TWI565751B - Epoxy resin molding materials and electronic components for packaging - Google Patents

Description

Epoxy resin molding material and electronic component device for packaging

The present invention relates to an epoxy resin molding material for encapsulation, and an electronic component device including the component encapsulated by the molding material.

In recent years, with the miniaturization, weight reduction, and high performance of electronic equipment, the mounting has been increasing in density, and the electronic component device has been developed into a surface mount type package from the past pin insertion type. In order to increase the mounting density and reduce the mounting height, the surface mount type IC, LSI, etc. are thin and small, and the area occupied by the element with respect to the package is large, and the package thickness can be extremely thin. In addition, these packages are different from those of past pin-inserted types. That is, when mounted on a wiring board, in the past, the pin-insertion type package was not directly exposed to a high temperature due to soldering from the back side of the wiring board after the pins were inserted into the wiring board. However, the surface mount package is directly exposed to the soldering temperature (reflow temperature) because the semiconductor device is entirely processed by a solder bath or a reflow device. As a result, when the package absorbs moisture, the moisture absorbing moisture rapidly expands during welding, and the generated water vapor acts as a peeling stress, causing peeling between the insert of the component, the lead frame, and the like, and the package material is peeled off. Become a package cracked hair The cause of poor bioelectricity or electrical properties. Therefore, it has been desired to develop an encapsulating material excellent in solder heat resistance (reflow resistance).

In order to cope with these requirements, various reviews have been made on the epoxy resin as the main material. However, only the improvement of the epoxy resin is accompanied by a decrease in heat resistance due to low moisture absorption, accompanied by density. The improvement of the sexual properties may result in a decrease in hardenability, and it is difficult to balance the physical properties. In view of the above, various epoxy resin modifiers have been reviewed, and one of them is a sulfur atom-containing compound which has been attracting attention in terms of improving adhesion to an insert such as a component or a lead frame (see, for example, Patent Documents 1 and 2). Further, a sulfonium coupling agent containing a sulfur atom (see, for example, Patent Document 3) or a fluorene styrene ‧ phenol copolymer oligomer (see, for example, Patent Document 4).

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Publication No. 11-12442

Patent Document 2: JP-A-2002-3704

Patent Document 3: JP-A-2000-103940

Patent Document 4: Japanese Patent Publication No. Hei 10-265650

However, when the sulfur atom-containing decane coupling agent described in the above Patent Document 3 is used, the adhesion improving effect with a noble metal such as Ag or Au is lacking, and the sulfur atom-containing compound described in Patent Documents 1 and 2 is used. Even if the amount disclosed in the literature is added, the improvement with precious metals cannot be fully improved. Sexuality, depending on the situation, may be considered to be due to the deterioration of electrical properties caused by sulfur in the compound. When the 茚 styrene ‧ phenol copolymerized oligomer described in Patent Document 4 is used, the other characteristics are not deteriorated, but the effect of improving the reflow resistance is not obtained.

As described above, in the past, the present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a package epoxy which is excellent in reflow resistance without lowering moldability or flame retardancy. A resin molding material, and an electronic component device having a component packaged using the material.

The present invention relates to an epoxy resin molding material containing a specific cerium-containing compound and an electronic component device including the component encapsulated by the epoxy resin molding material for packaging. More specifically, it is as follows.

(1) The present invention relates to an epoxy resin molding material for encapsulation comprising (A) an epoxy resin, (B) a hardener, (C) a hardening accelerator, (D) an inorganic filler, and (E) The ruthenium polymer (E) ruthenium-containing polymer has any two or all of the structures represented by the following general formula (I), the following general formula (II), and the following general formula (III), (E) The weight average molecular weight of the cerium-containing polymer is 1,500 or more and 7,000 or less.

In the formula (I), R ¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms, and at least one of the oxygen atoms is an oxygen atom constituting a siloxane coupling, and an oxygen atom other than the oxygen atom and a hydrogen atom Bonding.

In the formula (II), R ¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms, wherein R ¹ may be the same or different, and at least one of the oxygen atoms is an oxygen atom constituting a siloxane chain. And an oxygen atom other than the oxygen atom is bonded to a hydrogen atom.

In the formula (III), at least one of the oxygen atoms is an oxygen atom constituting a siloxane chain, and an oxygen atom other than the oxygen atom is bonded to a hydrogen atom.

(2) The present invention relates to the epoxy resin molding material for encapsulation according to (1), wherein (E) the content of the ruthenium-containing polymer is 2.5 with respect to the (A) epoxy resin in the epoxy resin molding material for encapsulation. The mass% is 40% by mass or less.

(3) based on the package of the present invention (1) or (2) of the epoxy resin molding material, wherein the encapsulating epoxy resin molding material of (E) The silicon-containing polymer in whole by ¹ R & lt The proportion of the substituted or unsubstituted phenyl group is 40 mol% or more and 100 mol% or less.

(4) The epoxy resin molding material for encapsulation according to any one of (1) to (3) further comprising a fluorene oligomer.

(5) The epoxy resin molding material for encapsulation according to any one of (1) to (4) further comprising a decane compound (a) represented by the following formula (IV),

In the formula (IV), R ¹ represents a cycloalkyl group or a cycloalkenyl group having 5 to 8 carbon atoms, R ² is the same as R ¹ or a hydrocarbon group having 1 to 6 carbon atoms, and R ³ represents a hydrocarbon group having 1 to 6 carbon atoms. ^One of the hydrogen atoms represented by R ¹ to R ³ may be substituted, p represents an integer of 1 to 3, and q represents an integer of 0 to 3.

(6) The present invention relates to an electronic component device comprising the component encapsulated by the epoxy resin molding material for encapsulation according to any one of (1) to (5).

According to the epoxy resin molding material for encapsulation obtained by the present invention, an electronic component device having high reliability and excellent reflow resistance without reducing moldability or flame retardancy can be obtained, and its industrial value is large.

The present invention is an epoxy resin molding material for encapsulation comprising (A) an epoxy resin, (B) a curing agent, (C) a curing accelerator, (D) an inorganic filler, and (E) a cerium-containing polymer. The invention is described in detail below.

[(E) cerium-containing polymer]

The (E) ruthenium-containing polymer used in the present invention must be a ruthenium-containing polymer having any two or all of the structures represented by the following general formula (I), general formula (II), and general formula (III). These polymers are a three-membered crosslinked ruthenium-containing polymer having a branched polyoxyalkylene, an oxime resin or an intermediate for oxime resin modification, and do not contain a linear polyoxyalkylene.

In the formula (I), R ¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms, and at least one of the oxygen atoms is an oxygen atom constituting a siloxane coupling, and an oxygen atom other than the oxygen atom and a hydrogen atom Bonding.

In the formula (II), R ¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms, wherein R ¹ may be the same or different, and at least one of the oxygen atoms is an oxygen atom constituting a siloxane chain. And an oxygen atom other than the oxygen atom is bonded to a hydrogen atom.

In the formula (III), at least one of the oxygen atoms is an oxygen atom constituting a siloxane chain, and an oxygen atom other than the oxygen atom is bonded to a hydrogen atom.

The ruthenium-containing polymer of the present invention has a structure of either or both of the structures represented by the above formula (I), formula (II), or formula (III), but in the case of both, it is difficult to ignite From the viewpoint of the nature, the formula (I) and the formula (II) are preferred.

R ¹ in the above formulae (I) and (II) is exemplified by an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a t-butyl group, a pentyl group or a hexyl group, and an ethylene group. An alkenyl group such as a group, an allyl group, a butenyl group, a pentenyl group or a hexenyl group; a phenyl group; and the like, wherein a methyl group, a propyl group and a phenyl group are preferred in terms of ease of availability, and fluidity and flame retardancy are preferable. From the standpoint of sex, it is better to use phenyl.

Most of the compounds which can be obtained by linear polyoxyalkylene represented by fluorenone oil are liquid, have poor handleability, and are not able to obtain sufficient effects related to reflow resistance, and are polluting and flame retardant to the surface of the cured product. Sex also worsened. Further, even when the branched polyoxyalkylene has a structure different from the present invention, for example, a branched polyoxyalkylene containing an epoxy group, the effect of lowering the modulus of elasticity is insufficient, and the reflow resistance is not obtained. Full effect.

Further, the weight average molecular weight (Mw) of the (E) cerium-containing polymer needs to be 1,500 or more and 7,000 or less. Further, it is preferably 2,000 or more and 5,500 or less, more preferably 2,000 or more and 3,500 or less. Weight average When the molecular weight (Mw) is less than 1,500, the ruthenium-containing polymer becomes liquid or semi-liquid at normal temperature, the handleability is deteriorated, and the volatile content due to the low molecular component is increased, so that the reflow resistance cannot be sufficiently improved, and further It is also impossible to fully obtain flame retardancy. On the other hand, when the weight average molecular weight (Mw) is as large as more than 7,000, the effect of lowering the modulus of elasticity in a high temperature region is insufficient, and the reflow resistance may not be sufficiently improved. In addition, from the viewpoint of fluidity, it is preferably from 2,000 to 3,500, and further, the lower the molecular weight in this range, the more excellent the fluidity and the flame retardancy. Herein, Mw is obtained by gel permeation chromatography (GPC) using a calibration curve using standard polystyrene, and the above Mw is used as a pump for GPC (L-6200 manufactured by Hitachi, Ltd.). Type), pipe column (TSKgel-G5000HXL+TSKgel-G2000HXL, all manufactured by TOSHO Co., Ltd.), detector (L-3300RI type manufactured by Hitachi, Ltd.), using tetrahydrofuran as the eluent at temperature The results were measured at 30 ° C and a flow rate of 1.0 ml/min.

Further, in terms of formability, reflow resistance, and flame retardancy, (E) ratio of substituted or unsubstituted phenyl groups in all of R ¹ in the ruthenium-containing polymer (Ph group ratio) It is preferably 40 mol% or more and 100 mol% or less, more preferably 50 mol% or more and 90 mol% or less. When it is 40 mol% or more, compatibility with an epoxy resin or a hardener is good, it is hard to penetrate the surface of a hardened|curing material, and it is hard to cause a malfunction. Moreover, the effect of reducing the elastic modulus in the room temperature region or the high temperature region can be easily sufficiently obtained, and the reflow resistance can be sufficiently improved. In addition, there is also a tendency to improve the flame retardancy. In particular, it is more preferably 50 mol% or more from the viewpoint of reflow resistance and flame retardancy. Further, from the viewpoint of easiness of production of the ruthenium-containing polymer and difficulty in obtaining the ruthenium-containing polymer, it is preferably 90 mol% or less. Further, even in this range, the higher the ratio of the Ph group, the more excellent the flame retardancy.

Here, the ratio of the Ph group can be calculated from the 1H NMR measurement of the ruthenium-containing polymer, except for the O atom of the Si-O-Si bond, and the substituents of the phenyl group relative to the Si atom (phenyl group, alkoxy group) are calculated. The molar ratio of the hydroxyl group, etc., as the ratio of the Ph group.

Further, in the present invention, attention is paid to dividing the ratio of the substituted or unsubstituted phenyl group (the ratio of the Ph group) in all of R ¹ in the above (E) ruthenium-containing polymer by the molecular weight (Ph/). At Mw), Ph/Mw is considered to be the ratio of the simple phenyl group to the ruthenium-containing polymer as a whole. The higher the Ph/Mw, the more excellent the fluidity, and the excellent the reflow resistance in the high-temperature region is excellent in the reflow resistance.

The (E) ruthenium-containing polymer can be obtained by the following production method, but as a commercial product, SH-6018 which is available from Toray Dow Corning Co., Ltd., an oxime resin or an oxime resin modification intermediate, 217 FLAKE, 220 FLAKE, 233 FLAKE and other commercial products.

(E) The method for producing the ruthenium-containing polymer can be produced by a conventional method without particular limitation. For example, an organochloromethane, an organoalkoxydecane, a decane, or the like which is a unit represented by the above formula (I), formula (II) or formula (III) can be formed by a hydrolysis condensation reaction. The partially hydrolyzed condensate is mixed in a mixed solution of an organic solvent capable of dissolving the raw material and the reaction product and water in an amount capable of hydrolyzing all the hydrolyzable groups of the raw material, and is hydrolyzed and condensed. It should be obtained. In this case, in order to reduce the amount of chlorine contained as an impurity in the epoxy resin forming material for encapsulation, it is preferred to use an organic alkoxysilane and/or a decane as a raw material. In this case, an acid, a base or an organometallic compound is preferably added as a catalyst for promoting the reaction. Further, the molecular weight (Mw) of the ruthenium-containing polymer and the ratio of the phenyl group can be adjusted depending on the feed ratio of the raw material for production, the organic solvent, water, the reaction catalyst, or the like, or the reaction temperature, the reaction time, and the like. The molecular weight is mainly affected by the concentration or feed ratio of the raw materials in the organic solvent, and the ratio of the phenyl group is mainly affected by the feed ratio of the raw materials.

The organoalkoxy decane and/or oxime which is a raw material of the (E) ruthenium-containing polymer is exemplified by methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, and ethyltriphenyl. Ethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, dimethyl dimethoxy decane, methyl phenyl dimethyl Oxy decane, methyl vinyl dimethoxy decane, phenyl vinyl dimethoxy decane, diphenyl dimethoxy decane, methyl phenyl diethoxy decane, methyl vinyl diethoxy矽, phenylvinyl diethoxy decane, diphenyl bis oxy decane, dimethyl diethoxy decane, tetramethoxy decane, tetraethoxy decane, dimethoxy diethoxy Decane, and such hydrolysis condensates and the like.

The content of the above (E) ruthenium-containing polymer is not particularly limited as long as it can reach the scope of the invention, but as the content increases, the modulus of elasticity in the room temperature region and the modulus of elasticity in the high-temperature region are lowered, and the reflow resistance is improved. The tendency to improve flame retardancy is also reduced. When the amount of blending is reduced, there is a tendency for the hardness to increase during heat. In view of this, compared with the epoxy resin molding material for encapsulation (A) The epoxy resin is preferably 2.5% by mass or more and 40% by mass or less, more preferably 5% by mass or more and 30% by mass or less, more preferably 10% by mass or more and 20% by mass or less.

[(A) Epoxy Resin]

The (A) epoxy resin used in the present invention is not particularly limited as long as it contains two or more epoxy groups in one molecule, and is exemplified by, for example, a phenol novolak type epoxy resin or an o-cresol novolac type epoxy. Resin, epoxy resin having a triphenylmethane skeleton, phenol, cresol, xylenol, meta-xylenol, catechol, bisphenol A, bisphenol F, etc., and/or α-naphthalene A novolac resin obtained by condensation or co-condensation of a naphthol such as phenol, β -naphthol or dihydroxynaphthalene with a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde or salicylaldehyde under an acidic catalyst. An epoxidized bisphenol A, bisphenol F, bisphenol S, biphenol, thiodiphenol, etc., bis-glycidyl ether, oxime epoxy, substituted by an alkyl group, an aromatic ring or an unsubstituted bisphenol A Polyglycidyl epoxy resin obtained by reacting a polybasic acid such as a resin, a hydroquinone type epoxy resin, a phthalic acid or a dimer acid with epichlorohydrin, a polyaminodiphenylmethane or an isocyanuric acid Ring of glycidylamine type epoxy resin, dicyclopentadiene and phenolic co-condensation resin obtained by reaction of amine with epichlorohydrin a phenolic aralkyl resin synthesized from an epoxy resin having a naphthalene ring, a phenol and/or a naphthol, and a dimethoxy-p-xylene or bis(methoxymethyl)biphenyl, naphthol An epoxide of an aralkyl type phenol resin such as an aralkyl resin, a trimethylolpropane type epoxy resin, a terpene-modified epoxy resin, a linear fat obtained by oxidizing an olefin bond with a peracid such as peracetic acid The epoxy resin, the alicyclic epoxy resin, etc. may be used alone or in combination of two or more.

Among them, in view of both fluidity and hardenability, a biphenyl type epoxy resin preferably containing a bis glycidyl ether of an alkyl group, an aromatic ring substituted or an unsubstituted biphenol is hardenable. From the viewpoint of low hygroscopicity, a dicyclopentadiene type epoxy resin is preferable, and it is preferable to contain a dicyclopentadiene type epoxy resin from the viewpoint of heat resistance and low warpage. The naphthalene type epoxy resin preferably contains a bisphenol F type ring of a bisglycidyl ether of bisphenol F substituted by an alkyl group, an aromatic ring or an unsubstituted one from the viewpoint of both fluidity and flame retardancy. Oxygen resin, in terms of both fluidity and reflowability, a thiodiphenol type epoxy preferably containing a diglycidyl ether of an alkyl substituted, an aromatic ring substituted or an unsubstituted thiodiphenol The resin preferably contains an alkyl-substituted, aromatic-substituted or unsubstituted phenol and dimethoxy-p-xylene or bis(methoxymethyl) from the viewpoint of both hardenability and flame retardancy. The epoxide of phenol and aralkyl resin synthesized by biphenyl, which has both stability and flame retardancy. It is preferred to contain an epoxide of a naphthol ‧ aralkyl resin synthesized from an alkyl substituted, an aromatic ring substituted or unsubstituted naphthol and dimethoxy p-xylene.

The biphenyl type epoxy resin is exemplified by an epoxy resin represented by the following general formula (V).

Wherein R ¹ to R ^{8 are selected} from a hydrogen atom and a substituted or unsubstituted one-valent hydrocarbon group having 1 to 10 carbon atoms, and may be all the same or different, and n represents an integer of 0 or 1 to 3.

The biphenyl type epoxy resin represented by the above formula (V) is obtained by reacting epichlorohydrin with a biphenol compound by a known method. R ¹ to R ⁸ in the formula (V) are exemplified by a hydrocarbon having 1 to 10 carbon atoms such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or a t-butyl group. A vinyl group having 1 to 10 carbon atoms such as a vinyl group, an allyl group or a butenyl group, and the like, wherein a hydrogen atom or a methyl group is preferred. These epoxy resins are exemplified by, for example, 4,4'-bis(2,3-epoxypropoxy)biphenyl or 4,4'-bis(2,3-epoxypropoxy)-3. , 3',5,5'-tetramethylbiphenyl as the main component of epoxy resin, making epichlorohydrin and 4,4'-biphenol or 4,4'-(3,3',5,5' -Epoxy resin obtained by the reaction of -tetramethyl)biphenol. Among them, an epoxy resin containing 4,4'-bis(2,3-epoxypropoxy)-3,3',5,5'-tetramethylbiphenyl as a main component is preferred. These epoxy resins are commercially available from YP-4000 and YL-6121H manufactured by Nippon Epoxy Resin Co., Ltd. In order to exhibit the performance, the biphenyl type epoxy resin is preferably used in an amount of 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more based on the total amount of the epoxy resin.

The thiodiphenol type epoxy resin is exemplified by an epoxy resin represented by the following formula (VI).

Wherein R ¹ to R ^{8 are selected} from a hydrogen atom and a substituted or unsubstituted one-valent hydrocarbon group having 1 to 10 carbon atoms, and may be all the same or different, and n represents an integer of 0 or 1 to 3.

The thiodiphenol type epoxy resin represented by the above formula (VI) is obtained by reacting epichlorohydrin with a thiodiphenol compound by a known method. R ¹ to R ⁸ in the formula (VI) are exemplified by a hydrocarbon having 1 to 10 carbon atoms such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or a t-butyl group. Or an alkenyl group having 1 to 10 carbon atoms such as a vinyl group, an allyl group or a butenyl group, and the like, and a hydrogen atom, a methyl group or a tert-butyl group is preferred. These epoxy resins are exemplified by an epoxy resin having a diglycidyl ether of 4,4'-dihydroxydiphenyl sulfide as a main component, and 2,2',5,5'-tetramethyl-4. , 4'-dihydroxydiphenyl sulfide diglycidyl ether as the main component of the epoxy resin, 2,2'-dimethyl-4,4'-dihydroxy-5,5'- two third Epoxy resin or the like as a main component of diglycidyl ether of butyl diphenyl sulfide, preferably 2,2'-dimethyl-4,4'-dihydroxy-5,5'-di Epoxy resin containing diglycidyl ether of tributyl diphenyl sulfide as a main component. These epoxy resins are commercially available from the trade name YSLV-120TE manufactured by Nippon Steel Chemical Co., Ltd. In order to exhibit the performance, the thiodiphenol type epoxy resin is preferably used in an amount of 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more based on the total amount of the epoxy resin. The bisphenol F-type epoxy resin is exemplified by an epoxy resin represented by the following general formula (VII).

Wherein R ¹ to R ^{8 are selected} from a hydrogen atom and a substituted or unsubstituted one-valent hydrocarbon group having 1 to 10 carbon atoms, and may be all the same or different, and n represents an integer of 0 or 1 to 3.

The bisphenol F type epoxy resin represented by the above formula (VII) is obtained by reacting epichlorohydrin with a bisphenol F compound by a known method. R ¹ to R ⁸ in the formula (VII) are exemplified by a hydrocarbon having 1 to 10 carbon atoms such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or a t-butyl group. A vinyl group having 1 to 10 carbon atoms such as a vinyl group, an allyl group or a butenyl group, and the like, wherein a hydrogen atom or a methyl group is preferred. These epoxy resins are exemplified by, for example, an epoxy resin having a diglycidyl ether of 4,4'-methylbis(2,6-dimethylphenol) as a main component, and a 4,4'-methyl group. Epoxy resin containing bis(2,3,6-trimethylphenol) diglycidyl ether as a main component, epoxy resin having 4,4′-methyl bisphenol diglycidyl ether as a main component, etc. Among them, an epoxy resin having a diglycidyl ether of 4,4'-methyl bis(2,6-dimethylphenol) as a main component is preferred. These epoxy resins are commercially available from the trade name YSLV-80XY manufactured by Nippon Steel Chemical Co., Ltd. In order to exhibit the performance, the bisphenol F-type epoxy resin is preferably used in an amount of 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more based on the total amount of the epoxy resin.

The novolac type epoxy resin is exemplified by an epoxy resin represented by the following formula (VIII).

Wherein R is selected from a hydrogen atom and a substituted or unsubstituted one-valent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10.

The novolac type epoxy resin represented by the above formula (VIII) can be easily obtained by reacting epichlorohydrin with a novolac type phenol resin. Wherein R in the above formula (VIII) is preferably an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group or an isobutyl group; a methoxy group and an ethoxy group; The alkoxy group having 1 to 10 carbon atoms such as a group, a propoxy group or a butoxy group is more preferably a hydrogen atom or a methyl group. n is preferably an integer from 0 to 3. Among the novolac type epoxy resins represented by the above formula (VIII), an o-cresol novolac type epoxy resin is preferred. These epoxy resins are commercially available from Sumitomo Chemical Industries, Ltd. under the trade name of ESCN-190. When a novolac type epoxy resin is used, the amount thereof is preferably 20% by mass or more, more preferably 30% by mass or more based on the total amount of the epoxy resin.

The dicyclopentadiene type epoxy resin is exemplified by an epoxy resin represented by the following formula (IX).

Wherein R ¹ is selected from a hydrogen atom and a substituted or unsubstituted one-valent hydrocarbon group having 1 to 10 carbon atoms, and R ² is selected from a substituted or unsubstituted one-valent hydrocarbon group having 1 to 10 carbon atoms. , n represents an integer from 0 to 10, and m represents an integer from 0 to 6.

R ¹ in the above formula (IX) is exemplified by an alkyl group such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group or a t-butyl group; a vinyl group, an allyl group, and a butenyl group; An alkenyl group; a halogenated alkyl group, an amine-substituted alkyl group, a mercapto-substituted alkyl group, or the like, a substituted or unsubstituted one-valent hydrocarbon group having 1 to 10 carbon atoms, preferably an alkyl group such as a methyl group or an ethyl group. And a hydrogen atom, more preferably a methyl group and a hydrogen atom. R ^{2 is} exemplified by an alkyl group such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group or a t-butyl group; an alkenyl group such as a vinyl group, an allyl group or a butenyl group; or an alkyl group; An amine-substituted alkyl group, a mercapto-substituted alkyl group, or the like, a substituted or unsubstituted one-valent hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrogen atom. When the dicyclopentadiene type epoxy resin is used, the amount thereof is preferably 20% by mass or more, more preferably 30% by mass or more based on the total amount of the epoxy resin.

The naphthalene type epoxy resin is exemplified by an epoxy resin represented by the following general formula (X).

Wherein, R ¹ to R ³ are selected from a substituted or unsubstituted one-valent hydrocarbon group having 1 to 12 carbon atoms, and all of the same may be different, p is 1 or 0, and m and n are 0 to 11 respectively. An integer, and (m+n) is an integer from 1 to 11 and (m+p) is an integer from 1 to 12, i represents an integer from 0 to 3, j represents an integer from 0 to 2, and k represents 0. An integer of ~4.

The naphthalene type epoxy resin represented by the above formula (X) is exemplified by a random copolymer which is randomly contained in m constituent units and n constituent units, an interactive copolymer which is alternately contained, and a copolymer which is regularly contained. Block copolymer containing block. Any of these may be used alone or in combination of two or more. These epoxy resins are commercially available from Nippon Chemical Co., Ltd. under the trade name of NC-7300. When these naphthalene type epoxy resins are used, in order to exhibit the performance, the blending amount is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 50% by mass or more in the total amount of the epoxy resin. .

The epoxide of the phenol ‧ aralkyl resin is exemplified by an epoxy resin represented by the following formula (XI) or (XII).

Wherein R ¹ to R ⁹ are a hydrogen atom, and are selected by a substituted or unsubstituted one-valent hydrocarbon group having 1 to 12 carbon atoms, all of which may be the same or different, i represents an integer of 0 or 1 to 3, and n represents 0 or an integer from 1 to 10.

Wherein R ¹ to R ⁴ are a hydrogen atom selected from a substituted or unsubstituted one-valent hydrocarbon group having 1 to 12 carbon atoms, all of which may be the same or different, and R 5 is substituted by a carbon number of 1 to 12 or The unsubstituted one-valent hydrocarbon group is selected, i represents 0 or an integer of 1 to 3, and n represents 0 or an integer of 1 to 10.

The epoxide of the phenol ‧ aralkyl resin having a biphenyl skeleton represented by the above formula (XI) can be obtained by a known method by substituting epichlorohydrin with an alkyl group, an aromatic ring or an unsubstituted group. The phenol is obtained by reacting with a phenol aralkyl resin synthesized from bis(methoxymethyl)biphenyl. R ¹ to R ⁹ in the formula (XI) are exemplified by, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, second butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, a chain alkyl group such as a decyl group or a dodecyl group; a cyclic alkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group or a cyclohexenyl group; and an aryl group such as a benzyl group or a phenethyl group; An alkyl group substituted with an alkyl group, a methoxy-substituted alkyl group, an ethoxy-substituted alkyl group, a butoxy-substituted alkyl group, an aminoalkyl group, an aminoalkyl group, a dimethylamino group, a diethylamine An alkyl group-substituted alkyl group, a hydroxy-substituted alkyl group, a phenyl group such as a phenyl group, a naphthyl group, a biphenyl group, or the like, an unsubstituted aryl group, a tolyl group, a dimethylphenyl group, an ethylphenyl group, and a butyl group. An alkyl-substituted aryl group such as phenyl, tert-butylphenyl or dimethylnaphthyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, tert-butoxyphenyl, A An alkoxy-substituted aryl group such as an oxynaphthyl group, an aryl group substituted with an amine group such as a dimethylamino group or a diethylamino group, an aryl group substituted with a hydroxy group, or the like, wherein a hydrogen atom or a methyl group is preferred. Further, the average of n in the general formula (XI) is preferably 6 or less, and these epoxy resins are commercially available from the product name NC-3000S manufactured by Nippon Kayaku Co., Ltd.

Moreover, it is preferably used in combination with the epoxy resin represented by the above formula (V) from the viewpoints of flame retardancy, reflow resistance, and fluidity, and more preferably R of the above formula (XI). ¹ to R ⁸ are a hydrogen atom, and R ¹ to R ⁸ of the above formula (V) are a hydrogen atom, and n = 0.

In addition, especially the quality of the blending is preferably (V) / (XI) = 50 / 50 ~ 5 / 95, more preferably 40 / 60 ~ 10 / 90, and more preferably 30 / 70 ~ 15 / 85. The compound which satisfies the blending quality ratio is commercially available as CER-3000L (trade name manufactured by Nippon Kayaku Co., Ltd.).

The epoxide of the phenol ‧ aralkyl resin represented by the above formula (XII) is obtained by a known method by using epichlorohydrin with a phenol and a dimethoxy group substituted by an alkyl group, an aromatic ring or an unsubstituted group. It is obtained by reacting a p-xylene synthesis phenol aralkyl resin. R ¹ to R ⁵ in the formula (XII) are exemplified by, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, second butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, a chain alkyl group such as a decyl group or a dodecyl group; a cyclic alkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group or a cyclohexenyl group; and an aryl group such as a benzyl group or a phenethyl group; An alkyl group substituted with an alkyl group, a methoxy-substituted alkyl group, an ethoxy-substituted alkyl group, a butoxy-substituted alkyl group, an aminoalkyl group, an aminoalkyl group, a dimethylamino group, a diethylamine An alkyl group-substituted alkyl group, a hydroxy-substituted alkyl group, a phenyl group such as a phenyl group, a naphthyl group, a biphenyl group, or the like, an unsubstituted aryl group, a tolyl group, a dimethylphenyl group, an ethylphenyl group, and a butyl group. An alkyl-substituted aryl group such as phenyl, tert-butylphenyl or dimethylnaphthyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, tert-butoxyphenyl, A An alkoxy-substituted aryl group such as an oxynaphthyl group, an aryl group substituted with an amine group such as a dimethylamino group or a diethylamino group, an aryl group substituted with a hydroxy group, or the like, wherein a hydrogen atom or a methyl group is preferred. Further, the average of n in the formula (XII) is more preferably 6 or less, and these epoxy resins are commercially available from the product name NC-2000L manufactured by Nippon Kayaku Co., Ltd.

The epoxide of the naphthol aralkyl resin is exemplified by an epoxy resin represented by the following formula (XIII).

Wherein R is selected from substituted or unsubstituted ones of carbon atoms of 1 to 12, all of which may be the same or different, i represents an integer of 0 or 1 to 3, and X represents a divalent organic group containing an aromatic ring. Base, n represents 0 or an integer from 1 to 10.

X is exemplified by an alkyl group-substituted aryl group such as a phenyl group, a phenylene group, an anthranyl group, a tolyl group, an alkyl group-substituted aryl group, an alkoxy group-substituted aryl group, and an aralkyl group-substituted aryl group. a divalent group derived from an aralkyl group such as a benzyl group or a phenethyl group, a divalent group containing an exoaryl group such as a xylyl group, etc., wherein From the standpoint of both flame retardancy and storage stability, it is preferred to extend the phenyl group and extend the biphenyl group.

The epoxide of a naphthol ‧ aralkyl resin represented by the above formula (XIII) can be obtained by a known method by using epichlorohydrin with naphthol substituted by an alkyl group, an aromatic ring or an unsubstituted group It is obtained by reacting a methoxy-p-xylene or a bis(methoxymethyl)biphenyl synthesized naphthol ‧ aralkyl resin. R in the formula (XIII) is exemplified by, for example, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, t-butyl, pentyl, hexyl, octyl, decyl, and ten. a chain alkyl group such as a dialkyl group, a cyclic alkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group or a cyclohexenyl group; an alkyl group substituted with an aryl group such as a benzyl group or a phenethyl group; An alkoxy-substituted alkyl group such as an oxy-substituted alkyl group, an ethoxy-substituted alkyl group or a butoxy-substituted alkyl group, an aminoalkyl group, a dimethylaminoalkyl group, a diethylaminoalkyl group, etc. An amino-substituted alkyl group, a hydroxy-substituted alkyl group, an unsubstituted aryl group such as a phenyl group, a naphthyl group or a biphenyl group, a tolyl group, a dimethylphenyl group, an ethylphenyl group, a butylphenyl group, An alkyl-substituted aryl group such as tributylphenyl or dimethylnaphthyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, tert-butoxyphenyl, methoxynaphthyl An alkoxy-substituted aryl group, an aryl group substituted with an amino group such as a dimethylamino group or a diethylamino group, an aryl group substituted with a hydroxy group, or the like, wherein a hydrogen atom or a methyl group is preferably used, for example, in the following formula: (XIV) or (XV) represented by naphthol ‧ An epoxide of an alkyl resin. n represents 0 or an integer of 1 to 10, and the average is preferably 6 or less. The epoxy resin represented by the following general formula (XIV) is exemplified by a commercially available product sold under the trade name ESN-375 manufactured by Nippon Steel Chemical Co., Ltd., and the epoxy resin represented by the following general formula (XV) is listed as Commercial products purchased from Nippon Steel Chemicals The trade name ESN-175 manufactured by the company. The amount of the epoxide of the naphthol ‧ aralkyl resin is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more based on the total amount of the epoxy resin. .

Where n represents 0 or an integer from 1 to 10.

Where n represents 0 or an integer from 1 to 10.

Further, an epoxy resin having the following structural formula (XVI) can also be used as the (A) epoxy resin.

R ¹ in the formula (XVI) is selected from a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms and a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, all of which may be the same or different. , n represents an integer from 0 to 4, and R ² is selected from a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms and a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, all of which may be the same. Alternatively, m represents an integer from 0 to 2.

The epoxy resin represented by the above formula (XVI) is exemplified by an epoxy resin represented by the following general formula (XVII) to (XXXV).

In the epoxy resin represented by the above formula (XVI), the epoxy resin represented by the above formula (XVII) is preferred from the viewpoint of flame retardancy and moldability. These compounds are commercially available as YX-8800 (trade name manufactured by Nippon Epoxy Resin Co., Ltd.).

In order to exhibit the performance of the above-mentioned epoxy resin, the blending amount is preferably 30% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more based on the total amount of the epoxy resin.

The (B) curing agent used in the present invention is not particularly limited as long as it is generally used for the epoxy resin molding material for encapsulation, and is exemplified by, for example, phenol, cresol, meta-xylenol, catechol, bisphenol A, and double. Phenols such as phenol F, phenylphenol, thiodiphenol, and aminophenol, and/or naphthols such as α-naphthol, β -naphthol, and dihydroxynaphthalene, and formaldehyde, benzaldehyde, salicylaldehyde, etc. A novolac type phenol resin obtained by condensation or co-condensation of an aldehyde group compound under an acidic catalyst, synthesized from phenols and/or naphthols and dimethoxy-p-xylene or bis(methoxymethyl)biphenyl Aromatic phenolic resin such as phenol/aralkyl resin, naphthol/aralkyl resin, phenol phenolic varnish structure and phenolic aralkyl structure in a random, block or interactive form Phenol ‧ aralkyl resin, p-xylene and / or m-xylene modified phenol resin, melamine modified phenol resin, terpene modified phenol resin, dicyclopentadiene modified phenol resin, cyclopentane A phenol resin modified with a diene, a phenol resin modified with a polycyclic aromatic ring, or the like may be used alone or in combination of two or more.

Among them, phenol ‧ aralkyl resin and naphthol ‧ aralkyl resin are preferred from the viewpoints of fluidity, flame retardancy and reflow resistance, and are preferably bicyclic in view of low hygroscopicity The pentadiene type phenol resin is preferably a novolac type phenol resin from the viewpoint of curability, and preferably contains at least one of the phenol resins.

The phenol ‧ aralkyl resin is exemplified by a resin represented by the following formula (XXXVI).

Wherein R is selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, all of which may be the same or different, i represents an integer of 0 or 1-3, and X represents an aromatic ring. A divalent organic group, and n represents an integer of 0 or 1 to 10.

R in the above formula (XXXVI) is exemplified by, for example, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, t-butyl, pentyl, hexyl, octyl, decyl, a chain alkyl group such as a dodecyl group; a cyclic alkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group or a cyclohexenyl group; an alkyl group substituted with an aryl group such as a benzyl group or a phenethyl group; An alkoxy-substituted alkyl group such as a methoxy-substituted alkyl group, an ethoxy-substituted alkyl group, a butoxy-substituted alkyl group, an aminoalkyl group, a dimethylaminoalkyl group, or a diethylaminoalkyl group. An alkyl group substituted with an amino group, a hydroxy-substituted alkyl group, an unsubstituted aryl group such as a phenyl group, a naphthyl group or a biphenyl group, a tolyl group, a dimethylphenyl group, an ethylphenyl group, a butylphenyl group An alkyl-substituted aryl group such as a tributylphenyl group or a dimethylnaphthyl group, a methoxyphenyl group, an ethoxyphenyl group, a butoxyphenyl group, a tert-butoxyphenyl group, or a methoxy group. An alkoxy-substituted aryl group such as a naphthyl group, an aryl group substituted with an amine group such as a dimethylamino group or a diethylamino group, an aryl group substituted with a hydroxy group, or the like, wherein a hydrogen atom or a methyl group is preferred.

Further, X represents a group containing an aromatic ring, and is exemplified by an alkyl group-substituted aryl group such as a phenyl group, a stretched phenyl group, an extended aryl group, a tolyl group, or an alkoxy group. a divalent group obtained from an aralkyl group such as a benzyl group or a phenethyl group, an arylalkyl group substituted with an aryl group or a xylyl group. The divalent group of the aryl group and the like. Among them, a substituted or unsubstituted biphenyl group is preferred from the viewpoint of both flame retardancy and reflow resistance, and is exemplified by, for example, a phenol ‧ aralkyl group represented by the following formula (XXXVII) The resin is preferably a substituted or unsubstituted phenyl group from the viewpoints of both flame retardancy, fluidity and hardenability, and is exemplified by a phenol ‧ aralkyl resin represented by the following formula (XXXVIII) . n represents 0 or an integer of 1 to 10, more preferably 6 or less.

Where n represents 0 or an integer from 1 to 10.

Where n represents 0 or an integer from 1 to 10.

The phenol ‧ aralkyl resin containing a biphenyl skeleton represented by the above formula (XXXVII) is exemplified by a commercially available product, commercially available from Minghe Chemical Co., Ltd., under the trade name MEH-7851, and represented by the formula (XXXVIII). The phenol ‧ aralkyl resin is exemplified by a commercially available product from the trade name XLC manufactured by Mitsui Chemicals, Inc. The blending amount of the phenol ‧ aralkyl resin is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more based on the total amount of the curing agent.

The naphthol ‧ aralkyl resin is exemplified by a resin represented by the following formula (XXXIX).

Wherein R is selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, all of which may be the same or different, i represents an integer of 0 or 1-3, and X represents an aromatic ring. A divalent organic group, and n represents an integer of 0 or 1 to 10.

R in the above formula (XXXIX) is exemplified by, for example, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, t-butyl, pentyl, hexyl, octyl, decyl, a chain alkyl group such as a dodecyl group; a cyclic alkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group or a cyclohexenyl group; an alkyl group substituted with an aryl group such as a benzyl group or a phenethyl group; Alkoxy-substituted alkyl group such as methoxy-substituted alkyl group, ethoxy-substituted alkyl group, butoxy-substituted alkyl group, aminoalkyl group, dimethylaminoalkyl group, diethylaminoalkyl group An amino group-substituted alkyl group, a hydroxy-substituted alkyl group, an unsubstituted aryl group such as a phenyl group, a naphthyl group or a biphenyl group, a tolyl group, a dimethylphenyl group, an ethylphenyl group, a butylphenyl group, An alkyl-substituted aryl group such as a butyl phenyl group or a dimethyl naphthyl group, a methoxyphenyl group, an ethoxyphenyl group, a butoxyphenyl group, a tert-butoxyphenyl group, or a methoxynaphthalene An aryl group substituted with an alkoxy group, an aryl group substituted with an amine group such as a dimethylamino group or a diethylamino group, an aryl group substituted with a hydroxy group, or the like, wherein a hydrogen atom or a methyl group is preferred.

Further, X represents a divalent organic group containing an aromatic ring, and is exemplified by an alkyl group-substituted aryl group such as a phenyl group, a phenylene group, a phenylene group, an alkyl group, or an alkoxy group. a divalent group obtained by an aryl group, an aralkyl group-substituted aryl group, an aralkyl group derived from a benzyl group or a phenethyl group, a divalent group containing an exoaryl group, and the like. Among them, from the viewpoint of storage stability and flame retardancy, a substituted or unsubstituted phenyl group and a phenyl group are preferred, and a phenyl group is more preferred, for example, by the following formula (XXXX) And naphthol aralkyl resin represented by (XXXXI). n represents 0 or an integer of 1 to 10, and more preferably an average of 6 or less.

Where n represents 0 or an integer from 1 to 10.

Where n represents 0 or an integer from 1 to 10.

The naphthol ‧ aralkyl resin represented by the above formula (XXXX) is exemplified by a commercially available product sold under the trade name SN-475 manufactured by Nippon Steel Chemical Co., Ltd., and the naphthol represented by the above formula (XXXXI) ‧ The aralkyl resin is listed as a commercial product sold under the trade name SN-170 manufactured by Nippon Steel Chemical Co., Ltd. The amount of the above naphthol ‧ aralkyl resin In order to exhibit the performance, the amount of the hardener is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more.

The phenol ‧ aralkyl resin represented by the above formula (XXXVI) and the naphthol ‧ aralkyl resin represented by the formula (XXXIX) are preferably partially or wholly in combination with terpene from the viewpoint of flame retardancy (acenaphthylene) premixed. Terpenes can be obtained by dehydrogenation of hydrazine, but commercially available products can also be used. Alternatively, a terpene polymer or a polymer of a terpene and another aromatic olefin may be used in place of the terpene. A method of obtaining a polymer of terpene or a polymer of a terpene and another aromatic olefin is exemplified by radical polymerization, cationic polymerization, anionic polymerization, and the like. Further, in the case of polymerization, a conventional catalyst can be used, but it is also possible to carry out heating only without using a catalyst. At this time, the polymerization temperature is preferably from 80 to 160 ° C, more preferably from 90 to 150 ° C. The softening point of the polymer of the obtained terpene or the polymer of the terpene and the other aromatic olefin is preferably from 60 to 150 ° C, more preferably from 70 to 130 ° C.

When the temperature is lower than 60 ° C, the moldability tends to decrease due to bleeding during molding. When the temperature is higher than 150 ° C, the compatibility with the resin tends to decrease. Other aromatic olefins copolymerized with terpenes are exemplified by styrene, α-methylstyrene, anthracene, benzothiophene, benzofuran, vinylnaphthalene, ethylenebiphenyl or such alkyl substituents. Further, in addition to the above aromatic olefin, an aliphatic olefin may be used in combination within a range not inhibiting the effects of the present invention. The aliphatic olefins are exemplified by (meth)acrylic acid and such esters, maleic anhydride, itaconic anhydride, fumaric acid, and the like. The amount of the aliphatic olefin to be used is preferably 20% by mass or less, more preferably 9% by mass or less based on the total amount of the polymerizable monomers.

a method of premixing a part or all of the hardener with decene to directly mix the hardener and the decene in a finely pulverized solid state; and to dissolve the solvent after dissolving the solvent in the solvent; The method of melt-mixing and mixing the two at a temperature equal to or higher than the softening point of the curing agent and/or the terpene is preferable, but a melt mixing method in which a homogeneous mixture is obtained and impurities are less mixed is preferable. A premix (decene-modified hardener) was produced by the aforementioned method. The melt mixing is not limited as long as it is at least the softening point of the curing agent and/or the terpene, but is preferably from 100 to 250 ° C, more preferably from 120 to 200 ° C. Further, the mixing time is not limited as long as the melt mixing can be uniformly mixed, but it is preferably from 1 to 20 hours, more preferably from 2 to 15 hours. When premixing the hardener with the terpene, it is also possible to polymerize the terpene in the mixture or react with the hardener.

The dicyclopentadiene type phenol resin is exemplified by a phenol resin represented by the following formula (XXXXII).

Wherein R ¹ and R ² are independently selected from a hydrogen atom and a substituted or unsubstituted one-valent hydrocarbon group having 1 to 10 carbon atoms; n represents an integer of 0 to 10, and m represents an integer of 0 to 6.

The above compound in which R ¹ and R ² are a hydrogen atom can be obtained from a commercially available product DPP (trade name manufactured by Nippon Petrochemical Co., Ltd.).

The novolac type phenol resin is exemplified by a novolac type phenol resin such as a phenol resin represented by the following formula (XXXXIII), a cresol novolak resin, and the like. Among them, a novolac type phenol resin represented by the following formula (XXXXIII) is preferred.

Wherein R is selected from a hydrogen atom and a substituted or unsubstituted one-valent hydrocarbon group having 1 to 10 carbon atoms; i represents an integer of 0 to 3, and n represents an integer of 0 to 10.

R in the above formula (XXXXIII) is exemplified by an alkyl group such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group or a t-butyl group, a vinyl group, an allyl group, a butenyl group or the like. An alkenyl group, a halogenated alkyl group, an amine-substituted alkyl group, a mercapto-substituted alkyl group, or the like, a substituted or unsubstituted one-valent hydrocarbon group having 1 to 10 carbon atoms, wherein an alkyl group such as a methyl group or an ethyl group The atom is preferably a hydrogen atom, and the average value of n is preferably from 0 to 8. The novolac type phenol resin represented by the above formula (XXXXIII) is commercially available from the product name: H-4 manufactured by Minghe Chemical Co., Ltd.

When the novolac type phenol resin is used, the amount thereof is preferably 30% by mass or more, more preferably 50% by mass or more based on the total amount of the curing agent.

The above-mentioned hardening agents may be used singly or in combination of two or more kinds, but the compounding amount in combination of two or more types is preferably a phenol resin. The total amount is 50% by mass or more, more preferably 60% by mass or more, and still more preferably 80% by mass or more.

In the present invention, the equivalent ratio of (A) epoxy resin to (B) hardener, that is, the ratio of the number of hydroxyl groups in the hardener to the epoxy group (the number of hydroxyl groups in the hardener / the number of epoxy groups in the epoxy resin) There is no particular limitation, but in order to suppress each unreacted component to a small amount, it is preferably set in the range of 0.5 to 2, more preferably in the range of 0.6 to 1.3. In order to obtain a molding epoxy resin molding material excellent in moldability and solder reflow resistance, it is preferably set in the range of 0.8 to 1.2.

[(C) hardening accelerator]

The (C) hardening accelerator used in the present invention can be used for a general user in the epoxy resin molding material for encapsulation without particular limitation. Listed as, for example, 1,8-diazabicyclo[5.4.0]undecene-7, 1,5-diazabicyclo[4.3.0]nonene-5,5,6-dibutylamino group -1,8-diazabicyclo[5.4.0]undecene-7 Cycloamidine compound and addition of maleic anhydride, 1,4-benzoquinone, 2,5- to these compounds Toluene, 1,4-naphthoquinone, 2,3-dimethylphenylhydrazine, 2,6-dimethylphenylhydrazine, 2,3-dimethoxy-5-methyl-1,4-benzoquinone a compound having a π bond such as a ruthenium compound such as 2,3-dimethoxy-1,4-benzoquinone or phenyl-1,4-benzoquinone, or a phenol resin, and having an intramolecular polarization a compound, a tertiary amine such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, ginseng (dimethylaminomethyl)phenol, and the like, 2-methylimidazole, 2-phenyl Imidazoles such as imidazole, 2-phenyl-4-methylimidazole, 2-heptadecynylimidazole, and the like And other derivatives, such as tributylphosphine, methyl diphenylphosphine, triphenylphosphine, ginseng (4-methylphenyl) phosphine, diphenylphosphine, phenylphosphine, and the like, and the like a phosphorus compound having an intramolecular polarization, a tetraphenylphosphonium tetraphenylborate or a tetraphenyl group, which is added with a compound having a π bond such as maleic anhydride, the above-mentioned hydrazine compound, diazophenylmethane or a phenol resin. a tetra-substituted 鏻tetra-substituted borate such as ethyltriphenylborate or tetrabutylphosphonium tetrabutylborate, 2-ethyl-4-methylimidazolium tetraphenylborate, N- The tetraphenylboron salt such as methylmorpholine or tetraphenylborate, and the like may be used singly or in combination of two or more.

Among them, from the viewpoint of hardenability and fluidity, an adduct of a tertiary phosphine and a ruthenium compound is preferred, and an adduct of triphenylphosphine and benzoquinone or tributylphosphine and benzoquinone is preferred. Additives. From the viewpoint of storage stability, it is preferably an adduct of a cyclic hydrazine compound and a phenol resin, more preferably a novolac type phenol resin salt of diazabicycloundecene.

The blending amount of the hardening accelerator is preferably 60% by mass or more, more preferably 80% by mass or more, based on the total amount of the hardening accelerator.

The tertiary phosphine used in the adduct of the tertiary phosphine and the hydrazine compound is not particularly limited, and is exemplified by, for example, tributylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, Triphenylphosphine, ginseng (4-methylphenyl)phosphine, ginseng (4-ethylphenyl)phosphine, ginseng (4-propylphenyl)phosphine, ginseng (4-butylphenyl)phosphine, ginseng (isopropylphenyl)phosphine, ginseng (t-butylphenyl)phosphine, ginseng (2,4-dimethylphenyl)phosphine, ginseng (2,6-dimethylphenyl)phosphine, ginseng 2,4,6-trimethylphenyl)phosphine, ginseng (2,6-dimethyl-4-ethoxyphenyl)phosphine, ginseng (4-methoxyphenyl)phosphine, ginseng (4- Ethoxyphenyl) phosphine The tertiary phosphine having an aryl group is preferably triphenylphosphine and tributylphosphine in terms of formability.

Further, the ruthenium compound used for the adduct of the tertiary phosphine and the ruthenium compound is not particularly limited, and examples thereof include o-benzoquinone, p-benzoquinone, diphenylguanidine, 1,4-naphthoquinone, anthracene, etc. From the viewpoint of moisture resistance or storage stability, p-benzoquinone is preferred.

The amount of the curing accelerator is not particularly limited as long as it can achieve the curing-promoting effect, but it is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the total of the (A) epoxy resin and the (B) curing agent. It is preferably 0.3 to 5 parts by mass. When it is less than 0.1 part by mass, it is difficult to harden in a short time, and when it exceeds 10 parts by mass, the curing rate is too early, and there is a tendency that a good molded article cannot be obtained.

[(D) Inorganic Filler]

The (D) inorganic filler used in the present invention is formulated in a molding material for the purpose of reducing hygroscopicity, decreasing coefficient of linear expansion, improving thermal conductivity, and improving strength, and is generally used as a user of an epoxy resin molding material for encapsulation. That is, there is no particular limitation, and examples thereof include, for example, molten cerium oxide, crystalline cerium oxide, aluminum oxide, zircon, calcium silicate, calcium carbonate, potassium titanate, strontium carbide, tantalum nitride, aluminum nitride, boron nitride, a powder such as cerium oxide, zirconium oxide, zircon, forsterite, talc (Steatite), spinel, mullite, or titanium oxide, or beads obtained by spheroidizing the cerium, Glass fiber or the like may be used alone or in combination of two or more. Among them, in terms of reducing the coefficient of linear expansion, it is preferred to be molten dioxygen. From the viewpoint of high thermal conductivity, cerium is preferably alumina, and the shape of the filler is preferably spherical in view of fluidity at the time of molding and mold attrition. It is preferable to be spherical molten cerium oxide from the viewpoint of balancing cost and performance.

The amount of the inorganic filler to be added is not particularly limited as long as it is within the scope of the invention, but it is preferably a ring for packaging from the viewpoints of flame retardancy, moldability, hygroscopicity, reduction in coefficient of linear expansion, and strength. 70 to 95% by mass in the oxygen resin molding material is more preferably 85 to 95% by mass in terms of hygroscopicity and coefficient of linear expansion, and when it is less than 70% by mass, it is flame retardant and reflow-resistant. When the tendency is lowered, when it exceeds 95% by mass, the fluidity tends to be insufficient.

The molding material of the present invention preferably contains a fluorene oligomer, and the oxime oligomer is a hydrazine such as hydrazine or alkyl hydrazine, and a styrene such as styrene or alkyl styrene. And a phenolic copolymer resin. As for the manufacturing method, Lewis acid, Bryanic acid (Br Nsted acid), a solid acid as a catalyst, obtained by cationic polymerization of the monomers. The proportion of the anthracene is preferably 60% by mass or more based on the total of the copolymerized resin component, and the other constituent monomer may contain an aromatic olefin such as coumarone. The oxime oligomer is not particularly limited, and is preferably one having a number average molecular weight of 300 to 1,000 and a softening point of 50 to 160 °C. These specific examples are listed as the trade name I-100 manufactured by Dongdu Chemical Co., Ltd., and the like. The amount of the oxime oligomer to be added is not particularly limited, but is preferably from 1 to 20 parts by mass based on 100 parts by mass of the epoxy resin of the component (A).

[the decane compound (a) represented by the formula (IV)]

The forming material of the present invention preferably contains a decane compound (a) represented by the following formula (IV) from the viewpoint of improving the reflow resistance. The compound represented by the following formula (I) is not particularly limited, and may be used singly or in combination of two or more.

In the formula (IV), R ¹ represents a cycloalkyl group or a cycloalkenyl group having 5 to 8 carbon atoms, R ² is the same as R ¹ or a hydrocarbon group having 1 to 6 carbon atoms, and R ³ represents a hydrocarbon group having 1 to 6 carbon atoms. A part of a hydrogen atom represented by R ¹ to R ³ may be substituted, p represents an integer of 1 to 3, and q represents an integer of 0 to 3.

R ¹ in the above formula (IV) is exemplified by, for example, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclohexenyl group, a cyclopentenyl group or the like, and preferably a cyclopentyl group and a cyclohexyl group. R ^{2 is} exemplified by methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, tert-butyl, phenyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl The group, cyclohexenyl group, cyclopentenyl group or the like is preferably a methyl group, an ethyl group, a cyclopentyl group or a cyclohexyl group. R3 is exemplified by methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, tert-butyl, phenyl, cyclopentyl, cyclohexyl, etc., preferably methyl and Ethyl. In addition, the groups may also be substituted.

Specific examples of preferred structures of the decane compound represented by the above formula (IV) are exemplified by the compounds shown below.

Among them, the balance between fluidity, moldability and reflow resistance is excellent, and it is preferable that the compound represented by the above formula (XXXXVIII) and (XXXXXX) is easy to obtain.

The compound represented by the formula (XXXXVIII) is commercially available from Toray Dow Corning Co., Ltd. under the trade name of Z6187, and the compound represented by the formula (XXXXXX) is commercially available from Toray Dow Corning Co., Ltd. Trade name: Z6228.

Further, a decane compound having a hydrolyzable group such as an alkoxyalkyl group or a phenoxyalkyl group is known to be hydrolyzed by moisture or the like in the air to form a stanol group, thereby producing a dehydrated condensate of stanol groups. The decane compound (a) represented by the above formula (IV) used in the present invention may further contain a stanol group and a dehydrated condensate obtained by hydrolyzing a decane compound.

The total amount of the decane compound (a) represented by the above formula (IV) is not particularly limited as long as it is within the range of the effect of the invention, but from the viewpoints of fluidity, formability and reflow resistance, It is preferably from 0.03 to 0.80% by mass, more preferably from 0.04 to 0.75% by mass, even more preferably from 0.05 to 0.7% by mass in the epoxy resin molding material for encapsulation. When the amount is less than 0.03 mass%, the effect of the present invention tends to be small, and when it exceeds 0.8 mass%, the fluidity is improved, but the moldability and the reflow resistance tend to be greatly lowered.

The molding material of the present invention preferably contains a decane compound (b) from the viewpoint of improving the adhesion between the resin component and the inorganic component in the molding material. The decane compound (b) is various decane-based compounds such as epoxy decane, decyl decane, amino decane, alkyl decane, ureido decane, and vinyl decane. Further, the decane compound (b) is excluded from the aforementioned decane compound (a). ) Repeated decane-based compounds.

When exemplified, vinyl trichloromethane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng ( β -methoxyethoxy) decane, γ -methyl propylene oxime trimethoxy Silane, γ - methyl Bing Xixi propyl triethoxysilane Silane, γ - methyl propyl methyl dimethoxy Bing Xixi Silane, γ - methyl group Bing Xixi propyl methyl diethoxy Silane, γ - Bing Xixi methyl propyl dimethyl methoxysilane Silane, γ - methyl propyl Bing Xixi dimethylethoxy Silane, γ - Bing Xixi Oxypropyltrimethoxydecane, γ -propyleneoxypropyltriethoxydecane, β- (3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ -glycidoxypropyl Trimethoxy decane, γ -glycidoxypropyl triethoxy decane, γ -glycidoxypropyl methyl dimethoxy decane, γ -glycidoxypropyl methyl diethoxy Decane, γ -glycidoxypropyl dimethyl methoxy decane, γ -glycidoxypropyl dimethyl ethoxy decane, vinyl triethoxy fluorene oxime Alkane, γ -mercaptopropyltrimethoxydecane, γ -mercaptopropyltriethoxydecane, bis(triethoxydecylpropyl)tetrasulfide, γ -aminopropyltrimethoxydecane, γ - Silane-aminopropyl triethoxysilane, γ - [bis (beta] - hydroxyethyl)] Silane-aminopropyl triethoxysilane, N- β - (aminoethyl) - gamma] - amino propyl Triethoxy decane, N-(trimethoxydecylpropyl)ethylenediamine, isocyanatopropyltrimethoxydecane, isocyanatepropyltriethoxydecane, methyltrimethoxydecane, methyltri Ethoxy decane, dimethyl dimethoxy decane, dimethyl diethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, diphenyl dimethoxy decane, diphenyl Diethoxydecane, diphenyldecanediol, triphenylmethoxydecane, triphenylethoxydecane, triphenylstanol, N-β-(N-vinylbenzylaminoethyl -γ-aminopropyltrimethoxydecane, γ -chloropropyltrimethoxydecane, hexamethyldioxane, γ -anilinopropyltrimethoxydecane, γ -anilinopropyltriethoxylate矽, 2-triethoxy Base alkyl-N-(1,3-dimethyl-butylene)propylamine, 3-triethoxydecyl-N-(1,3-dimethyl-butylene)propylamine, N -(3-triethoxydecylpropyl)phenylimine, 3-(3-(triethoxydecyl)propylamino)-N,N-dimethylpropionamide, N- Methyl triethoxy decyl propyl-β-alanine, decane such as 3-(triethoxydecylpropyl)dihydro-3,5-furandione or bis(trimethoxydecyl)benzene An imidazole compound such as a compound, 1H-imidazole, 2-alkylimidazole, 2,4-dialkylimidazole or 4-vinylimidazole, and γ -glycidoxypropyltrimethoxydecane, γ -glycidyloxy An imidazole-based decane compound of a reaction product of γ -glycidoxypropyl alkoxydecane such as propyltriethoxydecane. These may be used alone or in combination of two or more.

When the decane compound (b) is blended, the total amount of the compound is preferably from 0.06 to 2% by mass, more preferably from 0.1 to 0.75% by mass, in terms of moldability and adhesion. More preferably 0.2 to 0.7% by mass. When the amount is less than 0.06% by mass, the adhesion improving effect is less likely to be exhibited, and when it exceeds 2% by mass, molding defects such as voids tend to occur.

In the epoxy resin molding material for encapsulation of the present invention, a conventional coupling agent other than the above-described decane compound (b) may be blended from the viewpoint of improving the adhesion between the resin component and the inorganic component in the molding material. Listed as, for example, isopropyl triisostearate titanate, isopropyl cis (dioctyl pyrophosphate) titanate, isopropyl tris(N-aminoethyl-aminoethyl) titanium Acid ester, tetraoctyl bis(di-tridecylphosphonate) titanate, tetrakis(2,2-diallyloxymethyl-1-butyl)bis(di-tridecyl) Phosphonate titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctyl pyrophosphate) extended ethyl titanate, isopropyl trioctylide titanate, Isopropyl dimethyl propylene isostearyl decyl titanate, isopropyl isostearyl decyl dipropylene titanate, isopropyl tris(dioctyl phosphate) titanate, isopropyl A titanate coupling agent such as tricumylphenyl titanate or tetraisopropylbis(dioctylphosphonate) titanate, an aluminum chelating agent, an aluminum/zirconium compound, or the like, which can be used alone. One type may be used in combination of two or more types. In addition, when the coupling agent is blended, the total amount of the coupling agent is preferably from 0.06 to 2% by mass, more preferably from 0.1 to 0.75% by mass, in terms of moldability and adhesion. It is preferably 0.2 to 0.7% by mass. When it is less than 0.06 mass%, the adhesion to various package members tends to decrease, and when it exceeds 2 mass%, molding defects such as voids tend to occur.

Further, the epoxy resin molding material for encapsulation of the present invention may be formulated with an anion exchanger as needed to improve the moisture resistance and high-temperature placement characteristics of the IC. The anion exchanger is not particularly limited, and may be, for example, a hydrotalcite or an aqueous oxide of an element selected from magnesium, aluminum, titanium, zirconium or hafnium, which may be used alone. It is also possible to combine two or more types. Among them, hydrotalcite represented by the following composition formula (XXXXXXIV) is preferred.

Mg _1-X Al _X (OH) ₂ (CO ₃ ) _X/2 ‧mH ₂ O...(XXXXXXIV)

In the formula (XXXXXXIV), 0 < X ≦ 0.5, and m is a positive number.

The amount of the anion exchanger is not particularly limited as long as it can capture an anion such as a halogen ion, but is relative to the (A) epoxy tree. 100 parts by mass of the fat is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 5 parts by mass.

In order to further improve the adhesion, the epoxy resin molding material for encapsulation of the present invention may be optionally used as a reinforcing agent. The promoters are listed as derivatives such as imidazole, triazole, tetrazole, triazine, ortho-aminobenzoic acid, gallic acid, malonic acid, malic acid, maleic acid, aminophenol, quinoline, and the like. These derivatives, an aliphatic acid amide compound, a dithiocarbamate, a thiadiazole derivative, etc. may be used alone or in combination of two or more.

The epoxy resin molding material for encapsulation of the present invention may also be used as a release agent as needed. The release agent is preferably used in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the epoxy resin (A), and more preferably 0.1 to 5 parts by mass. When the amount is less than 0.01 part by mass, the mold release property tends to be insufficient, and if it exceeds 10 parts by mass, the adhesiveness tends to decrease. The oxidized or non-oxidized polyolefin is exemplified by a product name H4 manufactured by Hoechst Co., Ltd., or a low molecular weight polyethylene having a number average molecular weight of about 500 to 10,000, such as a PE or a PED series. In addition, the release agent other than the above is exemplified by carnauba wax, montanic acid ester, montanic acid, stearic acid, etc., and these may be used alone or in combination of two or more. When the other mold release agent is used in combination with the oxidized or non-oxidized polyolefin, the total amount thereof is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 3 parts by mass, per 100 parts by mass of the (A) epoxy resin. .

The epoxy resin molding material for encapsulation of the present invention can also be blended with a conventional flame retardant as needed to improve the flame retardancy of the molding material. List Examples thereof include inorganic substances such as brominated epoxy resin, antimony trioxide, red phosphorus, aluminum hydroxide, magnesium hydroxide, and zinc oxide, and/or phosphorus compounds such as red phosphorus and phosphate ester coated with a thermosetting resin such as a phenol resin. Melamine compounds such as melamine, melamine derivatives, melamine modified phenol resins, compounds having a triazine ring, cyanuric acid derivatives, isocyanuric acid derivatives, phosphorus compounds such as cyclophosphene, and nitrogen-containing compounds, hydrogen Alumina, magnesium hydroxide, and a composite metal hydroxide represented by the following composition formula (XXXXXXV).

p(M ¹ _a O _b )‧q(M ² _c O _d )‧r(M ³ _e O _f )‧mH ₂ O (XXXXXXV)

In the formula (XXXXXXV), M ¹ , M ² and M ³ represent different metal elements, and a, b, c, d, e, f, p, q and m represent a positive number, and r represents 0 or a positive number.

M ¹ , M ² and M ³ in the above composition formula (XXXXXXV) are not particularly limited as long as they are mutually different metal elements, but from the viewpoint of flame retardancy, M ^{1 is} preferably a metal element of the third period. , the alkaline earth metal element of Group IIA, the metal elements belonging to group IVB, IIB, VIII, IB, IIIA and IVA are selected, and M2 is preferably selected from the transition metal elements of group IIIB to IIB, M ^{1 is} more It is preferably selected from magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc, and M ^{2 is} more preferably selected from iron, cobalt, nickel, copper and zinc. From the viewpoint of fluidity, M ^{1 is} preferably magnesium, and M ^{2 is} preferably zinc or nickel, and r = 0. The molar ratio of p, q and r is not particularly limited. When r = 0, p/q is preferably from 1/99 to 1/1. Furthermore, the classification of metal elements is a periodic table with a typical element as the A subfamily and a transitional element of the B subfamily (Source: Kyoritsu Publishing Co., Ltd. issued "Chemical Dictionary 4" February 15, 1987 The condensed version of the 30th brush) is subject to approval. Further, examples thereof include compounds containing a metal element such as zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate, and dicyclopentadienyl iron. These may be used alone or in combination of two or more. use. The blending amount of the flame retardant is not particularly limited, but is preferably from 1 to 30 parts by mass, more preferably from 2 to 15 parts by mass, per 100 parts by mass of the (A) epoxy resin.

Further, as the epoxy resin molding material for encapsulation of the present invention, a coloring agent such as carbon black, an organic dye, an organic pigment, titanium oxide, lead trioxide or red iron oxide (Bengala) may be used. Further, as the other additives, a stress relieving agent such as an oxime oil or a ruthenium rubber powder may be blended as needed.

The epoxy resin molding material for encapsulation of the present invention may be prepared by uniformly dispersing and mixing various components, and may be prepared by various methods. However, in general, a method in which a component of a specific blending amount is sufficiently mixed by a kneading machine or the like is used, and mixing is carried out. After melting and kneading, such as a roll or an extruder, it is cooled and pulverized. For example, a specific amount of the above components may be uniformly stirred and mixed, preheated to 70 to 140 ° C, and obtained by kneading, cooling, pulverization, or the like by a kneader, a roll, an extruder, or the like. It is easily granulated by the size and quality of the molding conditions.

The electronic component device having the component encapsulated by the epoxy resin molding material obtained by the present invention is provided with a semiconductor die and a transistor on a support member such as a lead frame, a tape carrier, a wiring board, a glass, or a germanium wafer. An element such as an active element such as a diode or a thyristor (Thyristor), a passive element such as a capacitor, a resistor, or a coil, and an electronic zero obtained by encapsulating a necessary portion of the epoxy resin molding material for encapsulation of the present invention Device, etc. The electronic component device is exemplified by, for example, fixing a semiconductor element to a lead frame, and connecting the terminal portion and the lead portion of the component such as a pad by wire bonding or jumper bonding, and then using the epoxy resin molding material for encapsulation of the present invention by transferring Forming and other packages, DIP (dual-wire package), PLCC (plastic wire die carrier), QFP (quad rectangular package), SOP (small outline package), SOJ (small outline J-lead package), TSOP (thin A general resin-packaged IC such as a small-sized package) or a TQFP (thin-type quad flat package) is a TCP (tape) obtained by packaging a semiconductor die of a tape carrier with a jumper wire in an epoxy resin molding material for packaging of the present invention. The semiconductor die, the transistor, the diode, the thyristor, etc., which are connected to the wiring board or the wiring formed on the glass by wire bonding, flip chip bonding, soldering, etc., by the epoxy resin molding material for encapsulation of the present invention. a COB (substrate flip chip) module, a hybrid IC, a polycrystalline module, and an active component on a surface of an organic substrate on which a terminal for forming a wiring board is formed on the back surface, such as an active device and/or a passive component such as a capacitor, a resistor, or a coil, Jumper or hit After the wire is connected to the wiring formed on the organic substrate, a BGA (Ball Grid Array), a CSP (Grain Size Package), or the like of the component is packaged with the epoxy resin molding material of the present invention. Further, the epoxy resin forming material for encapsulation of the present invention can be effectively used in a printed circuit board.

The method of packaging an element using the epoxy resin molding material for encapsulation of the present invention is most commonly used in a low pressure transfer molding method, but an injection molding method, a compression molding method, or the like can also be used.

[Examples]

The invention is illustrated by the following examples, but the scope of the invention is not limited by the examples.

[Preparation of epoxy resin molding material for encapsulation of the present invention] (Examples 1 to 26, Comparative Examples 1 to 13)

The following components were blended in the mass ratios shown in the following Tables 1 to 3, and the kneading was carried out under the conditions of a kneading temperature of 80 ° C and a kneading time of 10 minutes to prepare the encapsulating rings of Examples 1 to 26 and Comparative Examples 1 to 13. Oxygen resin forming material. The blank column in the table indicates that it is not deployed.

(A) Epoxy resin The following: an o-cresol novolac type epoxy resin (epoxy resin 1, trade name ESCN-190 manufactured by Sumitomo Chemical Co., Ltd.) having an epoxy equivalent of 200 and a softening point of 67 ° C, Ethylene equivalent of 196, biphenyl type epoxy resin having a melting point of 106 ° C (epoxy resin 2, trade name YX-4000H manufactured by Nippon Epoxy Resin Co., Ltd.), epoxy equivalent 242, thiodiphenol type having a melting point of 118 ° C Epoxy resin (epoxy resin 3, trade name YSLV-120TE, manufactured by Nippon Steel Chemical Co., Ltd.), epoxy equivalent 241, softening point 96 ° C phenol ‧ aralkyl type epoxy resin containing extended biphenyl skeleton (Epoxy Resin 4, trade name CER-3000L manufactured by Nippon Kayaku Co., Ltd.), Epoxide equivalent 238, epoxide of phenol ‧ aralkyl resin with a softening point of 52 ° C (epoxy resin 5, trade name NC-2000L, manufactured by Nippon Kayaku Co., Ltd.), epoxy equivalent 375, softening point 80 ° C A bisphenol A type brominated epoxy resin (epoxy resin 6) having a bromine content of 48% by mass.

(B) The hardener is the following: a phenol ‧ aralkyl resin having a hydroxyl equivalent of 199 and a softening point of 89 ° C (hardener 1, trade name MEH-7851, manufactured by Minghe Chemical Co., Ltd.), hydroxyl equivalent 176, softening point 70 Phenol ‧ aralkyl resin (hardener 2, trade name Mirex XLC manufactured by Mitsui Chemicals, Inc.), phenolic phenolic resin with hydroxyl equivalent of 106, softening point of 64 ° C (hardener 3, Minghe Chemical Co., Ltd.) The manufactured product name is H-4).

(C) A hardening accelerator is a betaine-type adduct of triphenylphosphine and p-benzoquinone (hardening accelerator 1), a betaine-type adduct of tributylphosphine and p-benzoquinone (hardening promotion) The agent 2), (D) inorganic filler is a spherical molten cerium oxide having an average particle diameter of 17.5 μm and a specific surface area of 3.8 m ² /g.

The cerium-containing polymer of the component (E) is the following: weight average molecular weight (Mw) 2150, (E) ratio of substituted or unsubstituted phenyl groups to all side chains in the ruthenium-containing polymer (Ph-based ratio) 75 mol%, Ph base ratio divided by the Mw value (Ph/Mw) of 0.0349 cerium-containing polymer (containing cerium polymer 1, manufactured by Toray Dow Corning Co., Ltd. under the trade name 217 FLAKE), Mw3700, Ph base ratio of 46% by mole, Ph/Mw 0.0124 of cerium-containing polymer (containing cerium polymer 2, trade name 233FLAKE manufactured by Toray Dow Corning Co., Ltd.), Mw5350, Ph base ratio of 67% by mole , Rh/Mw 0.0125 ruthenium containing polymer (containing ruthenium polymer 3, trade name 220FLAKE manufactured by Toray Dow Corning Co., Ltd.), Mw3500, Ph base ratio of 52 mol%, Ph/Mw 0.0149 ruthenium containing polymer (Antimony polymer 4, trade name SH6018 manufactured by Toray Dow Corning Co., Ltd.).

Further, the ruthenium-containing polymers 1 and 3 have a structure represented by the general formula (I) and the general formula (II), and the ruthenium-containing polymers 2 and 4 have a structure represented by the general formulae (I) to (III).

In addition to the component (E), that is, the cerium-containing polymer other than the preferred range for achieving the present invention, the following is used: Mw850, a ratio of Ph group of 15 mol%, and a Ph/Mw 0.0177 cerium-containing polymer (containing cerium polymerization) 5, manufactured by Toray Dow Corning Co., Ltd. under the trade name DC3037), Mw1350, Ph base ratio of 33% by mole, Ph/Mw 0.0244 containing cerium polymer (containing cerium polymer 6, manufactured by Toray Dow Corning Co., Ltd. The trade name is DC3074), Mw7900, the ratio of Ph base is 34% by mole, and the Rh/Mw 0.0043 containing cerium polymer (containing cerium polymer 7, manufactured by Toray Dow Corning Co., Ltd. under the trade name 249FLAKE), Phenylmethyl fluorenone (containing fluorene polymer 8, trade name KF54, manufactured by Shin-Etsu Chemical Co., Ltd.) having a viscosity of 400 mPa·S at room temperature, polyoxyxane having an epoxy equivalent of 1,660 and a softening point of 80 ° C (including Neodymium Polymer 9, trade name AY42-119 manufactured by Toray Dow Corning Co., Ltd.).

Further, the ruthenium-containing polymers 5 and 6 have all of the structures in which the hydrogen atom bonded to the oxygen atom is substituted with a methyl group in each of the structures represented by the general formulae (I) to (III), and the ruthenium-containing polymer 7 All of the structures represented by the general formulae (I) to (III), the ruthenium-containing polymer 8 has only the structure represented by the general formula (II), and the ruthenium-containing polymer 9 contains an epoxy group in the structure.

The oxime oligomer was a trade name I-100 manufactured by Tohto Kasei Co., Ltd.

As the decane compound (a), bis-cyclopentyldimethoxydecane (trade name Z6228, manufactured by Toray Dow Corning Co., Ltd.) was used.

The decane compound (b) is γ -glycidoxypropyltrimethoxydecane (decane compound (b)-1), γ -anilinopropyltrimethoxydecane (decane compound (b)-2), γ - Mercaptopropyltrimethoxydecane (decane compound (b)-3).

Other added ingredients are carnauba wax, antimony trioxide, and carbon black.

[Evaluation of the shape of epoxy resin for packaging]

Then, the epoxy resin molding materials for packaging prepared in Examples 1 to 26 and Comparative Examples 1 to 13 were evaluated by the following characteristic tests of (1) to (5). characteristic. The evaluation results are shown in Tables 1 to 3 below. Further, unless otherwise specified, the molding of the epoxy resin molding material for encapsulation was carried out by a transfer molding machine at a mold temperature of 180 ° C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Further, the curing was carried out at 180 ° C for 5 hours as necessary.

(1) Spiral flow

According to EMMI-1-66, the epoxy molding material for encapsulation was molded under the above conditions using a mold for spiral flow measurement, and the flow distance (cm) was determined.

(2) Hardness during heat

The epoxy resin molding material for encapsulation was molded into a circular plate having a diameter of 50 mm and a thickness of 3 mm under the above-described conditions, and immediately after molding, it was measured using a Shore D type hardness meter (HD-1120 (D type) manufactured by Ueshima Seisakusho Co., Ltd.).

(3) room temperature bending modulus and 260 °C bending modulus

The epoxy resin molding material for encapsulation was molded into 10 mm × 70 mm × 3 mm under the above conditions, and post-hardened to prepare a test piece, using Tensilon manufactured by A&D Co., Ltd., in a thermostatic chamber at room temperature and 260 ° C according to JIS-K-6911 A three-point support bending test was performed to obtain a room temperature bending modulus (GPa) and a bending modulus (MPa) at 260 ° C, respectively.

(4) Reflow resistance

Using an epoxy resin molding material for encapsulation, an 80-pin flat package (QFP) having a size of 20 mm × 14 mm × 2 mm of 8 mm × 10 mm × 0.4 mm is mounted under the above-mentioned conditions (wire frame material: copper alloy, Soldering silver on the top of the solder joint and on the front end of the wire) Forming, post-hardening, humidification at 85 ° C, 85% RH for 168 hours, then reflow treatment at a specific temperature (235 ° C, 245 ° C, 255 ° C, 265 ° C), 10 seconds, Visually observe whether there is crack inside the package, and observe whether the inside of the package is peeled off by the ultrasonic flaw detection device (HYE-FOCUS manufactured by Hitachi Construction Machinery Co., Ltd.), and the sum of the number of packages for cracking and peeling is relative to the test package. The number (10) was evaluated.

(5) Flame retardancy

Using a mold of a test piece having a thickness of 1/16 inch (about 1.6 mm), the epoxy resin molding material for encapsulation was molded under the above conditions and post-hardened, and the flame retardancy was evaluated in accordance with the UL-94 test method.

As can be understood from Tables 1 to 3, Comparative Examples 1 to 13 in which the compound of the component (E) was not formulated were inferior in reflow resistance. Comparative Example 12 in which a linear polyoxyalkylene was blended was inferior in flame retardancy, and Comparative Example 13 in which a branched polyoxyalkylene group containing an epoxy group was blended did not sufficiently reduce the flexural modulus. The comparative examples 9 to 11 in which the weight average molecular weight of the compound of the component (E) was outside the range of the present invention were inferior in reflow resistance, and in Comparative Examples 9 and 10, the flame retardancy was poor and UL-94 V-0 could not be achieved.

On the other hand, in comparison with the composition of the same resin composition in which the compound of the component (E) is blended in a range different from the compounding composition of the cerium-containing polymer or the cerium compound (b) other than the component (E) In comparison with Examples, the reflow resistance of Examples 1 to 26 was good, and all of them were UL-94 V-0, which was excellent in flame retardancy and good in formability. Further, Examples 12 and 16 containing a fluorene-containing oligomer, and Examples 13 and 17 containing a decane compound (a) were particularly excellent in reflow resistance.

Claims (6)

An epoxy resin molding material for encapsulation, comprising (A) an epoxy resin, (B) a hardener, (C) a hardening accelerator, (D) an inorganic filler, and (E) a germanium-containing polymer, (E) The ruthenium-containing polymer has any two or all of the structures represented by the following general formula (I), the following general formula (II), and the following general formula (III), and (E) the weight average of the ruthenium-containing polymer The molecular weight is 1500 or more and 7000 or less. In the formula (I), R ¹ represents a substituted or unsubstituted phenyl group, and at least one of the oxygen atoms is an oxygen atom constituting a siloxane chain, and an oxygen atom other than the oxygen atom is bonded to a hydrogen atom. In the formula (II), R ¹ represents a substituted or unsubstituted phenyl group, wherein R ¹ may be the same or different, and at least one of the oxygen atoms is an oxygen atom constituting a siloxane chain, and the oxygen atom The oxygen atom other than the hydrogen atom is bonded to the hydrogen atom. In the formula (III), at least one of the oxygen atoms is an oxygen atom constituting a siloxane chain, and an oxygen atom other than the oxygen atom is bonded to a hydrogen atom. The epoxy resin molding material for encapsulation according to the first aspect of the invention, wherein the content of the (E) cerium-containing polymer is 2.5% by mass or more and 40% based on the (A) epoxy resin in the epoxy resin molding material for encapsulation. Below mass%. The epoxy resin molding material for encapsulation according to claim 1 or 2, wherein (E) the substituted epoxy resin in the encapsulating epoxy resin molding material is substituted or unsubstituted benzene in all R ¹ in the antimony polymer. The basis ratio is 40 mol% or more and 100 mol% or less. The epoxy resin molding material for encapsulation according to claim 1 or 2, which further contains a fluorene oligomer. The epoxy resin molding material for encapsulation according to claim 1 or 2, further comprising a decane compound (a) represented by the following formula (IV), In the formula (IV), R ¹ represents a cycloalkyl group or a cycloalkenyl group having 5 to 8 carbon atoms, R ² is the same as R ¹ or a hydrocarbon group having 1 to 6 carbon atoms, and R ³ represents a hydrocarbon group having 1 to 6 carbon atoms. ^One of the hydrogen atoms represented by R ¹ to R ³ may be substituted, p represents an integer of 1 to 3, and q represents an integer of 0 to 3. An electronic component device comprising an element encapsulated with an epoxy resin molding material for encapsulation according to any one of claims 1 to 5.