JP6111709B2 - Curable resin composition and electronic component device - Google Patents

Description

  The present invention relates to a curable resin composition and an electronic component device.

  Conventionally, epoxy resins have been widely used in the fields of molding materials, laminates and adhesives. Since these epoxy resins are required to have fast curability from the viewpoint of improving productivity, a compound that accelerates the curing reaction, that is, a curing accelerator is generally used in combination with the epoxy resin composition. Also, compositions based on epoxy resins are widely used in the field of sealing technology relating to elements of electronic components such as transistors and ICs. The reason for this is that epoxy resins are balanced in various properties such as moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to inserts. In particular, a combination of an ortho-cresol novolac type epoxy resin and a phenol novolac curing agent has an excellent balance in the above-mentioned characteristics, and thus has become the mainstream as a base resin for molding materials for transistors and IC sealing.

  In recent years, attention has been focused on power semiconductors such as inverters from the viewpoint of energy saving. Since power semiconductors generate a large amount of heat and may be used in a high temperature environment, there are many opportunities to be exposed to high temperatures. However, the curable resin composition containing an epoxy resin has a problem that heat resistance after curing is low, and development of a curable resin composition having high heat resistance is desired.

  In order to improve the heat resistance after curing of the curable resin composition, it is specified by a method containing an epoxy resin, a phenol resin, a curing accelerator and a maleimide compound (for example, see Patent Document 1) or a combination similar to Patent Document 1. A method of using a curing accelerator (see, for example, Patent Document 2) has been proposed.

Japanese Patent Laid-Open No. 01-188518 Japanese Patent Laid-Open No. 03-197527

  However, the method of Patent Document 1 has a problem that the fast curability is low and the moldability is not satisfied. Further, the method of Patent Document 2 has a problem that benzene is released into the environment due to the tetraphenylborate anion during molding and post-curing.

  An object of the present invention is to provide a curable resin composition excellent in reflow resistance and heat resistance after curing, and an electronic component device excellent in heat resistance.

Specific means for solving the above problems are as follows.
<1> (A) an epoxy resin, (B) a phenol resin, (C) a curing accelerator, and (D) a maleimide compound, wherein the (C) curing accelerator is represented by the following general formula (I-1) The curable resin composition which contains the compound and satisfy | fills at least one of the following.
(A) The epoxy resin contains an aralkyl type epoxy resin.
(B) A phenol resin contains an aralkyl type phenol resin.

In formula (I-1), R ^{1 to} R ³ are each independently a hydrocarbon group having 1 to 18 carbon atoms, and two or more of R ^{1 to} R ³ are bonded to each other to form a cyclic structure. R ^{4 to} R ⁷ are each independently a hydrogen atom, a hydroxyl group, or an organic group having 1 to 18 carbon atoms, and two or more of R ^{4 to} R ⁷ are bonded to each other to form a cyclic structure. May be formed.

<2> The curable resin composition according to <1>, wherein the (C) curing accelerator contains a compound represented by the following general formula (I-2).

In formula (I-2), R ^{1 to} R ³ are each independently a hydrocarbon group having 1 to 18 carbon atoms, and two or more of R ^{1 to} R ³ are bonded to each other to form a cyclic structure. R ^{4 to} R ⁷ are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, and two or more of R ^{4 to} R ⁷ are bonded to each other to form a cyclic structure. May be.

<3> The curable resin composition according to <1>, wherein the (C) curing accelerator contains a compound represented by the following general formula (I-3).

In formula (I-3), R ^{1 to} R ³ are each independently an aliphatic hydrocarbon group having 1 to 18 carbon atoms, and two or more of R ^{1 to} R ³ are bonded to each other to form a cyclic structure. R ^{4 to} R ⁶ are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, and two or more of R ^{4 to} R ⁶ are bonded to each other to form a cyclic structure. May be formed.

<4> (D) The curable resin composition according to any one of <1> to <3>, wherein the maleimide compound is a compound having two or more maleimide groups in one molecule.

<5> The curable resin composition according to any one of <1> to <4>, further comprising (E) an inorganic filler.

<6> (A) The epoxy resin is biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom containing type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, triphenylmethane type epoxy resin The curable resin composition according to any one of the above <1> to <5>, comprising one or more epoxy resins selected from the group consisting of: and copolymerizable epoxy resins.

<7> The above <1> to <6>, wherein the (B) phenol resin contains one or more phenol resins selected from the group consisting of dicyclopentadiene type phenol resins, salicylaldehyde type phenol resins, and novolac type phenol resins. The curable resin composition according to any one of the above.

<8> (D) The maleimide compound is 4,4′-diphenylmethane dimaleimide, N, N′-1,3-phenylene dimaleimide, 4-methyl-1,3-phenylene bismaleimide, polyphenylmethane maleimide, 2 , 2'-bis [4- (4-maleimidophenoxy) phenyl] propane, and at least one compound selected from the group consisting of 1,6-bismaleimide- (2,2,4-trimethyl) hexane The curable resin composition according to any one of <1> to <7>.

<9> An electronic component device comprising an element and a cured product of the curable resin composition according to any one of <1> to <8>, which seals the element.

  According to the present invention, a curable resin composition excellent in reflow resistance and heat resistance after curing, and an electronic component device excellent in heat resistance are provided.

  In the present specification, a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. Furthermore, the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.

[Curable resin composition]
The curable resin composition according to the present invention contains (A) an epoxy resin, (B) a phenol resin, (C) a curing accelerator, and (D) a maleimide compound, and the (C) curing accelerator is represented by the following general formula. It contains the compound represented by (I-1) and satisfies at least one of the following conditions.

(A) The epoxy resin contains an aralkyl type epoxy resin.
(B) A phenol resin contains an aralkyl type phenol resin.

The curable resin composition of the present invention contains the compound represented by the general formula (I-1) as (C) a curing accelerator, and at least one of the (A) epoxy resin and (B) phenol resin is aralkyl. By being a mold, it is excellent in reflow resistance and heat resistance after curing.
The curable resin composition according to the present invention may further contain an inorganic filler in addition to the components (A) to (D). Moreover, you may contain additives, such as a coupling agent, an ion exchanger, a mold release agent, a stress relaxation agent, a flame retardant, and a coloring agent, as needed. Hereinafter, main components constituting the curable resin composition of the present invention will be described.

(A) Epoxy resin The curable resin composition of the present invention includes (A) an epoxy resin. (B) When a phenol resin is not an aralkyl type phenol resin, an epoxy resin contains an aralkyl type epoxy resin. (B) When the phenol resin is an aralkyl type phenol resin, the epoxy resin may or may not contain an aralkyl type epoxy resin.

  The aralkyl type epoxy resin is an epoxidized product of an aralkyl type phenol resin such as a phenol aralkyl resin or a naphthol aralkyl resin.

  As the aralkyl type epoxy resin, synthesized from at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis (methoxymethyl) biphenyl, or derivatives thereof It is not particularly limited as long as it is an epoxy resin made from a phenol resin to be produced. For example, phenol synthesized from at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis (methoxymethyl) biphenyl, and derivatives thereof. A resin obtained by glycidyl etherification is preferable, and epoxy resins represented by the following general formulas (X) and (XI) are more preferable.

Among epoxy resins represented by the following general formula (X), i = 0, R- ³⁸ is a hydrogen atom, NC-3000 (Nippon Kayaku Co., Ltd., trade name), i = 0, and R ³⁸ is CER-3000 (Nippon Kayaku Co., Ltd., trade name) in which an epoxy resin that is a hydrogen atom and an epoxy resin in which all R ^{8 in} the general formula (II) are hydrogen atoms are mixed at a mass ratio of 80:20 is a commercial product Is available as Among epoxy resins represented by the following general formula (XI), ESN-175 (Nippon Steel Chemical Co., Ltd., trade name) in which i = 0, j = 0, and k = 0 is available as a commercial product. It is.

In the formulas (X) and (XI), R ³⁸ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. R ³⁷ and R ^{39 to} R ⁴¹ each represent a monovalent organic group having 1 to 18 carbon atoms, and may be all the same or different. i is independently an integer of 0 to 3, j is independently of an integer of 0 to 2, k is independently of an integer of 0 to 4, and l is independently of an integer of 0 to 6. n is an average value and shows the number of 0-10.

  From the viewpoint of further improving the reflow resistance, the total amount of the (A) epoxy resin preferably contains 30% by mass or more, more preferably 50% by mass or more of the aralkyl type epoxy resin.

  Examples of other epoxy resins that can be used in addition to the aralkyl epoxy resin include epoxy resins having two or more epoxy groups in one molecule. Specifically, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F and other phenol compounds and α-naphthol, β-naphthol, A novolak resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of naphthol compounds such as dihydroxynaphthalene and aliphatic aldehyde compounds such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst Epoxidized novolac type epoxy resin; obtained by condensation or cocondensation of the above phenolic compound and an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde under an acidic catalyst A triphenylmethane type epoxy resin obtained by epoxidizing a triphenylmethane type phenol resin; a copolymer type epoxy obtained by epoxidizing a novolak resin obtained by cocondensation of the above phenol compound and naphthol compound with an aldehyde compound under an acidic catalyst. Resin; Diphenylmethane type epoxy resin that is diglycidyl ether such as bisphenol A and bisphenol F; Biphenyl type epoxy resin that is diglycidyl ether of alkyl-substituted or unsubstituted biphenol; Stilbene type epoxy that is diglycidyl ether of stilbene phenol compound Resin; Sulfur atom-containing epoxy resin that is diglycidyl ether such as bisphenol S; Glycidi of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol Epoxy resin which is ether; Glycidyl ester type epoxy resin of polyvalent carboxylic acid compounds such as phthalic acid, isophthalic acid, tetrahydrophthalic acid; Active hydrogen bonded to nitrogen atom such as aniline, diaminodiphenylmethane, isocyanuric acid is replaced with glycidyl group Glycidylamine type epoxy resin; dicyclopentadiene type epoxy resin obtained by epoxidizing a co-condensation resin of dicyclopentadiene and a phenol compound; vinylcyclohexene diepoxide obtained by epoxidizing an intramolecular olefin bond; 3,4-epoxycyclohexyl Cycloaliphatic epoxy resins such as methyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane; Paraxylylene-modified epoxy resin that is a glycidyl ether of a xylylene-modified phenolic resin; Metaxylylene-modified epoxy resin that is a glycidyl ether of a metaxylylene-modified phenol resin; Terpene-modified epoxy resin that is a glycidyl ether of a terpene-modified phenol resin; Dicyclopentadiene type epoxy resin that is ether; Cyclopentadiene modified epoxy resin that is glycidyl ether of cyclopentadiene modified phenol resin; Polycyclic aromatic ring modified epoxy resin that is glycidyl ether of polycyclic aromatic ring modified phenol resin; Naphthalene ring-containing phenol Naphthalene type epoxy resin that is glycidyl ether of resin; Halogenated phenol novolac type epoxy resin; Examples include idroquinone type epoxy resins; trimethylolpropane type epoxy resins; linear aliphatic epoxy resins obtained by oxidizing olefinic bonds with peracids such as peracetic acid; diphenylmethane type epoxy resins; These may be used alone or in combination of two or more.

  Among the above-mentioned other epoxy resins, biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom-containing type epoxy resin, novolac type epoxy resin from the viewpoint of the balance of reflow crack resistance, fluidity and heat resistance Dicyclopentadiene type epoxy resin, triphenylmethane type epoxy resin, or copolymer type epoxy resin (these are referred to as “specific epoxy resins”) are preferable. These may be used alone or in combination of two or more.

  When the epoxy resin contains a specific epoxy resin, from the viewpoint of exhibiting the performance of the specific epoxy resin, it is preferable that the total amount of the (A) epoxy resin includes 30% by mass or more of the specific epoxy resin and the aralkyl epoxy resin, It is more preferable to include 50% by mass or more.

Among specific epoxy resins, biphenyl type epoxy resins, stilbene type epoxy resins, diphenylmethane type epoxy resins or sulfur atom-containing type epoxy resins are more preferable from the viewpoint of fluidity, and dicyclopentadiene type epoxy is preferable from the viewpoint of heat resistance. A resin or a triphenylmethane type epoxy resin is more preferable.
Specific examples of preferable specific epoxy resins are shown below.

The biphenyl type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton, and an epoxy resin represented by the following general formula (II) is preferable. Among the epoxy resins represented by the following general formula (II), the positions where the oxygen atom is substituted in R ⁸ are the methyl groups at the 3, 3 ′, 5, 5 ′ positions when the positions 4 and 4 ′ are the positions. , YX-4000H other ^{R 8} is a hydrogen atom (Japan epoxy Resins Co., Ltd., trade name), all ^{R 8} are hydrogen atoms 4,4'-bis (2,3-epoxypropoxy) biphenyl In the case where all R ⁸ are hydrogen atoms, and the positions where oxygen atoms are substituted in R ⁸ are the 4 and 4 ′ positions, the 3, 3 ′, 5, 5 ′ positions are methyl groups, and the others are YL-6121H (Japan Epoxy Resin Co., Ltd., trade name), which is a mixed product in the case of being a hydrogen atom, is available as a commercial product.

In the formula (II), R ⁸ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aromatic group having 4 to 18 carbon atoms, all of which may be the same or different, and n is an average value. The number of 0-10 is shown.

The stilbene type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton, but an epoxy resin represented by the following general formula (III) is preferable. Among the epoxy resins represented by the following general formula (III), the 3,3 ′, 5,5 ′ positions when R ⁹ is substituted with oxygen atoms at positions 4 and 4 ′ are methyl groups. The other R ⁹ is a hydrogen atom and all of R ¹⁰ are hydrogen atoms, and three of the R ⁹ positions 3, 3 ′, 5, 5 ′ are methyl groups, ESLV-210 (Sumitomo Chemical Co., Ltd., trade name), which is a mixture of the case where one is a tert-butyl group, the other R ⁹ is a hydrogen atom, and all of R ¹⁰ are hydrogen atoms, is commercially available It is available as a product.

In formula (III), R ⁹ and R ^{10 each} represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be all the same or different. n is an average value and shows the number of 0-10.

The diphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton, and an epoxy resin represented by the following general formula (IV) is preferable. Among the epoxy resins represented by the following general formula (IV), all of R ¹¹ are hydrogen atoms, and 3, 3 ′ when the positions where oxygen atoms are substituted in R ¹² are the 4 and 4 ′ positions. YSLV-80XY (Nippon Steel Chemical Co., Ltd., trade name) in which the methyl groups at the 5 and 5 'positions and the other R ¹² is a hydrogen atom are available as commercial products.

In formula (IV), R ¹¹ and R ^{12 each} represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be all the same or different. n is an average value and shows the number of 0-10.

As a sulfur atom containing type epoxy resin, if it is an epoxy resin containing a sulfur atom, it will not specifically limit, For example, the epoxy resin shown by the following general formula (V) is mentioned. Among the epoxy resins represented by the following general formula (V), the tert-butyl group is the 3,3 ′ position when the positions where the oxygen atom is substituted in R ¹³ are the 4 and 4 ′ positions, , 6′-position is a methyl group, and other R ¹³ is a hydrogen atom, YSLV-120TE (Nippon Steel Chemical Co., Ltd., trade name) is available as a commercial product.

In the formula (V), R ¹³ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all may be the same or different. n is an average value and shows the number of 0-10.

The novolak type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolak type phenol resin, and a novolak type phenol resin such as phenol novolak, cresol novolak, naphthol novolak, or the like is glycidyl etherified. Epoxy resins epoxidized using a technique are preferred, and for example, epoxy resins represented by the following general formula (VI) are more preferred. Among the epoxy resins represented by the following general formula (VI), all of R ¹⁴ are hydrogen atoms, R ¹⁵ is a methyl group, and i = 1, ESCN-190, ESCN-195 (Sumitomo Chemical Co., Ltd., (Trade name) etc. are commercially available.

In the formula (VI), R ¹⁴ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all may be the same or different. R ¹⁵ represents a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. i represents an integer of 0 to 3 independently. n is an average value and shows the number of 0-10.

  The dicyclopentadiene type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a compound having a dicyclopentadiene skeleton as a raw material, and an epoxy resin represented by the following general formula (VII) is preferable. Among epoxy resins represented by the following general formula (VII), HP-7200 (DIC Corporation, trade name) in which i = 0 is available as a commercial product.

In the formula (VII), R ¹⁶ represents a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, each i independently represents an integer of 0 to 3, n is an average Value, indicating a number from 0 to 10.

  The triphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin made from a compound having a triphenylmethane skeleton, and a novolak type phenol resin of a compound having a triphenylmethane skeleton and a compound having a phenolic hydroxyl group. A triphenylmethane type epoxy resin such as an epoxy resin obtained by glycidyl etherification of a triphenylmethane type phenol resin such as the above is preferable, and an epoxy resin represented by the following general formula (VIII) is more preferable. Among epoxy resins represented by the following general formula (VIII), 1032H60 (Japan Epoxy Resin Co., Ltd., trade name), iPN = 0, k = 0, EPPN-502H (Nippon Kayaku Co., Ltd., trade name), etc. It is available as a commercial product.

In the formula (VIII), R ¹⁷ and R ¹⁸ each represent a monovalent organic group having 1 to ¹⁸ carbon atoms, and may be all the same or different. i represents an integer of 0 to 3 each independently, and k represents an integer of 0 to 4 independently. n is an average value and shows the number of 0-10.

As a copolymerization type epoxy resin obtained by epoxidizing a novolak resin obtained from a naphthol compound and a phenol compound and an aldehyde compound, as long as it is an epoxy resin using a compound having a naphthol skeleton and a compound having a phenol skeleton as a raw material, there is a particular limitation. However, a novolak type phenol resin using a compound having a naphthol skeleton and a compound having a phenol skeleton is preferably glycidyl etherified, and more preferably an epoxy resin represented by the following general formula (IX). Among the epoxy resins represented by the following general formula (IX), NC-7300 (Nippon Kayaku Co., Ltd., trade name) in which R ²¹ is a methyl group, i = 1, j = 0, k = 0, etc. It is available as a commercial product.

In formula (IX), R ^{19 to} R ²¹ represent a monovalent organic group having 1 to 18 carbon atoms, and may be all the same or different. i is each independently an integer of 0 to 3, j is each independently an integer of 0 to 2, and k is each independently an integer of 0 to 4. Each of l and m is an average value and is a number from 0 to 10, and (l + m) is a number from 0 to 10. The terminal of the epoxy resin represented by the formula (IX) is either the following formula (IX-1) or (IX-2), and the formula (IX) is replaced by the formula (IX-1) or (IX-2). When the terminal structure is bonded, n = 1 when not via a methylene group, and n = 0 when via a methylene group.

  As the epoxy resin represented by the general formula (IX), a random copolymer containing 1 structural unit and m structural units randomly, an alternating copolymer containing alternately, a copolymer containing regularly, Examples thereof include a block copolymer contained in a block shape. Any one of these may be used alone, or two or more may be used in combination.

Regarding R ^{8 to} R ²¹ and R ^{37 to} R ^{41 in the} general formulas (II) to (XI), “all may be the same or different” means, for example, 8 to 8 in the formula (II) It means that all 88 R ⁸ may be the same or different. It means that all of R ^{9 to} R ²¹ and R ^{37 to} R ⁴¹ may be the same or different with respect to the respective numbers included in the formula. R ^{8 to} R ²¹ and R ^{37 to} R ⁴¹ may be the same as or different from each other. For example, all of R ⁹ and R ¹⁰ may be the same or different.
Moreover, it is preferable that the C1-C18 organic group in general formula (III)-(XI) is an alkyl group or an aryl group.

  N in the general formulas (II) to (XI) is an average value and is preferably in the range of 0 to 10. If it is 10 or less, the melt viscosity of the component (B) does not become too high, the viscosity at the time of melt molding of the curable resin composition decreases, and unfilled defects and bonding wires (gold wires connecting the element and the lead) Occurrence of deformation is suppressed. More preferably, n is set in the range of 0-4.

  As mentioned above, although the specific example of the preferable epoxy resin which can be used for the curable resin composition of this invention was demonstrated along the said general formula (II)-(XI), as a more specific preferable epoxy resin, a reflow crack-proof From the viewpoint of properties, 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl can be mentioned. From the viewpoint of moldability and heat resistance, 4'-bis (2,3-epoxypropoxy) -biphenyl.

  The epoxy equivalent of the epoxy resin is not particularly limited. Among these, from the viewpoint of balance of various properties such as moldability, reflow resistance, and electrical reliability, it is preferably 100 g / eq to 1000 g / eq, and more preferably 150 g / eq to 500 g / eq.

  The softening point or melting point of the epoxy resin is not particularly limited. Among these, from the viewpoint of moldability and reflow resistance, the softening point or melting point is preferably 40 ° C to 180 ° C, and from the viewpoint of handleability during preparation of the curable resin composition, it is 50 ° C to 130 ° C. It is more preferable.

  The content of the entire epoxy resin in the curable resin composition is preferably 0.5% by mass to 50% by mass from the viewpoint of strength, fluidity, heat resistance, moldability, and the like, and 2% by mass to 30% by mass. It is more preferable that

(B) Phenol resin The curable resin composition of the present invention contains (B) a phenol resin.
(A) When the epoxy resin is not an aralkyl type epoxy resin, the phenol resin contains an aralkyl type phenol resin. (A) When the epoxy resin is an aralkyl type epoxy resin, the phenol resin may or may not contain an aralkyl type phenol resin.

  The aralkyl type phenol resin is a phenol aralkyl resin, a naphthol aralkyl resin or the like synthesized from the above phenolic compound and dimethoxyparaxylene, bis (methoxymethyl) biphenyl or the like. The aralkyl type phenol resin may be further copolymerized with another phenol resin. Examples of the copolymerized aralkyl type phenol resin include a copolymer type phenol resin of a benzaldehyde type phenol resin and an aralkyl type phenol resin, a copolymer type phenol resin of a salicylaldehyde type phenol resin and an aralkyl type phenol resin, and a novolac type phenol resin. Examples thereof include copolymer type phenol resins with aralkyl type phenol resins.

  The aralkyl type phenol resin is particularly limited as long as it is a phenol resin synthesized from at least one selected from the group consisting of a phenol compound and a naphthol compound and dimethoxyparaxylene, bis (methoxymethyl) biphenyl, or a derivative thereof. However, phenol resins represented by the following general formulas (XII) to (XIV) are preferable.

In the formulas (XII) to (XIV), R ²³ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all may be the same or different. R ²² , R ²⁴ , R ²⁵ and R ²⁸ each represent a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. R ²⁶ and R ^{27 each} represent a hydroxyl group or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. i is each independently an integer of 0 to 3, k is each independently an integer of 0 to 4, j is each independently an integer of 0 to 2, and p is each independently an integer of 0 to 4. n is an average value and shows the number of 0-10.

Among the phenol resins represented by the general formula (XII), MEH-7851 (Maywa Kasei Co., Ltd., trade name) in which i = 0 and R ²³ are all hydrogen atoms is available as a commercial product.

  Among the phenol resins represented by the general formula (XIII), XL-225, XLC (Mitsui Chemicals, Inc., trade name), MEH-7800 (Maywa Kasei Co., Ltd., trade name) where i = 0 and k = 0. Etc. are available as commercial products.

Among the phenolic resins represented by the general formula (XIV), SN-170 (Nippon Steel Chemical Co., Ltd., trade name) where j = 0, k = 0, p = 0, j = 0, k = 1 R ²⁷ is a hydroxyl group, a p = 0 SN-395 (Nippon Steel Chemical Co., Ltd., trade name) and the like are available as commercial products.

  The copolymer type phenol resin of benzaldehyde type phenol resin and aralkyl type phenol resin is particularly limited as long as it is a copolymer type phenol resin of a phenol resin and an aralkyl type phenol resin using a compound having a benzaldehyde skeleton as a raw material. A phenol resin represented by the following general formula (XVII) is preferable.

  Among the phenolic resins represented by the following general formula (XVII), HE-510 (Air Water Chemical Co., Ltd., trade name) where i = 0, k = 0, q = 0 is available as a commercial product. is there.

In the formula (XVII), R ^{32 to} R ³⁴ represent a monovalent organic group having 1 to 18 carbon atoms, and may be all the same or different. i is each independently an integer of 0 to 3, k is each independently an integer of 0 to 4, and q is each independently an integer of 0 to 5. Each of l and m is an average value of 0 to 11 and (l + m) represents a number of 1 to 11.

  From the viewpoint of further improving the reflow resistance, the total amount of (B) phenolic resin preferably contains 30% by mass or more, more preferably 50% by mass or more of the aralkyl type phenolic resin.

  There is no restriction | limiting in particular as a kind of other phenol resin which can be used other than an aralkyl type phenol resin. For example, the phenol resin or polyhydric phenol which has two or more phenolic hydroxyl groups in 1 molecule generally used as a hardening | curing agent is mentioned. Specifically, compounds having two phenolic hydroxyl groups in one molecule such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorcin, catechol, bisphenol A, At least one phenolic compound selected from the group consisting of phenolic compounds such as bisphenol F, phenylphenol and aminophenol, and naphtholic compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene, and formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, A novolak-type phenol resin obtained by condensation or co-condensation with an aldehyde compound such as salicylaldehyde under an acidic catalyst; paraxylylene and / or metaxylylene Modified phenolic resin; melamine modified phenolic resin; terpene modified phenolic resin; dicyclopentadiene type phenolic resin and dicyclopentadiene type naphthol resin synthesized by copolymerization from the above phenolic compound and dicyclopentadiene; cyclopentadiene modified phenolic Resin; Polycyclic aromatic ring-modified phenol resin; Biphenyl type phenol resin; Triphenylmethane type phenol obtained by condensation or cocondensation of the above phenolic compound and aromatic aldehyde compound such as benzaldehyde and salicylaldehyde in the presence of an acidic catalyst Resin; copolymerized phenol resin obtained by copolymerizing two or more of these. These phenol resins may be used alone or in combination of two or more.

  Among other phenol resins, from the viewpoint of heat resistance, dicyclopentadiene type phenol resin, triphenylmethane type phenol resin, or novolac type phenol resin is preferable, and dicyclopentadiene type phenol resin or triphenylmethane type phenol resin. (Hereinafter sometimes referred to as “specific phenol resin”) is more preferable. The specific phenol resin may be used alone or in combination of two or more. When the phenol resin contains a specific phenol resin, it is preferable that the total amount of the specific phenol resin and the aralkyl resin is 30% by mass or more with respect to the total amount of the phenol resin from the viewpoint of exhibiting the performance of the specific phenol resin, It is more preferable to contain at least%.

  The dicyclopentadiene type phenol resin is not particularly limited as long as it is a phenol resin using a compound having a dicyclopentadiene skeleton as a raw material, and a phenol resin represented by the following general formula (XV) is preferable. Among the phenol resins represented by the following general formula (XV), DPP (Shin Nippon Petrochemical Co., Ltd., trade name) where i = 0 is available as a commercial product.

In the formula (XV), R ²⁹ represents a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. i represents an integer of 0 to 3 independently. n is an average value and shows the number of 0-10.

  The triphenylmethane type phenol resin is not particularly limited as long as it is a phenol resin using a compound having a triphenylmethane skeleton as a raw material, and a phenol resin represented by the following general formula (XVI) is preferable.

  Among the phenol resins represented by the following general formula (XVI), MEH-7500 (trade name, manufactured by Meiwa Kasei Co., Ltd.) where i = 0 and k = 0 is available as a commercial product.

In formula (XVI), R ³⁰ and R ³¹ each represent a monovalent organic group having 1 to 18 carbon atoms, and may be all the same or different. i represents an integer of 0 to 3 each independently, and k represents an integer of 0 to 4 independently. n is an average value and shows the number of 0-10.

  The novolak-type phenol resin is not particularly limited as long as it is a phenol resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of a phenol compound and a naphthol compound and an aldehyde compound under an acidic catalyst. It is not something. Among these, a phenol resin represented by the following general formula (XVIII) is preferable.

Among the phenol resins represented by the following general formula ^{(XVIII), i = 0,} R 35 are all hydrogen atoms TAMANOL 758, 759 (Arakawa Chemical Industries, Ltd., trade name), HP-850N (Hitachi Chemical Co., Ltd. , Trade names) etc. are available as commercial products.

In the formula (XVIII), R ³⁵ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all may be the same or different. R ³⁶ represents a monovalent organic group having 1 to 18 carbon atoms, and all may be the same or different. i represents an integer of 0 to 3 independently. n is an average value and shows the number of 0-10.

“All may be the same or different” described for R ^{22 to} R ³⁶ in the above general formulas (XII) to (XVIII) is, for example, that all i R ^{22s in} formula (XII) are the same. But it means they can be different from each other. For the other R ^{23 to} R ³⁶ , it means that all the numbers contained in the formula may be the same or different from each other. R ^{22 to} R ³⁶ may be the same as or different from each other. For example, all of R ²² and R ²³ may be the same or different, and all of R ³⁰ and R ³¹ may be the same or different.

  N in the general formulas (XII) to (XVIII) is preferably in the range of 0 to 10. If it is 10 or less, the melt viscosity of the resin component does not become too high, the viscosity at the time of melt molding of the curable resin composition also increases, and unfilled defects and bonding wire (gold wire connecting the element and the lead) are deformed. It becomes difficult to occur. The average n per molecule is preferably set in the range of 0-4.

  In the curable resin composition of the present invention, the blending ratio of (A) epoxy resin and (B) phenol resin is the ratio of the total hydroxyl equivalent of all phenol resins to the total epoxy equivalent of all epoxy resins (total in phenol resin). The number of hydroxyl groups / the total number of epoxy groups in the epoxy resin) is preferably set in the range of 0.1 to 2.0, more preferably in the range of 0.2 to 1.5, More preferably, it is set within the range of 1.3. When the ratio is 0.5 or more, the epoxy resin is sufficiently cured, and the heat resistance, moisture resistance, and electrical characteristics of the cured product tend to be further improved. On the other hand, when the ratio is 2.0 or less, the phenol resin component is not excessive, and the curing efficiency is further improved. Furthermore, since a large amount of phenolic hydroxyl group remains in the cured resin, the electrical characteristics and moisture resistance of the package tend to be further improved.

(C) Curing accelerator The curable resin composition of the present invention contains (C) a curing accelerator, and the curing accelerator is at least one selected from compounds represented by the following general formula (I-1). Contains compounds.

In formula (I-1), R ^{1 to} R ³ are each independently a hydrocarbon group having 1 to 18 carbon atoms, and two or more of R ^{1 to} R ³ are bonded to each other to form a cyclic structure. R ^{4 to} R ⁷ are each independently a hydrogen atom, a hydroxyl group, or an organic group having 1 to 18 carbon atoms, and two or more of R ^{4 to} R ⁷ are bonded to each other to form a cyclic structure. May be formed.

The “C1-C18 hydrocarbon group” described as R ^{1 to} R ^{3 in the} general formula (I-1) is an aliphatic hydrocarbon group having 1 to 18 carbon atoms and 6 to 18 carbon atoms. Contains some aromatic hydrocarbon groups. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may be substituted or unsubstituted.

  The aliphatic hydrocarbon group having 1 to 18 carbon atoms has 1 to 18 carbon atoms, and from the viewpoint of fluidity, the number of carbon atoms is preferably 1 to 8, and more preferably 2 to 6. More preferably, it is 4-6.

  The aliphatic hydrocarbon group having 1 to 18 carbon atoms may be linear, branched or cyclic. From the viewpoint of ease of production, it is preferably linear or branched.

  The aromatic hydrocarbon group having 1 to 18 carbon atoms has 6 to 18 carbon atoms, preferably 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms. When the aromatic hydrocarbon group has a substituent, the total number of carbon atoms contained in the aromatic hydrocarbon group and the substituent is preferably 6-18.

  Examples of the unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, Examples thereof include aliphatic hydrocarbon groups such as octyl group, decyl group, dodecyl group, allyl group and vinyl group. Examples of the substituent that the aliphatic hydrocarbon group may have include an alkoxy group, an aryl group, a hydroxyl group, an amino group, and a halogen atom. The substituents may be used alone or in combination of two or more. The aliphatic hydrocarbon group may have two or more substituents, and the substituents in that case may be the same or different. When the aliphatic hydrocarbon group has a substituent, the total number of carbon atoms contained in the aliphatic hydrocarbon group and the substituent is preferably 1-18. From the viewpoint of curability, an unsubstituted alkyl group having 1 to 18 carbon atoms is preferable, an unsubstituted alkyl group having 1 to 8 carbon atoms is more preferable, and n-butyl group, iso-butyl, n-pentyl group, n A -hexyl group or an n-octyl group is more preferable.

  Moreover, a C1-C18 aliphatic hydrocarbon group also contains a C3-C18 alicyclic hydrocarbon group. The alicyclic hydrocarbon group may or may not have a substituent. Examples of the unsubstituted alicyclic hydrocarbon group having 1 to 18 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, and a cyclohexenyl group. Examples of the substituent that the alicyclic hydrocarbon group may have include an alkyl group such as a methyl group, an ethyl group, a butyl group, and a tert-butyl group, a methoxy group, an ethoxy group, a butoxy group, and a tert-butoxy group. Aryl groups such as alkoxy groups, phenyl groups, naphthyl groups, aryloxy groups, hydroxyl groups, amino groups, halogen atoms, and the like. The substituents may be used alone or in combination of two or more. The alicyclic hydrocarbon group may have two or more substituents, and the substituents in that case may be the same or different. When the alicyclic hydrocarbon group has a substituent, the total number of carbon atoms contained in the alicyclic hydrocarbon group and the substituent is preferably 3 to 18. From the viewpoint of curability, an unsubstituted cycloalkyl group having 3 to 18 carbon atoms is preferable, an unsubstituted cycloalkyl group having 4 to 10 carbon atoms is more preferable, and a cyclohexyl group, a cyclopentyl group, or a cycloheptyl group is further preferable. .

Examples of the unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms include aryl groups such as a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Examples of the substituent that the aromatic hydrocarbon group may have include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, and a halogen atom. The substituents may be used alone or in combination of two or more. Examples of the alkyl group-substituted aryl group include a tolyl group, a dimethylphenyl group, an ethylphenyl group, a butylphenyl group, and a tert-butylphenyl group. Examples of the alkoxy group-substituted aryl include a methoxyphenyl group, an ethoxyphenyl group, a butoxyphenyl group, and a tert-butoxyphenyl group.
The aromatic hydrocarbon group having 6 to 18 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms including a substituent, more preferably an aryl group having 6 to 10 carbon atoms from the viewpoint of fluidity. More preferred are a phenyl group, a p-tolyl group, and a p-methoxyphenyl group.

The term “two or more of R ^{1 to} R ³ may be bonded to each other to form a cyclic structure” described as R ^{1 to} R ^{3 in the} general formula (I-1) means that R ^{1 to} R ³ Of these, two or more are bonded to form a divalent or trivalent hydrocarbon group as a whole. Examples of R ^{1 to} R ^{3 in} this case include alkylene groups such as ethylene, propylene, butylene, pentylene, and hexylene, and alkenylene groups such as ethylenylene, propyleneylene, and butyleneylene that can be bonded to a phosphorus atom to form a cyclic structure; Examples of the substituent include an aralkylene group such as a methylenephenylene group; an arylene group such as phenylene, naphthylene, and anthracenylene; and the like, which can be bonded to a phosphorus atom to form a cyclic structure. These substituents may be further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen atom, or the like.

In addition, as R < ¹ > -R < ³ > of the said general formula (I-1), it does not specifically limit, Each monovalent chosen from the group which consists of the alkyl group and aryl group which may be substituted each independently. It is preferable that it is a substituent. Among these, from the viewpoint of easy availability of raw materials, R ^{1 to} R ³ are each independently an unsubstituted aryl group such as a phenyl group, 1-naphthyl group, 2-naphthyl group; p-tolyl group, m-tolyl group. An aryl group substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group such as o-tolyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group; A chain or cyclic alkyl group such as an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-butyl group, a tert-butyl group, an octyl group, or a cyclohexyl group is more preferable. From the viewpoint of reliability, R ^{1 to} R ³ are each independently an unsubstituted aryl group such as a phenyl group, 1-naphthyl group, 2-naphthyl group; or p-tolyl group, m-tolyl group, o-tolyl group. More preferably, the aryl group is substituted with at least one selected from the group consisting of a group, an alkyl group such as a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, and an alkoxy group. From the viewpoint of heat resistance, R ^{1 to} R ³ are each independently a chain such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-butyl group, a tert-butyl group, an octyl group, or a cyclohexyl group. A cyclic or cyclic alkyl group is preferred.

The “organic group having 1 to 18 carbon atoms” described as R ^{4 to} R ^{7 in the} general formula (I-1) has 1 to 18 carbon atoms and may be substituted or unsubstituted. It is meant to include a hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbon oxy group, an aromatic hydrocarbon oxy group, a carbonyl group, an oxycarbonyl group, and a carbonyloxy group.

As an example of the said aliphatic hydrocarbon group and aromatic hydrocarbon, what was mentioned above as an example of the aliphatic hydrocarbon group and aromatic hydrocarbon group represented by R < ¹ > -R < ³ > is mentioned.

  As the aliphatic hydrocarbon oxy group, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, 2-butoxy group, tert-butoxy group, cyclopropyloxy group, cyclohexyloxy group, cyclopentyloxy group An oxy group having a structure in which an oxygen atom is bonded to the above-mentioned aliphatic hydrocarbon group, such as an allyloxy group and a vinyloxy group, and these aliphatic hydrocarbon oxy groups are further alkyl groups, alkoxy groups, aryl groups, aryloxy groups, Examples thereof include those substituted with an amino group, a halogen atom or the like.

  Examples of the aromatic hydrocarbon oxy group include an oxy having a structure in which an oxygen atom is bonded to the above aromatic hydrocarbon group such as a phenoxy group, a methylphenoxy group, an ethylphenoxy group, a methoxyphenoxy group, a butoxyphenoxy group, and a phenoxyphenoxy group. Groups and those in which these aromatic hydrocarbon oxy groups are further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, and the like.

  Examples of the carbonyl group include a formyl group, an acetyl group, an ethylcarbonyl group, a butyryl group, a cyclohexylcarbonyl group, an aliphatic hydrocarbon carbonyl group such as allylcarbonyl, an aromatic hydrocarbon carbonyl group such as a phenylcarbonyl group, and a methylphenylcarbonyl group. These aliphatic hydrocarbon carbonyl groups or aromatic hydrocarbon carbonyl groups are further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, and the like.

  Examples of the oxycarbonyl group include aliphatic hydrocarbon oxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, allyloxycarbonyl group, cyclohexyloxycarbonyl group, and aromatic groups such as phenoxycarbonyl group and methylphenoxycarbonyl group. Hydrocarbon oxycarbonyl groups, etc., these aliphatic hydrocarbon carbonyloxy groups or aromatic hydrocarbon carbonyloxy groups further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, etc. Etc.

  Examples of the carbonyloxy group include methylcarbonyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, allylcarbonyloxy group, cyclohexylcarbonyloxy group and other aliphatic hydrocarbon carbonyloxy groups, phenylcarbonyloxy group, methylphenylcarbonyloxy An aromatic hydrocarbon carbonyloxy group such as a group, and these aliphatic hydrocarbon carbonyloxy groups or aromatic hydrocarbon carbonyloxy groups are further alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, etc. And the like substituted with.

The term “two or more of R ^{4 to} R ⁷ may be bonded to each other to form a cyclic structure” described as R ^{4 to} R ^{7 in the} general formula (I-1) means 2 to 4 R It means that ^{4 to} R ⁷ may be bonded to form a divalent to tetravalent organic group as a whole. R ^{4 to} R ^{7 in} this case include, for example, an alkylene group such as ethylene, propylene, butylene, pentylene, and hexylene; an alkenyl group such as ethylenyl, propylenyl, and butenyl group; an aralkylene group such as a methylenephenylene group; a phenylene, naphthylene, anthracenylene, and the like A substituent that can form a cyclic structure such as: an oxy group or a dioxy group thereof. These substituents may be further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen atom, or the like.

R ^{4 to} R ^{7 in the} general formula (I-1) are not particularly limited, and are each independently a hydrogen atom; an alkyl group, an aryl group, an alkoxy group, an aryloxy group that may be substituted. A group; Among these, from the viewpoint of availability of raw materials, R ^{4 to} R ⁷ are each independently a hydrogen atom; an unsubstituted aryl group such as a phenyl group; a p-tolyl group, an m-tolyl group, an o-tolyl group, an aryl group substituted with at least one selected from the group consisting of an alkyl group such as p-methoxyphenyl group and an alkoxy group; a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert- It is preferably a chain or cyclic alkyl group such as a butyl group, an octyl group, or a cyclohexyl group. From the viewpoint of heat resistance and ease of production, it is preferable that R ^{4 to} R ⁷ are all hydrogen atoms, or that one of R ^{4 to} R ⁷ is a hydroxyl group and the rest are all hydrogen atoms. .

  From the viewpoint of rapid curing, the compound represented by the general formula (I-1) preferably includes at least one selected from the compounds represented by the following general formulas (I-2) and (I-3). .

In formula (I-2), R ^{1 to} R ³ are each independently a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, and two or more R ^{1 to} R ³ are bonded to each other. A cyclic structure may be formed, and R ^{4 to} R ⁷ are each independently a hydrogen atom or a substituted or unsubstituted organic group having 1 to 18 carbon atoms, and two or more R ^{4 to} R ⁷ are They may be bonded together to form a ring structure.

In formula (I-3), R ^{1 to} R ³ are each independently a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, and two or more R ^{1 to} R ³ are bonded to each other. And R ^{4 to} R ⁶ are each independently a hydrogen atom or a substituted or unsubstituted organic group having 1 to 18 carbon atoms, and two or more R ^{4 to} R 6 ⁶ may combine with each other to form a ring structure.

Specific examples of ^R 1 to R ⁷ in the formula (I-2) and formula (I-3) is the same as specific examples of ^R 1 to R ^7, respectively, in formula (I-1), preferable range It is the same.

  As the compound represented by the general formula (I-1), specifically, an addition reaction product of triphenylphosphine and 1,4-benzoquinone, an addition reaction product of tri-p-tolylphosphine and 1,4-benzoquinone, tris (P-methoxyphenyl) phosphine and 1,4-benzoquinone addition reaction product, tri-n-butylphosphine and 1,4-benzoquinone addition reaction product, 4-triphenylphosphoniophenolate, tricyclohexylphosphine and 1, 4-benzoquinone addition reaction product, dicyclohexylphenylphosphine and 1,4-benzoquinone addition reaction product, cyclohexyldiphenylphosphine and 1,4-benzoquinone addition reaction product, tri-iso-butylphosphine and 1,4-benzoquinone addition product Reactants, tricyclopentylphosphine and 1,4-benzox An addition reaction product of triphenylphosphine and 1,4-benzoquinone, an addition reaction product of tri-p-tolylphosphine and 1,4-benzoquinone, tri-n-butylphosphine and 1,4 -At least one selected from the group consisting of an addition reaction product of benzoquinone and 4-triphenylphosphoniophenolate, more preferably an addition reaction product of triphenylphosphine and 1,4-benzoquinone, tri-p-tolylphosphine And at least one selected from the group consisting of an addition reaction product of 1,4-benzoquinone and an addition reaction product of tri-n-butylphosphine and 1,4-benzoquinone is more preferable.

The compound represented by the general formula (I-1) can be synthesized by a known addition reaction. Specifically, in a solvent in which a corresponding tertiary phosphine such as triphenylphosphine and tri-p-tolylphosphine and a corresponding quinone derivative such as 1,4-benzoquinone and 2,5-toluquinone are dissolved together. And a corresponding tertiary phosphine such as triphenylphosphine and tri-p-tolylphosphine, and 4-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, etc. An example is a method in which a halogenated phenol compound is reacted and then subjected to a dehydrohalogenation step. Examples of the solvent include aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, ketone solvents, alcohol solvents, ether solvents, amide solvents, ester solvents, water, and the like. These solvents may be used alone or in combination of two or more.
The reaction temperature in the addition reaction is not limited as long as the reaction proceeds and the compound (product) represented by the general formula (I-1) to be generated is stably maintained. And from the viewpoint of the stability of the product, it is preferably −20 ° C. to 200 ° C.

  The curable resin composition of this invention may contain 1 or more types of hardening accelerators other than the compound shown by general formula (I-1) as a hardening accelerator. Examples of the curing accelerator other than the compound represented by the general formula (I-1) include 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) and 1,8-diazabicyclo [5.4. 0] Cyclic amidine compounds such as diazabicycloalkenes such as undecen-7 (DBU), 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; Derivatives; Phenol novolac salts of the cyclic amidine compounds or derivatives thereof; maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6 -Dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-di Quinone compounds such as toxi-1,4-benzoquinone and phenyl-1,4-benzoquinone, compounds having intramolecular polarization formed by adding a compound having a π bond, such as diazophenylmethane; tetraphenylborate salt of DBU, Cyclic amidinium compounds such as DBN tetraphenylborate salt, 2-ethyl-4-methylimidazole tetraphenylborate salt, N-methylmorpholine tetraphenylborate salt; pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine , Tertiary amine compounds such as dimethylaminoethanol and tris (dimethylaminomethyl) phenol; derivatives of the tertiary amine compounds; tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraacetate Ammonium salt compounds such as ethylammonium, tetra-n-hexylammonium benzoate, tetrapropylammonium hydroxide; triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (Alkyl / alkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetra Tertiary phosphines such as alkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine Compound: A phosphine compound such as a complex of the tertiary phosphine compound and an organic boron compound; the tertiary phosphine or the phosphine compound and maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone A compound having intramolecular polarization formed by adding a compound having a π bond, such as a quinone compound such as diazophenylmethane (excluding the compound represented by formula (I-1)); the tertiary phosphine or the phosphine Compounds with 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol, 2-iodophenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo- 2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6- A compound having intramolecular polarization (general formula (I-) obtained by reacting a halogenated phenol compound such as bromo-2-naphthol or 4-bromo-4'-hydroxybiphenyl and then dehydrohalogenating the compound. 1)), and phenoxy bonded to boron atoms such as tetraphenylphosphonium and tetra p-tolylborate. Tetra-substituted phosphonium tetra-substituted borate no Le group; and salts with tetraphenylphosphonium and phenol compounds.

  When the curable resin composition of the present invention contains a curing accelerator other than the compound represented by the general formula (I-1) as the (C) curing accelerator, it is represented by the general formula (I-1) with respect to the total amount of the curing accelerator. The total content of the compounds to be obtained is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably 70% by mass or more. When the content is 30% by mass or more, the curability of the curable resin composition is improved and the heat resistance after curing tends to be improved.

  The amount of the (C) curing accelerator in the curable resin composition of the present invention is not particularly limited as long as a curing acceleration effect can be achieved. From the viewpoint of improving the curability and fluidity at the time of moisture absorption of the curable resin composition, the total amount of the (C) curing accelerator is 0.1 to 30 parts by mass with respect to 100 parts by mass of the total (A) epoxy resin. It is preferable that it is a mass part, and it is more preferable that it is 1 mass part-15 mass parts. When the content of the curing accelerator is 0.1 parts by mass or more, the composition tends to be cured well in a short time, and when it is 30 parts by mass or less, a curing rate is not too high and a good molded product tends to be obtained. It is in.

(D) Maleimide compound The curable resin composition of the present invention comprises (D) a maleimide compound. As a maleimide compound, if the effect of this invention is acquired, it will not specifically limit.
For example, a compound having one maleimide group in a molecule such as N-phenylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, 4,4′-diphenylmethane dimaleimide (CAS: 13676-54-5), N, N '-1,3-phenylene dimaleimide (CAS: 3006-93-7), 2,2'-bis [4- (4-maleimidophenoxy) phenyl] propane (CAS: 79922-55-7), 3, 3 '-Dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide (CAS: 105391-33-1), 4-methyl-1,3-phenylenebismaleimide (CAS: 6422-83-9), 1,6-bismaleimide- (2,2,4-trimethyl) hexane (CAS: 39979-46-9), polyphenylmethane Imide (CAS: 67784-74-1) and compounds having two or more maleimide groups in the molecule, such as.

  Among these, a maleimide compound having two or more maleimide groups in one molecule is preferable from the viewpoint of curability. Among these, from the viewpoint of obtaining a cured product having a high glass transition temperature, 4,4′-diphenylmethane dimaleimide (CAS: 13676-54-5), N, N′-1,3-phenylene dimaleimide (CAS: 3006). -93-7), 4-methyl-1,3-phenylenebismaleimide (CAS: 6422-83-9) and polyphenylmethanemaleimide (CAS: 67784-74-1) are more preferable, and from the viewpoint of long-term heat resistance. 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane (CAS: 79922-55-7) is more preferable, and from the viewpoint of fluidity, 1,6-bismaleimide- (2,2 , 4-trimethyl) hexane (CAS: 39979-46-9) is more preferred. (D) A maleimide compound may be used individually by 1 type, or may be used in combination of 2 or more type.

  The content of the (D) maleimide compound used in the present invention is not particularly limited as long as the effects of the present invention are obtained, and the mass ratio [((A) component) + ((B) component) ]: (Component (D)) is preferably 1:20 to 20: 1, more preferably 1:10 to 10: 1, and still more preferably 1: 5 to 5: 1.

(E) Inorganic filler The curable resin composition of the present invention may further contain (E) an inorganic filler as necessary. In particular, when the curable resin composition is used as a molding material for sealing, it is preferable to contain an inorganic filler.

  The inorganic filler is not particularly limited as long as it is generally used for a sealing molding material. Fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, talc, Examples thereof include fine powders such as clay and mica, or beads obtained by spheroidizing these. An inorganic filler having a flame retardant effect may be used. Examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxide such as composite hydroxide of magnesium and zinc, zinc borate and the like. Among these, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. These inorganic fillers may be used alone or in combination of two or more.

  When the curable resin composition contains an inorganic filler, the content of the inorganic filler is not particularly limited, and is preferably 55% by volume to 90% by volume, and 60% by volume in the total amount of the curable resin composition. It is more preferable that it is -90 volume%, and it is still more preferable that it is 60 volume%-85 volume%. When the content of the inorganic filler in the curable resin composition is 55% by volume or more, characteristics such as the thermal expansion coefficient, thermal conductivity, and elastic modulus of the cured product tend to be further improved. When it is 90% by volume or less, an increase in the viscosity of the curable resin composition is suppressed, and the fluidity is further improved and the moldability tends to be better.

The average particle size of the inorganic filler is preferably 1 μm to 50 μm, more preferably 10 μm to 30 μm. There exists a tendency for the raise of the viscosity of curable resin composition to be suppressed more as an average particle diameter is 1 micrometer or more. When the average particle size is 50μm or less, the separation between the resin component and the inorganic Filling agent is suppressed, the cured product uniformity is improved, the cured product properties Ibaraki is more effectively suppressed, narrow gap There exists a tendency for the filling property to improve more. The average particle size of the inorganic filler can be measured as a volume average particle size by a laser scattering diffraction particle size distribution analyzer.

  From the viewpoint of the fluidity of the curable resin composition, the particle shape of the inorganic filler is preferably spherical rather than square, and (E) the particle size distribution of the inorganic filler is preferably distributed over a wide range. For example, when the content of the inorganic filler in the curable resin composition is 75% by volume or more, the inorganic filler is distributed over a wide range of 70% by mass or more of spherical particles and a particle size distribution of 0.1 μm to 80 μm. Is preferably occupied. Since such inorganic fillers tend to have a close-packed structure, an increase in viscosity is suppressed even when the content in the curable resin composition is increased, and a curable resin composition having superior fluidity is obtained. Can do.

[Various additives]
The curable resin composition of the present invention further contains various additives such as a coupling agent, an ion exchanger, a release agent, a stress relaxation agent, a flame retardant, and a colorant exemplified below in addition to the above-described components. May be. In addition, the curable resin composition of this invention may contain the various additives well-known in this technical field as needed other than the additive illustrated below.

(Coupling agent)
The sealing curable resin composition of the present invention may contain a coupling agent as necessary in order to enhance the adhesiveness between the resin component and the inorganic filler. As coupling agents, known coupling agents such as various silane compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, and vinyl silane; titanium compounds; aluminum chelate compounds; aluminum / zirconium compounds; Can be mentioned.

  When the curable resin composition contains a coupling agent, the content of the coupling agent in the curable resin composition is preferably 0.05% by mass to 5% by mass with respect to the inorganic filler, 0.1 mass%-2.5 mass% is more preferable. When the content is 0.05% by mass or more, the adhesion to the frame tends to be further improved, and when it is 5% by mass or less, the moldability of the package tends to be further improved.

(Ion exchanger)
The curable resin composition of the present invention may contain an ion exchanger as necessary. In particular, when a curable resin composition is used as a molding material for sealing, it may contain an ion exchanger from the viewpoint of improving the moisture resistance and high temperature storage characteristics of an electronic component device provided with an element to be sealed. preferable. There is no restriction | limiting in particular as an ion exchanger, A conventionally well-known thing can be used. Specific examples include hydrotalcite compounds and hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth. These ion exchangers can be used singly or in combination of two or more. Especially, the hydrotalcite shown by the following general formula (A) is preferable.

Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (A)
(0 <X ≦ 0.5, m is a positive number)

  When the curable resin composition contains an ion exchanger, the content is not particularly limited as long as it is an amount sufficient to trap ions such as halogen ions. For example, it is preferable that it is 0.1-30 mass% with respect to (A) epoxy resin, and it is more preferable that it is 1-5 mass%.

(Release agent)
The curable resin composition of the present invention may contain a release agent from the viewpoint of obtaining good release properties from the mold during molding. There is no restriction | limiting in particular as a mold release agent, A conventionally well-known thing can be used. Specific examples include carnauba wax, higher fatty acids such as montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene. These release agents may be used alone or in combination of two or more. Among these, oxidized or non-oxidized polyolefin wax is preferable. Examples of polyolefin waxes include low molecular weight polyethylene having a number average molecular weight of about 500 to 10,000, such as H4, PE, and PED series manufactured by Hoechst.

When the curable resin composition contains an oxidized or non-oxidized polyolefin wax, the content is preferably 0.01% by mass to 10% by mass with respect to the total amount of (A) epoxy resin. 1 mass%-5 mass% are more preferable. If the content of the polyolefin wax is 0.01% by mass or more, release properties tend to be sufficiently obtained, and if it is 10% by mass or less, better adhesiveness tends to be obtained.
Moreover, when using another mold release agent together with polyolefin-type wax, 0.1 mass%-10 mass% are preferable with respect to the total amount of (A) epoxy resin, and 0.5% of the content of another mold release agent is preferable. A mass% to 3 mass% is more preferable.

(Stress relaxation agent)
The curable resin composition of the present invention may contain a stress relaxation agent such as silicone oil or silicone rubber powder, if necessary. By containing the stress relaxation agent, warpage deformation of the package and generation of package cracks can be further reduced. As a stress relaxation agent, if it is a well-known flexible agent (stress relaxation agent) generally used, it will not specifically limit. Specifically, for example, silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, polybutadiene-based thermoplastic elastomers, NR (natural rubber), NBR (acrylonitrile-butadiene rubber) , Rubber particles such as acrylic rubber, urethane rubber and silicone powder, cores such as methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer -Rubber particles having a shell structure. These flexible agents may be used alone or in combination of two or more. Among these, silicone-based flexible agents are preferable, and examples of silicone-based flexible agents include those having an epoxy group, those having an amino group, and those obtained by modifying these with a polyether.

(Flame retardants)
The curable resin composition of this invention may contain a flame retardant as needed from a viewpoint of providing a flame retardance. There is no restriction | limiting in particular as a flame retardant, It can select suitably from the well-known flame retardant generally used. Specifically, a known organic or inorganic compound containing a halogen atom, an antimony atom, a nitrogen atom or a phosphorus atom, a metal hydroxide, and the like can be given. These flame retardants may be used alone or in combination of two or more. When the curable resin composition contains a flame retardant, the content is not particularly limited as long as the flame retardant effect is achieved. For example, 1 mass%-30 mass% are preferable with respect to the total amount of (A) epoxy resin, and 2 mass%-15 mass% are more preferable.

(Coloring agent)
The curable resin composition of the present invention may further contain a colorant as necessary. Examples of the colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, pitch, red lead, and bengara. The content of the colorant can be appropriately selected according to the purpose and the like.

[Method for Preparing Curable Resin Composition]
The method for preparing the curable resin composition is not particularly limited, and any method can be used as long as various components can be uniformly dispersed and mixed. As a general technique, there can be mentioned a method in which components of a predetermined blending amount are sufficiently mixed by a mixer or the like, then melt-kneaded by a mixing roll, an extruder or the like, cooled and pulverized. More specifically, for example, a predetermined amount of the above-mentioned components are uniformly stirred and mixed, kneaded with a kneader, roll, extruder, etc., heated to 70 ° C. to 140 ° C. in advance, cooled, and pulverized. Can be obtained. The curable resin composition is easy to handle if it is tableted with dimensions and mass that match the molding conditions of the package.

<Electronic component device>
The electronic component device of the present invention includes an element and a cured product of the above-described curable resin composition that seals the element. An electronic component device produced using the curable resin composition of the present invention is excellent in reliability.
Electronic component devices include, for example, lead frames, wired tape carriers, wiring boards, glass, silicon wafers, and other supporting members, active elements such as semiconductor chips, transistors, diodes, thyristors, capacitors, resistors, coils, etc. What encapsulated the element part obtained by mounting elements, such as these passive elements, with the curable resin composition of this invention is mentioned. More specifically, for example, after fixing a semiconductor element on a lead frame and connecting the terminal part of the element such as a bonding pad and the lead part by wire bonding, bumps, etc., the curable resin composition of the present invention is used. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outer Package), SOJ (Small Outer Jap) , TSOP (Thin Small Outline Package), TQFP (Thin Quad Flat Package), etc. TCP (Tape Carrier Package) having a structure in which connected semiconductor chips are sealed with the curable resin composition of the present invention; wire bonding, flip chip bonding, soldering, etc. on wiring formed on a wiring board or glass plate At least one element selected from the group consisting of active elements such as semiconductor chips, transistors, diodes, thyristors, etc., and passive elements such as capacitors, resistors, coils, etc., is sealed with the curable resin composition of the present invention. COB (Chip On Board) having a structure as described above: Module, hybrid IC, multi-chip module, device mounted on the surface of an organic substrate on which a wiring board connection terminal is formed on the back surface, and device and organic substrate by bump or wire bonding After connecting the wiring formed on, the curability of the present invention BGA having sealed structure elements in fat composition (Ball Grid Array), CSP (Chip Size Package); and the like. Moreover, the curable resin composition of this invention can be used effectively also in a wiring board.

  As a method for sealing an electronic component device using the curable resin composition of the present invention, a low-pressure transfer molding method is generally used, but an injection molding method, a compression molding method, or the like may be used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the scope of the present invention is not restrict | limited by the Example shown below.

[Preparation of curable resin composition and evaluation of its properties]
The following were prepared as epoxy resins.
Epoxy resin 1: triphenylmethane type epoxy resin having an epoxy equivalent of 168 and a softening point of 62 ° C. (Japan Epoxy Resin Co., Ltd., trade name: 1032H60)
Epoxy resin 2: Ortho-cresol novolac type epoxy resin having an epoxy equivalent of 195 and a softening point of 60 ° C. (DIC Corporation, trade name: N-500P1)
Epoxy resin 3: biphenylene aralkyl type epoxy resin having an epoxy equivalent of 282 and a softening point of 56 ° C. (Nippon Kayaku Co., Ltd., trade name NC-3000)

The following were prepared as phenolic resins.
Phenol resin 1: Triphenylmethane type phenol resin (trade name HE-910-10 manufactured by Air Water Co., Ltd.) having a hydroxyl group equivalent of 103 and a softening point of 84 ° C.
Phenol resin 2: phenol novolak resin having a hydroxyl group equivalent of 106 and a softening point of 85 ° C. (trade name HP-850N, manufactured by Hitachi Chemical Co., Ltd.)
-Phenol resin 3: A biphenylene aralkyl type phenol resin (trade name HE-200C-10, manufactured by Air Water Co., Ltd.) having a hydroxyl group equivalent of 190 and a softening point of 80 ° C was prepared.

The following were prepared as the curing accelerator according to the present invention.
Curing accelerator 1: addition reaction product of tri-n-butylphosphine and 1,4-benzoquinone

The following were prepared as maleimide compounds.
-Maleimide 1: Polyphenylmethane maleimide (Daiwa Kasei Kogyo Co., Ltd., trade name BMI-2300)

The following were prepared as inorganic fillers.
-Spherical fused silica having an average particle size of 17.5 μm and a specific surface area of 3.8 m ² / g

In addition, the following were prepared as various additives.
Coupling agent: Epoxy silane (γ-glycidoxypropyltrimethoxysilane) Coloring agent: Carbon black (Mitsubishi Chemical Corporation, trade name MA-100)
・ Release agent: Carnauba wax (Serarica NODA)

  The above components are blended in parts by weight shown in Table 1, and roll kneading is carried out under the conditions of a kneading temperature of 80 ° C. and a kneading time of 15 minutes, whereby the curable resins of Examples 1 and 2 and Comparative Examples 1 to 4, respectively. A composition was obtained.

  Next, the curable resin composition obtained by Examples 1-2 and Comparative Examples 1-4 was evaluated by the various tests shown below. The evaluation results are shown in Table 2. The curable resin composition was molded using a transfer molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Further, post-curing was performed at 250 ° C. for 6 hours.

(1) Spiral flow (fluidity index)
A curable resin composition was molded under the above conditions using a spiral flow measurement mold according to EMMI-1-66. Next, the flow distance (cm) of the molded product of the curable resin composition was measured.

(2) Hardness upon heating The curable resin composition was molded into a disk having a diameter of 50 mm and a thickness of 3 mm under the above conditions. Immediately after molding, the hardness of the molded product of the curable resin composition was measured using a Shore D hardness meter.

(3) Glass transition temperature (TMA)
The curable resin composition was molded into a 3.0 mm × 3.0 mm × 19 mm test piece under the above conditions and post-cured. Subsequently, the linear expansion curve was measured using a thermal analysis system (TMA / SS6000) manufactured by Seiko Instruments Inc. at a temperature rising rate of 5 ° C./min, and the inflection point was defined as the glass transition temperature (TMA) (° C.). .

(4) Glass transition temperature (DMA)
The curable resin composition was molded into a size of 80 mm length × 10 mm width × 3 mm thickness under the above conditions and post-cured. Next, it is cut into a length of 55 mm with a diamond cutter, using a viscoelasticity measuring device ARES (manufactured by Rheometric Scientific FE Co., Ltd.) in a dynamic mode under conditions of a heating rate of 5 ° C. and a frequency of 6.28 rad / s. The glass transition temperature (DMA) (° C.) was determined from the measurement of tan δ.

(5) 250 ° C. elastic modulus / 60 ° C. elastic modulus (index of heat resistance)
The storage elastic modulus at 60 ° C. and 250 ° C. was determined from the measurement in (4) above, and the ratio of the elastic modulus at 250 ° C. to the elastic modulus at 60 ° C. was calculated. It means that the larger the obtained value, the smaller the difference from room temperature at high temperature, and it can be judged that the heat resistance after curing is excellent.

(6) Reflow resistance 80mm flat package (QFP) with external dimensions of 20mm x 14mm x 2mm mounted with 8mm x 10mm x 0.4mm silicon chip (lead frame material: copper alloy, die pad top surface and lead tip silver plating Processed product) was molded under the above conditions using an epoxy resin molding material for sealing, and post-cured under the above conditions.
The resulting package was humidified for 168 hours at 30 ° C. and 60% RH. Thereafter, reflow treatment is performed under conditions of 245 ° C. for 10 seconds, the presence or absence of cracks outside the package is visually observed, and the presence or absence of peeling inside the package is detected with an ultrasonic flaw detector (HYE-FOCUS manufactured by Hitachi Construction Machinery Co., Ltd.) Each was observed. Reflow resistance was evaluated based on the total number of packages in which either cracks or peeling occurred with respect to the number of test packages (10).

As can be seen from Table 2, Examples 1 and 2 according to the present invention have excellent 250 ° C. elastic modulus / 60 ° C. elastic modulus, which is an index of heat resistance, high glass transition temperature, and excellent reflow resistance. It became. In addition, both are excellent in spiral flow and hot hardness and can be molded well.
On the other hand, Comparative Example 4 containing no maleimide compound according to the present invention has remarkably low 250 ° C. elastic modulus / 60 ° C. elastic modulus and glass transition temperature, which are heat resistance indicators. In Comparative Examples 1 to 3 in which the epoxy resin and the phenol resin are different from the present invention, the heat resistance index 250 ° C./60° C. was good, but the reflow resistance was poor.

Claims (9)

(A) an epoxy resin, (B) a phenol resin, (C) a curing accelerator, and (D) a maleimide compound, wherein the (C) curing accelerator is a compound represented by the following general formula (I-1) A curable resin composition containing and satisfying at least one of the following.
(A) The epoxy resin contains an aralkyl type epoxy resin.
(B) A phenol resin contains an aralkyl type phenol resin.

[In Formula (I-1), R ^{1 to} R ³ are each independently a hydrocarbon group having 1 to 18 carbon atoms, and two or more of R ^{1 to} R ³ are bonded to each other to form a cyclic structure. R ^{4 to} R ⁷ may each independently be a hydrogen atom, a hydroxyl group, or an organic group having 1 to 18 carbon atoms, and two or more of R ^{4 to} R ⁷ are bonded to each other to form a ring. A structure may be formed. ] (C) The curable resin composition of Claim 1 in which a hardening accelerator contains the compound shown by the following general formula (I-2).

[In Formula (I-2), R ^{1 to} R ³ are each independently a hydrocarbon group having 1 to 18 carbon atoms, and two or more of R ^{1 to} R ³ are bonded to each other to form a cyclic structure. R ^{4 to} R ⁷ are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, and two or more of R ^{4 to} R ⁷ are bonded to each other to form a cyclic structure. It may be formed. ] (C) The curable resin composition of Claim 1 in which a hardening accelerator contains the compound shown by the following general formula (I-3).

[In Formula (I-3), R ^{1 to} R ³ are each independently an aliphatic hydrocarbon group having 1 to 18 carbon atoms, and two or more of R ^{1 to} R ³ are bonded to each other to form a ring. R ^{4 to} R ⁶ are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, and two or more of R ^{4 to} R ⁶ are bonded to each other to form a structure. A structure may be formed. ]   (D) The curable resin composition according to any one of claims 1 to 3, wherein the maleimide compound is a compound having two or more maleimide groups in one molecule.   The curable resin composition according to any one of claims 1 to 4, further comprising (E) an inorganic filler.   (A) The epoxy resin is a biphenyl type epoxy resin, a stilbene type epoxy resin, a diphenylmethane type epoxy resin, a sulfur atom-containing type epoxy resin, a novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a triphenylmethane type epoxy resin, The curable resin composition according to any one of claims 1 to 5, comprising one or more epoxy resins selected from the group consisting of polymerizable epoxy resins.   The (B) phenol resin contains at least one phenol resin selected from the group consisting of a dicyclopentadiene type phenol resin, a salicylaldehyde type phenol resin, and a novolac type phenol resin. The curable resin composition according to Item.   (D) The maleimide compound is 4,4′-diphenylmethane dimaleimide, N, N′-1,3-phenylene dimaleimide, 4-methyl-1,3-phenylene bismaleimide, polyphenylmethane maleimide, 2,2 ′. 2. At least one compound selected from the group consisting of -bis [4- (4-maleimidophenoxy) phenyl] propane and 1,6-bismaleimide- (2,2,4-trimethyl) hexane. The curable resin composition according to claim 7.   An electronic component device comprising: an element; and a cured product of the curable resin composition according to any one of claims 1 to 8, which seals the element.