CN105531297A

CN105531297A - Epoxy resin mixture, epoxy resin composition, cured product and semiconductor device

Info

Publication number: CN105531297A
Application number: CN201480049986.XA
Authority: CN
Inventors: 中西政隆; 长谷川笃彦; 木村昌照
Original assignee: Nippon Kayaku Co Ltd
Current assignee: Nippon Kayaku Co Ltd
Priority date: 2013-09-10
Filing date: 2014-09-09
Publication date: 2016-04-27
Also published as: JPWO2015037584A1; TWI638850B; TW201522486A; WO2015037584A1; KR20160053907A; JP6366590B2

Abstract

Provided is an epoxy resin mixture capable of simultaneously satisfying properties such as the cured product having excellent heat resistance while also having excellent mechanical strength, flame resistance and high temperature elastic modulus and the mixture having low viscosity before curing, properties that conflict with said heat resistance. The mixture contains 60-75% (gel permeation chromatography area%) of a compound represented by formula (1) and 5-30% (same as above) of an epoxide of biphenol. (1) (In the formula, G represents a glycidyl group and R represents a hydrogen atom, etc.)

Description

Epoxy resin composition, composition epoxy resin, cured article and semiconductor device

Technical field

The present invention relates to the epoxy resin composition of the electric and electronic material applications being suitable for requirement thermotolerance, composition epoxy resin, its cured article and semiconductor device.

Background technology

Composition epoxy resin due to the excellence of operability and cured article thereof electrical characteristic, thermotolerance, tackiness, wet fastness (water tolerance) etc. and be widely used in the fields such as electrical and electronic parts, structure material material, tackiness agent, coating.

But in recent years, in electric and electronic field, along with its development, require the wet fastness of further raising headed by the high purity of resin combination, adhesivity, dielectric characteristics, for making the highly-filled lowering viscousity of filler (inorganic or organic filler), for shortening each characteristics such as the reactivity lifting of shaping cycle.In addition, as structured material, in aerospace material, leisure/sports equipment purposes etc., light weight is required and the material of mechanical properties excellence.Especially in encapsulating semiconductor field, along with the transition of this semi-conductor, substrate (substrate self or its periphery material) is thin layer, stacked, systematize, three dimensional stress and become complicated gradually, require the demand characteristicss such as very high-caliber thermotolerance, high workability.It should be noted that, especially along with the expansion of plastic package in vehicle-mounted purposes, the requirement improving thermotolerance becomes more strict.Specifically, due to the rising of the actuation temperature of semi-conductor, require the thermotolerance of more than 150 DEG C.Usually, the softening temperature of epoxy resin is higher, and its cured article tends to have higher thermotolerance.But, on the other hand, be difficult to use in sealing material owing to having the tendency of viscosity rising.For this problem, although attempt wanting by introducing naphthalene structure and show thermotolerance, exist hardeningly to become fragile, physical strength reduces such problem.In addition, have studied polyfunctional epoxy resin, but there is flame retardant resistance and significantly reduce such problem.

In addition, in recent years, the patience that the welding such as warpage, Reflow Soldering is impacted strongly is required.Especially in chip slimming, requirement can tolerate the temperature (260 DEG C) of pb-free solder, in order to avoid the stress that this welding is impacted, requires Young's modulus at high temperature low and the sealing material that can eliminate stress.In addition, about warpage, in order to suppress warpage, require the low elastic modulus under high heat resistance and high temperature, this low elastic modulus and thermotolerance and flame retardant resistance are similarly the characteristic of opposition, in order to improve thermotolerance improve cross-linking density time, the Young's modulus under high temperature uprises, produce such as the following problem: stress during Reflow Soldering not completely eliminate thus to chip applying load, and encapsulation on there is crackle, warpage.

Prior art document

Non-patent literature

Non-patent literature 1: " STRJ in 2008 reports semiconductor technology evolves planning commission (half Guide body ロー De マップ Graduate Door entrust STAFF meeting) Heisei 20 annual report ", the 8th chapter, p1-1, [online], Heisei in March, 21, semiconductor technology evolves planning commission of JEITA (company) electronic information technology industry association, [Heisei is retrieved on May 30th, 24],

<http://strj-jeita.elisasp.net/strj/nenjihoukoku-2008.cfm>

Non-patent literature 2: the grade of high storehouse letter, the vehicle-mounted hot operation IC of SUNX technical report car related device technology (Trucks Seki Even デバイス skill Intraoperative Trucks Load high temperature Move makes IC), the 74th phase, Japan, May 31 calendar year 2001,35-40 page

Non-patent literature 3: the technology trend of the positive will in middle village, SUNX technical report edge semiconductor sealing material (tip half Guide body sealing material material skill Intraoperative Move to), Vol.56No.4 [Heisei retrieval on June 6th, 25]

<http://panasonic.co.jp/ptj/pew/564j/pdfs/564_02.pdf>

Non-patent literature 4: " warping Analysis (the anti-リ of BGA パッケージ resolves) of BGA package " JEITA (company) electronic information technology industry association [Heisei retrieval on September 30th, 24]

<http://home.jeita.or.jp/ecb/material/No011.html>

Summary of the invention

Invent problem to be solved

As one of characteristic specially required in the multifunction of epoxy resin, the thermotolerance of cured article can be enumerated.All the time, although pay attention to the thermotolerance of the cured article of epoxy resin, but as previously mentioned, during this thermotolerance of usual raising, produce simultaneously and become fragile and the problem such as physical strength is deteriorated and (cured article) flame retardant resistance is deteriorated, viscosity uprises, Young's modulus under (cured article) high temperature uprises, be difficult to satisfied whole characteristic.

Therefore, the epoxy resin developing the thermotolerance can taking into account cured article and the characteristic opposed with this thermotolerance is expected.

Namely, the object of the present invention is to provide a kind of epoxy resin composition, it has the thermotolerance of excellent cured article, can meet simultaneously Young's modulus under the physical strength of the cured article as the characteristic opposed with this thermotolerance, flame retardant resistance, high temperature excellent, solidify before the characteristics such as viscosity is low.In addition, the object of the present invention is to provide the composition epoxy resin, cured article and the semiconductor device that use this epoxy resin composition.

For the means of dealing with problems

The present inventor, in view of above-mentioned present situation, conducts in-depth research, and result completes the present invention.

That is, the present invention relates to:

(1) epoxy resin composition, it contains the epoxide of the '-biphenyl diphenol of the compound and 5% ~ 30% (the same) shown in following formula (1) of 60% ~ 75% (gel permeation chromatography area %),

In formula, there is multiple G, R and exist independently of one another, G represents glycidyl, and R represents the alkyl of hydrogen atom, carbonatoms 1 ~ 6 or the alkoxyl group of carbonatoms 1 ~ 6.

(2) epoxy resin composition as described in preceding paragraph (1), its softening temperature is 80 DEG C ~ 100 DEG C.

(3) epoxy resin composition as described in preceding paragraph (1) or (2), the ICI melt viscosity (cone-plate method) at its 150 DEG C is 0.08 ~ 0.35Pas.

(4) composition epoxy resin, it contains epoxy resin composition according to any one of preceding paragraph (1) ~ (3) and solidifying agent.

(5) composition epoxy resin, it contains epoxy resin composition according to any one of preceding paragraph (1) ~ (3) and curing catalysts.

(6) cured article, it is by obtaining the epoxy resin composition described in preceding paragraph (4) or (5).

(7) semiconductor device, semi-conductor chip sealing obtains by using preceding paragraph (4) or the composition epoxy resin described in (5) by it.

Invention effect

The viscosity of epoxy resin composition of the present invention is low, its cured article has excellent characteristic in thermotolerance, water absorption character and flame retardant resistance, therefore, useful in electrical and electronic parts insulating material and plywood (printed wiring board, increase laminar substrate etc.), various matrix materials, tackiness agent, coating etc. headed by carbon fiber reinforced plastics (CFRP).

Accompanying drawing explanation

Fig. 1 is the figure representing the 96PinQFP lead frame used in embodiment 22.

Fig. 2 be represent in embodiment 22 make, the figure of test evaluation test film that the proper alignment that uses is anti-thread breakage.

Embodiment

Epoxy resin composition of the present invention relates to the epoxy resin composition containing the compound with phenolphthalein skeleton derivative structure.English Patent No. 1158606 publications (patent documentation 1) disclose the basic framework of the compound shown in formula of the present invention (1).According to patent documentation 1, disclose every kg epoxy equivalent (weight) be 3.4 (being converted into present epoxy equivalent (weight) is 294g/eq.), tone for Gardner 8 (40% methyl glycol solution), the epoxy resin with phenolphthalein skeleton derivative structure that softening temperature is 66 DEG C (Kolfer well heaters), cl content is 2.2%.And, disclose the solidification physical property with DDS (diaminodiphenylsulfone(DDS)).

Imply from above-mentioned data: the chlorine dose of epoxy resin recorded patent documentation 1 is very many, be not suitable for electronic material purposes, and due to coloring degree high, in the purposes needing color, be therefore difficult to use.Imply in addition: epoxy equivalent (weight) 294g/eq. is larger than theoretical value (252.7g/eq.); And due to chlorine dose many, therefore containing the non-closed loop of a large amount of epoxy and residual epihalohydrins structure.Although be difunctionality, if the structure that such oxirane ring unreacted is complete, be then cross-linked and can not carry out smoothly, being cured utilizing resol, utilizing the basic catalysts such as imidazoles to carry out anionoid polymerization, utilization when salt etc. carry out cationoid polymerisation, often have problems in its characteristic such as mechanical characteristics, water-absorbent.Especially in electronic material purposes, not only in these solidifications, and in the solidification of amine, also can expect the corrosion etc. of the wiring caused due to the free of chlorine during solidification, become the major cause that electrical reliability reduces.

In recent years, often use copper cash in the joint of especially semi-conductor chip and substrate, the problem of such electrocorrosion becomes more important, becomes the problem that solve.

In addition, the epoxy resin recorded in this patent documentation 1 is due to the problem of its intramolecular polarity, and viscosity uprises.And due to the characteristic of its structure, there is the tendency of physical strength, poor adhesion, be in the state of the purposes such as the sealing material being difficult to extend to semi-conductor.

The present invention is a kind of epoxy resin composition, and it contains the epoxide of the '-biphenyl diphenol of the compound and 5% ~ 30% (the same) shown in following formula (1) of 60% ~ 75% (gel permeation chromatography area %),

At this, when the content of the compound shown in above-mentioned formula (1) is greater than 75%, likely crystallinity uprises or likely observes toughness reduction.When the content of the compound shown in above-mentioned formula (1) is less than 60%, oxirane ring complete closed loop and containing the compound in a large number without functional group, therefore not preferred.In addition, in most cases the compound majority of these complete closed loops is containing chlorine, worries the corrosion of the free wiring with causing thus of the chlorion under hot and humid condition as electronic material purposes, therefore not preferred.

Most preferred in R is hydrogen atom.As the alkyl of the above-mentioned carbonatoms 1 ~ 6 shown in R, such as methyl, ethyl, propyl group, butyl, amyl group, hexyl etc. can be enumerated there is the alkyl of straight chain, side chain or ring texture.At this, R is preferably methyl, ethyl, is particularly preferably methyl.

As the alkoxyl group of the above-mentioned carbonatoms 1 ~ 6 shown in R, such as methoxyl group, oxyethyl group, propoxy-, butoxy etc. can be enumerated there is the alkoxyl group of straight chain, side chain or ring texture.At this, R is preferably methoxyl group, oxyethyl group, propoxy-, is particularly preferably methoxyl group.

When the epoxide of '-biphenyl diphenol is more than 30%, can not utilize completely and result from the thermotolerance of cured article of structure of the compound shown in above-mentioned formula (1), in addition, when being less than 5%, in lowering viscousity, physical strength, adhesivity, effect is few.The content of the epoxide of the '-biphenyl diphenol in epoxy resin composition of the present invention particularly preferably 5% ~ 25%.

The epoxy equivalent (weight) of epoxy resin composition of the present invention, relative to the theoretical epoxy equivalent weight of phenol skeleton becoming raw material, is generally 1.01 ~ 1.13 times, is preferably 1.02 ~ 1.10 times.When being less than 1.01 times, sometimes in the synthesis, purifying of epoxy, expending huge expense, in addition when being greater than 1.13 times, sometimes producing the problem caused by chlorine dose as described above.

In addition, be preferably below 5000ppm as total chlorine contained in epoxy resin of the present invention, be more preferably below 3000ppm, be particularly preferably below 2000ppm.About the detrimentally affect caused by chlorine dose as hereinbefore.It should be noted that, about chlorion, sodium ion, be preferably below 5ppm separately, be more preferably below 3ppm.Chlorion is recorded above needless to say, and the positively charged ions such as sodium ion are especially very important factor in power device purposes, becomes a reason of the fault mode when applying high-voltage.

At this, theoretical epoxy equivalent weight refers to the epoxy equivalent (weight) that the phenolic hydroxyl group as the phenolic compound of raw material calculates when just enough carrying out Glycidyl.

In addition, as the value of concrete epoxy equivalent (weight), when R is all hydrogen atom, preferred 210.0g/eq. ~ 280.0g/eq., particularly preferably 220.0g/eq. ~ 250.0g/eq., by making epoxy equivalent (weight) be in above-mentioned scope, the epoxy resin of the thermotolerance of cured article, electrical reliability excellence can be obtained.

Epoxy resin composition of the present invention has the resinoid form of softening temperature.Herein, be preferably 70 DEG C ~ 130 DEG C as softening temperature, be more preferably 80 DEG C ~ 120 DEG C.When substituent R is all hydrogen atom, is preferably 80 DEG C ~ 120 DEG C, is more preferably 80 DEG C ~ 100 DEG C.When softening temperature is too low, be adhesive into problem during preservation, the problem such as must to process at low temperatures is many.Otherwise, when softening temperature is too high, when mixing with other resin, sometimes produce the problems such as operability variation.

In addition, melt viscosity is preferably 0.08 ~ 0.35Pas (ICI melt viscosity 150 DEG C of cone-plate methods), is more preferably 0.08 ~ 0.3Pas, is particularly preferably 0.08 ~ 0.25Pas.When inorganic materials used in combination (filler etc.), produce the problems such as poor fluidity.

Below, the manufacture method of epoxy resin composition of the present invention is described.

The epoxide of the compound shown in above-mentioned formula (1) and '-biphenyl diphenol can mix by the ratio of regulation by epoxy resin composition of the present invention, also can pass through the phenolic compound (DPPI) shown in following formula (4) and the mixture of '-biphenyl diphenol and the reaction of epihalohydrins and synthesize.

(in formula, R represents the implication identical with the R of above-mentioned formula (1).)

Phenolic compound (DPPI) shown in above-mentioned formula (4) synthesizes (can enumerate such as Japanese Unexamined Patent Publication 2005-290378 publication) by phenolphthalein derivative and anils.

As phenolphthalein derivative, be well known that and with phthalic acid and corresponding various phenols synthesis, if the phenols used is phenol, phenol phthalein can be obtained, if be cresols, obtain cresolphthalein.

At this, as above-mentioned various phenols, such as phenol, cresols, ethylphenol, propylphenol, xylenol, methyl butyl phenol etc. can be enumerated.Preferably phenol phthalein is used in the present invention.

In addition, as the phenolphthalein derivative obtained by above-mentioned synthesis, the such as structure shown in following formula (2) can be enumerated.

As anils, the compound of the such as structure shown in following formula (3) can be enumerated.

(in formula, R represents the implication identical with the R of previously described formula (1).)

The amount of the residual phenolphthalein derivative in phenolic compound (DPPI) is preferably less than 2%, is more preferably less than 1%, and more preferably less than 0.5%, be particularly preferably less than 0.1% (use high-performance liquid chromatogram determination).During this phenolphthalein derivative residual, there is the tendency of painted increase during reaction.Anils too.Iron level (ICP emmission spectrometric analysis) residual in addition is also cause one of painted factor.Ferric remains content is preferably below 100ppm, is more preferably below 50ppm, is particularly preferably below 10ppm.Expect that the phenolic compound (DPPI) as main body is the purity of more than 95% in addition, be more preferably the purity of more than 98%.

The amount of residual phenolphthalein derivative can be regulated by the purifying of DPPI (cleaning, recrystallization, redeposition etc.).

In addition, the preferred softening temperature of the DPPI used in the present invention is more than 100 DEG C.Be more than 100 DEG C by softening temperature, contribute to the thermotolerance of the epoxy resin composition generated.The DPPI particularly used in the present invention preferably has fusing point, and preferably this fusing point is more than 200 DEG C.

The '-biphenyl diphenol that the present invention uses has the structure shown in following formula (5).

(in formula (5), there is multiple R ₁exist independently of one another, represent the alkyl of hydrogen atom or carbonatoms 1 ~ 3, k represents the integer of 1 ~ 4.)

The '-biphenyl diphenol of the structure shown in above-mentioned formula (5) such as exists 2,2 ' form, 2,4 ' form, 4,4 ' form etc., wherein the '-biphenyl diphenol of preferred 4,4 ' form.

In addition, the '-biphenyl diphenol of purity more than 95% can preferably be used.

Below, the method for the epoxy resin composition of the present invention obtained passing through phenolic compound (DPPI) and the mixture of '-biphenyl diphenol and the reaction of epihalohydrins is recorded.Below the mixture of phenolic compound (DPPI) and '-biphenyl diphenol is designated as the phenol mixture used in the present invention.

As long as the phenol mixture used in the present invention is the mixture of phenolic compound (DPPI) and '-biphenyl diphenol, the mixture ratio of phenolic compound (DPPI) and '-biphenyl diphenol is with terms of mole ratios, phenolic compound (DPPI): '-biphenyl diphenol is preferably 5:5 ~ 9:1, is more preferably 6:4 ~ 8:2.In addition, with mass ratio range, phenolic compound (DPPI): '-biphenyl diphenol is preferably 6:4 ~ 9:1, is more preferably 7:3 ~ 8.6:1.4.

As the epihalohydrins used in the synthetic method of epoxy resin composition of the present invention, be preferably the Epicholorohydrin industrially easily obtained.The usage quantity of epihalohydrins is generally 3.0 ~ 15 moles relative to the hydroxyl 1 mole of the phenol mixture used in the present invention, is preferably 3.0 ~ 10 moles, is more preferably 3.5 ~ 8.5 moles, is particularly preferably 4.0 ~ 6.0 moles.

When being less than 3.0 moles, epoxy equivalent (weight) increases sometimes, and in addition, the operability of the epoxy resin obtained likely is deteriorated.When being greater than 15 moles, solvent quantitative change is many, therefore not preferred from waste, productivity aspect.

Alkali metal hydroxide can be used in above-mentioned reaction.As the alkali metal hydroxide that can use in above-mentioned reaction, can sodium hydroxide, potassium hydroxide etc. be enumerated, can solids be utilized, also its aqueous solution can be used, in the present invention, especially from the viewpoint of solvability, operation, preferably use and be molded into laminar solids.

The usage quantity of alkali metal hydroxide is generally 0.90 ~ 1.5 mole relative to the hydroxyl 1 mole as the phenol mixture used in the present invention of raw material, is preferably 0.95 ~ 1.25 mole, is more preferably 0.99 ~ 1.15 mole.

In order to promote reaction, the quaternary ammonium salts such as tetramethyl ammonium chloride, 4 bromide, trimethyl benzyl ammonia chloride can be added as catalyzer.As the usage quantity of quaternary ammonium salt, be generally 0.1 ~ 15g relative to the hydroxyl 1 mole of raw material phenol mixture, be preferably 0.2 ~ 10g.

In the present reaction, except above-mentioned epihalohydrins and with non-polarity proton solvent (dimethyl sulfoxide (DMSO), dioxane, dimethyl-imidazolinone etc.), carbonatoms be preferably the alcohol of 1 ~ 5.Carbonatoms be 1 ~ 5 alcohol be the alcohols such as methyl alcohol, ethanol, Virahol.Non-polarity proton solvent or carbonatoms are that the usage quantity of the alcohol of 1 ~ 5 is generally 2 ~ 50 % by weight relative to the usage quantity of epihalohydrins, is preferably 4 ~ 25 % by weight.In addition, can by carrying out epoxidation while the moisture of the methods such as azeotropic dehydration in the hierarchy of control.

During washiness in system, the electrical reliability of the cured article of sometimes obtained epoxy resin composition is deteriorated, and preferably water sub-control is synthesized built in less than 5%.In addition, when using non-polarity proton solvent to obtain epoxy resin, the cured article of the epoxy resin of electrical reliability excellence can be obtained, therefore can preferably use non-polarity proton solvent.

Temperature of reaction is generally 30 DEG C ~ 90 DEG C, is preferably 35 DEG C ~ 80 DEG C.Especially in the present invention, in order to more highly purified epoxidation, preferably more than 60 DEG C, particularly preferably in close to the reaction under the condition of reflux conditions.Reaction times is generally 0.5 hour ~ 10 hours, be preferably 1 hour ~ 8 hours, be particularly preferably 1 hour ~ 3 hours.Reaction times, reaction was carried out not exclusively in short-term; During long reaction time, sometimes generate by product.

Washing rear by the reaction product of these epoxidation reactions or not washing, under heating decompression, remove epihalohydrins, solvent etc.And, in order to make the few epoxy resin composition of hydrolyzable halogen further, the epoxide reclaimed dissolves as solvent by the ketone compound (can enumerate such as hexone, methylethylketone, cyclopentanone, pimelinketone etc.) that can be also 4 ~ 7 using carbonatoms, add the aqueous solution of the alkali metal hydroxide such as sodium hydroxide, potassium hydroxide and react, thus reliably carrying out closed loop.The usage quantity of alkali metal hydroxide is now generally 0.01 ~ 0.3 mole relative to the hydroxyl 1 mole of the phenol mixture for using in epoxidised the present invention, is preferably 0.05 ~ 0.2 mole.Temperature of reaction is generally 50 DEG C ~ 120 DEG C, and the reaction times is generally 0.5 hour ~ 2 hours.

After reaction terminates, the salt generated is passed through the removings such as filtration, washing, then fall solvent at heating evaporated under reduced pressure, obtain epoxy resin composition of the present invention thus.

Epoxy resin composition of the present invention shows the arborescens of amorphous arborescens or semi-crystalline state.When epoxy resin composition of the present invention is the arborescens of semi-crystalline state, due to for low viscosity and be physical strength, mixture that adhesivity is high, therefore preferably.

In epoxy resin composition of the present invention, the compound shown in above-mentioned formula (1) and bisglycidyl base oxygen base biphenyl are (wherein, when its aromatic nucleus has substituting group, substituent quantity is less than 4, carbonatoms is less than 4) exist simultaneously, in reaction under optimum condition as above, also there is the structure that the phenol resins structure shown in above-mentioned formula (1) and '-biphenyl diphenol structure are formed by connecting by epihalohydrins.Therefore, by phenol mixture is carried out epoxidation simultaneously, generate aforementioned structure thus, and more easily reduce viscosity, as being preferred in the raising mobility of object of the present invention.

In addition, and only carry out compared with epoxidised situation to '-biphenyl diphenol, the crystallinity of the epoxy resin composition obtained by such method for making is low, therefore, owing to easily carrying out purifying, thus easily obtains the few epoxy resin composition of residual chlorine dose.

Composition epoxy resin of the present invention contains epoxy resin composition of the present invention and curing catalysts (curing catalyst) and/or solidifying agent.In addition, other epoxy resin is preferably contained as optional component.

In composition epoxy resin of the present invention, the epoxy resin of other kind can also be contained except epoxy resin composition of the present invention.In whole epoxy resin, the ratio of epoxy resin composition of the present invention is preferably more than 20 % by weight, is more preferably more than 30 % by weight, is particularly preferably more than 40 % by weight.

As can with epoxy resin composition of the present invention and other epoxy resin, can enumerate: phenolic resin varnish type epoxy resin, bisphenol-type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol aralkyl type epoxy resin etc.Specifically, dihydroxyphenyl propane can be enumerated, bisphenol S, thiobisphenol, bisphenol fluorene, terpene diphenol, 4, 4 '-'-biphenyl diphenol, 2, 2 '-'-biphenyl diphenol, 3, 3 ', 5, 5 '-tetramethyl--[1, 1 '-biphenyl]-4, 4 '-diphenol, Resorcinol, Resorcinol, naphthalenediol, three (4-hydroxy phenyl) methane, 1, 1, 2, 2-tetra-(4-hydroxy phenyl) ethane, phenols (phenol, alkyl substituted phenol, naphthols, alkyl-substituted naphthaline phenol, dihydroxy-benzene, dihydroxy naphthlene etc.) and formaldehyde, acetaldehyde, phenyl aldehyde, p-Hydroxybenzaldehyde, salicylaldhyde, parahydroxyacet-ophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4, 4 '-bis-(chloromethyl)-1, 1 '-biphenyl, 4, 4 '-bis-(methoxymethyl)-1, 1 '-biphenyl, 1, two (chloromethyl) benzene or 1 of 4-, the polycondensate of two (methoxymethyl) benzene of 4-etc. and their modifier, solid-state or the liquid-state epoxy resins such as the halogenated bisphenol classes such as tetrabromo-bisphenol and the glycidyl ether compound derived by alcohols, alicyclic epoxy resin, glycidyl amine epoxy resin, glycidyl esters based epoxy resin, silsesquioxane based epoxy resin (there is the epoxy resin of glycidyl and/or epoxy cyclohexane structure in the siloxane structure of chain, ring-type, scalariform or wherein at least two or more mixed structures), but be not limited thereto.

As the concrete example of operable curing catalysts in the present invention, can enumerate: triethylamine, tripropyl amine, the amine compound such as Tributylamine, pyridine, dimethyl aminopyridine, 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene, imidazoles, triazole, tetrazolium, glyoxal ethyline, 2-phenylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1 benzyl 2 methyl imidazole, 1-cyano ethyl-glyoxal ethyline, 1-cyano ethyl-2-phenylimidazole, 1-cyano ethyl-2-undecyl imidazole, 2,4-diamino-6 (2 '-Methylimidazole (1 ')) ethyl s-triazine, 2,4-diamino-6 (2 '-undecyl imidazole (1 ')) ethyl s-triazine, 2,4-diamino-6 (2 '-ethyl-4 '-Methylimidazole (1 ')) ethyl s-triazine, 2,4-diamino-6 (2 '-Methylimidazole (1 ')) ethyl s-triazine-isocyanuric acid adduct, the 2:3 affixture of glyoxal ethyline isocyanuric acid, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-hydroxymethyl-imidazole, 2-phenyl-4-methylol-5-Methylimidazole, the various hetero ring type compounds such as 1-cyano ethyl-2-phenyl-3,5-dicyano ethoxyl methyl imidazoles, and these hetero ring type compounds and phthalic acids, m-phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalic acid, toxilic acid, the salt that the polycarboxylic acids such as oxalic acid are formed, the amidess such as Dyhard RU 100, the diaza compounds such as 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene and their tetraphenyl borate salts, the salt of phenolic varnish etc., the salt formed with above-mentioned polycarboxylic acid class or phospho acid class, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, trimethylethyl ammonium hydroxide, thmethylpropyl ammonium hydroxide, trimethyl butyl ammonium hydroxide, trimethylammonium hexadecyl ammonium hydroxide, tricaprylmethyl ammonium hydroxide, tetramethyl ammonium chloride, 4 bromide, Tetramethylammonium iodide, tetramethyl ammonium acetate, the ammonium salts such as tricaprylmethyl ammonium acetate, triphenylphosphine, three (tolyl) phosphine, tetraphenylphosphonibromide bromide tetraphenyl the phosphine classes such as tetraphenyl borate salts or compound, 2, the metallic compound etc. of the phenols such as 4,6-triamino methylphenol, amine adduct, carboxylic metallic salt (zinc salt, pink salt, the zirconates of 2 ethyl hexanoic acid, stearic acid, docosoic, tetradecanoic acid etc.) or phosphate metal salt (zinc salt of octyl phosphate, phosphoric acid stearyl ester etc.), metal alkoxides salt (tri-butyl aluminum, tetrapropyl zirconium etc.), acetylacetonate (methyl ethyl diketone zirconium chelate, acetylacetone titanium chelate etc.) etc.In the present invention, from the viewpoint of solidification time painted, its change, particularly preferably salt, ammonium salt, metallic compound class.In addition, when using quaternary salt, the salt formed with halogen residual halogens sometimes in its cured article.

Curing catalyst uses 0.01 ~ 5.0 weight part as required relative to epoxy resin 100 weight part.

In composition epoxy resin of the present invention, preferably containing solidifying agent.Can enumerate such as: aminated compounds, anhydrides compound, amides, phenol resins, carboxylic acid compound etc.As the concrete example of operable solidifying agent, can enumerate: the nitrogenous compound (amine, amide compound) such as diaminodiphenyl-methane, diethylenetriamine, Triethylenetetramine (TETA), diaminodiphenylsulfone(DDS), isophorone diamine, Dyhard RU 100, the polyamide resin that synthesized by linolenic dipolymer and quadrol, Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, pyromellitic dianhydride, maleic anhydride, Tetra Hydro Phthalic Anhydride, methyl tetrahydrophthalic anhydride, methylnadic anhydride, carbic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylene-dimalonic acid acid anhydride, dicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, methyl bicycle [2.2.1] heptane-2,3-dicarboxylic acid anhydride, hexanaphthene-1,3, the acid anhydrides such as 4-tricarboxylic acid-3,4-acid anhydride, the carboxylic acid resin obtained by the addition reaction of various ethanol, carbinol-modified polysiloxane and above-mentioned acid anhydrides, dihydroxyphenyl propane, Bisphenol F, bisphenol S, bisphenol fluorene, terpene diphenol, 4, 4 '-'-biphenyl diphenol, 2, 2 '-'-biphenyl diphenol, 3, 3 ', 5, 5 '-tetramethyl--[1, 1 '-biphenyl]-4, 4 '-diphenol, Resorcinol, Resorcinol, naphthalenediol, three (4-hydroxy phenyl) methane, 1, 1, 2, 2-tetra-(4-hydroxy phenyl) ethane, phenols (phenol, alkyl substituted phenol, naphthols, alkyl-substituted naphthaline phenol, dihydroxy-benzene, dihydroxy naphthlene etc.) and formaldehyde, acetaldehyde, phenyl aldehyde, p-Hydroxybenzaldehyde, salicylaldhyde, parahydroxyacet-ophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4, 4 '-bis-(chloromethyl)-1, 1 '-biphenyl, 4, 4 '-bis-(methoxymethyl)-1, 1 '-biphenyl, 1, 4 '-bis-(chloromethyl) benzene or 1, the polycondensate of 4 '-bis-(methoxymethyl) benzene etc. and their modifier, the halogenated bisphenol classes such as tetrabromo-bisphenol, the phenol resins such as the condenses of terpenes and phenols, imidazoles, trifluoroboranes-amine complex, guanidine derivative compound etc., but be not limited thereto.These can be used alone, and also can use two or more.

In the present invention, particularly in order to for electronic material purposes, preferably above-mentioned phenol resins.

The usage quantity of the solidifying agent in composition epoxy resin of the present invention is preferably 0.7 ~ 1.2 equivalent relative to epoxy group(ing) 1 equivalent of epoxy resin.When being less than 0.7 equivalent relative to epoxy group(ing) 1 equivalent or more than 1.2 equivalent, solidification all sometimes not exclusively, cannot obtain good solidification physical property.

In addition, preferably use cyanate esters as other composition.Cyanate esters, except independent curing reaction, by the reaction with epoxy resin, can obtain the cured article of the higher thermotolerance of cross-linking density.As cyanate ester resin, can enumerate such as: 2, two (the 4-cyanogen oxygen phenyl) propane of 2-, two (3,5-dimethyl-4-cyanogen oxygen phenyl) methane, 2,2-two (4-cyanogen oxygen phenyl) ethane, their derivative, aromatic series cyanate esters etc.In addition, also can as recorded in such as above-mentioned solidifying agent, react to synthesize by various phenol resins and cyanic acid or its esters.In the present invention, particularly preferably as 2, two (4-cyanogen oxygen phenyl) the propane or derivatives thereof (partial polymer etc.) of 2-does not have the cyanate esters of the structure of the methylene radical structure of benzyl position like this in molecule, these cyanate esters can be used alone one, also can be used together two or more.

In composition epoxy resin of the present invention, also can containing P contained compound as the composition giving flame retardant resistance.As P contained compound, can be response type compound, also can be addition type compound.As the concrete example of P contained compound, can enumerate: trimethyl phosphite 99, triethyl phosphate, Tritolyl Phosphate, tricresyl phosphate (xylyl) ester, tricresyl phosphate base ester diphenyl, tricresyl phosphate base ester-2,6-bis-(xylyl) ester, 1,3-phenylene two (di(2-ethylhexyl)phosphate (xylyl) ester), 1,4-phenylene two (di(2-ethylhexyl)phosphate (xylyl) ester), 4, the phosphoric acid esters such as 4 '-biphenyl (di(2-ethylhexyl)phosphate (xylyl) ester); The phosphine classes such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxy phenyl)-10H-9-oxa--10-phospho hetero phenanthrene-10-oxide compound; Make the reactive with active hydrogen of epoxy resin and above-mentioned phosphine class and the phosphorous epoxy compounds, red phosphorus etc. that obtain, preferably phosphoric acid ester class, phosphine class or phosphorous epoxy compounds, particularly preferably 1,3-phenylene two (di(2-ethylhexyl)phosphate (xylyl) ester), 1,4-phenylene two (di(2-ethylhexyl)phosphate (xylyl) ester), 4,4 '-biphenyl (di(2-ethylhexyl)phosphate (xylyl) ester) or phosphorous epoxy compounds.The content of P contained compound is preferably P contained compound/all epoxy resin=0.1 ~ 0.6 (weight ratio).When being less than 0.1, flame retardant resistance is not enough, when being greater than 0.6, sometimes has a negative impact to the water absorbability of cured article, dielectric characteristics.

In addition, in composition epoxy resin of the present invention, also resin glue can be coordinated as required.As resin glue, can enumerate: butyral resinoid, acetal resin, acrylic resin, epoxy-nylon-based resin, NBR-phenolic resin, epoxy-NBR resinoid, polyamide-based resin, polyimide based resin, polysiloxane resinoid etc., but be not limited thereto.The use level of resin glue preferably, in the scope not damaging the flame retardant resistance of cured article, thermotolerance, usually uses 0.05 ~ 50 weight part as required relative to total 100 weight part of epoxy resin and solidifying agent, preferably uses 0.05 ~ 20 weight part.

In composition epoxy resin of the present invention, inorganic filler can be added as required.As inorganic filler, can enumerate: the powder of crystalline silica, fused silica, aluminum oxide, zircon, Calucium Silicate powder, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconium dioxide, forsterite, steatite, spinel, titanium dioxide, talcum etc. or they are made spherical and microballon etc. that is that obtain, but be not limited thereto.These packing materials can be used alone, and also can use two or more.For the content of these inorganic fillers, in composition epoxy resin of the present invention, although different according to purposes, but usually use the amount accounting for 0 ~ 95 % by weight, when particularly using in the purposes of sealing material, preferably: use respectively according to the shape of encapsulation being preferably 50 ~ 95 % by weight, in the scope that is particularly preferably 65 ~ 95 % by weight.In addition, in composition epoxy resin of the present invention, the various Synergist S-421 95 such as releasing agent, pigment, the various thermosetting resins such as antioxidant, photostabilizer, silane coupling agent, stearic acid, palmitinic acid, Zinic stearas, calcium stearate can be added.Particularly about coupling agent, preferably add and there is the coupling agent of epoxy group(ing) or there is the coupling agent of sulfydryl.

Composition epoxy resin of the present invention is by being obtained by mixing each uniform composition.Composition epoxy resin of the present invention can easily form its cured article by the method same with existing known method.Such as, forcing machine, kneader, roller, planetary-type mixer etc. epoxy resin ingredient and curing agent component and the curing catalyst used as required, P contained compound, resin glue, inorganic filling material and Synergist S-421 95 etc. is used to be fully mixed to evenly and to obtain composition epoxy resin as required, when obtained composition epoxy resin is liquid, by embedding, pour into a mould said composition is infiltrated up in base material, or be cast in mould and carried out cast molding, and make it solidify by heating.In addition, when obtained composition epoxy resin is solid-state, carry out cast molding after melting, or it is shaping to use transfer molding machine etc. to carry out, then makes it solidify by heating.As solidification value, time, it is at 80 DEG C ~ 200 DEG C 2 hours ~ 10 hours.As curing, can at high temperature disposal solidifying, but preferably heat up stage by stage and be cured reaction.Specifically, between 80 DEG C ~ 150 DEG C, carry out initial cure, between 100 DEG C ~ 200 DEG C, carry out after fixing.As the stage of solidification, be preferably divided into 2 ~ 8 stages to heat up, be more preferably 2 ~ 4 stages.

In addition, composition epoxy resin of the present invention is dissolved in toluene, dimethylbenzene, acetone, methylethylketone, hexone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone equal solvent, make curable resin composition varnish, make it be infiltrated up in the base materials such as glass fibre, carbon fiber, trevira, tynex, sapphire whisker, paper and carry out heat drying and obtain prepreg, by obtained prepreg hot compacting, the cured article of composition epoxy resin of the present invention can be obtained thus.Solvent is now used in the mixture of composition epoxy resin of the present invention and this solvent and usually accounts for 10 ~ 70 % by weight, preferably account for the amount of 15 ~ 70 % by weight.

In addition, also composition epoxy resin of the present invention can be used as film-type composition for sealing.When obtaining such pellicular resin composition, curable resin composition of the present invention being coated with on stripping film above-mentioned varnish and removing desolventizing under heating and carry out B-stage, obtaining the tackiness agent of sheet thus.This Web-form adhesive can be used as the interlayer insulating film of multilager base plate etc., the disposable diaphragm seal of photosemiconductor.

As the concrete purposes of these compositions, tackiness agent, coating, coating agent, shaped material (comprising sheet, film, fibre reinforced plastics (FRP) etc.), insulating material (comprising the sealing material of printed base plate, coating electric wire etc. and the cyanate resin composition for sealing material, substrate), the acrylic resin etc. as resist solidifying agent, the additive etc. that adds in other resin etc. can be enumerated.In the present invention, be particularly preferred for the insulating material (comprising the sealing material of printed base plate, coating electric wire etc. and the cyanate resin composition for sealing material, substrate) of electronic material.

As tackiness agent, the tackiness agent of building, for building, automobile, common transaction, therapeutic medical tackiness agent and electronic material can be enumerated.Among these, as the tackiness agent of electronic material, the installation such as the adhesive for semiconductor such as interlaminated adhesive, chip bonding agent, bottom filling, BGA Package (BGA) enhancing bottom filling, anisotropic conductive film (ACF), anisotropy conductiving glue (ACP) increasing the multilager base plates such as laminar substrate can be enumerated and stick with glue agent etc.

As sealing agent, substrate, electrical condenser can be enumerated, transistor, diode, photodiode, unicircuit (IC), the embedding of large-scale integrated circuit (LSI) etc., dipping, transfer molding seals, IC, the chip on board (COB) of LSI class, membrane of flip chip (COF), the perfusion sealing that coil type engages automatically (TAB) etc., the bottom filling of flip-chip etc., quad flat package (QFP), BGA, sealing (comprising enhancing bottom filling) when the IC encapsulation classes such as wafer-level package (CSP) are installed and base plate for packaging etc.In addition, be also suitable for network substrate, module substrate etc. and require functional substrate purposes.

Composition epoxy resin of the present invention is particularly preferred for semiconductor device.

Semiconductor device refers to the IC package group enumerated above.

Semiconductor device of the present invention can by sealing the silicon being arranged at the supporter such as base plate for packaging, tube core with composition epoxy resin of the present invention and obtaining.Described above about mold temperature, forming method.

Embodiment

Then, further illustrate the present invention by embodiment, hereinafter, unless otherwise specified, part is weight part.It should be noted that, the invention is not restricted to these embodiments.

Below, the various analytical procedures used in embodiment are recorded.

Epoxy equivalent (weight): according to JISK7236 (ISO3001)

ICI melt viscosity: according to JISK7117-2 (ISO3219)

Softening temperature: according to JISK7234

Total chlorine: according to JISK7243-3 (ISO21672-3)

Chlorion: according to JISK7243-1 (ISO21672-1)

GPC：

Post (ShodexKF-603, KF-602 × 2, KF-601 × 2)

Be tetrahydrofuran (THF) in conjunction with elutriant

Flow velocity is 0.5ml/ minute

Column temperature is 40 DEG C

Detect: RI (differential refractive detector)

Second-order transition temperature (Tg): TMA thermomechanical determinator TA-instruments system, Q400EM

Measure temperature range: 40 DEG C ~ 280 DEG C

Heat-up rate: 2 DEG C/min

Embodiment 1

Possess stirrer, reflux condensing tube, whipping appts 1L four-hole boiling flask in, (in previously described formula (1), substituent R is all the compound of hydrogen atom to add phenolic compound (DPPI1), SABICBPPPP, purity is more than 99%, residual phenolphthalein 200ppm, iron level <5ppm, fusing point 290 DEG C) 137.7 parts, '-biphenyl diphenol 27.9 parts, Epicholorohydrin 555 parts, dimethyl sulfoxide (DMSO) 139 parts, and by warming-in-water to 50 DEG C.When internal temperature is more than 45 DEG C, add 44 parts, laminar sodium hydroxide with 90 minutes substeps, and then carry out at 45 DEG C 2 hours, at 70 DEG C, carry out the rear reaction of 1 hour.Reaction terminate after, wash, use rotatory evaporator 140 DEG C, decompression under from oil reservoir, excessive Epicholorohydrin equal solvent is distilled.In residue, add hexone 505 parts and dissolve, by washing by removings such as the sodium-chlor of generation, then organic layer being warming up to 70 DEG C.Under agitation add the aqueous sodium hydroxide solution 20 parts of 30 % by weight, and carry out the reaction of 1 hour, then carry out washing till rinse water is neutrality, use rotatory evaporator 180 DEG C, decompression under the hexone etc. in obtained solution is distilled, obtain epoxy resin composition of the present invention (EP1) 210 parts thus.The epoxy equivalent (weight) of the epoxy resin composition obtained is 226g/eq., and softening temperature is 92 DEG C, and ICI melt viscosity is 0.15Pas (150 DEG C), and total chlorine amount is 505ppm, and hydrolyzable chlorine is 480ppm, and chlorion is 0.1ppm, and sodium ion is 0.1ppm.In addition, the compound of above-mentioned formula (1) is 72 area % (GPC), and the epoxide of '-biphenyl diphenol is 16 area % (GPC).In addition, the compound (a) of previously described formula (1) and the epoxide (b) of '-biphenyl diphenol for (a)/(b)=4.5, count 2.64 with molar ratio with mass ratio range.About other structure, comprise the compound of previously described formula (1) each other, '-biphenyl diphenol each other, previously described formula (1) and '-biphenyl diphenol mixing exist and bonding and the compound that obtains.

Synthesis example 1

Possess stirrer, reflux condensing tube, whipping appts 1L four-hole boiling flask in, (in previously described formula (1), substituent R is all the compound of hydrogen atom to add phenolic compound (DPPI1), SABICBPPPP, purity is more than 99%, residual phenolphthalein 200ppm, iron level <5ppm, fusing point 290 DEG C) 295 parts, Epicholorohydrin 971 parts, dimethyl sulfoxide (DMSO) 165 parts, and by warming-in-water to 45 DEG C.When internal temperature is more than 40 DEG C, add 66 parts, laminar sodium hydroxide with 90 minutes substeps, and then carry out at 45 DEG C 2 hours, at 70 DEG C, carry out the rear reaction of 1 hour.Reaction terminate after, wash, use rotatory evaporator 140 DEG C, decompression under from oil reservoir, excessive Epicholorohydrin equal solvent is distilled.In residue, add hexone 760 parts and dissolve, by washing by removings such as the sodium-chlor of generation, then organic layer being warming up to 70 DEG C.Under agitation add the aqueous sodium hydroxide solution 30 parts of 30 % by weight, and carry out the reaction of 1 hour, then carry out washing till rinse water is neutrality, use rotatory evaporator 180 DEG C, decompression under the hexone etc. in obtained solution is distilled, obtain the epoxy resin (EP4) 353 parts with the structure shown in previously described formula (1) thus.The epoxy equivalent (weight) of the epoxy resin obtained is 267g/eq., and softening temperature is 99 DEG C, and ICI melt viscosity is 0.91Pas (150 DEG C), and total chlorine amount is 540ppm, and hydrolyzable chlorine is 430ppm, and chlorion is 0.1ppm, and sodium ion is 0.1ppm.In addition, the compound of the structure of above-mentioned formula (1) is 88 area % (GPC), and remaining 12 area % are that the compound of the structure of previously described formula (1) bonds together the compound obtained.

Embodiment 2 and comparative example 1,2

Use the epoxy resin composition of the present invention (EP1) obtained in embodiment 1 and the epoxy resin (EP2 compared, phenol-biphenylene aralkyl-type epoxy resin Nippon Kayaku K. K NC-3000, EP3, three hydroxyphenyl methane type epoxy resin Nippon Kayaku K. K EPPN-502H), by epoxy resin and solidifying agent (phenolic varnish (bright and change into Industrial Co., Ltd H-1) or phenol aralkyl resin (Mitsui Chemicals, Inc MilexXLC-3L)) equivalent cooperation, and add curing catalysts (curing catalyst, triphenylphosphine (Bei Xing KCC TPP)) and filler as required (fused silica: the filler % in Long gloomy MSR-2122 table processed is the ratio relative to composition epoxy resin entirety), and use mixing roller to mix equably, mixing, thus obtain encapsulating epoxy resin composition.Use mixing machine to be pulverized by this composition epoxy resin, then make sheet with tabletting machine.This is made the present invention after sheet and the composition epoxy resin that compares carries out transfer molding (175 DEG C × 60 seconds), then after demoulding, be cured under the condition of 160 DEG C × 2 hours+180 DEG C × 6 hours, thus obtain evaluation test film.

It should be noted that, the physical property of cured article measures by following main points.In addition, according to the assessment item of cured article, the kind of the solidifying agent used as described in Table 1, the usage quantity of curing catalyst is set as 1% relative to weight epoxy in the sample for evaluating thermotolerance and shrinking percentage, in the sample for evaluating flame retardant resistance, be set as 2% relative to weight epoxy.

< cure shrinkage >

According to JISK-6911 (molding shrinkage)

< flame retardant test >

The judgement of flame retardant resistance: carry out according to UL94.But, sample size be width 12.5mm × length 150mm, thickness tests under being the condition of 0.8mm.

The residual flame time: the total connecing the residual flame time after flame for 10 times is carried out to the sample of 51 group

[table 1]

The excellent in flame retardance of the cured article of comparative example 1, but thermotolerance is low.The thermotolerance of the cured article of comparative example 2 is high, but without flame retardant resistance, perfect combustion in flame retardant test, relative with such result, can high heat resistance and flame retardant resistance be taken into account in the cured article of composition epoxy resin of the present invention.And shrinking percentage during known solidification is also good, excellent in dimensional stability.

Embodiment 3 and comparative example 3

Use the epoxy resin (EP4) of the comparison obtained in the epoxy resin composition of the present invention (EP1) and synthesis example 1 obtained in embodiment 1, by epoxy resin and solidifying agent (phenolic varnish (bright and change into Industrial Co., Ltd H-1) or phenol aralkyl resin (Mitsui Chemicals, Inc MilexXLC-3L)) equivalent cooperation, and add curing catalysts (curing catalyst, triphenylphosphine (Bei Xing KCC TPP)) and filler as required (fused silica: the filler % in Long gloomy MSR-2122 table processed is the ratio relative to epoxy resin integral), and use mixing roller to mix equably, mixing, thus obtain encapsulating epoxy resin composition.Use mixing machine to be pulverized by this composition epoxy resin, then make sheet with tabletting machine.This is made the present invention after sheet and the composition epoxy resin that compares carries out transfer molding (175 DEG C × 60 seconds), then after demoulding, be cured under the condition of 160 DEG C × 2 hours+180 DEG C × 6 hours, thus obtain evaluation test film.

It should be noted that, the physical property of cured article measures by following main points.In addition, according to the assessment item of cured article, the kind of the solidifying agent used as described in Table 2, the usage quantity of curing catalyst, being set as 1% for evaluating in thermotolerance, physical strength and adhering sample relative to weight epoxy, is set as 2% relative to weight epoxy in the sample for evaluating flame retardant resistance.

Thermomechanical determinator: TA-instruments system, Q400EM

Measure temperature range: 40 DEG C ~ 280 DEG C

Heat-up rate: 2 DEG C/min

< pliability test >

According to JISK6911, test at room temperature and 120 DEG C

< stripping strength >

180 DEG C of stripping tests, according to JISK-6854-2, use rolled copper foil

< flame retardant test >

[table 2]

Composition epoxy resin of the present invention has low-down melt viscosity, and its cured article keeps the thermotolerance deriving from the structure of previously described formula (1).And to it is evident that in flame retardant resistance that the residual flame time is short, therefore flame retardant resistance improves, and flexural strength, stripping strength are better compared with the cured article compared with composition epoxy resin in addition.

Synthesis example 2

In the flask possessing stirrer, reflux condensing tube, whipping appts, (in previously described formula (1), substituent R is all the compound of hydrogen atom to add phenolic compound (DPPI1), SABICPPPBP, purity is more than 99%, residual phenolphthalein 200ppm, iron level <5ppm) 256 parts, Epicholorohydrin 971 parts, benzyl trimethyl ammonium chloride 3 parts, and by warming-in-water to 70 DEG C.Drip 49% aqueous sodium hydroxide solution 100 parts wherein with 90 minutes, and then at 70 DEG C, carry out the rear reaction of 4 hours.Reaction terminate after, wash, use rotatory evaporator 140 DEG C, decompression under from oil reservoir, excessive Epicholorohydrin equal solvent is distilled, obtain the epoxy resin (EP5) 290 parts with the structure shown in previously described formula (1) thus.The epoxy equivalent (weight) with the epoxy resin of the structure shown in previously described formula (1) obtained is 297g/eq., and softening temperature is 95 DEG C, and ICI melt viscosity is 0.70Pas (150 DEG C), and total chlorine amount is 10450ppm, and hydrolyzable chlorine is 9700ppm.

Embodiment 4 and comparative example 4

Use the epoxy resin (EP5) of the comparison obtained in the epoxy resin composition of the present invention (EP1) and synthesis example 2 obtained in embodiment 1, by epoxy resin and solidifying agent (phenolic varnish (bright and change into Industrial Co., Ltd H-1)) equivalent cooperation, and interpolation is the triphenylphosphine as curing catalysts (curing catalyst) (Bei Xing KCC TPP) of 1% relative to the weight of epoxy resin), and use mixing roller to mix equably, mixing, thus obtain encapsulating epoxy resin composition.Use mixing machine to be pulverized by this composition epoxy resin, then make sheet with tabletting machine.This is made the composition epoxy resin after sheet and carry out transfer molding (175 DEG C × 60 seconds), then after demoulding, be cured under the condition of 160 DEG C × 2 hours+180 DEG C × 6 hours, thus obtain evaluation test film.

It should be noted that, the physical property of cured article measures by following main points.

Thermomechanical determinator: TA-instruments system, Q400EM

Measure temperature range: 40 DEG C ~ 280 DEG C

Heat-up rate: 2 DEG C/min

[table 3]

Can confirm that composition epoxy resin of the present invention is compared with existing known composition epoxy resin, its viscosity significantly reduces, and the thermotolerance of its cured article is more excellent.

Embodiment 5

In the flask possessing stirrer, reflux condensing tube, whipping appts, add '-biphenyl diphenol 100 parts, Epicholorohydrin 971 parts, methyl alcohol 97 parts, and by warming-in-water to 70 DEG C.Add 41 parts, laminar sodium hydroxide step by step wherein with 90 minutes, and then at 70 DEG C, carry out the rear reaction of 1 hour.After reaction, from solvent based, filter out the epoxy resin of precipitation and the mixture of sodium-chlor.Clean 5 times with 200 parts, the warm water of 70 DEG C, and dry, obtain the epoxy resin (EP7) 121 parts of the '-biphenyl diphenol type shown in previously described formula (5) thus.

The epoxy resin (EP4) obtained in the epoxy resin obtained (EP7) and synthesis example 1 is added in 300 parts of tetrahydrofuran (THF)s with the ratio of 20 parts and 80 parts respectively, by its former state use rotatory evaporator 180 DEG C, decompression under tetrahydrofuran (THF) is distilled, obtain composition epoxy resin of the present invention (EP8) thus.The epoxy resin composition (EP8) obtained is miocrystalline, and its epoxy equivalent (weight) is 247g/eq., and softening temperature is 95 DEG C, and ICI melt viscosity is 0.18Pas (150 DEG C), and total chlorine amount is 1820ppm, and hydrolyzable chlorine is 1670ppm.

Embodiment 6,7

Use the epoxy resin (EP8) obtained in the epoxy resin composition (EP1) and embodiment 5 obtained in previous embodiment 1, epoxy resin and solidifying agent (phenol aralkyl resin (Nippon Kayaku K. K KAYAHARDGPH-65)) equivalent are coordinated, and add curing catalysts (curing catalyst, add relative to the weight of epoxy resin be 2% triphenylphosphine (Bei Xing KCC TPP)) and filler as required (the Long gloomy MSR-2122 processed of fused silica show in filler % be ratio relative to composition epoxy resin entirety), and use mixing roller to mix equably, mixing, thus obtain encapsulating epoxy resin composition.Use mixing machine to be pulverized by this composition epoxy resin, then make sheet with tabletting machine.This is made the composition epoxy resin after sheet and carry out transfer molding (175 DEG C × 60 seconds), then after demoulding, be cured under the condition of 160 DEG C × 2 hours+180 DEG C × 6 hours, thus obtain evaluation test film.

Thermomechanical determinator: TA-instruments system, Q400EM

Measure temperature range: 40 DEG C ~ 280 DEG C

Heat-up rate: 2 DEG C/min

< flame retardant test >

[table 4]

It is evident that the flame retardant resistance of the cured article of composition epoxy resin of the present invention improves, and thermotolerance is good.

According to above result, it is evident that flame retardant resistance, the thermotolerance of epoxy resin composition mobility of the present invention excellence and its cured article are excellent especially, is useful in the known film substrate material (comprising interlayer dielectric) requiring the semiconductor-encapsulating material of multifunction and requirement height filler fillingization.

Embodiment 8

Possess stirrer, reflux condensing tube, whipping appts 1L four-hole boiling flask in, add phenolic compound (according to the method synthesis recorded in the embodiment 7 of English Patent 1158606, purity is more than 99%, residual phenolphthalein 14ppm, iron level <5ppm, fusing point 289-290 DEG C) 137.7 parts, '-biphenyl diphenol 27.9 parts, Epicholorohydrin 470 parts, dimethyl sulfoxide (DMSO) 120 parts, and by warming-in-water to 50 DEG C.When internal temperature is more than 45 DEG C, add 44 parts, laminar sodium hydroxide with 90 minutes substeps, and then carry out at 45 DEG C 2 hours, at 70 DEG C, carry out the rear reaction of 1 hour.Reaction terminate after, use rotatory evaporator 140 DEG C, decompression under excessive Epicholorohydrin equal solvent is distilled.In residue, add hexone 505 parts and dissolve, by washing by removings such as the sodium-chlor of generation, then organic layer being warming up to 70 DEG C.Under agitation add the aqueous sodium hydroxide solution 10 parts of 30 % by weight, and carry out the reaction of 1 hour, then carry out washing till rinse water is neutrality, use rotatory evaporator 180 DEG C, decompression under the hexone etc. in obtained solution is distilled, obtain epoxy resin composition of the present invention (EP13) 205 parts thus.The epoxy equivalent (weight) of the epoxy resin composition obtained is 236g/eq., and softening temperature is 92 DEG C, and ICI melt viscosity is 0.15Pas (150 DEG C), and total chlorine amount is 309ppm, and hydrolyzable chlorine is 278ppm, and chlorion is 0.1ppm, and sodium ion is 0.1ppm.In addition, the compound of above-mentioned formula (1) containing proportional be 65 area % (GPC), the epoxide of '-biphenyl diphenol containing proportional be 15 area % (GPC).In addition, the compound (a) of previously described formula (1) and the epoxide (b) of '-biphenyl diphenol for (a)/(b)=4.3, count 2.55 with molar ratio with mass ratio range.About other structure, comprise the compound of previously described formula (1) each other, '-biphenyl diphenol each other, the compound of previously described formula (1) and '-biphenyl diphenol mixing exist and bonding and the compound that obtains.

Embodiment 9

Possess stirrer, reflux condensing tube, whipping appts 1L four-hole boiling flask in, add phenolic compound (according to the method synthesis recorded in the embodiment 7 of English Patent 1158606, purity is more than 99%, residual phenolphthalein 14ppm, iron level <5ppm, fusing point 289-290 DEG C) 125.7 parts, '-biphenyl diphenol 33.6 parts, Epicholorohydrin 463 parts, dimethyl sulfoxide (DMSO) 116 parts, and by warming-in-water to 50 DEG C.When internal temperature is more than 45 DEG C, add 44 parts, laminar sodium hydroxide with 90 minutes substeps, and then carry out at 45 DEG C 2 hours, at 70 DEG C, carry out the rear reaction of 1 hour.Reaction terminate after, use rotatory evaporator 140 DEG C, decompression under excessive Epicholorohydrin equal solvent is distilled.In residue, add hexone 505 parts and dissolve, by washing by removings such as the sodium-chlor of generation, then organic layer being warming up to 70 DEG C.Under agitation add the aqueous sodium hydroxide solution 10 parts of 30 % by weight, and carry out the reaction of 1 hour, then carry out washing till rinse water is neutrality, use rotatory evaporator 180 DEG C, decompression under the hexone etc. in obtained solution is distilled, obtain epoxy resin composition of the present invention (EP14) 195 parts thus.The epoxy equivalent (weight) of the epoxy resin composition obtained is 225g/eq., and softening temperature is 81 DEG C, and ICI melt viscosity is 0.09Pas (150 DEG C), and total chlorine amount is 377ppm, and hydrolyzable chlorine is 281ppm, and chlorion is 0.1ppm, and sodium ion is 0.1ppm.In addition, the compound of above-mentioned formula (1) containing proportional be 63 area % (GPC), the epoxide of '-biphenyl diphenol containing proportional be 19 area % (GPC).In addition, the compound (a) of previously described formula (1) and the epoxide (b) of '-biphenyl diphenol for (a)/(b)=3.3, count 1.96 with molar ratio with mass ratio range.About other structure, comprise the compound of previously described formula (1) each other, '-biphenyl diphenol each other, the compound of previously described formula (1) and '-biphenyl diphenol mixing exist and bonding and the compound that obtains.

Embodiment 10

Possess stirrer, reflux condensing tube, whipping appts 1L four-hole boiling flask in, add phenolic compound (according to the method synthesis recorded in the embodiment 7 of English Patent 1158606, purity is more than 99%, residual phenolphthalein 14ppm, iron level <5ppm, fusing point 289-290 DEG C) 151.5 parts, '-biphenyl diphenol 21.4 parts, Epicholorohydrin 463 parts, dimethyl sulfoxide (DMSO) 116 parts, and by warming-in-water to 50 DEG C.When internal temperature is more than 45 DEG C, add 44 parts, laminar sodium hydroxide with 90 minutes substeps, and then carry out at 45 DEG C 2 hours, at 70 DEG C, carry out the rear reaction of 1 hour.Reaction terminate after, use rotatory evaporator 140 DEG C, decompression under excessive Epicholorohydrin equal solvent is distilled.In residue, add hexone 505 parts and dissolve, by washing by removings such as the sodium-chlor of generation, then organic layer being warming up to 70 DEG C.Under agitation add the aqueous sodium hydroxide solution 10 parts of 30 % by weight, and carry out the reaction of 1 hour, then carry out washing till rinse water is neutrality, use rotatory evaporator 180 DEG C, decompression under the hexone etc. in obtained solution is distilled, obtain epoxy resin composition of the present invention (EP15) 210 parts thus.The epoxy equivalent (weight) of the epoxy resin composition obtained is 248g/eq., and softening temperature is 83 DEG C, and ICI melt viscosity is 0.31Pas (150 DEG C), and total chlorine amount is 410ppm, and hydrolyzable chlorine is 299ppm, and chlorion is 0.1ppm, and sodium ion is 0.1ppm.In addition, the compound of above-mentioned formula (1) containing proportional be 72 area % (GPC), the epoxide of '-biphenyl diphenol containing proportional be 12 area % (GPC).In addition, the compound (a) of previously described formula (1) and the epoxide (b) of '-biphenyl diphenol for (a)/(b)=6.0, count 3.56 with molar ratio with mass ratio range.About other structure, comprise the compound of previously described formula (1) each other, '-biphenyl diphenol each other, the compound of previously described formula (1) and '-biphenyl diphenol mixing exist and bonding and the compound that obtains.

Embodiment 11 ~ 13 and comparative example 8 ~ 10

Use the epoxy resin composition (EP13 obtained in embodiment 8 ~ 10, 14, 15), epoxy resin 10 ~ 12 (EP10: Japanese chemical drug o-cresol phenolic resin varnish EOCN-1020-70 relatively, EP11: Mitsubishi Chemical biphenyl type epoxy resin YX-4000H, EP12: Japanese chemical drug biphenyl aralkyl epoxy resin NC-3000), by epoxy resin and solidifying agent (phenolic varnish: bright and change into industry H-1 processed) equivalent cooperation, and interpolation is the triphenylphosphine as curing catalyst of 1% relative to the weight of epoxy resin, and use mixing roller to mix equably, mixing, thus obtain encapsulating epoxy resin composition.Use mixing machine to be pulverized by this composition epoxy resin, then make sheet with tabletting machine.This is made the composition epoxy resin after sheet and carry out transfer molding (175 DEG C × 60 seconds), then after demoulding, be cured under the condition of 160 DEG C × 2 hours+180 DEG C × 6 hours, thus obtain evaluation test film.

< Young's modulus, thermotolerance (DMA) >

Measurement of Dynamic Viscoelasticity device: TA-instruments, DMA-2980

Measure temperature range :-30 ~ 280 DEG C

Cooling rate: 2 DEG C/min

Test film size: use the object (thickness about 800 μm) cutting into 5mm × 50mm

Tg: using the peak point of Tan-δ as Tg

[table 5]

	Epoxy resin/the mixture used	Young's modulus/MPa at 250 DEG C	Thermotolerance (tan-δ MAX)/DEG C
				Comparative example 8	EP10	93	193
Comparative example 9	EP11	35	164
				Comparative example 10	EP12	34	153
Embodiment 11	EP13	16	207
				Embodiment 12	EP14	14	201
Embodiment 13	EP15	15	210

Known according to table 5, the cured article of composition epoxy resin of the present invention, compared with the cured article of the composition epoxy resin in the past used, maintains high heat resistance, and the Young's modulus at when measuring under identical DMA 250 DEG C significantly reduces.

Embodiment 14 ~ 16 and comparative example 11

In embodiment 11 ~ 13 and comparative example 10, except solidifying agent being changed to biphenyl type phenol aralkyl resin (Japanese chemical drug KAYAHARDGPH-65), carry out same operation.

[table 6]

	Epoxy resin/the mixture used	Young's modulus/MPa at 250 DEG C	Thermotolerance (tan-δ MAX)/DEG C
				Comparative example 11	EP12	17	141
Embodiment 14	EP13	3	178
				Embodiment 15	EP14	3	175
Embodiment 16	EP15	4	182

Can confirm according to table 6, even if change solidifying agent, the cured article of composition epoxy resin of the present invention also demonstrates lower Young's modulus.

Embodiment 17 and comparative example 12

Use the epoxy resin composition (EP13) obtained in embodiment 8 and the epoxy resin (EP16: three hydroxyphenyl methane type epoxy resin Nippon Kayaku K. K EPPN-501H) compared, each epoxy resin and solidifying agent (biphenyl type phenol aralkyl resin: softening temperature 73 DEG C uses the method synthesis of hydroxy equivalent 207g/eq. recorded in the embodiment 1 of Japanese Unexamined Patent Publication 2003-113225) equivalent are coordinated, add three p-methylphenyl phosphines (be 1% relative to the weight of epoxy resin) as curing catalyst, and use mixing roller to mix equably, mixing, thus obtain encapsulating epoxy resin composition.Use mixing machine to be pulverized by this composition epoxy resin, then make sheet with tabletting machine.This is made the composition epoxy resin after sheet and carry out transfer molding (175 DEG C × 60 seconds), then after demoulding, be cured under the condition of 160 DEG C × 2 hours+180 DEG C × 6 hours, thus obtain evaluation test film, and carry out following mensuration.

Thermomechanical determinator: TA-instruments system, Q400EM

Measure temperature range: 40 DEG C ~ 280 DEG C

Heat-up rate: 2 DEG C/min

Measurement of Dynamic Viscoelasticity device: TA-instruments system, DMA-2980

Measure temperature range :-30 DEG C ~ 280 DEG C

Cooling rate: 2 DEG C/min

Test film size: use the object (thickness about 800 μm) cutting into 5mm × 50mm.

Analysis condition Tg: using the peak point (tan-δ MAX) of the Tan-δ in DMA mensuration as Tg.

The < condition determination of resistance to thermal decomposition characteristic >

The part circulation grinding machine of obtained test film is pulverized, makes powdery, sieve, collect by 100 μm of sieve apertures and the particle diameter stayed on 75 μm of sieve apertures, get 5-10mg sample, confirm thermal weight loss temperature with TG-DTA, the weightless temperature using 5% is as index.

Carry out measuring (Td5) with TG-DTA

Working sample: powdery (by 100 μm of sieve apertures and stay on 75 μm of sieve apertures) 5-10mg.

Condition determination: heat-up rate 10 DEG C/min, air-flow 200ml/ minute, measures 5% weightless temperature.

[table 7]

Solidifying agent uses biphenyl type phenol aralkyl resin

		Embodiment 17	Comparative example 12
					Epoxy resin/the mixture used	EP13	EP16
TMA	Tg(℃)	165	156
				DMA	tan-δMAX	185	180
TG-DTA	5% heat decomposition temperature	340	321

Known according to table 7, the cured article of composition epoxy resin of the present invention not only has high heat resistance, also has pyrolytic decomposition characteristic.

Embodiment 18

Possess stirrer, reflux condensing tube, whipping appts 1L four-hole boiling flask in, add phenolic compound (according to the method synthesis recorded in the embodiment 7 of English Patent 1158606, purity is more than 99%, residual phenolphthalein 14ppm, iron level <5ppm, fusing point 289-290 DEG C) 138 parts, '-biphenyl diphenol 28 parts, Epicholorohydrin 463 parts, dimethyl sulfoxide (DMSO) 115 parts, and by warming-in-water to 50 DEG C.When internal temperature is more than 45 DEG C, add 44 parts, laminar sodium hydroxide with 90 minutes substeps, and then carry out at 45 DEG C 2 hours, at 70 DEG C, carry out the rear reaction of 1 hour.Reaction terminate after, use rotatory evaporator 140 DEG C, decompression under excessive Epicholorohydrin equal solvent is distilled.In residue, add hexone 505 parts and dissolve, by washing by removings such as the sodium-chlor of generation, then organic layer being warming up to 70 DEG C.Under agitation add the aqueous sodium hydroxide solution 10 parts of 30 % by weight, and carry out the reaction of 1 hour, then carry out washing till rinse water is neutrality, use rotatory evaporator 180 DEG C, decompression under the hexone etc. in obtained solution is distilled, obtain epoxy resin (EP17) 189 parts thus.The epoxy equivalent (weight) of the epoxy resin obtained is 241g/eq., and softening temperature is 85.3 DEG C, and ICI melt viscosity is 0.15Pas (150 DEG C), and total chlorine amount is 460ppm, and hydrolyzable chlorine is 394ppm, and chlorion is 0.6ppm, and sodium ion is 0.7ppm.In addition, the structure of above-mentioned formula (1) is 69.5 area % (GPC), and the epoxide of '-biphenyl diphenol is 15.0 area % (GPC).In addition, the compound (a) of previously described formula (1) and the epoxide (b) of '-biphenyl diphenol for (a)/(b)=4.6, count 2.73 with molar ratio with mass ratio range.About other structure, comprise the compound of previously described formula (1) each other, '-biphenyl diphenol each other, the compound of previously described formula (1) and '-biphenyl diphenol mixing exist and bonding and the compound that obtains.

Embodiment 19

Possess stirrer, reflux condensing tube, whipping appts 1L four-hole boiling flask in, add phenolic compound (according to the method synthesis recorded in the embodiment 7 of English Patent 1158606, purity is more than 99%, residual phenolphthalein 14ppm, iron level <5ppm, fusing point 289-290 DEG C) 126 parts, '-biphenyl diphenol 34 parts, Epicholorohydrin 463 parts, dimethyl sulfoxide (DMSO) 116 parts, and by warming-in-water to 50 DEG C.When internal temperature is more than 45 DEG C, add 43 parts, laminar sodium hydroxide with 90 minutes substeps, and then carry out at 45 DEG C 2 hours, at 70 DEG C, carry out the rear reaction of 1 hour.Reaction terminate after, use rotatory evaporator 140 DEG C, decompression under excessive Epicholorohydrin equal solvent is distilled.In residue, add hexone 600 parts and make it dissolve, by washing by removings such as the sodium-chlor of generation, then organic layer being warming up to 70 DEG C.Under agitation add the aqueous sodium hydroxide solution 10 parts of 30 % by weight, and carry out the reaction of 1 hour, then carry out washing till rinse water is neutrality, use rotatory evaporator 180 DEG C, decompression under the hexone etc. in obtained solution is distilled, obtain epoxy resin (EP18) 190 parts thus.The epoxy equivalent (weight) of the epoxy resin obtained is 235g/eq., and softening temperature is 93.0 DEG C, and ICI melt viscosity is 0.09Pas (150 DEG C), and total chlorine amount is 467ppm, and hydrolyzable chlorine is 388ppm, and chlorion is 0.3ppm, and sodium ion is 0.4ppm.In addition, the structure of above-mentioned formula (1) is 65.0 area % (GPC), and the epoxide of '-biphenyl diphenol is 18.6 area % (GPC).In addition, the compound (a) of previously described formula (1) and the epoxide (b) of '-biphenyl diphenol for (a)/(b)=3.5, count 2.08 with molar ratio with mass ratio range.About other structure, comprise the compound of previously described formula (1) each other, '-biphenyl diphenol each other, the compound of previously described formula (1) and '-biphenyl diphenol mixing exist and bonding and the compound that obtains.

Comparative example 13

Possess stirrer, reflux condensing tube, whipping appts 1L four-hole boiling flask in, add phenolic compound (according to the method synthesis recorded in the embodiment 7 of English Patent 1158606, purity is more than 99%, residual phenolphthalein 14ppm, iron level <5ppm, fusing point 289-290 DEG C) 102 parts, '-biphenyl diphenol 45 parts, Epicholorohydrin 462 parts, dimethyl sulfoxide (DMSO) 116 parts, and by warming-in-water to 50 DEG C.When internal temperature is more than 45 DEG C, add 44 parts, laminar sodium hydroxide with 90 minutes substeps, and then carry out at 45 DEG C 2 hours, at 70 DEG C, carry out the rear reaction of 1 hour.Reaction terminate after, use rotatory evaporator 140 DEG C, decompression under excessive Epicholorohydrin equal solvent is distilled.In residue, add hexone 505 parts and dissolve, by washing by removings such as the sodium-chlor of generation, then organic layer being warming up to 70 DEG C.Under agitation add the aqueous sodium hydroxide solution 10 parts of 30 % by weight, and carry out the reaction of 1 hour, then carry out washing till rinse water is neutrality, use rotatory evaporator 180 DEG C, decompression under the hexone etc. in obtained solution is distilled, obtain epoxy resin (EP19) 177 parts thus.The epoxy equivalent (weight) of the epoxy resin obtained is 220g/eq., and softening temperature is 109 DEG C, and ICI melt viscosity is 0.03Pas (150 DEG C), and total chlorine amount is 457ppm, and hydrolyzable chlorine is 401ppm, and chlorion is 0.9ppm, and sodium ion is 0.8ppm.In addition, the structure of above-mentioned formula (1) is 58.0 area % (GPC), and the epoxide of '-biphenyl diphenol is 26.8 area % (GPC).In addition, the compound (a) of previously described formula (1) and the epoxide (b) of '-biphenyl diphenol for (a)/(b)=2.2, count 1.31 with molar ratio with mass ratio range.About other structure, mainly comprise the compound of previously described formula (1) each other, '-biphenyl diphenol each other, the compound of previously described formula (1) and '-biphenyl diphenol mixing exist and bonding and the compound that obtains.

Embodiment 20 ~ 21, comparative example 14

Use the epoxy resin composition (EP17,18,19) obtained in embodiment 18,19 and comparative example 13, biphenyl type phenol aralkyl resin (Japanese chemical drug KAYAHARDGPH-65) is coordinated as solidifying agent equivalent, interpolation is the curing catalyst (Xinghua, triphenylphosphine north length of schooling) of 1% relative to the weight of epoxy resin, and use mixing roller to mix equably, mixing, thus obtain composition epoxy resin.Use mixing machine to be pulverized by this composition epoxy resin, then make sheet with tabletting machine.This is made the composition epoxy resin after sheet and carry out transfer molding (175 DEG C × 60 seconds), then after demoulding, be cured under the condition of 160 DEG C × 2 hours+180 DEG C × 6 hours, thus obtain evaluation test film.

Use this evaluation test film, evaluate shrinkage rate and thermotolerance.Shrinking percentage by measure the forming composition that obtains with the difference of mould and confirm the size of molding shrinkage.Thermotolerance measures by following main points.

Thermomechanical determinator: TA-instruments system, Q400EM

Measure temperature range: 40 DEG C ~ 280 DEG C

Heat-up rate: 2 DEG C/min

< cure shrinkage >

According to JISK-6911 (molding shrinkage)

[table 8]

Confirm according to table 8, compared to epoxy resin composition of the present invention, the molding shrinkage employing the cured article of the epoxy resin composition compared becomes large.

Embodiment 22

For the composition epoxy resin of the present invention of the composition of aforesaid embodiment 6, carry out the test that proper alignment is anti-thread breakage.96PinQFP (chip size: 7mm × 7mm × thickness 0.1mm shown in the Fig. 1 made of copper being metal by surface, package dimension: 14mm × 14mm × thickness 1.35mm) lead frame (use object) before use by acetone abundant wipe surfaces after decontamination is as the anti-thread breakage evaluation lead frame of proper alignment, lead frame is arranged on transfer molding mould, composition epoxy resin transfer molding after sheet (175 DEG C × 60 seconds) will be made as described above, then be cured under the condition of 160 DEG C × 2 hours+180 DEG C × 6 hours after demoulding, thus obtain 3 samples (Fig. 2) of the anti-thread breakage test evaluation test film of proper alignment.For 3 test films obtained, place 5 hours in the thermostatic bath of relative humidity being set as 60 DEG C/85%RH and make its moisture absorption, then after this moisture absorption, carrying out the Reflow Soldering test in 280 DEG C × 10 seconds.For the generation of the encapsulation crackle produced by thermal shocking at this moment by visual confirmation crackle, arbitrary sample does not all see crackle.

Embodiment 23,24

By the epoxy resin composition of the present invention (EP18, EP19) obtained in embodiment 18,19 and solidifying agent (phenolic varnish (bright and change into Industrial Co., Ltd H-1)) equivalent cooperation, and interpolation is the triphenylphosphine as curing catalysts (curing catalyst) (Bei Xing KCC TPP) of 1% relative to the weight of epoxy resin, and use mixing roller to mix equably, mixing, thus obtain encapsulating epoxy resin composition.Use mixing machine to be pulverized by this composition epoxy resin, then make sheet with tabletting machine.This is made the composition epoxy resin after sheet and carry out transfer molding (175 DEG C × 60 seconds), then after demoulding, be cured under the condition of 160 DEG C × 2 hours+180 DEG C × 6 hours, thus obtain evaluation test film.Evaluation result is as shown in table 9.

Thermotolerance, dimensional stability (linear expansion velocity of variation)

Thermomechanical determinator: TA-instruments system, Q400EM

Measure temperature range: 40 DEG C ~ 280 DEG C

Heat-up rate: 2 DEG C/min

Measurement of Dynamic Viscoelasticity device: TA-instruments system, DMA-2980

Measure temperature range :-30 ~ 280 DEG C

Cooling rate: 2 DEG C/min

Test film size: use the test film (thickness about 800 μm) cutting into 5mm × 50mm.

Analysis condition Tg: using the peak point (MAX) of the Tan-δ in DMA mensuration as Tg.

< specific inductivity, loss tangent >

Use rhumbatron, and the fixture of the 1GHz using Northeast electronic application chemistry to manufacture carries out measuring (fixture that use cuts into 0.5mm × 70mm)

< pliability test >

According to JISK6911, test at room temperature and 120 DEG C

< stripping strength >

180 DEG C of stripping tests, according to JISK-6854-2, use rolled copper foil

< water suction, rate of moisture absorption >

By 85 DEG C, place 24 hours in the hot and humid groove of 85% after weight increase % and evaluate.

<KIC: destroy toughness test >

Compact tension specimen, according to ASTME-399

[table 9]

From this result, epoxy resin of the present invention obtains to be had high heat resistance and has high mechanical characteristics, low linear expansion and the cured article relative to the high moisture-proof of the level of thermotolerance, water-proofing performance, excellent dielectric characteristics.

Describe the present invention in detail with reference to specific mode, but without departing from the spirit and scope of the present invention, can carry out various changes and correction, this is apparent for those skilled in the art.

It should be noted that, the Japanese patent application (Patent 2014-143791) that the application proposes based on the Japanese patent application (Patent 2013-186859) proposed on September 10th, 2013 and on July 14th, 2014, its entirety has been incorporated by reference.In addition, all references of quoting herein are incorporated in this specification sheets all as a whole.

Industrial applicability

The characteristic that epoxy resin composition of the present invention is excellent because its cured article has in thermotolerance, water absorption character and flame retardant resistance, therefore useful in electrical and electronic parts insulating material and plywood (printed wiring board, increase laminar substrate etc.), various matrix materials, tackiness agent, coating etc. headed by CFRP.

Claims

1. an epoxy resin composition, it contains the epoxide of the '-biphenyl diphenol of the compound and 5% ~ 30% (the same) shown in following formula (1) of 60% ~ 75% (gel permeation chromatography area %),

2. epoxy resin composition as claimed in claim 1, its softening temperature is 80 DEG C ~ 100 DEG C.

3., as epoxy resin composition according to claim 1 or claim 2, the ICI melt viscosity (cone-plate method) at its 150 DEG C is 0.08 ~ 0.35Pas.

4. a composition epoxy resin, it contains epoxy resin composition according to any one of claims 1 to 3 and solidifying agent.

5. a composition epoxy resin, it contains epoxy resin composition according to any one of claims 1 to 3 and curing catalysts.

6. a cured article, it is by obtaining the epoxy resin composition described in claim 4 or 5.

7. a semiconductor device, semi-conductor chip sealing obtains by using the composition epoxy resin described in claim 4 or 5 by it.