CN105980441B

CN105980441B - Epoxy resin composition, curable resin composition, its solidfied material and semiconductor device

Info

Publication number: CN105980441B
Application number: CN201580008235.8A
Authority: CN
Inventors: 中西政隆; 川野裕介
Original assignee: Nippon Kayaku Co Ltd
Current assignee: Nippon Kayaku Co Ltd
Priority date: 2014-03-11
Filing date: 2015-03-10
Publication date: 2018-05-08
Anticipated expiration: 2035-03-10
Also published as: CN105980441A; JP2015172105A; TW201542616A; TWI647249B; WO2015137299A1

Abstract

Purpose is to provide the excellent epoxy resin composition of heat resistance, thermal decomposition characteristic, curable resin composition, its solidfied material.The epoxy resin composition of the present invention contains the compound represented by compound and following formula (2) represented by following formula (1), the content of two functional epoxy resins measures the area percentage in spectrogram with gel permeation chromatography (GPC) and is calculated as below 20 area %, the softening point of the epoxy resin composition is 80 DEG C~110 DEG C (according to ISO 4,625 2), (in formula (1), n represents repeat number, n be calculated as with average value 2~10 number, in addition, not every A is identical)

Description

Epoxy resin composition, curable resin composition, its solidfied material and semiconductor device

Technical field

The present invention relates to the epoxy resin composition of the excellent solidfied material of offer heat resistance and resistance to thermal decomposition characteristic.

In addition, the present invention relates to be suitable as requiring H.D electric and electronic material applications, be particularly the close of semiconductor Closure material, the epoxy resin composition of film substrate material, curable resin composition and its solidfied material and curable by this The semiconductor device that resin combination obtains.

Background technology

Curable resin composition is due to workability and its excellent electrical characteristics of solidfied material, heat resistance, adhesivity, moisture-proof Property (water resistance) etc. and be widely used in the fields such as electrical/electronic components, structural material, adhesive, coating.

But in recent years, as it develops in electrical/electronic field, it is desirable to further improve including resin combination Moisture-proof, adhesiveness, dielectric property including high purity, in order to make highly-filled low of filler (inorganic or organic filler) The various characteristics such as viscosity, reactive raising in order to shorten forming period.In addition, as structural material in space flight and aviation material Light weight and the excellent material of mechanical properties are required in material, leisure/sports apparatus purposes etc..Particularly in recent years, from energy saving sight Point considers that the concern for power device gradually increases (non-patent literature 1).

In the past, be mainstream with Silica hydrogel sealing for power device, but from now on, in terms of productivity, cost with And its from the aspect of intensity, reliability, want significantly to promote the transformation to thermosetting resin from this day.In addition, the power device The actuation temperature of part has the tendency risen year by year, is designed in silicon based semiconductor with more than 150 DEG C of actuation temperature, it is desirable to super Cross 150 DEG C of very high heat-resisting (non-patent literature 2).

Prior art literature

Non-patent literature

Non-patent literature 1：" 2008, STRJ reports, semiconductor development plan special commission, 2008 annual reports " (" STRJ Reported in 2008 accuse half Guide Ti ロー De マップ Graduate Door Wei STAFF and can accuse the year of Heisei 20 Reported "), the 8th chapter, p1-17, [online], in March, 2009, J EITA (corporations) electronic information technology industry association, semiconductor development plan special commission, [retrieval on May 30th, 2012], network address<URL:http://strj-jeita.elisasp.net/strj/nenjih oukoku-2008.cfm>

Non-patent literature 2：High storehouse letter etc., Matsushita Electrician technical report, car related device technology, vehicle-mounted high-temperature operation IC (Trucks Seki Even デバイス skill Intraoperative Trucks Load high temperature Move makees IC), the 74th phase, Japan, 31 days, 35-40 pages May in 2001

The content of the invention

Problem to be solved by the invention

The high epoxy resin of heat resistance is typically the high epoxy resin of crosslink density.

But the water absorption rate of the high epoxy resin of crosslink density is high, crisp, thermal decomposition characteristic is deteriorated.In addition electrical property has change The tendency of difference.In the case of the semiconductor of high temperature driven, not only thermal decomposition characteristic is important, and electrical characteristics are also important, therefore not It is preferred that.These characteristics are improved when reducing crosslink density, but heat resistance declines, and glass transition temperature (Tg) reduces.Driving In the case that temperature exceedes glass transition temperature, usually volume resistivity reduces at a temperature of more than Tg, therefore electricity Characteristic is deteriorated.

It is sometimes heat-resisting using being improved by increasing the molecular weight of resin itself in the case where attempting to improve above-mentioned characteristic Property method, but since viscosity becomes very high, need that whole semiconductor is completely covered in the sealing of semiconductor, therefore produce The unfilled parts such as raw gap, are not suitable as semiconductor-encapsulating material.

That is, it is an object of the invention to provide a kind of mobility and heat resistance, heat for having and being adapted to encapsulating semiconductor The excellent epoxy resin of resolution characteristic.

The means used to solve the problem

As a result the present inventor completes the present invention in view of the actual conditions conduct in-depth research.

I.e. the present invention relates to following (1)~(8).

(1) a kind of epoxy resin composition, it contains represented by compound and following formula (2) represented by following formula (1) Compound, the content of two functional epoxy resins measures the area percentage in spectrogram with gel permeation chromatography (GPC) and is calculated as Below 20 area %, and the softening point of the epoxy resin composition is 80 DEG C~110 DEG C (according to ISO 4625-2),

(in formula (1), n represent repeat number, n be calculated as with average value 2~10 number, in addition, not every A all phases Together)

(2) epoxy resin composition as described in preceding paragraph (1), wherein, the content of the compound represented by the formula (2) with Area percentage in gel permeation chromatography (GPC) measure spectrogram is calculated as the area % of 2 area %~18.

(3) epoxy resin composition as described in preceding paragraph (1) or (2), it is by being 120 DEG C~150 DEG C by softening point Naphthols-cresols mixing novolac resin mixes with 4,4 '-'-biphenyl diphenol and reacts and obtain with epihalohydrin in alkaline conditions Arrive.

(4) epoxy resin composition as any one of preceding paragraph (1)~(3), its melt viscosity at 150 DEG C are More than 0.05Pas and below 0.5Pas.

(5) a kind of curable resin composition, it contains the epoxy resin mixing any one of preceding paragraph (1)~(4) Thing and curing agent.

(6) a kind of curable resin composition, it contains the epoxy resin mixing any one of preceding paragraph (1)~(4) Thing and polymerization catalyst.

(7) a kind of solidfied material, it is obtained by the way that the curable resin composition described in preceding paragraph (5) or (6) is cured.

(8) a kind of semiconductor device, it by the curable resin composition described in preceding paragraph (5) or (6) by being configured to grain Shape or piece (tablet) shape and then covering semiconductor chip and more than 175 DEG C and less than 250 DEG C are formed and obtain.

Invention effect

The epoxy resin composition of the present invention provide the excellent curable resin composition of mobility, heat resistance, heat-resisting point Solve the solidfied material of excellent.In addition curable resin composition of the invention is used in encapsulating semiconductor, particularly power device Semiconductor element sealing in it is highly useful, good semiconductor device can be obtained.

Embodiment

The epoxy resin composition of the present invention contains naphthols-cresols mixing phenolic resin varnish type epoxy resin and 4,4 '-two rings Oxygen propoxyl group biphenyl.

In the epoxy resin composition of the present invention, using naphthols-cresols mixing phenolic resin varnish type epoxy resin as mainly Component, 4 in epoxy resin composition, (gel oozes the area % of the content preferably 2 area % of 4 '-diepoxy propoxyl group biphenyl~18 Saturating chromatography (detector：RI the area percentage in measure spectrogram)), the area of more preferably 2 area %~17.5 % is especially excellent Select the area % of 3 area %~17.

Containing 4,4 '-diepoxy propoxyl group biphenyl helps to improve mobility, by making its content be below 18 area %, Resistance to thermal decomposition characteristic, water-proofing performance are more effective, therefore preferably.

As the shape of the epoxy resin composition of the present invention, in the case of mixed uniformly, preferably there is band crystallinity Solid resin shape, the problem of formability from operability and when curing of softening point (according to ISO 4625-2) at this time considers For 80 DEG C~110 DEG C, preferably 100 DEG C~110 DEG C.

Easily produced when common resin is handled at room temperature it is viscous, preferably at least at a temperature of than softening point low 50 DEG C Use.Especially with regard to electronic material, it is contemplated that produced in Southeast Asia, it is contemplated that indoor more than 40 DEG C therefore soft by making Change point more than 100 DEG C, not only processing at room temperature becomes very easy, but also crushing, mixing are excellent, therefore preferably.But In the case where softening point is excessive, when not only having mixing the problem of endless running down, but also wanting to make resin melting and excessive When applying temperature, the possibility that when mixing reacts is high.Therefore the upper limit of softening point is 110 DEG C.

For the epoxy resin composition of the present invention, its melt viscosity at 150 DEG C be preferably 1.0Pas with Under, more preferably more than 0.05Pas and below 0.5Pas, particularly preferably more than 0.1Pas and 0.5Pas with Under.

Since line is thicker particularly in power device, can also be sealed even if viscosity height, but exceed During 1.0Pas, there is the tendency that formability goes wrong.

The epoxy resin composition of the present invention can uniformly mix each epoxy resin, in the present invention, preferably by that will make For naphthols-cresols mixing novolac resin and 4 of phenolic resin blend, 4 '-'-biphenyl diphenol mixes, and in alkaline conditions React and obtain with epihalohydrin.

In the case of simple mixing, the epoxidation and 4 of naphthols-cresols mixing novolaks, 4 '-biphenyl two are carried out respectively The epoxidation of phenol.In this case, it is partially polymerized each other and 4 that naphthols-cresols mixing novolaks occur in epoxidation, 4 '- The reaction that '-biphenyl diphenol is partly bonded each other.In this case, cresol novolak is mutual partially polymerized makes viscosity quickly Rise.In addition, 4, the crystallinity for the material that 4 '-'-biphenyl diphenol bonds together is very high, and poor compatibility, therefore, it is difficult to uniform Dissolving.In addition the reduction of heat resistance is also triggered.

On the other hand, carry out at the same time it is epoxidised in the case of, by can be formed naphthols-cresols mixing novolaks and Compound obtained from part is bonded occurs for '-biphenyl diphenol, so as to suppress the mutual polymerization of cresol novolak, promotes low viscosity Change.In addition, this compound has the characteristic of cresol novolak and both '-biphenyl diphenols, it is excellent in compatibility, and can be into one Step suppresses the reduction of heat resistance.

The naphthols used in the present invention-cresols mixing novolaks are (hereinafter also referred to as the phenolic aldehyde tree used in the present invention Fat) with naphthols (1- naphthols and/or beta naphthal), cresols (not limiting the position of substitution) and formaldehyde synthesis equivalent (refer to formalin, Paraformaldehyde etc..) synthesized for neccessary composition.

The phenolic resin used in the present invention can obtain in the following manner：Naphthols and cresols are being enumerated as water, first The ketones such as the aromatic hydrocarbon such as benzene, dimethylbenzene, methylisobutylketone, methyl ethyl ketone, cyclohexanone, cyclopentanone, methanol, ethanol, propyl alcohol etc. Dissolving in alcohols solvent (or water), or mixed with two coating systems, and it is anti-with formaldehyde to synthesize equivalent under acid or alkaline conditions Should.Using in the case of solvent, its usage amount relative to 100 parts by weight of total amount of naphthols and cresols be usually 5 parts by weight~ The scope of the parts by weight of 500 parts by weight, preferably 10 parts by weight~300.

As catalyst, acid or alkalescence any catalyst can be used.

As the concrete example for the acidic catalyst that can be used, can enumerate：The mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid；Grass The organic acids such as acid, toluenesulfonic acid, acetic acid；The heteropoly acid of wolframic acid etc., activated clay, inorganic acid, stannic chloride, zinc chloride, chlorination The acid organic and inorganic Barbiturates of iron etc., other displays；Urged Deng the acidity usually used in novolac resin manufacture purposes Agent etc..

As the concrete example for the basic catalyst that can be used, can enumerate：Lithium hydroxide, sodium hydroxide, potassium hydroxide Deng alkali metal hydroxide；The alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide；Sodium methoxide, sodium ethoxide, potassium methoxide, second The alkali metal alkoxides such as potassium alcoholate, potassium tert-butoxide；The alkaline-earth metal alkyl oxides such as magnesium methoxide, magnesium ethylate；Deng.

It can in addition contain which using amines catalyst, triethylamine, monoethanolamine, pyridine, piperidines, morpholine etc. can be enumerated.Especially It is that can also be also used as solvent in the case where using amines catalyst.

These catalyst are not limited to catalyst enumerated above, can be used alone can also and with two or more.

In the present invention, following three processes are particularly carried out：(a) novolaksization of naphthols and cresols are reacted；(b) naphthols Dimer (following formula (3)) pyrolysis；(c) formaldehyde equivalent is added, and is bonded to it and has used in process (b) Decompose the reaction of naphthols-cresol novolak of the naphthols of generation.

By undergoing the process, it is possible to reduce the dimer of the structure represented by following formula (4), and manufacture makes in the present invention The raw material of epoxy resin.

By this process, the epoxy resin that can cause becomes the excellent epoxy resin of resistance to thermal decomposition characteristic.Need Bright, process (b), (c) can be carried out at the same time, and catalyst at this time is the acidic catalyst shown in above-mentioned, if process (a) is Acidity, then can be used as it is the catalyst, or can also add acid catalyst, if process (a) is alkalescence, preferably in process (a) add acidic catalyst after and react in acid condition.It should be noted that for these catalyst, no matter respectively It it is preferably less than 2 times relative to the naphthols, the total mole number of cresols that at most use from for acid or alkalescence.In addition, in subtracting With when the amount that consumes in the case of, be usually the molar equivalent % of 0.01 molar equivalent %~0.3, more if acidic catalyst It is preferred that 0.01 molar equivalent %~0.25 molar equivalent %；If basic catalyst, then relative to the total moles of naphthols, cresols Number, it is often preferred that the molar equivalent % of 0.5 molar equivalent %~1.3, particularly preferred 0.5 molar equivalent %~1.1 mole are worked as Measure %.For reaction temperature, preferably it is controlled in process (a) with 0 DEG C~110 DEG C, especially for diminution molecule Amount distribution, preferably carries out first order reaction at 0 DEG C~70 DEG C, then carries out second order reaction at 30 DEG C~110 DEG C.In addition, When carrying out molecular weight control, following methods can also be used：Use basic catalysts more than 1.0 molar equivalent %, selectivity Ground manufactures the monomethylol form of naphthols, and by making its reaction control molecular weight distribution.

Here, the novolak type phenol tree as obtained from reacting the novolaksization of naphthols and cresols of process (a) In fat, weight average molecular weight preferably 500~1500.Here, structure represented by structure and formula (4) represented by above-mentioned formula (3) Total amount is preferably below 10 area % in terms of the area percentage in spectrogram is measured by GPC, particularly preferably below 8 area %.Separately Outside, the structure represented by the structure and formula (4) particularly preferably represented by above-mentioned formula (3) is respectively below 5 area %.For so Material, by undergoing (b) and (c) process, can more obtain target resin.

It should be noted that the naphthols used in process (a) is preferably using alpha-Naphthol and the mixture of betanaphthol.

(refer to formalin, paraformaldehyde etc. as the formaldehyde synthesis equivalent used in the process (a).) use Amount, is preferably 0.5 mole times~1.5 moles times, particularly preferably 0.7 mole times~1.2 moles times relative to the naphthols used. It should be noted that it is preferably less than 1.0 moles times, particularly preferred 0.5 mole times relative to the total mole number of naphthols and cresols ~0.95 mole times.

As the usage amount of the formaldehyde synthesis equivalent used in the process (c), residual naphthols or described is also depended on The residual quantity of structure represented by formula (4), usually can be with 1 weight relative to the formaldehyde synthesis equivalent used in process (a) Measure the ratio addition of the weight % of %~20.The weight % of more preferably 1 weight %~15.

Naphthols used in the phenolic resin blend used in the present invention obtained by this way -cresols mixing phenolic aldehyde Varnish can not also be purified according to purposes and use, but usually neutralization reaction mixture after the completion of reaction, then by Heating decompression is lower to be removed unreacting material and solvent and purifies and use.It should be noted that this neutralization step can add The salt such as various bases, phosphate or buffer solution etc., can also be washed etc., and with both when it is easier and effective.In addition, In the case where naphthols is not over reaction fully consumption, preferably made by bubbling of the inert gases such as thin-film distillation, nitrogen etc. Remaining naphthols amount is less than 2%, is preferably less than 1%.

As naphthols used in the phenolic resin blend used in the present invention obtained by this way -cresols mixing Novolaks, softening point are preferably 100 DEG C~140 DEG C, and hydroxyl equivalent is preferably 140g/eq.~160g/eq..

Formula (3) described in the phenolic resin used in the present invention, the content of the compound of the structure of formula (4) are with (solidifying in GPC Glue penetration chromatography, detector：RI the area percentage meter) measured in spectrogram is respectively below 12 area %, it is possible thereby to carry High resistance to thermal decomposition characteristic, therefore preferably.In the present invention preferably below 10 area %, particularly preferred below 6 area %.In addition it is preferred Its total amount is below 17 area %.It is possible thereby to easily meet the characteristic of the epoxy resin composition of the present invention, resistance to thermal decomposition Characteristic and heat resistance are more excellent.

It is more than 99% on the preferred purity of 4,4 '-'-biphenyl diphenol.In the case where being partially oxidized by oxidation etc., by In as a functional compound, heat resistance reduction may result in.

As the phenolic resin and the mixture of 4,4 '-'-biphenyl diphenol that are used in the present invention and the reaction side of epihalohydrin Method, is not particularly limited, and records an example of the synthetic method below.

In the reaction of epoxy resin composition of the present invention is obtained, pass through the phenolic resin (BN) for making to use in the present invention React with 4,4 '-'-biphenyl diphenol (BP) while with epihalohydrin and obtain epoxy resin composition.Here, as (BN) and (BP) Ratio (weight ratio) preferably BN/BP=1~70, more preferably 4~62, particularly preferred 4.5~22.From heat resistance, anti-flammability, stream This preferred scope from the aspect of the balance of dynamic property.(it should be noted that the mixture of following (BN) and (BP) are also referred to as this hair The bright middle phenolic resin blend used.)

In the reaction of epoxy resin composition of the present invention is obtained, preferably industrially it is readily available as epihalohydrin Epichlorohydrin.The usage amount of epihalohydrin is usually 3.0 relative to 1 mole of the hydroxyl of the phenolic resin blend used in the present invention Mole~15 moles, preferably 3.0 moles~10 moles, more preferably 3.5 moles~8.5 moles, particularly preferred 4.0 moles~6.0 Mole.

During less than 3.0 moles, epoxide equivalent becomes larger sometimes, in addition, the workability of the epoxy resin obtained sometimes is deteriorated, surpasses When crossing 15 moles, quantity of solvent is excessive sometimes.

Particularly in the present invention, naphthols-cresols mixed phenol used in the phenolic resin blend used in the present invention The reaction product of Novolac and '-biphenyl diphenol contributes to characteristic, therefore preferably less than 6.0 moles of epichlorohydrin amount.It is possible thereby to adjust Section naphthols-cresols mixing novolaks are bonded with '-biphenyl diphenol.

At this time, the introduction volume as '-biphenyl diphenol to naphthols-cresols mixing novolac resin, is measured in spectrogram with GPC Area percentage meter be preferably the area % of 1 area %~10, the area % of particularly preferably 1 area %~8.This amount is except can be with Reason when feeding intake beyond substantially being calculated by the molal quantity and GPC data of '-biphenyl diphenol and cresols with NMR etc., when can also be by synthesizing Substantially calculated by the area % of upper reactive ratio and GPC.As specific computational methods, theoretic two are confirmed by inventory The amount of glycidoxy biphenyl.On the other hand, according to the area of GPC ratio, with the peak area (detection of diepoxy propoxyl group biphenyl Device：RI content) is confirmed.Its difference is introduction volume.Only '-biphenyl diphenol when, '-biphenyl diphenol it is mutual bonding be it is preferential, still Under conditions of more than the amount of cresol novolak, cresol novolak is preferentially introduced to according to probability theory, therefore judge the difference Value is judged as introduction volume.It should be noted that in the measure using NMR, according to the proton of each benzene nucleus or the peak area ratio of carbon Rate calculates molar ratio.The amount of theoretic diepoxy propoxyl group biphenyl is confirmed according to the molar ratio.It is same as described above below. Alternatively, it is also possible to substantially be calculated relative to the difference of the theoretical epoxy equivalent weight calculated by the ratio that feeds intake according to actual epoxide equivalent Go out.

In above-mentioned reaction, preferably using alkali metal hydroxide in the reaction with epihalohydrin.As what can be used Alkali metal hydroxide, can enumerate sodium hydroxide, potassium hydroxide etc., can use solid content, can also use its aqueous solution, In the present invention particularly from the aspect of moisture, dissolubility, operability, preferably using laminar solid content is configured to.

The usage amount of alkali metal hydroxide relative to 1 mole of the hydroxyl of phenolic resin blend be usually 0.90 mole~ 1.5 moles, preferably 0.95 mole~1.25 moles, more preferably 0.99 mole~1.15 moles.

In order to promote to react, the quaternary ammoniums such as tetramethyl ammonium chloride, 4 bromide, trimethyl benzyl ammonia chloride can be added Salt is as catalyst.As the usage amount of quaternary ammonium salt, it is usually relative to 1 mole of the hydroxyl of the phenol mixture used in the present invention 0.1g~15g, is preferably 0.2g~10g.

Also and with aprotic polar solvent (dimethyl sulfoxide (DMSO), two preferably in addition to above-mentioned epihalohydrin in the present invention Alkane, dimethyl-imidazolinone etc., preferred dimethyl sulfoxide (DMSO), two in of the inventionAlkane.) or carbon number 1~5 alcohol.Carbon atom The alcohol of number 1~5 is the alcohols such as methanol, ethanol, isopropanol (preferred methanol in the present invention.).Aprotic polar solvent or carbon atom The usage amount of the alcohol of number 1~5 is usually the weight % of 2 weight %~50 relative to the usage amount of epihalohydrin, is preferably 4 weight % ~25 weight %.In addition, the methods of passing through azeotropic dehydration, moisture in control system while, carries out epoxidation.

In the case of in the reaction system washy, electric reliability decrease in the epoxy resin composition obtained sometimes, It is preferred that moisture control is synthesized below 5%.In addition, obtaining epoxy resin composition using aprotic polar solvent When, electricity epoxy resin composition excellent in reliability can be obtained, therefore can be preferably using aprotic polar solvent.

Reaction temperature is usually 30 DEG C~90 DEG C, preferably 35 DEG C~80 DEG C.Particularly in the present invention, for higher purity Preferably more than 60 DEG C of epoxidation, particularly preferably close to the reaction under conditions of counterflow condition.Reaction time is usually 0.5 small When~10 it is small when, preferably 1 it is small when~8 it is small when, it is particularly preferred 1 it is small when~3 it is small when.Reaction time reacts progress not exclusively in short-term, Sometimes accessory substance is produced when reaction time is long.

In the case where heating is depressurized by table halo in the case of not washing after the reactant of these epoxidation reactions is washed or Alcohol, solvent etc. remove.In addition to the less epoxy resin composition of hydrolyzable halogen is obtained, can also be with carbon number 4~7 Ketone compound (can enumerate for example, methyl iso-butyl ketone (MIBK), methyl ethyl ketone, cyclopentanone, cyclohexanone etc..) dissolved as solvent The epoxy resin composition of recycling, and the aqueous solution for adding the alkali metal hydroxides such as sodium hydroxide, potassium hydroxide is reacted, So as to reliably carry out closed loop.In this case the usage amount of alkali metal hydroxide is relative to in the epoxidised present invention 1 mole of the hydroxyl of the phenolic resin blend used is usually 0.01 mole~0.3 mole, preferably 0.05 mole~0.2 mole. Reaction temperature is usually 50 DEG C~120 DEG C, when the reaction time is usually 0.5 small~2 it is small when.

After reaction, the salt of generation is removed by filtering, washing etc., then it is molten by being distilled off under being depressurized in heating Agent and obtain the present invention epoxy resin composition.It should be noted that it is preferred that：In the case where heating is depressurized, solvent is distilled off, Then 110 DEG C~170 DEG C are maintained at, then below 100 DEG C, more preferably less than 80 DEG C of plate body (tabular, sheet, banding Etc. the plate body of shape) on be cast or be added dropwise, be thus configured to the shapes such as tabular, drops (hoodle shape) and take out.Need It is noted that can also be the stage cooling means for carrying out cooling down below 80 DEG C and then being cooled down again below 60 DEG C.This The solid content obtained in process shows transparent amorphous state or is dispersed with the state of the gonorrhoea of crystal, even if just in case solid content is Transparent amorphous state, the gonorrhoea of crystal is dispersed with by that can also be formed when heating 30 minutes~10 is small at 50 DEG C~100 DEG C State.

As the epoxy resin composition of the present invention, contain the epoxy resin described in above-mentioned formula (1).

It is preferred that component, the i.e. following formula (5) of n=1 and the ring described in (6) in epoxy resin and formula described in following formula (1) The poor epoxy resin composition of oxygen tree fat.In addition the content of the polymer of preferred more than n=5 is measured in spectrogram with GPC Area percentage be calculated as the epoxy resin composition of the area % of 10 area %~35.

Hereinafter, if not otherwise specified, then area % in this specification represent by GPC (gel permeation chromatography, Detector：RI the area percentage (area %) in spectrogram obtained from) measuring.

(in formula, n represent repeat number, n be calculated as with average value 2~10 number, in addition, not every A is identical.)

Compound represented by following formula (5) and following formula (6) is favourable in terms of heat resistance, mobility, but to heat Resolution characteristic has a negative impact.That is, by make the content of following formula (5) and the compound represented by (6) respectively for 9 area % with Under (gel permeation chromatography, detector：RI), resistance to thermal decomposition characteristic can be further improved, therefore preferably.

In addition, contain following compound in the epoxy resin composition of the present invention as two same functional components.From heat From the aspect of resolution characteristic, this compound similarly preferred content is few.Its content is 20 area %, and preferable scope is 2 faces Product %~18 area %.In gel permeation chromatography, the compound for stating formula (5) and the compound and following formula (2) of (6) Can not clearly it separate, but can be with substantial separation, it can be determined that its ratio, but be difficult to calculate accurate value.

In the epoxy resin composition of the present invention, particularly preferably with the formula (5) and the compound of (6) and following formula (2) The total amount of compound regulated and controled, the area % of its total amount preferably 2 area %~20 area %, particularly preferred 5 area %~18.

For the compound of the formula (5), methylene that naphthalene structure is connected to each other

Structure is easily broken off, so that easy low molecule quantization, therefore easily decompose and be discharged in thermal decomposition, on institute The compound of formula (6) is stated, since molecular weight is small, when the part generating unit of the network structure epoxy group open loop of solidfied material It is readily volatilized when disjunction is split therefore not preferred.

In addition, when the polymer of more than n=5 is more than 35 area % in the formula (1), since viscosity becomes excessive, shaping Become difficult therefore not preferred.But from the aspect of heat resistance preferably more than 10 area %.

The softening point of such epoxy resin composition is preferably 85 DEG C~100 DEG C (ring and ball method), particularly preferred 85 DEG C~ 95 DEG C of scope.In addition, during more than 100 DEG C, the rising of viscosity also becomes larger, not preferred from the aspect of formability.Need It is bright, when the novolaks of 80 DEG C~90 DEG C of curable resin composition and softening point of the invention cure, thermomechanical special Heat resistance is more than 150 DEG C in the measure of property (TMA).

The compound of n=0 in the epoxy resin composition of the present invention in the preferred formula (1) is below 1 area %, special It is not that preferred glycidoxy naphthalene is below 1 area % from the aspect of thermal decomposition characteristic.Containing glycidoxy naphthalene In the case of, usually contain the area % of 0.01 area %~1, the area of further preferably 0.01 area %~0.9 % is especially excellent Choosing contains the area % of 0.01 area %~0.8.

To human body caused by volatilization when in the case that glycidoxy naphthalene is more than 1 area %, may cause to be kneaded, shape Adverse effect and the release property difference when pollution of stove and mold fouling, shaping etc. influence.It is set at less than 0.01 area % When, substantial amounts of energy and discarded object are produced, thus it is not preferred from environment/industry perspective.

In addition, in the epoxy resin composition of the present invention, n=2,3,4 adds up to 40 area % in preferably described formula (1) ~85 area %.Width by making molecular weight distribution can reduce while easily having high-fire resistance within the range Viscosity, and thermal decomposition characteristic can be further improved.Here, the compound heat resistance of n=2, pyrolytic are excellent, and not Form the excessive material of molecular weight, thus by containing 20 area %~50 the compound of area %n=2 may insure to be more suitable for Physical property, the particularly preferably area % of 20 area %~40.

It should be noted that naphthol component and cresols structure must be contained in the formula (1) in the present invention, cannot be 0.Specifically preferred naphthol component:Cresols structure=1:1~5:1, particularly preferably 1:1~3:1, preferably there are more naphthalene Phenol structure.

As the present invention the preferable resin properties of epoxy resin composition, epoxide equivalent be preferably 180g/eq.~ 230g/eq., more preferably 200g/eq.~220g/eq..By making epoxide equivalent within the above range, solidfied material can be obtained Heat resistance, the more excellent epoxy resin of electric reliability.In the case that epoxide equivalent is more than 230g/eq., epoxide ring is not complete sometimes Closed-loop and containing a large amount of compounds for not having functional group, epoxide equivalent does not decline sometimes.In addition, in most cases in many Contain chlorine in the compound of these incomplete closed loops, can be produced as electronic material purposes sometimes chlorine under the conditions of high temperature and humidity from The corrosion of the wiring for dissociating and being generated by it of son.

It should be noted that the melt viscosity (ICI melt viscosity cone-plates method) at 150 DEG C is preferably below 0.5Pas, When viscosity is excessive, being not filled by portion and forming defective products, occur sometimes in poor fluidity when transfer molding or compression forming, therefore unexcellent Choosing, even if viscosity is too low, also easily carries gap secretly, therefore preferably has the viscosity of a certain degree.In the present invention particularly preferably 0.05Pas~0.5Pas, particularly preferred 0.05Pas~0.4Pas.

In addition, as the present invention epoxy resin composition in remaining total chlorine, preferably below 1500ppm, more preferably Below 1200ppm, particularly preferably below 900ppm.It should be noted that it is respectively preferably 5ppm for chlorion, sodium ion Hereinafter, it is more preferably below 3ppm.The harmful effect of chlorion is as described above.The cations such as sodium ion are particularly in power device Factor is also very important in part purposes, is a reason of fault mode when applying high voltage.

Hereinafter, it is (following to be also referred to as to the curable resin composition of the invention of the epoxy resin composition containing the present invention For curable resin composition) illustrate.

In the curable resin composition of the present invention, neccessary composition is used as using curing agent or polymerization catalyst.

Inorganic filler is preferably comprised in the curable resin composition of the present invention.As inorganic filler, crystal can be enumerated Silica, fused silica, aluminium oxide, zircon, calcium silicates, calcium carbonate, carborundum, silicon nitride, boron nitride, zirconium oxide, The powder of forsterite, steatite, spinelle, titanium dioxide, talcum etc. or by they be made it is spherical obtained from ball etc., but It is not limited to these.They can be used alone, and can also use two or more.The content of these inorganic fillers, preferably makes The usually weight of the weight % of 60 weight %~95, particularly 70 weight %~90 is accounted in the curable resin composition of the present invention Measure the amount of %.

During less than 60 weight %, it is possible to which water absorption rate, linear expansivity are excessive, in addition, possibly can not during more than 95 weight % Equably it is kneaded.In addition, sometimes mobility go wrong and be difficult to it is no it is unfilled in the case of sealed.

Hereinafter, the compounding ratio and other complexs of curable resin composition of the invention are illustrated.

As the polymerization catalyst that can be used (hereinafter also referred to as curing accelerator.) concrete example, can enumerate：2- The imidazoles such as methylimidazole, 2- ethyl imidazol(e)s, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8- phenodiazines The phosphines such as tertiary amines, triphenylphosphine such as miscellaneous-bicyclic (5.4.0) 11 carbon -7- alkene, 4-butyl ammonium, triisopropyl methyl ammonium salt, The quaternary ammonium salts such as trimethyldecylammonium ammonium salt, cetyltrimethyl ammonium salt, triphenylbenzylphosphoniumSalt, triphenyl ethylSalt, four fourths BaseThe seasons such as salt(counter ion counterionsl gegenions of quaternary salt are halogen, organic acid ion, hydroxide ion etc. to salt, are not specified, special Not preferred organic acid ion, hydroxide ion.), metallic compound such as tin octoate etc..In the case of using curing accelerator, Relative to 100 parts by weight of epoxy resin, as needed usually using the parts by weight of 0.01 parts by weight~5.0.

In curable resin composition, other asphalt mixtures modified by epoxy resin can be used together in addition to the epoxy resin composition of the present invention Fat.And in the case of using, shared ratio is preferably more than 30 weight % particularly preferably 40 weights in whole epoxy resin Measure more than %.

As the concrete example of other epoxy resin, can enumerate：Phenolic resin varnish type epoxy resin, bisphenol type epoxy tree Fat, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol aralkyl type epoxy resin etc..It can specifically arrange Lift：Bisphenol-A, 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, hydroquinone, resorcinol, naphthalenediol, three (4- hydroxy phenyls) methane, 1,1, 2,2- tetra- (4- hydroxy phenyls) ethane, phenols (phenol, alkyl substituted phenol, naphthols, alkyl-substituted naphthaline phenol, dihydroxy benzenes, dihydroxy Base naphthalene etc.) and formaldehyde, acetaldehyde, benzaldehyde, parahydroxyben-zaldehyde, salicylaldhyde, parahydroxyacet-ophenone, o-hydroxy second Ketone, dicyclopentadiene, furfural, 4,4 '-bis- (chloromethyls) -1,1 '-biphenyl, 4,4 '-bis- (methoxies) -1,1 '-biphenyl, The condensation polymer and their modifier of double (methoxy) benzene of double (chloromethyl) benzene of 1,4-, 1,4- etc., by tetrabromobisphenol A etc. Glycidyl etherified thing derived from halogenated bisphenol class, alcohols, alicyclic epoxy resin, glycidyl amine epoxy resin, Glycidyl esters based epoxy resin etc.；The epoxy resin of silsesquioxane alkanes is (in chain, ring-type, scalariform or wherein at least There is glycidyl and/or the epoxy resin of 7-oxa-bicyclo[4.1.0 structure) in the siloxane structure of two or more mixed structures Etc. solid-state or liquid-state epoxy resin, but it is not limited to these.

The curing agent that curable resin composition as the present invention contains, can enumerate such as phenol resin, phenols chemical combination Thing, aminated compounds, anhydrides compound, amides compound, carboxylic acid compound etc..And in the case of using, in curing agent In shared ratio be preferably more than 30 weight % particularly preferably more than 40 weight %.

Concrete example as the curing agent that can be used is as follows.

Phenol resin, phenolic compounds；It can enumerate：Bisphenol-A, Bisphenol F, bisphenol S, bisphenol fluorene, terpene diphenol, 4,4 '-biphenyl two Phenol, 2,2 '-'-biphenyl diphenol, 3,3 ', 5,5 '-tetramethyl-[1,1 '-biphenyl] -4,4 '-diphenol, hydroquinone, resorcinol, naphthalene Diphenol, three (4- hydroxy phenyls) methane, 1,1,2,2- tetra- (4- hydroxy phenyls) ethane, phenols (phenol, alkyl substituted phenol, naphthalene Phenol, alkyl-substituted naphthaline phenol, dihydroxy benzenes, dihydroxy naphthlene etc.) and formaldehyde, acetaldehyde, benzaldehyde, parahydroxyben-zaldehyde, o-hydroxy Formaldehyde, parahydroxyacet-ophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 1,4 '-bis- (chloromethyl) benzene, 1,4 '-bis- (first Epoxide methyl) condensation polymer of benzene etc. and the condensation of the halogenated bisphenol class, terpenes and phenols such as their modifier, tetrabromobisphenol A The Polyphenols such as thing, but it is not limited to these.These materials can be used alone, and can also use two or more.

As and preferable phenol resin in using, can enumerate phenol aralkyl resin (has aromatic series alkylen structures Resin), it is particularly preferably following resin：It is characterized in that for the knot selected from least one of phenol, naphthols, cresols Structure, and be that (can specifically be arranged selected from least one of benzene structure, naphthalene structure as the alkylene moiety of its linking group Lift phenol aralkyl, naphthols phenol aralkyl, phenol-naphthol novolak varnish gum etc.).

Aminated compounds, amides compound；It can enumerate：Diaminodiphenyl-methane, diethylenetriamines, Sanya second Urotropine, diaminodiphenylsulfone, isophorone diamine, dicyandiamide, the polyamide synthesized by linolenic dimer with ethylenediamine The nitrogenous compounds such as resin, but it is not limited to these.These materials can be used alone, and can also use two or more.

Sour glycosides compound, carboxylic acid compound；It can enumerate：Phthalic anhydride, trimellitic anhydride, pyromellitic acid Acid anhydride, maleic anhydride, tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylnadic anhydride, carbic anhydride, Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylene-dimalonic acid acid anhydride, bicyclic [2.2.1] heptane -2,3- dioctyl phthalate The acid anhydrides such as acid anhydride, methyl bicycle [2.2.1] heptane -2,3- dicarboxylic acid anhydrides, hexamethylene -1,3,4- tricarboxylic acid -3,4- acid anhydrides；By each Kind alcohol, carbinol-modified polysiloxanes and carboxylic acid resin obtained from the addition reaction of the acid anhydrides, but it is not limited to these.These Material can be used alone, and can also use two or more.

As the curing agent that other can be used together, the change of imidazoles, trifluoroboranes-amine complex, guanidine derivatives can be enumerated Compound etc., but it is not limited to these.These materials can be used alone, and can also use two or more.

Preferably using phenol resin particularly from the aspect of reliability in the present invention.

The usage amount of curing agent is worked as relative to the epoxy group 1 of whole epoxy resin in the curable resin composition of the present invention Amount is preferably the equivalent of 0.7 equivalent~1.2.Relative to 1 equivalent of epoxy group less than 0.7 equivalent in the case of or more than 1.2 equivalents In the case of, it can sometimes cure not exclusively and cannot get good curing physical property.

In the curable resin composition of the present invention, together with curing agent and curing accelerator can also be used.As can be with The concrete example of the curing accelerator used can enumerate above-mentioned curing accelerator.In the case of using curing accelerator, phase For 100 parts by weight of epoxy resin as needed usually using the parts by weight of 0.01 parts by weight~5.0.

In the curable resin composition of the present invention, phosphorus-containing compound can also be contained and assign component as anti-flammability.Make For phosphorus-containing compound, either the phosphorus-containing compound of the phosphorus-containing compound of response type or addition type.As containing phosphatization The concrete example of compound, can enumerate：Trimethyl phosphate, triethyl phosphate, tricresyl phosphate, tricresyl phosphate (xylyl) ester, Double (the di(2-ethylhexyl)phosphates (xylyl) of cresyl phosphate diphenyl ester, cresyl phosphate -2,6- two (xylyl) ester, 1,3- phenylenes Ester), the phosphoric acid ester such as 1,4- phenylenes double (di(2-ethylhexyl)phosphate (xylyl) ester), 4,4 '-biphenyl (di(2-ethylhexyl)phosphate (xylyl) ester)； Miscellaneous -10- phospho hetero phenanthrenes -10- the oxides of 9,10- dihydro-9-oxies, 10- (2,5- dihydroxy phenyls) -10H-9- oxa- -10- phosphas The phosphines such as phenanthrene -10- oxides；Epoxy resin and phosphorous epoxide, red phosphorus obtained from the reactive with active hydrogen of the phosphine Deng, preferably phosphoric acid ester, phosphine or phosphorous epoxide, the double (di(2-ethylhexyl)phosphates (xylyl) of particularly preferred 1,3- phenylenes Ester), 1,4- phenylenes double (di(2-ethylhexyl)phosphate (xylyl) esters), 4,4 '-biphenyl (di(2-ethylhexyl)phosphate (xylyl) ester) or phosphorous ring Oxygen compound.The preferred phosphorus-containing compound of content/whole epoxy resin=0.1~0.6 (weight ratio) of phosphorus-containing compound.0.1 When following may anti-flammability it is insufficient, the hygroscopicity of solidfied material, dielectric property reduce sometimes when more than 0.6.

In addition, antioxidant can be added as needed in the curable resin composition of the present invention.As can use Antioxidant, phenol antioxidant, sulfur-type antioxidant, antioxidant containing phosphorous can be enumerated.Antioxidant can be single Solely use or be used in combination.In curable resin composition of the usage amount of antioxidant relative to the present invention 100 parts by weight of resin component are usually the parts by weight of 0.008 parts by weight~1, be preferably 0.01 parts by weight~0.5 parts by weight.

As the concrete example of phenol antioxidant, may be exemplified：DBPC 2,6 ditertiary butyl p cresol, Butylated hydroxy fennel Ether, 2,6- di-t-butyls paraethyl phenol, β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid stearyl ester, 3- (bis- tertiary fourths of 3,5- Base -4- hydroxy phenyls) the different monooctyl ester of propionic acid, double just pungent sulfenyl -6- (4- hydroxyl -3,5- di-tert-butyls the amido) -1,3,5- of 2,4- The unitary phenols such as double [(pungent sulfenyl) methyl] o-cresols of triazine, 2,4-；2,2 '-di-2-ethylhexylphosphine oxide (4- methyl-6-tert-butylphenols), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 4,4 '-thiobis (3 methy 6 tert butyl phenol), 4,4 '-Aden Base double (3 methy 6 tert butyl phenols), triethylene glycol double [3- (the 3- tert-butyl group -5- methyl -4- hydroxy phenyls) propionic ester], 1, 6- hexylene glycols-bis- [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester], N, N '-hexamethylene bis (3,5- di-t-butyls- 4- hydroxyls-hydrocinnamamide), 2,2- it is thio-di ethylene bis [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester], 3,5- Double [1,1- dimethyl -2- { the β-(3- tertiary butyl-4-hydroxy -5- methyl of di-tert-butyl-4-hydroxyl benzyl diethyl phosphonate, 3,9- Phenyl) propionyloxy ethyl] 2,4,8,10- tetra- oxaspiro [5.5] hendecane, double (3,5- di-tert-butyl-4-hydroxyl benzyl sulphurs Acetoacetic ester) bisphenols such as calcium；1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyls) butane, 1,3,5- trimethyl -2,4, 6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene, four-[methylene -3- (3 ', 5 '-di-t-butyl -4 '-hydroxy phenyl) propionic acid Ester] methane, double [3,3 '-bis--(4 '-hydroxyl -3 '-tert-butyl-phenyl) butyric acid] glycol esters, (the bis- tertiary fourths of 3,5- of isocyanuric acid three Base -4- hydroxybenzyls) ester, 1,3,5- tri- (3 ', 5 '-di-t-butyl -4 '-hydroxybenzyl) guanamine, 4,6- (1H, 3H, 5H) The polymer electrolyte phenols such as triketone, tocopherol.

As the concrete example of sulfur-type antioxidant, may be exemplified：3,3 '-dilauryl thiodipropionate, 3,3 '-it is thio Two myristin of dipropionic acid, 3,3 '-distearylthiodi-propionate etc..

As the concrete example of the antioxidant containing phosphorous, may be exemplified：Triphenyl phosphite, diphenyl phosphite isodecyl ester, Phenyl-phosphite diisodecyl ester, phosphorous acid three (nonyl phenyl) ester, phosphorous acid diisodecyl ester pentaerythritol ester, phosphorous acid three (2, 4- di-tert-butyl-phenyls) ester, double (octadecyl) phosphite esters of ring-type neopentane four base, the double (2,4- bis- of four base of ring-type neopentane Tert-butyl-phenyl) phosphite ester, ring-type neopentane four base double (2,4- di-t-butyl -4- aminomethyl phenyls) phosphite ester, double [uncles 2- Butyl -6- methyl -4- { 2- (octadecane epoxide carbonyl) ethyl } phenyl] phosphorous acid esters such as H-Phosphonate；9,10- dihydros- 9- oxa- -10- phospho hetero phenanthrene -10- oxides, the miscellaneous -10- of 10- (3,5- di-tert-butyl-4-hydroxyl benzyls) -9,10- dihydro-9-oxies The oxa- phospho hetero phenanthrene oxygen such as the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of phospho hetero phenanthrene -10- oxides, 10- decyloxy -9,10- dihydro-9-oxies Compound class etc..

These antioxidants can each be used alone two or more to combine and be used in combination.It is particularly excellent in the present invention Select the antioxidant containing phosphorous.

In addition, in the curable resin composition of the present invention, light stabilizer can be added as needed.

As light stabilizer, hindered amine light stabilizer, particularly HALS etc. are suitable.As HALS, without special Limitation, as representational HALS, can enumerate：Dibutyl amine -1,3,5- triazines-N, N '-bis- (2,2,6,6- tetramethyl -4- piperazines The condensation polymer of piperidinyl -1,6- hexamethylene diamines and N- (2,2,6,6- tetramethyl -4- piperidyls) butylamine, dimethyl succinate - 1- (2- hydroxyethyls) -4- hydroxyl -2,2,6,6- tetramethyl piperidines condensation polymer, poly- [{ 6- (1,1,3,3- tetramethyl butyls) ammonia Base -1,3,5- triazine -2,4- diyls } { (2,2,6,6- tetramethyl -4- piperidyls) imino group } hexa-methylene { (2,2,6,6- tetra- Methyl -4- piperidyls) imino group], [[3,5- double (1,1- dimethyl ethyls) -4- hydroxy phenyls] methyl] butylmalonic acid is double Double (2,2,6,6- tetramethyl -4- piperidyls) ester of (1,2,2,6,6- pentamethyl -4- piperidyls) ester, decanedioic acid, decanedioic acid it is double (1, 2,2,6,6- pentamethyl -4- piperidyls) ester, double (1- octyloxy -2,2,6,6- tetramethyl -4- piperidyls) ester of decanedioic acid, 2- (3, 5- di-tert-butyl-4-hydroxyl benzyls) double (1,2,2,6,6- pentamethyl -4- piperidyls) esters of -2- n-butylmalonic acids etc..HALS can It is only a kind of with use, can also and with two or more.

In addition, resin glue can also be coordinated as needed in the curable resin composition of the present invention.As bonding Agent resin, can enumerate butyral resinoid, acetal resin, acrylic resin, epoxy-nylon-based resin, NBR- phenol Resinoid, epoxy-NBR resinoids, polyamide-based resin, polyimide based resin, polysiloxanes resinoid etc., but be not limited to These.The use level of resin glue is not preferably in the range of the anti-flammability of solidfied material, heat resistance is damaged, relative to asphalt mixtures modified by epoxy resin 100 parts by weight of fat component are as needed usually using the parts by weight of 0.05 parts by weight~50, the parts by weight of preferably 0.05 parts by weight~20.

In addition, cyanate ester resin, maleimide can be coordinated as needed in the curable resin composition of the present invention Resin, benzoPiperazine etc. is used to improving the resin of heat resistance, its use level relative to 100 parts by weight of epoxy resin ingredient, according to Need usually using the parts by weight of 10 parts by weight~50, preferably using the parts by weight of 15 parts by weight~40.

In addition, in the curable resin composition of the present invention, silane coupling agent, stearic acid, palmitic acid, tristearin can be added The various compounding agents such as the releasing agents such as sour zinc, calcium stearate, surfactant, dyestuff, pigment, ultra-violet absorber, various thermosettings Property resin, the total amount relative to curable resin composition is usually the weight % of 0.05 weight %~1.5, especially for 0.05 weight Measure the weight % of %~1.0.

The curable resin composition of the present invention can be by the way that each component be obtained by uniformly mixingg.The present invention's is curable Resin combination can be easily made its solidfied material by the method identical with existing known method.For example, by asphalt mixtures modified by epoxy resin Lipoprotein mixture and curing agent and/or curing accelerator, phosphorus-containing compound, resin glue, inorganic filling material and compounding agent etc. Crushed as needed, then carried out being obtained by mixing curable resin composition with extruder, kneader, roller etc., then will The curable resin composition crushes, and is made sheet or granular, and using transfer molding machine or compacting shape machine etc. 140 DEG C~ Be formed at 220 DEG C, then at 100 DEG C~220 DEG C heating 1 it is small when~10 it is small when, it is hereby achieved that the present invention curing Thing.

The semiconductor device of the present invention obtains in the following manner：Semiconductor element is installed on printed wiring board, incite somebody to action this The composition epoxy resin of invention is configured to cover semiconductor chip after granular or sheet, and more than 175 DEG C and less than 250 DEG C It is formed.Installation method, the encapsulating method of semiconductor element are not particularly limited.For example, use flip-chip bond device etc. Carry out the position alignment of the connecting electrode portion on multilayer printed-wiring board and the solder projection of semiconductor element.Then, will weld Material convex block is heated to more than fusing point, is connected by the way that printed wiring board is melted engagement with solder projection.Next, in printing cloth Filling liquid sealing resin and cured between line plate and semiconductor element.Thus, semiconductor device is obtained.So obtain Semiconductor device has excellent heat resistance and resistance to pyrolytic, therefore particularly useful in vehicle-mounted power device etc..

Embodiment

Hereinafter, the present invention is further illustrated by embodiment, hereinafter, if not otherwise specified, " part " For parts by weight.It should be noted that the present invention is not limited to these Examples.

Hereinafter, illustrated for the various analysis methods used in embodiment.

Epoxide equivalent：According to JIS K 7236 (ISO 3001)

ICI melt viscosities：According to JIS K 7117-2 (ISO 3219)

Softening point：According to JIS K 7234

GPC：Column (Shodex KF-603, KF-602.5, KF-602, KF-601x2)

It is tetrahydrofuran with reference to eluent

Flow velocity is 0.5ml/ minutes

Column temperature is 40 DEG C

Detection：RI (differential refractive detector)

Hereinafter, the present invention is specifically described by embodiment, comparative example.

(synthesis example 1)

In the flask for possessing mixer, reflux condensing tube, agitating device, betanaphthol is added while nitrogen purging is implemented 144 parts, 65 parts of o-cresol, 220 parts of methyl iso-butyl ketone (MIBK), and thereto add 48 parts concentration be 25% sodium hydroxide it is water-soluble Liquid, then at 10 DEG C be added dropwise concentration be 35% 88.4 parts of formalin, and at 10 DEG C stirring 2 it is small when, then add 35% 32 parts of concentrated hydrochloric acid is neutralized, when then stirring 3 is small at 30 DEG C.Methyl-isobutyl is added into obtained reaction solution 100 parts of ketone, 100 parts of water, then discard water layer, add 4.6 parts of paraformaldehyde and p-methyl benzenesulfonic acid, small with 4 at 75 DEG C When the compound of the formula (3) is thermally decomposed, be carried out at the same time novolaksization reaction.

5 parts of the sodium hydrate aqueous solution of addition 30% after reaction, and washed, organic layer is then taken out, with rotation Turn evaporator and solvent is distilled off.

The resin is dissolved in 300 parts of toluene again.The content of the compound of the formula (3) is 1.5 area % at this time, The compound of the formula (4) is 31 area %, and remaining naphthols is 4 area %.

In the flask for possessing mixer, reflux condensing tube, agitating device, it is molten while nitrogen purging is implemented to add this Liquid, then adds 1 part of p-methyl benzenesulfonic acid, is warming up to 80 DEG C, then add 15 parts of formalin, and stir 1 it is small when, Ran Hou Be warming up to 110 DEG C while slowly removing water, and carry out under reflux conditions 3 it is small when react.Then washed, by inciting somebody to action To organic layer solvent be distilled off under reduced pressure with rotary evaporator and obtain the phenolic resin (BN1) used in the present invention 213 parts.

The softening point of obtained phenolic resin is 138.1 DEG C, and the compound of the formula (3) is 0.2 area %, the formula (4) compound is 4.8 area %, and residual naphthols is 0.2 area %, and residual cresols is below 0.1 area %.In addition, hydroxyl Equivalent is 141g/eq..

(synthesis example 2)

In the flask for possessing mixer, reflux condensing tube, agitating device, betanaphthol is added while nitrogen purging is implemented 134 parts, 10 parts of alpha-Naphthol, 55 parts of o-cresol, 150 parts of methyl iso-butyl ketone (MIBK), and the concentrated hydrochloric acid of 20 part 35% of addition thereto, so Afterwards add 75 parts of formalin, and at 10 DEG C reaction 5 it is small when, at 45 DEG C react 4 it is small when.At this time, the chemical combination of the formula (3) The content of thing is 39 area %, and the compound of the formula (4) is 21 area %.

Here, removing water layer, then add 2 parts of 15 parts of paraformaldehyde and p-methyl benzenesulfonic acid and be warming up to 80 DEG C, by institute Formula (3) thermal decomposition is stated, is carried out at the same time novolaksization reaction.

5 parts of the sodium hydrate aqueous solution of addition 30% after reaction, and washed, organic layer is then taken out, is passed through Solvent is distilled off with rotary evaporator and obtains 212 parts of the phenolic resin (BN2) used in the present invention.

The softening point of obtained phenolic resin is 134.4 DEG C, and the compound of the formula (3) is 1.9 area %, the formula (4) compound is 4.7 area %, and residual naphthols is 0.8 area %, and residual cresols is below 0.1 area %.In addition, hydroxyl Equivalent is 148g/eq..

(synthesis example 3)

Following synthesis have been carried out according to No. 3935584 publications of Japan Patent.

In the flask for possessing mixer, reflux condensing tube, agitating device, betanaphthol is added while nitrogen purging is implemented 288 parts, 108 parts of o-cresol, 841 parts of methyl iso-butyl ketone (MIBK).67 parts of paraformaldehydes are added thereto, and progress 2 is small at 25 DEG C Shi Fanying.After reaction, add 41 part 35% of concentrated hydrochloric acid to be neutralized, then add 5.7 parts of p-methyl benzenesulfonic acid, and 25 React when progress 2 is small at DEG C, reacted when progress 2 is small at 80 DEG C.Then carry out being washed to reaction solution as neutrality, pressurize in heating Under solvent of oil reservoir etc. is distilled off, so as to obtain 410 parts of bakelite B N3.

The softening point of obtained phenolic resin is 108 DEG C, and the compound of the formula (3) is 8 area %, the formula (4) Compound is 36 area %, and residual naphthols is 3.5 area %, and residual cresols is below 0.1 area %.In addition, hydroxyl equivalent is 140g/eq.。

(embodiment 1)

In the flask for possessing mixer, reflux condensing tube, agitating device, the present invention is added while nitrogen purging is implemented Middle 92.6 parts of the phenolic resin (BN1) used, 4,21.2 parts of 4 '-'-biphenyl diphenol, 416 parts of epichlorohydrin, 95.8 parts of dimethyl sulfoxide (DMSO), Dissolve under agitation and be warming up to 45 DEG C.Next divided with 90 minutes and add 42 parts of laminar sodium hydroxides, then existed again Reacted when progress 2 is small at 45 DEG C, carry out reacting for 75 minutes at 70 DEG C.After reaction, with rotary evaporator under reduced pressure from Excessive epichlorohydrin equal solvent class is distilled off in oil reservoir.352 parts of methyl iso-butyl ketone (MIBK) is added in residue and is dissolved, is washed After be warming up to 75 DEG C.Add 13 parts of the sodium hydrate aqueous solution of 30 weight % under agitation, and carry out 1 it is small when react, Ran Houjin Row washing is changed into neutral up to the ejected wash water of oil reservoir, is distilled off under reduced pressure from obtained solution by using rotary evaporator Methyl iso-butyl ketone (MIBK) etc. and obtain the present invention 153 parts of epoxy resin composition (EP1).The epoxide equivalent of obtained epoxy resin For 187g/eq., softening point is that the ICI melt viscosities at 108 DEG C, 150 DEG C are 0.60Pas.

The theoretical amount of the diepoxy propoxyl group biphenyl calculated by raw material is 20%.On the other hand, gel permeation chromatography is passed through The amount for the diepoxy propoxyl group biphenyl that method calculates is about 16.9 area %.It can thus be appreciated that about 3.1% '-biphenyl diphenol structure is drawn Enter into cresol novolak structure.It should be noted that the total amount of the compound smaller than the n=2 molecular weight of above-mentioned formula (1) is 19.6 area %, and the compound of more than n=5 is 23 area %.

(embodiment 2)

In the flask for possessing reflux condensing tube, agitating device, add in the present invention and use while nitrogen purging is implemented 92.6 parts of phenolic resin (BN2), 4,21.2 parts of 4 '-'-biphenyl diphenol, 416 parts of epichlorohydrin, 95.8 parts of dimethyl sulfoxide (DMSO), are being stirred It is lower to dissolve and be warming up to 45 DEG C.Next divided with 90 minutes and add 42 parts of laminar sodium hydroxides, then again at 45 DEG C Carry out 2 it is small when react, carried out at 70 DEG C 75 minutes react.After reaction, with rotary evaporator under reduced pressure from oil reservoir Excessive epichlorohydrin equal solvent class is distilled off.352 parts of methyl iso-butyl ketone (MIBK) is added in residue and is dissolved, is heated up after washing To 75 DEG C.Add 13 parts of the sodium hydrate aqueous solution of 30 weight % under agitation, and carry out 1 it is small when react, then washed Until the ejected wash water of oil reservoir is changed into neutral, it is different that methyl is distilled off from obtained solution under reduced pressure by using rotary evaporator Butyl ketone etc. and obtain the present invention 160 parts of epoxy resin composition (EP2).The epoxide equivalent of obtained epoxy resin is 187g/eq., softening point are that the ICI melt viscosities at 109 DEG C, 150 DEG C are 0.29Pas, average molecular weight Mw 2019.

The theoretical amount of the diepoxy propoxyl group biphenyl calculated by raw material is 9.8%.On the other hand, gel permeation chromatography is passed through The amount for the diepoxy propoxyl group biphenyl that method calculates is 8.1 area %.It can thus be appreciated that 1.2% '-biphenyl diphenol structure is introduced in first In phenol novolac structure.It should be noted that the total amount of the compound smaller than the n=2 molecular weight of above-mentioned formula (1) is 10.5 faces Product %, and the compound of more than n=5 is 22 area %.

(Comparative examples A)

In the flask for possessing mixer, reflux condensing tube, agitating device, phenolic aldehyde tree is added while nitrogen purging is implemented 90.0 parts of fat (BN3), 4,23.3 parts of 4 '-'-biphenyl diphenol, 416 parts of epichlorohydrin, 95.8 parts of dimethyl sulfoxide (DMSO), dissolve simultaneously under agitation It is warming up to 45 DEG C.Next divided with 90 minutes and add 42 parts of laminar sodium hydroxides, when then progress 2 is small at 45 DEG C again Reaction, carries out reacting for 75 minutes at 70 DEG C.After reaction, it was distilled off under reduced pressure from oil reservoir with rotary evaporator The epichlorohydrin equal solvent class of amount.352 parts of methyl iso-butyl ketone (MIBK) is added in residue and is dissolved, 75 DEG C are warming up to after washing. Stirring lower 13 parts of sodium hydrate aqueous solution for adding 30 weight %, and carry out 1 it is small when react, then carry out washing until oil reservoir Ejected wash water is changed into neutral, be distilled off methyl iso-butyl ketone (MIBK) etc. from obtained solution under reduced pressure by using rotary evaporator and Obtain 149 parts of the epoxy resin composition (EP3) of comparative example.The epoxide equivalent of obtained epoxy resin is 179g/eq., softening Point is that the ICI melt viscosities at 111 DEG C, 150 DEG C are 0.43Pas, average molecular weight Mw 2410.

The theoretical amount of the diepoxy propoxyl group biphenyl calculated by raw material is 22 area %.On the other hand, gel infiltration is passed through The amount for the diepoxy propoxyl group biphenyl that chromatography calculates is 19.3 area %.It can thus be appreciated that 2.7% '-biphenyl diphenol structure is drawn Enter into cresol novolak structure.It should be noted that the total amount of the compound smaller than the n=2 molecular weight of above-mentioned formula (1) is 24.5 area %, and the compound of more than n=5 is 19 area %.

(comparative example 1)

In the flask for possessing mixer, reflux condensing tube, agitating device, added while nitrogen purging is implemented KAYAHARD CBN (softening point is 89 DEG C, the compound of the formula (5) is 0.3 area %, the compound of (6) be 31 area %, Residual naphthols is 1.6 area %, residual cresols is below 0.1 area %.In addition, hydroxyl equivalent is 140g/eq.) 98.4 parts, 4, 16.8 parts of 4 '-'-biphenyl diphenol, 416 parts of epichlorohydrin, 95.8 parts of dimethyl sulfoxide (DMSO), dissolve and are warming up to 45 DEG C under agitation.Connect down Add 42 parts of laminar sodium hydroxides to use to divide for 90 minutes, then again at 45 DEG C carry out 2 it is small when react, at 70 DEG C into Row reacts for 75 minutes.After reaction, it is molten that excessive epichlorohydrin etc. is distilled off from oil reservoir under reduced pressure with rotary evaporator Agent class.352 parts of methyl iso-butyl ketone (MIBK) is added in residue and is dissolved, 75 DEG C are warming up to after washing.30 weights are added under agitation Measure 13 parts of the sodium hydrate aqueous solution of %, and carry out 1 it is small when react, then carry out washing until the ejected wash water of oil reservoir is changed into Property, methyl iso-butyl ketone (MIBK) etc. is distilled off from obtained solution under reduced pressure by using rotary evaporator and obtains comparative example 149 parts of epoxy resin composition (EP4).The epoxide equivalent of obtained epoxy resin is 195g/eq., and softening point is 98 DEG C, 150 ICI melt viscosities at DEG C are 0.95Pas.

The theoretical amount of the diepoxy propoxyl group biphenyl calculated by raw material is 15.7 area %.On the other hand, oozed by gel The amount for the diepoxy propoxyl group biphenyl that saturating chromatography calculates is 13.1 area %.It can thus be appreciated that 2.6% '-biphenyl diphenol structure quilt It is incorporated into cresol novolak structure.It should be noted that the total amount of the compound smaller than the n=2 molecular weight of above-mentioned formula (1) For 40.3 area %, and the compound of more than n=5 is 3 area %.

(comparative example 2)

In the flask for possessing mixer, reflux condensing tube, agitating device, added while nitrogen purging is implemented KAYAHARD NHN (softening point be 89 DEG C, the formula (5), (6) compound total amount be 6.8 area %, residual naphthols be 4.3 area %, residual cresols are below 0.1 area %.In addition, hydroxyl equivalent is 143g/eq.) 107 parts, 4,4 '-'-biphenyl diphenol 23.3 parts, 416 parts of epichlorohydrin, 95.8 parts of dimethyl sulfoxide (DMSO), dissolve under agitation and be warming up to 45 DEG C.Next with 90 minutes points 42 parts of laminar sodium hydroxides of addition, are reacted when then progress 2 is small at 45 DEG C again, 75 minutes are carried out at 70 DEG C instead Should.After reaction, excessive epichlorohydrin equal solvent class is distilled off from oil reservoir under reduced pressure with rotary evaporator.Remaining 352 parts of methyl iso-butyl ketone (MIBK) is added in thing and is dissolved, 75 DEG C are warming up to after washing.The hydroxide of 30 weight % is added under agitation 13 parts of sodium water solution, progress 1 are reacted when small, then carry out washing until the ejected wash water of oil reservoir is changed into neutral, by using rotation steaming Hair device is distilled off methyl iso-butyl ketone (MIBK) etc. under reduced pressure from obtained solution and obtains the epoxy resin composition of comparative example (EP5) 175 parts.The epoxide equivalent of obtained epoxy resin is 196g/eq., and softening point is that the ICI meltings at 98 DEG C, 150 DEG C are viscous Spend for 0.15Pas.

The total amount of the compound smaller than the n=2 molecular weight of above-mentioned formula (1) is 24 area %, and the compound of more than n=5 For below 15 area % (peak ambiguously separates).

Embodiment 4~7 and comparative example 3~6

Thermomechanical measuring device：TA-instruments is manufactured, TMA-2980

Measuring temperature scope：40 DEG C~280 DEG C

Programming rate：2 DEG C/min

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

Measuring temperature scope：- 30 DEG C~280 DEG C

Ramp rates：2 DEG C/min

Test chip size：Use the test film for cutting into 5mm × 50mm (thickness is about 800 μm).

Analysis condition

Tg：The peak point (Tan δ MAX) of Tan δ during DMA is measured is as Tg.

Measured (Td5) using TG-DTA

Determination sample：Powdery (by 100 μm of sieve apertures, and stays on 75 μm of sieve apertures) 5-10mg

Determination condition：10 DEG C/min of programming rate, air-flow 200ml/ minutes

Determine 5% weightless temperature.

Table 1

Phenol novolacs：Bright and chemical conversion industry manufacture H-1

Curing accelerator：Triphenylphosphine north Xinghua length of schooling makes TPP

Curing accelerator usage amount：It is 1phr relative to epoxy resin

Epoxy resin-catalyst ratio：Equivalent

Condition of cure：Transfer molding at 175 DEG C, at 160 DEG C 2 it is small when, at 180 DEG C 6 it is small when

Table 2

Phenol aralkyl resin：Mitsui Chemicals manufacture Milex XLC-31.

Phenol novolacs：Bright and chemical conversion industry manufacture H-1

Curing accelerator：2E4MZ, four countries' chemical conversion manufacture, imidazole catalyst

Curing accelerator usage amount：It is 1phr relative to epoxy resin

Condition of cure：Transfer molding at 175 DEG C, at 160 DEG C 2 it is small when and 180 DEG C

Understood according to this result, height can be taken into account by having used the solidfied material of the composition of the epoxy resin composition of the present invention Heat resistance and resistance to thermal decomposition characteristic.

The present invention is described in detail by with reference to specific embodiment, still, will be apparent to those skilled in the art , without departing from the spirit and scope of the present invention, can make various changes and modifications.

It should be noted that Japanese patent application (the Patent 2014- that the application was proposed based on March 11st, 2014 047563), this application is quoted entirely through reference.In addition, all references cited herein are incorporated to this as a whole Specification.

Industrial applicability

The heat resistance of the epoxy resin composition of the present invention is high and resistance to thermal decomposition characteristic is excellent, therefore contains the ring of the present invention The curable resin composition of oxygen tree lipoprotein mixture is as electric and electronic material applications, particularly semiconductor encapsulant, film base Plate material is useful.

Claims

1. a kind of epoxy resin composition, it contains the chemical combination represented by compound and following formula (2) represented by following formula (1) Thing,

In terms of the area percentage for measuring in spectrogram by gel permeation chromatography (GPC), the content of two functional epoxy resins is 20 faces Product below %, the content of the polymer of more than n=5 are the area % of 10 area %~35, and

The softening point measured according to ISO 4625-2 of the epoxy resin composition is 80 DEG C~110 DEG C,

In formula (1), n represents repeat number, n be calculated as with average value 2~10 number, in addition, not every A is identical,

2. epoxy resin composition as claimed in claim 1, wherein, the content of the compound represented by the formula (2) is with solidifying Area percentage in glue penetration chromatography (GPC) measure spectrogram is calculated as the area % of 2 area %~18.

3. epoxy resin composition as claimed in claim 1 or 2, its by by naphthols that softening point is 120 DEG C~150 DEG C- Cresols mixing novolac resin mixes with 4,4 '-'-biphenyl diphenol and reacts and obtain with epihalohydrin in alkaline conditions.

4. epoxy resin composition as claimed in claim 1 or 2, its melt viscosity at 150 DEG C is more than 0.05Pas And below 0.5Pas.

5. epoxy resin composition as claimed in claim 3, its melt viscosity at 150 DEG C for more than 0.05Pas and Below 0.5Pas.

6. a kind of curable resin composition, it contains the epoxy resin composition any one of claim 1 to 5 and consolidates Agent.

7. a kind of curable resin composition, it contains the epoxy resin composition any one of claim 1 to 5 and gathers Close catalyst.

8. a kind of solidfied material, it is obtained by the way that the curable resin composition described in claim 6 or 7 is cured.

9. a kind of semiconductor device, it by the curable resin composition described in claim 6 or 7 by being configured to granular or piece Shape and then covering semiconductor chip and more than 175 DEG C and less than 250 DEG C are formed and obtain.