KR20200022379A - Compositions, epoxy resin curing agents, epoxy resin compositions, thermosetting compositions, cured products, semiconductor devices, and interlayer insulating materials - Google Patents

Abstract

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) The composition is a composition suitable as a curing agent of an epoxy resin composition capable of satisfying high flame retardancy, high heat resistance and low decomposition properties at high temperature, and has excellent storage stability. (In Formula (1), Ar ¹ is a substituent. Is an arylene group having 6 to 12 carbon atoms, X ¹ is a direct bond, a divalent hydrocarbon group having 1 to 6 carbon atoms, O, S, or SO ₂ , and p is an integer of 0 to 2 (Formula 2 ) of, Ar ² is included, and if there is an arylene group of 6 to 12 carbon atoms which is the substituent of the hydrocarbon group for hydroxyl group in the range of 0 to 2, X ² is a direct bond, a divalent hydrocarbon group of a carbon number of 1~6, O , S, or is SO _2, q is an integer of 0 to 2.) (in formula (3) of, Ar ³ is a 2 to 4 pan-allyl rider in a molecule With comprising allyl groups such that, an aryl group having a carbon number of 6-24, which comprises a hydroxyl group in the range of 0 to 2, X ³ is a direct bond, a divalent hydrocarbon group of a carbon number of 1~6, O, S, or SO ₂ , r is an integer of 0 to ₂ )

Description

Compositions, epoxy resin curing agents, epoxy resin compositions, thermosetting compositions, cured products, semiconductor devices, and interlayer insulating materials

This invention is a composition suitable as a component of the hardening | curing agent of an epoxy resin, or a component of a thermosetting composition, the epoxy resin hardening | curing agent containing this composition, the epoxy resin composition containing this epoxy resin hardening | curing agent, the hardened | cured material of this epoxy resin composition, The thermosetting composition containing the said composition, the hardened | cured material of this thermosetting composition, the semiconductor device enclosed with the said epoxy resin composition or said thermosetting composition, and the said epoxy resin composition or the said thermosetting composition containing It relates to an interlayer insulating material. In addition, in this specification, a "thermosetting composition" means the composition which has thermosetting, "epoxy resin composition" means the composition containing resin which has an epoxy group, and the concept of the term "thermosetting composition" and "epoxy" Resin composition "shall have the overlap part.

The phenolic hardening | curing agent which comprises a big group among the hardening | curing agents of an epoxy resin is used for various industries by the characteristics, such as low cost, in addition to abundant kind. They have been developed so far in order to meet various required performances with the advancement of industrial technology.

In the field of electronic materials, in recent years, with the miniaturization and thinning of semiconductor packages and the complexity of shapes, resins for semiconductor encapsulating materials are increasingly required to have low viscosity. If the viscosity is low, the fluidity is improved, so that it is possible to cope with complex packages such as BGA, and the filler can be filled with high viscosity, which is advantageous in terms of flame resistance, soldering heat resistance, and moisture resistance reliability required for these applications. Become.

In addition, due to consideration of the global environment, new flame retardant epoxy resin compositions that replace flame retardants such as halogen-containing compounds and antimony compounds that have been used so far have been increasing, and applications ranging from general purpose packages to front end packages. Phenol aralkyl resins, which have been used in the art, are also required to have excellent flame retardancy even without the use of halogen-based flame retardants and antimony compounds. As a material which meets such a request, the phenol aralkyl resin which introduce | transduced the biphenyl skeleton is known to be highly flame-retardant, and is used for the front end package use (for example, patent document 1 etc.).

Since the flame-retardant epoxy resin composition of patent document 1 has a tendency for glass transition temperature (Tg) to become low, and the fall of Tg generally causes high temperature reliability and heat resistance fall, of the epoxy resin hardening | curing agent which can improve this, Provision is desired. In particular, high heat resistance is required for the encapsulation material of power devices mounted in electric vehicles and hybrid vehicles, which are expected to become increasingly popular in the future. In addition, in connection with heat resistance, as a physical property request | requirement of the recent sealing material, it is also required to have a characteristic with low thermal decomposition property (henceforth "high temperature low decomposition property") under high temperature. In response to such a request, Patent Document 2 describes a maleimide compound and a composition obtained by melt-mixing a specific phenol compound in a constant ratio. It is suitable to use such a composition as a component of a thermosetting composition, such as a component of an epoxy resin hardening | curing agent, and by using the said composition, the thermosetting composition which can form the hardened | cured material which has high flame retardance, high heat resistance, and low decomposition property at high temperature is obtained. Lose.

Japanese Patent Application Laid-Open No. 2000-129092 Japanese Patent Application Laid-Open No. 2016-204626

By using the composition of patent document 2, the hardened | cured material which has the outstanding characteristic as above-mentioned is provided. While maintaining the excellent characteristic which this composition has, while being able to further improve storage stability (a thing which hardly changes a physical property even if it preserves for a long time), the value as an industrial product of this composition can be heightened further.

An object of the present invention is to provide a composition that is suitable as a component of a curing agent of an epoxy resin or a component of a thermosetting composition capable of satisfying high flame retardancy, high heat resistance and low decomposition properties at high temperature, and is excellent in storage stability. Moreover, this invention is an epoxy resin hardening | curing agent containing the said composition, an epoxy resin composition containing this epoxy resin hardening | curing agent, the hardened | cured material of this epoxy resin composition, the thermosetting composition containing the said composition, the hardened | cured material of this thermosetting composition, It is an object of the present invention to provide a semiconductor device encapsulated with the epoxy resin composition or the thermosetting composition and the interlayer insulating material containing the epoxy resin composition or the thermosetting composition.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, the present inventors found the aromatic amine compound in the component of the composition of patent document 2 easily to influence the melt viscosity and storage stability of a composition, and this aromatic amine compound By changing some of the plural amino groups in the hydroxyl group to an aminophenol compound, the melt viscosity of the composition, in particular, the melt viscosity of 150 ° C., can be lowered, and new knowledge that storage stability can be further improved.

This invention was completed based on said knowledge, In one aspect, the maleimide compound (A) represented by following General formula (1), the aminophenol compound (B) represented by following General formula (2), And a phenol compound (C) represented by the following General Formula (3).

(Formula (1) of, Ar ¹ is a substituent having a carbon number of 6 to 12 is present may be an arylene group which, X ¹ is a direct bond, a divalent hydrocarbon group of a carbon number of 1~6, O, and S, or SO _2, p Is an integer of 0 to 2)

(Formula (2) of, Ar ² includes a hydroxyl group in the range of 0 to 2, the aryl group of 6 to 12 carbon atoms which may be the substituent of the hydrocarbon present, X ² is a direct bond, a divalent group having 1 to 6 carbon atoms Hydrocarbon group, O, S, or SO ₂ , q is an integer of 0 to ₂ )

(Formula (3) of, Ar ³ is and notify the rider with including allyl groups such that the range of 2 to 4, an aryl group having a carbon number of 6-24, which comprises a hydroxyl group in the range of 0 to 2 in one molecule , X ³ is a direct bond, a divalent hydrocarbon group having 1 to 6 carbon atoms, O, S, or SO ₂ , r is an integer of 0 to ₂ )

It is preferable that 150 degreeC melt viscosity of said composition is 50 mPa * s or more and 1000 mPa * s or less, and hydroxyl equivalent is 300 g / eq or more and 1500 g / eq or less.

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

The said composition may be a melted mixture of the composition containing the said maleimide compound (A), the said aminophenol compound (B), and the said phenol compound (C).

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

It is preferable that the said phenol compound (C) contains the bisphenol compound (C1) represented by following General formula (4).

(In formula (4), R <^4> and R <^5> is a C1-C4 hydrocarbon group each independently, R <^6> and R <^7> is a hydrogen atom, a methyl group, and a phenyl group each independently, c and d are each independently 0 Is an integer of -3)

As for the said maleimide compound (A), it is preferable that p in the said General formula (1) is 0 or 1. Moreover, it is preferable that the said aminophenol compound (B) is a phenylenediamine compound (B1) represented by following General formula (5).

(In formula (5), R <^2> is a C1-C4 hydrocarbon group and b is an integer of 0-4.)

In another aspect, the present invention provides an epoxy resin curing agent comprising the composition according to the present invention.

As another aspect, the present invention provides an epoxy resin composition comprising the epoxy resin curing agent and epoxy resin according to the present invention.

The epoxy resin composition which concerns on said this invention may also contain a hardening accelerator further. In this case, it is preferable that the said hardening accelerator contains 1 type (s) or 2 or more types chosen from the group which consists of an imidazole compound, a urea type compound, and a phosphonium salt, and the said hardening accelerator is an imidazole type It is more preferable to include a compound and a urea-based compound.

The epoxy resin composition which concerns on said this invention may contain the inorganic filler further.

As another aspect, the present invention provides a cured product of the epoxy resin composition according to the present invention.

In another aspect, the present invention provides a thermosetting composition comprising the composition according to the present invention. Such thermosetting compositions may further contain an inorganic filler.

As another aspect, the present invention provides a cured product of the thermosetting composition according to the present invention.

As another aspect, the present invention provides a semiconductor device encapsulated with the epoxy resin composition according to the present invention or the thermosetting composition according to the present invention, and the epoxy resin composition according to the present invention or the thermosetting according to the present invention. An interlayer insulating material containing the composition is provided.

According to the present invention, there is provided a composition suitable as a component of a curing agent of an epoxy resin or a component of a thermosetting composition that satisfies high flame retardancy, high heat resistance and low decomposition properties at high temperatures, and provides a composition having excellent handleability and storage stability. Moreover, according to this invention, the epoxy resin hardening | curing agent containing the said composition, the epoxy resin composition containing this epoxy resin hardening | curing agent, the epoxy resin hardened | cured material of this epoxy resin composition, the thermosetting composition containing this composition, and this thermosetting composition The interlayer insulation material containing the hardened | cured material of said, said epoxy resin composition or said thermosetting composition, and said epoxy resin composition or said thermosetting composition is provided.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described.

The composition (henceforth this composition is also called "this composition") which concerns on one Embodiment of this invention is represented by the maleimide compound (A) represented by said General formula (1), and said General formula (2). The aminophenol compound (B) which becomes, and the phenol compound (C) represented by said General formula (3) are contained. In one embodiment, this composition is a melted mixture of the composition containing said maleimide compound (A), an aminophenol compound (B), and a phenol compound (C).

Preferable examples of the maleimide compound (A) can be easily obtained by condensing maleic anhydride and difunctional aromatic amines (see, for example, JP-A-60-260623). As a maleimide compound (A) which this composition contains, it is preferable that melting | fusing point has physical property of 100-250 degreeC.

As a specific example of a maleimide compound (A), N, N'-4,4'- diphenylmethane bismaleimide, N, N'-m-phenylene bismaleimide, N, N'-4,4'- Diphenyl ether bismaleimide, N, N'-m-xylene bismaleimide, etc. are mentioned. Among these, from a viewpoint of heat resistance provision, it is preferable that p in said General formula (1) is 0 or 1, and p in said General formula (1) is 1 in a maleimide compound (A). It is more preferable to contain N, N'-4,4'- diphenylmethane bismaleimide which is an example of the substance in the case of being, and it is especially preferable to consist of the said substance. In addition, in said general formula (1), N, N'-4,4'- diphenylmethane bismaleimide has Ar <^1> a phenylene group and X <^1> is a methylene group.

Specific examples of the aminophenol compound (B) include 2-aminophenol, 3-aminophenol, 4-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'-hydroxydiphenylether, 2-amino-3'-hydroxy Oxydiphenyl sulfide, 4-amino-3 ', 4'- dihydroxy diphenyl sulfone, etc. are mentioned. Among these, from the viewpoint of fluidity at the time of time and ease of acquisition, it is preferable that the value of q in the aminophenol compound (B) is 0, and in addition to the curability, Ar ² includes a substituent. It is more preferable that carbon number is 6-7. It is preferable that the hydroxyl group which an aminophenol compound (B) has is one from a viewpoint of especially improving storage stability.

As a phenol compound (C), the allylated compound of a bisphenol compound, an allylated phenol novolak resin, etc. are illustrated. Among these, it is preferable that a phenol compound (C) contains the bisphenol compound (C1) represented by said General formula (4), and it is more preferable that it consists of a bisphenol compound (C1). The specific structure of a bisphenol compound (C1) is not limited. Bisphenol A structure, bisphenol F structure, bisphenol AP structure, bisphenol BP structure, etc. are illustrated. By having such a structure, proper fluidity at the time of shaping | molding and suitable 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] and 4,4'-methylenebis [2- (2-propenyl) phenol] And 4,4 '-(dimethylmethylene) bis [2- (2-propenyl) -6-methylphenol]. In the case where the phenol compound (C) contains the bisphenol compound (C1), the bisphenol compound (C1) preferably contains 4,4 '-(dimethylmethylene) bis [2- (2-propenyl) phenol]. And, it is more preferable that the phenol compound (C) consists of 4,4 '-(dimethylmethylene) bis [2- (2-propenyl) phenol].

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

From the viewpoint of facilitating obtaining the above reaction product, the composition may be a melted mixture of a composition containing a maleimide compound (A), an aminophenol compound (B), and a phenol compound (C).

In this composition, the total number of the partial structures based on the maleimide group derived from a maleimide compound (A) is based on the partial structure based on the primary amino group derived from an aminophenol compound (B), and the allyl group derived from a phenol compound (C). It is preferable from a viewpoint of improving the heat resistance characteristic of the hardened | cured material of the thermosetting composition containing this composition as a component that it is 1.5 times or more and 2.5 times or less of the total number with based partial structure. Based on the partial structure based on the primary amino group derived from the aminophenol compound (B) of the total number of the partial structure based on said ratio (maleimide group derived from a maleimide compound (A), and the allyl group derived from a phenol compound (C) It is more preferable that it is 1.8 or more and 2.2 or less, and the ratio with respect to the total number with partial structure may be especially preferable that it is 1.9 or more and 2.1 or less.

When this composition is said melt mixture, the total number of maleimide groups derived from a maleimide compound (A) is the total number of the primary amino group derived from an aminophenol compound (B), and the allyl group derived from a phenol compound (C). The melt mixing may be performed at a component mixing ratio of 1.5 to 2.5 times. When melt mixing is performed on such conditions, the heat resistance characteristic of the hardened | cured material of the thermosetting composition containing this composition as a component may be improved in some cases. It is preferable that it is 1.8 or more and 2.2 or less, and, as for said component mixing ratio, it is more preferable that it is 1.9 or more and 2.1 or less.

The specific method in said melt mixing is not limited. Each component, such as a maleimide compound (A), an aminophenol compound (B), and a phenol compound (C), can be obtained by mixing under heating conditions, preferably under stirring conditions, in a normal mixing vessel. As a method of mixing a composition with these components, the method of melt-mixing a maleimide compound (A), an aminophenol compound (B), and a phenol compound (C) at once; The method etc. which mix a maleimide compound (A) after melt-mixing an aminophenol compound (B) and a phenol compound (C) are illustrated. From the viewpoint of improving the stability of the physical properties of the composition, it is preferable to melt-mix components other than the maleimide compound (A) first, and further mix the maleimide compound (A) with the obtained mixture to obtain a molten mixture.

The conditions of said melt mixing are not limited. If non-limiting example is given, it will stir and mix about 15 to 60 minutes in the temperature range of 100-200 degreeC. As mentioned above, since 150 degreeC melt viscosity of this composition contains an aminophenol compound (B) as a component, it is easy to set it as 20 mPa * s or more and 750 mPa * s or less. It is preferable that 150 degreeC melt viscosity of this composition is 30 mPa * s or more and 400 mPa * s or less from a viewpoint of improving the handleability of this composition. Moreover, it is preferable that it is 300 g / eq or more and 1500 g / eq or less, and, as for the hydroxyl equivalent of this composition, it is more preferable that they are 600 g / eq or more and 1200 g / eq or less.

In the mixed product of the present invention, it is assumed that the mixed components are commonly used in a state in which each component is in a compatible state or in a state in which components are partially reacted. As described above, the Michael adduct may be included.

In one embodiment of the present invention, the present composition is used as a component of a cured epoxy resin. The epoxy resin hardened | cured material which concerns on one Embodiment of this invention contains this composition, Preferably, it consists of this composition. Since the epoxy resin hardening | curing agent which concerns on one Embodiment of this invention is low in melt | fusion temperature in shaping | molding temperature range, and is excellent in flame retardancy and heat resistance, it can be used for a molding material, various binders, coating materials, laminated materials, etc.

The epoxy resin composition which concerns on one Embodiment of this invention is an epoxy resin composition containing the epoxy resin hardening | curing agent which concerns on one Embodiment of the said invention, and an epoxy resin. In the epoxy resin composition, examples of the epoxy resin that can be used together with the epoxy resin curing agent according to one embodiment of the present invention include bisphenol A type epoxy resins, bisphenol F type epoxy resins, cresol novolac type epoxy resins, and phenol nos. Epoxides of aralkyl resins by xylylene bonds, such as ballac type epoxy resins, biphenyl type epoxy resins, phenol biphenyl aralkyl type epoxy resins, phenols and naphthols, dicyclopentadiene type epoxy resins, and dihydroxy naphthalene type epoxys And epoxy compounds having two or more epoxy groups in one molecule such as glycidyl ether type epoxy resins such as resins and triphenol methane type epoxy resins, glycidyl ester type epoxy resins, and glycidylamine type epoxy resins. . These epoxy resins may be used alone or in combination of two or more. Considering moisture resistance, low elastic modulus at thermal and flame retardancy, bifunctional epoxy resins such as bisphenol F type epoxy resins and biphenyl type epoxy resins, and phenol biphenyl aralkyl type epoxy resins, such as phenol and naphthol, It is preferable to use the polyfunctional epoxy resin with many aromatic rings chosen from the epoxide of an aralkyl resin, etc.

In hardening of an epoxy resin, it is preferable to use a hardening accelerator together. As a hardening accelerator, a well-known hardening accelerator for hardening an epoxy resin with a phenolic hardening | curing agent can be used, For example, a tertiary amine compound, a quaternary ammonium salt, imidazole, a urea type compound, a phosphine compound And phosphonium salts. More specifically, triethylamine, triethylenediamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) undecene-7 and the like Tertiary amine compounds; Imidazoles such as 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole; 3-phenyl-1,1-dimethylurea, 3- (o-methylphenyl) -1,1-dimethylurea, 3- (p-methylphenyl) -1,1-dimethylurea, 1,1'-phenylenebis ( Urea compounds such as 3,3-dimethylurea) and 1,1 '-(4-methyl-m-phenylene) -bis (3,3-dimethylurea); Phosphine compounds such as triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine and tri (nonylphenyl) phosphine; Phosphonium salts such as triphenylphosphoniophenolite, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetranaphthoic acid borate, and the like. The use of the hardening accelerator which consists of 1 type (s) or 2 or more types chosen from the group which consists of imidazole, a urea type compound, and a phosphonium salt which shows high activity in both hardening of an epoxy resin and superposition | polymerization of bismaleimide is preferable. Do. It is more preferable that a hardening accelerator contains at least one of an imidazole compound and a urea compound, and the thing containing an imidazole compound and a urea compound, ie, using an imidazole compound and a urea compound together Especially preferred.

An inorganic filler, a coupling agent, a mold release agent, a coloring agent, a flame retardant, a low stress agent, etc. can be added to the epoxy resin composition which concerns on one Embodiment of this invention as needed, or can react beforehand. Moreover, you may use together another hardening | curing agent. As an example of such another hardening | curing agent, a phenol novolak resin, a phenol aralkyl resin, a phenol biphenyl aralkyl resin, a phenol naphthyl aralkyl resin, a naphthol aralkyl resin, a triphenol methane type novolak resin, etc. are mentioned.

Examples of the inorganic fillers include amorphous silica, crystalline silica, alumina, glass, calcium silicate, magnesite, clay, tark, mica, magnesia, barium sulfate, and the like, in particular amorphous silica, Crystalline silica and barium sulfate are preferable. In addition, when it is desired to increase the blending amount of the filler while maintaining excellent moldability, it is preferable to use a spherical filler having a wide particle size distribution that enables fine filling.

Examples of the coupling agent include silane coupling and titanium coupling agents such as mercaptosilane-based, vinylsilane-based, aminosilane-based and epoxysilane-based compounds, examples of mold release agents such as carnauba wax and paraffin wax, and carbon blacks as colorants. It can be illustrated. As an example of a flame retardant, a silicone rubber, a modified nitrile rubber, a modified butadiene rubber, a modified silicone oil etc. are mentioned as an example of a low stress agent, such as a phosphorus compound and a metal hydroxide.

When the compounding ratio of the epoxy resin curing agent and epoxy resin which concerns on one Embodiment of this invention considers heat resistance, a mechanical characteristic, etc., it is preferable that the equivalence ratio of an epoxy group / hydroxyl group exists in 0.5-1.5, especially the range of 0.8-1.2. Also in the case of using together with another hardening | curing agent, it is preferable to make it the equivalent ratio of an epoxy group / hydroxyl group become the said ratio. It is preferable to use a hardening accelerator in the range of 0.1-10 weight part with respect to 100 weight part of epoxy resins, considering a hardening characteristic and agent properties. Also when using multiple types of hardening accelerator together, it is preferable to make it the mass part with respect to 100 weight part of epoxys in the said range. The blending ratio of the inorganic filler is different depending on its type, but considering the soldering heat resistance, moldability (melt viscosity, fluidity), low stress, low water absorption, etc., the inorganic filler is 60-93% by weight of the whole composition. It is preferable to mix | blend in the ratio to make.

The thermosetting composition which concerns on one Embodiment of this invention contains this composition. As described above, the present composition can be used as a curing agent and can function as a curable material by itself. In this case, you may obtain hardened | cured material by self-polymerizing this composition contained in the thermosetting composition which concerns on one Embodiment of this invention. In this case, the thermosetting composition which concerns on one Embodiment of this invention may contain the other curable substance in addition to this composition.

In the thermosetting composition which concerns on one Embodiment of this invention, an inorganic filler, a coupling agent, a mold release agent, a coloring agent, a flame retardant, a low stress agent, etc. can be added or reacted beforehand as needed.

Examples of the inorganic fillers include amorphous silica, crystalline silica, alumina, glass, calcium silicate, magnesite, clay, tark, mica, magnesia, barium sulfate and the like, but in particular amorphous silica, crystalline silica, sulfuric acid Barium is preferred. In addition, when it is desired to increase the blending amount of the filler while maintaining excellent moldability, it is preferable to use a spherical filler having a wide particle size distribution that enables fine filling.

As a general method in the case of preparing 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 a molding material, each raw material having a predetermined ratio is sufficiently mixed by, for example, a mixer. After that, a kneading treatment is applied with a heat roll, a kneader, or the like, and after cooling and solidifying, grinding is carried out to an appropriate size, and tableting is performed as necessary. The molding material obtained in this way can seal a semiconductor by low pressure transfer molding etc., for example, and can manufacture a semiconductor device.

As a general method in the case of preparing 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, each raw material having a predetermined ratio is dissolved in a solvent, and this is a circuit board. It can be used as the varnish for interlayer insulation for apply | coating to this, and it can be made into the prepreg of the said use by impregnating this in glass fiber, and performing heat processing, or this adhesion | attachment of this use which heat-processed on the support film and made it into the film form You can make a sheet. These can be used as an interlayer insulation layer in any form.

The composition which concerns on one Embodiment of this invention, and the epoxy resin hardening | curing agent, epoxy resin composition, and thermosetting composition containing this composition can maintain the state which reaction hardly progresses, if it is a storage condition of 15 degrees C or less. Usually, the composition which has a thermosetting property like the composition which concerns on one Embodiment of this invention advances reaction, and fluidity | liquidity falls as a storage environment is high temperature, but the composition which concerns on one Embodiment of this invention does not produce such a fall of fluidity | liquidity easily. . When a specific example is shown, it is possible to make the change rate (ratio of viscosity rise) of 150 degreeC melt viscosity after one week in 35 degreeC environment to 100% or less, and to make it 50% or less in a preferable example. While the composition according to one embodiment of the present invention has such excellent storage stability, the epoxy resin curing agent, the epoxy resin composition, and the thermosetting composition containing the composition can advance the curing reaction at an appropriate temperature. For example, it can carry out in the temperature range of 100-250 degreeC.

The embodiments described above are described to facilitate understanding of the present invention and are not described to limit the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.

EXAMPLE

Although an Example and a comparative example demonstrate this invention more concretely below, this invention is not restrict | limited at all by these examples.

Example 1

4,4 '-(dimethylmethylene) bis [2- (2-propenyl) phenol] 30.8 g (0.10 mol) (manufactured by Yamato Chemical Co., Ltd., DABPA, hydroxyl equivalent 159 g / eq), 4-amino- 12.3 g (0.1 mol) of m-cresol and 143.2 g (0.40 mol) of 4,4'-diphenylmethane bismaleimide were stirred at 150 ° C for 20 minutes, and then cooled to room temperature to be homogeneous as a mixed product. 189.9 g of a reddish brown glassy melt (mixed product 1) were obtained.

The melt viscosity of the mixed product 1 in 150 degreeC measured with the ICI melt viscometer was 60 mPa * s. In addition, the hydroxyl equivalent of the mixed product 1 was computed at 621 g / eq based on the hydroxyl equivalent of 4,4 '-(dimethylmethylene) bis [2- (2-propenyl) phenol], and its component concentration. In the following description, the composition which consists of the mixed product 1 obtained in Example 1 may be called "hardening agent 1."

Example 2

Epoxy resin represented by the following general formula (6) ("NC3000" phenol biphenyl aralkyl type manufactured by Nihon Kayaku Co., epoxy equivalent 275 g / eq), curing agent 1 obtained in Example 1, fused silica, and urea-based curing accelerator (born child After mix | blending the hardening accelerator which consists of Prosa "U-CAT 3513N" in the ratio shown in Table 2 (the numerical value of Table 2 is the mass part, the same below), and after fully mixing, it is three minutes with two rolls of 85 +/- 3 degreeC The composition for molding was obtained as an epoxy resin composition by kneading, cooling and pulverizing. After molding this epoxy resin composition at a pressure of 100 kgf / cm 2 for 2 minutes at 175 ° C, a postcure was performed at 230 ° C for 6 hours to test glass transition temperature, 250 ° C weight loss rate, and flame retardancy test. Was prepared and the evaluation was performed. The results are shown in Table 2.

(Wherein G is a glycidyl group and n is a natural number of 1 to 10)

Example 3

In the mixing | blending ratio shown in Table 2, it carried out similarly to Example 1, and prepared the composition for shaping | molding, and obtained it as a thermosetting composition which uses the hardening | curing agent 1 as a main hardening component. Table 2 shows the results of the evaluation. In addition, in Table 2, although the thermosetting composition manufactured by Example 3 is shown like an epoxy resin composition on account of a display, it does not contain the component which has an epoxy group.

Comparative Example 1

Instead of the mixed product 1 obtained in Example 1, 4,4 '-(dimethylmethylene) bis [2- (2-propenyl) phenol] (DABPA) and 4,4'-diaminediphenylmethane, which are known curing agents, And 4,4'- diphenylmethane bismaleimide was stirred at 150 degreeC for 20 minutes, and cooled to room temperature, and the homogeneous red-brown glassy melt (mixed product 2) was obtained. The melt viscosity of the mixed product 2 in 150 degreeC measured with the ICI melt viscometer was 34 mPa * s. In addition, the hydroxyl equivalent of the mixed product 2 was computed at 969 g / eq based on the hydroxyl equivalent of 4,4 '-(dimethylmethylene) bis [2- (2-propenyl) phenol], and its component concentration. The composition which consists of the mixed product 2 obtained by the comparative example 1 may be called "hardening agent 2."

Table 1 shows the physical properties of the curing agent 1 prepared in Example 1 and the curing agent 2 prepared in Comparative Example 1.

TABLE 1

Comparative Example 2

The epoxy resin represented by the said General formula (6), the hardening | curing agent 2 obtained by the comparative example 1, fused silica, and a urea-type hardening accelerator ("U-CAT 3513N" by San Apro Co., Ltd.) are mix | blended in the ratio shown in Table 2, and In the same manner as in Example 2, a molding composition was prepared and obtained as an epoxy resin composition. Table 2 shows the results of the evaluation.

The physical properties of the epoxy resin composition and the thermosetting composition (hereinafter, collectively referred to as "epoxy resin composition" and the like) prepared in Examples and Comparative Examples and the storage stability of the curing agent 1 and the curing agent 2 were measured by the following method.

(1) glass transition temperature

The linear expansion coefficient of test pieces, such as an epoxy resin composition, was measured at the temperature increase rate of 10 degree-C / min using TMA (thermomechanical analyzer), and the inflection point of the linear expansion coefficient was made into glass transition temperature (unit: degreeC). Table 2 shows the measurement results.

(2) 250 ° C long term heat resistance (250 ° C weight loss rate)

The hardened | cured material was put into 250 degreeC oven, and the weight reduction rate (unit: wt%) after 360hr was measured. The lower the weight reduction rate, the better the low decomposition property at high temperature. Table 2 shows the measurement results.

(3) flame retardant

Samples (5 sheets per case), such as epoxy resin composition of thickness 1.6mm x width 10mm x length 135mm, were used, and residual flame time was measured and evaluated based on UL-94V. The longest time is Fmax (unit: second) of the residual flame time measured by performing two times of dyeing on each sample, and the total of the residual flame time by the test with 5 samples is Ftotal (unit: Seconds). The evaluation results are shown in Table 2.

(4) storage stability

Each hardening | curing agent was stored in 35 degreeC oven for 7 days, the viscosity measurement in 150 degreeC was performed with the ICI viscometer about each hardening | curing agent before and after storage, and the grade to which the viscosity rises was evaluated as a viscosity change rate (unit:%). The lower the rate of change of viscosity, the better the storage stability. The evaluation results are shown in Table 2.

TABLE 2

The epoxy resin composition containing the hardening | curing agent 1 of this invention is similar to the epoxy resin composition using a well-known hardening | curing agent (hardening | curing agent 2), and has a high glass transition temperature, is excellent also in low decomposition property at high temperature, and gives hardened | cured material excellent in heat resistance. The thing equivalent to the hardened | cured material produced from the epoxy resin composition using a well-known hardening | curing agent (hardening agent 2) also about the thing and the flame retardance of the hardened | cured material is understood from Table 2. In addition, as shown in Example 3, even if the present composition does not contain a substance having an epoxy group, a cured product can be obtained as a thermosetting composition, and the cured product is a component derived from a substance having an epoxy group. Since it does not contain, it was confirmed that heat resistance and flame retardance are especially excellent. Moreover, it was confirmed that the hardening | curing agent 1 of this invention is superior to the well-known hardening | curing agent 2 also from a viewpoint of storage stability.

The composition excellent in storage stability provided according to the present invention can be suitably used as an epoxy resin curing agent or a curable component of a thermosetting composition, which satisfies high flame retardancy, high heat resistance, and low thermal decomposition properties at high temperatures.

According to the present invention, there is also provided a novel epoxy resin composition using an epoxy resin curing agent, a cured product thereof, and a thermosetting composition and the cured product which satisfy high flame retardancy, high heat resistance, and low thermal decomposition property under high temperature.

According to the present invention, a composition which can form an epoxy resin composition which is particularly useful as an epoxy resin curing agent and is particularly excellent in flame retardancy, curability and higher heat resistance when used as an interlayer insulating material for encapsulating semiconductor and power devices, and The epoxy resin composition, the composition which can form a thermosetting composition, and its thermosetting composition are provided.

Claims (21)

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) Composition.

(Formula (1) of, Ar ¹ is a substituent having a carbon number of 6 to 12 is present may be an arylene group which, X ¹ is a direct bond, a divalent hydrocarbon group of a carbon number of 1~6, O, and S, or SO _2, p Is an integer of 0 to 2)

(Formula (2) of, Ar ² includes a hydroxyl group in the range of 0 to 2, the aryl group of 6 to 12 carbon atoms which may be the substituent of the hydrocarbon present, X ² is a direct bond, a divalent group having 1 to 6 carbon atoms Hydrocarbon group, O, S, or SO ₂ , q is an integer of 0 to ₂ )

(Formula (3) of, Ar ³ is and notify the rider with including allyl groups such that the range of 2 to 4, an aryl group having a carbon number of 6-24, which comprises a hydroxyl group in the range of 0 to 2 in one molecule , X ³ is a direct bond, a divalent hydrocarbon group having 1 to 6 carbon atoms, O, S, or SO ₂ , r is an integer of 0 to ₂ ) The method of claim 1,
The composition whose 150 degreeC melt viscosity is 20 mPa * s or more and 750 mPa * s or less, the hydroxyl equivalent is 300 g / eq or more and 1500 g / eq or less, and the rate of change of 150 degreeC melt viscosity after storing for 1 week in 35 degreeC environment is 100% or less. . The method according to claim 1 or 2,
The composition containing the reaction product of the said maleimide compound (A) and said aminophenol compound (B) further. The method of claim 3,
The reaction product is a composition of Michael adducts of the maleimide compound (A) and the aminophenol compound (B). The method according to any one of claims 1 to 4,
The composition which is a melt mixture of the composition containing the said maleimide compound (A), the said aminophenol compound (B), and the said phenol compound (C). The method according to any one of claims 1 to 5,
The total number of partial structures based on the maleimide group derived from the maleimide compound (A) is based on the partial structure based on the primary amino group derived from the aminophenol compound (B) and the allyl group derived from the phenol compound (C). The composition which is 1.5 times or more and 2.5 times or less of the total number with partial structure. The method according to any one of claims 1 to 6,
The said phenol compound (C) contains the bisphenol compound (C1) represented by following General formula (4).

(In formula (4), R <^4> and R <^5> is a C1-C4 hydrocarbon group each independently, R <^6> and R <^7> is a hydrogen atom, a methyl group, and a phenyl group each independently, c and d are each independently 0 Is an integer of -3) The method according to any one of claims 1 to 7,
The said maleimide compound (A) is a composition whose p in the said General formula (1) is 0 or 1. The method according to any one of claims 1 to 8,
The said aminophenol compound (B) is a composition which is a phenylenediamine compound (B1) represented by following General formula (5).

(In formula (5), R <^2> is a C1-C4 hydrocarbon group and b is an integer of 0-4.) The epoxy resin hardening | curing agent containing the composition of any one of Claims 1-9. The epoxy resin composition containing the epoxy resin hardener of Claim 10, and an epoxy resin. The method of claim 11,
Further epoxy resin composition comprising a curing accelerator. The method of claim 12,
The epoxy resin composition in which the said hardening accelerator contains 1 type (s) or 2 or more types chosen from the group which consists of an imidazole compound, a urea type compound, and a phosphonium salt. The method of claim 13,
The epoxy resin composition in which the said hardening accelerator contains an imidazole compound and a urea type compound. The method according to any one of claims 11 to 14,
An epoxy resin composition further comprising an inorganic filler. Hardened | cured material of the epoxy resin composition of any one of Claims 11-15. The thermosetting composition containing the composition of any one of Claims 1-9. The method of claim 17,
A thermosetting composition further comprising an inorganic filler. Hardened | cured material of the thermosetting composition of Claim 17 or 18. The semiconductor device sealed with the epoxy resin composition of any one of Claims 11-15, or the thermosetting composition of Claim 17 or 18. The interlayer insulation material containing the epoxy resin composition of any one of Claims 11-15, or the thermosetting composition of Claim 17 or 18.