JP2009102631A - Epoxy resin composition for sealing and electronic part device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition for sealing excellent especially in stress reduction, reflow resistance and thermal shock resistance without detriment to characteristics such as fluidity, flame retardancy and curability. <P>SOLUTION: This epoxy resin composition for sealing comprises (A) an epoxy resin, (B) a curing agent and (C) a silicon-containing polymer having a specific structural moiety (1) and 8,000-12,000 number-average molecular weight. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an epoxy resin composition for sealing and an electronic component device.

  Conventionally, in the field of element sealing of electronic component devices such as transistors and ICs, resin sealing has been the mainstream in terms of productivity and cost, and epoxy resin molding materials have been widely used. This is because epoxy resins are balanced in various properties such as electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness with inserts. In recent years, the package form of electronic parts has been reduced in size and thickness, and the number of BGA packages capable of increasing the number of pins and reducing the pitch is increasing. In the future, it is expected that the pitch will be further reduced, and a large capacitance is generated between the wirings, which lowers the signal propagation speed, and there is a concern that the operation speed of the LSI may be delayed. In order to solve this problem, with regard to the interlayer insulating film, development of an insulating material having a low relative dielectric constant (Low-k) is in progress, and there is a concern that it will become porous in the future and the strength will decrease. Is done.

Therefore, the package of these electronic components has a problem that the package cracks during a thermal cycle, and improvement in thermal shock resistance is desired. From such a technical background, development of a low-stress sealing material that prevents peeling of a weak interlayer insulating film is required. In order to improve the thermal shock resistance of the epoxy resin composition, there is a method of using a silicone polymer having a polyalkylene ether group as a flexible agent (see, for example, Patent Document 1).
JP-A-2-129220

  However, when a silicone polymer having a polyalkylene ether group is used as a flexible agent, although the elastic modulus of the epoxy resin composition is reduced, the fluidity, flame retardancy, and reflow resistance tend to deteriorate. As a method for sealing a BGA package, MAP (Mold Array Package) molding that collectively seals a plurality of ICs is increasing, and high fluidity is required for thinly sealing a large area.

  An object of the present invention is to provide an epoxy resin composition for sealing that is particularly excellent in low stress, reflow resistance, and thermal shock resistance without impairing properties such as fluidity, flame retardancy, and curability, and sealing by the same. It is to provide an electronic component device comprising the above elements.

As a result of intensive studies, the present inventors have found that an epoxy resin composition for sealing containing a silicon-containing polymer having a specific structural site and a number-average molecular weight in a specific range achieves the above-mentioned problems. It came to complete.
That is, the present invention is an epoxy resin composition for sealing containing (1) (A) an epoxy resin, (B) a curing agent and (C) a silicon-containing polymer, wherein (C) the silicon-containing polymer Has a structural moiety [1] represented by the following formula (1) and a structural moiety [2] represented by the following formula (2) in the main chain skeleton, and has a number average molecular weight of 8000 to 12000, The present invention relates to an epoxy resin composition for sealing.

(In formula (1), R ¹ represents an alkylene group having 1 to 10 carbon atoms.)

(A in the formula (2), ^{R 2} and ^{R 3} is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an epoxy group having 1 to 10 carbon atoms It is selected from a monovalent organic group, a monovalent organic group having a carboxyl group having 1 to 10 carbon atoms, or a polyalkylene ether group having 3 to 500 carbon atoms, and each may be the same or different.
Moreover, this invention relates to the epoxy resin composition for sealing as described in said (1) whose number average molecular weights of (2) said (C) silicon containing polymer are 9500-10500.

  In the present invention, (3) the ratio of the weight of the structural part [1] represented by the formula (1) to the weight of the structural part [2] represented by the above formula (2) is 2/8 to It is related with the epoxy resin composition for sealing as described in said (1) or (2) which is 5/5.

  In addition, according to the present invention, any one of (1) to (3), wherein (4) the content of the (C) silicon-containing polymer is 1 to 50 parts by weight with respect to 100 parts by weight of the (A) epoxy resin. It relates to the epoxy resin composition for sealing according to claim 1.

  Moreover, this invention is (5) Any of said (1)-(3) whose content of said (C) silicon-containing polymer is 5-25 weight part with respect to 100 weight part of (A) epoxy resin. It relates to the epoxy resin composition for sealing according to claim 1.

  The present invention also provides (6) a block copolymer in which the (C) silicon-containing polymer has a polymer block containing a structural moiety [1] and a polymer block containing a structural moiety [2]. It is related with the epoxy resin composition for sealing as described in any one of said (1)-(5) characterized by being.

  Further, the present invention provides (7) a triblock wherein the (C) silicon-containing polymer has a polymer block containing a structural site [1] bonded to both ends of a polymer block containing a structural site [2]. It is related with the epoxy resin composition for sealing as described in any one of said (1)-(6) which is a copolymer.

Moreover, this invention relates to the epoxy resin composition for sealing as described in said (6) whose (8) said (C) silicon containing polymer is a block polymer shown by following formula (3).

(In Formula (3), l is an integer of ₁ to 200, m ₁ is an integer of ₁ to 200, m ₂ is an integer of 1 to 200, and m ₁ + m ₂ is an integer of ₂ to 400. R ¹ is carbon. An alkylene group having 1 to 10 carbon atoms, wherein R ² and R ³ are an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an epoxy having 1 to 10 carbon atoms Selected from a monovalent organic group having a group, a monovalent organic group having a carboxyl group having 1 to 10 carbon atoms, or a polyalkylene ether group having 3 to 500 carbon atoms, and each may be the same or different. Well, R ⁴ represents a divalent hydrocarbon group having 1 to 10 carbon atoms.)
In the present invention, (9) the (A) epoxy resin is a biphenyl type epoxy resin, a stilbene type epoxy resin, a sulfur atom-containing epoxy resin, a novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin, It contains at least one of triphenylmethane type epoxy resin, bisphenol F type epoxy resin and biphenylene skeleton-containing phenol / aralkyl type epoxy resin, as described in any one of (1) to (8) above The present invention relates to an epoxy resin composition for sealing.

  In the present invention, (10) the curing agent (B) is a biphenylene skeleton-containing phenol-aralkyl resin, phenol-aralkyl resin, naphthol-aralkyl resin, dicyclopentadiene-type phenol resin, triphenylmethane-type phenol resin, novolak It is related with the epoxy resin composition for sealing as described in any one of said (1)-(9) characterized by containing at least 1 sort (s) of a type phenol resin and copolymerization type phenol aralkyl resin.

  Moreover, this invention relates to the epoxy resin composition for sealing as described in any one of said (1)-(10) characterized by containing (11) (D) inorganic filler.

  Further, the present invention provides (12) the sealing according to (11), wherein the content of the inorganic filler (D) is 65% by mass to 95% by mass with respect to the total weight of the epoxy resin composition. The present invention relates to a stopping epoxy resin composition.

  Moreover, this invention relates to the epoxy resin composition for sealing as described in any one of said (1)-(12) characterized by containing (13) (E) hardening accelerator.

  The present invention also provides (14) the epoxy resin composition for sealing according to the above (13), wherein the (E) curing accelerator is an adduct of a third phosphine compound and a quinone compound. About.

  Moreover, this invention relates to the epoxy resin composition for sealing as described in any one of said (1)-(14) characterized by containing (15) (F) coupling agent.

  Moreover, this invention is (16) The epoxy resin composition for sealing as described in said (15) characterized by the said (F) coupling agent containing the silane coupling agent which has a secondary amino group. About.

Moreover, this invention is the epoxy resin for sealing as described in said (16) in which the silane coupling agent which has (17) said (F) secondary amino group contains the compound shown by following General formula (4). Relates to the composition.

(In General Formula (4), R ¹ is selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to ² carbon atoms, and R ² is selected from an alkyl group having 1 to 6 carbon atoms and a phenyl group. R ³ represents a methyl group or an ethyl group, n represents an integer of 1 to 6, and m represents an integer of 1 to ^3. )
Moreover, this invention relates to the electronic component apparatus provided with the element sealed with the epoxy resin composition for sealing as described in any one of (18) said (1)-(17).

  According to the present invention, an epoxy resin composition for sealing that is particularly excellent in low stress, reflow resistance, and thermal shock resistance without impairing properties such as fluidity, flame retardancy, and curability, and sealing by the same. It is possible to provide an electronic component device including the above elements.

The epoxy resin composition for sealing of the present invention is an epoxy resin composition for sealing containing (A) an epoxy resin, (B) a curing agent, and (C) a silicon-containing polymer, and the (C) silicon The containing polymer has a structural site [1] represented by the following formula (1) and a structural site [2] represented by the following formula (2) in the main chain skeleton, and the number average molecular weight is 8000 to 12000. It is a feature.

(In formula (1), R ¹ represents an alkylene group having 1 to 10 carbon atoms.)

(A in the formula (2), ^{R 2} and ^{R 3} is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an epoxy group having 1 to 10 carbon atoms It is selected from a monovalent organic group, a monovalent organic group having a carboxyl group having 1 to 10 carbon atoms, or a polyalkylene ether group having 3 to 500 carbon atoms, and each may be the same or different.
Hereinafter, each component which comprises the epoxy resin composition for sealing of this invention is demonstrated.
(A) Epoxy resin As the (A) epoxy resin used in the present invention, a conventionally known epoxy resin can be used. Usable epoxy resins include, for example, phenol novolac type epoxy resins, orthocresol novolak type epoxy resins, epoxy resins having a triphenylmethane skeleton, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F And / or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene and compounds having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde in an acidic catalyst. Novolak-type epoxy resin obtained by epoxidizing the novolak resin obtained by bisphenol A, bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or non-substituted Diglycidyl ethers such as substituted biphenols; Stilbene type epoxy resins; Hydroquinone type epoxy resins; Glycidyl ester type epoxy resins obtained by reaction of polybasic acids such as phthalic acid and dimer acid and epichlorohydrin; Glycidylamine-type epoxy resin obtained by the reaction of chlorohydrin and epichlorohydrin; epoxidized product of co-condensation resin of dicyclopentadiene and phenols; epoxy resin having naphthalene ring; Epoxidized products of aralkyl-type phenol resins such as resins; trimethylolpropane-type epoxy resins; terpene-modified epoxy resins; olefinic bonds with peracids such as peracetic acid Alicyclic epoxy resins; sulfur atom-containing epoxy resin; to linear aliphatic epoxy resins obtained like, may be used in combination of two or more even with these alone.

  Among these, from the viewpoint of fluidity and reflow resistance, it is preferable to contain at least one selected from biphenyl type epoxy resins, bisphenol F type epoxy resins, stilbene type epoxy resins, and sulfur atom-containing epoxy resins. . Moreover, it is preferable to contain the novolak-type epoxy resin from a sclerosing | hardenable viewpoint, and it is preferable to contain the dicyclopentadiene-type epoxy resin from a low hygroscopic viewpoint. Moreover, it is preferable to contain at least 1 sort (s) chosen from a naphthalene type epoxy resin and a triphenylmethane type epoxy resin from a heat resistant and low curvature viewpoint. From the viewpoint of flame retardancy, it preferably contains at least one selected from biphenylene type epoxy resins and naphthol / aralkyl type epoxy resins. Further, it is preferable to use an epoxy resin having good flame retardancy to be non-halogen or non-antimony from the viewpoint of improving high-temperature storage characteristics.

The biphenyl type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton, and examples thereof include an epoxy resin represented by the following general formula (III).

(In General Formula (III), R ^{1 to} R ⁸ are selected from a hydrogen atom and a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and all may be the same or different. Good, n is an integer from 0 to 3.
The biphenyl type epoxy resin represented by the general formula (III) can be obtained by reacting a biphenol compound with epichlorohydrin by a known method. R ^{1 to} R ⁸ in the general formula (III) are selected from a hydrogen atom and a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, for example, a hydrogen atom An alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, or a tert-butyl group; a C 1-10 alkyl group such as a vinyl group, an allyl group, or a butenyl group; Alkenyl group; and the like. Among these, a hydrogen atom or a methyl group is preferable. Examples of such an epoxy resin include 4,4′-bis (2,3-epoxypropoxy) biphenyl or 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5 ′. -Epoxy resin mainly composed of tetramethylbiphenyl, epoxy resin obtained by reacting epichlorohydrin with 4,4'-biphenol or 4,4 '-(3,3', 5,5'-tetramethyl) biphenol Etc. Among these, an epoxy resin mainly composed of 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl is preferable. As such an epoxy resin, Japan Epoxy Resin Co., Ltd. product names: YX-4000H and YL-6121H are commercially available.

  The blending amount of the biphenyl type epoxy resin is preferably 30% by mass or more, more preferably 50% by mass or more, and more preferably 60% by mass or more in the total amount of the epoxy resin in order to exhibit its performance. Particularly preferred.

Examples of the bisphenol F type epoxy resin include an epoxy resin represented by the following general formula (IV).

(In General Formula (IV), R ^{1 to} R ⁸ are a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and all may be the same or different. N represents an integer of 0 to 3.)
The bisphenol F type epoxy resin represented by the general formula (IV) can be obtained by reacting a bisphenol F compound with epichlorohydrin by a known method. R ^{1 to} R ⁸ in the general formula (IV) are a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, such as a hydrogen atom; a methyl group, an ethyl group Group, propyl group, butyl group, isopropyl group, isobutyl group, tert-butyl group and other alkyl groups having 1 to 10 carbon atoms; vinyl group, allyl group, butenyl group and other alkenyl groups having 1 to 10 carbon atoms; Can be mentioned. Among these, a hydrogen atom or a methyl group is preferable. Examples of such an epoxy resin include an epoxy resin mainly composed of 4,4′-methylenebis (2,6-dimethylphenol) diglycidyl ether, and 4,4′-methylenebis (2,3,6-trimethyl). (Epoxy) epoxy resin mainly composed of diglycidyl ether, epoxy resin mainly composed of 4,4′-methylenebisphenol diglycidyl ether, etc., among others, 4,4′-methylene bis (2,6- An epoxy resin mainly composed of diglycidyl ether of (dimethylphenol) is preferred. In such an epoxy resin, R ¹ , R ³ , R ⁶ and R ⁸ are methyl groups, R ² , R ⁴ , R ⁵ and R ⁷ are hydrogen atoms, and Toto Kasei Co., Ltd. whose main component is n = 0. Product name: YSLV-80XY, etc., available as a commercial product.

  The blending amount of the bisphenol F-type epoxy resin is preferably 30% by mass or more, more preferably 50% by mass or more, and more preferably 60% by mass or more in the total amount of the epoxy resin in order to exhibit its performance. Is particularly preferred.

Examples of the stilbene type epoxy resin include an epoxy resin represented by the following general formula (V).

(In General Formula (V), R ^{1 to} R ⁸ are selected from a hydrogen atom and a monovalent hydrocarbon group having 1 to 5 carbon atoms which may have a substituent, and all may be the same or different. Good, n is an integer from 0 to 10.)
The stilbene type epoxy resin represented by the general formula (V) can be obtained by reacting a stilbene phenol as a raw material with epichlorohydrin in the presence of a basic substance. Examples of the raw material stilbene phenols include 3-tert-butyl-4,4′-dihydroxy-3 ′, 5,5′-trimethylstilbene, 3-tert-butyl-4,4′-dihydroxy-3. ', 5', 6-trimethylstilbene, 4,4'-dihydroxy-3,3 ', 5,5'-tetramethylstilbene, 4,4'-dihydroxy-3,3'-di-tert-butyl-5 , 5'-dimethylstilbene, 4,4'-dihydroxy-3,3'-di-tert-butyl-6,6'-dimethylstilbene, among others, 3-tert-butyl-4,4'- Dihydroxy-3 ', 5,5'-trimethylstilbene and 4,4'-dihydroxy-3,3', 5,5'-tetramethylstilbene are preferred. These stilbene type phenols may be used alone or in combination of two or more.

  The blending amount of the stilbene type epoxy resin is preferably 30% by mass or more, more preferably 50% by mass or more, and more preferably 60% by mass or more in the total amount of the epoxy resin in order to exhibit its performance. Is particularly preferred.

Examples of the sulfur atom-containing epoxy resin include an epoxy resin represented by the following general formula (VI).

(In General Formula (VI), R ^{1 to} R ⁸ are each a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, and an optionally substituted group having 1 to 10 carbon atoms. (Selected from alkoxy groups, all may be the same or different. N represents an integer of 0 to 3.)
Among the sulfur atom-containing epoxy resins represented by the general formula (VI), R ² , R ³ , R ⁶ and R ⁷ are hydrogen atoms, and R ¹ , R ⁴ , R ⁵ and R ⁸ are alkyl groups. An epoxy resin is preferred, and an epoxy resin in which R ² , R ³ , R ⁶ and R ⁷ are hydrogen atoms, R ¹ and R ⁸ are tert-butyl groups, and R ⁴ and R ⁵ are methyl groups is more preferred. As such a compound, Toto Kasei Co., Ltd. product name: YSLV-120TE etc. are available as a commercial item. Any one of these epoxy resins may be used alone, or two or more thereof may be used in combination.

  The blending amount of the sulfur atom-containing epoxy resin is preferably 30% by mass or more, more preferably 50% by mass or more, and more preferably 60% by mass or more in the total amount of the epoxy resin in order to exhibit its performance. It is particularly preferred.

Examples of the novolac type epoxy resin include an epoxy resin represented by the following general formula (VII).

(In General Formula (VII), R is selected from a hydrogen atom and a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and n represents an integer of 0 to 10)
The novolak-type epoxy resin represented by the general formula (VII) can be easily obtained by reacting novolak-type phenol resin with epichlorohydrin. Especially, as R in general formula (VII), it is a hydrogen atom; C1-C10 alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group; A methoxy group, an ethoxy group C1-10 alkoxyl groups such as propoxy group and butoxy group are preferred, and a hydrogen atom or a methyl group is more preferred. n is preferably an integer of 0 to 3. Among the novolak type epoxy resins represented by the general formula (VII), orthocresol novolak type epoxy resins are preferable. As such a compound, Nippon Kayaku Co., Ltd. brand name: EOCN-1020 etc. are available as a commercial item.

  The blending amount of the novolac type epoxy resin is preferably 30% by mass or more, more preferably 50% by mass or more, and more preferably 60% by mass or more in the total amount of the epoxy resin in order to exert its performance. Is particularly preferred.

Examples of the dicyclopentadiene type epoxy resin include an epoxy resin represented by the following general formula (VIII).

(In General Formula (VIII), R ¹ and R ² are each independently selected from a hydrogen atom and a monovalent hydrocarbon group having 1 to 10 carbon atoms that may have a substituent, and n is 0 to 0. 10 represents an integer, and m represents an integer of 0 to 6.)
R ¹ in the above formula (VIII) is, for example, a hydrogen atom; an alkyl group such as methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group; vinyl group, allyl group, butenyl group, etc. Alkenyl groups; substituted or unsubstituted monovalent hydrocarbon groups having 1 to 5 carbon atoms such as halogenated alkyl groups, amino group-substituted alkyl groups, mercapto group-substituted alkyl groups, etc., among which methyl groups and ethyl groups Alkyl groups and hydrogen atoms such as methyl groups and hydrogen atoms are more preferable. Examples of R ² include a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and a tert-butyl group; an alkenyl group such as a vinyl group, an allyl group, and a butenyl group; Examples thereof include substituted or unsubstituted monovalent hydrocarbon groups having 1 to 5 carbon atoms such as a group, an amino group-substituted alkyl group, and a mercapto group-substituted alkyl group, and among them, a hydrogen atom is preferable. As such a compound, Dainippon Ink Chemical Co., Ltd. product name: HP-7200 is available as a commercial product.

  The blending amount of the dicyclopentadiene type epoxy resin is preferably 30% by mass or more, more preferably 50% by mass or more, and more preferably 60% by mass or more in the total amount of the epoxy resin in order to exhibit its performance. It is particularly preferable to do this.

As a naphthalene type epoxy resin, the epoxy resin etc. which are shown with the following general formula (IX) etc. are mentioned, for example.

(In General Formula (IX), R ^{1 to} R ³ are selected from a hydrogen atom and a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, and all of them are the same or different. P is 1 or 0, l and m are each an integer of 0 to 11, and (l + m) is an integer of 1 to 11 and (l + p) is an integer of 1 to 12. i represents an integer of 0 to 3, j represents an integer of 0 to 2, and k represents an integer of 0 to 4.)
The naphthalene type epoxy resin represented by the general formula (IX) includes a random copolymer containing 1 constituent unit and m constituent units at random, an alternating copolymer containing alternating units, and a copolymer containing regularly. Examples thereof include block copolymers which are included in a combined or block form, and any one of these may be used alone, or two or more may be used in combination. Nippon Kayaku Co., Ltd. brand name: NC-7000 etc. can be obtained as a commercial item as said compound whose R < ¹ >, R < ² > is a hydrogen atom and R < ³ > is a methyl group.

  The blending amount of the naphthalene type epoxy resin is preferably 30% by mass or more, more preferably 50% by mass or more, and more preferably 60% by mass or more in the total amount of the epoxy resin in order to exhibit its performance. Is particularly preferred.

Examples of the triphenylmethane type epoxy resin include an epoxy resin represented by the following general formula (X).

(In general formula (X), R is selected from a hydrogen atom and a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and n represents an integer of 1 to 10)
As a triphenylmethane type | mold epoxy resin shown by the said general formula (X), Japan Epoxy Resin Co., Ltd. brand name: E-1032 etc. whose R is a hydrogen atom are available as a commercial item.

Examples of the biphenylene type epoxy resin include an epoxy resin represented by the following general formula (XI).

(In General Formula (XI), each of R ^{1 to} R ⁹ may be the same or different and is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms. (N is an integer of 0 to 10 selected from 10 aryl groups and C 6-10 aralkyl groups.)
In the following general formula (XI), examples of R ^{1 to} R ⁹ include a hydrogen atom; an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and an isobutyl group; C1-C10 alkoxyl groups such as methoxy group, ethoxy group, propoxy group and butoxy group; C6-C10 aryl groups such as phenyl group, tolyl group and xylyl group; Carbon numbers such as benzyl group and phenethyl group A 6-10 aralkyl group etc. are mentioned, Among these, a hydrogen atom or a methyl group is preferable. As a commercial product of biphenylene type epoxy resin, Nippon Kayaku Co., Ltd. brand name: NC-3000 is available.

  The blending amount of the biphenylene type epoxy resin is preferably 30% by mass or more, more preferably 50% by mass or more, and more preferably 60% by mass or more in the total amount of the epoxy resin in order to exert its performance. Is particularly preferred.

Examples of the naphthol / aralkyl type epoxy resin include an epoxy resin represented by the following general formula (XII).

(In General Formula (XII), R ^{1 to} R ² are selected from a hydrogen atom and a monovalent hydrocarbon group having 1 to 12 carbon atoms that may have a substituent, and all of them are the same or different. (N represents an integer of 1 to 10.)
As a commercial product of the naphthol / aralkyl type epoxy resin, trade name: ESN-175 manufactured by Toto Kasei Co., Ltd. is available as a commercial product.

  The blending amount of the naphthol / aralkyl type epoxy resin is preferably 30% by mass or more, more preferably 50% by mass or more, and more preferably 60% by mass or more in the total amount of the epoxy resin in order to exhibit its performance. It is particularly preferable to do this.

Moreover, in this invention, the epoxy resin of following structural formula (XIII) can also be used as (A) epoxy resin.

(R ¹ in the general formula (XIII) is selected from a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent and an alkoxy group having 1 to 12 carbon atoms which may have a substituent. All may be the same or different, n represents an integer of 0 to 4. R ² has an optionally substituted hydrocarbon group having 1 to 12 carbon atoms and a substituent. Selected from alkoxy groups having 1 to 12 carbon atoms, all of which may be the same or different, and m represents an integer of 0 to 2.)
Examples of the epoxy resin represented by the general formula (XIII) include epoxy resins represented by the following general formulas (XIV) to (XXXII).

  Among these, the epoxy resin represented by the general formula (XIV) is preferable from the viewpoints of flame retardancy and moldability. As such an epoxy resin, trade name: YX-8800 manufactured by Japan Epoxy Resin Co., Ltd. is available.

  The blending amount of the epoxy resin of the structural formula (XIII) is preferably 30% by mass or more, more preferably 50% by mass or more, and more preferably 60% by mass in the total amount of the epoxy resin in order to exhibit its performance. The above is particularly preferable.

Moreover, in this invention, the compound shown by the following general formula (XXXIII) can also be used as (A) epoxy resin.

(R ¹ in the general formula (XXXIII) is selected from a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms, all of which may be the same or different. R ² , R ³ is selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, all of which may be the same or different, n represents an integer of 1 to 20, and m represents an integer of 1 to ^3. )
In general formula (XXXIII), m is preferably 1 to 2 from the viewpoints of flame retardancy and curability. n represents an integer of 1 to 20, preferably 1 to 5. The compound represented by the general formula (XXXIII) is obtained by reacting an indole with a crosslinking agent in the presence of an acid catalyst and then reacting with an epihalohydrin compound.

  As the compound represented by the general formula (XXXIII), trade name: ENP-80 manufactured by Toto Kasei Co., Ltd. is available. The softening point of the compound represented by the general formula (XXXIII) is preferably 40 to 200 ° C, more preferably 50 to 160 ° C, and further preferably 60 to 120 ° C. When the softening point is less than 40 ° C., the curability decreases, and when it exceeds 200 ° C., the fluidity tends to decrease. Here, the softening point indicates a softening point measured based on the ring and ball method of JIS-K-6911.

  The compounding amount of the epoxy resin of the general formula (XXXIII) is preferably 30% by mass or more, more preferably 50% by mass or more, and more preferably 60% by mass in the total amount of the epoxy resin in order to exhibit its performance. The above is particularly preferable.

(B) Curing agent The (B) curing agent used in the present invention is not particularly limited as long as it is generally used in an epoxy resin composition for sealing. For example, phenol, cresol, resorcin, catechol, Acid catalysts for phenols such as bisphenol A, bisphenol F, phenylphenol and aminophenol and / or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene and compounds having an aldehyde group such as formaldehyde, benzaldehyde and salicylaldehyde Novolak type phenol resin obtained by condensation or co-condensation under the following conditions: phenol / aralkyl resin synthesized from phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl, biphenylene type phenol resin Aralkyl-type phenol resins such as aralkyl resins and naphthol-aralkyl resins; dicyclopentadiene-type phenol novolak resins and dicyclopentadiene-type naphthol novolaks synthesized by copolymerization from phenols and / or naphthols and dicyclopentadiene Dicyclopentadiene type phenolic resin such as resin; triphenylmethane type phenolic resin; terpene modified phenolic resin; paraxylylene and / or metaxylylene modified phenolic resin; melamine modified phenolic resin; cyclopentadiene modified phenolic resin; Phenol resin obtained by the above; These may be used alone or in combination of two or more.

Among these, from the viewpoint of flame retardancy and moldability, a phenol / aralkyl resin represented by the following general formula (XXXIV) is preferable.

(Here, R is selected from a hydrogen atom and a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and n represents an integer of 0 to 10).
A phenol / aralkyl resin in which R in the general formula (XXXIV) is a hydrogen atom and the average value of n is 0 to 8 is more preferable. Specific examples include p-xylylene type phenol / aralkyl resins, m-xylylene type phenol / aralkyl resins, and the like. As such a compound, a product name: XLC manufactured by Mitsui Chemicals, Inc. is commercially available. When these phenol-aralkyl resins are used, the blending amount is preferably 30% by weight or more, more preferably 50% by weight or more, based on the total amount of the (B) curing agent in order to exhibit the performance.

Examples of the naphthol / aralkyl resin include a phenol resin represented by the following general formula (XXXV).

Examples of the naphthol-aralkyl resin represented by the general formula (XXXV) include compounds in which R ¹ and R ² are all hydrogen atoms, and examples of such compounds include trade names of Nippon Steel Chemical Co., Ltd. : SN-170 is commercially available.

Examples of the dicyclopentadiene type phenol resin include a phenol resin represented by the following general formula (XXXVI).

(In General Formula (XXXVI), R ¹ and R ² are each independently selected from a hydrogen atom and a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and n is 0 to 0. 10 represents an integer, and m represents an integer of 0 to 6.)
In the above general formula (XXXVII), as a compound in which R ¹ and R ² are hydrogen atoms, Nippon Petrochemical Co., Ltd. trade name: DPP is commercially available. When a dicyclopentadiene type phenol resin is used, its blending amount is preferably 30% by weight or more, more preferably 50% by weight or more, based on the total amount of the (B) curing agent, in order to exhibit its performance. A mass% or more is particularly preferred.

From the viewpoint of reducing warpage, a triphenylmethane type phenol resin is preferable. Examples of the triphenylmethane type phenol resin include a phenol resin represented by the following general formula (XXXVII).

(In General Formula (XXXVII), R is selected from a hydrogen atom and a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and n represents an integer of 1 to 10).
As said compound whose R is a hydrogen atom in the said general formula (XXXVIII), Meiwa Kasei Co., Ltd. brand name: MEH-7500 etc. are available as a commercial item.

  The blending amount of the triphenylmethane type phenolic resin is preferably 10 to 50% by weight, and more preferably 15 to 30% by weight, based on the total amount of the (B) curing agent. When the blending amount is 10% by weight or more, the warp reduction effect is good, and when it is 50% by weight or less, flame retardancy is good.

  Examples of the novolak type phenol resin include a phenol novolak resin, a cresol novolak resin, a naphthol novolak resin, and the like. Among these, a phenol novolak resin is preferable. The blending amount of the novolak type phenol resin is preferably 30% by weight or more, more preferably 50% by weight or more, and particularly preferably 60% by weight or more based on the total amount of the (B) curing agent.

Examples of the biphenylene type phenol-aralkyl resin include a phenol resin represented by the following general formula (XXXVIII).

R ^{1 to} R ⁹ in the above formula (XXXVIII) may all be the same or different, and are a hydrogen atom; a C 1-10 such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group. An alkyl group of 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group; an aryl group of 6 to 10 carbon atoms such as a phenyl group, a tolyl group and a xylyl group; a benzyl group and a phenethyl group And the like. Among these, a hydrogen atom or a methyl group is preferable. n represents an integer of 0 to 10.

Examples of the biphenylene type phenol / aralkyl resin represented by the general formula (XXXVIII) include compounds in which R ^{1 to} R ⁹ are all hydrogen atoms, and in particular, from the viewpoint of melt viscosity, n is a condensation of 1 or more. A mixture of condensates containing 50% by weight or more of the body is preferred. As such a compound, Meiwa Kasei Co., Ltd. trade name: MEH-7851 is available as a commercial product.

  The above aralkyl-type phenol resin, naphthol-aralkyl resin, dicyclopentadiene-type phenol resin, triphenylmethane-type phenol resin, novolac-type phenol resin, biphenylene-type phenol-aralkyl resin can be used alone, Two or more kinds may be used in combination.

  Among the curing agents used in combination, a novolak type phenol resin is particularly preferable from the viewpoint of curability, and an aralkyl type phenol resin is preferable from the viewpoint of fluidity and reflow resistance.

In the present invention, as the (B) curing agent, a compound represented by the following general formula (XXXIX) can also be included.

(R ¹ in the general formula (XXXIX) is selected from a hydrogen atom and a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and R ² has a hydrogen atom and a substituent. Selected from monovalent hydrocarbon groups having 1 to 10 carbon atoms, n represents an integer of 0 to 10, m represents an integer of 0 to 10, and n and m are excluded except for 0. )
The compound represented by the general formula (XXXIX) can be obtained by reacting a phenol compound with an aromatic aldehyde and a biphenylene compound in the presence of an acid catalyst. As the phenol compound, substituted phenols such as phenol, cresol, ethylphenol and butylphenol are used. An aromatic aldehyde is an aromatic compound having one aldehyde group bonded to the aromatic. Aromatic aldehydes include benzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, tert-butylbenzaldehyde and the like. Examples of the biphenylene compound include biphenylene glycol, biphenylene glycol dimethyl ether, biphenylene glycol diethyl ether, biphenylene glycol diacetoxy ester, biphenylene glycol dipropoxy ester, biphenylene glycol monomethyl ether, and biphenylene glycol monoacetoxy ester. In particular, biphenylene glycol and biphenylene glycol dimethyl ether are preferable. Moreover, the biphenylene compound shown by the following general formula (b) can also be used.

  As the compound represented by the general formula (XXXIX), HE-610C, 620C and the like manufactured by Air Water Co., Ltd. are available.

  The compounding amount of the compound represented by the general formula (XXXIX) is preferably 50 to 90% by weight, more preferably 70 to 85% by weight based on the total amount of the curing agent (B). When the blending amount is 50% by weight or more, the flame retardancy is good, and when it is 90% by weight or less, the warp reduction effect is good.

  From the viewpoint of improving flame retardancy, the sealing epoxy resin composition of the present invention may contain acenaphthylene. Although acenaphthylene can be obtained by dehydrogenating acenaphthene, a commercially available product may be used. Further, it can be used as a polymer of acenaphthylene or a polymer of acenaphthylene and other aromatic olefins. Examples of a method for obtaining a polymer of acenaphthylene or a polymer of acenaphthylene and another aromatic olefin include radical polymerization, cationic polymerization, and anionic polymerization. In the polymerization, a conventionally known catalyst can be used, but it can also be carried out only by heat without using a catalyst. At this time, the polymerization temperature is preferably 80 to 160 ° C, more preferably 90 to 150 ° C. 60-150 degreeC is preferable and, as for the softening point of the polymer of the polymer of acenaphthylene obtained or acenaphthylene and another aromatic olefin, 70-130 degreeC is more preferable. If the softening point is lower than 60 ° C., the moldability tends to decrease due to oozing during molding, and if it is higher than 150 ° C., the compatibility with the resin tends to decrease.

  Examples of other aromatic olefins to be copolymerized with acenaphthylene include styrene, α-methylstyrene, indene, benzothiophene, benzofuran, vinylnaphthalene, vinylbiphenyl, and alkyl-substituted products thereof. In addition to the above-mentioned aromatic olefins, aliphatic olefins can be used in combination as long as the effects of the present invention are not hindered. Examples of the aliphatic olefin include (meth) acrylic acid and esters thereof, maleic anhydride, itaconic anhydride, fumaric acid and esters thereof. The amount of these aliphatic olefins used is preferably 20% by weight or less, more preferably 9% by weight or less, based on the total amount of the polymerization monomers.

  Furthermore, as acenaphthylene, the acenaphthylene premixed with a part or all of (B) hardening | curing agent can also be contained. (B) A premixed mixture of a part or all of the curing agent and one or more of acenaphthylene, a polymer of acenaphthylene, and a polymer of acenaphthylene and another aromatic olefin may be used. As a premixing method, (B) a method in which the curing agent and the acenaphthylene component are finely pulverized and mixed with a mixer or the like in a solid state, a method in which both components are uniformly dissolved in a solvent that dissolves both components, and then the solvent is removed. (B) Although it can carry out by the method of melt-mixing both at the temperature more than the softening point of a hardening | curing agent and / or an acenaphthylene component, the melt-mixing method with which a uniform mixture is obtained and impurities are few is preferable. Although melt mixing will not have a restriction | limiting, if it is the temperature more than the softening point of (B) hardening | curing agent and / or an acenaphthylene component, 100-250 degreeC is preferable and 120-200 degreeC is more preferable. Moreover, although melt mixing will not have a restriction | limiting in mixing time if both are mixed uniformly, 1 to 20 hours are preferable and 2 to 15 hours are more preferable.

  When the (B) curing agent and acenaphthylene are premixed, the acenaphthylene component may be polymerized or reacted with the (B) curing agent during mixing. In the epoxy resin composition for sealing of the present invention, from the viewpoint of improving flame retardancy due to dispersibility of the acenaphthylene component, the above-mentioned premix (acenaphthylene-modified curing agent) is 90% by weight in the (B) curing agent. It is preferable to be contained above. The amount of acenaphthylene and / or aromatic olefin polymer containing acenaphthylene contained in the acenaphthylene-modified curing agent is preferably 5 to 40% by weight, and more preferably 8 to 25% by weight. If the content is less than 5% by weight, the flame retardancy tends to decrease, and if it exceeds 40% by weight, the moldability tends to decrease. The content of the acenaphthylene structure contained in the epoxy resin composition of the present invention is preferably 0.1 to 5% by weight and more preferably 0.3 to 3% by weight from the viewpoints of flame retardancy and moldability. When the content is less than 0.1% by weight, the flame retardancy tends to be inferior, and when the content is more than 5% by weight, the moldability tends to deteriorate.

  In the present invention, the equivalent ratio of (A) epoxy resin and (B) curing agent, that is, the ratio of the number of hydroxyl groups in the curing agent to the number of epoxy groups in the epoxy resin (number of hydroxyl groups in curing agent / number of epoxy groups in epoxy resin) ) Is not particularly limited, but the equivalent ratio is preferably set in the range of 0.5 to 2 and more preferably 0.6 to 1.3 in order to suppress each unreacted component. In order to obtain a sealing epoxy resin composition excellent in moldability and reflow resistance, the equivalent ratio is more preferably set in the range of 0.8 to 1.2.

(C) Silicon-containing polymer It is important that the epoxy resin composition for sealing of the present invention contains a silicon-containing polymer having a specific structural site and a number-average molecular weight in a specific range. The task can be achieved. That is, it is possible to obtain an epoxy resin composition for sealing that is particularly excellent in stress reduction, reflow resistance, and thermal shock resistance without impairing properties such as fluidity, flame retardancy, and curability.

The (C) silicon-containing polymer used in the present invention has a structural moiety [1] represented by the following formula (1) and a structural moiety [2] represented by the following formula (2) in the main chain skeleton. It is characterized by.

(In formula (1), R ¹ represents an alkylene group having 1 to 10 carbon atoms.)

(A in the formula (2), ^{R 2} and ^{R 3} is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an epoxy group having 1 to 10 carbon atoms It is selected from a monovalent organic group, a monovalent organic group having a carboxyl group having 1 to 10 carbon atoms, or a polyalkylene ether group having 3 to 500 carbon atoms, and each may be the same or different.
In the above formula (1), R ¹ is an alkylene group having 1 to 10 carbon atoms, for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, hexamethylene group, heptamethylene group. , Octamethylene group, nonamethylene group, decylene group and the like. Among these, from the viewpoint of dispersibility, R ¹ is preferably a propylene group.

In the above formula (2), R ² and R ³ are, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, Alkyl groups having 1 to 10 carbon atoms such as heptyl group, octyl group, nonyl group and decyl group; aryl groups having 6 to 10 carbon atoms such as phenyl group, 1-naphthyl group and 2-naphthyl group; methoxy group, ethoxy group, C1-C10 alkoxy groups such as propoxy group and butoxy group; 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group, 2-glycidoxyethyl group, 3- Glycidoxypropyl group, 4-glycidoxybutyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl A monovalent organic group having an epoxy group having 1 to 10 carbon atoms, such as a carboxymethylene group, a carboxyethylene group, a carboxypropylene group, a carboxybutylene group, or a carboxypentylene group. A monovalent organic group; a polyalkylene ether group having 3 to 500 carbon atoms having a polyethyleneoxy group represented by the following formula (5), a polyalkylene having 3 to 500 carbon atoms having a polypropyleneoxy group represented by the following formula (6) Selected from an alkylene ether group, a polyalkylene ether group having 3 to 500 carbon atoms having a polyethyleneoxy group represented by the following formulas (5) and (6), and each may be the same or different. .

(A and b in Formula (5) and Formula (6) represent an integer of 1 to 100, and preferably an integer of 1 to 20)
Among these, from the viewpoint of the elastic modulus reduction effect, R ² and R ³ are preferably an alkyl group or an aryl group, and particularly preferably a methyl group.

  In the present invention, the (C) silicon-containing polymer comprises a polymer block containing the structural moiety [1] represented by the formula (1) and the structural moiety [2] represented by the formula (2). A block copolymer having a polymer block to be contained is preferable.

  The number of structural sites [1] in the block copolymer is preferably 20 to 80, and more preferably 30 to 50. The number of structural sites [2] in the block copolymer is preferably 2 to 400, more preferably 10 to 50, and still more preferably 20 to 30.

  The form of the block copolymer is not particularly limited to either a chain-type block or a star-type block, but as a preferred form, a polymer block containing the structural site [2] is preferably overlapped with a structural site [1] at both ends. It is a triblock copolymer in which a combined block is bonded. Such a triblock copolymer may have a binding site [3] between the polymer block containing the structural site [2] and the polymer block containing the structural site [1].

A preferred block copolymer is represented by the following formula (3).

(In Formula (3), l is an integer of ₁ to 200, m ₁ is an integer of ₁ to 200, m ₂ is an integer of 1 to 200, and m ₁ + m ₂ is an integer of ₂ to 400. R ¹ is carbon. An alkylene group having 1 to 10 carbon atoms, wherein R ² and R ³ are an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an epoxy having 1 to 10 carbon atoms Selected from a monovalent organic group having a group, a monovalent organic group having a carboxyl group having 1 to 10 carbon atoms, or a polyalkylene ether group having 3 to 500 carbon atoms, and each may be the same or different. Well, R ⁴ represents a divalent hydrocarbon group having 1 to 10 carbon atoms.)
In formula (3), l represents an integer of 1 to 200, preferably 20 to 80, and more preferably 30 to 50. If l is less than 1, the effect tends to be difficult to obtain, and if it exceeds 200, the molecular weight becomes too large. m ₁ and m ₂ are integers of 1 to 200, preferably 5 to 25, more preferably 10 to 20, and it is preferable that m ₁ and m ₂ are substantially the same.

In formula (3), R ¹ , R ² and R ³ are the same as those described above.

R ⁴ is a bonding site [3] that connects the polymer block containing the structural site [2] and the polymer block containing the structural site [1], and is a divalent hydrocarbon group having 1 to 10 carbon atoms. For example, alkylene groups such as ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decylene group; phenylene group, 1-naphthylene group, 2 An arylene group such as a naphthylene group;

  Among these, from the viewpoint of dispersibility, it is preferable that the number of carbon atoms is not single but has a distribution in the above range. In other words, it is preferable to use a plurality of substituent components having different carbon numbers in combination instead of using a single component with the same substituents, and the block copolymers are not all the same, but have a molecular weight, etc. It is preferable to have a certain distribution.

  In the present invention, it is important that the number average molecular weight of the (C) silicon-containing polymer is 8000 to 12000. By being in this range, an epoxy resin composition for sealing having excellent reflow resistance can be obtained. it can. The number average molecular weight is preferably 9500 to 10500, and more preferably 9750 to 10250. In the present invention, the number average molecular weight is obtained by measurement using a standard polystyrene calibration curve by gel permeation chromatography (GPC). In the present invention, the number average molecular weight is determined by using a pump (L-6200, manufactured by Hitachi, Ltd.), a column (TSKgel-G5000HXL and TSKgel-G2000HXL, both of which are trade names manufactured by Tosoh Corporation), a detector (Co., Ltd.). L-3300RI type manufactured by Hitachi, Ltd.) was used, and tetrahydrofuran was used as an eluent, and measurement was performed under conditions of a temperature of 30 ° C. and a flow rate of 1.0 ml / min.

Ratio of weight of structural part [1] represented by formula (1) to weight of structural part [2] represented by formula (2) (weight of structural part [1] represented by formula (1) / Weight of the structural part [2] represented by the formula (2) is preferably 2/8 to 5/5 from the viewpoint of the balance of elastic modulus reduction, fluidity, and reflow resistance. It is more preferably 7 to 4/6, and particularly preferably 3/7. The ratio of the weight of the structural moiety [1] represented by the formula (1) to the weight of the structural moiety [2] represented by the formula (2) is the proton of each structural moiety as determined by ¹ H-NMR measurement. It can be obtained from the integral value.

  Examples of the (C) silicon-containing polymer as described above include trade names SLM446200 series, SLJ1661-03, and SLJ44620-1065 manufactured by Wacker. The SLJ1661-03 has a number average molecular weight of 10968, and the weight ratio of the structural site [1] represented by the formula (1) to the structural site [2] represented by the formula (2) is 5/5. . The SLJ44620-1065 has a number average molecular weight of 10,000, and the weight ratio of the structural moiety [1] represented by the formula (1) to the structural moiety [2] represented by the formula (2) is 3/7. .

  The content of the (C) silicon-containing polymer is preferably 1 to 50 parts by weight, more preferably 2 to 30 parts by weight, with respect to 100 parts by weight of the (A) epoxy resin, The amount is particularly preferably 25 parts by weight, and most preferably 20 parts by weight. When the content is less than 1 part by weight, it becomes difficult to impart flexibility to the sealing epoxy resin composition, and when it exceeds 50 parts by weight, the fluidity of the sealing epoxy resin composition tends to decrease.

(D) Inorganic filler In this invention, (D) inorganic filler can be contained as needed. Inorganic fillers are blended into sealing epoxy resin compositions to improve hygroscopicity, linear expansion coefficient reduction, thermal conductivity improvement and strength improvement, and are generally used in sealing epoxy resin compositions. There is no particular limitation as long as it is. For example, fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, aluminum nitride, boron nitride, beryllia, zirconia, etc., or spherical beads of these, potassium titanate, silicon carbide, Examples thereof include single crystal fibers such as silicon nitride and alumina, and glass fibers. Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, and zinc borate. These inorganic fillers may be used alone or in combination of two or more. Among these inorganic fillers, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. The shape of the inorganic filler is preferably a spherical shape or a nearly spherical shape from the viewpoint of fluidity during molding and mold wear.

  The content of the inorganic filler is preferably 65 to 95% by mass with respect to the total mass of the epoxy resin composition for sealing, from the viewpoints of moldability, hygroscopicity, reduction of linear expansion coefficient and improvement of strength, and 70 to 95%. 95 mass% is more preferable, and 75 to 92 weight% is further more preferable. If the content is less than 65% by mass, the reflow resistance tends to decrease, and if it exceeds 95% by mass, the fluidity tends to be insufficient.

(E) Curing accelerator In the epoxy resin composition for sealing of the present invention, (E) a curing accelerator is used as necessary in order to promote the reaction between (A) the epoxy resin and (B) the curing agent. Can do. (E) The curing accelerator is not particularly limited as long as it is generally used in an epoxy resin composition for sealing. For example, 1,8-diazabicyclo [5.4.0] undecene-7, 1 , 5-diazabicyclo [4.3.0] nonene-5,5,6-dibutylamino-1,8-diazabicyclo [5.4.0] undecene-7 and the like, and maleic anhydride to these compounds 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2 , Such as quinone compounds such as 1,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, diazophenylmethane, phenol resin, etc. A compound having intramolecular polarization formed by adding a compound, tertiary amines such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and derivatives thereof, 2-methylimidazole, 2- Imidazoles such as phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole and their derivatives, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, phenyl Organic phosphines such as phosphine, and intramolecular polarization formed by adding π-bonded compounds such as maleic anhydride, quinone compounds, diazophenylmethane, and phenolic resins to these phosphines Phosphorus compounds, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate, tetrabutylphosphonium tetrabutylborate and other tetrasubstituted phosphonium tetrasubstituted borate, 2-ethyl-4-methylimidazole tetraphenylborate, N-methyl Examples thereof include tetraphenylboron salts such as morpholine tetraphenylborate and derivatives thereof. These curing accelerators may be used alone or in combination of two or more.

  Among these, from the viewpoint of curability and fluidity, an adduct of a tertiary phosphine compound and a quinone compound is preferable, and an adduct of tributylphosphine and benzoquinone is particularly preferable. From the viewpoint of storage stability, an adduct of a cycloamidine compound and a phenol resin is preferable, and a novolak-type phenol resin salt of diazabicycloundecene is more preferable. The total amount of these preferred curing accelerators is preferably 60% by weight or more, more preferably 80% by weight or more based on the total weight of the curing accelerator.

  Although there is no restriction | limiting in particular as a 3rd phosphine compound used for the addition product of a 3rd phosphine compound and a quinone compound, For example, a dibutyl phenyl phosphine, a tributyl phosphine, a butyl diphenyl phosphine, an ethyl diphenyl phosphine, a triphenyl phosphine, a tris (4 -Methylphenyl) phosphine, tris (4-ethylphenyl) phosphine, tris (4-propylphenyl) phosphine, tris (4-butylphenyl) phosphine, tris (isopropylphenyl) phosphine, tris (t-butylphenyl) phosphine, tris (2,4-dimethylphenyl) phosphine, tris (2,6-dimethylphenyl) phosphine, tris (2,4,6-trimethylphenyl) phosphine, tris (2,6-dimethyl-4-ethoxy) Examples thereof include tertiary phosphine compounds having an alkyl group and an aryl group such as phenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (4-ethoxyphenyl) phosphine, etc., and tributylphosphine and triphenylphosphine from the viewpoint of moldability. Is preferred. The quinone compound is not particularly limited, and examples thereof include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, anthraquinone, and the like. From the viewpoint of moisture resistance or storage stability, p-benzoquinone is preferred. preferable.

  (E) The content of the curing accelerator is not particularly limited as long as the curing acceleration effect is achieved, but with respect to 100 parts by weight of the total amount of (A) epoxy resin and (B) curing agent. 0.1 to 10 parts by weight is preferable, and 0.3 to 5 parts by weight is more preferable. If the content is less than 0.1 parts by weight, the curability in a short time tends to be inferior, and if it exceeds 10 parts by weight, the curing rate tends to be too high and a good molded product tends not to be obtained.

(F) Coupling agent In the present invention, when (D) an inorganic filler is used, the epoxy resin composition for sealing of the present invention has a resin component and (D) in order to enhance the adhesion between the inorganic filler. (F) It is preferable to further add a coupling agent. (F) The coupling agent is not particularly limited as long as it is generally used in an epoxy resin composition for sealing. For example, aminosilane, epoxysilane, mercaptosilane, alkylsilane, ureidosilane, vinylsilane, etc. And various silane compounds, titanium compounds, aluminum chelates, and aluminum / zirconium compounds. Specific examples of the coupling agent (F) include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl. Trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyl Dimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ- (N, N-dimethyl) amino Propyltrimethoxysilane, γ- (N, N-diethyl) aminopropyltrimethoxysilane, γ- (N, N-dibutyl) aminopropyltrimethoxysilane, γ- (N-methyl) anilinopropyltrimethoxysilane, γ- (N-ethyl) anilinopropyltrimethoxysilane, γ- (N, N-dimethyl) aminopropyltriethoxysilane, γ- (N, N-diethyl) aminopropyltriethoxysilane, γ- (N, N -Dibutyl) aminopropyltriethoxysilane, γ- (N-methyl) anilinopropyltriethoxysilane, γ- (N-ethyl) anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropylmethyldimethoxy Silane, γ- (N, N-diethyl) aminopropylmethyldimethoxysilane, γ- (N, N-dibu Til) aminopropylmethyldimethoxysilane, γ- (N-methyl) anilinopropylmethyldimethoxysilane, γ- (N-ethyl) anilinopropylmethyldimethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxy) Silane couplings such as methylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane Agents: isopropyl triisostearoyl titanate, isopropyl tris (dioctylpyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate Tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyro) Phosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, tetraisopropyl bis ( Dioctyl phosphite) titanate coupling agents such as titanate; These may be used alone or in combination of two or more.

Among these, a silane coupling agent having a secondary amino group is preferable from the viewpoints of fluidity, gold wire deformation reduction, and flame retardancy. The silane coupling agent having a secondary amino group is not particularly limited as long as it is a silane compound having a secondary amino group in the molecule. For example, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxy Silane, γ-anilinopropylmethyldimethoxysilane, γ-anilinopropylmethyldiethoxysilane, γ-anilinopropylethyldiethoxysilane, γ-anilinopropylethyldimethoxysilane, γ-anilinomethyltrimethoxysilane, γ -Anilinomethyltriethoxysilane, γ-anilinomethylmethyldimethoxysilane, γ-anilinomethylmethyldiethoxysilane, γ-anilinomethylethyldiethoxysilane, γ-anilinomethylethyldimethoxysilane, N- (p -Methoxyphenyl) -γ-aminopropyltrime Xisilane, N- (p-methoxyphenyl) -γ-aminopropyltriethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylmethyldimethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylmethyl Diethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylethyldiethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylethyldimethoxysilane, γ- (N-methyl) aminopropyltrimethoxy Silane, γ- (N-ethyl) aminopropyltrimethoxysilane, γ- (N-butyl) aminopropyltrimethoxysilane, γ- (N-benzyl) aminopropyltrimethoxysilane, γ- (N-methyl) aminopropyl Triethoxysilane, γ- (N-ethyl) aminopropyltriethoxy Silane, γ- (N-butyl) aminopropyltriethoxysilane, γ- (N-benzyl) aminopropyltriethoxysilane, γ- (N-methyl) aminopropylmethyldimethoxysilane, γ- (N-ethyl) aminopropyl Methyldimethoxysilane, γ- (N-butyl) aminopropylmethyldimethoxysilane, γ- (N-benzyl) aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ- ( β-aminoethyl) aminopropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane and the like. Among these, aminosilane coupling agents represented by the following general formula (4) are particularly preferable.

(In General Formula (4), R ¹ is selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to ² carbon atoms, and R ² is selected from an alkyl group having 1 to 6 carbon atoms and a phenyl group. R ³ represents a methyl group or an ethyl group, n represents an integer of 1 to 6, and m represents an integer of 1 to ^3. )
Specific examples of R ^{1 in} the general formula (4) include a hydrogen atom; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and an isobutyl group; a methoxy group or an ethoxy group R ² is an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and an isobutyl group; a phenyl group. And so on.

  The content of the coupling agent is preferably 0.037 to 5% by weight, more preferably 0.05 to 4.75% by weight, based on the total weight of the sealing epoxy resin composition, More preferably, it is 0.1 to 2.5 weight%. If the content is less than 0.037% by weight, the adhesion to the frame tends to be lowered, and if it exceeds 4.75% by weight, the moldability of the package tends to be lowered.

(Various additives)
The sealing epoxy resin composition of the present invention includes (A) an epoxy resin, (B) a curing agent, (C) a silicon-containing polymer, (D) an inorganic filler, (E) a curing accelerator, (F) In addition to the coupling agent, various additives such as a release agent and a colorant exemplified below may be added.

  There is no restriction | limiting in particular as a mold release agent, A conventionally well-known thing can be used. For example, higher fatty acids such as carnauba wax, montanic acid, stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, oxidized polyolefin waxes such as oxidized polyethylene, and nonoxidized polyolefin waxes such as nonoxidized polyethylene These may be used, and one of these may be used alone, or two or more may be used in combination. Among these, the oxidized polyolefin wax or the non-oxidized polyolefin wax is preferably used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the epoxy resin (A). It is more preferable. If the amount used is less than 0.01 parts by weight, the releasability tends to be insufficient, and if it exceeds 10 parts by weight, the adhesiveness tends to decrease. Examples of the oxidized polyolefin wax or the non-oxidized polyolefin wax include low molecular weight polyethylene having a number average molecular weight of 500 to 10,000, such as a product name manufactured by Hoechst Corporation: H4, PE, and PED series. These release agents may be used alone or in combination of two or more. In addition to oxidized polyolefin wax or non-oxidized polyolefin wax, a release agent such as carnauba wax, higher fatty acids such as montanic acid and stearic acid, higher fatty acid metal salts, and ester waxes such as montanic acid ester is used in combination. In this case, the total amount is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 3 parts by weight with respect to 100 parts by weight of the (A) epoxy resin. If the blending amount is less than 0.1 parts by weight, the releasability tends to be insufficient, and if it exceeds 10 parts by weight, the adhesiveness tends not to decrease.

  As the colorant, known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, and bengara can be used.

(Preparation of epoxy resin composition for sealing)
The sealing epoxy resin composition of the present invention can be prepared by any method as long as various components can be uniformly dispersed and mixed. As a general technique, there can be mentioned a method in which various components of a predetermined blending amount are sufficiently mixed by a mixer or the like, then melt-kneaded by a mixing roll, a kneader, an extruder or the like, then cooled and pulverized. For example, the above-described various components are uniformly stirred and mixed, kneaded with a kneader, roll, extruder, etc. that have been heated to 70 to 140 ° C., then cooled and pulverized. The epoxy resin composition for sealing of the invention can be obtained. In addition, the epoxy resin composition for sealing is easy to handle if it is tableted with dimensions and weight that meet the molding conditions as necessary.

(Electronic component equipment)
The electronic component device of the present invention comprises an element sealed with the sealing epoxy resin composition of the present invention. Electronic component devices include, for example, lead frames, wired tape carriers, wiring boards, glass, silicon wafers and other supporting members and mounting substrates, semiconductor chips, transistors, diodes, thyristors and other active elements, capacitors and resistors In addition, an electronic component device in which an element such as a coil or the like is mounted and a necessary part is sealed with the sealing epoxy resin composition of the present invention can be used.

  Here, the mounting substrate is not particularly limited. For example, an organic substrate, an organic film, a ceramic substrate, an interposer substrate such as a glass substrate, a liquid crystal glass substrate, an MCM (Multi Chip Module) substrate, and a hybrid IC substrate. Etc.

  As such an electronic component device, for example, a semiconductor element is fixed on a lead frame, a terminal portion of a device such as a bonding pad and a lead portion are connected by wire bonding or a bump, and then the sealing epoxy resin of the present invention is used. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Out Package), which are sealed by transfer molding using the composition. General resin-sealed ICs such as lead package, TSOP (Thin Small Outline Package), and TQFP (Thin Quad Flat Package) A semiconductor chip connected to a tape carrier by a bump is sealed with a tape carrier package (TCP) sealed with an epoxy resin composition for sealing of the present invention, wiring formed on a wiring board or glass, wire bonding, flip chip bonding, COB (Chip On) in which active elements such as semiconductor chips, transistors, diodes, thyristors and / or passive elements such as capacitors, resistors, coils, etc. connected by solder or the like are sealed with the sealing epoxy resin composition of the present invention. Board) Module, hybrid IC, multi-chip module, after mounting an element on the surface of an organic substrate on which a wiring board connection terminal is formed on the back, and connecting the element and the wiring formed on the organic substrate by bump or wire bonding The element with the epoxy resin composition for sealing of the present invention BGA (Ball Grid Array), CSP (Chip Size Package) and the like are encapsulated. Moreover, the epoxy resin composition for sealing of the present invention can also be used effectively for printed circuit boards.

  As a method for sealing an element using the epoxy resin composition for sealing of the present invention, a low-pressure transfer molding method is most common, but an injection molding method, a compression molding method, or the like may be used.

  EXAMPLES Next, although an Example demonstrates this invention, the scope of the present invention is not limited to these Examples.

[Silicon-containing polymers 1 to 4]
Silicon-containing polymers 1 to 4 used in Examples or Comparative Examples are shown below, and physical properties are shown in Table 1 below.

Silicon-containing polymer 1: manufactured by Wacker, developed product number “SLJ1661-01”
Silicon-containing polymer 2: manufactured by Wacker, product number “WAX OH350D”
Silicon-containing polymer 3: manufactured by Wacker, developed product number “SLJ44620-1065”
Silicon-containing polymer 4: developed by Wacker, product number “SLJ1661-03”

The silicon-containing polymers 1 to 4 are represented by the following formula (3) containing a structural site [1] represented by the following formula (1) and a structural site [2] represented by the following formula (2). It is a block polymer shown.

* 1: The number average molecular weight was determined by measurement using a standard polystyrene calibration curve by gel permeation chromatography (GPC). The number average molecular weight is GPC as a pump (L-6200 manufactured by Hitachi, Ltd.), a column (TSKgel-G5000HXL and TSKgel-G2000HXL, both of which are trade names manufactured by Tosoh Corporation), and a detector (L manufactured by Hitachi, Ltd.). -3300RI type), tetrahydrofuran was used as an eluent, and the temperature was 30 ° C. and the flow rate was 1.0 ml / min.

* 2: The ratio of the weight of the structural part [1] to the weight of the structural part [2] is the weight of the structural part [1] represented by the formula (1) / the structural part represented by the formula (2) [ 2] and was determined by the integral value of protons derived from each structural site by ¹ H-NMR measurement.

* 3, * 4: From the number average molecular weight, the ratio of the weight of the structural part [1] to the weight of the structural part [2], and the molecular weight of each structural part, m ₁ + m ₂ of the silicon-containing polymers 1 to 4 and l was estimated.

[Preparation of epoxy resin composition for sealing]
Examples 1-7, Comparative Examples 1-3
Examples 1 to 7 and Comparative Examples 1 to 3 were prepared by blending the following components in parts by mass shown in Tables 2 to 3 and performing roll kneading under conditions of a kneading temperature of 80 to 90 ° C. and a kneading time of 15 minutes. An epoxy resin composition for sealing was prepared.

  In addition, content of (D) inorganic filler is 82 mass% with respect to the total mass of the epoxy resin composition for sealing.

(A) Epoxy resin Epoxy resin 1: Biphenyl type epoxy resin having an epoxy equivalent of 196 and a melting point of 106 ° C. (trade name: YX-4000H manufactured by Japan Epoxy Resin Co., Ltd.)
(B) Curing Agent Curing Agent 1: Biphenylene skeleton-containing phenol / aralkyl resin having a hydroxyl equivalent of 199 and a softening point of 89 ° C. (trade name: MEH-7851 manufactured by Meiwa Kasei Co., Ltd.)
Curing agent 2: Triphenylmethane type phenol resin having a hydroxyl group equivalent of 104 and a softening point of 83 ° C. (trade name: MEH-7500-3S manufactured by Meiwa Kasei Co., Ltd.)
(C) Silicon-containing polymer Silicon-containing polymers 1 to 4: As described in Table 1 above, (D) Inorganic filler Inorganic filler 1: Spherical fused silica (average particle size 21.7 μm, specific surface area 1.3 m ² / G)
(E) Curing accelerator Curing accelerator 1: Addition reaction product of tri-n-butylphosphine and p-benzoquinone (F) Coupling agent Coupling agent 1: N-phenyl-γ-aminopropyltrimethoxysilane (release) Mold)
Polyethylene oxide: Brand name PED153 manufactured by Clariant Co., Ltd.
Montanate ester: Brand name manufactured by Clariant Hoechst-Wax E
(Coloring agent)
Carbon black

[Characteristic evaluation of epoxy resin composition for sealing]
The characteristics of the epoxy resin compositions for sealing produced in Examples 1 to 7 and Comparative Examples 1 to 3 were evaluated by the characteristic tests shown in (1) to (10) below. The evaluation results are shown in Tables 2 to 3.

  The sealing epoxy resin composition was molded using a transfer molding machine, and the sealing epoxy resin composition was molded at a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds.

(1) Gel time Using a JSR curast meter, 3 g of the sealing epoxy resin composition was measured at a temperature of 180 ° C., and the time until the rising of the torque curve was defined as the gel time (seconds).

(2) Hardness upon heating An epoxy resin composition for sealing was molded into a disk having a diameter of 50 mm and a thickness of 3 mm under the above conditions, and immediately after molding, a Shore D hardness tester (HD-1120 (type D, manufactured by Ueshima Seisakusho Co., Ltd.) )).

(3) Spiral flow The epoxy resin composition for sealing was molded under the above conditions using a spiral flow measurement mold according to EMMI-1-66, and the flow distance (cm) was determined.

(4) Disc flow Plate metal for measuring disc flow having an upper mold of 200 mm (W) x 200 mm (D) x 25 mm (H) and a lower mold of 200 mm (W) x 200 mm (D) x 15 mm (H) Using the mold, place 5 g of the sealing epoxy resin composition weighed on the upper balance on the center of the lower mold heated to 180 ° C., and after 5 seconds, close the upper mold heated to 180 ° C. and load The molded product was compression molded under the conditions of 78 N and a curing time of 90 seconds, and the major axis (mm) and minor axis (mm) of the molded product were measured with a caliper, and the average value (mm) was defined as a disc flow.

(5) Flexural modulus An epoxy resin composition for sealing was molded into dimensions of 70 mm × 10 mm × 3 mm under the above conditions and used as a test piece. Using Tensilon manufactured by A & D, a three-point support bending test in accordance with JIS-K-6911 was performed at room temperature and 260 ° C. to determine the flexural modulus.

(6) Glass transition temperature An epoxy resin composition for sealing was molded into a shape of 19 mm × 3 mm × 3 mm under the above conditions, and post-cured at 180 ° C. for 5 hours to prepare a test piece, manufactured by Rigaku Corporation. Using a thermomechanical analyzer (TAS-100), the glass transition temperature (hereinafter abbreviated as Tg) was determined from the inflection point of the linear expansion curve measured under the condition of a heating rate of 5 ° C./min.

(7) Linear expansion coefficient The linear expansion coefficient (α ₁ ) was determined from the slope of Tg or less obtained in (6), and the linear expansion coefficient (abbreviated as α ₂ ) was calculated from the slope of Tg or more.

(8) Flame retardancy Using a mold for molding a test piece having a thickness of 1/32 inch (0.8 mm), the sealing epoxy resin composition was molded under the above conditions and post-cured at 180 ° C. for 5 hours. A test piece was prepared, and flame retardancy was evaluated according to the UL-94 test method.

(9) Reflow resistance A silicone chip using 9 mm × 9 mm × 0.28 mm made by Hitachi Chemical Co., Ltd., HSG-255 (next-generation Low-k compatible interlayer insulating film; film Young's modulus 10 GPa), and a radius of 28 mm, A ball grid array (BGA) package with an external dimension of 40 mm x 40 mm x 2 mm is mounted on the above-mentioned conditions using an epoxy resin composition for sealing, which is equipped with a copper heat spreader with a chromium plating with a metal thickness of 0.3 mm. Then, it was post-cured at 180 ° C. for 5 hours to prepare a test piece. After the test piece was humidified under the conditions of Level 2 (85 ° C./65% RH / 168h), Level 2A (30 ° C./70% RH / 696h), Level 3 (30 ° C./70% RH / 168h) in accordance with JEDEC standards, 260 The reflow treatment was performed at 10 ° C. for 10 seconds. The presence or absence of delamination inside the package was observed with an ultrasonic imaging device (HYE-FOCUS) manufactured by Hitachi Construction Machinery Finetech Co., Ltd., and the number of crack generation packages relative to the number of test packages (5) was evaluated.

(10) Thermal shock resistance 9 mm × 9 mm × 0.28 mm manufactured by Hitachi Chemical Co., Ltd., HSG-255 (next-generation Low-k compatible interlayer insulating film; film Young's modulus 10 GPa) and a silicon chip having a radius of 28 mm, A ball grid array (BGA) package with an external dimension of 40 mm x 40 mm x 2 mm is mounted on the above-mentioned conditions using an epoxy resin composition for sealing, which is equipped with a copper heat spreader with a chromium plating with a metal thickness of 0.3 mm. Then, it was post-cured at 180 ° C. for 5 hours to prepare a test piece, and a temperature cycle test (−65 ° C./15 minutes, then 150 ° C./15 minutes as one cycle) was performed. The state of peeling inside the Low-k package was observed with an ultrasonic imaging device (HYE-FOCUS) manufactured by Hitachi Construction Machinery Finetech Co., Ltd., and evaluated by the number of defective packages against the number of test packages (8). did.

  The sealing epoxy resin composition of the present invention is particularly excellent in stress reduction, reflow resistance, and thermal shock resistance without impairing properties such as fluidity, flame retardancy, and curability. The sealing epoxy resin composition of Comparative Example 1 containing no silicon-containing polymer has poor thermal shock resistance and contains a silicon-containing polymer having a small number average molecular weight. The thing was inferior to reflow resistance.

Claims (18)

(A) An epoxy resin composition for sealing containing an epoxy resin, (B) a curing agent, and (C) a silicon-containing polymer, wherein the (C) silicon-containing polymer is represented by the following formula (1): An epoxy resin composition for sealing having a structural part [1] having a structure of [1] and a structural part [2] represented by the following formula (2) in a main chain skeleton, and having a number average molecular weight of 8000 to 12000.

(In formula (1), R ¹ represents an alkylene group having 1 to 10 carbon atoms.)

(A in the formula (2), ^{R 2} and ^{R 3} is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an epoxy group having 1 to 10 carbon atoms It is selected from a monovalent organic group, a monovalent organic group having a carboxyl group having 1 to 10 carbon atoms, or a polyalkylene ether group having 3 to 500 carbon atoms, and each may be the same or different.   2. The epoxy resin composition for sealing according to claim 1, wherein the number average molecular weight of the (C) silicon-containing polymer is 9500 to 10500. 3.   The ratio of the weight of the structural part [1] represented by the formula (1) to the weight of the structural part [2] represented by the formula (2) is 2/8 to 5/5. The epoxy resin composition for sealing according to 2.   Content of the said (C) silicon-containing polymer is 1-50 weight part with respect to 100 weight part of (A) epoxy resin, The epoxy resin composition for sealing as described in any one of Claims 1-3. object.   Content of the said (C) silicon-containing polymer is 5-25 weight part with respect to 100 weight part of (A) epoxy resin, The epoxy resin composition for sealing as described in any one of Claims 1-3. object.   The (C) silicon-containing polymer is a block copolymer having a polymer block containing a structural site [1] and a polymer block containing a structural site [2]. The epoxy resin composition for sealing as described in any one of 1-5.   The (C) silicon-containing polymer is a triblock copolymer in which a polymer block containing a structural site [1] is bonded to both ends of a polymer block containing a structural site [2]. The epoxy resin composition for sealing according to any one of 6. The epoxy resin composition for sealing according to claim 6, wherein the (C) silicon-containing polymer is a block polymer represented by the following formula (3).

(In Formula (3), l is an integer of ₁ to 200, m ₁ is an integer of ₁ to 200, m ₂ is an integer of 1 to 200, and m ₁ + m ₂ is an integer of ₂ to 400. R ¹ is carbon. An alkylene group having 1 to 10 carbon atoms, wherein R ² and R ³ are an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an epoxy having 1 to 10 carbon atoms Selected from a monovalent organic group having a group, a monovalent organic group having a carboxyl group having 1 to 10 carbon atoms, or a polyalkylene ether group having 3 to 500 carbon atoms, and each may be the same or different. Well, R ⁴ represents a divalent hydrocarbon group having 1 to 10 carbon atoms.)   The (A) epoxy resin is biphenyl type epoxy resin, stilbene type epoxy resin, sulfur atom-containing epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, triphenylmethane type epoxy resin, bisphenol F The epoxy resin composition for sealing according to any one of claims 1 to 8, comprising at least one of a type epoxy resin and a biphenylene skeleton-containing phenol / aralkyl type epoxy resin.   The (B) curing agent is a biphenylene skeleton-containing phenol-aralkyl resin, phenol-aralkyl resin, naphthol-aralkyl resin, dicyclopentadiene-type phenol resin, triphenylmethane-type phenol resin, novolac-type phenol resin, and copolymer-type phenol- The epoxy resin composition for sealing according to any one of claims 1 to 9, comprising at least one aralkyl resin.   (D) The epoxy resin composition for sealing as described in any one of Claims 1-10 containing an inorganic filler.   The epoxy resin composition for sealing according to claim 11, wherein the content of the (D) inorganic filler is 65% by mass to 95% by mass with respect to the total weight of the epoxy resin composition.   (E) The hardening epoxy resin composition is contained, The epoxy resin composition for sealing as described in any one of Claims 1-12 characterized by the above-mentioned.   The epoxy resin composition for sealing according to claim 13, wherein the (E) curing accelerator is an adduct of a third phosphine compound and a quinone compound.   (F) Coupling agent is contained, The epoxy resin composition for sealing as described in any one of Claims 1-14 characterized by the above-mentioned.   The epoxy resin composition for sealing according to claim 15, wherein the (F) coupling agent contains a silane coupling agent having a secondary amino group. The epoxy resin composition for sealing according to claim 16, wherein the (F) silane coupling agent having a secondary amino group contains a compound represented by the following general formula (4).

(In General Formula (4), R ¹ is selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to ² carbon atoms, and R ² is selected from an alkyl group having 1 to 6 carbon atoms and a phenyl group. R ³ represents a methyl group or an ethyl group, n represents an integer of 1 to 6, and m represents an integer of 1 to ^3. )   The electronic component apparatus provided with the element sealed with the epoxy resin composition for sealing as described in any one of Claims 1-17.