阅读说明：本技术 组合物、环氧树脂硬化剂、环氧树脂组合物、热硬化性组合物、硬化物、半导体装置及层间绝缘材料 (Composition, epoxy resin curing agent, epoxy resin composition, thermosetting composition, cured product, semiconductor device, and interlayer insulating material ) 是由 高桥航 村田清贵 于 2018-06-15 设计创作，主要内容包括：含有下述通式(1)所表示的马来酰亚胺化合物(A)、下述通式(2)所表示的氨基酚化合物(B)及下述通式(3)所表示的酚化合物(C)的组合物适合作为可满足高阻燃性、高耐热性及高温下低分解特性的环氧树脂组合物的硬化剂,且所述组合物具有优异的保存稳定性。(式(1)中,Ar<Sup>1</Sup>为可存在取代基的碳数6～12的亚芳基,X<Sup>1</Sup>为直接键、碳数1～6的二价烃基、O、S或SO<Sub>2</Sub>,p为0～2的整数)(式(2)中,Ar<Sup>2</Sup>为以0个～2个的范围包含羟基且可存在烃的取代基的碳数6～12的亚芳基,X<Sup>2</Sup>为直接键、碳数1～6的二价烃基、O、S或SO<Sub>2</Sub>,q为0～2的整数)(式(3)中,Ar<Sup>3</Sup>为以一分子内的烯丙基数成为2个～4个的范围的方式包含烯丙基且以0个～2个的范围包含羟基的碳数6～24的亚芳基,X<Sup>3</Sup>为直接键、碳数1～6的二价烃基、O、S或SO<Sub>2</Sub>,r为0～2的整数)<Image he="523" wi="700" file="DDA0002325728880000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(A composition containing a maleimide compound (A) represented by the following general formula (1), an aminophenol compound (B) represented by the following general formula (2) and a phenol compound (C) represented by the following general formula (3) is suitable as a curing agent for an epoxy resin composition which satisfies high flame retardancy, high heat resistance and low decomposition characteristics at high temperatures, and the composition has excellent storage stability. (in the formula (1), Ar 1 Is an arylene group having 6 to 12 carbon atoms in which a substituent may be present, X 1 Is a direct bond, carbon number1 to 6 divalent hydrocarbon group, O, S or SO 2 P is an integer of 0 to 2) (Ar in the formula (2) 2 An arylene group having 6 to 12 carbon atoms containing a hydroxyl group in the range of 0 to 2 and optionally having a hydrocarbon substituent, X 2 Is a direct bond, a C1-C6 divalent hydrocarbon group, O, S or SO 2 Q is an integer of 0 to 2) (Ar in the formula (3) 3 An arylene group having 6 to 24 carbon atoms which contains an allyl group so that the number of allyl groups in one molecule is in the range of 2 to 4 and a hydroxyl group in the range of 0 to 2, X 3 Is a direct bond, a C1-C6 divalent hydrocarbon group, O, S or SO 2 And r is an integer of 0 to 2))

1. A composition comprising a maleimide compound (A) represented by the following general formula (1), an aminophenol compound (B) represented by the following general formula (2), and a phenol compound (C) represented by the following general formula (3).

[ solution 1]

(in the formula (1), Ar¹Is an arylene group having 6 to 12 carbon atoms in which a substituent may be present, X¹Is a direct bond, a C1-C6 divalent hydrocarbon group, OS or SO₂And p is an integer of 0 to 2. )

[ solution 2]

(in the formula (2), Ar²An arylene group having 6 to 12 carbon atoms containing a hydroxyl group in the range of 0 to 2 and optionally having a hydrocarbon substituent, X²Is a direct bond, a C1-C6 divalent hydrocarbon group, O, S or SO₂And q is an integer of 0 to 2. )

[ solution 3]

(in formula (3), Ar³An arylene group having 6 to 24 carbon atoms which contains an allyl group so that the number of allyl groups in one molecule is in the range of 2 to 4 and a hydroxyl group in the range of 0 to 2, X³Is a direct bond, a C1-C6 divalent hydrocarbon group, O, S or SO₂And r is an integer of 0 to 2. )

2. The composition according to claim 1, wherein the melt viscosity at 150 ℃ is 20 mPas or more and 750 mPas or less, the hydroxyl equivalent weight is 300g/eq or more and 1500g/eq or less, and the rate of change in the melt viscosity at 150 ℃ after storage in an environment at35 ℃ for 1 week is 100% or less.

3. The composition according to claim 1 or 2, further comprising a reaction product of the maleimide compound (a) and the aminophenol compound (B).

4. The composition according to claim 3, wherein the reaction product is a Michael adduct of the maleimide compound (A) and the aminophenol compound (B).

5. The composition according to any one of claims 1 to 4, which is a melt-mixture of a composition comprising the maleimide compound (A), the aminophenol compound (B) and the phenol compound (C).

6. The composition according to any one of claims 1 to 5, wherein the total number of partial structures based on maleimide groups derived from the maleimide compound (A) is 1.5 times or more and 2.5 times or less the total number of partial structures based on primary amino groups derived from the aminophenol compound (B) and partial structures based on allyl groups derived from the phenol compound (C).

7. The composition according to any one of claims 1 to 6, wherein the phenol compound (C) comprises a bisphenol compound (C1) represented by the following general formula (4).

[ solution 4]

(in the formula (4), R⁴And R⁵Each independently a C1-4 hydrocarbon group, R⁶And R⁷Each independently represents a hydrogen atom, a methyl group, a phenyl group, and c and d each independently represents an integer of 0 to 3).

8. The composition according to any one of claims 1 to 7, wherein, in the maleimide compound (A), p in the general formula (1) is 0 or 1.

9. The composition according to any one of claims 1 to 8, wherein the aminophenol compound (B) is a phenylenediamine compound (B1) represented by the following general formula (5).

[ solution 5]

(in the formula (5), R²A C1-4 hydrocarbon group, b is an integer of 0-4).

10. An epoxy resin hardener comprising the composition of any one of claims 1 to 9.

11. An epoxy resin composition comprising the epoxy resin hardener of claim 10 and an epoxy resin.

12. The epoxy resin composition of claim 11, further comprising a hardening accelerator.

13. The epoxy resin composition according to claim 12, wherein the hardening accelerator comprises one or more selected from the group consisting of imidazole compounds, urea compounds and phosphonium salts.

14. The epoxy resin composition according to claim 13, wherein the hardening accelerator comprises an imidazole-based compound and a urea-based compound.

15. The epoxy resin composition according to any one of claims 11 to 14, further comprising an inorganic filler.

16. A cured product of the epoxy resin composition as claimed in any one of claims 11 to 15.

17. A thermosetting composition comprising the composition as claimed in any one of claims 1 to 9.

18. The thermosetting composition according to claim 17, further comprising an inorganic filler.

19. A cured product of the thermosetting composition according to claim 17 or 18.

20. A semiconductor device sealed with the epoxy resin composition according to any one of claims 11 to 15 or the thermosetting composition according to claim 17 or 18.

21. An interlayer insulating material comprising the epoxy resin composition according to any one of claims 11 to 15 or the thermosetting composition according to claim 17 or 18.

Technical Field

The present invention relates to a composition suitable as a component of a curing agent for an epoxy resin or a component of a thermosetting composition, an epoxy resin curing agent containing the composition, an epoxy resin composition containing the epoxy resin curing agent, a cured product of the epoxy resin composition, a thermosetting composition containing the composition, a cured product of the thermosetting composition, a semiconductor device sealed with the epoxy resin composition or the thermosetting composition, and an interlayer insulating material containing the epoxy resin composition or the thermosetting composition. In the present specification, the term "thermosetting composition" refers to a composition having thermosetting properties, and the term "epoxy resin composition" refers to a composition containing a resin having an epoxy group, and the term concept of the "thermosetting composition" overlaps with the term concept of the "epoxy resin composition".

Background

Phenol-based curing agents, which are a large group of curing agents for epoxy resins, are used in various industries due to their characteristics such as low cost, in addition to their wide variety. Many of these hardeners have been developed so far in order to meet various required performances accompanying the progress of industrial technology.

In the field of electronic materials, in recent years, with the miniaturization, thinning and complication of the shape of semiconductor packages, resins for semiconductor sealing materials are increasingly required to have low viscosity. When the viscosity is low, the fluidity is improved, and the resin composition can be applied to a package having a complicated shape, such as a Ball Grid Array (BGA), and the like, and also, by realizing high filling of a filler, it is advantageous in terms of flame retardancy, solder heat resistance, and moisture resistance reliability required for the above-mentioned applications.

In addition, in consideration of global environment, there is an increasing demand for a novel flame-retardant epoxy resin composition that replaces the flame retardants such as halogen-containing compounds and antimony compounds used so far, and there is a demand for a phenol aralkyl resin used in applications ranging from general encapsulation to advanced encapsulation, which has excellent flame retardancy without using a halogen-containing flame retardant and an antimony compound. As a material for meeting such a demand, a phenol aralkyl resin having a biphenyl skeleton introduced therein is known to have high flame retardancy and to be used for advanced sealing applications (for example, patent document 1).

The flame-retardant epoxy resin composition described in patent document 1 tends to have a low glass transition temperature (Tg), and a decrease in Tg generally causes a decrease in high-temperature reliability and heat resistance, and therefore it is desired to provide an epoxy resin hardener that can improve the above-mentioned situation. In particular, high heat resistance is required for a sealing material for power devices mounted in electric vehicles and hybrid vehicles which are expected to become more and more popular in the future. Further, as for heat resistance, the sealing material is also required to have a property of low thermal decomposition property at high temperatures (hereinafter referred to as "low decomposition property at high temperatures") as a physical property requirement of the sealing material in recent years. In response to the above-mentioned demand, patent document 2 describes a composition obtained by melt-mixing a specific phenol compound at a certain ratio in addition to a maleimide compound. The composition is suitable for use as a component of a thermosetting composition such as a component of an epoxy resin curing agent, and by using the composition, a thermosetting composition capable of forming a cured product having high flame retardancy, high heat resistance and low decomposition property at high temperature can be obtained.

Disclosure of Invention

Problems to be solved by the invention

By using the composition described in patent document 2, a cured product having the above-described excellent characteristics can be provided. If the excellent characteristics of the composition can be maintained and the storage stability can be further improved (the composition is less likely to undergo a biological change even after long-term storage), the value of the composition as an industrial product can be further improved.

The purpose of the present invention is to provide a composition which is suitable as a component of a curing agent for an epoxy resin or a component of a thermosetting composition that can satisfy high flame retardancy, high heat resistance, and low decomposition characteristics at high temperatures, and which also has excellent storage stability. Further, an object of the present invention is to provide an epoxy resin curing agent containing the above composition, an epoxy resin composition containing the epoxy resin curing agent, a cured product of the epoxy resin composition, a thermosetting composition containing the above composition, a cured product of the thermosetting composition, a semiconductor device sealed with the epoxy resin composition or the thermosetting composition, and an interlayer insulating material containing the epoxy resin composition or the thermosetting composition.

Means for solving the problems

As a result of diligent research to solve the above problems, the present inventors have found that the aromatic amine compound in the components of the composition described in patent document 2 easily affects the melt viscosity or storage stability of the composition, and have obtained the following new findings: by changing a part of the plurality of amino groups of the aromatic amine compound to a hydroxyl group to prepare an aminophenol compound, the melt viscosity of the composition, particularly the melt viscosity at 150 ℃, can be reduced, and the storage stability can be improved.

The present invention has been accomplished based on the above-mentioned findings, and in one embodiment, provides a composition containing a maleimide compound (a) represented by the following general formula (1), an aminophenol compound (B) represented by the following general formula (2), and a phenol compound (C) represented by the following general formula (3).

[ solution 1]

(in the formula (1), Ar¹Is an arylene group having 6 to 12 carbon atoms in which a substituent may be present, X¹Is a direct bond, a C1-C6 divalent hydrocarbon group, O, S or SO₂P is an integer of 0 to 2)

[ solution 2]

(in the formula (2), Ar²An arylene group having 6 to 12 carbon atoms containing a hydroxyl group in the range of 0 to 2 and optionally having a hydrocarbon substituent, X²Is a direct bond, a C1-C6 divalent hydrocarbon group, O, S or SO₂Q is an integer of 0 to 2)

[ solution 3]

(in formula (3), Ar³An arylene group having 6 to 24 carbon atoms which contains an allyl group so that the number of allyl groups in one molecule is in the range of 2 to 4 and a hydroxyl group in the range of 0 to 2, X³Is a direct bond, a C1-C6 divalent hydrocarbon group, O, S or SO₂And r is an integer of 0 to 2)

The composition preferably has a melt viscosity of 50 to 1000 mPas at 150 ℃ and a hydroxyl equivalent of 300 to 1500 g/eq.

The composition may also further contain a reaction product of the maleimide compound (A) and the aminophenol compound (B). The reaction product may be a Michael (Michael) adduct of the maleimide compound (a) and the aminophenol compound (B).

The composition may be a melt-mixture of the composition comprising the maleimide compound (a), the aminophenol compound (B) and the phenol compound (C).

In the composition, the total number of the partial structures based on the maleimide group derived from the maleimide compound (a) may be 1.5 times or more and 2.5 times or less the total number of the partial structures based on the primary amino group derived from the aminophenol compound (B) and the partial structure based on the allyl group derived from the phenol compound (C).

The phenol compound (C) preferably contains a bisphenol compound (C1) represented by the following general formula (4).

[ solution 4]

(in the formula (4), R⁴And R⁵Each independently a C1-4 hydrocarbon group, R⁶And R⁷Each independently represents a hydrogen atom, a methyl group, a phenyl group, c and d each independently represents an integer of 0 to 3)

The maleimide compound (A) is preferably such that p in the general formula (1) is 0 or 1. The aminophenol compound (B) is preferably a phenylenediamine compound (B1) represented by the following general formula (5).

[ solution 5]

(in the formula (5), R²A C1-4 hydrocarbon group, b is an integer of 0-4)

As another embodiment, the present invention provides an epoxy resin hardener comprising the composition of the present invention.

In another embodiment, the present invention provides an epoxy resin composition comprising the epoxy resin hardener of the present invention and an epoxy resin.

The epoxy resin composition of the present invention may also further comprise a hardening accelerator. In this case, the hardening accelerator preferably includes one or more selected from the group consisting of imidazole compounds, urea compounds and phosphonium salts, and the hardening accelerator more preferably includes imidazole compounds and urea compounds.

The epoxy resin composition of the present invention may further contain an inorganic filler.

In still another embodiment, the present invention provides a cured product of the epoxy resin composition of the present invention.

In still another embodiment, the present invention provides a thermosetting composition comprising the composition of the present invention. The thermosetting composition may further contain an inorganic filler.

In still another embodiment, the present invention provides a cured product of the thermosetting composition of the present invention.

In still another embodiment, the present invention provides a semiconductor device sealed with the epoxy resin composition of the present invention or the thermosetting composition of the present invention, and an interlayer insulating material containing the epoxy resin composition of the present invention or the thermosetting composition of the present invention.

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention provides a composition which is suitable as a component of a curing agent for an epoxy resin or a component of a thermosetting composition satisfying high flame retardancy, high heat resistance and low decomposition property at high temperature, and which is excellent in handling property and storage stability. Further, according to the present invention, there can be provided an epoxy resin curing agent containing the composition, an epoxy resin composition containing the epoxy resin curing agent, an epoxy resin cured product of the epoxy resin composition, a thermosetting composition containing the composition, a cured product of the thermosetting composition, a semiconductor device sealed with the epoxy resin composition or the thermosetting composition, and an interlayer insulating material containing the epoxy resin composition or the thermosetting composition.

Detailed Description

Hereinafter, embodiments of the present invention will be described.

The composition according to one embodiment of the present invention (hereinafter, the composition is also referred to as "the present composition") contains the maleimide compound (a) represented by the general formula (1), the aminophenol compound (B) represented by the general formula (2), and the phenol compound (C) represented by the general formula (3). In one embodiment, the present composition is a melt-mixture of the compositions comprising the maleimide compound (a), the aminophenol compound (B) and the phenol compound (C).

Preferred examples of the maleimide compound (A) can be easily obtained by condensing maleic anhydride with bifunctional aromatic amines (see, for example, Japanese patent laid-open No. Sho 60-260623). The maleimide compound (A) contained in the present composition preferably has a melting point of 100 to 250 ℃.

Specific examples of the maleimide compound (a) include: n, N '-4,4' -diphenylmethane bismaleimide, N '-m-phenylene bismaleimide, N' -4,4 '-diphenyl ether bismaleimide, N' -m-xylene bismaleimide, and the like. Among these compounds, the maleimide compound (a) is preferably one in which p in the general formula (1) is 0 or 1, more preferably one containing N, N '-4,4' -diphenylmethane bismaleimide as an example of a substance in which p in the general formula (1) is 1, and particularly preferably one formed from the above-mentioned substance, from the viewpoint of imparting heat resistance. Further, N, N '-4,4' -diphenylmethane bismaleimide in the general formula (1), Ar¹Is phenylene, X¹Is methylene.

Specific examples of the aminophenol compound (B) include: 2-aminophenol, 3-aminophenol, 4-phenyl-2-aminophenol, 4, 6-dimethyl-3-aminophenol, 3-methyl-4-aminophenol, 2-amino-2 '-hydroxybiphenyl, 3-amino-3' -hydroxydiphenylmethane, 4-amino-4 '-hydroxydiphenyl ether, 2-amino-3' -hydroxydiphenyl sulfide, 4-amino-3 ',4' -diHydroxydiphenylsulfone, and the like. Among these compounds, the value of q in the aminophenol compound (B) is preferably 0 from the viewpoint of fluidity under heat and easiness of acquisition, and further includes Ar from the viewpoint of curability²More preferably 6 to 7 carbon atoms inclusive of the substituent. From the viewpoint of particularly improving the storage stability, the aminophenol compound (B) preferably has one hydroxyl group.

Examples of the phenol compound (C) include allylated compounds of bisphenol compounds, allylated phenol novolac resins, and the like. Of these compounds, the phenol compound (C) preferably contains the bisphenol compound (C1) represented by the above general formula (4), and more preferably is formed of the bisphenol compound (C1). The specific structure of the bisphenol compound (C1) is not limited. Can exemplify: bisphenol A structure, bisphenol F structure, bisphenol AP structure, bisphenol BP structure, etc. By having such a structure, appropriate fluidity during molding and appropriate heat resistance of a molded article can be ensured. Specific examples of the bisphenol compound (C1) include: 4,4' - (dimethylmethylene) bis [2- (2-propenyl) phenol ], 4' -methylenebis [2- (2-propenyl) phenol ], 4' - (dimethylmethylene) bis [2- (2-propenyl) -6-methylphenol ], and the like. When the phenol compound (C) contains a bisphenol compound (C1), the bisphenol compound (C1) preferably contains 4,4'- (dimethylmethylene) bis [2- (2-propenyl) phenol ], and the phenol compound (C) is more preferably formed from 4,4' - (dimethylmethylene) bis [2- (2-propenyl) phenol ].

The present composition may further contain a reaction product of the maleimide compound (A) and the aminophenol compound (B). In this case, the reaction product may be a michael adduct of the maleimide compound (a) and the aminophenol compound (B).

From the viewpoint of easy availability of the reaction product, the present composition may be a melt-mixed body of a composition comprising the maleimide compound (a), the aminophenol compound (B) and the phenol compound (C).

In the present composition, there are the following cases: from the viewpoint of improving the heat resistance of a cured product of a thermosetting composition containing the present composition as a component, the total number of partial structures based on maleimide groups derived from the maleimide compound (a) is preferably 1.5 times or more and 2.5 times or less the total number of partial structures based on primary amino groups derived from the aminophenol compound (B) and partial structures based on allyl groups derived from the phenol compound (C). The ratio (ratio of the total number of the partial structures based on the maleimide groups derived from the maleimide compound (a) to the total number of the partial structures based on the primary amino groups derived from the aminophenol compound (B) and the allyl groups derived from the phenol compound (C)) is more preferably 1.8 or more and 2.2 or less, and particularly preferably 1.9 or more and 2.1 or less.

In the case where the present composition is the above-mentioned melt-blended composition, the total number of maleimide groups derived from the maleimide compound (a) may be 1.5 times or more and 2.5 times or less the total number of allyl groups derived from the phenol compound (C) and the primary amino groups derived from the aminophenol compound (B), and the melt-blended composition may be melt-blended. By melt-mixing under such conditions, the heat resistance of a cured product of a thermosetting composition containing the present composition as a component may be improved. The mixing ratio of the components is preferably 1.8 or more and 2.2 or less, and more preferably 1.9 or more and 2.1 or less.

The specific method of melt mixing is not limited. Can be obtained by the following steps: the maleimide compound (a), the aminophenol compound (B), the phenol compound (C) and the like are mixed in a usual mixing vessel under heating conditions, preferably under stirring conditions. Examples of a method for mixing these components into a composition include: a method of melt-mixing the maleimide compound (a), the aminophenol compound (B) and the phenol compound (C) all at once; a method in which the aminophenol compound (B) and the phenol compound (C) are melt-mixed and then the maleimide compound (A) is mixed. From the viewpoint of improving the stability of the physical properties of the composition, it is preferable that the components other than the maleimide compound (a) are first melt-mixed, and the maleimide compound (a) is further mixed with the obtained mixture to prepare a melt mixture.

The conditions for the melt mixing are not limited. The mixing may be carried out, for example, without limitation, by stirring and mixing at a temperature of 100 to 200 ℃ for about 15 to 60 minutes. As described above, since the composition contains the aminophenol compound (B) as a component, the melt viscosity at 150 ℃ of the present composition is easily set to 20 mPas or more and 750 mPas or less. From the viewpoint of improving the handleability of the present composition, the melt viscosity at 150 ℃ of the present composition is preferably from 30mPa · s to 400mPa · s. The hydroxyl group equivalent of the present composition is preferably 300g/eq or more and 1500g/eq or less, more preferably 600g/eq or more and 1200g/eq or less.

In the mixed product of the present invention, it is assumed that the mixed components are obtained by mixing the components in a compatible state or in a state where the components are partially reacted with each other. As noted above, Michael adducts may be included.

In one embodiment of the present invention, the present composition can be used as a component of a cured epoxy resin. The cured epoxy resin according to an embodiment of the present invention contains the present composition, and is preferably formed from the present composition. The epoxy resin curing agent of one embodiment of the present invention has a low melt viscosity in a molding temperature range, is excellent in processability, and is excellent in flame retardancy and heat resistance, and therefore, can be used for molding materials, various adhesives, coating materials, laminated materials, and the like.

The epoxy resin composition according to an embodiment of the present invention is an epoxy resin composition including the epoxy resin curing agent according to an embodiment of the present invention and an epoxy resin. Examples of the epoxy resin that can be used together with the epoxy resin hardener according to one embodiment of the present invention in the epoxy resin composition include: epoxy compounds having two or more epoxy groups in one molecule, such as bisphenol a type epoxy resins, bisphenol F type epoxy resins, cresol novolac type epoxy resins, phenol novolac type epoxy resins, biphenyl type epoxy resins, phenol biphenyl aralkyl type epoxy resins, epoxy compounds of aralkyl resins obtained by xylylene bond such as phenol and naphthol, dicyclopentadiene type epoxy resins, dihydroxynaphthalene type epoxy resins, glycidyl ether type epoxy resins such as triphenylolmethane type epoxy resins, glycidyl ester type epoxy resins, and glycidyl amine type epoxy resins. These epoxy resins may be used alone or in combination of two or more. In view of moisture resistance, low elastic modulus at heat, and flame retardancy, it is preferable to use a bifunctional epoxy resin such as a bisphenol F-type epoxy resin or a biphenyl-type epoxy resin, or a polyfunctional epoxy resin having a large number of aromatic rings such as an epoxy compound selected from a phenol biphenyl aralkyl-type epoxy resin, an aralkyl resin obtained by bonding a xylylene group such as phenol or naphthol, or the like.

When the epoxy resin is cured, a curing accelerator is preferably used in combination. As the hardening accelerator, known hardening accelerators for hardening an epoxy resin with a phenol-based hardening agent can be used, and examples thereof include: tertiary amine compounds, quaternary ammonium salts, imidazoles, urea compounds, phosphine compounds, phosphonium salts, and the like. More specifically, there may be mentioned: tertiary amine compounds such as triethylamine, triethylenediamine, benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, 1, 8-diazabicyclo (5,4,0) undecene-7 and the like; imidazoles such as 2-methylimidazole, 2, 4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and 2-phenyl-4-methylimidazole; urea compounds such as 3-phenyl-1, 1-dimethylurea, 3- (o-methylphenyl) -1, 1-dimethylurea, 3- (p-methylphenyl) -1, 1-dimethylurea, 1 '-phenylenebis (3, 3-dimethylurea), and 1,1' - (4-methyl-m-phenylene) -bis (3, 3-dimethylurea); phosphine compounds such as triphenylphosphine, tributylphosphine, tris (p-methylphenyl) phosphine, and tris (nonylphenyl) phosphine; phosphonium salts such as triphenylphosphonium phenolate, tetraphenylphosphonium tetraphenylborate, and tetraphenylphosphonium tetranaphthoate borate. It is preferable to use a curing accelerator containing one or more selected from the group consisting of imidazoles, urea compounds, and phosphonium salts, which exhibit high activity for both curing of epoxy resins and polymerization of bismaleimides. The hardening accelerator more preferably contains at least one of an imidazole compound and a urea compound, and particularly preferably contains an imidazole compound and a urea compound, that is, an imidazole compound and a urea compound are used in combination.

In the epoxy resin composition according to one embodiment of the present invention, an inorganic filler, a coupling agent, a mold release agent, a colorant, a flame retardant, a low stress agent, and the like may be added or previously reacted as necessary. In addition, other curing agents may be used in combination. Examples of such other curing agents include: phenol novolac resins, phenol aralkyl resins, phenol biphenyl aralkyl resins, phenol naphthyl aralkyl resins, naphthol aralkyl resins, trisphenolmethane type novolac resins, and the like.

Examples of the inorganic filler include amorphous silica, crystalline silica, alumina, glass, calcium silicate, magnesite, clay, talc, mica, magnesium oxide, and barium sulfate, and amorphous silica, crystalline silica, and barium sulfate are particularly preferable. When the amount of the filler to be blended is increased while maintaining excellent moldability, it is preferable to use a spherical filler having a wide particle size distribution which can be finely filled.

Examples of the coupling agent include silane coupling agents such as mercaptosilane coupling agents, vinylsilane coupling agents, aminosilane coupling agents, and epoxysilane coupling agents, and titanium coupling agents; examples of the release agent include carnauba wax and paraffin wax, and examples of the colorant include carbon black. Examples of the flame retardant include phosphorus compounds and metal hydroxides, and examples of the low-stress agent include silicone rubber, modified nitrile rubber, modified butadiene rubber, modified silicone oil, and the like.

Regarding the blending ratio of the epoxy resin curing agent and the epoxy resin according to one embodiment of the present invention, the equivalent ratio of epoxy group/hydroxyl group is preferably in the range of 0.5 to 1.5, particularly 0.8 to 1.2, in consideration of heat resistance, mechanical properties, and the like. When the epoxy resin composition is used in combination with another curing agent, the equivalent ratio of epoxy group/hydroxyl group is preferably set to the above ratio. The curing accelerator is preferably used in a range of 0.1 to 10 parts by weight per 100 parts by weight of the epoxy resin in consideration of curing characteristics and physical properties. When a plurality of curing accelerators are used in combination, the mass part based on 100 parts by weight of the epoxy resin is preferably within the above range. The blending ratio of the inorganic filler varies depending on the type thereof, but considering solder heat resistance, moldability (melt viscosity, fluidity), low stress property, low water absorption property, and the like, it is preferable to blend the inorganic filler in a proportion of 60 to 93% by weight based on the entire composition.

The thermosetting composition according to one embodiment of the present invention includes the present composition. The present composition can be used not only as a curing agent as described above, but also as a curing material itself. In this case, the present composition contained in the thermosetting composition of one embodiment of the present invention is self-polymerized to obtain a cured product. In this case, the thermosetting composition according to one embodiment of the present invention may contain other curable substances in addition to the present composition.

In the thermosetting composition according to one embodiment of the present invention, an inorganic filler, a coupling agent, a mold release agent, a colorant, a flame retardant, a low stress agent, and the like may be added or previously reacted as necessary.

Examples of the inorganic filler include amorphous silica, crystalline silica, alumina, glass, calcium silicate, magnesite, clay, talc, mica, magnesium oxide, and barium sulfate, and amorphous silica, crystalline silica, and barium sulfate are particularly preferable. When the amount of the filler to be blended is increased while maintaining excellent moldability, it is preferable to use a spherical filler having a wide particle size distribution which can be finely filled.

As a general method for producing the epoxy resin composition according to an embodiment of the present invention or the thermosetting composition according to an embodiment of the present invention as a molding material, the following methods can be mentioned: the raw materials are thoroughly mixed at a predetermined ratio by, for example, a mixer, kneaded by a hot roll, a kneader or the like, cooled and solidified, and pulverized into an appropriate size to be pelletized as needed. The molding material obtained in this manner can seal a semiconductor by, for example, low-pressure transfer molding or the like to manufacture a semiconductor device.

As a general method for producing the epoxy resin composition according to one embodiment of the present invention or the thermosetting composition according to one embodiment of the present invention as an insulating layer material, a varnish for interlayer insulation for applying the obtained solution to a circuit board may be prepared by dissolving each raw material in a solvent at a predetermined ratio, a prepreg for the above-mentioned application may be prepared by impregnating a glass fiber with the solution and performing heat treatment, or an adhesive sheet for the above-mentioned application may be prepared by heat treating the solution on a support film in a film form. They may be used in any manner to form an interlayer insulating layer.

The composition according to one embodiment of the present invention, and the epoxy resin curing agent, the epoxy resin composition, and the thermosetting composition each containing the composition can maintain a state in which the reaction hardly proceeds when the composition is stored at 15 ℃ or lower. In general, the fluidity of a composition having a thermosetting property such as the composition of one embodiment of the present invention is decreased as the reaction proceeds as the storage environment becomes higher, but such a decrease in fluidity is less likely to occur in the composition of one embodiment of the present invention. Specifically, the rate of change in the melt viscosity at 150 ℃ after leaving at35 ℃ for 1 week (the rate of increase in viscosity) can be set to 100% or less, and in a preferred example, can be set to 50% or less. As described above, the composition according to an embodiment of the present invention has excellent storage stability, and the epoxy resin curing agent, the epoxy resin composition, and the thermosetting composition containing the composition can be cured at an appropriate temperature, for example, in a temperature range of 100 to 250 ℃.

The embodiments described above are described for easy understanding of the present invention, and are not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design modifications and equivalents that fall within the technical scope of the present invention.