CN105980441A - Epoxy resin mixture, curable resin composition, cured product thereof, and semiconductor device - Google Patents

Abstract

The purpose of the present invention is to provide: an epoxy resin mixture having excellent heat resistance and thermal decomposition characteristics; a curable resin composition; and a cured product of the curable resin composition. An epoxy resin mixture according to the present invention contains a compound represented by formula (1) and a compound represented by formula (2), while containing a bifunctional epoxy resin in an amount of 20% by area or less in terms of an area percentage in a gel permeation chromatography (GPC) measurement chart and having a softening point of 80-110 DEG C (in accordance with ISO 4625-2). (In formula (1), n represents the number of repetitions, and n is a number having an average value of 2-10. In addition, there is no case where all A moieties are the same.).

Description

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

Technical field

The present invention relates to provide the epoxy resin of the solidfied material of thermostability and resistance to thermal decomposition characteristic excellence Mixture.

Additionally, the present invention relates to be suitable as requiring H.D electric and electronic material applications, spy It not the encapsulant of quasiconductor, the epoxy resin composition of film substrate material, curable tree Oil/fat composition and its solidfied material and the semiconductor device obtained by this curable resin composition.

Background technology

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

But in recent years, develop along with it in electrical/electronic field, it is desirable to improve bag further Include the high purity of resin combination interior moisture-proof, adhesiveness, dielectric property, in order to make The highly-filled lowering viscousity of filler (inorganic or organic filler), in order to shorten the anti-of forming period The various characteristic such as the raising of answering property.Additionally, as structural material aviation and wide, leisure/ Sports apparatus purposes etc. require light weight and the material of mechanical properties excellence.The most in recent years, From the viewpoint of energy-conservation, the concern for power device is gradually increased (non-patent literature 1).

In the past, sealing with Silica hydrogel for power device is main flow, but from now on, from life From the standpoint of productivity, one-tenth present aspect and its intensity, reliability, want from this day significantly to push away Transformation forward to thermosetting resin.Additionally, the actuation temperature of this power device has and rises year by year Tendency, is designed with the actuation temperature of more than 150 DEG C in silicon based semiconductor, it is desirable to more than 150 DEG C the highest heat-resisting (non-patent literature 2).

Prior art literature

Non-patent literature

Non-patent literature 1: " 2008, STRJ reported, quasiconductor development plan Senior Administrative Officer Meeting, 2008 annual reports " (" within 2008, STRJ accuses halfbody ロ De マ ッ プ committee Can accuse in Heisei 20 year "), the 8th chapter, p1-17, [online], and in March, 2009, J EITA (corporations) electronic information technology industry association, quasiconductor development plan special commission, [20 On May 30th, 12 is retrieved], network address < URL:http: //strj-jeita.elisasp.net/strj/nenjih oukoku-2008.cfm>

Non-patent literature 2: high storehouse letter etc., SUNX technical report, car related device skill Art, vehicle-mounted work in hot environment IC (デ バ イ ス skill high temperature makees IC), the 74 phases, Japan, May 31 calendar year 2001,35-40 page

Summary of the invention

Invent problem to be solved

The epoxy resin that thermostability is high is typically the epoxy resin that crosslink density is high.

But, the water absorption rate of the epoxy resin that crosslink density is high is high, crisp, thermal decomposition characteristic is deteriorated. Additionally electrical property has the tendency of variation.In the case of the quasiconductor of high temperature driven, not only thermally decompose Characteristic is important, and electrical characteristics are the most important, the most preferred.When reducing crosslink density, these are special Property improved, but thermostability decline, glass transition temperature (Tg) reduce.Actuation temperature exceedes In the case of glass transition temperature, as a rule specific insulation fall at a temperature of more than Tg Low, therefore electrical characteristics are deteriorated.

In the case of attempting to improve above-mentioned characteristic, sometimes use by increasing dividing of resin self Son amount and the method that improves thermostability, but owing to viscosity becomes the highest, close at quasiconductor Envelope needs to be completely covered whole quasiconductor, therefore produces the unfilled parts such as space, uncomfortable Cooperation is semiconductor-encapsulating material.

That is, it is an object of the invention to provide a kind of there is applicable encapsulating semiconductor mobility, And the epoxy resin that thermostability, thermal decomposition characteristic are excellent.

Means for solving the above

The present inventor conducts in-depth research in view of described practical situation, and result completes this Invention.

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

(1) a kind of epoxy resin composition, its contain the compound represented by following formula (1) and under Stating the compound represented by formula (2), the content of difunctional epoxy resin is with gel permeation chromatography (GPC) area percentage measured in spectrogram is calculated as 20 below area %, and described epoxy resin The softening point of mixture is 80 DEG C～110 DEG C (according to ISO 4625-2),

(in formula (1), n represents that repeat number, n are the numbers being calculated as 2～10 with meansigma methods, it addition, Not every A is the most identical)

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

(3) epoxy resin composition as described in preceding paragraph (1) or (2), it is by being 120 by softening point DEG C～the naphthols-cresol mixing novolac resin of 150 DEG C and 4,4 '-'-biphenyl diphenol mixing and React with epihalohydrin under the conditions of alkalescence and obtain.

(4) epoxy resin composition as according to any one of preceding paragraph (1)～(3), it is at 150 DEG C Under melt viscosity be more than 0.05Pa s and 0.5Pa below s.

(5) a kind of curable resin composition, it contains according to any one of preceding paragraph (1)～(4) Epoxy resin composition and firming agent.

(6) a kind of curable resin composition, it contains according to any one of preceding paragraph (1)～(4) Epoxy resin composition and polymerization catalyst.

(7) a kind of solidfied material, it is by by the curable resin composition described in preceding paragraph (5) or (6) Solidify and obtain.

(8) a kind of semiconductor device, it is by by the curable resin group described in preceding paragraph (5) or (6) Compound is configured to granular or sheet (tablet) shape, is then covered by semiconductor chip and at 175 DEG C Above and less than 250 DEG C form and obtain.

Invention effect

The epoxy resin composition of the present invention provide curable resin composition that mobility is excellent, The solidfied material that thermostability, resistance to thermal decomposition characteristic are excellent.The additionally curable resin combination of the present invention Thing is highly useful in the sealing of the semiconductor element of encapsulating semiconductor, particularly power device, Good semiconductor device can be obtained.

Detailed description of the invention

The epoxy resin composition of the present invention contains naphthols-cresol mixing phenolic varnish type asphalt mixtures modified by epoxy resin Fat and 4,4 '-diepoxy propoxyl group biphenyl.

In the epoxy resin composition of the present invention, with naphthols-cresol mixing nobolak type epoxy Resin is as main component, in epoxy resin composition 4, and the content of 4 '-diepoxy propoxyl group biphenyl Preferably 2 area %～18 area % (measuring in spectrogram of gel permeation chromatography (detector: RI) Area percentage), more preferably 2 area %～17.5 area %, particularly preferred 3 area %～17 Area %.

It is favorably improved mobility, by making its content be containing 4,4 '-diepoxy propoxyl group biphenyl 18 below area %, resistance to thermal decomposition characteristic, water-proofing performance are more effective, the most preferably.

As the shape of the epoxy resin composition of the present invention, in the case of mixed uniformly, excellent Choosing has the crystalline solid resin shape of band, and softening point (according to ISO 4625-2) now is from behaviour The problem of the formability when property made and solidification is thought of as 80 DEG C～110 DEG C, preferably 100 DEG C～110 ℃。

Viscous is easily produced, preferably at least than softening point when common resin at room temperature processes Use at a temperature of low 50 DEG C.Especially with regard to electronic material, it is contemplated that produce in Southeast Asia, It is contemplated that indoor are more than 40 DEG C, therefore by make softening point more than 100 DEG C, not only under room temperature Process become the easiest, and pulverize, mixing property excellent, the most preferably.But soft Change point too high in the case of, the problem not exclusively melted time the most mixing, and making wanting Resin melting and when excessively applying temperature, the probability reacted time mixing is high.Therefore soften The upper limit of point is 110 DEG C.

For the epoxy resin composition of the present invention, its melt viscosity at 150 DEG C is excellent Elect below 1.0Pa s as, more preferably more than 0.05Pa s and 0.5Pa below s, special You Xuanwei more than 0.1Pa s and 0.5Pa below s.

Particularly relatively thick, even if therefore viscosity height can also carry out close due to line in power device Envelope, but during more than 1.0Pa s, there is the tendency that formability goes wrong.

Each epoxy resin can uniformly be mixed by the epoxy resin composition of the present invention, in the present invention, Preferably by using as the naphthols-cresol mixing novolac resin of phenolic resin blend and 4,4 '- '-biphenyl diphenol mixes, and reacts with epihalohydrin in the basic conditions and obtain.

In the case of simple mixing, carry out the epoxidation of naphthols-cresol mixed phenol Novolac respectively Epoxidation with 4,4 '-'-biphenyl diphenol.In this case, naphthols-cresol is occurred to mix when epoxidation Close that novolaks are the most partially polymerized and the reaction of 4,4 '-'-biphenyl diphenol part bonding each other.This In the case of Zhong, cresol novolak each other partially polymerized makes viscosity rise quickly.It addition, 4, the bond together crystallinity of the material obtained of 4 '-'-biphenyl diphenol is the highest, and poor compatibility is therefore difficult With uniform dissolution.The most also the reduction of thermostability is caused.

On the other hand, carry out at the same time epoxidised in the case of, by naphthols-cresol can be formed The compound that mixed phenol Novolac and '-biphenyl diphenol occur part to be bonded and obtain, thus suppress first The polymerization each other of phenol novolaks, promotes lowering viscousity.Additionally, this compound has cresol phenol Novolac and the characteristic of both '-biphenyl diphenols, excellent compatibility, and can suppress resistance to further Hot reduction.

Naphthols-cresol mixed phenol the Novolac used in the present invention (makes hereinafter also referred to as in the present invention Phenolic resin) with naphthols (1-naphthols and/or beta naphthal), cresol (not limiting the position of substitution) and first Aldehyde synthesis equivalent (refers to formalin, paraformaldehyde etc..) it is that neccessary composition synthesizes.

The phenolic resin used in the present invention can obtain in the following manner: by naphthols and cresol It is being enumerated as aromatic hydrocarbon, methylisobutylketone, methyl ethyl ketone, the rings such as water, toluene, dimethylbenzene The alcohols solvents (or water) such as the ketone such as hexanone, Ketocyclopentane, methanol, ethanol, propanol dissolve, or With two coating systems mixing, and react with formaldehyde synthesis equivalent under acid or alkaline conditions.? In the case of using solvent, its usage amount is led to relative to total amount 100 weight portion of naphthols and cresol It is often 5 weight portions～500 weight portions, preferably 10 weight portions～the scope of 300 weight portions.

As catalyst, it is possible to use any one acid or alkaline catalyst.

As the concrete example of the acidic catalyst that can use, can enumerate: hydrochloric acid, sulphuric acid, The mineral acids such as phosphoric acid；The organic acids such as oxalic acid, toluenesulfonic acid, acetic acid；Wolframic acid etc. miscellaneous many Acid, activated clay, mineral acid, stannic chloride, zinc chloride, iron chloride etc., other show acidity Organic and inorganic Barbiturates；Deng the acidity generally used in novolac resin manufactures purposes Catalyst etc..

As the concrete example of the base catalyst that can use, can enumerate: Lithium hydrate, hydrogen The alkali metal hydroxide such as sodium oxide, potassium hydroxide；The alkaline earth such as magnesium hydroxide, calcium hydroxide gold Belong to hydroxide；The alkali metal such as Feldalat NM, Sodium ethylate, Feldalat KM, potassium ethoxide, potassium tert-butoxide Alkoxide；The alkaline-earth metal alkyl oxide such as Bis(methoxy)magnesium, Diethoxymagnesium；Deng.

It can in addition contain use amines catalyst, can enumerate triethylamine, ethanolamine, pyridine, Piperidines, morpholine etc..Particularly can also be also used as in the case of using amines catalyst Solvent.

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

In the present invention, particularly carry out three below operation: (a) naphthols and the novolaks of cresol Change reaction；The pyrolysis of the dimer (following formula (3)) of (b) naphthols；C () adds formaldehyde equivalence Thing, and it is clear to make it be bonded to employ the naphthols-cresol novolac of the naphthols decomposing generation in operation (b) The reaction of paint.

By experiencing this operation, it is possible to reduce the dimer of the structure represented by following formula (4), and Manufacture the raw material of the epoxy resin used in the present invention.

By this operation to epoxy resin become the ring that resistance to thermal decomposition characteristic is excellent Epoxy resins.It should be noted that operation (b), (c) can be carried out simultaneously, catalyst now is Acidic catalyst shown in above-mentioned, if operation (a) is acid, then can be used as it is this catalyst, Or acid catalyst can also be added, if operation (a) is alkalescence, preferably add after operation (a) terminates Plus acidic catalyst and react in acid condition.It should be noted that for these catalyst, No matter it is respectively acid or alkaline, excellent relative to the total mole number of the naphthols at most used, cresol Elect less than 2 times as.It addition, in the case of the amount consumed when deducting neutralization, if acid Catalyst, usually 0.01 molar equivalent %～0.3 molar equivalent %, work as more preferably 0.01 mole Amount %～0.25 molar equivalent %；If base catalyst, then relative to naphthols, cresol total Molal quantity, it is often preferred that 0.5 molar equivalent %～1.3 molar equivalent %, particularly preferred 0.5 rubs You are equivalent %～1.1 molar equivalent %.For reaction temperature, preferably with 0 in operation (a) DEG C～110 DEG C be controlled, especially for reducing molecular weight distribution, preferably at 0 DEG C～70 DEG C Under carry out first order reaction, then at 30 DEG C～110 DEG C, carry out secondary response.It addition, carry out During molecular weight control, it is possible to use following methods: use the alkalescence of 1.0 more than molar equivalent % Catalyst, optionally manufactures the monomethylol form of naphthols, and controls by making it react Molecular weight distribution.

Here, the phenolic aldehyde obtained by the novolaksization reaction of naphthols and cresol of operation (a) In varnish-type phenolic resin, weight average molecular weight preferably 500～1500.Here, above-mentioned formula (3) institute table The total amount of the structure represented by the structure shown and formula (4) measures the area percentage in spectrogram with GPC Meter is preferably 10 below area %, particularly preferably 8 below area %.It addition, particularly preferably Structure represented by above-mentioned formula (3) and the structure represented by formula (4) are respectively 5 below area %.Right In such material, by experience (b) and (c) operation, target resin more can be obtained.

It should be noted that the naphthols used in operation (a) is preferably used alpha-Naphthol and betanaphthol Mixture.

(formalin, paraformaldehyde is referred to as the formaldehyde synthesis equivalent used in described operation (a) Deng.) usage amount, be preferably 0.5 mole times～1.5 moles times relative to the naphthols used, special You Xuanwei 0.7 mole times～1.2 moles times.It should be noted that relative to naphthols and cresol Total mole number be preferably less than 1.0 moles times, particularly preferred 0.5 mole times～0.95 mole times.

As the usage amount of the formaldehyde synthesis equivalent used in described operation (c), also depend on residual Stay the residual quantity of structure represented by naphthols or described formula (4), relative to the first used in operation (a) Aldehyde synthesis equivalent generally can add with the ratio of 1 weight %～20 weight %.More preferably 1 Weight %～15 weight %.

The naphthols that the phenolic resin blend used in the present invention obtained by this way is used -cresol mixed phenol Novolac can not also be purified and use according to purposes, but generally at reaction knot Reactant mixture is neutralized, then by removing unreacting material and solvent under heating decompression after bundle Class and purification also use.It should be noted that this neutralization step can add various bases, phosphorus Salt or the buffer etc. such as hydrochlorate, it is also possible to carry out washing etc., and with easier time both and have Effect.It addition, in the case of naphthols fully consumes not over reaction, preferably steamed by thin film Evaporate, the bubbling etc. of the noble gas such as nitrogen makes the naphthols amount of residual be less than 2%, and preferably 1% Below.

Used as the phenolic resin blend used in the present invention obtained by this way Naphthols-cresol mixed phenol Novolac, softening point is preferably 100 DEG C～140 DEG C, and hydroxyl equivalent is preferred For 140g/eq.～160g/eq..

Described in the phenolic resin used in the present invention, the compound of the structure of formula (3), formula (4) contains Measure with the area percentage meter in measuring spectrogram at GPC (gel permeation chromatography, detector: RI) It is respectively 12 below area %, thus can improve resistance to thermal decomposition characteristic, the most preferably.This Preferably 10 below area % in bright, particularly preferred 6 below area %.Additionally preferably its total amount is 17 below area %.Thus can easily meet the characteristic of the epoxy resin composition of the present invention, Resistance to thermal decomposition characteristic and thermostability are more excellent.

It is more than 99% about the preferred purity of 4,4 '-'-biphenyl diphenol.By oxidation etc. by part oxygen In the case of change, owing to becoming a functional compound, may result in thermostability and reduce.

Mixture and table halo as the phenolic resin used in the present invention and 4,4 '-'-biphenyl diphenol The reaction method of alcohol, is not particularly limited, an example of this synthetic method set forth below.

In obtaining the reaction of epoxy resin composition of the present invention, by making use in the present invention Phenolic resin (BN) and 4,4 '-'-biphenyl diphenol (BP) react with epihalohydrin and obtain epoxy simultaneously Resin compound.Here, as ratio (weight ratio) the preferably BN/BP=1～70 of (BN) with (BP), More preferably 4～62, particularly preferred 4.5～22.From thermostability, anti-flammability, the balance of mobility From the standpoint of preferred this scope.(it should be noted that the mixture of following (BN) and (BP) is also It is referred to as in the present invention phenolic resin blend used.)

In obtaining the reaction of epoxy resin composition of the present invention, as the preferred work of epihalohydrin The chloropropylene oxide being readily available in industry.The usage amount of epihalohydrin is relative to the phenol used in the present invention The hydroxyl of urea formaldehyde mixture 1 mole usually 3.0 moles～15 moles, preferably 3.0 moles～ 10 moles, more preferably 3.5 moles～8.5 moles, particularly preferred 4.0 moles～6.0 moles.

During less than 3.0 moles, epoxide equivalent becomes big sometimes, it addition, the asphalt mixtures modified by epoxy resin sometimes obtained The workability of fat is deteriorated, during more than 15 moles, and quantity of solvent excess sometimes.

The most in the present invention, the naphthalene that the phenolic resin blend used in the present invention is used Phenol-cresol mixed phenol Novolac contributes to characteristic with the product of '-biphenyl diphenol, and the most preferably 6.0 Chloropropylene oxide amount below mole.Thus can regulate naphthols-cresol mixed phenol Novolac and biphenyl two The bonding of phenol.

Now, as '-biphenyl diphenol to the introduction volume of naphthols-cresol mixing novolac resin, with The area percentage meter that GPC measures in spectrogram is preferably 1 area %～10 area %, the most excellent Elect 1 area %～8 area % as.This amount is except can be with NMR etc. by '-biphenyl diphenol and cresol Molal quantity and beyond GPC data substantially calculates, it is also possible to by when feeding intake when synthesizing in theory Reactive ratio and the area % of GPC substantially calculate.As concrete computational methods, by feeding intake Amount confirms the amount of theoretic diepoxy propoxyl group biphenyl.On the other hand, according to the area of GPC Ratio, confirms content with the peak area (detector: RI) of diepoxy propoxyl group biphenyl.Its difference is for drawing Enter amount.When being only '-biphenyl diphenol, '-biphenyl diphenol bonding each other is preferential, but at cresol Under conditions of the amount of novolaks is many, preferentially it is introduced to cresol novolak according to theory of probability, because of This judges this difference is judged as introduction volume.It should be noted that in the mensuration using NMR, Proton or the peak area ratio of carbon according to each benzene nucleus calculate molar ratio.According to this molar ratio Confirm the amount of theoretic diepoxy propoxyl group biphenyl.The most same as described above.Additionally, it is possible to With according to actual epoxide equivalent relative to the difference of the theoretical epoxy equivalent weight calculated by the ratio that feeds intake Substantially calculate.

In above-mentioned reaction, alkali metal hydroxide is being preferably used in the reaction of epihalohydrin. As the alkali metal hydroxide that can use, sodium hydroxide, potassium hydroxide etc. can be enumerated, Solid content can be used, it is possible to use its aqueous solution, particularly from moisture, molten in the present invention From the standpoint of Xie Xing, operability, it is preferably used and is configured to laminar solid content.

The usage amount of alkali metal hydroxide is led to relative to the hydroxyl 1 mole of phenolic resin blend Being often 0.90 mole～1.5 moles, preferably 0.95 mole～1.25 moles, more preferably 0.99 rubs You～1.15 moles.

In order to promote reaction, tetramethyl ammonium chloride, 4 bromide, trimethyl can be added The quaternary ammonium salts such as benzyl ammonium chloride are as catalyst.As the usage amount of quaternary ammonium salt, relative to this The hydroxyl of the phenol mixture of bright middle use 1 mole usually 0.1g～15g, preferably 0.2g～ 10g。

In the present invention preferably in addition to above-mentioned epihalohydrin also and with aprotic polar solvent (two Methyl sulfoxide, twoAlkane, dimethyl-imidazolinone etc., preferred dimethyl sulfoxide in the present invention, twoAlkane.) or the alcohol of carbon number 1～5.The alcohol of carbon number 1～5 is methanol, ethanol, different The alcohols such as propanol (preferred methanol in the present invention.).Aprotic polar solvent or carbon number 1～5 The usage amount of alcohol be usually 2 weight %～50 weight % relative to the usage amount of epihalohydrin, excellent Elect 4 weight %～25 weight % as.It addition, by methods such as azeotropic dehydrations, in control system Moisture while carry out epoxidation.

In the case of washy in reaction system, in the epoxy resin composition sometimes obtained Electricity reliability decrease, preferably synthesizes moisture Control below 5%.It addition, it is non-using When proton polar solvent obtains epoxy resin composition, the epoxy that electricity is of excellent in reliability can be obtained Resin compound, therefore can be preferably used 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 In, for the epoxidation preferably more than 60 DEG C of higher purity, particularly preferably close to counterflow condition Under conditions of reaction.Response time is usually 0.5 hour～10 hours, preferably 1 hour～8 Hour, particularly preferred 1 hour～3 hours.Response time reacts in short-term and carries out not exclusively, reaction Sometimes by-product is produced when time is long.

Subtract in heating in the case of or not washing after the reactant of these epoxidation reactions is washed Depress and epihalohydrin, solvent etc. are removed.In addition to obtain the epoxy that hydrolyzable halogen is less Resin compound, it is also possible to (can enumerate such as, methyl with the ketonic compound of carbon number 4～7 Isobutyl ketone, methyl ethyl ketone, Ketocyclopentane, Ketohexamethylene etc..) ring reclaimed is dissolved as solvent Epoxy resins mixture, and add the water-soluble of the alkali metal hydroxide such as sodium hydroxide, potassium hydroxide Liquid reacts, thus reliably carries out closed loop.In this case the making of alkali metal hydroxide Consumption rubs relative to the hydroxyl 1 of the phenolic resin blend used in the epoxidised present invention You have usually 0.01 mole～0.3 mole, preferably 0.05 mole～0.2 mole.Reaction temperature is led to Being often 50 DEG C～120 DEG C, the response time is usually 0.5 hour～2 hours.

After reaction terminates, the salt generated is removed by filtration, washing etc., then by heating Evaporated under reduced pressure removes solvent and obtains the epoxy resin composition of the present invention.It should be noted that Preferably: under heating decompression, solvent is distilled off, is then maintained at 110 DEG C～170 DEG C, Then below 100 DEG C, the plate body (shape such as tabular, lamellar, banding of more preferably less than 80 DEG C The plate body of shape) on be cast or drip, be thus configured to tabular, drops (hoodle shape) etc. Shape is also taken out.It should be noted that can also be to carry out cooling down existing the most again below 80 DEG C The stage cooling means of 60 DEG C of cool below.The solid content obtained in this operation shows transparent Amorphous state or be dispersed with the state of nebulousurine of crystal, even if just in case solid content is transparent amorphous State, can also be formed by heating at 50 DEG C～100 DEG C and be dispersed with crystalline substance for 30 minutes～10 hours The state of the nebulousurine of body.

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

The preferably composition of n=1, i.e. following formula (5) in epoxy resin described in following formula (1) and formula (6) the poor epoxy resin composition of the epoxy resin described in.Additionally preferably more than n=5 The area percentage that measures in spectrogram with GPC of the content of polymer be calculated as 10 area %～35 The epoxy resin composition of area %.

Hereinafter, if not otherwise specified, then the area % in this specification represents (solidifying by GPC Glue penetration chromatography, detector: RI) measure and area percentage (area in the spectrogram that obtains %).

(in formula, n represents that repeat number, n are the numbers being calculated as 2～10 with meansigma methods, it addition, not It is that all of A is the most identical.)

Compound represented by following formula (5) and following formula (6) is to have in terms of thermostability, mobility Profit, but thermal decomposition characteristic is had a negative impact.That is, by making following formula (5) and (6) institute table The content of the compound shown is respectively 9 below area % (gel permeation chromatography, detector: RI), Resistance to thermal decomposition characteristic can be improved further, the most preferably.

It addition, containing following compound as same two in the epoxy resin composition of the present invention Functional component.From the standpoint of thermal decomposition characteristic, this compound preferred content too is few.Its Content is 20 area %, preferably in the range of 2 area %～18 area %.At gel infiltration color In spectrometry, described in state formula (5) and (6) the compound of compound and following formula (2) cannot clearly divide From, but can be with substantial separation, it can be determined that its ratio, but be difficult to calculate and be worth accurately.

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

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

Structure is easily broken off, thus easily low molecule quantifies, and therefore easily decomposes and quilt when thermal decomposition Discharge, about the compound of described formula (6), owing to molecular weight is little, therefore when the network of solidfied material During the part generation portion fractures of structure epoxy group open loop, readily volatilized, the most preferred.

During it addition, the polymer of more than n=5 is more than 35 area % in described formula (1), due to viscosity Become too high, shape and become difficulty, the most preferred.But it is excellent from the standpoint of thermostability Select 10 more than area %.

The softening point of such epoxy resin composition is preferably 85 DEG C～100 DEG C (ring and ball method), special The most preferably 85 DEG C～the scope of 95 DEG C.It addition, during more than 100 DEG C, the rising of viscosity also becomes big, From the standpoint of formability the most preferred.It should be noted that the curable resin group of the present invention When the novolaks of compound and softening point 80 DEG C～90 DEG C solidify, at thermo-mechanical property (TMA) In mensuration, thermostability is more than 150 DEG C.

In the epoxy resin composition of the present invention, the compound of the n=0 in preferred described formula (1) is 1 Below area %, particularly from the standpoint of thermal decomposition characteristic, preferred glycidoxy naphthalene is 1 Long-pending below %.In the case of containing glycidoxy naphthalene, usually contain 0.01 area %～1 Long-pending %, further preferably containing 0.01 area %～0.9 area %, particularly preferably containing 0.01 Long-pending %～0.8 area %.

In the case of glycidoxy naphthalene is more than 1 area %, be likely to result in mixing, shape time Volatilization cause to when the adverse effect of human body and the pollution of stove and mold fouling, shaping The impacts such as release property difference.When being set at less than 0.01 area %, produce substantial amounts of energy and discard Thing, therefore the most preferred from environment/industry perspective.

It addition, in the epoxy resin composition of the present invention, n=2,3,4 in the most described formula (1) Add up to 40 area %～85 area %.By making the width of molecular weight distribution within the range, Viscosity can be reduced while easily there is high-fire resistance, and heat point can be improved further Solve characteristic.Here, the compound thermostability of n=2, pyrolytic are excellent, and it is formed without molecule Measure too high material, therefore permissible by the compound containing 20 area %～50 area %n=2 Guarantee the physical property being more suitable for, particularly preferably 20 area %～40 area %.

It should be noted that described formula (1) in the present invention must contain naphthol component and cresol Structure, can not be all 0.Preferred naphthol component specifically: cresol structure=1:1～5:1, especially It is preferably 1:1～3:1, preferably there is more naphthol component.

As the preferred resin properties of epoxy resin composition of the present invention, epoxide equivalent is preferably 180g/eq.～230g/eq., more preferably 200g/eq.～220g/eq..By making epoxide equivalent exist In above-mentioned scope, the thermostability of solidfied material, the electricity more excellent epoxy resin of reliability can be obtained. In the case of epoxide equivalent is more than 230g/eq., sometimes epoxide ring completely closed loop and containing a large amount of the most not Having the compound of functional group, epoxide equivalent does not declines sometimes.It addition, in most cases permitted Containing chlorine in the compound of these incomplete closed loops many, sometimes can produce as electronic material purposes The corrosion of the wiring dissociating and being generated by of the chloride ion under the conditions of high temperature and humidity.

It should be noted that the melt viscosity (ICI melt viscosity cone-plate method) at 150 DEG C is preferably Below 0.5Pa s, when viscosity is too high, poor fluidity when transfer molding or compression forming, sometimes go out Now it is not filled by portion and forms defective products, the most not preferred, even if viscosity is too low, the most easily carry secretly Space, the most preferably has the viscosity of a certain degree.In the present invention particularly preferably 0.05Pa s～ 0.5Pa s, particularly preferred 0.05Pa s～0.4Pa s.

Additionally, as total chlorine of residual, preferably 1500ppm in the epoxy resin composition of the present invention Hereinafter, more preferably below 1200ppm, particularly preferably below 900ppm.Need explanation It is below 5ppm to be respectively preferably for chloride ion, sodium ion, more preferably below 3ppm. The harmful effect of chloride ion is as described above.The cationes such as sodium ion are particularly used at power device Also it is very important factor in Tu, a reason of fault mode when being to apply high voltage.

Hereinafter, the curable resin group to the present invention of the epoxy resin composition containing the present invention Compound (hereinafter also referred to curable resin composition) illustrates.

In the curable resin composition of the present invention, use firming agent or polymerization catalyst conduct Neccessary composition.

The curable resin composition of the present invention preferably comprises inorganic filler.As inorganic filler, Crystalline silica, fused silica, aluminium oxide, zircon, calcium silicates, carbon can be enumerated Acid calcium, carborundum, silicon nitride, boron nitride, zirconium oxide, forsterite, steatite, point are brilliant The powder of stone, titanium dioxide, Talcum etc. or they are made ball etc. that is spherical and that obtain, but It is not limited to these.They can be used alone, it is possible to use two or more.These are inorganic The content of filler, is preferably used in the curable resin composition of the present invention and accounts for usually 60 Weight %～95 weight %, particularly 70 weight %～the amount of 90 weight %.

During less than 60 weight %, it is possible to water absorption rate, linear expansivity are too high, it addition, more than 95 During weight %, possibly cannot be the most mixing.It addition, mobility goes wrong and is difficult to not have sometimes Have unfilled in the case of seal.

Hereinafter, compounding ratio and other coordination compounds to the curable resin composition of the present invention are entered Row explanation.

As the polymerization catalyst that can use (hereinafter also referred to as curing accelerator.) concrete example, Can enumerate: the imidazoles such as 2-methylimidazole, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-(two Methylaminomethyl) phenol, 1, the tertiary amines such as 8-diaza-dicyclo (5.4.0) 11 carbon-7-alkene, three The phosphine classes such as Phenylphosphine, 4-butyl ammonium, triisopropyl methyl ammonium salt, trimethyldecylammonium ammonium salt, The quaternary ammonium salts such as cetyltrimethyl ammonium salt, triphenylbenzylphosphoniumSalt, triphenyl ethylSalt, The tetrabutylThe seasons such as saltSalt (counter ion counterionsl gegenions of quaternary salt be halogen, organic acid ion, hydroxyl from Sons etc., do not specify, particularly preferred organic acid ion, hydroxide ion.), tin octoate Deng metallic compound etc..In the case of using curing accelerator, relative to epoxy resin 100 Weight portion, the most generally uses 0.01 weight portion～5.0 weight portions.

In curable resin composition, permissible in addition to the epoxy resin composition of the present invention And use other epoxy resin.And with in the case of, ratio shared in whole epoxy resin is excellent Elect more than 30 weight % as, more than particularly preferably 40 weight %.

As the concrete example of other epoxy resin, can enumerate: phenolic resin varnish type epoxy resin, Bisphenol A type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol Aralkyl-type epoxy resin etc..Can enumerate specifically: 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 phenyl) methane, 1,1,2,2-tetra-(4-hydroxy phenyl) ethane, phenols (phenol, alkyl substituted phenol, naphthols, alkyl Substituted naphthol, dihydroxy benzenes, dihydroxy naphthlene etc.) and formaldehyde, acetaldehyde, benzaldehyde, para hydroxybenzene Formaldehyde, salicylaldhyde, parahydroxyacet-ophenone, o-hydroxyacetophenone, dicyclopentadiene, Furfural, 4,4 '-bis-(chloromethyls)-1,1 '-biphenyl, 4,4 '-bis-(methoxies)-1,1 '-biphenyl, 1,4- The condensation polymer of double (methoxy) benzene of double (chloromethyl) benzene, 1,4-etc. and their modifier, By the derivative glycidyl etherified thing of the halogenated bisphenol classes such as tetrabromobisphenol A, alcohols, ester ring type Epoxy resin, glycidyl amine epoxy resin, glycidyl esters based epoxy resin etc.； The epoxy resin of silsesquioxane alkanes (chain, ring-type, scalariform or at least a part of which two kinds with On mixed structure siloxane structure in there is glycidyl and/or 7-oxa-bicyclo[4.1.0 structure Epoxy resin) etc. solid-state or liquid-state epoxy resin, but be not limited to these.

The firming agent contained as the curable resin composition of the present invention, can enumerate such as phenol Resin, phenolic compound, aminated compounds, anhydrides compound, amides compound, carboxylic Acid compounds etc..And with in the case of, ratio shared in firming agent is preferably 30 weight More than %, more than particularly preferably 40 weight %.

Concrete example as the firming agent that can use is as follows.

Phenol resin, phenolic compounds；Can enumerate: bisphenol-A, 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, hydroquinone, resorcinol, naphthalenediol, three (4-hydroxy phenyl) methane, 1,1,2,2- Four (4-hydroxy phenyl) ethane, phenols (phenol, alkyl substituted phenol, naphthols, alkyl-substituted naphthaline phenol, Dihydroxy benzenes, dihydroxy naphthlene etc.) and formaldehyde, acetaldehyde, benzaldehyde, hydroxy benzaldehyde, adjacent hydroxyl Benzaldehyde, parahydroxyacet-ophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 1,4 '- The condensation polymer of double (chloromethyl) benzene, 1,4 '-bis-(methoxy) benzene etc. and their modifier, The Polyphenols such as the condensation substance of the halogenated bisphenol classes such as tetrabromobisphenol A, terpenes and phenols, but be not limited to These.These materials can be used alone, it is possible to use two or more.

As and with in preferred phenol resin, phenol aralkyl resin can be enumerated and (there is aromatic series The resin of alkylen structures), following resin: it is characterized in that as having selected from benzene The structure of at least one in phenol, naphthols, cresol, and as the alkylene base portion of its linking group Be divided in benzene structure, naphthalene structure at least one (can enumerate specifically phenol aralkyl, Naphthols phenol aralkyl, phenol-naphthol novolak varnish gum etc.).

Aminated compounds, amides compound；Can enumerate: diaminodiphenyl-methane, two Ethylenetriamine, trien, DADPS, isophorone diamine, dicyandiamide, The nitrogen-containing compounds such as the polyamide synthesized with ethylenediamine by linolenic dimer, but not It is limited to these.These materials can be used alone, it is possible to use two or more.

Acid glycosides compound, carboxylic acid compound；Can enumerate: phthalic anhydride, inclined benzene Three anhydride, pyromellitic dianhydride, maleic anhydride, tetrabydrophthalic anhydride, methyl tetrahydrochysene neighbour's benzene Dicarboxylic acid anhydride, methylnadic anhydride, carbic anhydride, hexahydrophthalic anhydride, methyl Hexahydrophthalic anhydride, ethylene-dimalonic acid acid anhydride, dicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, first The anhydride such as base dicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, hexamethylene-1,3,4-tricarboxylic acid-3,4-anhydride； The carboxylic acid obtained by various alcohol, carbinol-modified polysiloxanes and the additive reaction of described anhydride Resin, but it is not limited to these.These materials can be used alone, it is possible to use two kinds with On.

The firming agent that can be used together as other, can enumerate imidazoles, trifluoroboranes-amine complex, The compound etc. of guanidine derivatives, but it is not limited to these.These materials can be used alone, also Can use two or more.

From the standpoint of reliability, phenol resin is particularly preferably used in the present invention.

In the curable resin composition of the present invention, the usage amount of firming agent is relative to whole asphalt mixtures modified by epoxy resin Epoxy radicals 1 equivalent of fat is preferably 0.7 equivalent～1.2 equivalents.Relative to epoxy radicals 1 equivalent not Foot 0.7 equivalent in the case of or more than 1.2 equivalents in the case of, all can sometimes cannot not solidify completely Entirely can not get good solidification physical property.

In the curable resin composition of the present invention, it is also possible to promote together with firming agent and with solidification Enter agent.Concrete example as the curing accelerator that can use can enumerate above-mentioned solidification promotion Agent.In the case of using curing accelerator, relative to epoxy resin 100 weight portion according to need Generally to use 0.01 weight portion～5.0 weight portions.

In the curable resin composition of the present invention, it is also possible to containing phosphorus-containing compound as fire-retardant Property give composition.As phosphorus-containing compound, both can be the phosphorus-containing compound of response type, it is possible to To be the phosphorus-containing compound of addition type.As the concrete example of phosphorus-containing compound, can enumerate: phosphorus Acid trimethyl, triethyl phosphate, tricresyl phosphate, tricresyl phosphate (xylyl) ester, phosphoric acid first Double (the di(2-ethylhexyl)phosphate (two of phenyl ester diphenyl ester, cresyl phosphate-2,6-two (xylyl) ester, 1,3-phenylene Tolyl) ester), 1,4-phenylene double (di(2-ethylhexyl)phosphate (xylyl) ester), 4,4 '-biphenyl (di(2-ethylhexyl)phosphate (two Tolyl) ester) etc. phosphoric acid ester；9,10-dihydro-9-oxy miscellaneous-10-phospho hetero phenanthrene-10-oxide, The phosphine classes such as 10-(2,5-dihydroxy phenyl)-10H-9-oxa--10-phospho hetero phenanthrene-10-oxide；Asphalt mixtures modified by epoxy resin The reactive with active hydrogen of fat and described phosphine class and obtain phosphorous epoxide, red phosphorus etc., preferably Phosphoric acid ester, phosphine class or phosphorous epoxide, the double (di(2-ethylhexyl)phosphate (two of particularly preferred 1,3-phenylene Tolyl) ester), 1,4-phenylene double (di(2-ethylhexyl)phosphate (xylyl) ester), 4,4 '-biphenyl (di(2-ethylhexyl)phosphate (two Tolyl) ester) or phosphorous epoxide.The preferred phosphorus-containing compound of content of phosphorus-containing compound/ All epoxy resin=0.1～0.6 (weight ratios).Time below 0.1, possible anti-flammability is insufficient, When more than 0.6, the hygroscopicity of solidfied material, dielectric property reduce sometimes.

Additionally, the curable resin composition of the present invention can add antioxidant as required. As the antioxidant that can use, can enumerate phenol antioxidant, sulfur-type antioxidant, Containing phosphorous antioxidant.Antioxidant may be used singly or two or more in combination.Anti- The usage amount of oxidant is relative to the resinous principle 100 in the curable resin composition of the present invention Weight portion is usually 0.008 weight portion～1 weight portion, is preferably 0.01 weight portion～0.5 weight Part.

As the concrete example of phenol antioxidant, can illustrate: 2,6 ditertiary butyl p cresol, fourth Base BHA, 2,6-di-t-butyl paraethyl phenol, β-(3,5-di-t-butyl-4-hydroxy benzenes Base) propanoic acid stearyl ester, 3-(3,5-di-tert-butyl-hydroxy phenyl) the different monooctyl ester of propanoic acid, 2,4-be double the most pungent Sulfenyl-6-(4-hydroxyl-3,5-di-tert-butyl amido)-1,3,5-triazine, 2,4-are double [(pungent sulfenyl) methyl] The unitary phenols such as orthoresol；2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol), 2,2 '-methylene Double (4-ethyl-6-tert-butyl phenols), 4,4 '-thiobis (3 methy 6 tert butyl phenol), 4,4 '-Asia Double [3-(the 3-tert-butyl group-5-methyl-4-the hydroxyl of butyl double (3 methy 6 tert butyl phenol), triethylene glycol Phenyl) propionic ester], 1,6-HD-bis-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], N, N '-hexa-methylene double (3,5-di-t-butyl-4-hydroxyl-hydrocinnamamide), 2,2-sulfur generation-diethylidene Double [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic esters], 3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids Diethylester, 3,9-pair [1,1-dimethyl-2-{ β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy } Ethyl] 2,4,8,10-tetra-oxaspiro [5.5] hendecane, double (3,5-di-tert-butyl-4-hydroxyl benzyl sulfonic acid Ethyl ester) bisphenols such as calcium；1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5- Trimethyl-2,4,6-three (3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, four-[methylene-3-(3 ', 5 '-two uncles Butyl-4 '-hydroxy phenyl) propionic ester] methane, double [3,3 '-bis--(4 '-hydroxyl-3 '-tert-butyl-phenyl) fourth Acid] glycol ester, isocyanuric acid three (3,5-di-tert-butyl-4-hydroxyl benzyl) ester, 1,3,5-tri-(3 ', 5 '- Di-t-butyl-4 '-hydroxybenzyl) guanamine, 4,6-(1H, 3H, the 5H) macromolecule such as triketone, tocopherol Type phenols.

As the concrete example of sulfur-type antioxidant, can illustrate: 3,3 '-thiodipropionic acid dilauryl Osmanthus ester, 3,3 '-thio-2 acid two myristin, 3,3 '-distearylthiodi-propionate etc..

As the concrete example containing phosphorous antioxidant, can illustrate: triphenyl phosphite, phosphorous Diphenyl phthalate isodecyl ester, phenyl-phosphite two isodecyl ester, tricresyl phosphite (nonyl phenyl) ester, phosphorous Acid two isodecyl ester pentaerythritol esters, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, ring-type neopentane Double (octadecyl) phosphite ester of four bases, ring-type neopentane four base double (2,4-di-tert-butyl-phenyl) are sub- Phosphate ester, ring-type neopentane four base double (2,4-di-t-butyl-4-aminomethyl phenyl) phosphite ester, double [2- The tert-butyl group-6-methyl-4-{2-(octadecane epoxide carbonyl) ethyl } phenyl] phosphorous acid such as H-Phosphonate Esters；9,10-dihydro-9-oxy miscellaneous-10-phospho hetero phenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxyl Base benzyl)-9,10-dihydro-9-oxy miscellaneous-10-phospho hetero phenanthrene-10-oxide, 10-decyloxy-9,10-dihydro The oxa-phospho hetero phenanthrenes such as-9-oxa--10-phospho hetero phenanthrene-10-oxide are oxide-based.

These antioxidants can each be used alone can also two or more combinations using.Especially It it is the antioxidant the most preferably containing phosphorous.

Additionally, in the curable resin composition of the present invention, light can be added as required steady Determine agent.

As light stabilizer, hindered amine light stabilizer, particularly HALS etc. are applicable. As HALS, it is not particularly limited, as representational HALS, can enumerate: dibutyl amine -1,3,5-triazine-N, N '-bis-(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylene diamine with N-(2,2,6,6-tetramethyl-4-piperidyl) condensation polymer of butylamine, dimethyl succinate-1-(2-hydroxyl second Base)-4-hydroxyl-2,2,6,6-tetramethyl piperidine condensation polymer, poly-[{ 6-(1,1,3,3-tetramethyl butyl) amino -1,3,5-triazine-2,4-diyl } { (2,2,6,6-tetramethyl-4-piperidyl) imino group } hexa-methylene { (2,2,6,6-tetramethyl-4-piperidyl) imino group }], [[double (1,1-dimethyl ethyl)-4-hydroxyl of 3,5- Phenyl] methyl] double (1,2,2,6,6-pentamethyl-4-piperidyl) ester of butylmalonic acid, decanedioic acid be double Double (1,2,2,6,6-pentamethyl-4-piperidyl) ester of (2,2,6,6-tetramethyl-4-piperidyl) ester, decanedioic acid, Decanedioic acid double (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) ester, 2-(3,5-di-t-butyl-4-hydroxyl Base benzyl) double (1,2,2,6,6-pentamethyl-4-piperidyl) esters of-2-n-butylmalonic acid etc..HALS can Only a kind of to use, it is also possible to and with two or more.

Additionally, the curable resin composition of the present invention can also coordinate binding agent as required Resin.As resin glue, can enumerate butyral resinoid, acetal resin, third Olefin(e) acid resinoid, epoxy-nylon-based resin, NBR-phenolic resin, epoxy-NBR resinoid, Polyamide-based resin, polyimide based resin, polysiloxanes resinoid etc., but it is not limited to this A bit.The use level of resin glue is preferably at the model not damaging the anti-flammability of solidfied material, thermostability In enclosing, relative to epoxy resin ingredient 100 weight portion the most generally use 0.05 weight portion～ 50 weight portions, preferably 0.05 weight portion～20 weight portions.

It addition, the curable resin composition of the present invention can coordinate cyanate resin as required Fat, maleimide resin, benzoPiperazines etc. are for improving the resin of thermostability, its use level phase For epoxy resin ingredient 100 weight portion, the most generally use 10 weight portions～50 weight Part, 15 weight portions～40 weight portions are preferably used.

Additionally, in the curable resin composition of the present invention, silane coupler, hard can be added The releasing agents such as fat acid, Palmic acid, zinc stearate, calcium stearate, surfactant, dyestuff, The various compounding ingredient such as pigment, UV absorbent, various thermosetting resin, relative to curable The total amount of resin combination is usually 0.05 weight %～1.5 weight %, especially for 0.05 weight %～1.0 weight %.

The curable resin composition of the present invention can be by being obtained by uniformly mixingg each composition. The curable resin composition of the present invention can be held by the method identical with existing known method Change places and make its solidfied material.Such as, epoxy resin composition is promoted with firming agent and/or solidification Agent, phosphorus-containing compound, resin glue, inorganic filling material and compounding ingredient etc. enter as required Row is pulverized, and then carries out being obtained by mixing curable resin group with extruder, kneader, roller etc. Compound, then this curable resin composition is pulverized, make lamellar or granular, and use transmission Forming machine or compacting shape machine etc. form at 140 DEG C～220 DEG C, then at 100 DEG C～220 Heat 1 hour～10 hours at DEG C, it is hereby achieved that the solidfied material of the present invention.

The semiconductor device of the present invention obtains in the following manner: install half on printed wiring board Conductor element, covers after the composition epoxy resin of the present invention is configured to granular or lamellar and partly leads Body chip, and more than 175 DEG C and less than 250 DEG C form.The installation side of semiconductor element Method, encapsulating method are not particularly limited.Such as, flip-chip bond device etc. is used to carry out multilamellar The position alignment of the solder projection of the connecting electrode portion on printed wiring board and semiconductor element. Then, solder projection is heated to more than fusing point, by being melted with solder projection by printed wiring board Fuse conjunction and connect.It follows that filling liquid is close between printed wiring board and semiconductor element Envelope resin is also solidified.Thus, semiconductor device is obtained.The semiconductor device so obtained There is the thermostability of excellence and resistance to pyrolytic, the most particularly in vehicle-mounted power device etc. Useful.

Embodiment

Hereinafter, by embodiment, the present invention is further illustrated, hereinafter, if do not had Having special instruction, " part " is weight portion.It should be noted that it is real to the invention is not restricted to these Execute example.

Hereinafter, the various analysis methods for using in embodiment illustrate.

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

ICI melt viscosity: according to JIS K 7117-2 (ISO 3219)

Softening point: according to JIS K 7234

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

It is oxolane in conjunction with eluent

Flow velocity is 0.5ml/ minute

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 possessing blender, reflux condensing tube, agitating device, implementing nitrogen purging While add betanaphthol 144 parts, orthoresol 65 parts, methyl iso-butyl ketone (MIBK) 220 parts, and to Wherein add the sodium hydrate aqueous solution that concentration is 25% of 48 parts, then drip dense at 10 DEG C Degree is the formalin 88.4 parts of 35%, and stirs 2 hours at 10 DEG C, is subsequently adding 35% Concentrated hydrochloric acid 32 parts be neutralized, then at 30 DEG C stir 3 hours.To the reactant liquor obtained Middle addition methyl iso-butyl ketone (MIBK) 100 parts, 100 parts of water, then discard water layer, add many Polyformaldehyde 4.6 parts and p-methyl benzenesulfonic acid, with 4 hours compounds by described formula (3) at 75 DEG C Thermal decomposition, carries out novolaks reaction simultaneously.

The sodium hydrate aqueous solution 5 parts of 30% is added in reaction after terminating, and washes, then Take out organic layer, solvent is distilled off by rotary evaporator.

Again this resin is dissolved in 300 parts of toluene.Containing of the compound of the most described formula (3) Amount is 1.5 area %, and the compound of described formula (4) is 31 area %, and the naphthols of residual is 4 Long-pending %.

In the flask possessing blender, reflux condensing tube, agitating device, implementing nitrogen purging While add this solution, then add p-methyl benzenesulfonic acid 1 part, be warming up to 80 DEG C, then Add formalin 15 parts, and stir 1 hour, be then warming up to while slowly removing water 110 DEG C, and under reflux conditions carry out reaction in 3 hours.Then wash, by obtaining Organic layer rotary evaporator under reduced pressure solvent is distilled off and obtain in the present invention use 213 parts of phenolic resin (BN1).

The softening point of the phenolic resin obtained is 138.1 DEG C, and the compound of described formula (3) is 0.2 Long-pending %, the compound of described formula (4) is 4.8 area %, and residual naphthols is 0.2 area %, residual Cresol is 0.1 below area %.It addition, hydroxyl equivalent is 141g/eq..

(synthesis example 2)

In the flask possessing blender, reflux condensing tube, agitating device, implementing nitrogen purging While add betanaphthol 134 parts, alpha-Naphthol 10 parts, orthoresol 55 parts, methyl-isobutyl Ketone 150 parts, and it is added to the concentrated hydrochloric acid of 20 part 35%, then add formalin 75 Part, and react 5 hours at 10 DEG C, react 4 hours at 45 DEG C.Now, described formula (3) The content of compound be 39 area %, the compound of described formula (4) is 21 area %.

Here, removing water layer, then add paraformaldehyde 15 parts with p-methyl benzenesulfonic acid 2 parts also It is warming up to 80 DEG C, described formula (3) is thermally decomposed, carries out novolaks reaction simultaneously.

The sodium hydrate aqueous solution 5 parts of 30% is added in reaction after terminating, and washes, then Take out organic layer, obtain use in the present invention by solvent being distilled off by rotary evaporator 212 parts of phenolic resin (BN2).

The softening point of the phenolic resin obtained is 134.4 DEG C, and the compound of described formula (3) is 1.9 Long-pending %, the compound of described formula (4) is 4.7 area %, and residual naphthols is 0.8 area %, residual Cresol is 0.1 below area %.It addition, hydroxyl equivalent is 148g/eq..

(synthesis example 3)

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

In the flask possessing blender, reflux condensing tube, agitating device, implementing nitrogen purging While add betanaphthol 288 parts, orthoresol 108 parts, methyl iso-butyl ketone (MIBK) 841 parts.To Wherein add 67 parts of paraformaldehydes, and at 25 DEG C, carry out reaction in 2 hours.After reaction terminates, The concentrated hydrochloric acid adding 41 part 35% is neutralized, and then adds p-methyl benzenesulfonic acid 5.7 parts, and Carry out reaction in 2 hours at 25 DEG C, at 80 DEG C, carry out reaction in 2 hours.Then it is washed to Reactant liquor is neutral, the solvent etc. of oil reservoir is distilled off adding to depress, thus has obtained 410 Part bakelite B N3.

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

(embodiment 1)

In the flask possessing blender, reflux condensing tube, agitating device, implementing nitrogen purging While add 92.6 parts of phenolic resin (BN1), the 4,4 '-'-biphenyl diphenol 21.2 used in the present invention Part, chloropropylene oxide 416 parts, dimethyl sulfoxide 95.8 parts, under agitation dissolve and be warming up to 45 DEG C. Next divided with 90 minutes and add 42 parts of laminar sodium hydroxide, the most again at 45 DEG C Carry out reaction in 2 hours, at 70 DEG C, carry out reaction in 75 minutes.After reaction terminates, steam with rotating Send out device from oil reservoir, the chloropropylene oxide equal solvent class of excess is under reduced pressure distilled off.In residue Add methyl iso-butyl ketone (MIBK) 352 parts and dissolve, after washing, being warming up to 75 DEG C.Under agitation add The sodium hydrate aqueous solution of 30 weight % 13 parts, and carry out reaction in 1 hour, then wash Until the rinse water of oil reservoir becomes neutral, by under reduced pressure molten from obtain by rotary evaporator Methyl iso-butyl ketone (MIBK) etc. is distilled off in liquid and obtains the epoxy resin composition of the present invention (EP1) 153 parts.The epoxide equivalent of the epoxy resin obtained is 187g/eq., and softening point is 108 DEG C, ICI melt viscosity at 150 DEG C is 0.60Pa s.

The theoretical amount of the diepoxy propoxyl group biphenyl calculated by raw material is 20%.On the other hand, logical The amount crossing the diepoxy propoxyl group biphenyl that gel permeation chromatography calculates is about 16.9 area %.By This '-biphenyl diphenol structure understanding about 3.1% is introduced in cresol novolak structure.Need Bright, the total amount of the compound less 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 possessing reflux condensing tube, agitating device, add while implementing nitrogen purging Enter 92.6 parts of the phenolic resin (BN2) of use, 4,4 '-'-biphenyl diphenol 21.2 parts, table chlorine in the present invention Alcohol 416 parts, dimethyl sulfoxide 95.8 parts, under agitation dissolve and be warming up to 45 DEG C.Next Divided with 90 minutes and add 42 parts of laminar sodium hydroxide, at 45 DEG C, carry out 2 the most again Hour reaction, carry out at 70 DEG C 75 minutes reaction.After reaction terminates, exist by rotary evaporator From oil reservoir, the chloropropylene oxide equal solvent class of excess is distilled off under decompression.First is added in residue Base isobutyl ketone 352 parts also dissolves, and is warming up to 75 DEG C after washing.Under agitation add 30 weight The sodium hydrate aqueous solution of % 13 parts, and carry out 1 hour reaction, then carry out washing until oil The rinse water of layer becomes neutral, by under reduced pressure steaming from the solution obtained by rotary evaporator Evaporate removing methyl iso-butyl ketone (MIBK) etc. and obtain the epoxy resin composition (EP2) 160 parts of the present invention. The epoxide equivalent of the epoxy resin obtained is 187g/eq., and softening point is 109 DEG C, at 150 DEG C ICI melt viscosity is 0.29Pa s, and average molecular weight Mw is 2019.

The theoretical amount of the diepoxy propoxyl group biphenyl calculated by raw material is 9.8%.On the other hand, logical The amount crossing the diepoxy propoxyl group biphenyl that gel permeation chromatography calculates is 8.1 area %.Thus may be used Know that the '-biphenyl diphenol structure of 1.2% is introduced in cresol novolak structure.It should be noted that The total amount of the compound less than the n=2 molecular weight of above-mentioned formula (1) is 10.5 area %, and n=5 with On compound be 22 area %.

(Comparative examples A)

In the flask possessing blender, reflux condensing tube, agitating device, implementing nitrogen purging While add phenolic resin (BN3) 90.0 parts, 4,4 '-'-biphenyl diphenol 23.3 parts, chloropropylene oxide 416 Part, dimethyl sulfoxide 95.8 parts, under agitation dissolve and be warming up to 45 DEG C.Next with 90 Minute divide and to add 42 parts of laminar sodium hydroxide, carry out at 45 DEG C the most again 2 hours anti- Should, at 70 DEG C, carry out reaction in 75 minutes.After reaction terminates, by rotary evaporator under reduced pressure The chloropropylene oxide equal solvent class of excess is distilled off from oil reservoir.Methyl tert-butyl is added in residue Base ketone 352 parts also dissolves, and is warming up to 75 DEG C after washing.Under agitation add the hydrogen of 30 weight % Aqueous solution of sodium oxide 13 parts, and carry out reaction in 1 hour, then carries out washing until oil reservoir clear Wash water becomes neutral, by being under reduced pressure distilled off from the solution obtained by rotary evaporator Methyl iso-butyl ketone (MIBK) etc. and obtain the epoxy resin composition (EP3) 149 parts of comparative example.Obtain The epoxide equivalent of epoxy resin is 179g/eq., and softening point is 111 DEG C, and the ICI at 150 DEG C melts Viscosity is 0.43Pa s, and average molecular weight Mw is 2410.

The theoretical amount of the diepoxy propoxyl group biphenyl calculated by raw material is 22 area %.On the other hand, The amount of the diepoxy propoxyl group biphenyl calculated by gel permeation chromatography is 19.3 area %.By This '-biphenyl diphenol structure understanding 2.7% is introduced in cresol novolak structure.Need explanation , the total amount of the compound less 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 possessing blender, reflux condensing tube, agitating device, implementing nitrogen purging While add KAYAHARD CBN (softening point is 89 DEG C, and the compound of described formula (5) is 0.3 area %, the compound of (6) are 31 area %, residual naphthols is 1.6 area %, residual first Phenol is 0.1 below area %.It addition, hydroxyl equivalent is 140g/eq.) 98.4 parts, 4,4 '-biphenyl two 16.8 parts of phenol, chloropropylene oxide 416 parts, dimethyl sulfoxide 95.8 parts, under agitation dissolve and heat up To 45 DEG C.Next divided with 90 minutes and add 42 parts of laminar sodium hydroxide, the most again At 45 DEG C, carry out reaction in 2 hours, at 70 DEG C, carry out reaction in 75 minutes.After reaction terminates, From oil reservoir, the chloropropylene oxide equal solvent class of excess is under reduced pressure distilled off by rotary evaporator.? Residue add methyl iso-butyl ketone (MIBK) 352 parts and dissolves, after washing, being warming up to 75 DEG C.Stirring Mix the sodium hydrate aqueous solution 13 parts of lower addition 30 weight %, and carry out reaction in 1 hour, then Carry out washing until the rinse water of oil reservoir becomes neutral, by with rotary evaporator under reduced pressure from Methyl iso-butyl ketone (MIBK) etc. is distilled off in the solution obtained and obtains the epoxy resin mixing of comparative example Thing (EP4) 149 parts.The epoxide equivalent of the epoxy resin obtained is 195g/eq., and softening point is 98 DEG C, the ICI melt viscosity at 150 DEG C is 0.95Pa s.

The theoretical amount of the diepoxy propoxyl group biphenyl calculated by raw material is 15.7 area %.With this phase Right, the amount of the diepoxy propoxyl group biphenyl calculated by gel permeation chromatography is 13.1 area %. It can thus be appreciated that the '-biphenyl diphenol structure of 2.6% is introduced in cresol novolak structure.Need Bright, the total amount of the compound less than the n=2 molecular weight of above-mentioned formula (1) is 40.3 area %, And the compound of more than n=5 is 3 area %.

(comparative example 2)

In the flask possessing blender, reflux condensing tube, agitating device, implementing nitrogen purging While add KAYAHARD NHN (softening point is 89 DEG C, described formula (5), the chemical combination of (6) The total amount of thing is 6.8 area %, residual naphthols is 4.3 area %, residual cresol is 0.1 area % Below.It addition, hydroxyl equivalent is 143g/eq.) 107 parts, 4,4 '-'-biphenyl diphenol 23.3 parts, table Chloropharin 416 parts, dimethyl sulfoxide 95.8 parts, under agitation dissolve and be warming up to 45 DEG C.Connect down Use 90 minutes to divide and add 42 parts of laminar sodium hydroxide, carry out at 45 DEG C the most again Reaction in 2 hours, carries out reaction in 75 minutes at 70 DEG C.After reaction terminates, use rotary evaporator From oil reservoir, the chloropropylene oxide equal solvent class of excess is under reduced pressure distilled off.Residue adds Methyl iso-butyl ketone (MIBK) 352 parts also dissolves, and is warming up to 75 DEG C after washing.Under agitation add 30 weights Amount % sodium hydrate aqueous solution 13 parts, carry out 1 hour reaction, then carry out washing until oil The rinse water of layer becomes neutral, by under reduced pressure steaming from the solution obtained by rotary evaporator Evaporate removing methyl iso-butyl ketone (MIBK) etc. and obtain the epoxy resin composition (EP5) 175 parts of comparative example. The epoxide equivalent of the epoxy resin obtained is 196g/eq., and softening point is 98 DEG C, the ICI at 150 DEG C Melt viscosity is 0.15Pa s.

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

Embodiment 4～7 and comparative example 3～6

<TMA condition determination>

Thermomechanical determinator: TA-instruments manufactures, TMA-2980

Mensuration temperature range: 40 DEG C～280 DEG C

Programming rate: 2 DEG C/min

<DMA condition determination>

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

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

Ramp rates: 2 DEG C/min

Test film size: use cut into 5mm × 50mm test film (thickness be about 800μm)。

Analysis condition

Tg: the peak point (Tan δ MAX) of the Tan δ in being measured by DMA is as Tg.

<condition determination of resistance to thermal decomposition characteristic>

TG-DTA is used to measure (Td5)

Mensuration sample: powdery (by 100 μm sieve apertures, and staying on 75 μm sieve apertures) 5-10mg

Condition determination: programming rate 10 DEG C/min, air-flow 200ml/ minute

Determine 5% weightless temperature.

Table 1

Phenol novolacs: bright and chemical conversion industry manufactures H-1

Curing accelerator: Xinghua, triphenylphosphine north length of schooling makes TPP

Curing accelerator usage amount: be 1phr relative to epoxy resin

Epoxy resin-catalyst ratio: equivalent

Condition of cure: transfer molding at 175 DEG C, at 160 DEG C 2 hours, at 180 DEG C 6 hours

Table 2

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

Phenol novolacs: bright and chemical conversion industry manufactures H-1

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

Curing accelerator usage amount: be 1phr relative to epoxy resin

Condition of cure: transfer molding at 175 DEG C, at 160 DEG C 2 hours and 180 DEG C

Understand according to this result, employ the consolidating of compositions of the epoxy resin composition of the present invention Compound can take into account high thermostability and resistance to thermal decomposition characteristic.

It is described in detail by the present invention with reference to specific embodiment, but, for this area skill Art personnel are it is readily apparent that without departing from the spirit and scope of the present invention, permissible Make various changes and modifications.

It should be noted that the Japan Patent Shen that the application proposed based on March 11st, 2014 Please (Patent 2014-047563), the quoting entirely through quoting of this application.It addition, at this That quotes is all of with reference to as being integrally incorporated this specification.

Industrial applicability

The thermostability of the epoxy resin composition of the present invention is high and resistance to thermal decomposition characteristic excellent, therefore The curable resin composition of the epoxy resin composition containing the present invention is as electric and electronic material Purposes, particularly semiconductor encapsulant, film substrate material are useful.

Claims (8)

1. an epoxy resin composition, it contains the compound represented by following formula (1) and following Compound represented by formula (2),

The content of difunctional epoxy resin measures the face in spectrogram with gel permeation chromatography (GPC) Long-pending percentage is 20 below area %, and

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

In formula (1), n represents that repeat number, n are the numbers being calculated as 2～10 with meansigma methods, it addition, not It is that all of A is the most identical,

2. epoxy resin composition as claimed in claim 1, wherein, described formula (2) is represented The content of compound measure in terms of the area percentage in spectrogram by gel permeation chromatography (GPC) It is 2 area %～18 area %.

3. epoxy resin composition as claimed in claim 1 or 2, it is by by softening point being The naphthols of 120 DEG C～150 DEG C-cresol mixing novolac resin and 4,4 '-'-biphenyl diphenol mixing and React with epihalohydrin in the basic conditions and obtain.

4. epoxy resin composition as claimed any one in claims 1 to 3, it is 150 Melt viscosity at DEG C is more than 0.05Pa s and 0.5Pa below s.

5. a curable resin composition, it contains according to any one of Claims 1-4 Epoxy resin composition and firming agent.

6. a curable resin composition, it contains according to any one of Claims 1-4 Epoxy resin composition and polymerization catalyst.

7. a solidfied material, it is by combining the curable resin described in claim 5 or 6 Thing solidifies and obtains.

8. a semiconductor device, it is by by the curable resin described in claim 5 or 6 Compositions is configured to granular or lamellar, be then covered by semiconductor chip and more than 175 DEG C and Less than 250 DEG C form and obtain.