CN102585438A - Epoxy resin composition for encapsulation and electronic component device - Google Patents

Abstract

The invention relates to an epoxy resin composition for encapsulation and electronic component device. The epoxy resin composition for encapsulation includes the components as following: (A) more than two epoxy resin with epoxy groups included in one molecule; (B) a hardening agent; and (C) diphenyl ketone derivatives with more than one phenolic group in one molecule. Perferably, the content of (C) is from 0.1 mass% to 1.0 mass%, and more perperably, (D) silane compound, (E) harding promoting agent and inorganic filler (F) are included.

Description

Encapsulating epoxy resin composition and electronic part apparatus

Technical field

The present invention relates to encapsulating epoxy resin composition and possess with the electronic part apparatus of sealing with the element of composition epoxy resin sealing.

Background technology

All the time, in electronic part encapsulation fields such as transistor, IC, encapsulating epoxy resin composition is widely used.Its reason is, epoxy resin can obtain electrical characteristic, wet fastness, thermotolerance, mechanical characteristics, with the balance of the cementability of inserts etc.Especially, the balance aspect that is combined in above-mentioned characteristic of o-cresol phenolic epoxy varnish and phenolic varnish type phenol solidifying agent is very excellent, has become the main flow of the base resin of composition for sealing.

Along with miniaturized, lightweight, the high performance of electronic machine in recent years, the densification of installation constantly advances, and electronic part apparatus has been developed into the encapsulation of surface installing type gradually by the encapsulation of existing pin type (Pin insertion type).When being installed to semiconductor device on the wiring board, if adopt existing pin type encapsulation, carry out soldering from the wiring board back side after then inserting a needle into wiring board, therefore encapsulation can directly not be exposed under the high temperature.But if adopt the surface installing type encapsulation, it is all then to handle semiconductor device through solder bath, reflux etc., and therefore encapsulation is exposed under the soldering temperature.Consequently, under the situation of encapsulation moisture absorption, there are hygroscopic moisture violent expansion the and bonding interface takes place peel off, encapsulate crackle, the problem that the package reliability when installing is descended when soldering.

As the countermeasure that addresses the above problem, taked to IC carry out damp proof bale packing or before being installed to wiring board in advance to methods such as IC carry out using after the thorough drying, to reduce the inner hygroscopic moisture of semiconductor device.But these methods are taken time and energy and cost is also high.

As other countermeasure, can enumerate the method for the content that increases the weighting agent in the encapsulating epoxy resin composition.But though this method has reduced the hygroscopic moisture of the hermetic unit of semiconductor device inside, existence causes the problem that the flowability of encapsulating epoxy resin composition declines to a great extent.If encapsulating epoxy resin composition is mobile low, can produce problems such as gold thread flowability, space, pin hole take place during moulding.

In addition, the resin composition for encapsulating semiconductor that a kind of size-grade distribution that makes the packing material that is matched with epoxy resin is in specified range is disclosed in the japanese kokai publication hei 06-224328 communique.And point out to adopt this resin composition for encapsulating semiconductor, and having increased the content of packing material and can not damage flowability, thermal expansion character, thermal conduction characteristic, anti-water absorbability and flexural strength improve.

And then; Japanese kokai publication hei 09-165433 communique discloses a kind of method of manufacture of epoxy resin; It is made in the method for epoxy resin making the reaction of polyatomic phenol and epihalohydrin, and the mixture that uses dihydroxy benaophenonel and other polyatomic phenol is as polyatomic phenol.In this invention, use dihydroxy benaophenonel, thus obtained epoxy resin and phenol novolac resin, SiO 2 powder etc. are mixed together and prepare composition epoxy resin at the synthesis phase of epoxy resin.And point out that this composition epoxy resin is in solidified nature, excellent aspect mobile, and be amorphism.

Summary of the invention

The problem that invention will solve

Improved solidified nature and flowability though can know the invention of above-mentioned japanese kokai publication hei 09-165433 communique, the cementability with metal under the high temperature reduces sometimes.From improving the viewpoint of anti-backflow property, hope to improve under the high temperature cementability with metal.

The present invention makes in view of this present situation just, and problem is to provide a kind of high temperature under with the encapsulating epoxy resin composition of the cementability height of metal and anti-backflow property excellence and possesses the electronic part apparatus with the element of its sealing.

The means of dealing with problems

The present invention relates to following scheme.

(1) a kind of encapsulating epoxy resin composition contains: (A) contain the benzophenone derivates that has 1 above phenolic hydroxyl group in the epoxy resin, (B) solidifying agent of 2 above epoxy group(ing) and (C) 1 molecule in 1 molecule.

(2) according to aforementioned (1) described encapsulating epoxy resin composition, wherein, the containing ratio that has the benzophenone derivates of 1 above phenolic hydroxyl group in said (C) 1 molecule is 0.1 quality %～1.0 quality %.

(3) according to aforementioned (1) or (2) described encapsulating epoxy resin composition, wherein, also contain (D) silane compound.

(4) according to any described encapsulating epoxy resin composition in aforementioned (1)～(3), wherein, also contain (E) curing catalyst.

(5) according to any described encapsulating epoxy resin composition in aforementioned (1)～(4), wherein, also contain (F) inorganic filler.

(6) a kind of electronic part apparatus possesses the element with any described encapsulating epoxy resin composition sealing in aforementioned (1)～(5).

The invention effect

According to the present invention, can provide under a kind of high temperature with the encapsulating epoxy resin composition that cementability is high and anti-backflow property is excellent of metal and possess electronic part apparatus with the element of its sealing.

Embodiment

Below the present invention is elaborated.

Explain, in this specification sheets, "～" expression be comprise the numerical value of record before and after it and respectively with it as minimum value and peaked scope.In addition, in this specification sheets, with regard to the amount of each composition in the compsn, when in compsn, having the multiple material that is equivalent to each composition, short of special declaration then is meant the total amount of this multiple material that exists in the compsn.

< encapsulating epoxy resin composition >

Encapsulating epoxy resin composition of the present invention contains: (A) contain the benzophenone derivates that has 1 above phenolic hydroxyl group in the epoxy resin, (B) solidifying agent of 2 above epoxy group(ing) and (C) 1 molecule in 1 molecule.Encapsulating epoxy resin composition of the present invention is down solid-state in room temperature (25 ℃).

Below each composition that constitutes encapsulating epoxy resin composition of the present invention is described.

((A) epoxy resin)

The epoxy resin that contains 2 above epoxy group(ing) in (A) 1 molecule that uses among the present invention is so long as normally used getting final product, not restriction especially in the encapsulating epoxy resin composition.For example can enumerate out with phenol novolak type epoxy resin, o-cresol phenolic epoxy varnish, epoxy resin with tritane skeleton is master's resin, its be phenols such as phenol, cresols, xylenol, Resorcinol, pyrocatechol, dihydroxyphenyl propane, Bisphenol F, naphthyl alcohol, β-Nai Fen, dihydroxy naphthlene and formaldehyde, acetaldehyde, propionic aldehyde, phenyl aldehyde, salicylic aldehyde etc. are had an aldehyde radical compound under an acidic catalyst condensation or cocondensation and novolac resin through epoxidised product; Diglycidylethers such as alkyl replacement, aromatic nucleus replacement or non-substituted dihydroxyphenyl propane, Bisphenol F, bisphenol S, '-biphenyl diphenol, sulfo-biphenol; Stilbene type epoxy resin; Hydroquinone type epoxy resin; The glycidyl ester type epoxy resin that reaction through polyprotonic acids such as phthalic acid, dimeracid and Epicholorohydrin obtains; The glycidyl amine type epoxy resin that reaction through polyamines such as diaminodiphenyl-methane, isocyanuric acid and Epicholorohydrin obtains; The epoxide of the cocondensation resin of Dicyclopentadiene (DCPD) and phenols; Epoxy resin with naphthalene nucleus; By phenols and dimethoxy p-Xylol or two (methoxymethyl) biphenyl synthetic phenol aralkyl resin; The epoxide of aralkyl-type phenol resin such as naphthols aralkyl resin; Trimethylolpropane type epoxy resin; The terpene modified epoxy; With peracid olefin oxide key such as peroxy acetic acid the wire aliphatic epoxy resin; Cycloaliphatic epoxy resin; Deng.Can use a kind of in these separately, also can combination more than 2 kinds be used.

Wherein, From taking into account the viewpoint of mobile and solidified nature; The diglycidylether that preferably contains alkyl replacement, aromatic nucleus replacement or non-substituted '-biphenyl diphenol is a biphenyl type epoxy resin; Viewpoint from solidified nature; Preferably contain phenolic resin varnish type epoxy resin,, preferably contain naphthalene type epoxy resin and/or tritane type epoxy resin from the viewpoint of thermotolerance and low warpage properties; From taking into account the viewpoint of mobile and flame retardant resistance; The diglycidylether that preferably contains alkyl replacement, aromatic nucleus replacement or non-substituted Bisphenol F is a bisphenol f type epoxy resin, and from taking into account the viewpoint of mobile and backflow property, the diglycidylether that preferably contains alkyl replacement, aromatic nucleus replacement or non-substituted sulfo-xenol is the sulfo-united phenol-type epoxy resin; From taking into account the viewpoint of solidified nature and flame retardant resistance; Preferably contain epoxide,, preferably contain epoxide by alkyl replacement, aromatic nucleus replacement or non-substituted aphthols and dimethoxy p-Xylol synthetic naphthols aralkyl resin from taking into account the viewpoint of storage stability and flame retardant resistance by alkyl replacement, aromatic nucleus replacement or non-substituted phenol and two (methoxymethyl) biphenyl synthetic phenol aralkyl resin.

As aforementioned biphenyl type epoxy resin, for example, can enumerate the epoxy resin shown in the formula (I) etc.

[Chemical formula 1]

In the general formula (I), R ¹～R ⁸Replacement or the non-substituted monovalence alkyl of representing Wasserstoffatoms or carbonatoms 1～10 independently of one another.R ¹～R ⁸Can be all identical also can be different.N representes 0～3 integer.

Biphenyl type epoxy resin shown in the above-mentioned general formula (I) can obtain Epicholorohydrin and the reaction of '-biphenyl diphenol compound through known method.

As the R in the general formula (I) ¹～R ⁸, for example can enumerate out independently of one another: Wasserstoffatoms; The alkyl of carbonatomss 1～10 such as methyl, ethyl, propyl group, butyl, sec.-propyl, isobutyl-, the tertiary butyl; The thiazolinyl of carbonatomss 1～10 such as vinyl, allyl group, crotonyl; Deng.Wherein, preferred independently of one another Wasserstoffatoms or methyl.

As such epoxy resin, for example can enumerate out with 44 '-two (2, the 3-glycidoxy) biphenyl or 4; 4 '-two (2, the 3-glycidoxy)-3,3 ', 5; 5 '-tetramethyl biphenyl is the epoxy resin of staple, makes Epicholorohydrin and 4,4 '-'-biphenyl diphenol or 4,4 '-(3; 3 ', 5,5 '-tetramethyl-) the '-biphenyl diphenol reaction and epoxy resin etc.

Wherein, preferably with 4,4 '-two (2, the 3-glycidoxy)-3,3 ', 5,5 '-tetramethyl biphenyl is the epoxy resin of staple.As such epoxy resin, can obtain the trade(brand)name YX-4000 of Mitsubishi chemical Co., Ltd (former Japan Epoxyresin Co., Ltd.) system with commercially available article form.

When stating biphenyl type epoxy resin in the use, in order to bring into play its performance, it is more than the 20 quality % that its containing ratio preferably is made as in the epoxy resin total amount, more preferably more than the 30 quality %, further is preferably more than the 50 quality %.

As aforementioned sulfo-united phenol-type epoxy resin, can enumerate for example epoxy resin shown in the formula (II) etc.

[Chemical formula 2]

In the general formula (II), R ¹～R ⁸Replacement or the non-substituted monovalence alkyl of representing Wasserstoffatoms or carbonatoms 1～10 independently of one another.R ¹～R ⁸Can be all identical also can be different.N representes 0～3 integer.

Sulfo-united phenol-type epoxy resin shown in the above-mentioned general formula (II) can obtain Epicholorohydrin and the reaction of sulfo-diphenol compound through known method.

As the R in the general formula (II) ¹～R ⁸, can enumerate out for example Wasserstoffatoms independently of one another; The alkyl of carbonatomss 1～10 such as methyl, ethyl, propyl group, butyl, sec.-propyl, isobutyl-, the tertiary butyl; The thiazolinyl of carbonatomss 1～10 such as vinyl, allyl group, crotonyl; Deng.Wherein, preferred independently of one another Wasserstoffatoms, methyl or the tertiary butyl.

As such epoxy resin, for example can enumerate out with 4, the diglycidylether of 4 '-dihydroxyl diphenyl sulfide is the epoxy resin of staple, with 2; 2 ', 5,5 '-tetramethyl--4; The diglycidylether of 4 '-dihydroxyl diphenyl sulfide is the epoxy resin of staple, with 2; 2 '-dimethyl--4,4 '-dihydroxyl-5, the diglycidylether of 5 '-two-tertiary butyl diphenyl sulfide are the epoxy resin of staple etc.

Wherein, preferably with 2,2 '-dimethyl--4,4 '-dihydroxyl-5, the diglycidylether of 5 '-two-tertiary butyl diphenyl sulfide are the epoxy resin of staple.As such epoxy resin, can obtain the trade(brand)name YSLV-120TE of Nippon Steel Chemical Co., Ltd's system with commercially available article form.

When stating the sulfo-united phenol-type epoxy resin in the use, in order to bring into play its performance, it is more than the 20 quality % that its containing ratio preferably is made as in the epoxy resin total amount, more preferably more than the 30 quality %, further is preferably more than the 50 quality %.

As aforementioned bisphenol f type epoxy resin, can enumerate for example epoxy resin shown in the formula (III) etc.

[chemical formula 3]

In the general formula (III), R ¹～R ⁸Replacement or the non-substituted monovalence alkyl of representing Wasserstoffatoms or carbonatoms 1～10 independently of one another.R ¹～R ⁸Can be all identical also can be different.N representes 0～3 integer.

Bisphenol f type epoxy resin shown in the above-mentioned general formula (III) can obtain Epicholorohydrin and the reaction of Bisphenol F compound through known method.

As the R in the general formula (III) ¹～R ⁸, can enumerate out for example Wasserstoffatoms independently of one another; The alkyl of carbonatomss 1～10 such as methyl, ethyl, propyl group, butyl, sec.-propyl, isobutyl-, the tertiary butyl; The thiazolinyl of carbonatomss 1～10 such as vinyl, allyl group, crotonyl; Deng.Wherein, preferred independently of one another Wasserstoffatoms or methyl.

As such epoxy resin; For example can enumerate out with 4, the diglycidylether of 4 '-methylene-bis (2, the 6-xylenol) is the epoxy resin of staple, with 4; 4 '-methylene-bis (2; 3,6-pseudocuminol) diglycidylether is the epoxy resin of staple, with 4, the diglycidylether of 4 '-methylene radical bis-phenol is the epoxy resin of staple etc.Wherein, preferably with 4, the diglycidylether of 4 '-methylene-bis (2, the 6-xylenol) is the epoxy resin of staple.As such epoxy resin, can obtain the trade(brand)name YSLV-80XY of Nippon Steel Chemical Co., Ltd's system with commercially available article form.

When stating bisphenol f type epoxy resin in the use, in order to bring into play its performance, it is more than the 20 quality % that its containing ratio preferably is made as in the epoxy resin total amount, more preferably more than the 30 quality %, further is preferably more than the 50 quality %.

As aforementioned phenolic resin varnish type epoxy resin, can enumerate out for example epoxy resin shown in the formula (IV) etc.

[chemical formula 4]

In the general formula (IV), R representes Wasserstoffatoms or the replacement or the non-substituted univalent perssad of the carbonatoms 1～10 that is made up of the element that is selected from carbon atom, Wasserstoffatoms, the Sauerstoffatom independently of one another, and n representes 0～10 integer.

Phenolic resin varnish type epoxy resin shown in the above-mentioned general formula (IV) can obtain through making Epicholorohydrin and phenolic varnish type reactive modified phenolic resin.

R as in the above-mentioned general formula (IV) is preferably Wasserstoffatoms independently of one another; The alkyl of carbonatomss 1～10 such as methyl, ethyl, propyl group, butyl, sec.-propyl, isobutyl-; The alkoxyl group of carbonatomss 1～10 such as methoxyl group, oxyethyl group, propoxy-, butoxy; More preferably Wasserstoffatoms or methyl.N is preferably 0～3 integer.

In the phenolic resin varnish type epoxy resin shown in the above-mentioned general formula (IV), preferred o-cresol phenolic epoxy varnish.As such epoxy resin, can obtain the trade(brand)name N500P-1 of Dainippon Ink. & Chemicals Inc's system with commercially available article form.

When using phenolic resin varnish type epoxy resin, in order to bring into play its performance, it is more than the 20 quality % that its containing ratio preferably is made as in the epoxy resin total amount, more preferably more than the 30 quality %.

As aforementioned naphthalene type epoxy resin, can enumerate for example epoxy resin shown in the formula (V) etc.As aforementioned tritane type epoxy resin, can enumerate for example epoxy resin shown in the formula (VI) etc.

[chemical formula 5]

In the logical formula V, R ¹～R ³Replacement or the non-substituted monovalence alkyl of representing carbonatoms 1～12 independently of one another.R ¹～R ³Can be all identical also can be different.P is 1 or 0, and m and n are 0～11 integer independently of one another, (m+n) is 1～11 integer, and is that the mode of 1～12 integer is selected p, m and n according to (m+p).I representes 0～3 integer, and j representes 0～2 integer, and k representes 0～4 integer.

As the R in the above-mentioned logical formula V ¹～R ³, can enumerate out independently of one another: the alkyl of carbonatomss 1～10 such as methyl, ethyl, propyl group, butyl, sec.-propyl, isobutyl-, the tertiary butyl; The thiazolinyl of carbonatomss 1～10 such as vinyl, allyl group, crotonyl, etc.Wherein, more preferably methyl.

[chemical formula 6]

In the general formula (VI), R representes the replacement or the non-substituted monovalence alkyl of Wasserstoffatoms or carbonatoms 1～10 independently of one another.N representes 1～10 integer.

R as in the above-mentioned general formula (VI) can enumerate out: Wasserstoffatoms independently of one another; The alkyl of carbonatomss 1～10 such as methyl, ethyl, propyl group, butyl, sec.-propyl, isobutyl-, the tertiary butyl; The thiazolinyl of carbonatomss 1～10 such as vinyl, allyl group, crotonyl; Deng.Wherein, more preferably Wasserstoffatoms or methyl.N is preferably 0～3 integer.

As the naphthalene type epoxy resin shown in the aforementioned formula (V), can enumerate out randomly contain m constitute the unit with n constitute unitary random copolymers, alternately contain m constitute unit and n constitute unitary alternating copolymer, regularly contain m formation unit and n unitary multipolymer of formation, contain m formation unit and n the unitary segmented copolymer of formation to block-wise.Can use in these any one separately, also can two or more combinations be used.

In addition, the not special restriction of the tritane type epoxy resin shown in the aforementioned formula (VI) is preferably salicylic aldehyde type epoxy resin.

These naphthalene type epoxy resin and tritane type epoxy resin can use any one separately, also can both be made up use.During in using naphthalene type epoxy resin and tritane type epoxy resin at least one; In order to bring into play its performance; Its containing ratio preferably is made as and in the epoxy resin total amount, adds up to more than the 20 quality %, more preferably is made as more than the 30 quality %, further preferably is made as more than the 50 quality %.

As the epoxide of aforementioned phenol aralkyl resin, can enumerate out for example epoxy resin shown in the epoxy resin shown in the formula (VII), the formula (VIII) etc.

[chemical formula 7]

In the general formula (VII), R ¹～R ⁴Replacement or the non-substituted monovalence alkyl of representing Wasserstoffatoms or carbonatoms 1～12 independently of one another.R ¹～R ⁴Can be all identical also can be different.R ⁵Replacement or the non-substituted monovalence alkyl of representing carbonatoms 1～12 independently of one another.When there being a plurality of R ⁵The time, its can be all identical also can be different.I representes 0～3 integer, and n representes 0～10 integer.

[chemical formula 8]

In the general formula (VIII), R ¹～R ⁸Replacement or the non-substituted monovalence alkyl of representing Wasserstoffatoms or carbonatoms 1～12 independently of one another.R ¹～R ⁸Can be all identical also can be different.R ⁹Replacement or the non-substituted monovalence alkyl of representing carbonatoms 1～12 independently of one another.When there being a plurality of R ⁹The time, its can be all identical also can be different.I representes 0～3 integer, and n representes 0～10 integer.

The epoxide of the phenol aralkyl resin shown in the above-mentioned general formula (VII) can make Epicholorohydrin and obtained by alkyl replacement, aromatic nucleus replacement or non-substituted phenol and dimethoxy p-Xylol synthetic phenol aralkyl resin reaction through known method.In addition, the epoxide of the phenol aralkyl resin that contains the biphenylene skeleton shown in the above-mentioned general formula (VIII) can make Epicholorohydrin and obtained by alkyl replacement, aromatic nucleus replacement or non-substituted phenol and two (methoxymethyl) biphenyl synthetic phenol aralkyl resin reaction through known method.

As the R in the general formula (VII) ¹～R ⁵And the R in the general formula (VIII) ¹～R ⁹The replacement of represented carbonatoms 1～12 or non-substituted monovalence alkyl can be enumerated out for example chain-like alkyls such as methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec.-butyl, the tertiary butyl, amyl group, hexyl, octyl group, decyl, dodecyl; Cyclic alkyls such as cyclopentyl, cyclohexyl, suberyl, cyclopentenyl, cyclohexenyl; Aryl such as benzyl, styroyl substituted alkyl; Alkoxyl group substituted alkyls such as methoxyl group substituted alkyl, oxyethyl group substituted alkyl, butoxy substituted alkyl; Amino substituted alkyls such as aminoalkyl group, dimethylamino alkyl, diethylin alkyl; The hydroxyl substituted alkyl; No substituted aryls such as phenyl, naphthyl, xenyl; Alkyl substituting aromatic bases such as tolyl, xylyl, ethylbenzene base, butylbenzene base, trimethylphenylmethane base, dimethyl-naphthyl; Alkoxyl group substituted aryls such as methoxyphenyl, phenelyl, butoxyphenyl, uncle's butoxyphenyl, methoxyl group naphthyl; Amino substituted aryl such as dimethylamino, diethylin; The hydroxyl substituted aryl; Deng.

Wherein, as the R in the general formula (VII) ¹～R ⁴And the R in the general formula (VIII) ¹～R ⁸, preferred independently of one another Wasserstoffatoms or methyl.As the R in the general formula (VII) ⁵And the R in the general formula (VIII) ⁹, be preferably methyl.

I in general formula (VII) and the general formula (VIII) representes 0～3 integer independently of one another, is preferably 0 or 1.

In addition, the n in general formula (VII) and the general formula (VIII) representes 0～10 integer independently of one another, and more preferably average out to is below 6.As such epoxy resin, general formula (VII) can obtain the trade(brand)name NC-2000L of Nippon Kayaku K. K's system with commercially available article form, and general formula (VIII) can obtain the trade(brand)name NC-3000S of Nippon Kayaku K. K's system with commercially available article form.

When using phenol aralkyl resin, in order to bring into play its performance, it is more than the 20 quality % that its containing ratio preferably is made as in the epoxy resin total amount, more preferably more than the 30 quality %.

In addition,, preferably contain the epoxy resin shown in the above-mentioned general formula (I) from taking into account the viewpoint of flame retardant resistance and anti-backflow property, flowability, wherein, the R of more preferably above-mentioned general formula (VIII) ¹～R ⁸R for Wasserstoffatoms, above-mentioned general formula (I) ¹～R ⁸Be Wasserstoffatoms, n=0.In addition, especially it contains mass ratio and is preferably general formula (I)/general formula (VIII)=50/50～5/95, and more preferably 40/60～10/90, further be preferably 30/70～15/85.As satisfying such compound that contains mass ratio, can obtain CER-3000L (trade(brand)name of Nippon Kayaku K. K's system) etc. with commercially available article form.

As the epoxide of naphthols aralkyl resin, can enumerate for example epoxy resin shown in the formula (IX) etc.

[chemical formula 9]

In the general formula (IX), R representes the replacement or the non-substituted monovalence alkyl of carbonatoms 1～12 independently of one another.A plurality of R can be all identical also can be different.I representes 0～3 integer, and X representes to have the divalent organic group of aromatic nucleus independently of one another, and n representes 0～10 integer.

The epoxide of the naphthols aralkyl resin shown in the above-mentioned general formula (IX) can make Epicholorohydrin and replaced by alkyl through known method, aromatic nucleus replaces or non-substituted naphthols and dimethoxy p-Xylol or two (methoxymethyl) biphenyl synthetic naphthols aralkyl resin reaction obtain.

X can enumerate out for example arylidene such as phenylene, biphenylene, naphthylidene independently of one another; Alkyl such as methylene phenyl replace arylidene; Alkoxyl group replaces arylidene; Aralkyl replaces arylidene; The divalent group that obtains by aralkyl such as benzyl, styroyls; Xylylenes etc. contain the divalent group of arylidene; Deng.Wherein, from taking into account the viewpoint of flame retardant resistance and storage stability, be preferably phenylene or biphenylene independently of one another.

As the R in the general formula (IX), can enumerate out for example chain-like alkyls such as methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec.-butyl, the tertiary butyl, amyl group, hexyl, octyl group, decyl, dodecyl independently of one another; Cyclic alkyls such as cyclopentyl, cyclohexyl, suberyl, cyclopentenyl, cyclohexenyl; Aryl such as benzyl, styroyl substituted alkyl; Alkoxyl group substituted alkyls such as methoxyl group substituted alkyl, oxyethyl group substituted alkyl, butoxy substituted alkyl; Amino substituted alkyls such as aminoalkyl group, dimethylamino alkyl, diethylin alkyl; The hydroxyl substituted alkyl; No substituted aryls such as phenyl, naphthyl, xenyl; Alkyl substituting aromatic bases such as tolyl, xylyl, ethylbenzene base, butylbenzene base, trimethylphenylmethane base, dimethyl-naphthyl; Alkoxyl group substituted aryls such as methoxyphenyl, phenelyl, butoxyphenyl, uncle's butoxyphenyl, methoxyl group naphthyl; Amino substituted aryl such as dimethylamino, diethylin; The hydroxyl substituted aryl; Deng.Wherein, the R in the general formula (IX) is preferably methyl independently of one another, and i is preferably 1 or 2.As such general formula (IX), can enumerate out formula (X) for example or (XI) shown in the epoxide of naphthols alkyl resin.

N representes 0～10 integer, and more preferably average out to is below 6.As the epoxy resin shown in the formula (X), can enumerate trade(brand)name ESN-375 as Nippon Steel Chemical Co., Ltd's system of commercially available article.As the epoxy resin shown in the formula (XI), can enumerate trade(brand)name ESN-175 as Nippon Steel Chemical Co., Ltd's system of commercially available article.

When stating the epoxide of naphthols aralkyl resin in the use, in order to bring into play its performance, it is more than the 20 quality % that its containing ratio preferably is made as in the epoxy resin total amount, more preferably is made as more than the 30 quality %, further preferably is made as more than the 50 quality %.

[Chemical formula 1 0]

In the general formula (X), X representes to have the divalent organic group of aromatic nucleus independently of one another, and n representes 0～10 integer.

[Chemical formula 1 1]

In the general formula (XI), X representes to have the divalent organic group of aromatic nucleus independently of one another, and n representes 0～10 integer.

The epoxide of above-mentioned biphenyl type epoxy resin, sulfo-united phenol-type epoxy resin, bisphenol f type epoxy resin, phenolic resin varnish type epoxy resin, naphthalene type epoxy resin, tritane type epoxy resin, phenol aralkyl resin and the epoxide of naphthols aralkyl resin; Can use any one separately, also can make up two or more and use.When the two or more combinations in these were used, containing ratio preferably was made as and in the epoxy resin total amount, adds up to more than the 50 quality %, more preferably more than the 60 quality %, further is preferably more than the 80 quality %.Wherein, preferably biphenyl type epoxy resin being made as in the epoxy resin total amount is more than the 50 quality %, more preferably more than the 60 quality %, further is preferably more than the 80 quality %.And, preferably use the above-mentioned epoxy resin beyond the biphenyl type epoxy resin simultaneously.

((B) solidifying agent)

(B) solidifying agent that uses among the present invention is so long as normally used getting final product, not restriction especially in the encapsulating epoxy resin composition.Can enumerate out compound that phenols such as for example phenol, cresols, Resorcinol, pyrocatechol, dihydroxyphenyl propane, Bisphenol F, phenylphenol, sulfo-xenol, amino-phenol, naphthyl alcohol, β-Nai Fen, dihydroxy naphthlene and formaldehyde, phenyl aldehyde, salicylic aldehyde etc. have an aldehyde radical under an acidic catalyst condensation or cocondensation and phenolic varnish type resol; By phenols and dimethoxy p-Xylol or aralkyl-type phenol resin such as two (methoxymethyl) biphenyl synthetic phenol aralkyl resin, naphthols aralkyl resin; Phenol phenolic structure and phenol aralkyl structure are random, block or alternately repeated copoly type phenol aralkyl resin; P-Xylol and/or m-xylene modified phenolic resins; Cyanurotriamide modified resol; The terpene modified phenolic resins; The Dicyclopentadiene (DCPD) modified phenolic resins; The cyclopentadiene modified phenolic resins; Many ring aromatic nucleus modified phenolic resinss; Deng.These can use separately and a kind ofly also can two or more combinations be used.

Wherein, Viewpoint from flowability, flame retardant resistance and anti-backflow property; Preferred phenol aralkyl resin, copoly type phenol aralkyl resin and naphthols aralkyl resin, from the viewpoint of thermotolerance, low thermal expansion and low warpage properties, preferred tritane type resol; From the viewpoint of solidified nature, preferred phenolic varnish type resol.Preferably contain at least a kind in these resol.

As aforementioned phenol aralkyl resin, can enumerate the for example resin shown in the formula (XII).

[Chemical formula 1 2]

In the general formula (XII), R representes the replacement or the non-substituted monovalence alkyl of carbonatoms 1～12 independently of one another.A plurality of R can be all identical also can be different.I representes 0～3 integer independently of one another, and X representes to have the divalent organic group of aromatic nucleus independently of one another, and n representes 0～10 integer.

As the R in the above-mentioned general formula (XII), can enumerate out for example chain-like alkyls such as methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec.-butyl, the tertiary butyl, amyl group, hexyl, octyl group, decyl, dodecyl independently of one another; Cyclic alkyls such as cyclopentyl, cyclohexyl, suberyl, cyclopentenyl, cyclohexenyl; Aryl such as benzyl, styroyl substituted alkyl; Alkoxyl group substituted alkyls such as methoxyl group substituted alkyl, oxyethyl group substituted alkyl, butoxy substituted alkyl; Amino substituted alkyls such as aminoalkyl group, dimethylamino alkyl, diethylin alkyl; The hydroxyl substituted alkyl; No substituted aryls such as phenyl, naphthyl, xenyl; Alkyl substituting aromatic bases such as tolyl, xylyl, ethylbenzene base, butylbenzene base, trimethylphenylmethane base, dimethyl-naphthyl; Alkoxyl group substituted aryls such as methoxyphenyl, phenelyl, butoxyphenyl, uncle's butoxyphenyl, methoxyl group naphthyl; Amino substituted aryl such as dimethylamino, diethylin; The hydroxyl substituted aryl; Deng.

Wherein, the R in the general formula (XII) is preferably methyl independently of one another.In addition, the i in the general formula (XII) representes 0～3 integer independently of one another, is preferably 1 or 2.

X in the above-mentioned general formula (XII) representes to have the group of aromatic nucleus independently of one another.Can enumerate out for example arylidene such as phenylene, biphenylene, naphthylidene independently of one another; Alkyl such as methylene phenyl replace arylidene; Alkoxyl group replaces arylidene; The divalent group that obtains by aralkyl such as benzyl, styroyls; Aralkyl replaces arylidene; Xylylenes etc. contain the divalent group of arylidene; Deng.

Wherein, from taking into account the viewpoint of flame retardant resistance, flowability and solidified nature, X preferably independently of one another for replacing or non-substituted phenylene, for example can enumerate the phenol aralkyl resin shown in the formula (XIII) as above-mentioned general formula (XII).In addition, from taking into account the viewpoint of flame retardant resistance and anti-backflow property, X is preferably independently of one another and replaces or non-substituted biphenylene, for example can enumerate the phenol aralkyl resin shown in the formula (XIV) as above-mentioned general formula (XII).

N representes 0～10 integer, and more preferably average out to is below 6.

[Chemical formula 1 3]

In the general formula (XIII), n representes 0～10 integer.

[Chemical formula 1 4]

In the general formula (XIV), n representes 0～10 integer.

As the phenol aralkyl resin shown in the above-mentioned general formula (XIII), can enumerate out trade(brand)name XLC as Mitsui Chemicals, Inc's system of commercially available article.As the phenol aralkyl resin that contains the biphenylene skeleton shown in the general formula (XIV), can enumerate as the bright of commercially available article and the trade(brand)name MEH-7851 that changes into Co., Ltd.'s system.

When stating phenol aralkyl resin in the use, in order to bring into play its performance, it is more than the 20 quality % that its containing ratio preferably is made as in the solidifying agent total amount, more preferably more than the 30 quality %, further is preferably more than the 50 quality %.

As aforementioned naphthols aralkyl resin, can enumerate out the for example resin shown in the formula (XV).

[Chemical formula 1 5]

In the general formula (XV), R representes the replacement or the non-substituted monovalence alkyl of carbonatoms 1～12 independently of one another.A plurality of R can be all identical also can be different.I representes 0～3 integer independently of one another, and X representes to have the divalent organic group of aromatic nucleus independently of one another, and n representes 0～10 integer.

As the R in the above-mentioned general formula (XV), can enumerate out for example chain-like alkyls such as methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec.-butyl, the tertiary butyl, amyl group, hexyl, octyl group, decyl, dodecyl independently of one another; Cyclic alkyls such as cyclopentyl, cyclohexyl, suberyl, cyclopentenyl, cyclohexenyl; Aryl such as benzyl, styroyl substituted alkyl; Alkoxyl group substituted alkyls such as methoxyl group substituted alkyl, oxyethyl group substituted alkyl, butoxy substituted alkyl; Amino substituted alkyls such as aminoalkyl group, dimethylamino alkyl, diethylin alkyl; The hydroxyl substituted alkyl; No substituted aryls such as phenyl, naphthyl, xenyl; Alkyl substituting aromatic bases such as tolyl, xylyl, ethylbenzene base, butylbenzene base, trimethylphenylmethane base, dimethyl-naphthyl; Alkoxyl group substituted aryls such as methoxyphenyl, phenelyl, butoxyphenyl, uncle's butoxyphenyl, methoxyl group naphthyl; Amino substituted aryl such as dimethylamino, diethylin; The hydroxyl substituted aryl; Deng.

Wherein, the R in the general formula (XV) is preferably methyl.In addition, the i in the general formula (XV) representes 0～3 integer independently of one another, is preferably 1 or 2.

X in the above-mentioned general formula (XV) representes to have the divalent organic group of aromatic nucleus independently of one another.Can enumerate out for example arylidene such as phenylene, biphenylene, naphthylidene independently of one another; Alkyl such as methylene phenyl replace arylidene; Alkoxyl group replaces arylidene; Aralkyl replaces arylidene; The divalent group that obtains by aralkyl such as benzyl, styroyls; Xylylenes etc. contain the divalent group of arylidene; Deng.Wherein, from the viewpoint of storage stability and flame retardant resistance, X is preferably independently of one another and replaces or non-substituted phenylene and biphenylene; Phenylene more preferably; For example, as above-mentioned general formula (XV), can enumerate formula (XVI) and (XVII) shown in naphthols aralkyl resin.

N representes 0～10 integer, and more preferably average out to is below 6.

[Chemical formula 1 6]

In the general formula (XVI), n representes 0～10 integer.

[Chemical formula 1 7]

In the general formula (XVII), n representes 0～10 integer.

As the naphthols aralkyl resin shown in the above-mentioned general formula (XVI), can enumerate out trade(brand)name SN-475 as Nippon Steel Chemical Co., Ltd's system of commercially available article.As the naphthols aralkyl resin shown in the above-mentioned general formula (XVII), can enumerate out trade(brand)name SN-170 as Nippon Steel Chemical Co., Ltd's system of commercially available article.

When stating naphthols aralkyl resin in the use, in order to bring into play its performance, it is more than the 20 quality % that its containing ratio preferably is made as in the solidifying agent total amount, more preferably more than the 30 quality %, further is preferably more than the 50 quality %.

From the viewpoint of flame retardant resistance, the phenol aralkyl resin shown in preferably a part of or whole above-mentioned general formulas (XII), naphthols aralkyl resin and the acenaphthylene premix shown in the general formula (XV).Acenaphthylene can also can use commercially available article through the acenaphthene dehydrogenation is obtained.In addition, also can use the polymkeric substance of acenaphthylene or the polymkeric substance of acenaphthylene and other aromatic olefin to replace acenaphthylene.

As the method for the polymkeric substance of the polymkeric substance that obtains acenaphthylene or acenaphthylene and other aromatic olefin, can enumerate out radical polymerization, cationoid polymerisation, anionoid polymerization etc.In addition, can use existing known catalyzer during polymerization, but also can not use catalyzer and only under heating, carry out.At this moment, polymerization temperature is preferably 80 ℃～160 ℃, more preferably 90 ℃～150 ℃.The softening temperature of the polymkeric substance of the polymkeric substance of the acenaphthylene that obtains or acenaphthylene and other aromatic olefin is preferably 60 ℃～150 ℃, more preferably 70 ℃～130 ℃.Be more than 60 ℃ the time, oozing out in the time of can suppressing moulding has the excellent tendency of formability, is being below 150 ℃ the time, has the tendency that the consistency with resin improves.

As with other aromatic olefin of acenaphthylene copolymerization, can enumerate out vinylbenzene, alpha-methyl styrene, indenes, thionaphthene, cumarone, vinyl naphthalene, vinyl biphenyl or their alkyl substituent etc.In addition, except above-mentioned aromatic olefin, in the scope that does not influence effect of the present invention, can also use aliphatics alkene simultaneously.As aliphatics alkene, can enumerate out (methyl) vinylformic acid and its ester, maleic anhydride, itaconic anhydride, fumaric acid and their ester etc.It is below the 20 quality % that the usage quantity of these aliphatics alkene is preferably in the polymerization single polymerization monomer total amount, more preferably below the 9 quality %.

As a part or the whole solidifying agent and the method for pre mixing of acenaphthylene, can through with solidifying agent and the fine respectively pulverizing of acenaphthylene and keeping solid-like and through method of mixing such as stirrer, in the solvent of dissolving two compositions after the homogeneous dissolving except that the method for desolvating, under the temperature more than the softening temperature of solidifying agent and/or acenaphthylene, the method for both melting mixing etc. is carried out.In these methods, preferably can obtain homogeneous mixture and impurity sneak into few melting mixing method.Can make pre-composition (acenaphthylene modified firming agent) through preceding method.

With regard to the temperature condition during with regard to melting mixing, so long as the above temperature of the softening temperature of solidifying agent and/or acenaphthylene gets final product not restriction.Particularly, be preferably 100 ℃～250 ℃, more preferably 120 ℃～200 ℃.In addition, melting mixing is so long as get final product both homogeneous mixing not restriction on the mixing time, preferred 1 hour～20 hours, more preferably 2 hours～15 hours.With solidifying agent and acenaphthylene premix the time, acenaphthylene generation polymerization or react with solidifying agent that also it doesn't matter in the mixing.

As tritane type resol, can enumerate for example resol shown in the formula (XVIII) etc.

[Chemical formula 1 8]

In the general formula (XVIII), R representes the replacement or the non-substituted monovalence alkyl of Wasserstoffatoms or carbonatoms 1～10 independently of one another, and n representes 0～10 integer.

R as in the above-mentioned general formula (XVIII) can enumerate out for example Wasserstoffatoms independently of one another; Alkyl such as methyl, ethyl, propyl group, butyl, sec.-propyl, the tertiary butyl; Thiazolinyls such as vinyl, allyl group, crotonyl; Halogenated alkyl; Amino substituted alkyl; The sulfydryl substituted alkyl; Deng.Wherein, R is preferably alkyl or Wasserstoffatomss such as methyl, ethyl, more preferably methyl or Wasserstoffatoms independently of one another.

When using tritane type resol, in order to bring into play its performance, it is more than the 30 quality % that its containing ratio preferably is made as in the solidifying agent total amount, more preferably more than the 50 quality %.

As phenolic varnish type resol, can enumerate for example phenolic varnish type resol, cresols novolac resin etc. such as resol shown in the formula (XIX).Wherein, the phenolic varnish type resol shown in the preferred formula (XIX).

[Chemical formula 1 9]

In the general formula (XIX), R representes the replacement or the non-substituted monovalence alkyl of Wasserstoffatoms or carbonatoms 1～10 independently of one another, and n representes 0～10 integer.

R as in the above-mentioned general formula (XIX) can enumerate out for example Wasserstoffatoms independently of one another; Alkyl such as methyl, ethyl, propyl group, butyl, sec.-propyl, the tertiary butyl; Thiazolinyls such as vinyl, allyl group, crotonyl; Halogenated alkyl; Amino substituted alkyl; The sulfydryl substituted alkyl; Deng.Wherein, R is preferably alkyl or Wasserstoffatomss such as methyl, ethyl, more preferably Wasserstoffatoms independently of one another.

N representes 0～10 integer, and preferred MV is 0～8.

As the phenolic varnish type resol shown in the aforementioned formula (XIX), can enumerate as the bright of commercially available article and the trade(brand)name H-100 that changes into Co., Ltd.'s system.

When using phenolic varnish type resol, in order to bring into play its performance, it is more than the 30 quality % that its containing ratio preferably is made as in the solidifying agent total amount, more preferably more than the 50 quality %.

As copoly type phenol aralkyl resin, can enumerate the for example resol shown in the formula (XX).

[Chemical formula 2 0]

In the general formula (XX), R representes replacement or the non-substituted monovalence alkyl or the hydroxyl of Wasserstoffatoms, carbonatoms 1～12 independently of one another.A plurality of R can be all identical also can be different.In addition, X representes to have the divalent group of aromatic nucleus independently of one another.N and m represent 0～10 integer independently of one another.

R as in the above-mentioned general formula (XX) can enumerate out for example Wasserstoffatoms independently of one another; Chain-like alkyls such as methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec.-butyl, the tertiary butyl, amyl group, hexyl, octyl group, decyl, dodecyl; Cyclic alkyls such as cyclopentyl, cyclohexyl, suberyl, cyclopentenyl, cyclohexenyl; Aryl such as benzyl, styroyl substituted alkyl; Alkoxyl group substituted alkyls such as methoxyl group substituted alkyl, oxyethyl group substituted alkyl, butoxy substituted alkyl; Amino substituted alkyls such as aminoalkyl group, dimethylamino alkyl, diethylin alkyl; The hydroxyl substituted alkyl; No substituted aryls such as phenyl, naphthyl, xenyl; Alkyl substituting aromatic bases such as tolyl, xylyl, ethylbenzene base, butylbenzene base, trimethylphenylmethane base, dimethyl-naphthyl; Alkoxyl group substituted aryls such as methoxyphenyl, phenelyl, butoxyphenyl, uncle's butoxyphenyl, methoxyl group naphthyl; Amino substituted aryl such as dimethylamino, diethylin; The hydroxyl substituted aryl; Deng.Wherein, R is preferably Wasserstoffatoms or methyl independently of one another.

In addition, n and m represent 0～10 integer independently of one another, and more preferably average out to is below 6.

As the X in the above-mentioned general formula (XX), can enumerate out for example arylidene such as phenylene, biphenylene, naphthylidene; Alkyl such as methylene phenyl replace arylidene; Alkoxyl group replaces arylidene; Aralkyl replaces arylidene; The divalent group that obtains by aralkyl such as benzyl, styroyls; Xylylenes etc. contain the divalent group of arylidene; Deng.Wherein, from the viewpoint of storage stability and flame retardant resistance, be preferably replacement or non-substituted phenylene or biphenylene.As the compound shown in the general formula (XX), can obtain HE-510 (trade(brand)name of Air Water Inc. system) etc. with commercially available article form.

As the copoly type phenol aralkyl resin shown in the aforementioned formula (XX), can enumerate out randomly contain m constitute the unit with n constitute unitary random copolymers, alternately contain m constitute unit and n constitute unitary alternating copolymer, regularly contain m formation unit and n unitary multipolymer of formation, contain m formation unit and n the unitary segmented copolymer of formation to block-wise.Can use in these any one separately, also can two or more combinations be used.

When using copoly type phenol aralkyl resin, in order to bring into play its performance, it is more than the 30 quality % that its containing ratio preferably is made as in the solidifying agent total amount, more preferably more than the 50 quality %.

Above-mentioned phenol aralkyl resin, naphthols aralkyl resin, tritane type resol, phenolic varnish type resol and copoly type phenol aralkyl resin can use any one separately, also can make up two or more and use.Make up two or more and containing ratio when using preferably is made as and in the resol total amount, adds up to more than the 50 quality %, more preferably more than the 60 quality %, further be preferably more than the 80 quality %.

((C) benzophenone derivates)

Encapsulating epoxy resin composition of the present invention contains the benzophenone derivates that has 1 above phenolic hydroxyl group in (C) 1 molecule.Thus, can obtain under the high temperature the encapsulating epoxy resin composition that cementability is high and anti-backflow property is excellent with metal.

The benzophenone derivates that has 1 above phenolic hydroxyl group in (C) 1 molecule that uses among the present invention; So long as replace or the material of 1 above hydroxyl of Direct Bonding on aromatic nucleus such as non-substituted UVNUL MS-40, naphthalene phenyl ketone, dinaphthyl ketone, xanthone, Fluorenone get final product, do not limit especially.(C) benzophenone derivates that has 1 above phenolic hydroxyl group in 1 molecule can use a kind separately, also can make up two or more and uses.

Particularly, can enumerate out O-hydroxyl-diphenyl ketone, a dihydroxy benaophenonel, to dihydroxy benaophenonel, 2-hydroxyl-4-methoxy benzophenone, 2-hydroxyl-4-n-octyl oxygen UVNUL MS-40,2-hydroxyl-4-allyloxy UVNUL MS-40,2,4 dihydroxyl benzophenone, 4,4 '-dihydroxy benaophenonel, 2; 2 '-dihydroxyl-4-methoxy benzophenone, 2,2 '-dihydroxyl-4,4 '-dimethoxy-benzophenone, 2,3; 4-trihydroxybenzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenone, 2; 3,4,4 '-tetrahydroxybenzophenone, 2,3; 3 ', 4,4 ', 5-hexahydroxy-UVNUL MS-40 and their positional isomers, substituent etc.From reducing the viewpoint of thermal stresses (reducing reflux temperature Young's modulus down), preferably O-hydroxyl-diphenyl ketone, a dihydroxy benaophenonel, to dihydroxy benaophenonel, 2-hydroxyl-4-methoxy benzophenone, 2-hydroxyl-4-octyl group oxygen UVNUL MS-40, from the viewpoint of further raising cementability; Preferred 2; 4-dihydroxy benaophenonel, 4,4 '-dihydroxy benaophenonel, 2,2 '-dihydroxyl-4-methoxy benzophenone, 2; 2 '-dihydroxyl-4,4 '-dimethoxy-benzophenone.

It is more than the 0.1 quality %, below the 1.0 quality % that the total containing ratio that has the benzophenone derivates of 1 above phenolic hydroxyl group in (C) 1 molecule that uses among the present invention is preferably in encapsulating epoxy resin composition.When being 0.1 quality % when above, have the tendency that can bring into play the invention effect fully, when being 1.0 quality % when following, have the tendency that can fully keep the hardness of encapsulating epoxy resin composition.

In the present invention, the total hydroxyl value that (A) have the equivalence ratio of the benzophenone derivates of 1 above phenolic hydroxyl group in epoxy resin and (B) solidifying agent and (C) 1 molecule, promptly has in the benzophenone derivates of 1 above phenolic hydroxyl group in (B) solidifying agent and (C) 1 molecule does not limit with respect to the ratio of the epoxy radix of (A) epoxy resin (having the epoxy radix in the epoxy resin of total hydroxyl value in the benzophenone derivates of 1 above phenolic hydroxyl group/(A) in (B) solidifying agent and (C) 1 molecule) especially.For unreacted component that will be separately is suppressed at less degree, aforementioned equivalence ratio preferably sets the scope 0.5～2.0, and more preferably 0.6～1.3.In order to obtain the excellent encapsulating epoxy resin composition of formability, further preferably set scope 0.8～1.2.

((D) silane compound)

Formed material of the present invention can also contain (D) silane compound.(D) silane compound is meant various silane-based compounds such as epoxy silane, hydrosulphonyl silane, aminosilane, alkyl silane, urea groups silane, vinyl silanes.If these are carried out illustration; Can enumerate out: vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxyl silane, γ-methacryloxypropyl methyl dimethoxysilane, γ-methacryloxypropyl methyldiethoxysilane, γ-methacryloxypropyl dimethyl methyl TMOS, γ-methacryloxypropyl dimethylethoxysilane, γ-acryloxy propyl trimethoxy silicane, γ-acryloxy propyl-triethoxysilicane, β-(3; The 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, γ-glycidoxy propyl group methyl dimethoxysilane, γ-glycidoxy propyl group methyldiethoxysilane, γ-glycidoxy propyl-dimethyl methoxy silane, γ-glycidoxy propyl-dimethyl Ethoxysilane, vinyltriacetoxy silane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-sulfydryl propyl-triethoxysilicane, two (triethoxysilylpropyl) tetrasulfide, gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, γ-[two (beta-hydroxy ethyl)] aminopropyltriethoxywerene werene, N-β-(amino-ethyl)-γ-An Jibingjisanyiyangjiguiwan, N-(trimethoxy-silylpropyl) quadrol, isocyanic ester propyl trimethoxy silicane, isocyanic ester propyl-triethoxysilicane, methyltrimethoxy silane, Union carbide A-162, dimethyldimethoxysil,ne, dimethyldiethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, diphenyl silanodiol, triphenyl methoxy silane, triphenyl Ethoxysilane, triphenyl silanol, N-β-(N-vinyl benzyl amino-ethyl)-gamma-amino propyl trimethoxy silicane, γ-r-chloropropyl trimethoxyl silane, hexamethyldisilane, γ-anilino propyl trimethoxy silicane, γ-anilino propyl-triethoxysilicane, 2-triethoxysilyl-N-(1; 3-dimethyl--butylidene) propyl group amine, 3-triethoxysilyl-N-(1; 3-dimethyl--butylidene) propyl group amine, N-(3-triethoxysilylpropyltetrasulfide) phenyl imine, 3-(3-(triethoxysilyl) third amino)-N; N-dimethyl propylene acid amides, N-triethoxysilylpropyltetrasulfide-Beta-alanine methyl esters, 3-(triethoxysilylpropyltetrasulfide) dihydro-3, silane-based compounds such as 5-furandione, two (trimethoxysilyl) benzene; 1H-imidazoles, 2-alkyl imidazole, 2, the reactant of imidazolium compounds such as 4-dialkylimidazolium, 4-vinyl imidazole and γ-glycidoxypropyltrime,hoxysilane, γ-γ-glycidoxy propyl group organoalkoxysilanes such as glycidoxy propyl-triethoxysilicane is that imidazoles is a silane compound.Can use a kind of in these separately, also can combination more than 2 kinds be used.

When containing (D) silane compound; From formability and mobile viewpoint; (D) to be preferably in encapsulating epoxy resin composition be 0.06 quality %～2 quality % to total containing ratio of silane compound; More preferably 0.1 quality %～0.75 quality % further is preferably 0.2 quality %～0.7 quality %.When being 0.06 quality % when above, have and suppress the mobile tendency that reduces, when being 2 quality % when following, have the bad tendencies of moulding such as suppressing to take place the space.

In the encapsulating epoxy resin composition of the present invention, can also cooperate the existing known coupling agent beyond (D) silane compound.For example can enumerate out: titanic acid ester such as sec.-propyl three isostearoyl base titanic acid ester, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, sec.-propyl three (N-amino-ethyl-amino-ethyl) titanic acid ester, two (two three decyl phosphorous acid acyloxy) titanic acid ester, four (2,2-diallyl oxygen methyl isophthalic acid-butyl) two (two three decyls) the phosphorous acid acyloxy titanic acid ester of four octyl groups, two (dioctylphyrophosphoric acid acyloxy) oxo acetic ester titanic acid ester, two (dioctylphyrophosphoric acid acyloxy) ethylene titanic acid ester, sec.-propyl three hot acyloxy titanic acid ester, sec.-propyl dimethyl propylene enoyl-isostearoyl base titanic acid ester, isopropyl stearyl-two acryl titanic acid ester, sec.-propyl three (dioctyl phosphoryl) titanic acid ester, sec.-propyl three cumyl phenyl titanium acid esters, two (the dioctyl phosphorous acid acyloxy) titanic acid ester of tetra isopropyl are coupling agent, aluminum chelate class, aluminium/zirconium compound etc.Can use a kind of in these separately, also can combination more than 2 kinds be used.

Viewpoint from formability and cementability; (D) to be preferably in encapsulating epoxy resin composition be 0.06 quality %～2 quality % to total containing ratio of the coupling agent beyond the silane compound; More preferably 0.1 quality %～0.75 quality % further is preferably 0.2 quality %～0.7 quality %.When being 0.06 quality % when above, have and suppress the mobile tendency that reduces, when being 2 quality % when following, have the bad tendencies of moulding such as suppressing to take place the space.

((E) curing catalyst)

Encapsulating epoxy resin composition of the present invention can also contain (E) curing catalyst.(E) curing catalyst that uses among the present invention is so long as normally used then not use especially restrictedly in the encapsulating epoxy resin composition.

For example can enumerate out 1,8-diazabicyclo [5.4.0] undecylene-7,1,5-diazabicyclo [4.3.0] nonene-5,5,6-dibutylamino-1; Cyclic amidine compounds such as 8-diazabicyclo [5.4.0] undecylene-7 grade, and to these compound addition maleic anhydrides, 1,4-benzoquinones, 2; 5-toluquinone, 1,4-naphthoquinones, 2,2; 6-phlorone, 2,3-dimethoxy-5-methyl isophthalic acid, 4-benzoquinones, 2; 3-dimethoxy-1,4-benzoquinones, phenyl-1, naphtoquinone compounds such as 4-benzoquinones, two benzene diazonium methane, resol etc. have the π key compound and have an intramolecularly polar compound; Imidazoles and their verivates such as tertiary amines such as benzyldimethylamine, trolamine, dimethylaminoethanol, three (dimethylamino methyl) phenol and their verivate, glyoxal ethyline, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-seven decyl imidazoles; Tertiary phosphine class such as tributylphosphine, methyldiphenyl base phosphine, triphenylphosphine, three (4-tolyl) phosphine, diphenylphosphine, Phenylphosphine and to these tertiary phosphine class addition maleic anhydrides, above-mentioned naphtoquinone compounds, two benzene diazonium methane, resol etc. have the π key compound and have an intramolecularly polar phosphorus compound; Tetraphenyl squama tetraphenyl boric acid ester, tetraphenyl squama ethyl triphenyl boric acid ester, tetrabutylphosphoniubromide tetrabutyl boric acid esters etc. four replace tetraphenyl boron salt and their verivates such as squama four substituted boracic acid esters, 2-ethyl-4-methylimidazole tetraphenyl boric acid ester, N-methylmorpholine tetraphenyl boric acid ester; Deng.Can use a kind of in these separately, also can combination more than 2 kinds be used.

The not special restriction of the tertiary phosphine class of using in the affixture to tertiary phosphine class and naphtoquinone compounds.Can enumerate out for example dibutyl Phenylphosphine, butyl diphenyl phosphine, ethyl diphenylphosphine, triphenylphosphine, three (4-tolyl) phosphine, three (4-ethylbenzene base) phosphine, three (4-propyl phenyl) phosphine, three (4-butylbenzene base) phosphine, three (cumyl) phosphine, three (trimethylphenylmethane base) phosphine, three (2; The 4-xylyl) phosphine, three (2; The 6-xylyl) phosphine, three (2; 4; The 6-trimethylphenyl) phosphine, three (2,6-dimethyl--4-phenelyl) phosphine, three (4-methoxyphenyl) phosphine, three (4-phenelyl) phosphine etc. has the tertiary phosphine class of aryl.From the viewpoint of formability, triphenylphosphine.

In addition, the not special restriction of the naphtoquinone compounds that uses in the affixture to tertiary phosphine class and naphtoquinone compounds.Can enumerate out for example adjacent benzoquinones, para benzoquinone, diphenoquinone, 1,4-naphthoquinones, anthraquinone etc.Viewpoint from wet fastness or storage stability is preferably para benzoquinone.

With regard to the content of (E) curing catalyst, get final product not special restriction so long as can realize the amount of solidifying facilitation effect.Particularly, measure 100 mass parts, be preferably 0.1 mass parts～10 mass parts, more preferably 0.3 mass parts～5 mass parts with respect to the total that has the benzophenone derivates of 1 above phenolic hydroxyl group in (A) epoxy resin, (B) solidifying agent, (C) 1 molecule.Being 0.1 mass parts when above, can solidify in the short period of time, when 10 mass parts are following, can the appropriate inhibition curing speed, have the tendency that obtains good moulding article.

((F) inorganic filler)

Can also contain (F) inorganic filler in the encapsulating epoxy resin composition of the present invention.(F) inorganic filler that uses among the present invention is engaged in the encapsulating epoxy resin composition for water absorbability, reduction linear expansivity, raising heat conductivity and intensity; So long as normally used getting final product in the encapsulating epoxy resin composition, not special restriction.Can enumerate out for example powder or the pearl that these spheroidizations are formed, spun glass etc. such as fused silica, crystalline silica, aluminum oxide, zircon, Calucium Silicate powder, lime carbonate, potassium titanate, silit, silicon nitride, aluminium nitride AlN, SP 1, beryllium oxide, zirconium white, zircon, forsterite, steatite, spinel, mullite, titanium oxide.These can use a kind of separately, also can two or more combinations be used.

Wherein, from the viewpoint of reduction linear expansivity, preferred molten silicon-dioxide, from the viewpoint of high thermal conductivity, preferred aluminum oxide, the viewpoint of flowability during from moulding and mould abrasion property, the weighting agent shape is preferably sphere.Especially, from the equilibrated viewpoint of cost and performance, preferred spherical fused silica.

The median size of inorganic filler (D50) is preferably 0.1 μ m～50 μ m, more preferably 10 μ m～30 μ m.Through aforementioned median size is made as more than the 0.1 μ m, the viscosity that can suppress encapsulating epoxy resin composition rises, and can reduce separating of resinous principle and inorganic filler through being set at below the 50 μ m.Therefore, in the scope that is set in above-mentioned median size, can prevent that cured article heterogeneity, cured article characteristic are unbalanced, the fillibility of narrow space is reduced.

Explain that volume average particle size (D50) is meant, in size distribution, when side is described the volume integral distribution curve from the small-particle footpath, is accumulate to the particle diameter of 50 volume %.Mensuration can utilize laser diffraction formula particle size distribution device (for example (strain) Shimadzu Seisakusho Ltd. system SALD-3000J) to carry out through sample is distributed in the purified water that contain tensio-active agent.

From the viewpoint of flowability, to compare with dihedral, the particle shape of inorganic filler is preferably sphere.In addition, from the viewpoint of flowability, the specific surface area of inorganic filler is preferably 0.1m ²/ g～10m ²/ g, more preferably 0.5m ²/ g～6.0m ²/ g.

From the viewpoint of flame retardant resistance, formability, water absorbability, reduction linear expansivity and raising intensity, it is 70 quality %～95 quality % that the containing ratio of inorganic filler is preferably in encapsulating epoxy resin composition.When being 70 quality % when above, have the tendency of excellent in flame retardance, when being 95 quality % when following, have mobile excellent tendency.

(other additive)

Encapsulating epoxy resin composition of the present invention can also contain following illustrative various additives such as anion ion exchange body, releasing agent, fire retardant, tinting material, stress negative catalyst as required on the basis of containing above-mentioned (A) epoxy resin, (B) solidifying agent, (C) benzophenone derivates, (D) silane compound, (E) curing catalyst and (F) inorganic filler.But encapsulating epoxy resin composition of the present invention can append various additive as known in the art as required, and is not limited to following additive.

(anion ion exchange body)

In the encapsulating epoxy resin composition of the present invention, can cooperate anion ion exchange body as required from the purpose of the wet fastness that improves IC, high-temperature standing properties.The not special restriction of anion ion exchange body can be used existing known ion exchanger.For example can enumerate out hydrotalcite and be selected from hydrous oxide of the element in magnesium, aluminium, titanium, zirconium, the bismuth etc.Can use a kind of in these separately, also can combination more than 2 kinds be used.Wherein, the hydrotalcite shown in the preferred following composition formula (XXI).

[Chemical formula 2 1]

Mg _1-xAl _x(OH) ₂(CO ₃) _x/2·mH ₂O ····(XXI)

In the composition formula (XXI), 0＜X≤0.5, m representes positive number.

With regard to the containing ratio of anion ion exchange body, get final product not special restriction so long as can be enough to catch anionic amount such as halide-ions.Particularly, be preferably 0.1 mass parts～30 mass parts with respect to (A) epoxy resin 100 mass parts, more preferably 1 mass parts～5 mass parts.

(releasing agent)

At encapsulating epoxy resin composition of the present invention, can contain releasing agent as required.As releasing agent, preferably use the 0.01 mass parts～oxidized form of 10 mass parts or the polyolefine of non-oxide type with respect to (A) epoxy resin 100 mass parts, more preferably use 0.1 mass parts～5 mass parts.Being 0.01 mass parts when above, have release property and be inclined to fully, be that 10 mass parts have tendency excellent in adhesion when following.

As the polyolefine of oxidized form or non-oxide type, the number-average molecular weight such as trade(brand)name H4, PE, PED series that can enumerate out He Xisite joint-stock company is low molecular weight polyethylene of about 500～10000 etc.In addition, as releasing agent in addition, can enumerate out for example POLISHING WAX-103, montanate, montanic acid, Triple Pressed Stearic Acid etc.Can use a kind of in these separately, also can combination more than 2 kinds be used.

When the releasing agent that uses simultaneously on the polyolefinic basis in oxidized form or non-oxide type beyond above-mentioned, with respect to (A) epoxy resin 100 mass parts, its containing ratio amounts to and is preferably 0.1 mass parts～10 mass parts, more preferably 0.5 mass parts～3 mass parts.

(fire retardant)

Can cooperate existing known fire retardant in the encapsulating epoxy resin composition of the present invention as required.For example can enumerate out: phosphorus compounds such as the red phosphorus of linings such as thermosetting resins such as inorganics such as brominated epoxy resin, ANTIMONY TRIOXIDE SB 203 99.8 PCT, red phosphorus, white lake, Marinco H, zinc oxide and/or resol, SULPHOSUCCINIC ACID ESTER; Nitrogenous compounds such as trimeric cyanamide, melamine derivative, cyanurotriamide modified resol, compound, cyanogen urea acid derivative, isocyanuric acid verivate with triazine ring; Phosphorous and nitrogen compounds such as ring phosphonitrile, the complex metal hydroxide shown in white lake, Marinco H and the following composition formula (XXII) etc.

[Chemical formula 2 2]

p(M ¹ _aO _b)·q(M ² _cO _d)·r(M ³ _eO _f)·mH ₂O ····(XXII)

In the composition formula (XXII), M ¹, M ²And M ³The metallic element that differs from one another of expression, a, b, c, d, e, f, p, q and m represent positive number, r representes 0 or positive number.

M in the above-mentioned composition formula (XXII) ¹, M ²And M ³So long as the metallic element that differs from one another gets final product not special restriction.Explain, the classification of metallic element based on typical element as the A subtribe, transition element is carried out as the periodic table of elements of the LP type of B subtribe (source: upright altogether publish the 30th printing of brush version of contracting in " chemical voluminous dictionary 4 " on February 15th, 1987 that Co., Ltd. publishes).

From the viewpoint of flame retardant resistance, preferably, M ¹Be selected from metallic element, the IIA family in the 3rd cycle alkali earth metal, belong to the metallic element of IVB family, IIB family, VIII family, IB family, IIIA family and IVA family, M ²Be selected from the transition metal of IIIB～IIB family, more preferably M ¹Be selected from magnesium, calcium, aluminium, tin, titanium, iron, cobalt, nickel, copper and zinc, M ²Chosen from Fe, cobalt, nickel, copper and zinc.From the viewpoint of flowability, preferred M ¹Be magnesium, M ²Be zinc or nickel, r=0 person.

The not special restriction of the mol ratio of p, q and r, preferred r=0, p/q is 1/99～1/1.

In addition, can enumerate out zinc oxide, zinc, zinc borate, red stone, molybdenum oxide, zinc molybdate, ferrocene etc. and contain compound of metallic element etc.Can use a kind of in these separately, also can combination more than 2 kinds be used.

The not special restriction of the containing ratio of fire retardant is preferably 1 mass parts～30 mass parts with respect to (A) epoxy resin 100 mass parts, more preferably 2 mass parts～15 mass parts.

(tinting material, stress negative catalyst)

In addition, encapsulating epoxy resin composition of the present invention can also contain tinting materials such as carbon black, organic dye, pigment dyestuff, titanium oxide, red lead, colcother.And then can cooperate silicone oil as other additive, silicone rubber powder equal stress negative catalyst etc. as required.

< preparation of encapsulating epoxy resin composition >

With regard to encapsulating epoxy resin composition of the present invention, so long as can the method for various uniform component dispersing and mixing then can be prepared through any means.As usual method, after can enumerating out composition with the regulation use level and using melting mixings such as mixing roll, forcing machine again after through thorough mixing such as stirrers, the method for cooling off, pulverizing.For example, can stir equably through mentioned component, mix and method that kneader, roller, extrusion machine through being heated to 70 ℃～140 ℃ in advance etc. carry out mixing, cooling, pulverizing etc. obtains specified amount.Then to use more easily with corresponding size of condition of molding and quality sheetization.

< electronic part apparatus >

Electronic part apparatus as the element that possesses the encapsulating epoxy resin composition sealing that obtains with the present invention; Can enumerate out on support member such as the carrier band after lead frame, the wiring, wiring board, glass, silicon wafer and carry active members such as semi-conductor chip, transistor, diode, thyristor, the electronic part apparatus that elements such as passive devices such as electrical condenser, resistance, coil also form with the necessary part of encapsulating epoxy resin composition sealing of the present invention etc.

As such electronic part apparatus; For example can enumerate: on the lead frame fixedly semiconductor element and connect the portion of terminal and wire portion of elements such as pad through wire bonding, salient point after, dual-in-line package), PLCC (Plastic Leaded Chip Carrier: plastic leaded chip carrier), QFP (Quad Flat Package: four row flat package), SOP (Small Outline Package: the small size encapsulation), SOJ (Small Outline J-lead package: little external form J pin encapsulation), TSOP (Thin Small Outline Package: the thin-type small-size encapsulation), TQFP (Thin Quad Flat Package: common plastic molded type IC such as slim quad flat package) use (Dual Inline Package: such as the DIP that encapsulating epoxy resin composition of the present invention is sealed to form through transfer molding etc.; Seal with salient point through encapsulating epoxy resin composition of the present invention and to be connected to the TCP that the semi-conductor chip on the carrier band forms (Tape Carrier Package: band carries encapsulation); To be connected to passive devices such as active member such as the semi-conductor chip that is formed at wiring board, wiring on glass, transistor, diode, thyristor and/or electrical condenser, resistance, coil through wire bonding, flip-chip combination, scolding tin etc., the COB that is sealed to form through encapsulating epoxy resin composition of the present invention (Chip On Board: chip on board) module, mix IC or multi-chip modules; Element mounting is formed with the surface of organic substrate of wiring board terminal for connecting in the back side; BGA), CSP (Chip Size Package: chip size packages) be connected to form after the wiring of element and organic substrate the BGA that forms through encapsulating epoxy resin composition sealing element of the present invention (Ball Grid Array: through salient point or wire bonding; Deng.In addition, also can use encapsulating epoxy resin composition of the present invention effectively on the PC board.

As the method for using encapsulating epoxy resin composition sealing element of the present invention, modal is low pressure transfer molding method, but also can use injection moulding, compressed moulding method etc.

[embodiment]

The present invention will be described through embodiment below, but scope of the present invention is not limited by these embodiment.Explain that " % " is not meant " quality % " when having special declaration.

< preparation of encapsulating epoxy resin composition >

Following composition is cooperated according to the mass parts shown in the below table 1～6 respectively, is that 80 ℃, mixing time are that to carry out roller under 10 minutes the condition mixing at melting temperature, makes the encapsulating epoxy resin composition of embodiment 1～24 and comparative example 1～24.Explain that the empty hurdle in the table is represented not cooperate.

As (A) epoxy resin, use:

Epoxy resin 1: epoxy equivalent (weight) be 196g/eq, fusing point be 106 ℃ biphenyl type epoxy resin (the trade(brand)name YX-4000 of Japan Epoxyresin Co., Ltd. system),

Epoxy resin 2: epoxy equivalent (weight) be 240g/eq, softening temperature be 96 ℃ the phenol aralkyl-type epoxy resin that contains the biphenylene skeleton (the trade(brand)name CER-3000L of Nippon Kayaku K. K's system),

Epoxy resin 3: epoxy equivalent (weight) be 238g/eq, softening temperature be 55 ℃ phenol aralkyl-type epoxy resin (the trade(brand)name NC-2000L of Nippon Kayaku K. K's system),

Epoxy resin 4: epoxy equivalent (weight) is that 200g/eq, softening temperature are 60 ℃ o-cresol phenolic epoxy varnish (the trade(brand)name N500P-1 of Dainippon Ink. & Chemicals Inc's system).

As (B) solidifying agent, use:

Solidifying agent 1: hydroxyl equivalent be 175g/eq, softening temperature be 70 ℃ phenol aralkyl resin (bright with change into the trade(brand)name MEH-7800 of Co., Ltd.'s system),

Solidifying agent 2: hydroxyl equivalent is that 106g/eq, softening temperature are 83 ℃ phenol novolac resin (bright with change into the trade(brand)name H-100 of Co., Ltd.'s system).

As the benzophenone derivates that has 1 above phenolic hydroxyl group in (C) 1 molecule (below be designated as the hydroxy benzophenone ketone compound), use:

Hydroxy benzophenone ketone compound 1: to dihydroxy benaophenonel,

Hydroxy benzophenone ketone compound 2: O-hydroxyl-diphenyl ketone,

Hydroxy benzophenone ketone compound 3:2-hydroxyl-4-methoxy benzophenone,

Hydroxy benzophenone ketone compound 4:2, the 4-dihydroxy benaophenonel,

Hydroxy benzophenone ketone compound 5:4,4 '-dihydroxy benaophenonel.

In addition, in the comparative example,, use as the material of the surrogate that is used as the hydroxy benzophenone ketone:

Phenolic compound 1: phenol,

Phenolic compound 2: p-cresol,

Phenolic compound 3: pyrocatechol,

Phenolic compound 4: Resorcinol,

Phenolic compound 5: quinhydrones,

Benzophenone cpd 1: UVNUL MS-40,

Benzophenone cpd 2: to methoxy benzophenone.

As (D) silane compound, use:

Silane compound 1: γ-glycidoxypropyltrime,hoxysilane.

As (E) curing catalyst, use:

Curing catalyst 1: the betaine type affixture of triphenylphosphine and para benzoquinone.

As (F) inorganic filler, use:

Inorganic filler 1: median size is that 17.5 μ m, specific surface area are 3.8m ²The spheroidal fused silicon-dioxide of/g.As other added ingredients, montanate, carbon black have been used.

[table 1]

[table 2]

[table 3]

[table 4]

[table 5]

[table 6]

< evaluation >

Through the various characteristics test of following (1)～(7), the encapsulating epoxy resin composition of embodiment and comparative example is estimated.Below table 7～12 is summed up and be shown in to evaluation result.Explain, short of special instruction, then the moulding of encapsulating epoxy resin composition is carried out under 180 ℃ of die temperatures, forming pressure 6.9MPa, the condition of 90 seconds set times through the transfer molding machine.In addition, after fixing is under 180 ℃, to carry out 5 hours.

(1) helical flow

Use is measured based on the helical flow of EMMI-1-66 and is used mould, will seal with the moulding under these conditions of epoxy formed material, obtains distance of flow (cm).

(2) hot hardness

It is that 50mm, thickness are the plectane of 3mm that encapsulating epoxy resin composition is shaped to diameter under these conditions, uses Shore (Shore) D type hardness tester meter (island makes made HD-1120 (model D) in Co., Ltd.) to measure after the moulding immediately.

(3) hot hardness during moisture absorption

Before the moulding in carrying out (2), encapsulating epoxy resin composition 25 ℃, the condition held of 50%RH 72 hours, is carried out moulding then and exists side by side and promptly use Shore D type hardness tester meter (island makes made HD-1120 (model D) in Co., Ltd.) to measure.

(4) water-intake rate

The plectane of moulding in (2) is carried out after fixing under these conditions; 85 ℃, the condition held of 60%RH 168 hours; Measure the quality change before and after placing, water-intake rate (quality %)={ the plectane quality before (the plectane quality before the plectane quality-placement after the placement)/placement } * 100 are estimated.

Bending elastic modulus (hot bend test) under (5) 260 ℃

Use flexing machine (the A&D Company of Co., Ltd., Limited makes TENSILON), carry out 3 pliability tests based on JIS-K-6911, the limit remains on 260 ℃ of limits through thermostatic bath and obtains bending elastic modulus (E) through following formula.Mensuration is to use encapsulating epoxy resin composition is shaped to the test film of 10mm, 70mm, 3mm under these conditions and is to carry out under the condition of 1.5mm/min in head speed.

[several 1]

$E=\frac{l^3}{4w{h}^3}\frac{\mathrm{\&Delta;P}}{\mathrm{\&Delta;y}}$

$S=\frac{3I}{2{\mathrm{wh}}^2}{o}_{\max }$

$\mathrm{\&epsiv;}=\frac{6h}{l^2}{y}_{\max }$

E: bending elastic modulus (Pa); S: flexural strength (Pa); ε: elongation at break (%); P: the value of load cell (N); Y: displacement (mm); I: span=48mm; W: test film width=10mmh: test film thickness=3mm (following target max representes peak)

(6) 260 ℃ down with the mensuration (shearing resistance mensuration) of the bonding force of metal

With encapsulating epoxy resin composition under these conditions respectively the diameter that is shaped to the bottom surface on copper coin or the sheffield plate be the diameter of 4mm, upper surface be 3mm, highly for after the size of 4mm; Carry out after fixing; The limit makes the temperature of various copper coins remain on 260 ℃ through bonding strength trier (bond tester) (デ ィ ジ ジ ャ パ Application Co., Ltd. system series 4000), and shear bond power is measured with velocity of shear 50 μ m/s in the limit.

(7) anti-backflow property

The physical dimension that to carry the silicon of 8mm * 10mm * 0.4mm is 80 pin flat package (the lead frame materials: copper alloy of 20mm * 14mm * 2mm; Chip bonding pad (die pad) portion's upper surface and lead leading section are through the product of silver-plated processing), use encapsulating epoxy resin composition to carry out moulding, after fixing in above-mentioned condition.With it at 85 ℃, the condition held of 60%RH after 1 week; Embodiment 1～16 carries out reflow treatment with comparative example 1～16 under 240 ℃; Embodiment 17～20 carries out reflow treatment with comparative example 17～20 under 230 ℃, embodiment 21～24 carries out reflow treatment with comparative example 21～24 under 220 ℃.Observe resin/frame interface in the encapsulation after the reflow treatment through ultrasonic flaw detecting device (Hitachi Construction Machinery Co., Ltd. system HYE-FOCUS) and have or not and peel off, encapsulate number (5) through the encapsulation number of peeling off with respect to test and estimate.

[table 7]

[table 8]

[table 9]

230 ℃ of (* 1) reflux temperatures, 220 ℃ of (* 2) reflux temperatures

[table 10]

[table 11]

[table 12]

230 ℃ of (* 1) reflux temperatures, 220 ℃ of (* 2) reflux temperatures

Through the combination of identical epoxy resin and solidifying agent, compare for the characteristic of above-mentioned (1)～(7) of embodiment and comparative example.For example, to as the embodiment 1～16 of the combination of epoxy resin 1 and 2/ solidifying agent 1 and comparative example 1～16, as the embodiment 17～20 of the combination of epoxy resin 1 and 3/ solidifying agent 1 and comparative example 17～20, compare as the embodiment 21～24 and the comparative example 21～24 of the combination of epoxy resin 1 and 4/ solidifying agent 2.

Observation table 7～12 can be known; Compare with comparative example; Added 260 ℃ of shear bond power (silver and copper) height of the embodiment of hydroxy benzophenone ketone compound, does not peel off at resin/frame interface in 85 ℃, the reflow treatment of condition held after 1 week of 60%RH, and anti-backflow property is excellent.

The ratio of hydroxy benzophenone ketone compound is the embodiment 5 below the 0.1 quality %; Compare with 6～16 with embodiment 1～4 for the combination of identical epoxy resin/solidifying agent; Bonding force is low, shows that the effect of invention diminishes, and the ratio of hydroxy benzophenone ketone compound is the above embodiment 23 of 1.0 quality %; Compare decrease of hardness with the embodiment 21,22,24 that is the combination of identical epoxy resin/solidifying agent.But among all embodiment, does not all peel off at resin/frame interface.

On the other hand, form the comparative example different and can not realize the object of the invention with the present invention.Compare with embodiment, 260 ℃ of shear bond power (silver and copper) are in below the peer-level, and in 85 ℃, the reflow treatment of condition held after 1 week of 60%RH, peel off at resin in more than half encapsulation/frame interface, and anti-backflow property is poor.

Claims (6)

1. encapsulating epoxy resin composition contains: (A) contain the benzophenone derivates that has 1 above phenolic hydroxyl group in the epoxy resin, (B) solidifying agent of 2 above epoxy group(ing) and (C) 1 molecule in 1 molecule.

2. encapsulating epoxy resin composition according to claim 1, wherein, the containing ratio that has the benzophenone derivates of 1 above phenolic hydroxyl group in said (C) 1 molecule is 0.1 quality %～1.0 quality %.

3. encapsulating epoxy resin composition according to claim 1 and 2 wherein, also contains (D) silane compound.

4. according to any described encapsulating epoxy resin composition in the claim 1～3, wherein, also contain (E) curing catalyst.

5. according to any described encapsulating epoxy resin composition in the claim 1～4, wherein, also contain (F) inorganic filler.

6. an electronic part apparatus possesses the element with any described encapsulating epoxy resin composition sealing in the claim 1～5.