TW201229124A - Epoxy resin molding material for sealing and electronic component device equipped with element sealed by molding material - Google Patents

Abstract

An epoxy resin molding material for sealing includes: an epoxy resin having at least two epoxy groups in the epoxy resin molecule, a curing agent, and a monovalent or divalent phenol derivative having at least one nitrile group in the molecular structure. An electronic component device has an element sealed by the epoxy resin molding material for sealing.

Description

201229124 SUMMARY OF THE INVENTION [Technical Field] The present invention relates to an epoxy resin molding material for sealing and an electronic component device including an element sealed by the molding material. [Prior Art] Epoxy resin molding materials have been widely used in the field of sealing electronic components such as transistors and 1C. The reason for this is that the epoxy resin can be balanced in electrical properties, moisture resistance, heat resistance, mechanical properties, and subsequent properties of the insert. In particular, the combination of an o-cresol novolak-type epoxy resin and a novolak-type phenol curing agent is extremely excellent in achieving such balance, and is a mainstream of a matrix resin for a molding material for sealing. With the increase in the size, weight, and performance of electronic devices in recent years, the electronic component device has gradually become a surface-mount package by the conventional pin type. When the semiconductor device is mounted on the wiring board, the conventional pin-type package is inserted into the wiring board and then soldered from the back surface of the wiring board, so that the package is not directly exposed to high temperatures. However, the entire system of the semiconductor device is disposed in a surface-molded package by a metal melting bath or a reflow device, and is directly exposed to the soldering temperature. As a result, when the package is moisture-absorbing, the moisture absorbing moisture rapidly expands during welding, and peeling of the interface or cracking of the package occurs, and the reliability of packaging at the time of mounting is lowered. In order to solve the above-mentioned problems, in order to reduce the moisture absorption moisture inside the semiconductor device, a method of using a 1C moisture-proof bag or a method of sufficiently drying I c before using it to be mounted on the wiring board is used (for example, Reference to the semiconductor division of Hitachi, Ltd., "The mounting technology of the surface-mounted LSI package and the enhancement of its reliability", and the application of the technology publication published on January 1, 2016, 254-256 pages), but These methods are complicated and costly. Further, as another measure, there is a method of increasing the content of the sputum. This method can reduce the moisture absorption inside the semiconductor device, but it causes a problem that the fluidity is largely lowered. When the fluidity of the epoxy resin molding material for sealing is low, problems such as the flow of gold wires, voids, pinholes, and the like may occur during molding (for example, refer to Japanese Patent Application Laid-Open No. Hei 06-2243-28, The Information Society compiled "High Reliability of Semiconductor Sealing Resins", Technical Information Association, January 31, 990, 1 72-1 76 pages). [Problem to be Solved by the Invention] The present invention has been made in view of the above circumstances, and is intended to provide a sealing epoxy which can be formed into a cured product which is formed at a high temperature and has high metal adhesion and excellent reflow resistance. A resin molding material and an electronic component device having the components sealed thereby. [Means for Solving the Problem] The present invention includes the following aspects. (1) An epoxy resin molding material for sealing, comprising (A) an epoxy resin having two or more epoxy groups in one molecule, (B) a curing agent, and (C) having one in a molecular structure The above-mentioned nitrile group is a monovalent or divalent phenol derivative-6 - 201229124 organism. (2) The epoxy resin molding material for sealing according to the above (1), wherein the content of the (C) phenol derivative is 〇.10% by mass to 1_08% by mass 〇(3) as described above (1) Or the epoxy resin molding material for sealing described in (2), wherein the hydrazine contains (D) a decane compound. (4) The epoxy resin molding material for sealing according to any one of (1) to (3), wherein the crucible contains (E) a curing accelerator. (5) The epoxy resin molding material for sealing according to any one of the above aspects (1) to (4), wherein the cerium contains (F) an inorganic cerium. (6) An electronic component device, which is an element sealed by the epoxy resin molding material for sealing according to any one of the above (1) to (5). [Effect of the Invention] The cured product obtained by using the epoxy resin molding material for sealing obtained by the present invention can be improved in adhesion to metal at a high temperature, thereby obtaining an electron having excellent reflow resistance and high reliability. The parts are installed, so the industrial price is extremely high. [Embodiment] In the present specification, the range of numbers indicated by "~" means that the number after the "~" is included in the range of the minimum and maximum of each. Further, in the present specification, the amount of each component in the composition 201229124 'when a plurality of substances of the respective components are present in the composition, when there is no particular definition, it means the total amount of the plural substances present in the composition. . <Epoxy resin molding material for sealing> The epoxy resin molding material for sealing contains at least one of (A) at least one epoxy resin having two or more epoxy groups in one molecule, and at least one of (B) a curing agent. And (C) having at least one of a monovalent or divalent phenol derivative of one or more nitrile groups in a molecular structure, and containing other components as necessary. The cured product formed of the epoxy resin molding material for sealing having such a structure is excellent in adhesion to metal at a high temperature and excellent in reflow resistance. However, it can be considered that, for example, the phenol derivative acting as a hardener of the epoxy resin has at least one nitrile group and the nitrile group interacts with the metal of the object to enhance the adhesion between the hardened material and the metal. Further, the epoxy resin molding material for sealing is preferably a solid epoxy resin composition which is solid at normal temperature (25 t). In this way, the stability is excellent. * and * at a normal temperature, the solid state means that the melting point (JIS K-7121) exceeds 25 ° C, and the softening point according to the orbital method (JIS K-2 207) is 40 ° C or more. (A) Epoxy Resin The epoxy resin molding material for sealing contains at least one of an epoxy resin (hereinafter also referred to as "specific epoxy resin") having two or more epoxy groups in one molecule. The specific epoxy resin described above can be suitably selected from the general users of the epoxy resin molding material by the sealing of 201229124. Specifically, a phenol novolak type epoxy resin, an o-phenol novolak type epoxy resin, and an epoxy resin having a triphenylmethane skeleton, such as phenol cresol, indophenol, and m-benzene, may be mentioned. Diphenol, catechol, bisphenol A' bisphenol F, α-naphthol, β-naphthol, anthraquinone and the like, and having awakening, acetonide, propionic acid, benzaldehyde, salicylaldehyde, etc. a novolac resin obtained by condensation or co-condensation of an aldehyde group compound under an acidic catalyst, and an epoxidized novolac type epoxy resin; an alkyl-substituted, aromatic ring-substituted or unsubstituted bisphenol A, Epoxy resin of bisphenol F, bisphenol S, biphenol, thiodiphenol, etc.; oxime type epoxy resin; hydroquinone type epoxy resin; by tannic acid, two A glycidyl ester type epoxy resin obtained by reacting a polyacid such as a polyacid with epichlorohydrin; a polyamine and epichlorohydrin by a diaminodiphenylmethane or an isomeric cyanuric acid Epoxypropylamine type epoxy resin obtained by the reaction; epoxide of a cocondensation resin of dicyclopentadiene and phenol; naphthalene having a naphthalene ring Epoxy resin: triphenylmethane type epoxy resin with triphenylmethyl group; phenolic aralkyl resin synthesized from phenols and dimethoxy oxime or bis(methoxymethyl)biphenyl An epoxide of an aralkyl type phenol resin such as a naphthol/aralkyl resin; a trimethylolpropane type epoxy resin; a terpene modified epoxy resin; and an olefin bond to a peracid such as peracetic acid A linear aliphatic epoxy resin obtained by oxidation; an alicyclic epoxy resin or the like. These may be used alone or in combination of two or more. Among them, a biphenyl type epoxy resin containing a di-epoxypropyl ether of an alkyl group-substituted, an aromatic ring-substituted or an unsubstituted biphenol is preferred from the viewpoint of establishing both fluidity and hardenability. Further, from the viewpoint of hardenability, a varnish-type epoxy resin containing phenol-9-201229124 is preferred. Further, from the viewpoint of heat resistance and low warpage, at least one of a naphthalene type epoxy resin and a triphenylmethane type epoxy resin is preferable. Further, from the viewpoint of establishing both fluidity and flame retardancy, a bisphenol F-type epoxy resin containing an alkyl group-substituted, aromatic ring-substituted or unsubstituted bisphenol F diglycidyl ether is preferred. Further, from the viewpoint of simultaneously establishing fluidity and reflowability, a thiodiphenol type epoxy resin containing a di-epoxypropyl ether of an alkyl substituted, an aromatic ring substituted or an unsubstituted thiodiphenol is preferred. Further, from the viewpoint of establishing both curability and flame retardancy, a phenolic aralkyl resin synthesized from a phenol having an alkyl group, an aromatic ring or an unsubstituted bisphenol and bis(methoxymethyl)biphenyl The epoxide is preferred. Further, a naphthol aralkyl resin synthesized from a naphthol substituted with an alkyl group, an aromatic ring or an unsubstituted, and a dimethoxy oxime is used from the viewpoint of establishing both storage stability and flame retardancy. The epoxide is preferred. The biphenyl type epoxy resin may, for example, be an epoxy resin represented by the following general formula (I).

In the general formula (I), R^R8 each independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. η represents an integer of 0 to 3. The biphenyl type epoxy resin represented by the above general formula (I) can be obtained by reacting a biphenol compound with epichlorohydrin in a known manner. In the general formula (I), R1 to R8' may have a carbon number of 1 to 1 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 tert-butyl group. An alkyl group of 201229124; an alkenyl group having 1 to 10 carbon atoms such as a vinyl group, an allyl group, a butenyl group or the like. Among them, a hydrogen atom or a methyl group is also preferred. The epoxy resin may be, 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, epoxy chlorinated with 4,4'-biphenol or 4,4'-(3,3',5 An epoxy resin obtained by reacting 5'-tetramethyl) phenol. Among them, an epoxy resin containing 4,4'-bis(2,3-epoxypropoxy)-3,3',5,5'-tetramethylbiphenyl as a main component is preferred. As a commercial product of such an epoxy resin, it can be obtained by the trade name YX-4000 manufactured by Mitsubishi Chemical Corporation (formerly Japan Epoxy Resin Co., Ltd.). In order to exhibit the performance, the content of the biphenyl type epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more. The thiodiphenol type epoxy resin may, for example, be an epoxy resin represented by the following general formula (II). [Chemical 2]

In the general formula (II), R1 to R8 each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. η represents an integer from 0 to 3. The thiodifluorene type epoxy resin represented by the above general formula (II) can be obtained by reacting a thiodiphenol compound with epichlorohydrin in a known manner. R1 to R8 in the general formula (II) include a carbon number of 1 to 1 such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a tert-butyl group or the like. An alkyl group of -11 - 201229124; an alkenyl group having a carbon number of 10, such as a vinyl group, an allyl group, a butenyl group, etc., wherein a hydrogen atom, a methyl group or a tert-butyl group is also preferred. Such an epoxy resin is exemplified by an epoxy resin containing a di-epoxypropyl ether of 4,4'-dihydroxydiphenyl sulfide as a main component, and 2,2',5,5'-tetramethyl. Epoxy resin containing bis-epoxypropyl ether of keto-4,4'-dihydroxydiphenyl sulfide as main component, 2,2'-dimethyl-4,4'-dihydroxy-5,5 An epoxy resin containing a di-epoxypropyl ether of '-di-tert-butyl diphenyl sulfide as a main component, and also 2,2'-dimethyl-4,4'-dihydroxy-5 An epoxy resin containing a di-epoxypropyl ether of 5'-di-tert-butyldiphenyl sulfide as a main component is preferred. A commercially available product of such an epoxy resin is available from Nippon Steel Chemical Co., Ltd. under the trade name YSLV-120TE. In order to exhibit the performance, the content of the thiodiphenol type epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, and 50% by mass or more. good. The bisphenol F-type epoxy resin may, for example, be an epoxy resin represented by the following general formula (III). [化3]

R1 R2 Rs R6

In the general formula (III), R1 to R8 each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. η represents an integer of 〇~3. The bisphenol F type epoxy resin represented by the above general formula (III) can be obtained by reacting a bisphenol F compound with epichlorohydrin in a known manner. R1 to R8 in the general formula (ΙΠ) include a hydrogen atom, a methyl group, an ethyl group, a propyl-12-201229124, a butyl group, an isopropyl group, an isobutyl group, a tert-butyl group, etc.; The carbon number of the allyl group, the butenyl group or the like is preferably a hydrogen atom or a methyl group. Such an epoxy resin is exemplified by a epoxide of a cyclomethyl bis(2,3,6-trimethylphenol) having a di-epoxypropyl ether of 4,4' methylphenol) as a main component. Propylene resin, diepoxypropoxy resin with 4,4'. methylene bisphenol. Among them, epoxy resin containing 4,4'-methylenebis(2,6-oxopropyl ether as the main component is preferred. It is commercially available and can be obtained from Nippon Steel Chemical Co., Ltd. 80 XY. The content of the phenolic F-type epoxy resin is preferably 20% by mass or more, more preferably 50% by mass or more, based on the total amount of the epoxy resin. The novolac type epoxy resin is exemplified by the following Epoxy resin, etc. [Chemical 4]

base. η represents an integer of 〇~1〇. The above general formula (lacquer-type epoxy resin can be easily obtained by making a novolac type phenolic tree. It is based on the number 1 to 1 〇 of the hospital base-10 alkenyl group, etc. among them - methylene double (2, 6 - The second ring of a dioxyl resin and a cyclic dimethyl phenol containing a 4,4 '-subunit ether as a main component as a main component, the trade name of the epoxy resin is YSLV- The performance, preferably, is replaced by a monovalent substitution of a phenolic resin represented by 30 masses of the atom of the formula (IV) or a substituted monovalent IV) and epichlorohydrin counter-13-201229124 R The base may be a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms and a substituted or unsubstituted monovalent alkoxy group having 1 to 10 carbon atoms. Wherein R as the above general formula (IV) is also an alkyl group having a carbon number of 1 to 10 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 preferred, and a hydrogen atom or a methyl group is more preferred. The η system is preferably an integer of 0 to 3. Among the novolac type epoxy resins represented by the above general formula (IV), an o-cresol novolac type epoxy resin is also preferred. In the case of using a novolak-type epoxy resin, the content thereof is preferably 20% by mass or more, and more preferably 30% by mass or more, based on the total amount of the epoxy resin. The naphthalene type epoxy resin may, for example, be an epoxy resin represented by the following general formula (V), and the triphenylmethane type epoxy resin may, for example, be an epoxy resin represented by the following general formula (VI). . The naphthalene type epoxy resin represented by the following general formula (V) may be exemplified by 'm constituent units and n constituent units, random copolymers containing irregularities, and alternating copolymers containing alternating Any one of these may be used alone or in combination of two or more kinds. Further, the triphenylmethane type epoxy resin represented by the following general formula (VI) is not particularly limited, but a stillaldehyde type epoxy resin is preferred. -14- 201229124 【化5】

1-p (V) In the general formula (V), R1 to R3 each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. p represents 1 or 0, and m and η are each an integer of 0 to 11 ’ (m+n) is an integer of 1 to 11 and is selected from (m+p) is an integer of 1 to 12. i represents an integer of 0 to 3, j represents an integer of 〇~2, and k represents an integer of 0-4. In the general formula (V), when any one of R1, R2 and R3 is present, the plural R1, R2 and R3 may be mutually identical or mutually different. R1 to R3 in the above general formula (V) include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an η-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, and a octyl group. a chain alkyl group such as a thiol group, a fluorenyl group, a cyclopentenyl group, a cyclohexyl group or the like; a benzyl group, a phenethyl group or the like; Aryl substituted alkyl; methoxy substituted alkyl; ethoxy substituted alkyl, butoxy substituted alkyl, etc. alkoxy substituted alkyl, aminoalkyl, dimethylaminoalkyl, diethyl An amino group-substituted alkyl group such as an aminoalkyl 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, and a butyl group; a substituted aryl group of a phenyl group, a tert-butylphenyl group, a dimethyl phenyl group or the like; a methoxyphenyl group, an ethoxyphenyl group, a butoxyphenyl group, a tert-butoxyphenyl group, a An alkoxy group such as an oxynaphthyl group substituted with an aryl group; an amino group-substituted aryl group such as a dimethylaminophenyl group or a diethylaminophenyl hydrazine; a hydroxy-substituted aryl group; and the like. Among them, a hydrogen atom or a methyl group is also preferred. -15- 201229124 【化6】

In the general formula (VI), R each independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. η represents an integer of 1 to 10. The R in the above general formula (VI) may, for example, be 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 tert-butyl group; a vinyl group, an allyl group or a butyl group; An alkenyl group such as an alkenyl group; a halogenated alkyl group; an amine-substituted alkyl group; a substituted or unsubstituted monovalent hydrocarbon group having a carbon number of 1 to 10, such as a mercapto-substituted alkyl group; Among them, an alkyl group such as a methyl group or an ethyl group or a hydrogen atom is preferred, and a methyl group or a hydrogen atom is more preferred. These naphthalene type epoxy resins and triphenylmethane type epoxy resins may be used singly or in combination of two or more kinds. In addition, in order to exhibit the performance, the content of the epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 50% by mass or more. . The epoxide of the phenolic aralkyl resin may, for example, be an epoxy resin represented by the following general formula (VII). -16- 201229124 【化7】

In the general formula (νιι), R1 to r8 each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. R9 each independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. i represents an integer of 0 to 3' η represents an integer of 〇 10 . In the general formula (VII), in the presence of the plural R9, the plural R9 may be the same or mutually different. The epoxide of the phenolic aralkyl resin containing the exophenylene skeleton represented by the above general formula (VII) can be obtained by substituting an alkyl group, an aromatic ring or an unsubstituted phenol with a bis(methoxy group) The phenolic aralkyl resin synthesized from biphenyl is reacted with epichlorohydrin in a known manner. The substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms in R1 to R9 in the general formula (VII) may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, an η-butyl group or a sec group. a chain alkyl group of a butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group. An alkoxy-substituted alkyl group such as an aryl-substituted alkyl group such as a cyclic alkyl group, a benzyl group or a phenethyl group, a methoxy-substituted alkyl group, an ethoxy-substituted alkyl group or a butoxy-substituted alkyl group; An amino-substituted alkyl group such as an aminoalkyl group, a dimethylaminoalkyl group or a diethylaminoalkyl group, an unsubstituted aryl group such as a hydroxy-substituted alkyl group, a phenyl group, a naphthyl group or a biphenyl group, or a toluene An alkyl-substituted aryl group, a methoxyphenyl group, an ethoxyphenyl group, a dimethylphenyl group, an ethylphenyl group, a butylphenyl group, a tert-butylphenyl group, a dimethylnaphthyl group, or the like. Butoxyphenyl, tert- -17- 201229124 Alkoxy-substituted aryl group such as butoxyphenyl group, methoxynaphthyl group, etc., amine-substituted aryl group such as dimethyl s-sodium, diethylamino group a group, a hydroxy group, an aryl group or the like. Among them, R1 to R8 are preferably a hydrogen atom or a methyl group. It is better to use the 9 for the people, and it is better for the cockroaches. Further, the η in the general formula (VII) is preferably 6 or less on average, and the commercially available product of the epoxy resin is available from Nippon Kayaku Co., Ltd. under the trade name NC-3000S. In addition, the epoxy resin molding material for sealing contains the epoxy resin represented by the above general formula (I) and the above general formula (VII) from the viewpoint of simultaneously establishing flame retardancy, gj resistance, and fluidity. The epoxy resin is preferably an epoxy resin containing R1 to R8 of the above general formula (VII) as a hydrogen atom, and R1 to R8 of the above general formula (I) are hydrogen atoms and n=〇 epoxy Resin is preferred. Further, the mass ratio thereof is preferably (I) / (VII) = 50/50 to 5/95, preferably 40/60 to 10/90, and more preferably 3 0/70 to 15/85. The compound which satisfies the above-mentioned mass ratio is obtained from CER-3000L (trade name, manufactured by Nippon Kayaku Co., Ltd.) of a commercial product. The epoxide of the naphthol/aralkyl resin may, for example, be an epoxy resin represented by the following general formula (VIII). 【化8】

(VIII) -CH^CH2 In the general formula (VIII), R each independently represents a carbon number 12 substitution -18-201229124 or an unsubstituted monovalent hydrocarbon group. i represents an integer of 〇~3. χ represents a divalent organic group containing an aromatic ring. η represents an integer of 〇~1〇. X specifically includes an alkyl-substituted aryl group such as a stretching phenyl group, a stretching phenyl group, a stretching naphthyl group, an alkyl group-extended phenyl group, an alkoxy-substituted aryl group, and an aryl group. The divalent group derived from an aralkyl group such as an aryl group or a benzyl group, or a divalent group containing an extended aryl group such as a fluorenyl group. Among them, from the viewpoint of making the flame retardancy and the preservation stability at the same time, it is preferable to extend the phenyl group and extend the biphenyl group. The epoxide of the naphthol. aralkyl resin represented by the above general formula (VIII) can be obtained by reacting an alkyl group, an aromatic ring or an unsubstituted naphthoquinone with a dimethoxy group or a bis(methoxy group). The naphthol aralkyl resin synthesized from the methyl group) biphenyl is reacted with epichlorohydrin in a known manner. R in the general formula (VIII), for example, formazan, ethyl, propyl, isopropyl, η-butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, a aryl group such as a fluorenyl group, a tetradecyl group or the like, a cyclic alkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group or a cyclohexenyl group; an aryl group such as a benzyl group or a phenethyl group; a substituted alkyl group, an methoxy-substituted alkyl group, an ethoxy-substituted alkyl group, a butoxy-substituted phenyl group, an anthracene group, an amine group, an amino group, a dimethylamino group, a diethylamine An amino group-substituted alkyl group, a hydroxy-substituted alkyl group, a phenyl group, a naphthyl group, a biphenyl group, etc., an unsubstituted aryl fluorene, a tolyl group, a dimethylphenyl group, an ethylphenyl group, a butylphenyl group An alkyl-substituted aryl group such as tert-butyl phenyl, dimethylnaphthyl or the like, a methoxyphenyl group, an ethoxyphenyl group, a butoxyphenyl group, a tert-butoxyphenyl group, a methoxy group. The alkoxy group such as a naphthyl group is substituted with an aryl group such as an aryl group, a dimethylamino group or a diethylamino group, and the hydroxy group is a -19-201229124 aryl group. Among them, methyl is preferred, and i-based 0 is preferred. The epoxy resin may, for example, be an epoxide of a naphthol·alkyl resin represented by the following general formula (IX) or (X). η represents an integer of 0 to 1 ’, and an average of 6 or less is preferable. The commercially available product of the epoxy resin represented by the following general formula (IX) is exemplified by Nippon Steel Chemical Co., Ltd., trade name ESN-375, and is represented by the following general formula (X). As a commercial item of an oxygen resin, the brand name ESN·175 of Nippon Steel Chemical Co., Ltd. is mentioned. The content of the epoxide of the naphthol aralkyl resin is set to 20 mass in the total amount of the epoxy resin in order to exert its performance. /. The above is preferable, 30% by mass or more is preferable, and 50% by mass or more is more preferable. 【化9】

rCH-CHj

V 〇 a 2 In the general formula (IX), 'X represents a divalent organic group containing an aromatic ring, and η represents an integer of 0 to 10. 【化10】

In the general formula (X), 'X represents a divalent organic group containing an aromatic ring, and an integer of 0 to 10 is shown. -20- 201229124 The aromatic ring represented by the general formula (IX) and the general formula (X) The preferred embodiment of the divalent organic group is as described above. The above biphenyl type epoxy resin, thiodiene type epoxy resin, double 酣F type epoxy resin, novolak type epoxy resin, naphthalene type epoxy resin, triphenylmethane type epoxy resin, phenol. The argon oxide of the aralkyl resin and the epoxide of the naphthol-based resin may be used singly or in combination of two or more kinds. The content of the two or more types of the epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 8% by mass or more. The content of the epoxy resin contained in the epoxy resin molding material for sealing is not particularly limited, and may be appropriately selected depending on the purpose. (B) Hardener The above-mentioned epoxy resin molding material for sealing contains at least one hardener. The curing agent is not particularly limited as long as it is generally used for a sealing epoxy resin molding material. Specifically, for example, phenol, cresol, m-benzoquinone, catechin, diterpene A, diacid F, benzoic acid, thiodiamine, amine hydrazine, α-naphthol, β- a phenolic phenol resin obtained by condensing or co-condensing a phenol such as naphthol or dihydroxynaphthalene with a aldehyde group such as formaldehyde, benzophenone or salicylaldehyde under an acidic catalyst; Phenol. Aralkyl oxime resin synthesized by dimethoxy or bis(methoxymethyl)biphenyl; naphthoic acid; aralkyl type phenol resin such as aralkyl resin, phenol novolac structure and @ • The aralkyl structure is a random, block or alternating repeating copolymerized phenol. aryl-21 - 201229124 alkyl resin; a retinoic phenol resin; an oxime phenolic resin; a melamine modified phenol resin; Phenolic resin; dicyclopentadiene modified phenol resin; cyclopentadiene modified phenol resin; polycyclic aromatic ring modified phenol resin. These may be used alone or in combination of two or more. Among them, a phenolic aralkyl resin, a copolymerized phenolic aralkyl resin, and a naphthol aralkyl resin are preferred from the viewpoints of fluidity, flame retardancy, and reflow resistance. Further, from the viewpoint of heat resistance, low expansion ratio, and low warpage, a triphenylmethane type phenol resin is preferred. Further, a phenol novolak type phenol resin is preferred from the viewpoint of curability. The aforementioned hardener is preferably one containing at least one of these phenol resins. The phenolic aralkyl resin may, for example, be a resin represented by the following general formula (XI). [1 1]

In the general formula (XI), R each independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. i represents an integer of 〇~3. X represents a 2-valent organic group containing an aromatic ring. η represents an integer from 0 to 10. Examples of R in the above general formula (XI) include methyl, ethyl, propyl, isopropyl, η-butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, a carboxyl group such as a fluorenyl 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; an aryl group such as a benzyl group or a phenethyl group; Substituted alkyl; methoxy substituted alkyl, ethoxy substituted fluorenyl-22-201229124, butoxy substituted alkyl, etc. alkoxy substituted alkyl; amine based, dimethylaminoalkyl, An amino-substituted alkyl group such as diethylaminoalkyl; 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, An alkyl-substituted aryl group such as butylphenyl, tert-butylphenyl or dimethylnaphthyl; methoxyphenyl 'ethoxyphenyl, butoxyphenyl, tert-butoxyphenyl An alkoxy group such as a methoxynaphthyl group substituted with an aryl group; an amino group-substituted aryl group such as a dimethylamino group or a diethylamino group; a hydroxy-substituted aryl group; and the like. Among them, methyl is preferred, and i-based 0 is preferred. Further, X represents a divalent organic group containing an aromatic ring. Specific examples thereof include an extended aryl group such as a phenylene group, a biphenylene group, an anthranyl group, and the like; an alkyl group substituted with an alkyl group such as a phenyl group; an alkoxy group substituted with an aryl group; a divalent group derived from an aralkyl group such as phenethyl; an aralkyl group substituted with an aryl group; a divalent group of a aryl group containing a fluorenyl group. In particular, a phenyl group which is substituted or unsubstituted is preferable, and a phenolic aralkyl resin represented by the following general formula (XII) is mentioned, for example, from the viewpoint that the flame retardancy, fluidity, and hardenability are simultaneously established. . In addition, it is preferable that the non-substituted biphenyl group is substituted or unsubstituted, and the phenol aralkyl resin represented by the following general formula (XIII) is exemplified. η represents an integer of 0 or 1 to 10, and is preferably 6 or less on average. [1 2]

-23- (XIII) (XIII) 201229124 [Chem. 1 3]

In the general formula (XIII), η represents an integer of 0 to 10. The phenolic aralkyl resin represented by the above general formula (ΧΠ) is commercially available as Mitsubishi Chemical Co., Ltd. under the trade name XLC. In addition, the phenolic aralkyl resin containing a bisphenylene skeleton represented by the general formula (XIII), and a commercial product of the product of 明-7 8 5 1 In order to exhibit the performance, the content of the base resin is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more. The naphthol aralkyl resin may, for example, be a resin represented by the following general formula (XIV).

In the general formula (XIV), R each independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 2 carbon atoms. i represents an integer from 〇~3. X represents a divalent organic group containing an aromatic ring. η represents an integer of 0 to 10. R in the above general formula (XIV) may, for example, be methyl, ethyl, propyl, isopropyl, η-butyl, sec-butyl, tert-butyl, pentyl, hexyl or octyl. a chain alkyl group such as a fluorenyl group or a dodecyl group; a cyclic alkyl group such as a cyclopentyl group, a cyclohexyl-24 - 201229124, a cycloheptyl group, a cyclopentenyl group or a cyclohexenyl group; an aryl group such as an ethyl group; a substituted alkyl group; a methoxy-substituted alkyl group; an alkoxy-substituted alkyl group such as an ethoxy group or a butoxy-substituted alkyl group; an amine group such as an aminomethylaminoalkyl 'diethylaminoalkyl group; Substituting an alkyl group for a substituted alkyl group; an unsubstituted aryl group such as a phenyl group, a naphthyl group or a biphenyl group; an alkyl group such as a dimethylphenyl group, an ethylphenyl group, a butylphenyl group or a tert-butylmethylnaphthyl group; Aryl; methoxyphenyl, ethoxybutoxyphenyl, tert-butoxyphenyl, methoxyxanthene, etc.; arylaminophenyl, diethylaminobenzene An aryl group such as a hydroxy group; an aryl group substituted with an aryl group; Among them, methyl is preferred, and it is also preferred. Further, 'X represents a divalent organic group containing an aromatic ring, specifically, an extended aryl group such as a phenyl group, a biphenyl group or a naphthyl group; a phenyl group substituted with an aryl group; and an alkoxy group substituted with an aryl group. An aralkyl group-substituted benzyl group, a phenethyl group or the like, a divalent group derived from an aralkyl group; a divalent group derived from an aryl group; and the like. Among them, a phenyl group or a phenyl group which is substituted or unsubstituted is preferable, and more preferably, it is preferable. For example, a general formula (XV) and a naphthol aralkyl resin represented by any one of the following formulas are preferable, and an integer of 0 to 10 in the following chemical formula is preferable, and an average of 6 or less is more preferable. a phenyl-substituted alkane group, a diyl group; a hydroxy group; a tolylphenyl group; a diphenyl group; and an alkoxy group substituted with an amine group, wherein the alkyl group is an alkyl group such as a group; The phenylene of the flammability is XVI), and η means [Chemical 15]

In the general formula (XV), η represents an integer of 〇~1〇. -25- (XV) 201229124 【化16】

In the general formula (XVI), η represents an integer of 0 to 1 。. The commercially available product of the naphthol/aralkyl resin represented by the above general formula (XV) is SN-475, manufactured by Nippon Steel Chemical Co., Ltd., and is represented by the above general formula (XVI). A commercially available product of naphthol/aralkyl resin is SN-1 70, manufactured by Nippon Steel Chemical Co., Ltd. In order to exhibit the performance, the amount of the above-mentioned 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. The phenolic aralkyl resin represented by the above general formula (XI) and the naphthol aralkyl resin represented by the general formula (XIV) are partially or completely premixed with vinyl naphthalene from the viewpoint of flame retardancy. It is better. The vinyl naphthalene may be obtained by dehydrogenating ethane naphthalene, but a commercially available product may also be used. Further, a polymer of ethylene naphthalene or a polymer of vinyl naphthalene and another aromatic olefin may be used instead of ethylene naphthalene. The method of obtaining a polymer of vinyl naphthalene or a polymer of vinyl naphthalene and another aromatic olefin may, for example, be a radical polymerization, a cationic polymerization or an anionic polymerization. Further, in the case of polymerization, a conventionally known catalyst can be used, and it is also possible to carry out heat only without using a catalyst. In this case, the polymerization temperature is preferably from 80 ° C to 160 ° C, and preferably from 90 ° C to 150 ° C. The softening point of the obtained polymer of vinyl naphthalene or the polymer of ethylene naphthalene and other aromatic olefins is preferably 6 ° C to 150 X: and 70 ° C to 130 ° C is preferably -26 to 201229124. When the temperature is lower than 6 ° C, the moldability tends to decrease due to bleeding during molding, and if it is higher than 15 ° C, the compatibility with the resin tends to be lowered. Examples of the other aromatic olefin copolymerized with ethylene naphthalene include styrene, α-methylstyrene, anthracene, benzothiophene, benzofuran, vinylnaphthalene, vinylbiphenyl, and the like. Things and so on. The amount of the aromatic olefin used is preferably 50% by mass or less based on the ethylene naphthalene, and preferably 20% by mass or less. Further, in addition to the above aromatic olefin, an aliphatic olefin can be used without departing from the effects of the present invention. The aliphatic olefin may, for example, be (meth)acrylic acid, anhydrous maleic acid, anhydrous itaconic acid, fumaric acid, or the like. The amount of the aliphatic olefin to be used is preferably 20% by mass or less, and preferably 9% by mass or less based on the total amount of the polymerizable monomers. A method in which a part or all of the curing agent is preliminarily mixed with the vinyl naphthalene, and the two components are uniformly dissolved in the solvent by mixing the curing agent and the vinyl naphthalene into a fine solid state by a mixer or the like. A method of removing a solvent, a method of melt-mixing the two at a temperature higher than a softening point of at least one of a curing agent and an ethylene naphthalene, and the like, but a melt mixture method in which a homogeneous mixture is obtained and impurities are mixed less It is better. The pre-mixture (vinyl naphthalene-modified hardener) is produced by the above-described method and melt-mixed to a temperature above the softening point of at least one of the hardener and the vinyl naphthalene, that is, without limitation. Among them, 100 ° c to 250 ° C is preferred, and 120 ° C to 200 ° C is preferred. Further, the melt mixing is not limited as long as the mixing time of the two can be uniformly mixed -27-201229124. It is preferably from 1 hour to 20 hours, and preferably from 2 hours to 15 hours. When the hardener and the vinyl naphthalene are mixed in advance, it is also possible to polymerize or react with the hardener in the mixing. The triphenylmethane type phenol resin may, for example, be a phenol resin represented by the following general formula (XVII). 【化17】

In the general formula (XVII), R each independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. η represents an integer of 0 to 10. R in the above general formula (XVII) specifically includes 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 tert-butyl group; a vinyl group, an allyl group, An alkenyl group such as a butenyl group; a halogenated alkyl group; an amine-substituted alkyl group; a substituted or unsubstituted monovalent hydrocarbon group having a carbon number of a mercapto-substituted alkyl group or the like. Among them, an alkyl group such as a methyl group or an ethyl group or a hydrogen atom is preferred, and a methyl group or a hydrogen atom is preferred. When the triphenylmethane type phenol resin is used, the content thereof is preferably 30% by mass or more, and more preferably 50% by weight or more, based on the total amount of the curing agent. The novolak-type phenol resin, such as a novolac type phenol resin, a cresol novolak resin, etc. of the phenol resin of the following general formula (XVIII), -28-201229124. Among them, a novolac type phenol resin represented by the following general formula (XVIII) is preferred. [化1 8]

In the general formula (XVIII), R each independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. η represents an integer of 0 to 10. The R in the above general formula (XVIII) may, for example, be 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 tert-butyl group; a vinyl group, an allyl group or a butyl group; Alkenyl group such as alkenyl group; halogenated alkyl group; amine-substituted alkyl group: a substituted or unsubstituted monovalent hydrocarbon group having a carbon number of 1 to 1 fluorene, such as a mercapto-substituted alkyl group. Among them, an alkyl group such as a methyl group or an ethyl group or a hydrogen atom is preferred, and a hydrogen atom is preferred. Further, the η system is preferably 0 to 8. In the case of using a novolak-type phenol resin, it is preferable that the amount is more than 30% by mass or more, more preferably 50% by mass or more, based on the total amount of the curing agent. The copolymerized phenolic aralkyl resin may, for example, be a phenol resin represented by the following general formula (ΧΙΧ). -29- 201229124 【化1 9】

In the general formula (XIX), R each independently represents a hydrogen atom 'a substituted or unsubstituted monovalent hydrocarbon group or a hydroxyl group having 1 to 12 carbon atoms. Further, X represents a divalent organic group containing an aromatic ring. η and m each independently represent an integer of 〇~1〇. The substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms of r in the above general formula (XIX) may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, an η-butyl group or a sec- group. a chain alkyl group such as a butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group or a dodecyl group; a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group or the like. a cyclic alkyl group; an aryl group-substituted alkyl 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 or a butoxy-substituted alkyl group; An amino-substituted alkyl group such as an alkyl group, a dimethylaminoalkyl group or a diethylaminoalkyl 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 hospital-substituted aryl group such as dimethylphenyl, ethylphenyl, butylphenyl, tert-butylphenyl or dimethylnaphthyl; methoxyphenyl, ethoxyphenyl, butoxy An alkoxy-substituted aryl group such as a phenyl group, a tert-butoxyphenyl group or a methoxynaphthyl group; an amine-substituted aryl group such as a dimethylaminophenyl group or a diethylaminophenyl group; Substituting aryl and the like. Among them, R is preferably a hydrogen atom or a methyl group. Further, although η and m each independently represent an integer of 〇~1〇, it is preferably 6 or less. -30- 201229124 The X in the above general formula (XIX) may, for example, be an alkyl group-substituted aryl group such as a phenyl group, a phenylene group or a naphthyl group; a substituted aryl group; an aralkyl group substituted with an aryl group; a benzyl group, a phenethyl group or the like obtained from an aralkyl group; a divalent group containing an extended aryl group such as a fluorenyl group. Among them, a substituted or unsubstituted phenyl group or a biphenyl group is preferred from the viewpoint of preserving stability and flame retardancy. The compound represented by the general formula (XIX) can be obtained from a commercial product such as HE-510 (trade name, manufactured by Air Water Co., Ltd.). In the case of using a copolymerized phenol/aralkyl resin, the content thereof is preferably 30% by mass or more, and preferably 50% by mass or more, based on the total amount of the curing agent. The above phenolic aralkyl resin, naphthol arylalkyl resin, dicyclopentadiene phenol resin, triphenylmethane phenol resin, novolac phenol resin and copolymerized phenolic aralkyl resin Any one of them may be used alone or in combination of two or more. The content of the group and the two or more types of the phenol resin is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 80% by mass or more. The content of the curing agent contained in the epoxy resin molding material for sealing is not particularly limited, and may be appropriately selected depending on the purpose. (C) Phenol derivative The above-mentioned epoxy resin molding material for sealing contains at least one monovalent or divalent phenol derivative containing one or more nitrile groups in the molecular structure (hereinafter, 'also -31 - 201229124 is called "nitrile-phenol" Compound"). The nitrile-phenol compound is not particularly limited as long as it is a compound having one or two hydroxyl groups bonded to an aromatic ring and containing one or more nitrile groups. Examples thereof include decyl-cyanophenol, m-cyanophenol, p-cyanophenol, hydrazine-hydroxyphenylacetonitrile, m-hydroxyphenylacetonitrile, p-hydroxyphenylacetonitrile, 4-cyano-4' -hydroxybiphenyl, 4-cyano-4'-hydroxydiphenyl ether, 4-cyano-4'-hydroxydiphenylmethane, 2,2.(4-cyano-4'-hydroxy)diphenyl Propane, 4-cyano-4'-hydroxybenzophenone, 6-cyano-2-naphthol, 4-hydroxyphthalonitrile, 3,4-dihydroxybenzonitrile, 2.3-dicyanohydroquinone And such positional isomers, as well as derivatives thereof. These may be used alone or in combination of two or more. Among these, from the viewpoint of reducing thermal stress (that is, reducing the elastic modulus at the reflow temperature) and maintaining the hardenability at the time of moisture absorption, it is selected from the group consisting of ρ-cyanophenol and 〇-cyanophenol 'm-cyanide At least one of phenol, hydrazine-hydroxyphenylacetonitrile, m-hydroxyphenylacetonitrile, P-hydroxyphenylacetonitrile, 4-hydroxyphthalonitrile, 3,4-dihydroxybenzonitrile and 2.3-dicyanohydroquinone Preferably, it is selected from the group consisting of p_cyanophenol, phthalocyanol, m-cyanophenol, 4-hydroxyphthalonitrile and 3,4-dihydroxybenzonitrile, 2,3-dicyanohydroquinone At least one is preferably selected from at least one selected from the group consisting of p-cyanophenol, decyl-cyanophenol, m-cyanophenol and 4-hydroxyphthalonitrile. The total content of the monovalent or divalent phenol derivative having one or more nitrile groups in the molecule (C) 1 contained in the epoxy resin molding material for sealing, and the epoxy resin for sealing The molding material is preferably 〇.1 〇 mass% to 1.08 mass%, and 11.5 mass% to 0.60 mass% is preferable. If it is 〇·10% by mass or more, there is a tendency to sufficiently obtain the effect of the invention. In addition, when it is 1.08 mass% or less, the strength of the molding material for sealing epoxy resin -32-201229124 can be suppressed from decreasing. In addition, the epoxy resin molding material for sealing contains the above-mentioned (C) 1 molecule or the total content of the curing agent from the viewpoint of suppressing the adhesion and the strength of the epoxy resin molding material for sealing. In the molecular structure, the monovalent or divalent phenol derivative having one or more nitrile groups is preferably 1.2% by mass to 22.2% by mass, and more preferably 3.5% by mass to 15.0% by mass. In addition, the epoxy resin molding material for sealing is contained in the above-mentioned (C) molecule or the total content of the epoxy resin from the viewpoint of suppressing the adhesion and the strength of the epoxy resin molding material for sealing. The monovalent or divalent phenol derivative having one or more nitrile groups in the molecular structure is preferably 〇 mass% to 1 〇. 〇 mass% is preferably from 3.0% by mass to 5.0% by mass. The epoxy resin molding material for sealing has a viewpoint of reducing the thermal stress (reducing the elastic modulus at the reflow temperature), maintaining the hardenability at the time of moisture absorption, and suppressing the decrease in the strength of the epoxy resin molding material for sealing. - the phenolic compound is selected from the group consisting of P-cyanophenol, phthalocyanol, m-cyanophenol, 4-hydroxyphthalonitrile, 3,4-dihydroxybenzonitrile and 2,3-dicyanohydrogen At least one of 0.1% by mass to 1.0% by mass of ruthenium is preferred to contain at least one selected from the group consisting of P-cyanophenol, 0-cyanophenol, m-cyanophenol, and 4-hydroxyphthalonitrile, 0.15 mass% to 0.6 mass. % is preferred. In the present invention, the equivalent ratio of the (A) epoxy resin to the (B) hardener and (C) molecular structure or a monovalent or divalent phenol derivative having one or more nitrile groups in one molecule, that is, epoxy The ratio of the base number to the hardener and the number of hydroxyl groups in the monovalent or divalent phenols having one or more nitrile groups in one molecule (a hardener and a monovalent or divalent phenol having one or more nitrile groups in one molecule) The hydroxy group-33-201229124 base number/epoxy group number in the epoxy resin is not particularly limited, and in order to make each of the unreacted components small, it is preferably in the range of 0.5 to 2, more preferably 〇. Further, from the viewpoint of obtaining a sealing oxyresin molding material excellent in moldability and reflow resistance, a range of 〇 8 to 1.2 is more preferable. (D) decane compound The epoxy resin molding material for sealing is preferably more than at least one D) decane compound. The decane compound means various decane-based compounds such as epoxy decane, decyl decane, amino decyl decane, ureido decane, and vinyl decane. Specific examples thereof include vinyltrichlorodecane, vinyltrimethylnonane, vinyltriethoxydecane, vinylstilbene (β-methoxy)decane, and γ-methylpropenyloxypropane. Trimethoxy decane, γ-propylene methoxypropyl triethoxy decane, γ·methacryloxypropyl dimethoxy decane, γ-methyl propylene methoxy propyl methyl di Oxytomane ' γ-methacryloxypropyl dimethyl methoxy decane, γ-methylene methoxypropyl dimethyl ethoxy decane, γ-propylene methoxy propyl decane, An unsaturated combination of γ-acryloxypropyltriethoxydecane, vinyl methoxy decane or the like contains a decane compound; β-(3 oxycyclohexyl)ethyltrimethoxy decane, γ-epoxy propyl Oxypropyl methoxy decane, γ-glycidoxypropyl triethoxy decane, γ-epoxy propyl methyl dimethoxy decane, γ-glycidoxypropyl methyl 2 An epoxy group such as decane, γ-glycidoxypropyl dimethyl methoxy decane or γ-epoxy propyl dimethyl ethoxy decane contains decane compound inhibition 6~1. Species Alkane, methoxyethoxymethylmethylmethyl propyl propyltrimethyltricarboxylate, 4-cyclotrimethylpropoxy oxypropylpropane; -34- 201229124 γ-mercaptopropyltrimethoxydecane, γ-mercapto a sulfur atom-containing decane compound such as propyltriethoxydecane or bis(triethoxydecylpropyl)tetrasulfide, γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxylate Base decane, γ-[bis(β-hydroxyethyl)]aminopropyltriethoxydecane, Ν-β-(aminoethyl)-γ-amine-based two-group triethoxy sand, Ν An amino group-containing decane compound such as (trimethoxysilylpropyl)ethylenediamine; an isocyanate group-containing decane compound such as isocyanate propyl trimethoxy decane or isocyanate propyl triethoxy decane; methyltrimethoxy Base decane, methyl triethoxy decane, dimethyl dimethoxy decane, dimethyl diethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, diphenyl dimethyl oxide Base decane, diphenyldiethoxy decane, diphenyl decane diol, triphenyl methoxy decane, triphenyl ethoxy decane, triphenyl Phytanol, Ν-β-(Ν-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxydecane, γ-chloropropyltrimethoxydecane, hexamethyldioxane, γ-aniline Propyltrimethoxydecane, γ-anilinopropyltriethoxydecane, 2-triethoxyindolyl-indole-(1,3-dimethyl-butylene)propylamine, 3-tri Ethoxymercapto-indole-(1,3-dimethyl-butylene)propylamine, Ν-(3-triethoxymercaptopropyl)phenylimine, 3_(3-(tri-ethyl) Oxyfluorenyl)propylamino)-indole, hydrazine-dimethylpropionamide, hydrazine-triethoxydecyl propyl-β-alanine methyl ester, 3-(triethoxy fluorenyl) a decane compound such as propyl)dihydro-3,5-furandione or bis(trimethoxyindenyl)benzene, and 1 -imidazole, 2-alkylimidazole, 2,4-dialkylimidazole, 4 - an imidazole compound such as vinyl imidazole and a glycidoxypropyl alkoxy decane such as γ-glycidoxypropyltrimethoxydecane or γ-glycidoxypropyltriethoxydecane The imidazole-based decane compound of the reactants. -35- 201229124 These may be used alone or in combination of two or more. The total content of the decane compound in the epoxy resin molding material for sealing is preferably 质量·〇6 by mass% by mass of the epoxy resin molding material for sealing, from the viewpoint of moldability and adhesion. The mass %~〇. 7 5 mass% is preferably, and 0.2 mass% to 0.7 mass% is more preferable. When it is 0.06 mass% or more, the adhesion to various package members tends to be improved. In addition, when it is 2% by mass or less, it is possible to suppress the occurrence of molding defects such as voids. Further, the epoxy resin molding material for sealing may further contain at least one of conventionally known coupling agents. Specific examples of the coupling agent include isopropyl triisostearate titanate, isopropyl hydrazide (dioctyl pyrophosphate) titanate, and isopropyl tris(N-aminoethyl- Aminoethyl) titanate, tetraoctyl bis (bistridecyl phosphite) titanate, bismuth (2,2-diallyloxymethyl-1.butyl) bis (double ten Tribasic) phosphite titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)exylethylate, isopropyl trioctyl Titanate, isopropyldipropenylisostearyl strontium titanate, isopropylisostearyl bismuth diacrylate, isopropyl tris(dioctylphosphonate) titanate, different a titanate coupling agent such as propyltriisopropylphenylphenyl titanate or tetraisopropylbis(dioctylphosphite) titanate, an aluminum chelate compound, an aluminum/chromium compound, or the like . These may be used alone or in combination of two or more. Further, the total content of the couplants is preferably from 0. 0% by mass to 2% by mass in the epoxy resin molding material for sealing from the viewpoint of moldability and adhesion. '0 · 1% by mass to 0. · 7 5 mass% is preferred, 〇 · 2 mass% ~. 7 mass% -36- 201229124 is better. When it is 0.06 mass% or more, the adhesion to various package members tends to be improved. When the amount is 2% by mass or less, it is possible to suppress the occurrence of molding defects such as voids. (E) Hardening accelerator The above-mentioned epoxy resin molding material for sealing preferably contains at least one hardening accelerator. The hardening accelerator is not particularly limited as long as it is generally used as a sealing material for sealing epoxy resin. Specifically, 1,8-dioxabicyclo[5.4.0]undecene-7, 1,5-difluorenebicyclo[4.3.0]nonene-5,5,6-dibutylamino group- a cyclic oxime compound such as 1,8-diindole bicyclo[5.4.0]undecene-7, and the addition of anhydrous maleic acid, 1,4-benzoquinone, 2,5-toluene, 1 to these compounds , 4-naphthoquinone, 2,3·dimethylphenylhydrazine, 2,6-dimethylphenylhydrazine, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3 - an intramolecular compound having a π-bonded compound such as dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone or the like, a diazophenylmethane or an anthracene resin a compound of a polar group; a tertiary amine such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, ginseng (dimethylaminomethyl)phenol, and the like; and 2-methylimidazole , imidazoles such as 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, and the like; and tributylphosphine, methyl diphenylphosphine 'triphenylphosphine And organic phosphines such as (4-methylphenyl)phosphine, diphenylphosphine, phenylphosphine, and the like, and the addition of the maleic acid to the phosphine, the above-mentioned hydrazine compound, a phosphorus compound having an intramolecular polarization formed by a compound having a π bond such as azobenzene methane or a phenol resin; tetraphenyl iron tetraphenylboron-37-201229124 acid salt, tetraphenyl squaternium ethylbenzene a tetrasubstituted scale tetra-substituted borate such as a borate or a tetrabutyl salt; 2-ethyl-4-phenylphenylborate, N-methylmorpholine, tetraphenylborate, etc., and the like . These can be used alone or in combination. The third limitation of the addition of the third-stage phosphine to the ruthenium compound. Specific examples thereof include dibutylphenylphosphine, butyldiphenylphosphine, triphenylphosphine, cis(4-methylphenyl)phenyl)phosphine, and stilbene (4-propylphenyl)phosphine. , ginseng (4-, cis (isopropylphenyl) phosphine, ginseng (tert_butylbenzene: 2,4-dimethylphenyl) phosphine, ginseng (2,6-dimethylbenzene g 2,4) , 6-trimethylphenyl)phosphine, ginseng (2,6-dimethyl-4-phosphine, stilbene (4-methoxyphenyl)phosphine, ginseng (4-ethoxyl group having aryl group) The phosphine is not particularly limited as long as the addition of the third-stage phosphine and the ruthenium compound is used from the viewpoint of formability, and specifically, hydrazine-benzoquinone, P-benzoquinone, and 1,4-naphthoquinone are mentioned.蒽醌, 蒽醌, etc. P-benzoquinone is preferred for moisture resistance or preservation. The amount of the hardening accelerator is not particularly limited as long as it can be hardened. Compared with (A) epoxy resin, (BC) The molecule contains one or more valences of one or more nitrile groups, preferably 0.1 parts by mass to 10 parts by mass, more preferably ΐ by mass. Iron tetrabutylboronic acid-methylimidazole. Phenyl boron salt, can also be used as two grades of phosphine without special diphenylphosphine, ethyl phosphine, ginseng (4-B Triphenylphosphine such as phenyl)phosphinyl)phosphine, sulfonium (S)phosphine, ginseng (ethoxyphenyl)phenylphosphine, etc., which are preferred as the ruthenium compound and diphenyl benzene, promotes the effect. (amount) hardener, (the total amount of phenols is 0.3 parts by mass to 5 - 38 - 201229124. If it is 〇 1 part by mass or more, it can be hardened for a short time. If it is less than or equal to 1 part by mass, it can be suppressed. The curing rate tends to be too fast and the formability is lowered. (F) Inorganic sizing agent The sealing epoxy resin molding material preferably contains at least one inorganic hydrazine agent. Further, the inorganic hydrazine filler is further contained. The effect of reducing the moisture absorption, lowering the coefficient of linear expansion, improving the thermal conductivity, and increasing the strength can be obtained. The inorganic chelating agent is not particularly limited as long as it is generally used for the epoxy resin molding material for sealing. For example, molten cerium oxide, crystalline cerium oxide, aluminum oxide, bismuth, calcium silicate, calcium carbonate, potassium titanate, strontium carbide, tantalum nitride, aluminum nitride, boron nitride, cerium oxide, oxidation Zirconium, zircon, magnesium silicate And a powder such as a talc, a spinel, a mullite, or a titanium oxide, a bead which is spheroidized, or a glass fiber, etc. These may be used alone or in combination of two or more. Among them, from the viewpoint of reducing the coefficient of linear expansion, it is preferable to use molten cerium oxide. From the viewpoint of high thermal conductivity, alumina is preferred, and the shape of the ruthenium filler is spherical from the viewpoint of fluidity at the time of molding and mold loss. Especially, from the viewpoint of cost and performance balance, spherical molten cerium oxide is preferred. The amount of inorganic cerium filling agent is based on the viewpoints of flame retardancy, formability, hygroscopicity, reduction of linear expansion coefficient and strength. The epoxy resin molding material for sealing is preferably 70% by mass to 95% by mass. -39-201229124 If it is 70% by mass or more, the flame retardancy and the reflow resistance tend to be increased. Further, when it is at most 95 mass%, the fluidity tends to be lowered. Further, the epoxy resin molding material for sealing may contain an anion exchanger if necessary. Thereby, the moisture resistance and high-temperature setting characteristics of 1C can be improved. The anion exchanger is not particularly limited, and conventionally known ones can be used, and for example, hydrotalcites or hydrous oxides selected from the group consisting of magnesium, aluminum, titanium, and pin's and yttrium can be used alone. Two or more types can also be used in combination. Among them, hydrotalcite represented by the following composition formula (XX) is preferred. [Chemical 2 0] A 1x(〇H)2 (C〇3 ) x/2 ·γπΗ2〇·...0〇<) In the general formula (XX), X represents a number satisfying 0CXS0.5, and m represents A positive number. The content of the anion exchanger is not particularly limited as long as it is sufficient to capture an anion such as a halogen ion, and is preferably 0.1 parts by mass to 30 parts by mass based on 100 parts by mass of the (A) epoxy resin. 1 part by mass to 5 parts by mass is preferred. The epoxy resin molding material for sealing may contain a release agent as necessary. The release agent is based on (A) epoxy resin! The 00 parts by mass is preferably 0.01 parts by mass to 10 parts by mass of the oxidized or non-oxidized polyolefin, and more preferably 0.1 parts by mass to 5 parts by mass. If it is at least 0 part by mass, the tendency to obtain sufficient release property is obtained. -40- 201229124 In addition, if it is less than 1 part by mass, there is a tendency to suppress the decrease in adhesion. The oxidized or non-oxidized polyolefin may, for example, be a low molecular weight polyethylene having a number average molecular weight of from 500 to 10,000, such as the trade name H4 or PE, PED series, manufactured by Hoechst Co., Ltd. Further, examples of the release agent other than the oxidized or non-oxidized polyolefin include palm wax, octadecanoic acid ester, octadecanoic acid, and stearic acid. These may be used alone or in combination of two or more. In addition to the oxidized or non-oxidized polyolefin, when the other release agents are used, the total amount thereof is 0.1 parts by mass to 1 part by mass based on 1 part by mass of the (A) epoxy resin. Preferably, the mass fraction is preferably 0.5 parts by mass to 3 parts by mass. The epoxy resin molding material for sealing may contain a conventionally known flame retardant as necessary. Specifically, the flame retardant is coated with at least one of an inorganic substance such as a brominated epoxy resin, antimony trioxide, red phosphorus, aluminum hydroxide, magnesium hydroxide or zinc oxide, or a thermosetting resin such as a phenol resin. a phosphorus compound such as red phosphorus or phosphoric acid ester, a melamine, a melamine derivative, a melamine-modified phenol resin, a compound having a triazine ring, a cyanuric acid derivative, a nitrogen-containing compound such as an isocyanuric acid derivative, or the like, A compound containing phosphorus and nitrogen such as cyclophosphazene, aluminum hydroxide, magnesium hydroxide, or a composite metal hydroxide represented by the following composition formula (XXI). [Chemical 2 1] pCM^Ob)^ (M2cOJ * r (Μ3,0^*1111120 *···(ΧΧΙ) In the composition formula (XXI), 'Μ1, Μ2, and Μ3 indicate mutually different metallic elements. a , b, c, d, p, q, and m represent a positive number. r denotes a 〇 or a positive number. Μ1, Μ2, and Μ3 in the above composition formula (XXI) are as long as they differ from each other -41 - 201229124 genus element is not particularly limited From the viewpoint of flame retardancy, Μ 1 is a metal element selected from the group consisting of metal elements belonging to the third cycle, the alkaline earth metal elements of the steroid family, 'IVB group, lank group, VIII group, lanthanum group, lank group and group IVA group, Μ 2 is preferably a migration metal element selected from the group consisting of lanthanum lanthanum, lanthanum 1 selected from the group consisting of magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc, and lanthanum 2 is selected from the group consisting of iron 'cobalt, nickel, Copper and zinc are preferred. From the viewpoint of fluidity, Μ 1 is magnesium, Μ 2 is zinc or nickel, and r = 〇 is preferred. Although the molar ratios of P, q and r are not particularly limited, r = 〇, p / 9 is ! / 99~1/1 is better. Moreover, the classification of metal elements is based on the long-period periodic table in which the typical element is set to the A subfamily and the migration element is set to the B subfamily ( Code: Total Publishing Co., Ltd. issued "Chemical Dictionary 4" in February 1987, 15 brushed version of the 30th brush). Also, 'flammable agents can be zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, molybdenum A compound containing a metal element such as zinc hydride or dicyclopentadienyl iron. The flame retardant may be used singly or in combination of two or more. The blending amount of the flame retardant is not particularly limited. It is preferably 1 part by mass to 30 parts by mass, more preferably 2 parts by mass to 15 parts by mass, based on 100 parts by mass of the (A) epoxy resin, and the epoxy resin molding material for sealing is also used. A coloring agent such as a carbon black, an organic dye, an organic pigment, a titanium oxide, a dandan, or a dandan may be contained. Further, a stress relieving agent such as a polyoxygenated oil or a polyoxyethylene rubber powder may be contained as the other. -42- 201229124 The method for producing the epoxy resin molding material for sealing is not particularly limited as long as it can uniformly disperse and mix various components, and can be prepared by any method. The general method can be used to make a predetermined fit. Quantity of ingredients After being sufficiently mixed by a mixer or the like, the mixture is melted and kneaded by a kneading roll, an extruder, or the like, and then cooled and pulverized. For example, the components can be uniformly stirred and mixed, and preheated by a predetermined amount. The kneading machine, the roller, the extruder, etc., which are 70 °c to 1 4 〇r, are obtained by kneading, cooling, pulverizing, etc., and the sealing epoxy resin molding material is matched with the size and quality of the molding conditions. The electronic component device including the element sealed by the epoxy resin molding material for sealing obtained by the present invention may be mentioned as a lead frame, a carrier tape for wiring, a wiring board, and a glass. A support member such as a semiconductor wafer, a transistor, a diode, or a thyristor, or a passive element such as a capacitor, a resistor, or a coil is mounted on a supporting member such as a silicon wafer, and the necessary portion is made of the sealing epoxy. An electronic component device or the like sealed by a resin molding material. In the electronic component device, for example, the terminal portion and the lead portion of the element in which the semiconductor element is fixed to the lead frame by wire bonding or bump bonding, or the like, and the sealing epoxy resin forming material are used. DIP 'Dual Inline Package, sealed by plastic transfer, PLCP (Plastic Leaded Chip Carrier), Quad Flat Package (QFP), small Contour package (S0P, SmaU 〇utHne

Package), small form factor J pin package (s〇J, Small Outline J-lead -43- 201229124

Package), thin small outline package (TSOP), thin quad flat package (TQFP, Thin Quad Flat Package), etc., general semiconductor, grease-sealed IC, bump-bonded semiconductor wafer on carrier tape a tape carrier package (TCP, Tape Carrier Package) sealed with the epoxy resin molding material for sealing; a semiconductor wafer connected by wire bonding, flip chip bonding, soldering, or the like to a wiring formed on a wiring board or glass At least one of an active component such as a transistor, a diode, a thyristor, and a passive component such as a capacitor, a resistor, a coil, or the like, is packaged on the substrate (COB ' Chip On Board) sealed by the sealing epoxy molding material. Module, hybrid 1C, multi-chip module; on the surface of the organic substrate on which the terminal for wiring board connection is formed, the component is mounted on the surface of the organic substrate, and the wiring formed on the organic substrate is connected by bump or wire bonding' BGA' Ball Grid Array, Sealed Epoxy Molding Material Sealing Element, CSP, Chip Size Pack Age) and so on. Further, the above-mentioned epoxy resin molding material for sealing can be effectively used for a printed circuit board. The method of sealing the element for sealing the epoxy resin molding material is the most general method of the low pressure transfer molding method, but an injection molding method, a compression molding method, or the like may be used. [Examples] Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited by the examples. Moreover, "%" is a quality benchmark without special definition. -44- 201229124 Preparation of epoxy resin molding materials for sealing The following components were blended in the mass parts shown in the following Tables 1 to 8 to perform roll kneading at a kneading temperature of 80 ° C and a kneading time of 10 minutes. Further, the epoxy resin molding materials for sealing of Examples 1 to 31 and Comparative Examples 1 to 31 were produced. Moreover, the "-" in the hollow column of the table represents no cooperation. (A) The epoxy resin system uses the following. Epoxy resin 1: biphenyl type epoxy resin having an epoxy equivalent of 196 and a melting point of 1061 (trade name YX-4000, manufactured by Mitsubishi Chemical Corporation) Epoxy resin 2: Epoxy equivalent 241, softening point of 96 ° C The biphenyl skeleton contains a phenol/aralkyl type epoxy resin (trade name CER-3000L, manufactured by Nippon Kayaku Co., Ltd.) Epoxy resin 3: epoxide equivalent 238, softening point 55 ° C phenol. Aralkyl type Epoxy resin (trade name NC-2000 L, manufactured by Nippon Kayaku Co., Ltd.) Epoxy resin 4: o-cresol novolak-type epoxy resin with epoxy equivalent 202 and softening point of 60 °C (Daily Ink Chemical Industry Co., Ltd. Co., Ltd. product name N-660) (B) The hardener is used as follows. Hardener 1: hydroxyl equivalent 176, softening point 7 (TC phenol·aralkyl resin (trade name: XMC, manufactured by Mitsui Chemicals, Inc.) Hardener 2: phenolic novolac with hydroxyl equivalent of 1 〇6, softening point of 83 °C Resin (trade name: H_100, manufactured by Megumi Kasei Co., Ltd.) -45- 201229124 (c) A monovalent or divalent phenol derivative having one or more nitrile groups in the molecular structure (hereinafter, also referred to as "nitrile-phenol" For the compound "), the following are used. Nitrile-phenol compound 1: p-cyanophenol nitrile-phenol compound 2: cyanophenol nitrile-phenol compound 3: 4-hydroxyindole nitrile-phenol compound 4 : 3,4- Dihydroxybenzonitrile-phenol compound 5: 2,3-dicyanohydroquinone In addition, in the comparative example, the following material was used instead of the nitrile-phenol compound. Phenol Compound 1: Phenol Phenol Compound 2: p - Cresol phenol compound 3 : catechol phenol compound 4 : resorcinol phenol compound 5 : hydroquinone nitrile 1 : stearyl nitrile 2 : ( Z) -9-octadecenonitrile (D) decane compound The following are used. Decane compound 1 : γ-glycidoxypropyltrimethoxydecane (Ε) hardening accelerator is the use of the following: Hardening accelerator 1: Triphenyl Betaine-type adducts of phosphine and hydrazine-benzoquinone-46- 201229124 (F) Inorganic chelating agents are used. Inorganic chelating agent 1: globular melting of average particle size Βμηι, specific surface area 3.17 m2 / g Cerium oxide inorganic chelating agent 2: globular molten cerium oxide having an average particle diameter of 55 μmη and a specific surface area of 7 m 2 /g, and other added components are octadecyl ester and carbon black. [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Epoxy Resin 1 80 80 80 80 80 80 80 Epoxy Resin 2 20 20 20 20 20 20 20 Hardener 1 83 83 76 68.5 80 76 68.5 Nitrile - phenolic compound 1 5 10 5 10 3 5 10 decane compound 1 6.8 6.8 6.8 6.8 6.8 6.8 6.8 Hardening accelerator 1 4.0 4.0 4.0 4.0 4.4 5.0 6.0 Inorganic chelating agent 1 1408 1442 1359 1343 1369 1365 1357 Inorganic chelating agent 2 156 160 151 149 152 152 151 Ternary acid ester 1 1 1 1 1 1 1 Carbonium 3.5 3.5 3.5 3.5 3.5 3.5 3.5 Nitrile-phenolic content (%) 0.28 0.55 0.29 0.59 0.17 0.29 0.59 Nitrile for hardener - content of phenolic compound (%) 6.0 12.0 6.6 14.6 3.8 6.6 14.6 Nitrile of epoxy resin - Content of compound (%) 5.0 10.0 5.0 10.0 3.0 5.0 10.0 Number of epoxy groups / hydroxyl number 0. 93 0.86 1.00 1.00 1.00 1.00 1.00 1.00 -47 - 201229124 [Table 2] Example 8 Example 9 Example 10 Example 11 Implementation Example 12 Example 13 Example 14 Example 15 Epoxy Resin 1 80 80 80 80 80 80 80 80 Epoxy Resin 2 20 20 20 20 20 20 20 20 Hardener 1 87.5 87.5 73 58.5 86 83 80 73 Nitrile-phenol compound 1 5 10 10 10 3 5 10 decane compound 1 7 7 7 7 7 7 7 7 Hardening accelerator 1 4.0 4.0 .4.0 4.0 4.2 4.6 5.0 6.0 Inorganic chelating agent 1 1590 1630 1515 1405 1550 1545 1540 1530 1 1 1 1 1 1 1 1 Carbon black 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 Content of nitrile-phenol compound (%) 0.28 0.54 0.58 0. 63 0.06 0.17 0.29 0. 58 Nitrile-phenol compound for hardener Rate (%> 5.7 11.4 13.7 17.1 1.2 3.6 6.3 13.7 Nitrile-brewed compound content of epoxy resin (%) 5.0 10.0 10.0 10.0 1.0 3.0 5.0 10.0 Epoxy number / hydroxyl number 1.08 1.17 1.00 0. 83 1.00 1.00 1.00 1.00 [Table 3] Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 Epoxy Resin 1 80 80 80 80 80 80 80 80 Ring Resin 2 20 20 20 20 20 20 20 20 Hardener 1 83 80 84 81 80 75 81 77 Nitrile-酣Compound 2 3 5 - - - - - - Nitrile-phenol compound 3 - - 3 5 - - - - Nitrile-phenol compound 4 - - - - 3 5 - - Nitrile-phenol compound 5 - - - - - - 3 5 decane Compound 1 7 7 7 7 7 7 7 7 Hardening accelerator 1 4.6 5.0 4.6 5.0 5.8 7.0 5.2 6.0 Inorganic chelating agent 1 1545 1540 1540 1535 1530 1515 1535 1520 Ternary acid ester 1 1 1 1 1 1 1 1 Carbon black 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 Content of nitrile-phenol compound (%) 0.17 0.29 0.17 0.29 0.17 0.29 0.17 0. 29 Content of nitrile-phenol compound to hardener (%) 3.6 6.3 3.6 6.2 3.8 6.7 3.7 6.5 The content of the nitrile-phenol compound of the epoxy resin (%) 3.0 5.0 3.0 5.0 3.0 5.0 3.0 5.0 Epoxy number / hydroxyl number 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 -48 - 201229124 [Table 4] Example 24 Example 25 Example 26 Example 27 Example 28 Solid 29 Example 30 Example 31 Epoxy Resin 1 60 60 60 60 5 5 5 5 Epoxy Resin 3 40 40 4 0 40 - - - - Epoxy Resin 4 - - - - 95 95 95 95 Hardener 1 80 77 80.5 78 - - - - Hardener 2 - - - - 50 49 45 51 Nitrile-phenol compound 1 3 5 - - 3 5 10 - Nitrile-phenol compound 3 - - 3 5 - - - 3 decane compound 1 7 7 7 7 7 7 7 7 Hardening accelerator 1 2.8 3.0 2.8 3.0 3.1 3.4 3.1 3.4 Inorganic chelating agent 1 1255 1250 1265 1260 750 755 760 755 octadecyl ester 1 1 1 1 3 3 3 3 Carbon black 3.0 3.0 3.0 3.0 2.0 2.0 2.0 2.0 Nitrile-phenol compound content (%) 0.21 0.35 0.21 0.34 0.33 0,54 1.08 0.32 Nitrile to hardener - content of phenolic compound (%) 3.8 6.5 3,7 6.4 6.0 10.2 22.2 5.9 The content of nitrile-phenol compound for epoxy resin W 3.0 5.0 3.0 5.0 3.0 5.0 10.0 3.0 Epoxy number / hydroxyl number 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 [Table 5] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Epoxy Resin 1 80 80 80 80 80 80 80 Epoxy Resin 2 20 20 20 20 20 20 20 Hardener 1 83 83 83 78 73 83 83 Phenol compound 1 - 10 — - - - - Phenol compound 2 - - 10 - - - - Phenol compound 3 - - - 5 10 - - Nitrile compound 1 - - - - - 5 10 decane compound 1 6.8 6.8 6.8 6.8 6.8 6.8 6.8 Hardening accelerator 1 4.0 4.0 4.0 5.0 6.0 4.0 4.0 Inorganic chelating agent 1 1374 1442 1442 1380 1380 1408 1442 Inorganic chelating agent 2 153 160 160 153 153 156 160 octadecyl ester 1 1 1 1 1 1 1 carbon black 3.5 3.5 3.5 3.5 3.5 3.5 3.5 content of nitrile-phenol compound (%) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 nitrile-phenol compound for hardener Content ratio (%) 0.0 0.0 0.0 0.0 0.0 0.0 0.0 The content of the nitrile-phenol compound in the epoxy resin (%) 0.0 0.0 0.0 0.0 0.0 0.0 0.0 The number of epoxy groups / the number of hydroxyl groups 1.00 0.83 0. 85 1.00 1.00 1.00 1.00 - 49-201229124 [Table 6] Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 Comparative Example 15 Epoxy Resin 1 80 80 80 80 80 80 80 80 Epoxy Resin 2 20 20 20 20 20 20 20 20 Hardener 1 87.5 87.5 87.5 82 78 69 87.5 87.5 Phenol compound 1 - 5 10 3 5 10 - - Phenol compound 2 - - - - - - 5 10 Nitrile compound 1 - - - - - - - - Decane Compound 1 7 7 7 7 7 7 7 7 Hardening accelerator 1 4.0 4.0 4.0 4.6 5.0 6.0 4.0 4.0 Inorganic Tamping agent 1 1555 1590 1630 1535 1525 1500 1590 1630 28 acid vinegar 1 1 1 1 1 1 1 1 Carbon black 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 Nitrile phenol compound content (%) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Content of nitrile-phenol compound to hardener (%) 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Nitrile-phenol compound content of epoxy resin (%) 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Epoxy Base/pass base 1.00 1.11 1.21 1.00 1.00 1.00 1.09 1.19 [Table 7] Comparative Example 16 Comparative Example 17 Comparative Example 18 Comparative Example 19 Comparative Example 20 Comparative Example 21 Comparative Example 22 Comparative Example 23 Epoxy Resin 1 80 80 80 80 80 80 80 80 Epoxy 2 20 20 20 20 20 20 20 20 Hardener 1 79 71 72 56 72 72 87.5 87.5 Phenol compound 2 5 10 - - - - - - Phenol compound 3 - - 5 10 - - - - Phenol compound 4 - - - - 5 - - - Phenol compound 5 - - - - - 5 - - Nitrile compound 1 - - - - - - 5 - Nitrile compound 2 - - - - - - - 5 decane compound 1 7 7 7 7 7 7 7 7 Hardening accelerator 1 5.0 6.0 5.0 6.0 5.0 5.0 4.0 4.0 Inorganic chelating agent 1 1535 1520 1475 1400 1475 1475 1590 1590 Twenty Acid ester 1 1 1 1 1 1 1 1 Carbon black 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 Nitrile-phenol compound content (%) 0. 00 0.00 0. 00 0.00 0.00 0.00 0. 00 0.00 Nitrile for hardener - Content of phenolic compound (%) 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 The content of nitrile-phenol compound in epoxy resin (%) 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Number of epoxy groups / number of bases 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 -50- 201229124 [Table 8] Comparative Example 24 Comparative Example 25 Comparative Example 26 Comparative Example 27 Comparative Example 28 Comparative Example 29 Comparative Example 30 Comparative Example 31 Epoxy Resin 1 60 60 60 60 5 5 5 5 Epoxy Resin 3 40 40 40 40 - - _ Epoxy Resin 4 - - - - 95 95 95 95 Hardener 1 84 75 68 84 - - - - Hardener 2 - - - - 53 47.5 43.5 53 Phenol Compound 1 - 5 - - - 5 - — Phenol compound 3 - - 5 - - 5 - Nitrile compound 1 - - - 5 - - 5 decane compound 1 7 7 7 7 7 7 7 7 Hardening accelerator 1 2.4 3.0 3.0 2.4 2.7 3.4 3.4 2.7 Inorganic hydrazine Charge 1 1265 1240 1200 1295 750 750 730 770 28 acid ester 1 1 1 1 3 3 3 3 carbon black 3.5 3.5 3.5 3.5 2.0 2.0 2.0 2.0 nitrile-phenol combination Content rate (%) 0.00 0.00 0.00 0.00 0.00 0.00 0.00. 00 0.00 Content of nitrile-phenol compound to hardener (%) 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 The content of nitrile-phenol compound in epoxy resin (%) 0.0 0.0 0.0 0.0 0.0 〇.〇0.0 0.0 The number of epoxy groups/hydroxyl number 1.00 1.00 1.00 1.00 1.00 1.00 1:00 1.00 1.00 The evaluation examples and comparative examples were carried out according to the following various characteristic tests (1) to (6). Sealing epoxy resin molding material. The evaluation results are collectively shown in Tables 9 to 16 below. Further, the molding of the epoxy resin molding material for sealing was carried out under the conditions of a mold temperature of 180 ° C and a molding pressure of 6.9 MPa 'hardening time of 90 seconds by a transfer molding machine. Further, the post-hardening was carried out at 180 ° C for 5 hours. Also the "-" in the table represents the unevaluated. (1) Spiral flow using a mold for spiral flow measurement based on EMMI-1-66, forming a sealing epoxy molding material under the above conditions, and calculating a flow distance (cm) -51 - 201229124 (2) Hardness at heat The epoxy resin molding material for sealing was molded into a circular plate having a diameter of 50 mm and a thickness of 3 mm under the above-mentioned conditions, and was formed by using a Sharon-type hardness tester (HD-1 120 (model 〇) manufactured by Ueshima Seisakusho Co., Ltd.) after molding. measuring. (3) Water absorption rate (2) The formed circular plate was post-hardened under the above conditions, placed under conditions of 85 ° C and 60% RH for 168 hours, and the mass change before and after standing was measured, and the water absorption rate was evaluated. (% by mass) = {(quality of the disc after placement - mass of the disc before placement) / mass of the disc before placement 丨 xl00 (4) Elasticity at 260 °C (high temperature bending test) Using a bending tester ( Tensilon manufactured by A&D Co., Ltd. was subjected to a 3-point bending test based on JIS_K-691 1 and maintained at 2 60 °C in a constant temperature bath to obtain bending modulus (5), bending strength (51) and fracture drawing. Stretch (ε). For the measurement, the test epoxy resin molding material was molded into a test piece of 10 mm x 70 mm x 3 mm under the above conditions, and the test was carried out under the conditions of a chuck speed of 1.5 mm/min. Moreover, the bending modulus (5) is defined by the following formula. -52- 201229124 mu -/3 ^ 方: bending modulus (Pa) 4wh3 Ay Household: 测 (9) 7: displacement (mm) 』: span = 48 ram if: test piece width = 1〇mm Force: Test piece thickness = 3 mm (maximum value of upper and lower standard indicates maximum 値) (5) Measurement of adhesion force with metal in 260 °C (measurement of shear strength) Sealing epoxy resin forming material on copper plate under the above conditions Or a silver-plated copper plate is formed into a cylindrical shape having a diameter of 4 mm and a height of 5 mm, and is post-hardened. The temperature of each copper plate is maintained at 260 ° C by a Bond Tester (Dage company series 4000) at a cutting speed of 50 μm. / s measures the shearing force. (6) Reflow resistance is applied to an 80-pin grid package (lead frame material: copper alloy, crystal pad top, and lead tip silver plated material) of a size of 20χ14χ 2mm mounted on an 8x10x0.4mm polyfluorene wafer. The epoxy resin molding material for sealing was formed by post-hardening under the above conditions, and after being placed under conditions of 85 ° C and 60% RH for one week, Examples 1 to 23 and Comparative Examples 1 to 23 were in 240. At ° C, Examples 24 to 27 and Comparative Examples 24 to 27 were at 230 ° C (* 1), and Examples 27 to 31 and Comparative Examples 27 to 31 were reflowed at 220 ° C (* 2 ). The presence or absence of peeling at the resin/frame interface was observed using an ultrasonic detecting device (HYE-FOCUS manufactured by Hitachi Construction Machinery Co., Ltd.), and the number of peeling packages was evaluated with respect to the number of five test packages. -53- 201229124 [Table 9] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 S Example 7 Spiral flow (cm) - - - - - - - Thermal hardness (Shore D) 78 76 78 76 78 78 78 Water absorption (W - - - - - - - 2603⁄4 bending modulus (MPa) - - - - - - - 260 °C shearing force m) (MPa) 0.83 0.83 0.88 0. 96 0.99 1.01 1.01 260°C Shear force (M) (MPa) 1.41 1.49 1.46 1.68 1.44 1.48 1.46 Reflow resistance (peel number/total) 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 [Table 1 0] Example 8 a Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Spiral flow (cm) 136 166 165 160 93 103 115 138 Thermal hardness (萧尔D) 78 76 76 75 78 78 78 78 Water absorption (W 0.136 0.139 0.136 0.133 0.131 0.129 0.130 0.133 260 ° C bending modulus (MPa) 618 376 593 523 798 767 692 605 260 ° C shearing force m) (MPa) 0.90 0.90 0.96 0.94 0.87 0. 99 1.01 1.01 260 °C shearing force (copper) (MPa) 1.50 1.49 1.68 1.65 1.48 1.64 1.68 1.66 Reflow resistance (peeling number / total) 0/5 0/5 0 /5 0/5 0/5 0/5 0/5 0/5 [Table 1 1] Example 16 Example 17 Example 18 Example 19 S Example 20 Example 21 Example 22 Example 23 Spiral flow (cm) 103 115 121 140 130 145 98 106 Thermal hardness (Shore D) 78 78 78 78 78 78 79 79 Water absorption (%) 0.130 0.131 0.134 0.135 0.139 0.141 0.143 0.146 260°C bending modulus (MPa) 762 689 745 676 915 975 903 969 260°C shearing force (silver) (MPa) 0.97 0. 95 1.02 1.03 0.97 0.94 1.01 1.01 260°C shearing force (copper) (MPa) 1.58 1.61 1.75 1.78 1.58 1.54 1.71 1.74 Reflow resistance (peeling number/total) 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 -54- 201229124 [Table 1 2] Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 Spiral flow (cm) 165 185 156 184 100 103 110 110 Thermal hardness (Shore D) 77 77 76 76 82 81 77 81 Water absorption (W 0.123 0.122 0.125 0.126 0.196 0.197 0. 202 0. 201 260 ° C bending modulus (MPa) 644 628 634 614 784 745 639 732 260 ° C shearing force m) (MPa) 0. 69 0. 73 0. 74 0.75 0. 89 0.88 0.85 0. 93 260 ° C shearing force (copper) (MPa) 1.30 1.42 1.54 1.55 1.04 1.09 1.05 1.15 Reflow resistance (peeling number/total) 0/5w> 0/5(,,) 0/5 (·" 0/5 w) 0/5W) 0/5(10) 0/5 (*2) 0/5 (*2>

(*1) Reflow temperature 2 3 0 ° C, (*2) Reflow temperature 2 2 0 ° C [Table 1 3] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Spiral Flow (cm) - - - - - - - Heat hardness (Shore D) 78 77 78 78 76 78 78 Water absorption (%) - Two - - - - - 260 °C bending modulus (MPa) - - - - - - - 260 °C shearing force m) (MPa) 0.79 0. 69 0.71 0. 79 0,79 0. 73 0.75 260 °C shearing force (copper) (MPa) 1.29 0. 94 1.21 1.28 1.24 1.36 1.39 Reflow resistance (peel number/total) 5/5 5/5 3/5 5/5 5/5 5/5 5/5 [Table 1 4] Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 Comparative Example 15 Spiral flow (cm) 90 115 122 92 98 104 99 104 Thermal hardness (Shore D) 78 77 77 77 77 77 78 78 Water absorption rate (W 0. 134 0.136 0.138 0.133 0.132 0.129 0.135 0.138 260°C bending modulus (MPa) 818 665 472 775 700 612 654 472 260°C shearing force m) (MPa) 0. 79 0.70 0.69 0.73 0. 71 0. 70 0. 69 0.71 260 ° C shear adhesion (copper) (MPa) 1.29 1.12 0.94 1.12 1.09 1.03 1.01 1.21 Reflow resistance (peeling number / total 5/5 5/5 3/5 5/5 5/5 5/5 5/5 3/5 -55- 201229124 [Table 1 5] Comparative Example 16 Comparative Example 17 Comparative Example 18 Comparative Example 19 Comparative Example 20 Comparison Example 21 Comparative Example 22 Comparative Example 23 Spiral flow (cn〇91 99 122 92 98 104 99 104 Thermal hardness (Shore D) 78 78 78 78 78 78 78 78 Water absorption W 0.134 0.132 0.139 0.142 0.143 0.142 0.145 0.143 260° C bending modulus (MPa) 781 712 813 815 823 811 755 734 260 ° C shearing force (silver) (MPa) 0. 72 0.73 0.65 0. 66 0. 63 0. 65 0.71 0.69 260 ° C shear followed by Force (copper) (MPa) 1.21 1.19 0.94 0. 98 0.94 0.95 1.14 1.15 Reflow resistance (peeling number / total) 4/5 3/5 5/5 5/5 5/5 5/5 5/5 3/5 [Table 16] Comparative Example 24 Comparative Example 25 Comparative Example 26 Comparative Example 27 Comparative Example 28 Comparative Example 29 Comparative Example 30 Comparative Example 31 Spiral flow (cm) 135 161 157 158 92 97 95 93 Thermal hardness (Shore D) 78 77 77 78 82 82 82 82 Water absorption rate (54) 0.120 0.124 0.122 0.127 0.198 0. 201 0. 203 0.205 260°C bending modulus (MPa) 667 625 675 608 825 790 832 779 260°C shearing force ( Silver) (MPa) 0.61 0.55 0.51 0.52 0.71 0. 65 0. 65 0.62 2603⁄4 shearing force m) (MPa) 1.15 0. 89 0.87 0.91 0. 87 0. 85 0.98 0. 96 Reflow resistance <peeling number / total number 5/5(6) 5/5 w) 5/5 (*° 5/5(,,) 5/5(*z) 5/5 W) 5/5 (*2> 5/5 (·2)

(*1) Reflow temperature 2 3 0 ° C, (*2) Reflow temperature 2 2 0 ° C The characteristics of the above (1) to (6) were compared with the comparative examples by the combination of the same epoxy resin and hardener. . For example, Examples 24 to 27 comparing the combination of the epoxy resin 1 and the 2/hardener 1 and the comparative examples 1 to 2 3 and the comparative epoxy resin 1 and the 3/hardener 1 are combined with Examples 24 to 27 and Comparative Examples 24 to 27, Comparative Examples 28 to 31 and Comparative Examples 28 to 31 of a combination of epoxy resin 1 and 4/hardener 2 were compared. Referring to Tables 7 to 12, the examples in which the nitrile-phenol compound was added, the shearing force (silver and copper) at 2 60 ° C was higher than that of the comparative example, and at 85 ° C, 60% RH. In the reflow treatment after leaving for one week, peeling at the resin/frame interface was not caused, and the reflow resistance was also excellent. -56-201229124 In Examples 8 to 19 using nitrile-phenol compounds 1 to 3, the modulus of elasticity at a high temperature became small, and the effect of reducing thermal stress was greater. Moreover, no peeling of the resin/frame interface occurred in any of the examples. On the other hand, in the comparative example of the composition different from the present invention, the object of the present invention was not satisfied. Compared with the examples, the shearing force at 260 ° C (silver and copper) is equal to or less, and in the reflow treatment after being left for 1 week at 85 ° C and 60% RH, the resin is contained in most of the packages. / Frame interface is produced, and its reflow resistance is also poor. The entire disclosure of Japanese Patent Application No. 2010-0263558, and Japanese Patent Application No. 20 1 1 -240690 is hereby incorporated by reference. All documents, patent applications, and technical specifications described in this specification are incorporated by reference, their respective documents, patent applications, and technical specifications, which are incorporated in the same extent as the specific In this manual. -57-

Claims (1)

201229124 VII. Patent application scope: 1. Sealing epoxy resin molding material containing epoxy resin having two or more epoxy groups in (A), (B) hardener, and (c) in molecular structure A phenolic derivative having a valence of one or more nitrile groups or a divalent phenol derivative. The sealing epoxy resin molding material of the above-mentioned (C) phenol derivative, wherein the content of the (C) phenol derivative is 0.10% by mass. 08% by mass. 3. The sealing epoxy resin molding material according to claim 1, wherein the hydrazine contains (D) a decane compound. 4. The epoxy resin molding material for sealing according to claim 1, wherein the crucible contains a (?) hardening accelerator. 5. The epoxy resin molding material for sealing according to claim 1, wherein the bismuth contains (F) an inorganic filler. 6. An electronic component device comprising an element sealed by a sealing epoxy molding material according to any one of the claims ～ to 5, - 58- 201229124, a designated representative map: (1) The representative picture is: None (2) The symbol of the symbol of this representative figure is simple: No 201229124 If there is a chemical formula in the case of this case, please reveal the chemical formula that best shows the characteristics of the invention: None