JP6052868B2 - Epoxy resin curing agent, production method, and use thereof - Google Patents

Description

The present invention relates to a curing agent for an epoxy resin useful for a molding material, various binders, a coating material, a laminated material, and the like, a composition using the same, a cured product, and use thereof. More specifically, the present invention relates to an epoxy resin curing agent excellent in flame retardancy and heat resistance, a composition using the same, a cured product, and use thereof.

Among the hardeners for epoxy resins, phenolic hardeners, which form a large group, are used in various industries due to the advantages of low cost, in addition to the wide variety. Various types of these have been developed so far in order to meet various performance requirements accompanying industrial technological innovation.

In recent years, in the field of electronic materials, as semiconductor packages have become smaller, thinner and more complicated in shape, resins for semiconductor sealing materials are increasingly required to have low viscosity. If the viscosity is low, its fluidity will improve and it will be possible to deal with packages with complex shapes, such as BGA. It is also advantageous in terms of solder heat resistance and moisture resistance reliability.

In addition, due to consideration for the global environment, there is an increasing demand for new flame retardant epoxy resin compositions to replace flame retardants such as halogen-containing compounds and antimony compounds that have been used so far. The phenol aralkyl resin that has been used for packaging purposes is also required to have excellent flame retardancy without using a halogen-based flame retardant and an antimony compound (for example, Patent Document 1). Among them, the phenol aralkyl resin introduced with a biphenyl skeleton is known to have high flame retardancy and is used in advanced package applications, but has a drawback that the glass transition temperature (Tg) is low (for example, Patent Document 2). Since a decrease in Tg generally causes a decrease in high temperature reliability and heat resistance, it has been desired to provide an epoxy resin curing agent that can improve this.

On the other hand, triphenolmethane type novolak resins are known as phenolic curing agents having heat resistance, and some have high fluidity (for example, Patent Documents 3 to 4). However, it has been difficult for such a resin having a triphenolmethane structure to have poor flame resistance (for example, Patent Document 5).

JP 5-97965 JP 2000-129092 A JP 2002-275228 A JP 2010-229203 A JP2011-252037

  Since the bismaleimide monomer has high crystallinity and is difficult to be compatible with other ingredients, application examples to epoxy materials have been limited. In particular, it is unsuitable for application to a product form that requires a homogeneous compatible state, and there is no report of compatibilizing a bismaleimide monomer with a known phenol-based curing agent for the purpose of achieving high heat resistance.

  As a result of intensive studies on curing agents that can solve the problems of the prior art, the present inventors have reached the present invention. The present inventors consider that the blending of bismaleimide monomer as a means for imparting heat resistance to the material is a simple and effective technique, and by adding a specific dihydroxynaphthalene, a highly crystalline bismaleimide monomer is converted into a phenolic system. It has been found that a phenolic curing agent that is compatible with a resin and satisfies high heat resistance, high flame retardancy and high fluidity can be obtained.

  The present invention provides a novel phenolic curing agent satisfying high flame retardancy, high heat resistance and high fluidity, a composition using the same, and a cured product thereof.

The present invention is a phenol compound having a hydroxyl group equivalent of 50 to 250 g / eq and a 150 ° C. melt viscosity of 50 to 500 mPa · s and having two or more phenolic hydroxyl groups in one molecule, represented by the following general formula (1). The weight ratio of the bismaleimide compound and the dihydroxynaphthalene compound represented by the following general formula (3) to the phenol compound of the bismaleimide compound is 0.5 to 5.0, and the weight ratio of the dihydroxynaphthalene compound to the phenol compound is 0.1. Provided is a method for producing an epoxy resin curing agent having a melt viscosity of 50 to 500 mPa · s and a hydroxyl group equivalent of 250 to 400 g / eq, mixed at a temperature range of 100 to 200 ° C. To do.

In formula (1), Ar ¹ is an arylene group represented by formula (2), X is a methylene group, dimethylmethylene group, oxygen atom, sulfur atom or direct bond, and n is an integer of 0 to 1. . In Formula (2), R ¹ is a hydrocarbon group having 1 to 4 carbon atoms, and a is an integer of 0 to 4. In formula (3), R ² and R ³ are hydrocarbon groups having 1 to 4 carbon atoms, b and c are integers of 0 to 4, d and e are each an integer of 0 to 2, and d + e = 2.

The above-mentioned epoxy resin curing agent in which the phenol compound is a compound represented by the following general formula (4) is a preferred embodiment of the present invention.
In the formula, n is a number of 1 or more, and the hydroxyl equivalent is a number satisfying 50 to 250 g / eq.

The above-mentioned epoxy resin curing agent in which the phenol compound is a compound represented by the following general formula (5) is a preferred embodiment of the present invention.
In the formula, n is a number of 1 or more, and the hydroxyl equivalent is a number satisfying 50 to 250 g / eq.

The above-mentioned epoxy resin curing agent in which the phenol compound is a compound represented by the following general formula (6) is a preferred embodiment of the present invention.
In the formula, m and n are each a number of 0.4 to 6.0 satisfying the relationship of m + n = 1 to 10 and m / n = 0.7 to 1.5, and the hydroxyl group equivalent is 50 to 250 g. This is a number satisfying / eq.

  The aforementioned epoxy resin, wherein the phenol compound is an addition compound of a compound represented by the general formula (4), (5) or (6) and a benzoquinone represented by the following general formula (7) or (8) Curing agents are also a preferred embodiment of the present invention.

In formulas (7) and (8), R ⁴ ~ R ⁹ Are each hydrogen or a hydrocarbon group having 1 to 6 carbon atoms; ¹⁰ Is a hydrocarbon group having 1 to 6 carbon atoms, and y is an integer of 0 to 4.

The method for producing the above-described epoxy resin curing agent in which the bismaleimide compound is added after the phenol compound and the dihydroxynaphthalene compound are melt-mixed is a preferred embodiment of the present invention.
In addition, a method for producing the above-described epoxy resin curing agent in which the temperature at which the bismaleimide compound is added is lower than the melt mixing temperature of the phenol compound and the dihydroxynaphthalene compound is also a preferred aspect of the present invention.

  The present invention also provides an epoxy resin composition comprising the above-described epoxy resin curing agent and an epoxy resin, and an epoxy resin curing agent obtained by curing the epoxy resin composition.

The present invention also provides a method for sealing a semiconductor device using the epoxy curing agent described above.

The present invention provides a method for producing a phenolic curing agent that satisfies high flame retardancy, high heat resistance, and high fluidity.
The present invention also provides a method for producing a composition using a novel phenolic curing agent that satisfies high flame retardancy, high heat resistance and high fluidity.

The present invention also provides a method for producing a cured product of a composition using a novel phenolic curing agent that satisfies high flame retardancy, high heat resistance, and high fluidity.

2 is a GPC analysis chart of the mixed product 1 obtained in Example 1. FIG.

In the present invention, 0.5 to 5.0 parts by weight of the bismaleimide compound represented by the general formula (1) and 0.5% by weight of the dihydroxynaphthalene compound represented by the general formula (3) with respect to 1 part by weight of the phenol compound. The present invention provides a method for producing an epoxy resin curing agent in which 1 to 1.0 part by weight is mixed in a temperature range of 100 to 200 ° C.

The phenol compound used in the present invention has two or more phenolic hydroxyl groups in one molecule, is easily compatible with the aforementioned bismaleimide compound and dihydroxynaphthalene compound, and is a highly fluid mixed product. The one that gives is used. For example, bisphenol compounds such as bisphenol F, bisphenol A, bisphenol S, novolak compounds such as phenol novolak resin, cresol novolak resin, naphthol novolak resin, aralkyl compounds such as phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, triphenol Known polyphenol compounds such as methane resin can be used. In consideration of the balance of high heat resistance, high flame retardancy, and high fluidity, a hydroxyl group equivalent of 50 to 250 g / eq and a 150 ° C. melt viscosity of 50 to 500 mPa · s are suitable. Of these, the use of aralkyl compounds is preferred, and these aralkyl compounds are obtained by reacting paraxylylene glycol, bis (hydroxymethyl) biphenyl, or a derivative thereof with a phenolic hydroxyl group-containing compound such as phenols or naphthols using a crosslinking agent. Can be obtained.

The bismaleimide compound represented by the general formula (1) used in the present invention can be easily obtained by condensing maleic anhydride and a bifunctional aromatic amine (for example, JP-A-60). -260623 etc.). As the bismaleimide compound used in the present invention, those having a physical property of a melting point of 100 to 250 ° C. , more preferably 120 to 250 ° C. are preferable.

  As the dihydroxynaphthalene compound represented by the general formula (3) used in the present invention, those having a physical property of a melting point of 100 to 200 ° C. are preferable. For example, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene In view of reactivity with the epoxy resin, those in which the hydroxyl groups are not adjacent to each other are particularly preferable.

  In mixing the phenol compound, the bismaleimide compound represented by the general formula (1), and the dihydroxynaphthalene compound represented by the general formula (3), the weight ratio of the phenol compound to the bismaleimide compound is preferably 0.5. -5.0, more preferably 1.0-4.5, and the weight ratio of the phenolic compound and dihydroxynaphthalene compound is 0.1-1.0, more preferably 0.2-0.8. Is desirable.

There is no restriction | limiting in particular in the said mixing method, Preferably it mixes on stirring conditions in a normal mixing container. There are no particular restrictions on the mixing conditions, but by mixing the components in a temperature range of 120 to 200 ° C., a mixed product having a 150 ° C. melt viscosity of 50 to 500 mPa · s and a hydroxyl group equivalent of 250 to 400 g / eq. Can be obtained. The mixing time varies depending on the mixing temperature, but is preferably about 15 to 60 minutes.

  The mixed product obtained by mixing the phenol compound, the bismaleimide compound represented by the general formula (1), and the dihydroxynaphthalene compound represented by the general formula (3) is a component in which each component is in a homogeneous compatible state. It is estimated to be. According to the GPC (gel permeation chromatograph) analysis, the mixed product obtained by the present invention has peaks corresponding to the mixed components, as shown in the examples below. It is considered to exist in a mixed state.

The reaction ratio of the general formula (7) or (8) with respect to the compound represented by the general formula (4), (5) or (6) is usually 0.2-5. 0 mole times benzoquinones are used.
There are no particular restrictions on the reaction conditions, but a catalyst may be added as necessary to achieve a temperature range of about 80 to 200 ° C.

  The epoxy resin curing agent comprising the mixed product thus obtained has a low melt viscosity in the molding temperature range and excellent workability, and is excellent in flame retardancy and heat resistance. It can be used for coating materials, laminated materials and the like.

  The epoxy resin composition of the present invention is an epoxy resin composition containing the above-described epoxy resin curing agent and an epoxy resin. Examples of the epoxy resin that can be used with the epoxy resin curing agent in the epoxy resin composition include bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolak type epoxy resin, and biphenyl type epoxy. Resin, phenol biphenyl aralkyl type epoxy resin, epoxidized aralkyl resin by xylylene bond such as phenol, naphthol, glycidyl ether type epoxy resin such as dicyclopentadiene type epoxy resin, dihydroxynaphthalene type epoxy resin, triphenolmethane type epoxy resin, Examples include epoxy compounds having two or more epoxy groups in one molecule such as glycidyl ester type epoxy resin and glycidyl amine type epoxy resin. It is. These epoxy resins may be used alone or in combination of two or more. In consideration of moisture resistance, low elastic modulus during heat and flame retardancy, bifunctional epoxy resins such as bisphenol F type epoxy resin and biphenyl type epoxy resin, phenol biphenyl aralkyl type epoxy resin, xylylene such as phenol and naphthol It is preferable to use a polyfunctional epoxy resin having many aromatic rings selected from epoxidized aralkyl resins by bonding.

  In curing the epoxy resin, it is preferable to use a curing accelerator in combination. As the curing accelerator, a known curing accelerator for curing an epoxy resin with a phenol-based curing agent can be used. For example, a tertiary amine compound, a quaternary ammonium salt, an imidazole, a urea compound, a phosphine compound, Examples thereof include phosphonium salts. More specifically, tertiary amine compounds such as triethylamine, triethylenediamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) undecene-7 Imidazoles such as 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 3-phenyl-1,1-dimethylurea 3- (o-methylphenyl) -1,1-dimethylurea, 3- (p-methylphenyl) -1,1-dimethylurea, 1,1′-phenylenebis (3,3-dimethylurea), 1 , 1 ′-(4-methyl-m-phenylene) -bis (3,3-dimethylurea) and other urea compounds, Phosphine compounds such as triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, triphenylphosphoniphenolate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetranaphthoate borate, etc. Although phosphonium salts can be mentioned, it is preferable to use imidazoles, urea compounds and phosphonium salts which exhibit high activity in both curing of epoxy resins and polymerization of bismaleimide.

  In the epoxy resin composition of the present invention, an inorganic filler, a coupling agent, a release agent, a colorant, a flame retardant, a low stress agent, or the like can be added or reacted in advance if necessary. Other curing agents can be used in combination. Examples of such other curing agents include phenol novolak resins, phenol aralkyl resins, phenol biphenyl aralkyl resins, phenol naphthyl aralkyl resins, naphthol aralkyl resins, and triphenolmethane type novolak resins.

  Examples of inorganic fillers include amorphous silica, crystalline silica, alumina, glass, calcium silicate, magnesite, clay, talc, mica, magnesia, barium sulfate, etc., especially amorphous silica, Crystalline silica and barium sulfate are preferred. 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 packing.

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

  The mixing ratio of the epoxy resin curing agent and the epoxy resin of the present invention is such that the equivalent ratio of hydroxyl group / epoxy group is 0.5 to 1.5, particularly 0.8 to 1. A range of 2 is preferable. Further, even when used in combination with another curing agent, it is preferable that the equivalent ratio of hydroxyl group / epoxy group is the above-mentioned ratio. The curing accelerator is preferably used in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin in consideration of curing characteristics and various physical properties. The blending ratio of the inorganic filler varies depending on the type, but considering the solder heat resistance, moldability (melt viscosity, fluidity), low stress, low water absorption, etc., the inorganic filler is added to the entire composition. It is preferable to mix | blend in the ratio which occupies 60 to 93 weight%.

  As a general method for preparing an epoxy resin composition as a molding material, a predetermined proportion of each raw material is sufficiently mixed by, for example, a mixer, then kneaded by a hot roll or a kneader, and further cooled and solidified. Examples of the method include pulverization of a large size and tableting as necessary. The molding material thus obtained can be used for sealing a semiconductor by, for example, low-pressure transfer molding to manufacture a semiconductor device.

  As a general method for preparing an epoxy resin composition as an insulating layer material, a predetermined proportion of each raw material can be dissolved in a solvent, and this can be used as an interlayer insulating varnish for application to a circuit board. The glass sheet can be impregnated with a glass fiber and subjected to a heat treatment to obtain a prepreg for the application, or it can be a heat treatment on a support film to form a film-like adhesive sheet. . Any of these forms can be used as an interlayer insulating layer.

  Curing of the epoxy resin composition can be performed in a temperature range of 100 to 250 ° C., for example, in any product form.

  The present invention will be described more specifically with reference to examples and comparative examples below, but the present invention is not limited to these examples.

[Reference example]
1030.6 g (10.964 mol) of phenol and 498.1 g (4.698 mol) of 1,4-benzoquinone were charged into a four-necked flask having an outlet at the bottom, and 10% trifluoro was kept at an internal temperature of 60 ° C. 0.89 g of an aqueous solution of romethanesulfonic acid was added dropwise. Thereafter, an additional 1.25 g of 10% trifluoromethanesulfonic acid aqueous solution maintained at 80 ° C. for 2 hours was added dropwise. Thereafter, it was kept at 120 ° C. for 1 hour. At this stage, unreacted 1,4-benzoquinone did not remain, and it was confirmed by gas chromatography that all had reacted. Thereafter, 260.0 g (1.566 mol) of para-xylene glycol dimethyl ether was added, and the generated low boiling point component was volatilized out of the system and maintained at an internal temperature of 150 ° C. for 4 hours. At this stage, no unreacted para-xylene glycol dimethyl ether remained, and it was confirmed by gas chromatography that all had reacted. Thereafter, phenol was removed under reduced pressure at 150 ° C. at 30 torr until unreacted phenol was not detected by gas chromatography. This reaction product was extracted at 150 ° C. to obtain 1159.6 g of a black-brown 1,4-benzoquinone-modified phenol aralkyl resin. When the softening point of this resin was measured based on JIS K 2207, it was 77 ° C. The melt viscosity at 150 ° C. measured with an ICI melt viscometer was 95 mPa · s. Furthermore, the hydroxyl group equivalent measured by the acetylation back titration method was 94 g / eq.

[Example 1]
Phenol biphenyl aralkyl resin 24.41g (Air Water Co., Ltd., HE200C-10, hydroxyl group equivalent 205g / eq, 150 ° C melt viscosity 100mPa · s) and 1,6-dihydroxynaphthalene 5.61g (35mmol) 150 After melt mixing at 30 ° C. for 30 minutes, the liquid temperature was lowered to 120 ° C. and 35.91 g (100 mmol) of 4,4′-diphenylmethane bismaleimide was added. This was stirred at the same temperature for 30 minutes and then cooled to room temperature to obtain 65.93 g (mixed product 1) of a homogeneous black-brown glassy melt as a mixed product.
The melt viscosity at 150 ° C. of the mixed product 1 measured with an ICI melt viscometer was 100 mPa · s. Furthermore, the hydroxyl group equivalent of the melt measured by the acetylation back titration method was 350 g / eq.
The mixed product 1 obtained above was subjected to GPC analysis under the following conditions.
GPC analysis conditions (1) Equipment used: HLC-8220 GPC, manufactured by Tosoh Corporation
(2) Column: manufactured by Tosoh Corporation, TSKgel G2000HXL + G1000HXL (6 mm × 30 cm 2 pieces)
(3) Solvent: Tetrahydrofuran (4) Flow rate: 1.000 ml / min
(5) Temperature: 40 ° C
(6) Detector: RI, HLC-8220 GPC built-in RI detector A chart obtained by GPC analysis is shown in FIG. The retention time (RT) of 10.8 to 13.1 minutes in FIG. 1 is a peak corresponding to phenol biphenyl aralkyl resin and the area percentage is 50%, and RT 13.9 minutes is a peak corresponding to bismaleimide and the area percentage is 43. RT 14.6 min was a peak corresponding to 1,6-dihydroxynaphthalene, and the area percentage was 7%.
The mixed product 1 obtained in Example 1 is referred to as an epoxy curing agent 1.

[Example 2]
After 24.41 g of phenol biphenyl aralkyl resin (HE200C-10, manufactured by Air Water Co., Ltd.) and 11.22 g (70 mmol) of 1,6-dihydroxynaphthalene were melt-mixed at 150 ° C. for 30 minutes, the liquid temperature was 120 ° C. Then, 35.91 g (100 mmol) of 4,4′-diphenylmethane bismaleimide was added. The mixture was stirred at the same temperature for 30 minutes and then cooled to room temperature, whereby 71.54 g of a homogeneous black-brown glassy melt (mixed product 2) was obtained as a mixed product.
The melt viscosity of the melt at 150 ° C. measured by the ICI melt viscometer of the mixed product 2 was 80 mPa · s. Furthermore, the hydroxyl group equivalent of the melt measured by the acetylation back titration method was 295 g / eq.
The mixed product 2 obtained in Example 2 is referred to as an epoxy curing agent 2.

[Example 3]
1159.6 g of 1,4-benzoquinone modified phenol aralkyl resin (hydroxyl equivalent 94 g / eq, 150 ° C. melt viscosity 95 mPa · s) and 626.8 g (3.917 mol) of 2,7-dihydroxynaphthalene obtained in Reference Example ) Was melt-mixed at 150 ° C. for 30 minutes, the liquid temperature was lowered to 135 ° C., and 4675.1 g (13.059 mol) of 4,4′-diphenylmethane bismaleimide was added. This was stirred at the same temperature for 30 minutes and then cooled to room temperature to obtain 6461.3 g (mixed product 3) of a homogeneous black-brown glassy melt as a mixed product.
The melt viscosity of the melt at 150 ° C. measured by the ICI melt viscometer of the mixed product 2 was 150 mPa · s. Furthermore, the hydroxyl equivalent of the melt measured by the acetylation back titration method was 397 g / eq.
The mixed product 3 obtained in Example 3 is referred to as an epoxy curing agent 3.

[Example 4]
18.8 g of phenol novolac-modified triphenol methane resin (manufactured by Air Water Co., Ltd., HE910C-10, hydroxyl group equivalent 100 g / eq, 150 ° C. melt viscosity 110 mPa · s) and 2,7-dihydroxynaphthalene 9.6 g (60 mmol) ) Was melt mixed at 150 ° C. for 30 minutes, the liquid temperature was lowered to 120 ° C., and 71.6 g (200 mmol) of 4,4′-diphenylmethane bismaleimide was added. This was stirred at the same temperature for 30 minutes and then cooled to room temperature to obtain 100.0 g of a homogeneous black-brown glassy melt (mixed product 4) as a mixed product.
The melt viscosity of the mixed product 4 at 150 ° C. measured by an ICI melt viscometer was 80 mPa · s. Furthermore, the hydroxyl group equivalent of the melt measured by the acetylation back titration method was 295 g / eq.
The mixed product 4 obtained in Example 4 is referred to as an epoxy curing agent 4.

[Comparative Example 1]
After 24.41 g of phenol biphenyl aralkyl resin (manufactured by Air Water Co., HE200C-10) and 35.91 g (100 mmol) of 4,4′-diphenylmethane bismaleimide were melt-mixed at 120 ° C. for 30 minutes, another 30 minutes By stirring, 60.32 g of a homogeneous blackish brown glassy melt (mixed product 5) was obtained.
The melt viscosity at 150 ° C. measured by an ICI melt viscometer was 400 mPa · s. Furthermore, the hydroxyl group equivalent of the melt measured by the acetylation back titration method was 510 g / eq.

  The physical properties of the mixed products 1 to 4 obtained in Examples 1 to 4 are compared with the mixed product 5 prepared in Comparative Example 1 and the known epoxy resin curing agents 5 to 7 used in Comparative Examples 2 to 4. The results are shown in Table 1.

[Example 5]
Epoxy resin represented by the following general formula (9) (NC-3000 manufactured by Nippon Kayaku Co., Ltd., phenol biphenyl aralkyl type, epoxy equivalent 275 g / eq), epoxy curing agent 1 obtained in Example 1, fused silica and A urea curing accelerator (manufactured by San Apro, U-CAT 3512T) is blended in the proportions shown in Table 2, mixed thoroughly, kneaded for 3 minutes with two rolls at 85 ± 3 ° C., cooled, and pulverized. Thus, a molding composition was obtained. This molding composition was molded at 175 ° C. for 2 minutes at a pressure of 100 kgf / cm ² with a transfer molding machine, and then post-cured at 180 ° C. for 6 hours to prepare test pieces for glass transition temperature measurement and flame retardancy test. And evaluated. The results are shown in Table 2.

(In the formula, G is a glycidyl group, n is a number of 1 to 10)

[Example 6]
In Example 5, a molding composition was prepared in the same manner as in Example 5 except that the epoxy curing agent 2 was used instead of the epoxy curing agent 1 used, and the blending ratio was as shown in Table 2. Thus, test pieces for glass transition temperature measurement and flame retardancy test were obtained. The results are shown in Table 2.

[Example 7]
In Example 5, a molding composition was prepared in the same manner as in Example 5 except that the epoxy curing agent 3 was used instead of the epoxy curing agent 1 used, and the blending ratio was as shown in Table 2. Thus, test pieces for glass transition temperature measurement and flame retardancy test were obtained. The results are shown in Table 2.

[Example 8]
In Example 5, a molding composition was prepared in the same manner as in Example 5 except that the epoxy curing agent 4 was used instead of the epoxy curing agent 1 used, and the blending ratio was as shown in Table 2. Thus, test pieces for glass transition temperature measurement and flame retardancy test were obtained. The results are shown in Table 2.

[Comparative Example 2]
In Example 5, in place of the epoxy curing agent 1, a phenol novolac-modified triphenolmethane resin (manufactured by Air Water Co., Ltd., HE910C-10, hydroxyl group equivalent 100 g / eq, 150 ° C. melt viscosity 110 mPa · s) (this resin Except for using epoxy curing agent 5), a molding composition was prepared in the same manner as in Example 5 to obtain test pieces for measuring the glass transition temperature and for the flame retardancy test. The results are shown in Table 2.

[Comparative Example 3]
In Example 5, instead of epoxy curing agent 1, instead of phenol aralkyl resin (Air Water Co., Ltd., HE100C-10, hydroxyl group equivalent 168 g / eq, 150 ° C. melt viscosity 1100 mPa · s) (this resin Except for using epoxy curing agent 6), a molding composition was prepared in the same manner as in Example 5, and test pieces for glass transition temperature measurement and flame retardancy test were obtained therefrom. The results are shown in Table 2.

[Comparative Example 4]
In Example 5, instead of the epoxy curing agent 1, the same as in Example 5 except that the 1,4-benzoquinone-modified phenol aralkyl resin obtained from the reference example (this resin is referred to as an epoxy curing agent 7) is used. Thus, a molding composition was prepared, and test pieces for glass transition temperature measurement and flame retardancy test were obtained therefrom. The results are shown in Table 2.

The physical properties of these molding materials were measured by the following method.
(1) Melt viscosity of composition 2.5 g of the epoxy resin composition was used as a tablet, and measured with a high and low flow tester (temperature: 175 ° C., orifice diameter: 1 mm, length: 1 mm).
(2) Glass transition temperature The linear expansion coefficient of the test piece was measured by TMA at a heating rate of 10 ° C./min, and the inflection point of the linear expansion coefficient was taken as the glass transition temperature.
(3) Flame retardance Using a sample having a thickness of 1.6 mm, a width of 10 mm, and a length of 135 mm, the after flame time was measured and evaluated in accordance with UL-94V.
These evaluation results are shown in Table 2.

In Table 1, the curing agents provided by the present invention shown in Examples 1 to 4 have the same melt viscosity as the known curing agents shown in Comparative Examples 2 to 4. On the other hand, in Comparative Example 1, it can be seen that if the addition of the dihydroxynaphthalene compound, which is a blending component of the curing agent of the present invention, is omitted, a curing agent having a low melt viscosity cannot be obtained, which is disadvantageous in realizing high fluidity.
In Table 2, it turns out that the fluidity | liquidity of the epoxy resin composition containing the hardening | curing agents 1-4 of this invention is equivalent to the epoxy resin composition derived from a well-known hardening | curing agent. The cured product is excellent in heat resistance and flame retardancy, and achieves both heat resistance behavior and flame retardancy behavior when using curing agents 5-7. In particular, paying attention to Example 7, Comparative Example 4, Example 8 and Comparative Example 2, it can be seen that heat resistance and flame retardancy can be remarkably improved by modifying the original curing agent with the formulation of the present invention.
Accordingly, the present invention enables an epoxy resin composition having high fluidity, high heat resistance, and high flame retardance, which has been difficult to realize with the prior art.

The epoxy resin curing agent provided by the present invention is an epoxy resin curing agent that satisfies high flame retardancy, high heat resistance, and high fluidity.
In addition, the present invention provides a composition using a novel epoxy resin curing agent that satisfies high flame retardancy, high heat resistance, and high fluidity, and a cured product thereof.
According to the present invention, phenol which is particularly useful as an epoxy resin curing agent, and can form an epoxy resin composition excellent in low melt viscosity and flame retardancy, particularly when used as a semiconductor sealing and interlayer insulating material. A polymer and its epoxy resin composition are provided.

Claims (12)

A phenol compound having a hydroxyl group equivalent of 50 to 250 g / eq and a 150 ° C. melt viscosity of 50 to 500 mPa · s and having two or more phenolic hydroxyl groups in one molecule, a bismaleimide compound represented by the following general formula (1), In the dihydroxynaphthalene compound represented by the following general formula (3), the weight ratio of the bismaleimide compound to the phenol compound is 0.5 to 5.0, and the weight ratio of the dihydroxynaphthalene compound to the phenol compound is 0.1 to 1.0. The method of manufacturing the epoxy resin hardening | curing agent whose 150 degreeC melt viscosity is 50-500 mPa * s and whose hydroxyl equivalent is 250-400 g / eq mixed in the temperature range of 100-200 degreeC.
(In the formula (1), Ar ¹ is an arylene group represented by the formula (2), X is a methylene group, a dimethylmethylene group, an oxygen atom, a sulfur atom or a direct bond, and n is an integer of 0 to 1. In formula (2), R ¹ is a hydrocarbon group having 1 to 4 carbon atoms, and a is an integer of 0 to 4. In formula (3), R ² and R ³ are 1 to 4 carbon atoms. And b and c are integers of 0 to 4, and d and e are each an integer of 0 to 2 and d + e = 2.)   The method for producing an epoxy resin curing agent according to claim 1, wherein the bismaleimide compound is added after the phenol compound and the dihydroxynaphthalene compound are melt-mixed. The method for producing an epoxy resin curing agent according to claim 1 or 2 , wherein the phenol compound is a compound represented by the following general formula (4).
(In the formula, n is a number of 1 or more, and the hydroxyl equivalent is a number satisfying 50 to 250 g / eq.) The method for producing an epoxy resin curing agent according to any one of claims 1 to 3, wherein the phenol compound is a compound represented by the following general formula (5).
(In the formula, n is a number of 1 or more, and the hydroxyl equivalent is a number satisfying 50 to 250 g / eq.) The method for producing an epoxy resin curing agent according to any one of claims 1 to 3, wherein the phenol compound is a compound represented by the following general formula (6).
(In the formula, m and n are numbers of 0.4 to 6.0 satisfying the relationship of m + n = 1 to 10 and m / n = 0.7 to 1.5, respectively, and the hydroxyl equivalent is 50 to It is a number that satisfies 250 g / eq.) The phenol compound is an addition compound of a compound represented by the general formula (4), (5) or (6) and a benzoquinone represented by the following general formula (7) or (8) The method to manufacture the epoxy resin hardening | curing agent in any one of Claims 1-3.
(In the formulas (7) and (8), R ^{4 to} R ⁹ are each hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and R ¹⁰ is a hydrocarbon group having 1 to 6 carbon atoms. Y is an integer of 0 to 4.) The method for producing an epoxy resin curing agent according to any one of claims 1 to 6 , wherein the bismaleimide compound has a melting point of 120 to 250 ° C, and the dihydroxynaphthalene compound has a melting point of 100 to 200 ° C. Method for producing an epoxy resin composition for mixing the epoxy resin curing agent and an epoxy resin produced by the production method according to any one of claims 1 to 7. In the production method of the epoxy resin composition according to claim 8, the production method of the epoxy resin composition for mixing further a curing accelerator. The method for producing an epoxy resin composition according to claim 8 or 9, further comprising mixing an inorganic filler. Method for producing a cured epoxy resin to the thermosetting epoxy resin composition produced by the method according to any one of claims 8-10. The method to seal a semiconductor device using the epoxy resin composition manufactured by the manufacturing method in any one of Claims 8-10 .