TWI802711B - Epoxy resin composition and its hardened product - Google Patents

Abstract

The present invention provides an epoxy resin composition and a cured product thereof capable of obtaining a cured product having excellent heat resistance and adhesion and a lower dielectric tangent. Specifically, an epoxy resin composition is used, which contains an α-naphthol biphenyl aralkyl type epoxy resin and a hardener, and the hardener contains an active ester structure. The α-naphthol biphenyl aralkyl type epoxy resin preferably has a structure represented by formula (1). The hardener preferably has a structure represented by formula (2). The hardening agent is preferably an active ester compound or resin that uses a compound having two or more phenolic hydroxyl groups and an aromatic monocarboxylic acid or its acyl halide as essential reaction raw materials.

Description

Epoxy resin composition and its hardened product

The present invention relates to an epoxy resin composition and its cured product.

Epoxy resin compositions containing epoxy resin and its hardener as essential components are widely used in electronic parts such as semiconductors and multilayer printed circuit boards because the cured products exhibit excellent heat resistance and insulation properties. Patent Document 1 discloses an epoxy resin composition with a predetermined structure, which is a resin composition having high heat resistance, low water absorption, and high adhesiveness. Patent Document 2 discloses an epoxy resin with a predetermined structure, which is excellent in flame retardancy, moisture resistance, heat resistance, low thermal expansion, and adhesion to metal substrates.

In the application of electronic parts, in the technical field of printed wiring board materials, in order to cope with the high-speed processing of information, it is necessary to improve the dielectric properties. As materials with excellent dielectric properties, hardened resin compositions including epoxy resins and active ester resins have been examined. For example, Patent Document 3 proposes an epoxy resin composition having an aryloxycarbonyl group at the chain end and using a polycondensate of an aromatic polycarboxylic acid and an aromatic polyhydroxy compound as a hardener for the epoxy resin. This epoxy resin composition has excellent heat resistance and can provide a low dielectric tangent epoxy resin cured product. In addition, research on reducing the surface roughness of the copper foil for improving the dielectric properties of the substrate has also been carried out; at this time, although the dielectric properties can be improved, the adhesion with the resin layer will deteriorate, and various question. From the above, the electronic component market requires resins with good heat resistance, dielectric properties, and adhesion.

[Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 6-271654

[Patent Document 2] Japanese Unexamined Patent Publication No. 2006-160868

[Patent Document 3] Japanese Patent Laid-Open No. 2008-291279

The present invention is the result of further research on the above-mentioned technology, and aims to provide an epoxy resin composition and its cured product which can obtain a cured product having excellent heat resistance and adhesion and a lower dielectric tangent.

The inventors of the present case have found that, as a result of repeated research, the use of α-naphthol biphenyl aralkyl type epoxy resin in combination with the ester structure generated by phenolic groups and aromatic carboxylic acid groups (hereinafter also referred to as "active resins") The hardening agent of ester structure") can solve the above-mentioned problems, and finally completes the present invention.

That is, the present invention is related to the following [1]~[8]:

An epoxy resin composition, which contains α-naphthol biphenyl aralkyl epoxy resin and a hardener, and the hardener has an active ester structure.

The epoxy resin composition as in [1], wherein the aforementioned α-naphthol biphenyl aralkyl type epoxy resin has the structure shown in the following formula (1):

(In the formula (1), R ¹ represents a hydrogen atom, a halogen atom, a glycidyloxy group, an allyl group, an alkyl group, an alkoxy group, or an aryl group; n is an integer of 1 to 20).

The epoxy resin composition as in [1] or [2], wherein the hardener has a structure represented by the following formula (2):

(In formula (2), X represents a compound residue containing a monovalent phenolic hydroxyl group, Y represents a compound residue containing a divalent phenolic hydroxyl group; n is an integer of 0 to 20).

The epoxy resin composition of [1] or [2], wherein the aforementioned hardener is an active ester compound that uses a compound having two or more phenolic hydroxyl groups and an aromatic monocarboxylic acid or its acyl halide as essential reaction materials, or resin.

The epoxy resin composition according to any one of [1] to [4], which further contains a curing accelerator.

A cured product, which is a cured product of the epoxy resin composition according to any one of [1] to [5].

A printed wiring board using the epoxy resin composition according to any one of [1] to [5].

A semiconductor packaging material, which uses the epoxy resin composition according to any one of [1] to [5].

According to the present invention, it is possible to provide an epoxy resin composition and a cured product thereof capable of obtaining a cured product having excellent heat resistance and adhesiveness and a lower dielectric tangent.

Fig. 1 is the GPC spectrum of the α-naphthol biphenyl aralkyl type epoxy resin (A-2) obtained in Synthesis Example 2.

Fig. 2 is the GPC spectrum of the α-naphthol aralkyl type epoxy resin (B-2) obtained in Comparative Synthesis Example 2.

Fig. 3 is the GPC spectrum of the β-naphthol aralkyl type epoxy resin (B-4) obtained in Comparative Synthesis Example 4.

4 is a GPC spectrum of the methoxy-modified α-naphthol biphenyl aralkyl type epoxy resin (B-6) obtained in Comparative Synthesis Example 6.

[Mode for Carrying Out the Invention]

An embodiment of the present invention will be described in detail below. This invention is not limited to the following embodiment, In the range which does not impair the effect of this invention, it can change suitably and implement.

[Epoxy resin composition]

The epoxy resin composition of this embodiment (hereinafter also referred to as "resin composition") contains an α-naphthol biphenyl aralkyl type epoxy resin and a hardener.

(epoxy resin)

The α-naphthol biphenyl aralkyl type epoxy resin is an epoxy resin having a functional group derived from α-naphthol and a biphenyl group in the molecular main skeleton. By combining an epoxy resin having such a molecular main skeleton and a hardening agent having an active ester structure described later, it is possible to obtain a cured product that provides excellent heat resistance and adhesion, and has better dielectric properties than ever before. Epoxy resin composition.

As the α-naphthol biphenyl aralkyl type epoxy resin, an epoxy resin having a structure represented by the following formula (1) can be used.

However, in formula (1), R ¹ represents a hydrogen atom, a halogen atom, a glycidoxy group, an allyl group, an alkyl group, an alkoxy group, or an aryl group. n is 1-20, preferably 1-15, more preferably an integer of 1-12. As a halogen atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example. Examples of the alkyl group include those having 1 to 20 carbon atoms, preferably those having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, n-hexyl, and cyclohexyl. Examples of the alkoxy group include alkoxy groups having 1 to 10 carbon atoms, preferably alkoxy groups having 1 to 6 carbon atoms. Examples of alkoxy groups with 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tertiary butoxy, pentyloxy, and n-hexyloxy , Cyclohexyl and so on. Examples of the aryl group include phenyl, benzyl, naphthyl, methoxynaphthyl and the like. Among them, R ¹ is preferably a hydrogen atom in view of the balance of impregnation into base materials such as reinforcing fibers, heat resistance and toughness of cured products.

The softening point of the α-naphthol biphenyl aralkyl epoxy resin is not particularly limited, but it is preferably 70°C to 140°C, more preferably 75°C to 130°C in terms of solvent solubility and good heat resistance of the hardened product. °C, more preferably 80 °C~120 °C. In addition, a softening point is measured based on JISK7234.

The epoxy equivalent of α-naphthol biphenyl aralkyl type epoxy resin is preferably 280~450g/equivalent in view of the heat resistance of the hardened product and the impregnation property of the base material such as reinforced fiber. scope.

The production method of α-naphthol biphenyl aralkyl type epoxy resin is not particularly limited, epichlorohydrin can be used to form polycondensate of α-naphthol and biphenyl compounds such as dichloromethyl biphenyl to form polypropylene oxide derived from base ethers.

(hardener)

The hardener system has an active ester structure. "Active ester structure" refers to an ester structure derived from a phenolic group and an aromatic carboxylic acid group. The hardener can be composed of a compound or resin having an active ester structure (hereinafter also referred to as "active ester resin"). Specific examples of active ester resins include compounds selected from compounds having one phenolic hydroxyl group (a1), compounds having two or more phenolic hydroxyl groups (a2), and aromatic polycarboxylic acids or their acyl halides (a3). The active ester resin (I) of the compound as the reaction raw material is selected from the compound (b1) having more than 2 phenolic hydroxyl groups, aromatic monocarboxylic acid or its acyl halide (b2) and aromatic polycarboxylic acid or its The compound of acyl halide (b3) is used as the active ester resin (II) of the reaction raw material. These can be used alone or in combination.

Compounds (a1) having one phenolic hydroxyl group include, for example, phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, 2,6-xylenol, o-phenylphenol, Aromatic monohydroxy compounds such as p-phenylphenol, 2-benzylphenol, 4-benzylphenol, 4-(α-cumyl)phenol, α-naphthol, and β-naphthol. Wherein, through the curing agent having residues of α-naphthol, β-naphthol-o-phenylphenol and/or p-phenylphenol, a cured product with lower dielectric tangent can be obtained.

Examples of compounds (a2) and (b1) having two or more phenolic hydroxyl groups include aromatic polyhydric hydroxyl compounds. Examples of the aromatic polyhydric hydroxyl compound include resorcinol, hydroquinone, trimethylhydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,6-naphthalenediol, 2,6 -Naphthalenediol, 2,3-naphthalenediol, 2,7-naphthalenediol, 1,4-naphthalenediol, 3,3',5,5'-tetramethylbisphenol F, 3,3' ,5,5'-tetramethylbiphenol and other aromatic dihydroxy compounds; 1,3,5-trihydroxybenzene, 1,2,3-trihydroxybenzene, 2,4,4'-trihydroxybenzophenone Aromatic trihydroxy compounds such as ketones and trisphenol methane; 2,2',4,4'-tetrahydroxybenzophenone, 1,1,2,2-tetraphenolethane, etc.

Moreover, compounds (a2) and (b1) may be compounds represented by the following formula (4).

(However, in formula (4), m is an integer from 0 to 20)

In the above formula (4), Ar ¹ each independently represents a substituent containing a phenolic hydroxyl group, and Z each independently represents an oxygen atom, a sulfur atom, a sulfonyl group, a substituted or unsubstituted alkane having 1 to 20 carbon atoms group, a substituted or unsubstituted cycloalkylene group with 3 to 20 carbon atoms, an arylylene group with 6 to 20 carbon atoms, or an aralkylene group with 8 to 20 carbon atoms.

^Ar1 is not particularly limited, and examples include phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, 2,6-xylenol, o-phenylphenol, p-phenylene Residues of aromatic monohydroxy compounds such as phenol, 2-benzylphenol, 4-benzylphenol, 4-(α-cumyl)phenol, α-naphthol, β-naphthol, etc.

There are no particular limitations on the aforementioned alkylene groups with 1 to 20 carbon atoms, and examples include methylene, ethylidene, propylidene, 1-methylmethylene, 1,1-dimethylmethylene Methyl, 1-methylethylenyl, 1,1-dimethylethylenyl, 1,2-dimethylethylenyl, propylenyl, butylene, 1-methylpropylenyl, 2 -methylpropylidene, pentylene, hexylene and the like.

There are no particular limitations on the aforementioned cycloalkylene groups with 3 to 20 carbon atoms, and examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentyl, and cycloheptyl. and cycloalkylene groups represented by the following formulas (5-1) to (5-4), etc.

In addition, in the above-mentioned formulas (5-1) to (5-4), "*" represents a bonding site with Ar ¹ .

The arylylene group having 6 to 20 carbon atoms is not particularly limited, and arylylene groups represented by the following formula (6-1) and the like are exemplified.

In addition, in the above-mentioned formula (6-1), "*" represents a bonding site with Ar ¹ .

The aralkylene groups having 8 to 20 carbon atoms are not particularly limited, and examples thereof include aralkylene groups represented by the following formulas (7-1) to (7-5).

In addition, in the formulas (7-1) to (7-5), "*" represents a bonding site with Ar ¹ .

Among the above, Z in formula (4) is preferably a cycloalkylene group with 3 to 20 carbon atoms, an arylalkyl group with 6 to 20 carbon atoms, and an aralkylene group with 8 to 20 carbon atoms; Those represented by formulas (5-3), (5-4), (6-1), (7-1) to (7-5) are more preferable from the viewpoint of adhesiveness and dielectric properties. m in formula (4) is 0 or an integer of 1-10, preferably 0-8; based on the viewpoint of solvent solubility, preferably 0-5.

In addition, compounds (a2) and (b1) may have a structure described in the following formula (8).

(However, in formula (8), 1 represents an integer of 1 or more, and R ³ represents a hydrogen atom, an alkyl group, or an aryl group).

In formula (8), l is preferably 1-20, more preferably 1-15, and still more preferably an integer of 1-12. Examples of the alkyl group include those having 1 to 20 carbon atoms, preferably those having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, n-hexyl, and cyclohexyl. Examples of the aryl group include benzyl, naphthyl, and methoxynaphthyl.

With regard to compounds (a2), (b1), among the above, in terms of solvent solubility and dielectric properties of the reaction product, the compounds shown in formulas (4) and (8) are preferred; moreover, more preferably In formula (4), Ar ^is the residue of phenol, o-cresol, or α-naphthol, β-naphthol, and Z is formula (5-3), (6-1), (7-1) ~(7-5) and formula (8).

As the aromatic monocarboxylic acid or its acyl halide (b2), benzoic acid and benzoyl chloride are specifically mentioned.

Aromatic polycarboxylic acids or their acyl halides (a3) and (b3) include, for example, isophthalic acid, phthalic acid, 1,4-, 2,3- or 2,6-naphthalene dicarboxylic acid, etc. Aromatic dicarboxylic acids; aromatic tricarboxylic acids such as trimellitic acid and trimellitic acid; pyromellitic acid; and their acyl chlorides, etc. Among them, isophthalic acid or a mixture of isophthalic acid and terephthalic acid is preferred because the reactant has excellent melting point or solvent solubility.

The active ester resins having the above structure include, for example, the following active ester resins (I) and (II).

The active ester resin (I) includes, for example, an active ester resin having a structure represented by the following formula (2).

In formula (2), X represents a compound residue containing a monovalent phenolic hydroxyl group, and Y represents a compound residue containing a divalent phenolic hydroxyl group. n is 0-20, preferably 0-15, more preferably an integer of 0-10.

The active ester resin (II) includes, for example, active ester resins having a structure represented by the following formula (3).

In formula (3), Y represents a compound residue containing a divalent phenolic hydroxyl group, and R ² represents a hydrogen atom or an alkyl group. n is 0-20, preferably 0-15, more preferably an integer of 0-10. Examples of the alkyl group include those having 1 to 20 carbon atoms, preferably those having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, n-hexyl, and cyclohexyl.

Among them, the active ester resin (I) represented by the formula (2) is preferable in terms of its excellent moisture and heat resistance.

The esterification equivalent weight of the active ester resin is preferably 150-400 g/eq, more preferably 160-350 g/eq, and even more preferably 170-300 g/eq. When the esterification equivalent weight of the active ester resin is within the above range, a balanced heat resistance and dielectric properties can be obtained.

The melt viscosity of the active ester resin is preferably 0.01-500dPa‧s, more preferably 0.01-400dPa‧s, and even more preferably 0.01-300dPa‧s as measured by an ICI viscometer at 200°C. When the melt viscosity of the active ester resin is within the above range, well-balanced moldability and heat resistance of the cured product can be obtained.

The softening point of the active ester resin is not particularly limited, but it is preferably 200°C or lower, more preferably 190°C or lower, and even more preferably 170°C or lower in terms of solvent solubility. In addition, the softening point is as above.

The method for producing the active ester resin is not particularly limited, and it can be produced by well-known and commonly used synthesis methods such as the acetic anhydride method, the interfacial polymerization method, and the solution method.

The curing agent may further contain other curing agents for epoxy resins in addition to the active ester resin. Examples of the curing agent for epoxy resins that can be used here include curing agents such as amine compounds, amide compounds, acid anhydride compounds, and phenol compounds. When using the curing agent for epoxy resin together, the usage amount is preferably in the range of 1% by mass to 30% by mass in the entire resin composition.

(blend amount)

The blending amount of the α-naphthol biphenyl aralkyl type epoxy resin and the active ester resin in the resin composition is 1 mole of epoxy groups in the α-naphthol biphenyl aralkyl type epoxy resin , preferably the blending amount of the aryloxycarbonyl group in the active ester resin is 0.15-5 moles, more preferably 0.9-2.0 moles. If the above blending amount is used, the curing of the α-naphthol biphenyl aralkyl type epoxy resin can be sufficiently advanced, and an epoxy resin composition capable of providing a cured product with a low dielectric tangent can be easily obtained.

(hardening accelerator)

The resin composition may contain a hardening accelerator as needed. Examples of the hardening accelerator include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine zirconium salts, and the like. Especially when it is used as a build-up material or a circuit board, dimethylaminopyridine or imidazole is preferable because of excellent heat resistance, dielectric properties, and solder resistance. Especially when used as a semiconductor packaging material, in terms of excellent hardening properties, heat resistance, electrical properties, moisture resistance and reliability, the phosphorus compound is preferably triphenylphosphine, and the tertiary amine is preferably 1,8- Diazabicyclo-[5.4.0]-undecene (DBU). The amount of the hardening accelerator used is preferably in the range of 0.01 to 5.0 parts by mass, more preferably in the range of 0.01 to 2.0 parts by mass, based on 100 parts by mass of the α-naphthol biphenyl aralkyl type epoxy resin. By setting it as the said range, the resin composition which can provide the hardened|cured material which can obtain sufficient hardening reaction rate and is more excellent in heat resistance can be obtained.

(other added ingredients)

樹脂；以二烯丙基雙酚或三聚異氰酸三烯丙酯為代表之含烯丙基樹脂；聚磷酸酯或磷酸酯-碳酸酯共聚物等。此等可各自單獨使用，亦可併用2種以上。 The resin composition may further contain other resin components. Other resin components include, for example, cyanate resin; bismaleimide resin; benzo

Resin; allyl-containing resin represented by diallyl bisphenol or triallyl isocyanate; polyphosphate or phosphate-carbonate copolymer, etc. These may be used individually, respectively, and may use 2 or more types together.

The blending ratio of these other resin components is not particularly limited, and can be appropriately adjusted depending on desired properties of the cured product and the like. As an example of the blending ratio, the range of 1 to 50% by mass of the entire resin composition may be taken.

化合物、三聚氰酸化合物、異三聚氰酸化合物、啡噻

等氮系難燃劑；聚矽氧油、聚矽氧橡膠、聚矽氧樹脂等聚矽氧系難燃劑；金屬氫氧化物、金屬氧化物、金屬碳酸鹽化合物、金屬粉、硼化合物、低熔點玻璃等無機難燃劑等。使用此等難燃劑時，較佳為全部樹脂組成物中0.1~20質量%的範圍。 The resin composition may also contain various additives such as flame retardants, inorganic fillers, silane coupling agents, mold release agents, pigments, and emulsifiers as required. Examples of the flame retardant include red phosphorus, ammonium phosphate such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium polyphosphate, inorganic phosphorus compounds such as phosphoramide; phosphoric acid ester compounds, phosphonic acid (phosphonic acid) compounds, secondary Phosphinic acid compound, phosphine oxide compound, phosphorane compound, organic nitrogen-containing phosphorus compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10 -(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,7-dihydroxynaphthyl)-10H-9-oxa- cyclic organophosphorus compounds such as 10-phosphaphenanthrene-10-oxide, and derivatives obtained by reacting the above-mentioned cyclic organophosphorus compounds with compounds such as epoxy resins or phenolic resins, etc.;

Compounds, cyanuric acid compounds, isocyanuric acid compounds,

Nitrogen-based flame retardants; polysiloxane-based flame retardants such as polysiloxane oil, polysiloxane rubber, and polysiloxane resin; metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, Inorganic flame retardants such as low melting point glass, etc. When using such a flame retardant, it is preferable that it is the range of 0.1-20 mass % in the whole resin composition.

The inorganic filler is blended, for example, when the resin composition is used for a semiconductor encapsulating material. Examples of inorganic fillers include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Among them, fused silica is preferred because more inorganic fillers can be blended. Fused silica can be used in either crushed or spherical form, and it is preferable to mainly use spherical ones in order to increase the blending amount of fused silica and suppress the increase of the melt viscosity of the resin composition. Furthermore, in order to increase the blending amount of spherical silica, it is preferable to properly adjust the particle size distribution of spherical silica. In terms of the filling ratio, it is preferable to blend in the range of 0.5 to 95 parts by mass with respect to 100 parts by mass of the resin component.

The preparation method of the resin composition is not particularly limited, for example, it can be obtained by using a stirring device or a three-roll mill to uniformly mix the above-mentioned components at, for example, 0°C to 200°C.

[hardened object]

The resin composition can be molded by heating and hardening in a temperature range of about 20 to 250°C, for example, by a well-known and commonly used thermosetting method.

The hardened resin composition of this embodiment has a glass transition temperature of 140°C or higher, excellent heat resistance and a low dielectric tangent of less than 2.0×10 ^-3 at 1 GHz, and the adhesion is also comparable to conventional ones. Knowledge equivalent or higher. From the above, it can be preferably used for electronic materials such as printed wiring boards, semiconductor packaging materials, and resist materials.

[Printed wiring boards, etc.]

When the resin composition is used for printed wiring boards or build-up adhesive films, it is generally preferable to mix it with an organic solvent and dilute it. Examples of organic solvents include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl celluloid, ethylene glycol acetate, Propylene glycol monomethyl ether acetate, etc. The type or blending amount of the organic solvent can be appropriately adjusted depending on the use environment of the resin composition. For example, in the application of printed wiring boards, it is preferable that the boiling point of methyl ethyl ketone, acetone, dimethylformamide, etc. is below 160°C The polar solvent is preferably used at a ratio of 40 to 80% by mass of non-volatile matter. For build-up adhesive films, it is preferable to use ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, celluloid acetate, propylene glycol monomethyl ether acetate, Acetate solvents such as benzyl acetate, carbitol solvents such as celluloid and butyl carbitol, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like are preferably used in a ratio of 30 to 70% by mass of the nonvolatile matter.

The method of manufacturing a printed wiring board using a resin composition includes, for example, a method of impregnating a reinforcing base material with a resin composition and curing it to obtain a prepreg, and then laminating this on a copper foil and performing thermocompression bonding. Examples of the reinforcing base material include paper, glass cloth, glass nonwoven fabric, amide paper, amide cloth, glass felt, glass gauze cloth, and the like. The impregnation amount of the resin composition is not particularly limited, but it is usually preferably adjusted so that the resin content in the prepreg reaches 20 to 80% by mass.

[Semiconductor Packaging Materials]

When the resin composition is used as a semiconductor packaging material, it is generally better to mix the above-mentioned inorganic filler. The semiconductor encapsulating material can be prepared by kneading a compound using, for example, an extruder, a kneader, a roll, or the like. The method of molding a semiconductor package using the obtained semiconductor package material includes, for example, molding the semiconductor package material using a mold, transfer molding machine, injection molding machine, etc., and further heating at a temperature of 50 to 200°C for 2 to 10 minutes. hourly method; according to this method, a semiconductor device that is a molded object can be obtained.

[Example]

Examples are shown below to describe the present invention more specifically, but the present invention is not limited to these Examples. Below, "parts" and "%" are quality standards unless otherwise specified. In addition, the softening point measurement, the GPC measurement, and the melt viscosity were measured under the following conditions.

(1) Determination of softening point

Based on JIS K7234.

(2) GPC determination

Apparatus: Measurement was performed under the following conditions with "HLC-8220 GPC" manufactured by TOSOH Co., Ltd.

‧Column: Guard column "HXL-L" manufactured by TOSOH Co., Ltd. + "TSK-GEL G2000HXL" manufactured by TOSOH Co., Ltd. + "TSK-GEL G2000HXL" manufactured by TOSOH Co., Ltd. GEL G3000HXL” + TOSOH Co., Ltd. “TSK-GEL G4000HXL”

‧Column temperature: 40℃,

‧Solvent: THF

‧Flow rate: 1mL/min

‧Detector: RI

(3) Determination of melt viscosity

Measurement was performed with "Cone and Plate Viscometer CV-1S" manufactured by (Toa Industrial Co., Ltd.).

<Synthesis of epoxy resin> [Synthesis Example 1] Synthesis of α-Naphthol Biphenyl Aralkyl Type Resin (A-1)

360 parts of α-naphthol, 586 parts of toluene, and 377 parts of dichloromethylbiphenyl were added to a flask equipped with a stirrer, a cooling pipe, and a nitrogen gas sealing port while blowing nitrogen gas, and heated to 80°C. After dropping 245 parts of 49% sodium hydroxide aqueous solution there over 1 hour, it heated to 90 degreeC, and maintained it for 11 hours. Use 85% phosphoric acid to neutralize until the pH is neutral, stop stirring and take out the lower layer. Add 15 parts of p-toluenesulfonic acid, heat to 180°C for 2 hours while distilling off volatile components, neutralize with 49% sodium hydroxide aqueous solution until the pH becomes neutral, and distill off under reduced pressure while maintaining the internal temperature After volatilization, the obtained resin was taken out and (alpha)-naphthol biphenyl aralkyl resin (A-1) was obtained. The hydroxyl equivalent weight is 272g/eq.

[Synthesis example 2] Synthesis of α-naphthol biphenyl aralkyl type epoxy resin (A-2)

One side of the flask equipped with a thermometer, cooling pipe and stirrer is implemented nitrogen blowing, and one side adds 272g of α-naphthol biphenyl aralkyl resin (A-1) (hydroxyl equivalent 1.0g/ eq), 740 g (8.0 moles) of epichlorohydrin, and 53 g of n-butanol were dissolved. After heating up to 50° C., 220 g (1.10 mol) of a 20% sodium hydroxide aqueous solution was added over 3 hours, and then further reacted at 50° C. for 1 hour. After the reaction, unreacted epichlorohydrin was distilled off under reduced pressure at 150°C. Next, 600 g of methyl isobutyl ketone and 100 g of n-butanol were added to the obtained crude epoxy resin and dissolved. Furthermore, 15 parts of 10 weight% sodium hydroxide aqueous solutions were added to this solution, and it reacted at 80 degreeC for 2 hours, and washed with 200g of water three times until pH of a washing|cleaning liquid became neutral. Next, the system was dehydrated by azeotropy, and after precision filtration, the solvent was distilled off under reduced pressure to obtain epoxy resin (A-2). The obtained epoxy resin (A-2) had a softening point of 100° C. and an epoxy equivalent of 325 g/eq. Fig. 1 shows the GPC spectrum of the obtained epoxy resin (A-2).

[Comparative Synthesis Example 1] Synthesis of α-Naphthol Aralkyl Resin (B-1)

α-Naphthol aralkyl resin (B-1) was obtained in the same manner as in Synthesis Example 1-1, except that dichloromethylbiphenyl was changed to 263 parts of p-xylene dichloride. The hydroxyl equivalent weight is 224 g/eq.

[Comparative synthesis example 2] Synthesis of α-naphthol aralkyl type epoxy resin (B-2)

Except that the α-naphthol biphenyl aralkyl resin (A-1) was changed to 224 parts of the α-naphthol aralkyl resin (B-1) obtained in Comparative Synthesis Example 1, it was carried out in the same manner as in Synthesis Example 2 The operation, and obtain epoxy resin (B-2). The obtained epoxy resin (B-2) had a softening point of 83° C. and an epoxy equivalent of 274 g/eq. Fig. 2 shows the GPC spectrum of the obtained epoxy resin (B-2).

[Comparative Synthesis Example 3] Synthesis of β-Naphthol Aralkyl Resin (B-3)

Except that dichloromethylbiphenyl was changed to 263 parts of p-xylene dichloride, and α-naphthol was changed to 360 parts of β-naphthol, the same operation was performed as in Synthesis Example 1-1 to obtain β- Naphthol aralkyl resin (B-3). The hydroxyl equivalent weight is 224 g/eq.

[Comparative synthesis example 4] Synthesis of β-naphthol aralkyl type epoxy resin (B-4)

Except that α-naphthol biphenyl aralkyl resin (A-1) was changed to 224 parts of β-naphthol aralkyl resin (B-3) obtained in comparative synthesis example 3, the system was carried out in the same way as synthesis example 2 The operation, and obtain epoxy resin (B-4). The obtained epoxy resin (B-4) had a softening point of 95° C. and an epoxy equivalent of 292 g/eq. Fig. 3 shows the GPC spectrum of the obtained epoxy resin (B-4).

[Comparative Synthesis Example 5] Synthesis of methoxy-modified α-naphthol biphenyl aralkyl resin (B-5)

Add 360 parts of α-naphthol, 208 parts of p-xylylene glycol dimethyl ether, and 11 parts of p-toluenesulfonic acid while blowing nitrogen gas into the flask equipped with a stirrer, cooling pipe and nitrogen gas sealing port, and heat while distilling off the volatile matter to an internal temperature of 180°C. After maintaining it for 2 hours, it was neutralized with a 49% aqueous sodium hydroxide solution until the pH became neutral. After heating to 190° C., while maintaining the internal temperature, pressure reduction and steam distillation were performed to distill off volatile matter. The resulting resin was taken out to obtain a methoxy-modified α-naphthol biphenyl aralkyl resin (B-5). The hydroxyl equivalent weight is 298g/eq. The methoxylation ratio calculated from the dinuclear body peak of GPC was 20%.

[Comparative Synthesis Example 6] Synthesis of methoxy-modified α-naphthol biphenyl aralkyl type epoxy resin (B-6)

In addition to changing α-naphthol biphenyl aralkyl resin (A-1) into 298 parts of methoxy-modified α-naphthol aralkyl resin (B-5) obtained in Comparative Synthesis Example 5, the system carried out An epoxy resin (B-6) was obtained in the same manner as in Synthesis Example 2. The obtained epoxy resin had a softening point of 96° C. and an epoxy equivalent of 357 g/eq. Fig. 4 shows the GPC spectrum of the obtained epoxy resin (B-6).

<Synthesis of active ester resin> [Synthesis Example 3] Synthesis of Active Ester Resin (C-1)

Add 202.0 g of isophthaloyl chloride (the mole number of yl chloride group: 2.0 moles) and 1250 g of toluene to the flask equipped with thermometer, dropping funnel, cooling pipe, fractionating tube and stirrer, and reduce the temperature in the system. Nitrogen pressure was replaced to dissolve. Next, 288.0 g (2.0 moles) of α-naphthol was added, and the inside of the system was substituted with nitrogen under reduced pressure to dissolve it. Thereafter, 0.63 g of tetrabutylammonium bromide was dissolved, and nitrogen blowing was performed while controlling the inside of the system to 60° C. or lower, and 420 g of 20% sodium hydroxide aqueous solution was dripped over 3 hours. Next, stirring was continued for 1.0 hour under this condition. After the reaction, the liquid was separated and the water layer was removed. Further, water was added to the toluene layer in which the reactants were dissolved, and stirred for about 15 minutes, then left to stand for liquid separation, and the water layer was removed. This operation was repeated until the pH of the aqueous layer became 7. Then, it dried under heat and reduced pressure, and obtained active ester resin (C-1). The esterification equivalent weight of the active ester resin 1 is 209 g/eq, and the melt viscosity is 0.04 dPa‧s (200° C.). The softening point is 79°C. In addition, the active ester resin C-1 is equivalent to the active ester resin having a structure in which X is an α-naphthol residue and n is 0 in the above-mentioned formula (2).

[Synthesis Example 4] Synthesis of Active Ester Resin (C-2)

Add 165g of dicyclopentadiene and phenol polyaddition reaction resin (hydroxyl equivalent: 165g/eq, softening point 85°C) to the flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, α- 72g (0.5 mole) of naphthol and 630g of toluene were dissolved by substituting nitrogen under reduced pressure in the system. Next, 152 g (0.75 mol) of isophthaloyl chloride was added, and the system was substituted with nitrogen under reduced pressure to dissolve it. Thereafter, 210 g of a 20% sodium hydroxide aqueous solution was dropped over 3 hours while controlling the inside of the system to 60° C. or lower while carrying out nitrogen blowing. Next, stirring was continued for 1.0 hour under this condition. After the reaction, the liquid was separated and the water layer was removed. Further, water was added to the toluene layer in which the reactants were dissolved, and stirred for about 15 minutes, then left to stand for liquid separation, and the water layer was removed. This operation was repeated until the pH of the aqueous layer became 7. Thereafter, the active ester resin (C-2) was synthesized by drying under heat and reduced pressure. The esterification equivalent of this active ester resin (C-2) was 223 g/eq, and the softening point was 150°C. The melt viscosity is 100dPa‧s (200°C). In addition, the active ester resin (C-2) is equivalent to X being α-naphthol residue in the above-mentioned formula (2), n is 2 on average, Y is represented by chemical formula (4) and Z is (5-3) , Ar ¹ is an active ester resin with a structure of phenolic residues.

[Example 1]

α-Naphthol biphenyl aralkyl type epoxy resin (A-2), active ester (C-1) and hardening accelerator (N,N-dimethyl-4-aminopyridine, Wako Pure Chemical Industries, Ltd. Co., Ltd., special grade) were blended as shown in Table 1, heated and mixed using a hot air dryer at 150° C., cooled and solidified to obtain an epoxy resin composition.

[Comparative example 1~4]

An epoxy resin composition was obtained in the same manner as in Example 1 except that the formulation shown in Table 1 was used. In addition, in Comparative Example 4, Nippon Kayaku Co., Ltd. phenol and biphenyl aralkyl type epoxy resin (epoxy equivalent weight: 278 g/eq) was used as the epoxy resin system.

<assessment>

For the test pieces prepared using the epoxy resin compositions of Examples and Comparative Examples and using the following methods, the heat resistance and dielectric properties were evaluated according to the following methods. The results are shown in Table 1.

[Creation of test piece]

The epoxy resin compositions of Examples and Comparative Examples were pressurized at 150°C for 10 minutes to harden and formed, and then heated at 175°C for 5 hours to obtain test pieces of 80mm×100mm×thickness 1.6mm.

[heat resistance (glass transition temperature)]

Using a viscoelasticity measuring device (DMA: Solid Viscoelasticity Measuring Device RSAII manufactured by Rheometric Co., Ltd., rectangular tension method; frequency 1 Hz, heating rate 3°C/min), the temperature at which the change in elastic modulus reaches the maximum (tan δ maximum) is taken as the glass transition temperature to evaluate.

[dielectric tangent]

According to JIS-C-6481, the value at 1 GHz of the test piece was measured after drying out and stored in a room at 23°C and 50% humidity for 24 hours with an impedance material analyzer "HP4291B" manufactured by Agilent Technologies Co., Ltd. The dielectric tangent of the cured product of the epoxy resin composition of Example 1 is 0.0020 or less, and a cured product with excellent dielectric properties can be obtained.

[Table 1]

[Example 2]

After measuring the epoxy resin (A-2) and active ester resin (C-2) with the formula shown in Table 2, adjust the non-volatile content to 60% with methyl ethyl ketone (MEK) and dissolve it with a rotary mixer . Adjust N,N-dimethyl-4-aminopyridine as a catalyst so that the gelation time is within 5-7 minutes and mix it, then make a glass cloth laminate under the following conditions.

(Conditions for making laminates)

Substrate: Glass cloth "#2116" (210×280mm) manufactured by Nitto Bosho Co., Ltd.

Copper foil: "JTC foil" (18μm) manufactured by JX Nippon Oil Metal Co., Ltd.

Layers: 6

Prepreg condition: 160°C

Hardening conditions: 1.5 hours at 200°C, 40kg/cm ²

Plate thickness after forming: 0.8mm

[Comparative example 5, 6]

Except adopting the formulation of Table 2, the laminated board was made in the same manner as in Example 2.

<assessment> [Peel strength]

Regarding the laminated boards of Examples and Comparative Examples, according to JIS-6911, the previously obtained laminated board was cut into a size of 10 mm in width and 200 mm in length, which was used as a test piece to measure the peeling strength of copper foil, and the results are shown in Table 2. The laminated boards of the examples have the same or higher peel strength than conventional ones.

[Table 2]

Claims (6)

A kind of epoxy resin composition, it is to contain α-naphthol biphenyl aralkyl type epoxy resin and curing agent, and aforementioned curing agent is the active ester resin shown in following formula (2) or (3), and aforementioned α -naphthol biphenyl aralkyl type epoxy resin has the structure shown in the following formula (1);

(In the formula (1), ^R1 represents a hydrogen atom, a halogen atom, a glycidoxy group, an allyl group, an alkyl group, an alkoxy group, or an aryl group; n is an integer of 1 to 20);

(In formula (2), X represents a compound residue containing a monovalent phenolic hydroxyl group, Y represents a compound residue containing a divalent phenolic hydroxyl group; n is an integer of 0 to 20);

(In the formula (3), Y represents a compound residue containing a divalent phenolic hydroxyl group, ^R2 represents a hydrogen atom or an alkyl group, and n is an integer of 0 to 20). Such as the epoxy resin composition of claim 1, wherein the esterification equivalent of the aforementioned active ester resin is 150~350g/eq. The epoxy resin composition according to claim 1 or 2, which further contains a hardening accelerator. A cured product, which is a cured product of the epoxy resin composition according to any one of claims 1 to 3. A printed wiring board using the epoxy resin composition according to any one of Claims 1 to 3. A semiconductor packaging material, which uses the epoxy resin composition according to any one of claims 1 to 3.

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