CN104419121B

CN104419121B - Resin composition for encapsulating semiconductor and the semiconductor device with its hardening thing

Info

Publication number: CN104419121B
Application number: CN201410427482.9A
Authority: CN
Inventors: 长田将; 长田将一; 萩原健司; 横田竜平
Original assignee: Shin Etsu Chemical Co Ltd
Current assignee: Shin Etsu Chemical Co Ltd
Priority date: 2013-08-29
Filing date: 2014-08-27
Publication date: 2018-04-10
Anticipated expiration: 2034-08-27
Also published as: KR20150026857A; TW201508022A; CN104419121A; KR102219584B1; TWI636088B

Abstract

The present invention provides a kind of resin composition for encapsulating semiconductor and semiconductor device and the manufacture method of semiconductor device with its hardening thing.The resin composition for encapsulating semiconductor, comprising：(A) there are the cyanate esters of more than 2 cyanato-s in 1 molecule, (B) there are more than 2 phenolic hydroxyl group in 1 molecule shown in formula (2), and the phenolic compounds with specific structure, (C) inorganic filler, and (D) formula (3) or the epoxy resin with specific structure shown in formula (4), (B) phenolic hydroxyl group in phenolic compounds is 0.2~0.4 relative to the mol ratio of the cyanato- in (A) cyanate esters, and the epoxy radicals in (D) epoxy resin is 0.04~0.25 relative to the mol ratio of the cyanato- in (A) cyanate esters.

Description

Resin composition for encapsulating semiconductor and the semiconductor device with its hardening thing

Technical field

The present invention relates to a kind of resin composition for encapsulating semiconductor.Specifically, it is related to a kind of and copper (Cu) lead frame The excellent composition of frame (Lead Frame, LF) or silver-plated (Ag) adhesion and long-term thermal stability at high temperature can be formed Property it is excellent and can be in hot and humid lower maintenance and adhesion, the resin combination of hardening thing excellent in reliability of metal substrate Thing and with the composition hardening thing semiconductor device.

Moreover, it relates to a kind of provided hot and humid lower with long-term excellent heat endurance, Cu lead frames (LF), plate that corrosion or the migration of Ag or Cu lines are few, the resin combination of semiconductor device excellent in reliability and with described The semiconductor device of the hardening thing of composition.

Moreover, the present invention relates to it is a kind of can be provided in it is hot and humid it is lower with heat endurance excellent for a long time and with With Cu lead frames (LF) or plating Ag excellent adhesion, hardening thing excellent in reliability, and metaideophone (transfer) shaping Property excellent composition and the hardening thing with the composition semiconductor device.

Background technology

In recent years, semiconductor device welcomes eye-catching technological innovation.Smart mobile phone (smartphone), tablet personal computer Etc. (tablet) silicon path (through silicon via, TSV) technology is used in portable information terminal, communication terminal, so as to Large Copacity information can be handled at high speed.In the technology, first by semiconductor element carry out multilayer connection, and at 8 inches or Flip-chip (flip chip) connection is carried out in 12 inches of silicon intermediary layer (silicon interposer).Then, together with taking The intermediary layer of multiple semiconductor elements through multilayer connection is loaded with, is sealed by thermosetting resin.By on semiconductor element Unwanted hardening resin be ground after, separated and can be obtained slim, small-sized, multi-functional and can be with high speed processing Semiconductor device.However, the entire surface coating thermosetting resin on 8 inches or 12 inches of thin silicon intermediary layer is sealed When, due to the difference of silicon and the thermal coefficient of expansion of thermosetting resin, and produce big warpage.If warpage is big, can not apply In grinding steps or separating step thereafter, and turn into big technical task.

In addition, in recent years, as global warming countermeasure, the horizontal environment pair of the earth such as the energy conversion from fossil fuel Plan makes progress.Therefore, the production number of units of hybrid electric vehicle or electric automobile increase.In addition, the emerging nation such as China or India Household electric appliances in, the machine of inverter motor (inverter motor) is carried as strategy of Saving Energy also to be increased.

In hybrid electric vehicle or electric automobile, inverter motor, give play to and exchange is changed into direct current, direct current is changed into friendship The power semiconductor of the effect of voltage progress transformation is become important by stream.However, the silicon (Si) as semiconductor is close all the year round Performance boundary, it is difficult to expect that tremendous performance improves.Therefore, using materials such as carborundum (SiC), gallium nitride (GaN), diamonds Next die power semiconductor of material attracts attention.For example, loss during in order to reduce electrical power conversion, and require power metal oxygen Compound semiconductcor field effect transistor (Metal-Oxide-Semiconductor Field Effect Transistor, MOSFET low resistance).But in the Si-MOSFET of current main-stream, it is difficult to realize significantly low resistance.Therefore, use Exploitation as the SiC of the semiconductor of band gap wide (broad-band gap) low wasted power MOSFET makes progress.

SiC or GaN has about 3 times that band gap is Si, destroys the excellent characteristic that electric-field intensity is more than 10 times.In addition, Also there are hot operation (report that 650 DEG C of work in SiC be present), high thermal conductivity (SiC and Cu is arranged side by side), big saturated electrons The features such as drift velocity.If as a result, using SiC or GaN, the connection resistance of power semiconductor can be reduced, and significantly Cut down the power loss of power conversion circuit.

Power semiconductor is generally coagulated by the metaideophone shaping (transfer molding) using epoxy resin, using silicone The perfusion sealing of glue is protected.Recently, from the point of view of small-sized, light-weighted viewpoint (particularly mobile applications), asphalt mixtures modified by epoxy resin is utilized The metaideophone shaping of fat is increasingly becoming main flow.But epoxy resin is taken on formability, with the adhesion of base material, mechanical strength The thermosetting resin of excellent balance was obtained, but at a temperature of more than 200 DEG C, the thermal decomposition of crosslinking points can be carried out, and was worried Under the working environment for the high temperature expected SiC, GaN, the effect (non-patent literature 1) as encapsulant is not played.

Therefore, the material excellent as heat-resistant quality and studying the thermosetting resin group for including cyanate ester resin always Compound.For example, recorded in patent document 1 by epoxy resin in the hardening thing of phenol resol resins by multivalence cyanic acid The reaction of ester and epoxy resin and form oxazole ring, so as to obtain stable heat resistance.Recorded in patent document 1 relative to ring 1 epoxide equivalent of oxygen tree fat, and the hydroxyl equivalent of phenol resol resins is 0.4~1.0, the cyanate of multivalence cyanate is worked as Measure as 0.1~0.6, the hardening thing of heat resistance and excellent water resistance can be thereby provided.In addition, included described in patent document 2 The thermosetting resin composition of cyanate esters, phenolic compounds and inorganic filler with specific structure, and record institute The excellent heat resistance of resin combination is stated, and there is high mechanical strength.

[prior art literature]

[patent document]

[patent document 1] Japanese Patent Laid-fair 6-15603 publications

[patent document 2] Japanese Patent Laid-Open 2013-53218 publications

[non-patent literature]

[non-patent literature 1]《Industrial materials》In November, 2011 number (vol 59No.11)

The content of the invention

[inventing problem to be solved]

But the composition described in patent document 1 needs when the reaction by epoxy and cyanato- forms oxazole ring High temperature and prolonged thermmohardening are wanted, and the problem of production difference be present.In addition, composition described in patent document 2 due to Moisture-proof is insufficient, therefore problems be present：If it is hot and humid it is lower it is long-term place, CuLF or plating Ag and hardening thing it is close Connecing property is reduced and is peeling or crackle.Therefore, the present invention is in view of the situation, it is therefore an objective to provides a kind of tree excellent in reliability Oil/fat composition, even if its offer is placed more than 200 DEG C, at a high temperature of such as 200 DEG C~250 DEG C and thermally decompose (weight for a long time Reduce) even if also with CuLF or plating Ag adhesion also excellent hardening thing less and under hot and humid environment.

Moreover, the present invention is in view of the situation, it is therefore an objective to a kind of resin combination is provided, even if it can be formed 200 Place for a long time more than DEG C, at a high temperature of such as 200 DEG C~250 DEG C and thermally decompose (weight reduction) even if also less and in high temperature height The hardening thing excellent with CuLF or plating Ag adhesion under wet environment, and metaideophone has excellent formability.

[means for solving problem]

Present inventor et al. makes great efforts to study to solve the problem, as a result finds, by containing cyanate chemical combination In the composition of thing and inorganic filler, phenolic compounds and epoxy resin of the allotment with specific structure, and by phenolic compounds phase Allotment amount and epoxy resin for cyanate esters are set in specific scope relative to the allotment amount of cyanate esters, And the hardening thing with excellent heat endurance can be obtained, even if the hardening thing is chronically exposed to hot and humid building ring Under border, thermal decomposition (weight reduction) is also few, and can maintain with CuLF or plate Ag excellent adhesion, so as to complete this hair It is bright.

That is, the first invention of the invention is a kind of composition, comprising：

(A) there are the cyanate esters of more than 2 cyanato-s in 1 molecule；

(B) phenolic compounds shown in following formulas (2),

[changing 1]

(in formula, R⁵And R⁶The independently of one another alkyl of hydrogen atom or carbon number 1~4, R⁷It is independently of one another following any Kind,

[changing 2]

R⁴Independently of one another hydrogen atom or methyl, m are 0~10 integer)；

(C) inorganic filler；And

(D) following formulas (3) or the epoxy resin shown in formula (4),

[changing 3]

[changing 4]

(in the formula (3) and formula (4), k and p are independently of one another more than 0, less than 10 integer, and j is 1~6 integer, R¹⁰The independently of one another alkyl of hydrogen atom or carbon number 1~4, R¹¹And R¹²It is independently of one another following any)；And

[changing 5]

(B) phenolic hydroxyl group in phenolic compounds relative to the mol ratio of the cyanato- in (A) cyanate esters for 0.2~ 0.4, and the epoxy radicals in (D) epoxy resin relative to the mol ratio of the cyanato- in (A) cyanate esters for 0.04~ 0.25。

Moreover, present inventor et al. has found, by alkoxy of the allotment containing mercaptopropyi in the first chamber Silane compound, and the adhesion of metal substrate and hardening thing can be significantly increased.But problems be present：If described group Compound is placed for a long time at high temperature, then can aoxidize the alkoxysilane compound containing trialkylsilyl group in molecular structure containing mercaptopropyi and produce sulfate ion, Therefore metal substrate corrodes and changed colour.

Therefore, present inventor et al. further makes great efforts to study to solve described problem, as a result finds, by described Allocate in first chamber in the composition of the alkoxysilane compound containing trialkylsilyl group in molecular structure containing mercaptopropyi, further allocated in the lump in nothing The material and houghite compound (hydrotalcite-like compound) of molybdic acid metal salt are carried with airborne body, and The corrosion of caused metal substrate when can suppress to place for a long time at high temperature, and hardening thing can be maintained for metal substrate Excellent adhesion, so as to complete the present invention.

That is, the second invention of the invention is a kind of composition, and it is included：

(A) there are the cyanate esters of more than 2 cyanato-s in 1 molecule；

(B) phenolic compounds shown in following formulas (2),

[changing 6]

(in formula (2), R⁵And R⁶The independently of one another alkyl of hydrogen atom or carbon number 1~4, R⁷Independently of one another following One kind,

[changing 7]

(C) inorganic filler；

(D) following formulas (3) or the epoxy resin shown in formula (4),

[changing 8]

[changing 9]

(in the formula (3) and formula (4), k and p are independently of one another more than 0, less than 10 integer, and j is 1~6 integer, R¹⁰The independently of one another alkyl of hydrogen atom or carbon number 1~4, R¹¹And R¹²It is independently of one another following any)

[changing 10]

(E) compound shown in following formulas (5),

[changing 11]

R⁸ _d(R⁹O)_(3-d)Si-C₃H₆-SH (5)

(in formula (5), R⁸And R⁹The independently of one another alkyl of carbon number 1~3, d are 0~2 integer)；

(F) material that molybdic acid metal salt forms is held on inorganic carrier；And

(G) calcined material of houghite compound and/or houghite compound；And

Moreover, present inventor et al. is studied the progressive forming for improving the first chamber, as a result find, By the releasing agent that further allotment acid number is less than 30 in the first chamber and saponification number is less than 150 (wherein, Saponification number is more than 80, less than 150 when acid number is less than 5, and acid number is more than 20, less than 30 when saponification number is less than 5), and can carry The progressive forming of high resin composition, so as to complete the present invention.

That is, the 3rd invention of the invention is a kind of composition, and it is included：

(A) there are the cyanate esters of more than 2 cyanato-s in 1 molecule；

(B) phenolic compounds shown in following formulas (2),

[changing 12]

[changing 13]

(C) inorganic filler；

(D) following formulas (3) or the epoxy resin shown in formula (4),

[changing 14]

[changing 15]

(in the formula (3) and formula (4), k and p are independently of one another more than 0, less than 10 integer, and j is 1~6 integer, R¹⁰The independently of one another alkyl of hydrogen atom or carbon number 1~4, R¹¹And R¹²Group independently of one another shown in following formula)

[changing 16]

And

(H) (saponification number is 80 to the releasing agent that acid number is less than 30 and saponification number is less than 150 when wherein, acid number is less than 5 Above, less than 150, acid number is more than 20, less than 30 when saponification number is less than 5)；And

[The effect of invention]

Even if the first chamber of the present invention can be provided more than 200 DEG C, at a high temperature of particularly 200 DEG C~250 DEG C Long-term place and thermally decompose (weight reduction) even if also less, it is also excellent with CuLF or plating Ag adhesion under hot and humid environment Hardening thing different and with high insulating properties.Therefore, the semiconductor sealed by the hardening thing of the composition of the present invention fills Put has long-term reliability under hot and humid.

The second chamber of the present invention can suppress more than 200 DEG C, at a high temperature of particularly 200 DEG C~250 DEG C for a long time The discoloration of metal substrate during placement, even and if under hot and humid environment it is long-term place can also maintain CuLF or plating Ag with it is hard The excellent adhesion of compound.Therefore, the semiconductor device sealed by the hardening thing of the composition of the present invention is in high temperature There is long-term reliability under high humidity.

Placed for a long time under the conditions of hot and humid even if the 3rd composition of the present invention can provide and thermally decompose that (weight subtracts It is few) also less, with plating Ag adhesion also excellent hardening thing after CuLF.Therefore, enter by the hardening thing of the composition of the present invention The semiconductor device of row sealing has the long-term reliability under hot and humid.In addition, the 3rd composition of the present invention is due to even It is continuous to have excellent formability, therefore metaideophone molding material can be suitable for use as.

Embodiment

Hereinafter, the present invention will be described in more detail.

(A) cyanate esters

In the first chamber of the present invention, second chamber and the 3rd composition, (A) composition is to have 2 in 1 molecule The cyanate esters of above cyanato-.As long as the cyanate esters in the present invention have more than 2 cyanato-s in 1 molecule , generally well-known cyanate esters can be used.The cyanate esters for example can be by following formulas (1) table Show.

[changing 17]

(in formula (1), R¹And R²The independently of one another alkyl of hydrogen atom or carbon number 1~4, R³Independently of one another following It is a kind of.

[changing 18]

R⁴For hydrogen atom or methyl, n is 0~10 integer)

The cyanate esters of the present invention can for example be enumerated：Double (4- cyanato-s phenyl) methane, double (3- methyl -4- cyanogen Phenyl) methane, double (3- ethyl -4- cyanato-s phenyl) methane, double (3,5- dimethyl -4- cyanato-s phenyl) methane, 1, Double (the 4- cyanato-s phenyl) ethane of 1-, double (the 4- cyanato-s phenyl) propane of 2,2-, double (the 4- cyanato-s phenyl) -1,1,1,3 of 2,2-, 3,3- HFC-236fas, the cyanato- benzene of 1,3- bis- and the cyanato- benzene of 1,4- bis-, the cyanato- benzene of the 2- tert-butyl groups -1,4- two, 2,4- diformazans The cyanato- benzene of base -1,3- two, the cyanato- benzene of 2,5- di-t-butyl -s 1,4- bis-, the cyanato- benzene of tetramethyl -1,4- two, 1,3,5- tri- Cyanato- benzene, the cyanato- of 2,2 '-two cyanato- biphenyl or 4,4 '-two cyanato- biphenyl, 3,3 ', 5,5 '-tetramethyl -4,4 '-two Biphenyl, the cyanato- naphthalenes of 1,3- bis-, the cyanato- naphthalenes of 1,4- bis-, the cyanato- naphthalenes of 1,5- bis-, the cyanato- naphthalenes of 1,6- bis-, the cyanato-s of 1,8- bis- Naphthalene, the cyanato- naphthalenes of 2,6- bis- or the cyanato- naphthalenes of 2,7- bis-, the cyanato- naphthalenes of 1,3,6- tri-；1,1,1- tri- (4- cyanato-s phenyl) second Alkane, double (4- cyanato-s phenyl) ethers；4,4 '-(1,3- phenylenediisopropylidenes) diphenyl cyanates, double (4- cyanato- benzene Base) thioether, double (4- cyanato-s phenyl) sulfones, three (4- cyanato-s-phenyl) phosphines, three (4- cyanato-s phenyl) phosphates, phenol phenol Novolac type cyanate, cresol novolak type cyanate, dicyclopentadiene novolac type cyanate, phenyl aralkyl-type cyanogen Acid esters, biphenyl aralkyl-type cyanate and naphthalene aralkyl-type cyanate etc..The cyanate esters can be used alone Or mix two or more and use.

The cyanate esters obtain by making phenols be reacted with cyanogen chloride under alkalescence.The cyanate esters can Using according to its structure from softening point as 106 DEG C of solid cyanate esters under normal temperature for the cyanate esters of liquid untill The cyanate esters with broad characteristic in, suitably selected according to purposes.Such as in manufacture liquid epoxy resin group During compound, preferably using the compound under normal temperature being liquid, be dissolved in solvent and when varnish is made, preferably according to dissolubility or Solution viscosity is selected.In addition, when being shaped by metaideophone for power semiconductor seal applications, preferably select at normal temperatures For the compound of solid.

In addition, the equivalent of cyanato- is small, i.e. the small composition of molecular weight between functional group, can obtain curing shrinkage it is small and The hardening thing of low-thermal-expansion, high Tg.The big composition of cyanato- equivalent, Tg is in a slight decrease, but triazine crosslinked interval is changed into flexible, Low elasticity, high Strengthening and Toughening, low water suctionization can be expected.The chlorine of bond or remaining is suitably 50ppm in cyanate esters Hereinafter, more preferably below 20ppm.If the amount of chlorine is more than 50ppm, because of thermal decomposition and free during long-term placement at high temperature Chlorine or chlorion, by oxidized Cu frameworks or Cu lines, plating Ag corrosion, and the stripping that is possible to cause hardening thing or electrically not It is good.Furthermore, it is possible to also reduce the insulating properties of resin.

(B) phenolic compounds

In the first chamber of the present invention, second chamber and the 3rd composition, (B) phenolic compounds is that have in 1 molecule There are more than 2 phenolic hydroxyl group and the phenolic compounds represented by following formulas (2).

[changing 19]

In the formula, R⁵And R⁶The independently of one another alkyl of hydrogen atom or carbon number 1~4, m are 0~10 integer.

In the formula, R⁷It is independently of one another following any.

[changing 20]

(in the formula, R⁴Independently of one another hydrogen atom or methyl)

In the first chamber of the present invention, phenolic compounds does not include R in the formula (2)⁷For CH₂Phenolic compounds (such as benzene Phenol novolac resin).R⁷For CH₂Phenolic compounds following worry be present：Easily cause heat point during long-term placement at high temperature Solution, and be peeling at the interface of copper lead frame and hardening thing or crackle.

Phenolic compounds shown in the 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.It is described to can be used alone or two or more kinds may be used.

In the second chamber of the present invention and the 3rd composition, R in the formula (2) can be included⁷For CH₂Compound (example Such as phenol resol resins).But there is the worry of poor heat resistance or because of cyanate esters and describedization in the composition Reactive too fast and formability difference the worry of compound.It is therefore especially preferred that in the second chamber of the present invention and the 3rd combination R in thing⁷Also it is CH₂In addition.

In the past, the hardening catalyst of cyanate esters used the (Japanese Patent Laid-Open No. Sho such as metal salt, metal complex 64-43527 publications, Japanese Patent Laid-Open 11-106480 publications, Japanese Patent Laid 2005-506422 publications). But may be used as metal salt, metal complex is transition metal, transition metal-type has promotes organic resin at high temperature Oxidative degradation worry.In the present compositions, the phenolic compounds has given play to the cyclisation as cyanate esters The function of the catalyst of reaction.Therefore, without use metal salt and metal complex.Thereby can further it improve under high temperature Long-term keeping stability.

In addition, the phenolic compounds with least two above hydroxyl can be expected as triazine ring is connected in a molecule Crosslinking agent.Phenolic compounds is different from epoxide or amines, is bonded by with cyanate esters, and can be formed- Structure shown in C-O-Ar-.The triazine ring structure formed when the structure is with cyanate esters are individually hardened is similar, because This can expect the heat resistance for further improving the hardening thing of gained.

In addition, the small phenolic compounds of hydroxyl equivalent, such as hydroxyl equivalent are less than 110 phenolic compounds, with cyanato- It is reactive high.Therefore situations below be present：Sclerous reaction is carried out when composition being melted and is kneaded below 120 DEG C, and is substantially damaged Evil mobility, it is not preferred for metaideophone shaping.Therefore, the particularly preferred hydroxyl equivalent of phenolic compounds is more than 111.

In the present invention, the allotment amount of phenolic compounds is 1 mole of the cyanato- relative to cyanate esters and hydroxyl is 0.2 Mole~0.4 mole of amount.If the amount of phenolic compounds is less than the lower limit, the reaction of cyanato- is insufficient, and remaining is not The cyanato- of reaction.The cyanato- of remaining can be hydrolyzed under high humidity environment.Therefore, if in hot and humid lower placement, The reduction of mechanical strength can be caused or reduced with the contiguity power of base material.In addition, if the amount of phenolic compounds is more than the higher limit, Then sclerous reaction is carried out from low temperature.Therefore, the mobility of composition can be damaged, and formability is deteriorated.In addition, the phenolic compounds In halogens or alkali metal etc., during extraction under 120 DEG C, 2 air pressure, preferably 10ppm, it is especially desirable for 5ppm with Under.

(C) inorganic filler

In the first chamber of the present invention, second chamber and the 3rd composition, the species of inorganic filler has no especially Limitation, the inorganic filler of resin composition for encapsulating semiconductor can use known inorganic filler.Such as it can enumerate： Silica-based, aluminum oxide, silicon nitride, the nitrogen such as fused silica, crystallinity silica, cristobalite (cristobalite) Change aluminium, boron nitride, titanium oxide, glass fibre, magnesia and zinc oxide etc..The average grain diameter or shape of the inorganic filler As long as selected according to purposes.Wherein, in order to obtain the thermal coefficient of expansion close to silicon, preferred molten silica, shape Shape is suitably spherical.The average grain diameter of inorganic filler is preferably 0.1 μm~40 μm, more preferably 0.5 μm~15 μm.It is described flat Equal particle diameter as by weighed average (or intermediate value) laser diffractometry etc. such as can obtain.

It is miscellaneous as being extracted under 120 DEG C, 2.1 air pressure under sample 5g/ water 50g extraction conditions in inorganic filler Matter, chlorion are suitably below 10ppm, and sodium ion is suitably below 10ppm.If more than 10ppm, have and sealed by composition Semiconductor device resistance to moisture performance reduce situation.

In the present invention, the allotment amount of inorganic filler can be set to the mass % of 60 overall mass % of composition~94, excellent Choosing is set to the mass % of 70 mass %~92, is more preferably set to the mass % of 75 mass %~90.

For reinforced resin and the bond intensity of inorganic filler, inorganic filler is preferably allocated：By silane coupling agent, The inorganic filler that the coupling agents such as titanate esters coupling agent are surface-treated in advance.Such a coupling agent preferably uses：γ-shrink is sweet Oily epoxide propyl trimethoxy silicane, γ-glycidoxypropyl diethoxy silane, β-(3,4- epoxycyclohexyls) The epoxy silanes such as ethyl trimethoxy silane, N- β (amino-ethyl)-gamma-amino propyl trimethoxy silicane, imidazoles and γ-contracting Reactant, γ aminopropyltriethoxy silane, the N- phenyl-gamma-amino propyl group of water glycerine epoxide propyl trimethoxy silicane The amino silanes such as trimethoxy silane, γ-hydrosulphonyl silane, γ-epithio epoxide propyl trimethoxy silicane (γ- The silane coupling agent such as hydrosulphonyl silane such as episulfidoxypropyltrimethoxysilane).But at second group of the present invention In compound, it can use and carry out surface by hydrosulphonyl silanes such as γ-hydrosulphonyl silane, γ-epithio epoxide propyl trimethoxy silicanes The inorganic filler of processing, but it is less preferred.Herein, for surface treatment coupling agent allotment amount and surface treatment method simultaneously It is not particularly limited.

(D) epoxy resin

(D) composition is the epoxy resin shown in following formula (3) or formula (4).

[changing 21]

[changing 22]

In the formula (3) and formula (4), k and p are independently of one another more than 0, less than 10 integer, and j is 1~6 integer, R¹⁰The independently of one another alkyl of hydrogen atom or carbon number 1~4, R¹¹And R¹²It is independently of one another following any.

[changing 23]

The epoxy resin can for example be enumerated：Phenol aralkyl type epoxy resin, biphenyl aralkyl-type epoxy resin, naphthalene Type aralkyl base epoxy etc..Epoxy resin forms oxazole ring with cyanate ester resin, but compared with the triazine ring of cyanato- is formed, It is reactive slow.In addition, if the ratio of epoxy radicals is more, firm time is elongated and is unfavorable for metaideophone shaping.Herein, also have using such as The example of the tertiary amine of triethylamine, but the worry for thering is keeping quality to be deteriorated.

The epoxy resin reacts with cyanate esters and forms oxazole ring.In the present invention, relative to cyanate chemical combination 1 mole of the cyanato- of thing, the addition of epoxy resin compound turn into 0.04 mole~0.25 mole of amount for epoxide equivalent. If the amount of epoxy resin is less than the lower limit, the moisture absorption quantitative change of hardening thing is more, and in lead frame under high-temperature high-humidity It is peeling between hardening thing.In addition, if the amount of epoxy resin is more than the higher limit, hardening becomes insufficient, and draws Play the reduction of the glass transition temperature of hardening thing or the reduction of hot and humid keeping characteristic.

In the composition of the present invention, in addition to being formed by the triazine ring of the cyclization of cyanate esters, also carry out： The reaction (formation of oxazole ring) of epoxide and cyanate esters, the reaction of phenolic compounds and cyanate esters and The reaction of epoxide and phenolic compounds.The composition of the present invention causes institute by under the basis of the specific allotment ratio Reaction is stated, and can provide hot and humid patience extremely excellent hardening thing.

First chamber

The first form of the present invention is to include the resin combination of described (A) composition~(D) composition.The first of the present invention is close In envelope resin combination in addition to described (A) composition~(D) composition, can further it allocate as needed：It is releasing agent, fire-retardant The various additives such as agent, ion capturing agent, antioxidant, bonding imparting agent, low stress agent.In addition, adhesion imparting agent can be with Use described coupling agent.In order to improve the adhesion with metal framework, sulfydryl system silane coupling agent Te Do are suitable.

There is no particular restriction for releasing agent, can use known releasing agent.Such as it can enumerate：Brazil wax (carnauba wax), rice bran wax (rice wax), may ground lira wax (candelilla wax), polyethylene, oxidic polyethylene, Polypropylene, montanic acid (montanic acid) are montanic acid and saturated alcohols, 2- (2- Hydroxy-ethylaminos)-ethanol, ethylene glycol, sweet The ester compounds of oil etc. are montanic acid wax, stearic acid, stearate, stearic amide, ethylenebis stearic amide, ethene with Copolymer of vinyl acetate etc..It is described to can be used alone or combine two or more and use.

There is no particular restriction for fire retardant, can use known whole fire retardants.Such as it can enumerate：Phosphonitrile (phosphazene) compound, silicone compounds, zinc molybdate hold talcum, zinc molybdate holds zinc oxide, aluminium hydroxide, hydrogen-oxygen Change magnesium, molybdenum oxide and antimony trioxide.

There is no particular restriction for ion capturing agent, can use known ion capturing agent.Such as it can enumerate：Hydrotalcite Class, bismuth hydroxide compound, rare-earth oxide etc..

Second chamber

The present invention the second form be further comprised in addition to (A) composition~(D) composition following (E) compositions~ (G) resin combination of composition.

(E) alkoxysilane compound containing trialkylsilyl group in molecular structure containing mercaptopropyi

(E) composition is the compound shown in following formulas (5).

[changing 24]

R⁸ _d(R⁹O)_(3-d)Si-C₃H₆-SH (5)

In the formula (5), R⁸And R⁹The independently of one another alkyl of carbon number 1~3, d are 0~2 integer.It is described to contain mercapto The alkoxysilane compound containing trialkylsilyl group in molecular structure of base propyl group can for example be enumerated：3-mercaptopropyi trimethoxy silane, the ethoxy of 3- mercaptopropyis three Base silane, 3- mercaptopropyis methyl dimethoxysilane and 3- mercaptopropyi methyldiethoxysilanes etc..

The second chamber of the present invention is by containing the alkoxy silane chemical combination containing mercaptopropyi shown in the formula (5) Thing, and be significantly increased Cu alloy lead frames, plating Ag, gold-plated (Au) and plating NiPdAu (NiPdAu) etc. metal substrate with it is hard The adhesion of compound.Relative to total 100 parts by weight of (A) composition and (B) composition, the allotment amount of (E) composition is 0.3 parts by weight The parts by weight of~1.0 parts by weight, preferably 0.4 parts by weight~0.8.If the amount of (E) composition is less than the lower limit, there is Metal Substrate The possibility of the adhesion of plate and hardening thing deficiency.In addition, the amount of (even if E) composition exceedes the higher limit, adhesion is not yet Can further it improve, thus it is economically not preferred.

(F) molybdic acid metal salt holds material

(F) composition is that the material that molybdic acid metal salt forms is held on inorganic carrier.(F) composition has：By composition PH value is changed into the effect of partial neutral from acidity and suppresses or catch the trip of Cu ions or Ag ions from lead frame or plating From effect.The second chamber of the present invention：(F) composition is allocated together with following described (G) compositions.Thereby, can be with Caused metal frame when the device for suppressing to seal by the hardening thing of sealing resin composition is placed for a long time at high temperature The corrosion of frame, and the excellent adhesion of hardening thing and metal framework can be maintained at high temperature.

Holding the inorganic carrier of molybdic acid metal salt can use：Enumerated as (C) inorganic filler without airborne Body.Such as it can enumerate：Fused silica, crystallinity silica etc. are silica-based, talcum, zinc oxide, aluminum oxide, nitrogen SiClx, aluminium nitride, boron nitride, titanium oxide, glass fibre etc..The inorganic carrier can be identical with (C) composition, can also It is different.Particularly preferably silica, talcum, zinc oxide.

Molybdic acid metal salt can use：Zinc molybdate, calcium molybdate, strontium molybdate, barium molybdate or described mixture.In addition, can To combine the oxide of the metals such as zinc, calcium, strontium, barium in molybdic acid metal salt.Preferably zinc molybdate.Molybdenum is held on inorganic carrier The material that sour zinc forms can for example 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 held on inorganic carrier be preferably 5 mass %~ 40 mass %, particularly preferably the mass % of 10 mass %~30.If the content of molybdic acid metal salt is very few, having can not obtain fully Effect situation, if in addition, the content of molybdic acid metal salt is excessive, situation that mobility, hardening when having a shaping reduce.

Relative to total 100 parts by weight of (A) composition and (B) composition, the addition of (F) composition is preferably set to 3 parts by weight ~30 parts by weight, more preferably it is set to the parts by weight of 5 parts by weight~20., can not be abundant when the amount of (F) composition is less than the lower limit Obtain effect.In addition, when the amount for adding (F) composition exceedes the higher limit, there is the situation for causing mobility to reduce.

(G) houghite compound

(G) composition is the calcined material of houghite compound and/or houghite compound.So-called houghite chemical combination Thing, the layered double-hydroxide shown in for example, following composition formulas, has given play to the function as anion exchanger.

[M²⁺ _1-xM³⁺ _x(OH)₂]x⁺[(A^n- _x/n)·mH₂O]^x-

In the formula, M²⁺For Mg²⁺、Ca²⁺、Zn²⁺、Co²⁺、Ni²⁺、Cu²⁺、Mn²⁺Deng divalent metal ion, M³⁺For Al³⁺、Fe³ ⁺、Cr³⁺Etc. trivalent metal ion, A^n-For OH^-、Cl^-、CO₃ ^2-、SO₄ ^2-Deng n valency anion.X is number more than 0, particularly 0.10~ 0.50th, especially 0.20~0.33, m is 0 or the number more than 0, particularly 0~10, especially 0~4.Houghite compound Calcined material is, for example, can be by formula M²⁺ _1-xM³⁺ _xO_1+x/2The double oxide that (x is positive number) represents.In addition, the present invention (G) into Dividing to use：Mg₃ZnAl₂(OH)₁₂CO₃·wH₂O、Mg₃ZnAl₂(OH)₁₂CO₃Deng zinc modification hydrotalcite based compound, (w is Real number).

The calcined material of houghite compound and houghite compound has anion exchange function.Therefore with as follows Effect：It can catch by the oxidation of (D) composition and caused sulfate ion, thereby prevent Cu lead frames or plate Ag vulcanization Or corrosion.In addition, as described above, it is used together by by (G) composition with (F) composition, and can extremely effective prevents Cu, Ag Corrosion or migration the problems such as.

(G) composition of the present invention is preferably hydrotalcite compound and/or the hydrotalcite chemical combination shown in following formulas (6) The calcined material of thing.

Mg_aAl_b(OH)_cCO₃·nH₂O (6)

In the formula (6), a, b and c are the number for being more than 0 for meeting 2a+3b-c=2, and n is the number for meeting 0≤n≤4.

Hydrotalcite compound shown in the formula (6) can for example be enumerated：Mg_4.5Al₂(OH)₁₃CO₃·3.5H₂O、 Mg_4.5Al₂(OH)₁₃CO₃、Mg₄Al₂(OH)₁₂CO₃·3.5H₂O、Mg₆Al₂(OH)₁₆CO₃·4H₂O、Mg₅Al₂(OH)₁₄CO₃· 4H₂O、Mg₃Al₂(OH)₁₀CO₃·1.7H₂O etc..Commercially available product can be enumerated：Trade name " DHT-4A ", " DHT-6 ", " DHT-4A-2 " (being the manufacture of consonance chemical industrial company) etc..

Relative to total 100 parts by weight of (A) composition and (B) composition, the allotment amount of (F) composition is preferably set to 1 parts by weight ~10 parts by weight, more preferably it is set to the parts by weight of 2 parts by weight~8.The amount of (if F) composition is less than the lower limit, can not be abundant Obtain effect.In addition, when the addition of (F) composition exceedes the higher limit, there are the feelings for causing hardening or adhesion to reduce Condition.

In the second sealing resin composition of the present invention, can further it allocate as needed：Releasing agent, fire retardant, resist The various additives such as the coupling agent beyond oxidant, bonding imparting agent, low stress agent, (E) composition.

There is no particular restriction for releasing agent, can use known releasing agent.Such as it can enumerate：Brazil wax, rice bran Wax, bear ground lira wax, polyethylene, oxidic polyethylene, polypropylene, montanic acid, montanic acid and saturated alcohols, 2- (2- hydroxyethyl ammonia Base) ester compounds of-ethanol, ethylene glycol, glycerine etc. are montanic acid wax, stearic acid, stearate, stearic amide, ethylidene Copolymer of double stearic amides, ethene and vinyl acetate etc..It is described to can be used alone or combine two or more and make With.

(E) coupling agent beyond composition can incite somebody to action：γ-glycidoxypropyltrimewasxysilane, γ-glycidol The epoxy silanes such as epoxide hydroxypropyl methyl diethoxy silane, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane, N- β (ammonia Base ethyl)-gamma-amino propyl trimethoxy silicane, imidazoles and γ-glycidoxypropyltrimewasxysilane reaction The silane such as the amino silanes such as thing, γ aminopropyltriethoxy silane, N- phenyl-gamma-amino propyl trimethoxy silicane are coupled Agent is used alone a kind, or combines two or more and use.

There is no particular restriction for fire retardant, can use known fire retardant.Such as it can enumerate：Phosphazene compound, silicone Compound, aluminium hydroxide, magnesium hydroxide, molybdenum oxide and antimony trioxide.

3rd composition

The 3rd form of the present invention is that following (H) compositions are further comprised in addition to (A) composition~(D) composition Resin combination.

(H) releasing agent

In the 3rd composition of the present invention (H) composition used be acid number be less than 30 and saponification number be less than 150 it is de- Mould agent.Acid number is preferably 10~25.In addition, saponification number is preferably 70~140, more preferably 70~100.Acid number and saponification number Any one can be 0.But need acid number be less than 5 when, saponification number be more than 80, less than 150, preferably more than 100,150 with Under, when saponification number is less than 5, acid number is more than 20, less than 30, preferably more than 25, less than 30.Acid number and saponification number are too small Releasing agent due to the intermiscibility with resin it is excessively good, therefore sufficient stripping result (i.e. progressive forming) can not have been given play to, and It is not preferred.In addition, if acid number, saponification number are excessive, there is the oozing out serious and situation of bad order on hardening thing surface.Particularly If saponification number exceedes the higher limit, it is not at room temperature solid but the worry of liquid (lubricating oil) to have releasing agent.If Such a releasing agent is added in composition and is formed, then is had and is passed through with the time and ooze out and damage the load of the outward appearance of hardening thing Sorrow, thus it is not preferred.

The releasing agent of the present invention can for example be enumerated：Brazil wax, rice bran wax, oxidic polyethylene, montanic acid, montanic acid With the wax such as ester compounds of saturated alcohols, 2- (2- Hydroxy-ethylaminos)-ethanol, ethylene glycol or glycerine etc.；Stearic acid, stearic acid Copolymer of ester, ethene and vinyl acetate etc., it is described to can be used alone, two or more can also be combined and used.Its In, preferably oxidic polyethylene or fatty acid ester.The allotment amount of releasing agent is the matter of 0.3 overall mass % of composition~1.5 Measure %, the mass % of preferably 0.35 mass %~0.8 mass %, more preferably 0.35 mass %~0.5.

In the 3rd sealing resin composition of the present invention, can further it allocate as needed：Fire retardant, ion-catching The various additives such as agent, antioxidant, bonding imparting agent, low stress agent.In addition, adhesion imparting agent can use described idol Mixture.In order to improve the adhesion with metal framework, sulfydryl system silane coupling agent is particularly suitable.

There is no particular restriction for fire retardant, can use known fire retardant.Such as it can enumerate：Phosphazene compound, silicone Compound, zinc molybdate hold talcum, zinc molybdate holds zinc oxide, aluminium hydroxide, magnesium hydroxide, molybdenum oxide and antimony trioxide.

There is no particular restriction for the manufacture method of the composition of the present invention.Such as it can be obtained by the following manner：One side root According to need simultaneously or separately to (A) composition~(D) composition, (A) composition~(G) composition or (A) composition~ (D) composition and (H) composition, which apply, heats, while being stirred, dissolving, mix, disperseing, and is according to circumstances mixed in described Other additives are added in compound to be mixed, stirred, disperseed.Device used in mixing etc. is not particularly limited, and can be made With：Possess stirring, the mixing and kneading machine of heater, two rollers, three rollers, ball mill, continuous extruder, planetary mixer, quality head-on collision Machine (mass collider) etc..Can also appropriately combined described device and use.

The composition of the present invention is effective for transistor-type, modular type, dual-inline package (Dual In-line Package, DIP) type, small profile (Small Outline, SO) type, flat package (flat pack) type, ball grid array (Ball Grid Array) semiconductor packages such as type.Used forming process since as long as the shaping of the composition of the present invention is deferred in the past .Such as it can utilize：Metaideophone shaping, compression molding, injection molding, casting method etc..Particularly preferably metaideophone shapes.This hair The forming temperature of bright composition is preferably 45 seconds~180 seconds at 160 DEG C~190 DEG C, solidify afterwards (post cure) It it is 2 hours~16 hours preferably at 170 DEG C~250 DEG C.

The first chamber of the present invention is long-term at a high temperature of can be provided in more than 200 DEG C, particularly 200 DEG C~250 DEG C Thermal decomposition (weight reduction) during placement less, with CuLF or plate Ag adhesion it is excellent, there is the hardening thing of high insulating properties.Cause This, the semiconductor device sealed by the hardening thing of the composition of the present invention can have high temperature long-term reliability.In addition, The first chamber of the present invention, therefore can be with being typically used as the epoxy of metaideophone moulding material because progressive forming is good in the past Resin combination is used for same device, and can use same molding condition.And productivity is also excellent.

The second chamber of the present invention more than 200 DEG C, particularly at a high temperature of 200 DEG C~250 DEG C it is long-term certainly when It is few to thermally decompose (weight reduction).Even if in addition, long-term place can also be maintained with CuLF's or plating Ag under hot and humid environment Excellent adhesion, and can effectively suppress the corrosion of metal framework.Therefore, by the hardening of second chamber of the invention The semiconductor device that thing is sealed can have high temperature long-term reliability.Furthermore it is possible to being typically used as metaideophone shaping in the past The composition epoxy resin of material is used for same device, and can use same molding condition.And productivity is also excellent.

The 3rd composition of the present invention is long-term at a high temperature of can be provided in more than 200 DEG C, particularly 200 DEG C~250 DEG C The hardening thing of thermal decomposition (weight reduction) less, excellent with CuLF or plating Ag adhesion during placement.Even if in addition, in high temperature height The excellent adhesion with metal framework can also be maintained under wet environment.Therefore, by the hardening of the 3rd composition of the invention The semiconductor device that thing is sealed can have it is hot and humid under long-term reliability.Moreover, the 3rd composition of the present invention Because progressive forming is excellent, therefore metaideophone moulding material can be used as with particularly suitable.

[embodiment]

Hereinafter, embodiment and comparative example are represented, the present invention is described in more detail, but the present invention is not limited to following implementations Example.In addition, part in each example is mass parts.

[embodiment and comparative example]

Following shown each compositions are allocated with forming shown in 1~table of table 6, after equably being mixed by high-speed mixer, Crushed after being equably kneaded, cool down by two rollers of heating, thereby obtain resin combination.

[composition (A)~composition (D) used in first chamber, second chamber and the 3rd composition]

(A) cyanate esters

(a) (Premacy's Saite (Primaset) PT-60, Japan dragon are husky for the cyanate esters shown in following formula (7) The manufacture of (Lonza Japan) limited company, cyanato- equivalent are 119)

[changing 25]

(mixtures of n=0~10)

(b) in following synthesis examples 1 gained cyanate esters

[synthesis example 1]

100g phenolic compounds MEH-7851SS (bright and chemical conversion manufacture) is dissolved in 600g butyl acetate.Its is molten Liquid is cooled to about -15 DEG C, and imports 32g gas shape cyanogen chloride.Then, last about 30 minutes and addition 50g is added dropwise under agitation Triethylamine, therebetween, temperature remains less than -10 DEG C.At said temperatures further keep 30 minutes after, stop cooling and Reactant mixture is filtered.Then filtrate is passed into ion exchanger filling column.Then, under reduced pressure, bath temperature be 70 Solvent is removed at DEG C, then using membranous type evaporator is flowed down, volatile impurity is removed at 1mbar, 130 DEG C, and (bag is solvent-laden Residue, free triethylamine, diethyl cyanamide).The product of gained is the cyanate esters shown in following formula (8) (cyanato- equivalent is 208).

[changing 26]

(mixtures of n=0~10)

(B) phenolic compounds

(c) phenolic compounds shown in following formula (9) (MEH-7800SS, bright and chemical conversion manufacture, phenolic hydroxyl group equivalent are 175)

[changing 27]

(mixtures of n=0~10)

(d) (MEH-7851SS, bright and chemical conversion manufacture, phenolic hydroxyl group equivalent are the phenolic compounds shown in following formula (10) 203)

[changing 28]

(mixtures of n=0~10)

(e) comparative example phenolic compounds

Phenolic compounds (TD-2131, big Japanese ink chemistry (Dainippon Ink and shown in following formula (11) Chemicals, DIC) manufacture, 110) phenolic hydroxyl group equivalent is

[changing 29]

(mixtures of n=0~10)

(C) inorganic filler

(f) the melting spherical silicon dioxide (the gloomy manufacture of dragon) that average grain diameter is 15 μm

(D) epoxy resin

(g) epoxy resin compound shown in following formula (12) (NC-3000, the manufacture of Japanese chemical drug, epoxide equivalent 272)

[changing 30]

(mixtures of n=0~10)

(h) epoxy resin compound shown in following formula (13) (HP-4770, the manufacture of Japanese chemical drug, epoxide equivalent 204)

[changing 31]

(n and m be 0 or 1)

[other compositions used in first chamber]

Brazil wax (TOWAX-131, East Asia chemical conversion manufacture)

Silane coupling agent：3-mercaptopropyi trimethoxy silane (KBM-803, Shin-Etsu Chemial Co., Ltd's manufacture)

Imidazoles (manufacture of chemical conversion company of four countries)

[composition (E)~composition (G) and other compositions used in second chamber]

(i) 3-mercaptopropyi trimethoxy silane：(CH₃O)₃-Si-C₃H₆-SH

(F) composition

(j) zinc molybdate holds zinc oxide (Kai Mujiade (KEMGARD) -911B, Xuan Wei (SHERWIN-WILLIAMS) system Make)

(k) zinc molybdate holds talcum (Kai Mujiade (KEMGARD) -911C, Xuan Wei (SHERWIN-WILLIAMS) are manufactured)

(G) houghite compound

(l)Mg₆Al₂(CO₃)(OH)₁₆·4H₂O calcining product (DHT-4A-2, the manufacture of consonance chemistry)

Other compositions

Brazil wax (TOWAX-131, East Asia chemical conversion manufacture)

Imidazoles (manufacture of chemical conversion company of four countries)

[composition (H) and other compositions used in the 3rd composition]

(H) releasing agent

(m) releasing agent 1：Oxidic polyethylene (inner section's wax PED-522 (Licowax PED- that acid number is 25, saponification number is 0 522), Clariant (Clariant) company manufactures)

(n) releasing agent 2：Fatty acid ester (TOWAX-131, the East Asia chemical conversion limited public affairs of share that acid number is 10, saponification number is 85 Department's manufacture)

(o) releasing agent 3：Acid number is 25, fatty acid ester that saponification number is 140 (ITO-WAX TP NC-133, her rattan liquefaction Limited company manufactures)

Comparative test releasing agent

(p) releasing agent 4：The polyethylene (Licowax PE-522, Clariant Corporation manufacture) that acid number is 0, saponification number is 0

(q) releasing agent 5：Polypropylene and maleic anhydride multipolymer (the Ai Laike Bristols that acid number is 86, saponification number is 0 D121-41 (Elector D121-41), Nissan Chemical Industries Ltd.'s manufacture)

Other compositions

Imidazoles (manufacture of chemical conversion company of four countries)

The evaluation of first chamber

Following evaluation is carried out to embodiment 1-1~embodiment 1-6 and comparative example 1-1~comparative example 1-5 each composition Experiment.It the results are shown in table 1 below and table 2.

[helical flow]

Using the mould according to low-light microscope (Emission Microscope, EMMI) standard, in 175 DEG C, 6.9N/ mm², curring time be 180 seconds under conditions of be measured.

[weight change when being taken care of under high temperature]

Metaideophone shaping is carried out under conditions of being 6.9MPa in 175 DEG C × 120 seconds, forming pressure, is then entered at 180 DEG C The row solidify afterwards of 4 hours, thereby obtain 10mm × 100mm × 4mm test film.Test film is taken care of 500 in 250 DEG C of baking ovens Hour, determine weight reduction rates.

[confirming -1 with the adhesion of the CuLF through plating Ag]

Use the Cu alloy (Olympics of die paddle (die pad) portion (8mm × 8mm) and routing junction surface through plating Ag (Olin) C7025) system 100 pins (pin) flat-four-side encapsulation (Quad Flat Package, QFP) lead frame, 175 DEG C × 120 seconds, forming pressure be 6.9MPa under conditions of carry out metaideophone shaping.Then, the solidify afterwards of 4 hours are carried out at 180 DEG C. Lacing wire (tie bar) is cut off by lead frame cutting machine, and obtains 20mm × 14mm × 2.7mm QFP encapsulation.

It will be encapsulated in 250 DEG C of baking ovens and take care of 500 hours described in 12, split after keeping by visual to confirm to be packaged with nothing Line.Underbead crack and the stripping with lead frame are whether there is in addition, being observed using ultrasonic flaw detecting device.Crackle or stripping will be generated From the number of encapsulation be recorded in table 1 and table 2.

[confirming -2 with the adhesion of the CuLF through plating Ag]

Made using die paddle portion (8mm × 8mm) and routing junction surface through plating Ag Cu alloys (Olympic (Olin) C7025) 100 pin QFP lead frames, metaideophone shaping is carried out under conditions of being 6.9MPa in 175 DEG C × 120 seconds, forming pressure.Then, The solidify afterwards of 4 hours are carried out at 180 DEG C.Lacing wire is cut off by lead frame cutting machine, and obtain 20mm × 14mm × 2.7mm QFP encapsulation.

(121 DEG C × 100%RH of pressure steaming cooker experiment (Pressure Cooker Test, PCT) will be encapsulated in described in 12 Keeping 96 hours in 2.1atm), observe whether there is underbead crack and the stripping with lead frame using ultrasonic flaw detecting device after keeping From.The number for the encapsulation for cracking or peeling off is recorded in table 1 and table 2.

[formability]

80 pin QFP (14mm × 20mm × 2.7mm) are carried out under 175 DEG C × 120 seconds, 6.9MPa project for 20 times into Shape, observe the injection number attached on mould or untill curling and runner (runner) bending is produced.

[table 1]

[table 2]

By phenolic hydroxyl group relative to the mol ratio or epoxy radicals of cyanato- relative at least one of the mol ratio of cyanato- Hardening thing obtained by being unsatisfactory for comparative example 1-3~comparative example 1-5 of the scope of the present invention composition, 500 are placed at 250 DEG C Weight reduction rates when hour are big.If in addition, the hardening thing is taken care of or under hot and humid environment for a long time at high temperature Place, be then peeling and crackle at the interface with the Cu lead frames through plating Ag.Moreover, one of the mol ratio exceedes this The progressive forming of the comparative example 1-3 and comparative example 1-4 of the higher limit of the scope of invention composition is poor.In contrast, by this Weight reduction rates when hardening thing obtained by the composition of invention is placed 500 hours at 250 DEG C are small, even if hot and humid Lower long-time placement is not also peeling or crackle.In addition, the progressive forming of the composition of the present invention is also excellent.

The evaluation of second chamber

Following evaluation is carried out to embodiment 2-1~embodiment 2-7 and comparative example 2-1~comparative example 2-6 each composition Experiment.It the results are shown in Table 3 below and table 4.

[CuLF corrosion confirms]

Cu alloys (Olympic (Olin) C7025) are made into 100 pin QFP lead frames (die paddle portion) at 175 DEG C × 120 seconds Clock, forming pressure carry out metaideophone shaping under conditions of being 6.9MPa, and the solidify afterwards of 4 hours are then carried out at 180 DEG C.By drawing Wire frame cutting machine cuts off lacing wire, and obtains 20mm × 14mm × 2.7mm QFP encapsulation.

Described be encapsulated in 225 DEG C of baking ovens is taken care of 1000 hours.Mechanical destruction is carried out to sealing resin after keeping, and Die paddle portion inside observation whether there is discoloration.

[plating Ag corrosion confirms]

Die paddle portion (8mm × 8mm) and routing junction surface is set to be made through plating Ag Cu alloys (Olympic (Olin) C7025) 100 pin QFP lead frames, metaideophone shaping is carried out under conditions of being 6.9MPa in 175 DEG C × 120 seconds, forming pressure, is then existed The solidify afterwards of 4 hours are carried out at 180 DEG C.Lacing wire is cut off by lead frame cutting machine, and obtains 20mm × 14mm × 2.7mm QFP encapsulation.

Described be encapsulated in 225 DEG C of baking ovens is taken care of 1000 hours.Mechanical destruction is carried out to sealing resin after keeping, and Plating Ag die paddles portion inside observation whether there is discoloration.

[confirming -1 with the adhesion of the CuLF through plating Ag]

It will be encapsulated in 225 DEG C of baking ovens and take care of 1000 hours described in 12.Ultrasonic flaw detecting device is used after keeping, is observed Whether there is underbead crack and the stripping with lead frame.The number for the encapsulation for cracking or peeling off is recorded in table 3 and table 4.

[confirming -2 with the adhesion of the CuLF through plating Ag]

Made using die paddle portion (8mm × 8mm) and routing junction surface through plating Ag Cu alloys (Olympic (Olin) C7025) 100 pin QFP lead frames, metaideophone shaping is carried out under conditions of being 6.9MPa in 175 DEG C × 120 seconds, forming pressure, is then existed The solidify afterwards of 4 hours are carried out at 180 DEG C.Lacing wire is cut off by lead frame cutting machine, and obtains 20mm × 14mm × 2.7mm QFP encapsulation.

Keeping 96 hours in PCT (121 DEG C × 100%RH 2.1atm) will be encapsulated in described in 12, ultrasound is used after keeping Wave inspection device, observation whether there is underbead crack and the stripping with lead frame.By the individual number scale for the encapsulation for cracking or peeling off It is loaded in table 3 and table 4.

[table 3]

[table 4]

In not containing molybdic acid metal salt and holding any composition of material or houghite compound, at high temperature It can not suppress the discoloration of metal framework during long-term placement, and be peeling at the interface of metal framework and hardening thing.Relative to This, the test body sealed by the composition of the present invention, at 225 DEG C placing 1000 hours metal frameworks does not also change colour, also not It is peeling or crackle.Even if in addition, the hardening thing as obtained by the second chamber of the present invention also may be used under hot and humid environment To maintain the excellent adhesion to metal substrate.

The evaluation of 3rd composition

Following evaluation is carried out to embodiment 3-1~embodiment 3-6 and comparative example 3-1~comparative example 3-5 each composition Experiment.It the results are shown in table 5 below and table 6.

[helical flow]

Using the mould according to EMMI standards, in 175 DEG C, 6.9N/mm², curring time be 180 seconds under conditions of carry out Measure.

[weight change when being taken care of under high temperature]

Metaideophone shaping is carried out under conditions of being 6.9MPa in 175 DEG C × 120 seconds, forming pressure, is then entered at 180 DEG C The row solidify afterwards of 4 hours, thereby obtain 10mm × 100mm × 4mm test film.The test film is protected in 250 DEG C of baking ovens Pipe 500 hours, and determine weight reduction rates.

[confirming -1 with the adhesion of the CuLF through plating Ag]

Die paddle portion (8mm × 8mm) and routing junction surface is set to be made through plating Ag Cu alloys (Olympic (Olin) C7025) 100 pin QFP lead frames carry out metaideophone shaping under conditions of being 6.9MPa in 175 DEG C × 120 seconds, forming pressure, then exist The solidify afterwards of 4 hours are carried out at 180 DEG C.Lacing wire is cut off by lead frame cutting machine, and obtains 20mm × 14mm × 2.7mm QFP encapsulation.

It will be encapsulated in 250 DEG C of baking ovens and take care of 500 hours described in 12, split after keeping by visual to confirm to be packaged with nothing Line.Underbead crack and the stripping with lead frame are whether there is in addition, being observed using ultrasonic flaw detecting device.It will crack or peel off The number of encapsulation be recorded in table 5 and table 6.

[confirming -2 with the adhesion of the CuLF through plating Ag]

Keeping 96 hours in PCT (121 DEG C × 100%RH 2.1atm) will be encapsulated in described in 12.Ultrasound is used after keeping Wave inspection device, observation whether there is underbead crack and the stripping with lead frame.By the individual number scale for the encapsulation for cracking or peeling off It is loaded in table 5 and table 6.

[formability]

80 pin QFP (14mm × 20mm × 2.7mm) are carried out under 175 DEG C × 120 seconds, 6.9MPa project for 100 times into Shape, and observe the attaching on mould or the injection number untill curling and runner bending is produced.

[table 5]

[table 6]

The composition of the releasing agent of the scope of the present invention is unsatisfactory for containing acid number and saponification number, progressive forming is poor.Relatively In this, the progressive forming of the 3rd composition of the invention is excellent.Moreover, even if the 3rd composition of the present invention is grown at high temperature Phase places weight reduction rates also less, and can maintain the adhesion with metal framework for a long time under the conditions of hot and humid.

[industrial applicability]

The formability of the resin combination of the present invention is good, even if its hardening thing is more than 200 DEG C, such as 200 DEG C~250 Placed for a long time at a high temperature of DEG C and thermally decompose (weight reduction) and also lack, even if close with CuLF or plating Ag under hot and humid environment Connecing property is also excellent.It is, therefore, possible to provide the semiconductor device that long-term reliability under the conditions of hot and humid is excellent.Moreover, this hair The discoloration of metal framework when the hardening thing of bright second chamber effectively can suppress to place for a long time at high temperature, and in height The excellent adhesion with metal framework can be maintained under warm high humidity environment.Therefore, composition of the invention can provide high temperature The excellent semiconductor device of long-term reliability under high humidity.Moreover, the hardening thing of the 3rd composition of the present invention is hot and humid There is down long-term thermal stability, the excellent adhesion with metal framework can be maintained, can be provided in hot and humid lower long-term Semiconductor device excellent in reliability, and the composition due to progressive forming it is excellent, therefore can be suitable for use as metaideophone into Shape material.

Claims

1. a kind of resin composition for encapsulating semiconductor, it is characterised in that include：

(A) there are the cyanate esters of more than 2 cyanato-s in 1 molecule；

(B) phenolic compounds shown in following formulas (2),

In formula (2), R⁵And R⁶The independently of one another alkyl of hydrogen atom or carbon number 1~4, R⁷It is independently of one another following any,

-CH(CH₃)-、-O-、-S-、-SO₂-、

R⁴Independently of one another hydrogen atom or methyl, m are 0~10 integer；

(C) inorganic filler；

(D) following formulas (3) or the epoxy resin shown in formula (4),

In the formula (3) and formula (4), k and p are independently of one another more than 0, less than 10 integer, and j is 1~6 integer, R¹⁰Phase Mutually it independently is the alkyl of hydrogen atom or carbon number 1~4, R¹¹And R¹²It is independently of one another following any,

-CH₂-、

(E) compound shown in following formulas (5),

R⁸ _d(R⁹O)_(3-d)Si-C₃H₆-SH (5)

In formula (5), R⁸And R⁹The independently of one another alkyl of carbon number 1~3, d are 0~2 integer；

(G) calcined material of houghite compound and/or houghite compound；And

(B) phenolic hydroxyl group in phenolic compounds is 0.2~0.4 relative to the mol ratio of the cyanato- in (A) cyanate esters, And the epoxy radicals 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, it is characterised in that (G) composition is following formula institute The houghite compound and/or the calcined material of houghite compound shown：

[M²⁺ _1-xM³⁺ _x(OH)₂]^x+[(A^n- _x/n)·mH₂O]^x-

In the formula, M²⁺For Mg²⁺、Ca²⁺、Zn²⁺、Co²⁺、Ni²⁺、Cu²⁺Or Mn²⁺, M³⁺For Al³⁺、Fe³⁺Or Cr³⁺, A^n-For OH^-、 Cl^-、CO₃ ^2-Or SO₄ ^2-, x is the number more than 0, and m is 0 or the number more than 0.

3. resin composition for encapsulating semiconductor according to claim 1, it is characterised in that (F) composition is selected from two The material of the molybdic acid metal salt is held on the inorganic carrier of silica, talcum and zinc oxide.

4. resin composition for encapsulating semiconductor according to claim 1, it is characterised in that the molybdic acid metal salt is molybdenum Sour zinc.

5. resin composition for encapsulating semiconductor according to claim 2, it is characterised in that (G) composition is following formulas (6) calcined material of compound and/or the compound shown in,

Mg_aAl_b(OH)_cCO₃·nH₂O (6)

In formula (6), a, b and c are the number for being more than 0 for meeting 2a+3b-c=2, and n is the number for meeting 0≤n≤4.

6. resin composition for encapsulating semiconductor according to claim 1, it is characterised in that (A) composition is following formulas (1) compound shown in,

In formula (1), R¹And R²The independently of one another alkyl of hydrogen atom or carbon number 1~4, R³It is independently of one another following any,

-CH₂-、-O-、-S-、-SO₂-

R⁴Independently of one another hydrogen atom or methyl, n are 0~10 integer.

7. resin composition for encapsulating semiconductor according to claim 1, it is characterised in that (C) inorganic filler Selected from fused silica, aluminum oxide, cristobalite and silicon nitride.

8. resin composition for encapsulating semiconductor according to claim 7, it is characterised in that (C) inorganic filler For spheroidal fused silica.

9. a kind of semiconductor device, it is characterised in that there is the encapsulating semiconductor as any one of claim 1 to 8 to use The hardening thing of resin combination.

10. semiconductor device according to claim 9, it is characterised in that carry partly leading comprising carborundum or gallium nitride Volume elements part.