all too small releasing agent of acid number and saponification value due to the intermiscibility with resin excessively good, therefore cannot give play to sufficient stripping result (i.e. continuous molding), and not preferred.In addition, if acid number, saponification value are excessive, then what have hardening thing surface oozes out the seriously situation of bad order.If particularly saponification value exceedes described higher limit, then releasing agent is had at room temperature not to be solid but the worry of liquid (lubricating oil).Form if this kind of releasing agent is added in composition, then have in time through and ooze out and damage the worry of the outward appearance of hardening thing, therefore not preferred.
Releasing agent of the present invention such as can be enumerated: carnauba wax, rice bran wax, oxidic polyethylene, montanic acid, the wax such as ester cpds of montanic acid and saturated alcohol, 2-(2-Hydroxy-ethylamino)-ethanol, ethylene glycol or glycerine etc.; Stearic acid, stearate, the multipolymer etc. of ethene and vinyl-acetic ester, described in can be used alone a kind, also can combine two or more and use.Wherein, preferential oxidation polyethylene or fatty acid ester.The allotment amount of releasing agent is the overall 0.3 quality % ~ 1.5 quality % of composition, is preferably 0.35 quality % ~ 0.8 quality %, is more preferably 0.35 quality % ~ 0.5 quality %.
In 3rd sealing resin composition of the present invention, can allocate further as required: the various additive such as fire retardant, ion capturing agent, antioxidant, bonding imparting agent, low-stress agent.In addition, adhesion imparting agent can use described coupler.In order to improve the adhesion with metal frame, sulfydryl system silane coupling agent is suitable especially.
There is no particular restriction for fire retardant, can use known fire retardant.Such as can enumerate: phosphazene compound, silicone compounds, zinc molybdate hold talcum, zinc molybdate holds zinc oxide, aluminium hydroxide, magnesium hydroxide, molybdenum oxide and ANTIMONY TRIOXIDE SB 203 99.8 PCT.
There is no particular restriction for ion capturing agent, can use known ion capturing agent.Such as can enumerate: hydrotalcite, bismuth hydroxide compound, rare-earth oxide etc.
There is no particular restriction for the manufacture method of composition of the present invention.Such as can obtain by with under type: heat treated is applied to described (A) composition ~ (D) composition, described (A) composition ~ (G) composition or described (A) composition ~ (D) composition and (H) composition as required simultaneously or separately, while carry out stirring, dissolve, mix, disperse, and in described mixture, according to circumstances add other additives carry out mixing, stir, disperse.The device that mixing etc. uses is not particularly limited, and can use: the arena stain machine, two rollers, three rollers, ball mill, continuous extruder, planetary mixer, quality collider (mass collider) etc. that possess stirring, heating unit.Also can appropriately combined described device and using.
Composition of the present invention is effective to transistor-type, modular type, dual-in-line package (DualIn-line Package, DIP) semiconductor packages such as type, little profile (Small Outline, SO) type, flat package (flat pack) type, ball grid array (Ball Grid Array) type.As long as the moulding method that the shaping of composition of the present invention has adopted since deferring in the past.Such as can utilize: metaideophone shaping, compression molding, injection molding, teeming practice etc.Be particularly preferably metaideophone to be shaped.The forming temperature of composition of the present invention be desirably at 160 DEG C ~ 190 DEG C be 45 second ~ 180 seconds, it is 2 hours ~ 16 hours that after fixing (post cure) is desirably at 170 DEG C ~ 250 DEG C.
First composition of the present invention to can be provided under the high temperature of more than 200 DEG C, particularly 200 DEG C ~ 250 DEG C long-term thermolysis (weight minimizings) when placing less, with CuLF or plate the adhesion excellence of Ag, there is the hardening thing of high insulativity.Therefore, the semiconductor device being undertaken sealing by the hardening thing of composition of the present invention can have high temperature long-term reliability.In addition, the first composition of the present invention due to continuous molding good, therefore can be typically used as the composition epoxy resin of metaideophone shaped material in the past for same device, and same molding condition can be used.And productivity is also excellent.
The thermolysis (weight minimizings) of second composition of the present invention more than 200 DEG C, under the high temperature of particularly 200 DEG C ~ 250 DEG C during long-term keeping is lacked.In addition, even if long-term placement also can maintain and CuLF or the adhesion of excellence of plating Ag under hot and humid environment, and the corrosion of metal frame can effectively be suppressed.Therefore, the semiconductor device being undertaken sealing by the hardening thing of the second composition of the present invention can have high temperature long-term reliability.In addition, can be typically used as the composition epoxy resin of metaideophone shaped material in the past for same device, and same molding condition can be used.And productivity is also excellent.
3rd composition of the present invention can be provided in long-term thermolysis (weight minimizings) when placing under the high temperature of more than 200 DEG C, particularly 200 DEG C ~ 250 DEG C less, and CuLF or plate the hardening thing of adhesion excellence of Ag.In addition, even if the adhesion with the excellence of metal frame also can be maintained under hot and humid environment.Therefore, the semiconductor device being undertaken sealing by the hardening thing of the 3rd composition of the present invention can have hot and humid under long-term reliability.And the 3rd composition of the present invention, due to continuous molding excellence, therefore can be suitable for being used as metaideophone shaped material especially.
[embodiment]
Below, represent embodiment and comparative example, the present invention is illustrated in greater detail, but the present invention is not limited to following embodiment.In addition, the part in each example is mass parts.
[embodiment and comparative example]
With shown in table 1 ~ table 6 composition allotment following shown in each composition, after mixing equably by high-speed mixer, mix equably by heating two roller, cool after pulverize, obtain resin combination by this.
[composition (A) used in the first composition, the second composition and the 3rd composition ~ composition (D)]
(A) cyanate esters
Cyanate esters (Premacy's Saite (Primaset) PT-60, the manufacture of Japan dragon husky (Lonza Japan) limited-liability company, cyanato-equivalent are 119) shown in (a) following formula (7)
[changing 25]
(mixtures of n=0 ~ 10)
The cyanate esters of gained in (b) following synthesis example 1
[synthesis example 1]
The phenolic compound MEH-7851SS of 100g (bright and change into manufacture) is dissolved in the butylacetate of 600g.Its solution is cooled to about-15 DEG C, and imports the gas shape mauguinite of 32g.Then, last about 30 minutes and under agitation drip the triethylamine adding 50g, therebetween, temperature remains less than-10 DEG C.Keep further at said temperatures after 30 minutes, stop cooling and reaction mixture is filtered.Then filtrate is passed to ion exchanger filling column.Then, under reduced pressure, at bath temperature is 70 DEG C except desolventizing, then use and flow down membranous type vaporizer, remove volatile impunty (wrapping solvent-laden residue, free triethylamine, diethyl cyanamide) at 1mbar, at 130 DEG C.The product of gained is the cyanate esters (cyanato-equivalent is 208) shown in following formula (8).
[changing 26]
(mixtures of n=0 ~ 10)
(B) phenolic compound
Phenolic compound shown in (c) following formula (9) (MEH-7800SS, bright and change into manufacture, phenolic hydroxyl group equivalent is 175)
[changing 27]
(mixtures of n=0 ~ 10)
Phenolic compound shown in (d) following formula (10) (MEH-7851SS, bright and change into manufacture, phenolic hydroxyl group equivalent is 203)
[changing 28]
(mixtures of n=0 ~ 10)
(e) comparative example phenolic compound
Phenolic compound (TD-2131, large Japanese ink chemistry (Dainippon Inkand Chemicals, DIC) manufacture, phenolic hydroxyl group equivalent are 110) shown in following formula (11)
[changing 29]
(mixtures of n=0 ~ 10)
(C) inorganic filler
F () median size is the melting spherical silicon dioxide (imperial gloomy manufacture) of 15 μm
(D) epoxy resin
Epoxy resin compound (NC-3000, Japanese chemical drug manufacture, epoxy equivalent (weight) are 272) shown in (g) following formula (12)
[changing 30]
(mixtures of n=0 ~ 10)
Epoxy resin compound (HP-4770, Japanese chemical drug manufacture, epoxy equivalent (weight) are 204) shown in (h) following formula (13)
[changing 31]
(n and m is 0 or 1)
[other compositions used in the first composition]
Carnauba wax (TOWAX-131, East Asia change into manufacture)
Silane coupling agent: 3-mercaptopropyi Trimethoxy silane (KBM-803, Shin-Etsu Chemial Co., Ltd manufacture)
Imidazoles (four countries change into company and manufacture)
[composition (E) used in the second composition ~ composition (G) and other compositions]
(E) alkoxysilane compound containing trialkylsilyl group in molecular structure containing mercaptopropyi
(i) 3-mercaptopropyi Trimethoxy silane: (CH 3o) 3-Si-C 3h 6-SH
(F) composition
J () zinc molybdate holds zinc oxide (Kai Mujiade (KEMGARD)-911B, Xuan Wei (SHERWIN-WILLIAMS) manufacture)
K () zinc molybdate holds talcum (Kai Mujiade (KEMGARD)-911C, Xuan Wei (SHERWIN-WILLIAMS) manufacture)
(G) houghite compound
(1) Mg 6al 2(CO 3) (OH) 164H 2the calcining product (DHT-4A-2, consonance chemistry manufacture) of O
Other compositions
Carnauba wax (TOWAX-131, East Asia change into manufacture)
Imidazoles (four countries change into company and manufacture)
[composition (H) used in the 3rd composition and other compositions]
(H) releasing agent
(m) releasing agent 1: the oxidic polyethylene (inner section wax PED-522 (Licowax PED-522), Clariant (Clariant) company manufacture) that acid number is 25, saponification value is 0
(n) releasing agent 2: the fatty acid ester (TOWAX-131, East Asia change into limited-liability company and manufactures) that acid number is 10, saponification value is 85
(o) releasing agent 3: the fatty acid ester (ITO-WAX TPNC-133, her rattan liquefaction limited-liability company manufacture) that acid number is 25, saponification value is 140
Comparison test releasing agent
(p) releasing agent 4: the polyethylene (Licowax PE-522, Clariant Corporation manufacture) that acid number is 0, saponification value is 0
(q) releasing agent 5: acid number is 86, saponification value is 0 polypropylene and maleic anhydride copolymer (Ai Laike Bristol D121-41 (Elector D121-41), Nissan Chemical Industries Ltd. manufacture)
Other compositions
Silane coupling agent: 3-mercaptopropyi Trimethoxy silane (KBM-803, Shin-Etsu Chemial Co., Ltd manufacture)
Imidazoles (four countries change into company and manufacture)
The evaluation of the first composition
Following evaluation test is carried out to each composition of embodiment 1-1 ~ embodiment 1-6 and comparative example 1-1 ~ comparative example 1-5.The results are shown in following table 1 and table 2.
[helicoidal flow]
Use the mould according to low-light microscope (Emission Microscope, EMMI) standard, at 175 DEG C, 6.9 N/mm 2, curring time is measure under the condition in 180 seconds.
[changes in weight under high temperature during keeping]
Carry out metaideophone shaping in 175 DEG C × 120 seconds, compacting pressure under being the condition of 6.9MPa, at 180 DEG C, then carry out the after fixing of 4 hours, obtain the test film of 10mm × 100mm × 4mm by this.Test film is taken care of 500 hours in 250 DEG C of baking ovens, gravimetry decrement.
[confirming-1 with the adhesion of the CuLF through plating Ag]
Die paddle (die pad) portion (8mm × 8mm) and the routing junction surface Cu alloy (Olympic (Olin) C7025) through plating Ag is used to make 100 pins (pin) flat-four-side encapsulation (Quad Flat Package, QFP) lead frame, carries out metaideophone shaping in 175 DEG C × 120 seconds, compacting pressure under being the condition of 6.9MPa.Then, at 180 DEG C, carry out the after fixing of 4 hours.By lead frame cutting machine, lacing wire (tie bar) is cut off, and obtain the QFP encapsulation of 20mm × 14mm × 2.7mm.
Taking care of being encapsulated in described in 12 in 250 DEG C of baking ovens 500 hours, confirming to be packaged with flawless by visual after keeping.In addition, ultrasonic flaw detecting device is used to observe with or without internal fissure and the stripping with lead frame.The number of the encapsulation creating crackle or stripping is recorded in table 1 and table 2.
[confirming-2 with the adhesion of the CuLF through plating Ag]
Using die paddle portion (8mm × 8mm) and the routing junction surface Cu alloy (Olympic (Olin) C7025) through plating Ag to make 100 pin QFP lead frames, carrying out metaideophone shaping in 175 DEG C × 120 seconds, compacting pressure under being the condition of 6.9MPa.Then, at 180 DEG C, carry out the after fixing of 4 hours.By lead frame cutting machine, lacing wire is cut off, and obtain the QFP encapsulation of 20mm × 14mm × 2.7mm.
Pressure steaming cooker test (Pressure Cooker Test will be encapsulated in described in 12, PCT) take care of 96 hours in (121 DEG C × 100%RH 2.1atm), after keeping, use ultrasonic flaw detecting device to observe with or without internal fissure and the stripping with lead frame.The number of the encapsulation cracking or peel off is recorded in table 1 and table 2.
[plasticity]
80 pin QFP (14mm × 20mm × 2.7mm) being carried out 20 injection moldings under 175 DEG C × 120 seconds, 6.9MPa, observing to attach on mould or until producing the injection number till the bending of curling and runner (runner).
[table 1]
[table 2]
Do not meet the composition of the comparative example 1-3 ~ comparative example 1-5 of of the present invention scope and the hardening thing that obtain relative to the mol ratio of cyanato-or epoxy group(ing) relative at least one of the mol ratio of cyanato-by phenolic hydroxyl group, the weight reduction rates placed when 500 hours at 250 DEG C is large.In addition, if described hardening thing is at high temperature taken care of for a long time or places under hot and humid environment, be then peeling and crackle at the interface with the Cu lead frame through plating Ag.And the continuous molding exceeding the comparative example 1-3 of the higher limit of scope of the present invention and the composition of comparative example 1-4 of described mol ratio is poor.In contrast, the weight reduction rates that the hardening thing obtained by composition of the present invention is placed when 500 hours at 250 DEG C is little, even if be not also peeling or crackle in hot and humid lower long-time placement.In addition, the continuous molding of composition of the present invention is also excellent.
The evaluation of the second composition
Following evaluation test is carried out to each composition of embodiment 2-1 ~ embodiment 2-7 and comparative example 2-1 ~ comparative example 2-6.The results are shown in following table 3 and table 4.
[corrosion of CuLF confirms]
Cu alloy (Olympic (Olin) C7025) is made 100 pin QFP lead frames (die paddle portion) and carries out metaideophone shaping in 175 DEG C × 120 seconds, compacting pressure under being the condition of 6.9MPa, at 180 DEG C, then carry out the after fixing of 4 hours.By lead frame cutting machine, lacing wire is cut off, and obtain the QFP encapsulation of 20mm × 14mm × 2.7mm.
Described being encapsulated in 225 DEG C of baking ovens is taken care of 1000 hours.After keeping, mechanical destruction is carried out to sealing resin, and observe inner die paddle portion with or without variable color.
[corrosion of plating Ag confirms]
Die paddle portion (8mm × 8mm) and the routing junction surface Cu alloy (Olympic (Olin) C7025) through plating Ag is made to make 100 pin QFP lead frames, carry out metaideophone shaping in 175 DEG C × 120 seconds, compacting pressure under being the condition of 6.9MPa, at 180 DEG C, then carry out the after fixing of 4 hours.By lead frame cutting machine, lacing wire is cut off, and obtain the QFP encapsulation of 20mm × 14mm × 2.7mm.
Described being encapsulated in 225 DEG C of baking ovens is taken care of 1000 hours.After keeping, mechanical destruction is carried out to sealing resin, and observe inner plating Ag die paddle portion with or without variable color.
[confirming-1 with the adhesion of the CuLF through plating Ag]
Die paddle portion (8mm × 8mm) and the routing junction surface Cu alloy (Olympic (Olin) C7025) through plating Ag is made to make 100 pin QFP lead frames, carry out metaideophone shaping in 175 DEG C × 120 seconds, compacting pressure under being the condition of 6.9MPa, at 180 DEG C, then carry out the after fixing of 4 hours.By lead frame cutting machine, lacing wire is cut off, and obtain the QFP encapsulation of 20mm × 14mm × 2.7mm.
Take care of being encapsulated in described in 12 in 225 DEG C of baking ovens 1000 hours.Use ultrasonic flaw detecting device after keeping, observe with or without internal fissure and the stripping with lead frame.The number of the encapsulation cracking or peel off is recorded in table 3 and table 4.
[confirming-2 with the adhesion of the CuLF through plating Ag]
Articles for use grain welding disk (8mm × 8mm) and the routing junction surface Cu alloy (Olympic (Olin) C7025) through plating Ag is made to make 100 pin QFP lead frames, carry out metaideophone shaping in 175 DEG C × 120 seconds, compacting pressure under being the condition of 6.9MPa, at 180 DEG C, then carry out the after fixing of 4 hours.By lead frame cutting machine, lacing wire is cut off, and obtain the QFP encapsulation of 20mm × 14mm × 2.7mm.
Taking care of being encapsulated in described in 12 in PCT (121 DEG C × 100%RH2.1atm) 96 hours, using ultrasonic flaw detecting device after keeping, observing with or without internal fissure and the stripping with lead frame.The number of the encapsulation cracking or peel off is recorded in table 3 and table 4.
[table 3]
[table 4]
Do not holding in the composition of any one of material or houghite compound containing molybdic acid metal-salt, the variable color of metal frame cannot suppressed when at high temperature placing for a long time, and be peeling at the interface of metal frame and hardening thing.In contrast, the test body sealed by composition of the present invention, at 225 DEG C, place metal frame also non-variable color in 1000 hours, be not also peeling or crackle.In addition, even if the hardening thing obtained by the second composition of the present invention also can maintain the adhesion of the excellence to metal substrate under hot and humid environment.
The evaluation of the 3rd composition
Following evaluation test is carried out to each composition of embodiment 3-1 ~ embodiment 3-6 and comparative example 3-1 ~ comparative example 3-5.The results are shown in following table 5 and table 6.
[helicoidal flow]
Use the mould according to EMMI standard, at 175 DEG C, 6.9N/mm 2, curring time is measure under the condition in 180 seconds.
[changes in weight under high temperature during keeping]
Carry out metaideophone shaping in 175 DEG C × 120 seconds, compacting pressure under being the condition of 6.9MPa, at 180 DEG C, then carry out the after fixing of 4 hours, obtain the test film of 10mm × 100mm × 4mm by this.Described test film is taken care of 500 hours in 250 DEG C of baking ovens, and gravimetry decrement.
[confirming-1 with the adhesion of the CuLF through plating Ag]
Make die paddle portion (8mm × 8mm) and the routing junction surface Cu alloy (Olympic (Olin) C7025) through plating Ag make 100 pin QFP lead frames and carry out metaideophone shaping in 175 DEG C × 120 seconds, compacting pressure under being the condition of 6.9MPa, at 180 DEG C, then carry out the after fixing of 4 hours.By lead frame cutting machine, lacing wire is cut off, and obtain the QFP encapsulation of 20mm × 14mm × 2.7mm.
Taking care of being encapsulated in described in 12 in 250 DEG C of baking ovens 500 hours, confirming to be packaged with flawless by visual after keeping.In addition, ultrasonic flaw detecting device is used to observe with or without internal fissure and the stripping with lead frame.The number of the encapsulation cracking or peel off is recorded in table 5 and table 6.
[confirming-2 with the adhesion of the CuLF through plating Ag]
Die paddle portion (8mm × 8mm) and the routing junction surface Cu alloy (Olympic (Olin) C7025) through plating Ag is made to make 100 pin QFP lead frames, carry out metaideophone shaping in 175 DEG C × 120 seconds, compacting pressure under being the condition of 6.9MPa, at 180 DEG C, then carry out the after fixing of 4 hours.By lead frame cutting machine, lacing wire is cut off, and obtain the QFP encapsulation of 20mm × 14mm × 2.7mm.
Take care of being encapsulated in described in 12 in PCT (121 DEG C × 100%RH2.1atm) 96 hours.Use ultrasonic flaw detecting device after keeping, observe with or without internal fissure and the stripping with lead frame.The number of the encapsulation cracking or peel off is recorded in table 5 and table 6.
[plasticity]
80 pin QFP (14mm × 20mm × 2.7mm) are carried out 100 injection moldings under 175 DEG C × 120 seconds, 6.9MPa, and observes attaching on mould or until producing the injection number till curling and runner bending.
[table 5]
[table 6]
Do not meet the composition of the releasing agent of scope of the present invention containing acid number and saponification value, continuous molding is poor.In contrast, the continuous molding of the 3rd composition of the present invention is excellent.And, even if the 3rd composition of the present invention at high temperature places weight reduction rates also less for a long time, and the adhesion with metal frame can be maintained for a long time under hot and humid condition.
[utilizability in industry]
The plasticity of resin combination of the present invention is good, even if its hardening thing long-term placement and thermolysis (weight minimizings) is also lacked more than 200 DEG C, under the high temperature of such as 200 DEG C ~ 250 DEG C, even if with CuLF or to plate the adhesion of Ag also excellent under hot and humid environment.Therefore, the semiconductor device of the long-term reliability excellence under hot and humid condition can be provided.And the hardening thing of the second composition of the present invention can suppress the variable color of metal frame when at high temperature placing for a long time effectively, and can maintain the adhesion with the excellence of metal frame under hot and humid environment.Therefore, composition of the present invention can provide hot and humid under the semiconductor device of long-term reliability excellence.And, the hardening thing of the 3rd composition of the present invention has long-term thermal stability under hot and humid, the adhesion with the excellence of metal frame can be maintained, can be provided in the semiconductor device of hot and humid lower long-term reliability excellence, and described composition is due to continuous molding excellence, therefore can be suitable for being used as metaideophone molding material.

Claims (15)

1. a resin composition for encapsulating semiconductor, is characterized in that, comprises:
(A) there is in 1 molecule the cyanate esters of more than 2 cyanato-s;
(B) phenolic compound shown in following general formula (2),
[changing 1]
In formula (2), R 5and R 6be the alkyl of hydrogen atom or carbon number 1 ~ 4 independently of each other, R 7be independently of each other following any one,
[changing 2]
R 4be hydrogen atom or methyl independently of each other, m is the integer of 0 ~ 10;
(C) inorganic filler; And
(D) following general formula (3) or the epoxy resin shown in general formula (4),
[changing 3]
[changing 4]
In described formula (3) and formula (4), k and p is the integer of more than 0, less than 10 independently of each other, and j is the integer of 1 ~ 6, R 10be the alkyl of hydrogen atom or carbon number 1 ~ 4 independently of each other, R 11and R 12be independently of each other following any one,
[changing 5]
And the phenolic hydroxyl group (B) in phenolic compound is 0.2 ~ 0.4 relative to the mol ratio of the cyanato-in (A) cyanate esters, and the epoxy group(ing) in (D) epoxy resin is 0.04 ~ 0.25 relative to the mol ratio of the cyanato-in (A) cyanate esters.
2. resin composition for encapsulating semiconductor according to claim 1, is characterized in that, (A) composition is the compound shown in following general formula (1),
[changing 6]
In formula (1), R 1and R 2be the alkyl of hydrogen atom or carbon number 1 ~ 4 independently of each other, R 3be independently of each other following any one,
[changing 7]
R 4be hydrogen atom or methyl independently of each other, n is the integer of 0 ~ 10.
3. a resin composition for encapsulating semiconductor, is characterized in that, comprises:
(A) there is in 1 molecule the cyanate esters of more than 2 cyanato-s;
(B) phenolic compound shown in following general formula (2),
[changing 8]
In formula (2), R 5and R 6be the alkyl of hydrogen atom or carbon number 1 ~ 4 independently of each other, R 7be independently of each other following any one,
[changing 9]
R 4be hydrogen atom or methyl independently of each other, m is the integer of 0 ~ 10;
(C) inorganic filler;
(D) following general formula (3) or the epoxy resin shown in general formula (4),
[changing 10]
[changing 11]
In described formula (3) and formula (4), k and p is the integer of more than 0, less than 10 independently of each other, and j is the integer of 1 ~ 6, R 10be the alkyl of hydrogen atom or carbon number 1 ~ 4 independently of each other, R 11and R 12be independently of each other following any one,
[changing 12]
(E) compound shown in following general formula (5),
[changing 13]
R 8 d(R 9O) (3-d)Si-C 3H 6-SH (5)
In formula (5), R 8and R 9be the alkyl of carbon number 1 ~ 3 independently of each other, d is the integer of 0 ~ 2;
(F) on inorganic carrier, hold the material of molybdic acid metal-salt; And
(G) calcined material of houghite compound and/or houghite compound; And
(B) phenolic hydroxyl group in phenolic compound is 0.2 ~ 0.4 relative to the mol ratio of the cyanato-in (A) cyanate esters, and the epoxy group(ing) in (D) epoxy resin is 0.04 ~ 0.25 relative to the mol ratio of the cyanato-in (A) cyanate esters.
4. resin composition for encapsulating semiconductor according to claim 3, is characterized in that, (F) composition is the material holding described molybdic acid metal-salt on the inorganic carrier being selected from silicon-dioxide, talcum and zinc oxide.
5. resin composition for encapsulating semiconductor according to claim 3, is characterized in that, described molybdic acid metal-salt is zinc molybdate.
6. resin composition for encapsulating semiconductor according to claim 3, is characterized in that, the calcined material that (G) composition is the compound shown in following general formula (6) and/or described compound,
Mg aAl b(OH) cCO 3·nH 2O (6)
In formula (6), a, b and c be meet 2a+3b-c=2 be greater than 0 number, n is the number of satisfied 0≤n≤4.
7. resin composition for encapsulating semiconductor according to claim 3, is characterized in that, (A) composition is the compound shown in following general formula (1),
[changing 14]
In formula (1), R 1and R 2be the alkyl of hydrogen atom or carbon number 1 ~ 4 independently of each other, R 3be independently of each other following any one,
[changing 15]
R 4be hydrogen atom or methyl independently of each other, n is the integer of 0 ~ 10.
8. a semiconductor device, is characterized in that, has the hardening thing of the resin composition for encapsulating semiconductor according to any one of claim 1 to 7.
9. semiconductor device according to claim 8, is characterized in that, carries the semiconductor element comprising silicon carbide or gan.
10. a resin composition for encapsulating semiconductor, is characterized in that, comprises:
(A) there is in 1 molecule the cyanate esters of more than 2 cyanato-s;
(B) phenolic compound shown in following general formula (2),
[changing 16]
In formula (2), R 5and R 6be the alkyl of hydrogen atom or carbon number 1 ~ 4 independently of each other, R 7be independently of each other following any one,
[changing 17]
R 4be hydrogen atom or methyl independently of each other, m is the integer of 0 ~ 10;
(C) inorganic filler;
(D) following general formula (3) or the epoxy resin shown in general formula (4),
[changing 18]
[changing 19]
In described formula (3) and formula (4), k and p is the integer of more than 0, less than 10 independently of each other, and j is the integer of 1 ~ 6, R 10be the alkyl of hydrogen atom or carbon number 1 ~ 4 independently of each other, R 11and R 12be independently of each other following any one,
[changing 20]
and
(H) acid number is less than 30 and saponification value is the releasing agent of less than 150, and wherein, when acid number is less than 5, saponification value is more than 80, less than 150, and when saponification value is less than 5, acid number is more than 20, less than 30; And
(B) phenolic hydroxyl group in phenolic compound is 0.2 ~ 0.4 relative to the mol ratio of the cyanato-in (A) cyanate esters, and the epoxy group(ing) in (D) epoxy resin is 0.04 ~ 0.25 relative to the mol ratio of the cyanato-in (A) cyanate esters.
11. resin composition for encapsulating semiconductor according to claim 10, is characterized in that, (H) composition is at least a kind that is selected from fatty acid ester and oxidic polyethylene.
12. resin composition for encapsulating semiconductor according to claim 10, is characterized in that, (A) composition is the compound shown in following general formula (1),
[changing 21]
In formula (1), R 1and R 2be the alkyl of hydrogen atom or carbon number 1 ~ 4 independently of each other, R 3be independently of each other following any one,
[changing 22]
R 4be hydrogen atom or methyl independently of each other, n is the integer of 0 ~ 10.
13. 1 kinds of semiconductor devices, is characterized in that, have the hardening thing of the resin composition for encapsulating semiconductor according to any one of claim 10 to 12.
14. semiconductor devices according to claim 13, is characterized in that, carry the semiconductor element comprising silicon carbide or gan.
The manufacture method of 15. 1 kinds of semiconductor devices as described in claim 13 or 14, is characterized in that, comprising: be shaped the step of the resin composition for encapsulating semiconductor shaping such as according to any one of claim 10 to 12 by metaideophone.
CN201410427482.9A 2013-08-29 2014-08-27 Resin composition for encapsulating semiconductor and the semiconductor device with its hardening thing Active CN104419121B (en)

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