Epoxy resin composition and cured product thereof

Abstract

Provided is an epoxy resin composition that can yield a cured product having excellent heat resistance, adhesion, and a lower dielectric loss tangent, and a cured product thereof. Specifically, an epoxy resin composition containing an α-naphthol diphenyl aralkyl-type epoxy resin and a curing agent, the curing agent containing an active ester structure. The α-naphthol diphenyl aralkyl-type epoxy resin preferably has a structure represented by formula (1). The curing agent preferably has a structure represented by formula (2). The curing agent is preferably an active ester compound or resin that uses, as essential reaction raw materials, a compound having two or more phenolic hydroxyl groups and an aromatic monocarboxylic acid or an acid halide thereof.

Description

Technical Field

[0001] This invention relates to epoxy resin compositions and their cured products. Background Technology

[0002] Epoxy resin compositions, with epoxy resin and its curing agent as essential components, are widely used in electronic components such as semiconductors and multilayer printed circuit boards due to the excellent heat resistance and insulation properties of their cured products. Patent Document 1 discloses an epoxy resin composition with a defined structure, possessing high heat resistance, low water absorption, and high adhesion. Patent Document 2 discloses an epoxy resin with a defined structure, exhibiting excellent flame retardancy, moisture resistance, heat resistance, low thermal expansion, and excellent adhesion to metal substrates.

[0003] In the technical field of printed circuit board materials used in electronic components, improved dielectric properties are required to meet the demands of high-speed information processing. Materials with excellent dielectric properties are being researched, particularly curable resin compositions formed from epoxy resins and reactive ester resins. For example, Patent Document 3 discloses an epoxy resin composition using a condensation polymer of an aromatic polycarboxylic acid and an aromatic polyhydroxy compound having aryloxycarbonyl groups at the chain ends as a curing agent for the epoxy resin. This epoxy resin composition provides cured epoxy resins with excellent heat resistance and low dielectric loss tangent. Furthermore, to improve the dielectric properties of the substrate, research has been conducted on reducing the surface roughness of the copper foil used. While this improves dielectric properties, it also reduces adhesion to the resin layer, making it more prone to various defects. For these reasons, the electronic component market demands resins with good heat resistance, dielectric properties, and adhesion.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 6-271654

[0007] Patent Document 2: Japanese Patent Application Publication No. 2006-160868

[0008] Patent Document 3: Japanese Patent Application Publication No. 2008-291279 Summary of the Invention

[0009] The problem the invention aims to solve

[0010] The present invention is a further development of the above-mentioned technology, and the objective is to provide an epoxy resin composition and the cured product thereof that can produce a cured product with excellent heat resistance, adhesion and a lower dielectric loss tangent.

[0011] Solution for solving the problem

[0012] Through repeated and in-depth research, the inventors discovered that by combining α-naphthol biphenyl aralkyl epoxy resin with a curing agent having an ester structure (hereinafter also referred to as "active ester structure") formed from phenolic groups and aromatic carboxylic acid groups, the above-mentioned problems can be solved, thus completing the present invention.

[0013] That is, the present invention relates to the following [1] to [8].

[0014] [1] An epoxy resin composition comprising an α-naphthol biphenyl aralkyl type epoxy resin and a curing agent having an active ester structure.

[0015] [2] According to the epoxy resin composition of [1], wherein the aforementioned α-naphthol biphenyl aralkyl type epoxy resin has the structure shown in formula (1).

[0016]

[0017] (In equation (1), R) 1 This 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 from 1 to 20.

[0018] [3] The epoxy resin composition according to [1] or [2], wherein the aforementioned curing agent has the structure shown in formula (2).

[0019]

[0020] (In formula (2), X represents a monovalent compound residue containing a phenolic hydroxyl group, and Y represents a divalent compound residue containing a phenolic hydroxyl group. n is an integer from 0 to 20.)

[0021] [4] The epoxy resin composition according to [1] or [2], wherein the aforementioned curing agent is 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 reactants.

[0022] [5] The epoxy resin composition according to any one of [1] to [4] further contains a curing accelerator.

[0023] Cured products of any one of the epoxy resin compositions described in [6][1] to [5].

[0024] [7] A printed circuit board using any one of [1] to [5] of the epoxy resin composition.

[0025] [8] A semiconductor sealing material, which uses the epoxy resin composition described in any one of [1] to [5].

[0026] The effects of the invention

[0027] The present invention provides epoxy resin compositions and cured products that have excellent heat resistance, adhesion and lower dielectric loss tangent. Attached Figure Description

[0028] Figure 1 The image shows the GPC diagram of the α-naphthol biphenyl aralkyl type epoxy resin (A-2) obtained in Synthesis Example 2.

[0029] Figure 2 To compare the GPC diagrams of the α-naphthol aralkyl epoxy resin (B-2) obtained in Synthesis Example 2.

[0030] Figure 3 To compare the GPC diagrams of the β-naphthol aralkyl epoxy resin (B-4) obtained in Synthesis Example 4.

[0031] Figure 4 To compare the GPC diagrams of the methoxy-modified α-naphthol biphenyl aralkyl epoxy resin (B-6) obtained in Synthesis Example 6. Detailed Implementation

[0032] The following is a detailed description of one embodiment of the present invention. The present invention is not limited to the following embodiment, and appropriate modifications can be made to implement it without suppressing the effects of the present invention.

[0033] [Epoxy Resin Composition]

[0034] The epoxy resin composition of this embodiment (hereinafter also referred to as the "resin composition") contains an α-naphthol biphenyl aralkyl type epoxy resin and a curing agent.

[0035] (Epoxy resin)

[0036] α-Naphthol-biphenyl aralkyl type epoxy resins are epoxy resins whose molecular backbone has functional groups derived from α-naphthol and biphenyl groups. By combining epoxy resins with such molecular backbones and curing agents with active ester structures described later, epoxy resin compositions that provide cured products with excellent heat resistance and adhesion, as well as superior dielectric properties compared to the past, can be obtained.

[0037] As an α-naphthol biphenyl aralkyl type epoxy resin, an epoxy resin having the structure shown in formula (1) can be used.

[0038]

[0039] In equation (1), R 1 This refers to a hydrogen atom, a halogen atom, a glycidyloxy group, an allyl group, an alkyl group, an alkoxy group, or an aryl group. n is 1 to 20, preferably 1 to 15, and more preferably an integer from 1 to 12. Examples of halogen atoms include chlorine, bromine, and iodine. Examples of alkyl groups include those with 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Examples of alkyl groups with 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, n-hexyl, and cyclohexyl. Examples of alkoxy groups include those with 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. Examples of alkoxy groups with 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, pentoxy, n-hexoxy, and cyclohexoxy. Examples of aryl groups include phenyl, benzyl, naphthyl, and methoxynaphthyl. Among them, R excels in its excellent balance of impregnation with reinforcing fibers and other substrates, heat resistance of the cured product, and toughness. 1 Hydrogen atoms are preferred.

[0040] There is no particular limitation on the softening point of α-naphthol biphenyl aralkyl type epoxy resin. However, considering good solvent solubility and heat resistance of the cured product, a softening point of 70℃ to 140℃ is preferred, more preferably 75℃ to 130℃, and even more preferably 80℃ to 120℃. It should be noted that the softening point was determined according to JIS K7234.

[0041] Considering both the excellent heat resistance of the cured product and its excellent impregnation properties on substrates such as reinforcing fibers, the epoxy equivalent of α-naphthol biphenyl aralkyl type epoxy resin is preferably in the range of 280 to 450 g / equivalent.

[0042] There are no particular limitations on the preparation method of α-naphthol biphenyl aralkyl type epoxy resin. It can be obtained by polyglycidyl etherification of the condensation polymer of α-naphthol and biphenyl compounds such as dichloromethyl biphenyl using epichlorohydrin or the like.

[0043] (Curing agent)

[0044] The curing agent 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 curing agent can be composed of compounds or resins having an active ester structure (hereinafter also referred to as "active ester resins"). Specific examples of active ester resins include: active ester resin (I) using 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) ​​as reactants; and active ester resin (II) using compounds selected from compounds having two or more phenolic hydroxyl groups (b1), aromatic monocarboxylic acids or their acyl halides (b2), and aromatic polycarboxylic acids or their acyl halides (b3) as reactants. These can be used alone or in combination.

[0045] Examples of compounds having one phenolic hydroxyl group (a1) include aromatic monohydroxyl compounds such as phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, 2,6-xylenol, o-phenylphenol, p-phenylphenol, 2-benzylphenol, 4-benzylphenol, 4-(α-cumyl)phenol, α-naphthol, and β-naphthol. Among these, curing agents containing residues of α-naphthol, β-naphthol, o-phenylphenol, and / or p-phenylphenol can yield cured products with lower dielectric loss tangents.

[0046] As compounds (a2) and (b1) having two or more phenolic hydroxyl groups, aromatic polyhydroxy compounds can be cited as examples. Examples of aromatic polyhydroxy compounds include resorcinol, hydroquinone, trimethylhydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,6-naphthodiol, 2,6-naphthodiol, 2,3-naphthodiol, 2,7-naphthodiol, 1,4-naphthodiol, 3,3',5,5'-tetramethylbisphenol F, 3,3',5,5'-tetramethylbiphenol, etc.; aromatic trihydroxy compounds such as 1,3,5-trihydroxybenzene, 1,2,3-trihydroxybenzene, 2,4,4'-trihydroxybenzophenone, triphenolmethane, etc.; and 2,2',4,4'-tetrahydroxybenzophenone, 1,1,2,2-tetraphenol ethane, etc.

[0047] Alternatively, compounds (a2) and (b1) can also be compounds represented by formula (4) below.

[0048]

[0049] (In equation (4), m is an integer from 0 to 20)

[0050] In equation (4) above, Ar 1Each of the following groups independently represents a substituent containing a phenolic hydroxyl group, and Z is independently an oxygen atom, a sulfur atom, a sulfonyl group, a substituted or unsubstituted alkylene group with 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group with 3 to 20 carbon atoms, an arylene group with 6 to 20 carbon atoms, or an arylene group with 8 to 20 carbon atoms.

[0051] As Ar 1 There are no particular restrictions, and examples include residues of aromatic monohydroxy compounds such as phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, 2,6-xylenol, o-phenylphenol, p-phenylphenol, 2-benzylphenol, 4-benzylphenol, 4-(α-cumyl)phenol, α-naphthol, and β-naphthol.

[0052] There are no particular limitations on the alkylene groups with 1 to 20 carbon atoms mentioned above, and examples include methylene, ethylene, propylene, 1-methylmethylene, 1,1-dimethylmethylene, 1-methylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, propylene, butylene, 1-methylpropylene, 2-methylpropylene, pentylene, and hexylene.

[0053] There are no particular limitations on the aforementioned cycloalkylene groups with 3 to 20 carbon atoms, and examples include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclopentylene, cycloheptylene, and cycloalkylene groups shown in formulas (5-1) to (5-4) below.

[0054]

[0055] It should be noted that in the above equations (5-1) to (5-4), "*" indicates that it is related to Ar. 1 The bonding site.

[0056] There are no particular limitations on the aforementioned arylene groups with 6 to 20 carbon atoms, and examples include the arylene groups shown in the following formula (6-1).

[0057]

[0058] It should be noted that in the above formula (6-1), "*" represents the symbol related to Ar. 1 The bonding site.

[0059] There are no particular limitations on the aforementioned arylene alkyl groups with 8 to 20 carbon atoms, and examples include the arylene alkyl groups shown in formulas (7-1) to (7-5) below.

[0060]

[0061] It should be noted that in equations (7-1) to (7-5), "*" indicates that it is related to Ar. 1 The bonding site.

[0062] In the above, Z in formula (4) is preferably a cycloalkylene group with 3 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, or an arylalkylene group with 8 to 20 carbon atoms. From the viewpoint of adhesion and dielectric properties, the groups shown in formulas (5-3), (5-4), (6-1), (7-1) to (7-5) are more preferred. In formula (4), m is an integer from 0 to 1 to 10, preferably from 0 to 8, and from the viewpoint of solvent solubility, preferably from 0 to 5.

[0063] Alternatively, compounds (a2) and (b1) can also have the structures described in formula (8).

[0064]

[0065] (wherein, in equation (8), l represents an integer greater than 1, R) 3 (This represents hydrogen atoms, alkyl groups, and aryl groups.)

[0066] In formula (8), l is preferably 1 to 20, more preferably 1 to 15, and even more preferably an integer from 1 to 12. Examples of alkyl groups include those with 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Examples of alkyl groups with 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, n-hexyl, cyclohexyl, etc. Examples of aryl groups include benzyl, naphthyl, methoxynaphthyl, etc.

[0067] For compounds (a2) and (b1), from the perspective of solvent solubility and dielectric properties of the reaction products, compounds represented by formulas (4) and (8) are preferred, and Ar in formula (4) is even more preferred. 1 Z is a compound of formula (5-3), (6-1), (7-1) to (7-5), and a compound of formula (8).

[0068] Examples of aromatic monocarboxylic acids or their acyl halides (b2) include benzoic acid and benzoyl chloride.

[0069] Examples of aromatic polycarboxylic acids or their acyl halides (a3) ​​and (b3) include, for example, isophthalic acid, terephthalic acid, 1,4-, 2,3-, or 2,6-naphthalenedicarboxylic acid, aromatic dicarboxylic acids; pyromellitic acid, trimellitic acid, and other aromatic tricarboxylic acids; pyromellitic tetracarboxylic acid; and their acyl chlorides. Among these, isophthalic acid, or a mixture of isophthalic acid and terephthalic acid, is preferred in terms of excellent melting point and solvent solubility of the reactants.

[0070] Examples of active ester resins having the above-described structure include, for example, the following active ester resins (I) and (II).

[0071] Examples of active ester resins (I) include active ester resins having the structure shown in formula (2).

[0072]

[0073] In formula (2), X represents a monovalent compound residue containing a phenolic hydroxyl group, and Y represents a divalent compound residue containing a phenolic hydroxyl group. n is 0 to 20, preferably 0 to 15, and more preferably an integer from 0 to 10.

[0074] Examples of active ester resins (II) include active ester resins having the structure shown in formula (3).

[0075]

[0076] In formula (3), Y represents a divalent compound residue containing a phenolic hydroxyl group, and R 2 This indicates a hydrogen atom or an alkyl group. n is 0 to 20, preferably 0 to 15, and more preferably an integer from 0 to 10. Examples of alkyl groups include those with 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Examples of alkyl groups with 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, n-hexyl, and cyclohexyl.

[0077] Among them, the active ester resin (I) shown in formula (2) is preferred in terms of excellent resistance to damp heat.

[0078] The esterification equivalent of the reactive ester resin is preferably 150–400 g / eq, more preferably 160–350 g / eq, and even more preferably 170–300 g / eq. By setting the esterification equivalent of the reactive ester resin within the above range, a good balance between heat resistance and dielectric properties can be achieved.

[0079] For the melt viscosity of the reactive ester resin, measured at 200°C using an ICI viscometer, it is preferably 0.01 to 500 dPa·s, more preferably 0.01 to 400 dPa·s, and even more preferably 0.01 to 300 dPa·s. By setting the melt viscosity of the reactive ester resin within the above range, a good balance can be achieved between moldability and the heat resistance of the cured product.

[0080] There are no particular limitations on the softening point of the reactive ester resin. From the perspective of solvent solubility, it is preferably below 200°C, more preferably below 190°C, and even more preferably below 170°C. It should be noted that the softening point is as described above.

[0081] There are no particular limitations on the preparation method of reactive ester resins. They can be manufactured using well-known and commonly used synthesis methods such as acetic anhydride method, interfacial polymerization method, and solution method.

[0082] In addition to reactive ester resins, the curing agent may also contain other epoxy resin curing agents. Examples of epoxy resin curing agents that can be used here include, for instance, amine compounds, amide compounds, acid anhydride compounds, and phenolic compounds. When epoxy resin curing agents are used in combination, their usage is preferably in the range of 1% to 30% by mass of the total resin composition.

[0083] (mixing amount)

[0084] Regarding the mixing amounts of α-naphthol biphenyl aralkyl epoxy resin and reactive ester resin in the resin composition, it is preferable that the mixing amount is 0.15 to 5 moles of aryloxycarbonyl groups in the reactive ester resin relative to 1 mole of epoxy groups in the α-naphthol biphenyl aralkyl epoxy resin, and more preferably 0.9 to 2.0 moles. With the above mixing amounts, the curing of the α-naphthol biphenyl aralkyl epoxy resin is sufficiently achieved, and an epoxy resin composition that provides a low dielectric loss tangent can be easily obtained.

[0085] (Curing accelerator)

[0086] The resin composition may contain a curing accelerator as needed. Examples of curing accelerators include phosphorus compounds, tertiary amines, imidazoles, metal salts of organic acids, Lewis acids, and amine salts. Dimethylaminopyridine and imidazoles are preferred, especially for applications involving multilayer materials and circuit boards, due to their superior heat resistance, dielectric properties, and solderability. For applications involving semiconductor sealing materials, triphenylphosphine is preferred among phosphorus compounds, and 1,8-diazabicyclo-[5.4.0]-undecene (DBU) is preferred among tertiary amines, due to its superior curability, heat resistance, electrical properties, and moisture resistance. The amount of curing accelerator relative to 100 parts by weight of α-naphthol biphenyl aralkyl epoxy resin is preferably in the range of 0.01 to 5.0 parts by weight, more preferably in the range of 0.01 to 2.0 parts by weight. By setting the amount within the above range, a sufficient curing reaction rate can be obtained, and a resin composition providing a cured product with superior heat resistance can be obtained.

[0087] (Other added ingredients)

[0088] The resin composition may also contain other resin components. Examples of other resin components include cyanate resins; bismaleimide resins; benzoxazine resins; allyl-containing resins, such as diallyl bisphenol and triallyl isocyanurate; polyphosphate esters, phosphate ester-carbonate copolymers, etc. These can be used individually or in combination of two or more.

[0089] The mixing ratio of these other resin components is not particularly limited and can be adjusted appropriately according to the desired properties of the cured product. As an example, the mixing ratio can be set in the range of 1 to 50% by mass in the total resin composition.

[0090] The resin composition may also contain various additives such as flame retardants, inorganic fillers, silane coupling agents, release agents, pigments, and emulsifiers, as needed. Examples of flame retardants include, for instance, red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium polyphosphate, and other inorganic phosphorus compounds such as ammonium phosphate and phosphoramide; phosphate esters, phosphonic acid compounds, phosphine oxide compounds, phosphine oxide compounds, orthophosphine compounds, organic nitrogen- and phosphorus-containing compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-(2,7-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide. Organophosphorus compounds such as cyclic organophosphorus compounds (hydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and their derivatives formed by reacting them with compounds such as epoxy resin and phenolic resin; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine; organosilicon-based flame retardants such as silicone oil, silicone rubber, and organosilicon resin; and inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting-point glasses. When using these flame retardants, the preferred concentration is in the range of 0.1% to 20% by mass of the total resin composition.

[0091] For inorganic filler materials, such as those used in semiconductor sealing materials, the resin composition is formulated. Examples of inorganic filler materials include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Among these, fused silica is preferred from the perspective of allowing for a greater amount of inorganic filler material to be incorporated. Both broken and spherical fused silica can be used, but to increase the amount of fused silica incorporated and to suppress the increase in the melt viscosity of the resin composition, it is preferable to primarily use spherical fused silica. Furthermore, to increase the amount of spherical silica incorporated, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling rate relative to 100 parts by weight of the resin component is preferably in the range of 0.5 to 95 parts by weight.

[0092] There are no particular limitations on the method of preparing the resin composition. For example, it can be obtained by uniformly mixing the above components at a temperature of, for example, 0°C to 200°C using a stirring device, a three-roll mill, etc.

[0093] [cured material]

[0094] The resin composition can be molded using a known and conventional thermosetting method, for example, by heating and curing it at a temperature range of about 20 to 250°C.

[0095] The cured resin composition of this embodiment has a glass transition temperature of over 140°C, excellent heat resistance, and exhibits a dielectric loss tangent of less than 2.0 × 10⁻⁶ at 1 GHz. -3 It exhibits a low dielectric loss tangent and its sealing performance is comparable to or better than that of conventional materials. Based on the above, it is preferably used in electronic materials applications such as printed circuit boards, semiconductor sealing materials, and corrosion-resistant materials.

[0096] [Printed circuit boards, etc.]

[0097] When using resin compositions for printed circuit board applications or laminated adhesive film applications, it is generally preferable to dilute them with an organic solvent. Examples of organic solvents include methyl ethyl ketone (MEK), acetone, dimethylformamide, methyl isobutyl ketone (MEK), methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. The type and amount of organic solvent can be appropriately adjusted according to the application environment of the resin composition. For example, in printed circuit board applications, polar solvents with boiling points below 160°C, such as MEK, acetone, and dimethylformamide, are preferred, and it is preferable to use them at a ratio of 40-80% by mass of non-volatile components. In applications involving laminated adhesive films, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone are preferred; ethyl acetate, butyl acetate, acetic acid solvents such as propylene glycol monomethyl ether acetate and carbitol acetate are preferred; carbitol solvents such as butyl carbitol are preferred; aromatic hydrocarbon solvents such as toluene and xylene are preferred; dimethylformamide, dimethylacetamide, and N-methylpyrrolidone are preferred; and the non-volatile components are preferred to be used in proportions of 30 to 70% by mass.

[0098] Examples of methods for manufacturing printed circuit boards using resin compositions include: impregnating a resin composition into a reinforcing substrate and curing it to obtain a prepreg, then overlapping it with copper foil and heat-pressing it. Examples of reinforcing substrates include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass pads, and glass roving. The amount of resin composition impregnated is not particularly limited, but it is generally preferred that the resin content in the prepreg is 20-80% by mass.

[0099] [Semiconductor sealing materials]

[0100] When using resin compositions for semiconductor sealing material applications, it is generally preferable to incorporate inorganic filler materials as described above. Semiconductor sealing materials can be prepared, for example, by mixing the compound using an extruder, kneader, roller, or similar equipment. Methods for molding a semiconductor encapsulation body using the obtained semiconductor sealing material include, for example, molding the semiconductor sealing material using a casting or transfer molding machine, injection molding machine, or similar equipment, and then heating it at a temperature of 50–200°C for 2–10 hours. Using such methods, a semiconductor device as a molded product can be obtained.

[0101] Example

[0102] The following examples illustrate the invention in further detail, but the invention is not limited to these examples. Unless otherwise specified, "parts" and "%" refer to mass. It should be noted that the softening point, GPC, and melt viscosity were determined under the following conditions.

[0103] (1) Softening point determination

[0104] According to JIS K7234.

[0105] (2) GPC determination

[0106] Apparatus: The measurements were performed using an HLC-8220GPC manufactured by Tosoh Corporation under the following conditions.

[0107] • Column: Protective column "HXL-L" manufactured by Tosoh Corporation

[0108] + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation

[0109] + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation

[0110] + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation

[0111] + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation

[0112] Column temperature: 40℃

[0113] Solvent: Tetrahydrofuran

[0114] • Flow rate: 1 mL / min

[0115] • Detector: RI

[0116] (3) Melt viscosity determination

[0117] The measurement was performed using a cone-plate viscometer (CV-1S) manufactured by Toa Kogyo Co., Ltd.

[0118] Synthesis of Epoxy Resins

[0119] [Synthetic Example 1] Synthesis of α-naphthol biphenyl aryl resin (A-1)

[0120] In a flask equipped with a stirrer, condenser, and nitrogen-sealed inlet, 360 parts of α-naphthol, 586 parts of toluene, and 377 parts of dichloromethylbiphenyl were added while nitrogen was purging, and the mixture was heated to 80°C. After adding 245 parts of a 49% sodium hydroxide aqueous solution dropwise over 1 hour, the mixture was heated to 90°C and maintained for 11 hours. The pH was neutralized to neutral using 85% phosphoric acid, stirring was stopped, and the lower layer was extracted. 15 parts of p-toluenesulfonic acid were added, and the mixture was heated to 180°C over 2 hours while distilling off volatile components. The pH was then neutralized to neutral using a 49% sodium hydroxide aqueous solution, and the internal temperature was maintained while the pressure was reduced. The volatile components were then distilled off, and the resulting resin was collected to obtain α-naphthol biphenyl aralkyl resin (A-1). The hydroxyl equivalent was 272 g / eq.

[0121] [Synthetic Example 2] Synthesis of α-naphthol biphenyl aryl epoxy resin (A-2)

[0122] In a flask equipped with a thermometer, condenser, and stirrer, 272 g of α-naphthol biphenyl aralkyl resin (A-1) obtained in Synthesis Example 1-1 (hydroxyl equivalent 1.0 g / eq), 740 g (8.0 mol) of epichlorohydrin, and 53 g of n-butanol were added and dissolved while purging with nitrogen. The temperature was raised to 50°C, and 220 g (1.10 mol) of 20% sodium hydroxide aqueous solution was added over 3 hours, followed by further reaction at 50°C for 1 hour. After the reaction was complete, unreacted epichlorohydrin was removed by distillation 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 for dissolution. Then, 15 parts of 10% sodium hydroxide aqueous solution were added to this solution, and the mixture was reacted at 80°C for 2 hours. The solution was then washed three times with 200 g of water until the pH of the washing solution was neutral. The system was then dehydrated via azeotropic distillation, followed by microfiltration and solvent removal under reduced pressure to obtain epoxy resin (A-2). The resulting epoxy resin (A-2) had a softening point of 100°C and an epoxy equivalent of 325 g / eq. Figure 1 The GPC diagram of the obtained epoxy resin (A-2) is shown.

[0123] [Comparative Synthesis Example 1] Synthesis of α-Naphthol Aryl Resin (B-1)

[0124] Except for replacing 263 parts of dichloromethylbiphenyl with dichloro-p-xylene, the procedure was carried out in the same manner as in Synthesis Example 1-1 to obtain α-naphthol aralkyl resin (B-1). The hydroxyl equivalent was 224 g / eq.

[0125] [Comparative Synthesis Example 2] Synthesis of α-Naphthol Arylalkyl Epoxy Resin (B-2)

[0126] Except for replacing 224 parts of the α-naphthol biphenyl aralkyl resin (A-1) with 224 parts of the α-naphthol aralkyl resin (B-1) obtained in Comparative Synthesis Example 1, the same operation as in Synthesis Example 2 was performed to 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. Figure 2 The GPC diagram of the obtained epoxy resin (B-2) is shown.

[0127] [Comparative Synthesis Example 3] Synthesis of β-Naphthol Aryl Resin (B-3)

[0128] By replacing 263 parts of dichloromethylbiphenyl with dichloro-p-xylene and 360 parts of α-naphthol with β-naphthol, the same procedure as in Synthesis Example 1 was performed to obtain β-naphthol aralkyl resin (B-3). The hydroxyl equivalent was 224 g / eq.

[0129] [Comparative Synthesis Example 4] Synthesis of β-Naphthol Arylalkyl Epoxy Resin (B-4)

[0130] Except for replacing α-naphthol biphenyl aralkyl resin (A-1) with 224 parts of β-naphthol aralkyl resin (B-3) obtained in Comparative Synthesis Example 3, the same operation as in Synthesis Example 2 was performed to obtain epoxy resin (B-4). The obtained epoxy resin (B-4) has a softening point of 95°C and an epoxy equivalent of 292 g / eq. Figure 3 The GPC diagram of the obtained epoxy resin (B-4) is shown.

[0131] [Comparative Synthesis Example 5] Synthesis of Methoxylated Modified α-Naphthol Biphenyl Aryl Resin (B-5)

[0132] In a flask equipped with a stirrer, condenser, and nitrogen-sealed inlet, 360 parts of α-naphthol, 208 parts of p-xylenol dimethyl ether (P-XYLENE GLYCOL DIMETHYL ETHER), and 11 parts of p-toluenesulfonic acid were added while nitrogen was purging. The internal temperature was raised to 180°C while distilling off volatile components. After maintaining this state for 2 hours, the pH was neutralized to neutral using a 49% sodium hydroxide aqueous solution. The temperature was then raised to 190°C, and steam distillation was performed under reduced pressure while maintaining the internal temperature to remove volatile components. The resulting resin was collected as a methoxylated α-naphthol biphenyl aralkyl resin (B-5). The hydroxyl equivalent was 298 g / eq. The methoxylation rate, calculated based on the binuclear peaks of GPC, was 20%.

[0133] [Comparative Synthesis Example 6] Synthesis of Methoxylated α-Naphthol Biphenyl Aryl Acrylate Epoxy Resin (B-6)

[0134] Except for replacing 298 parts of the methoxy-modified α-naphthol biphenyl aralkyl resin (A-1) obtained in Comparative Synthesis Example 5, the same operation as in Synthesis Example 2 was performed to obtain epoxy resin (B-6). The obtained epoxy resin had a softening point of 96°C and an epoxy equivalent of 357 g / eq. Figure 4 The GPC diagram of the obtained epoxy resin (B-6) is shown.

[0135] Synthesis of Active Ester Resins

[0136] [Synthesis Example 3] Synthesis of Active Ester Resin (C-1)

[0137] In a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer, 202.0 g of isophthaloyl chloride (2.0 mol of acyl chloride group) and 1250 g of toluene were added, and the system was subjected to nitrogen purging under reduced pressure to dissolve it. Then, 288.0 g of α-naphthol (2.0 mol) was added, and the system was subjected to nitrogen purging under reduced pressure to dissolve it. Next, 0.63 g of tetrabutylammonium bromide was dissolved, and while purging with nitrogen, the system temperature was controlled below 60°C. 420 g of 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. Then, stirring was continued under these conditions for 1 hour. After the reaction was completed, the mixture was allowed to stand and separated to remove the aqueous layer. Then, water was added to the toluene layer containing the reactants and stirred for about 15 minutes to mix. The mixture was allowed to stand and separated to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Finally, the mixture was dried under thermal reduced pressure to obtain the active ester resin (C-1). The esterification equivalent of the active ester resin 1 is 209 g / eq, and the melt viscosity is 0.04 dPa·s (200℃). The softening point is 79℃. It should be noted that the active ester resin C-1 is equivalent to an active ester resin having the structure in the above formula (2) where X is an α-naphthol residue and n is 0.

[0138] [Synthesis Example 4] Synthesis of Reactive Ester Resin (C-2)

[0139] In a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer, 165 g of a dicyclopentadiene-phenol addition polymerization resin (hydroxyl equivalent: 165 g / eq, softening point 85 °C), 72 g (0.5 mol) of α-naphthol, and 630 g of toluene were added. The system was then subjected to nitrogen purging under reduced pressure to dissolve the resin. Next, 152 g (0.75 mol) of isophthaloyl chloride was added, and the system was subjected to nitrogen purging under reduced pressure to dissolve the resin. Then, while purging with nitrogen and maintaining the system temperature below 60 °C, 210 g of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. The mixture was then stirred for another 1 hour under these conditions. After the reaction was complete, the mixture was allowed to stand and separated, removing the aqueous layer. Then, water was added to the toluene layer containing the reactants and stirred for approximately 15 minutes. The mixture was allowed to stand and separated, removing the aqueous layer. This process was repeated until the pH of the aqueous layer reached 7. Finally, the mixture was dried under reduced pressure to synthesize the reactive ester resin (C-2). The esterification equivalent of this reactive ester resin (C-2) is 223 g / eq, and its softening point is 150 °C. Its melt viscosity is 100 dPa·s (200 °C). It should be noted that the reactive ester resin (C-2) is equivalent to having X as α-naphthol residues, n averaging 2, Y represented by chemical formula (4), Z as (5-3), and Ar... 1 An active ester resin with a structure consisting of phenol residues.

[0140] [Example 1]

[0141] The α-naphthol biphenyl aralkyl type epoxy resin (A-2), the active ester (C-1), and the curing accelerator (N,N-dimethyl-4-aminopyridine, manufactured by Wako Pure Chemical Industries, Ltd., premium grade) were mixed by heating at 150°C using a hot air dryer, and then cooled and solidified to obtain an epoxy resin composition.

[0142] [Comparative Examples 1-4]

[0143] Except for the formulation shown in Table 1, the epoxy resin composition was obtained in the same manner as in Example 1. It should be noted that in Comparative Example 4, a phenol-biphenyl aralkyl type epoxy resin (epoxy equivalent 278 g / eq) manufactured by Nippon Kayaku Co., Ltd. was used as the epoxy resin.

[0144] <Evaluation>

[0145] Using the epoxy resin compositions of the examples and comparative examples, the heat resistance and dielectric properties of test pieces prepared according to the following methods were evaluated. The results are shown in Table 1.

[0146] [Production of the experimental film]

[0147] The epoxy resin compositions of the examples and comparative examples were pressed at 150°C for 10 minutes to cure and shape them, and then heated at 175°C for 5 hours to obtain test pieces of 80mm×100mm×1.6mm thickness.

[0148] [Heat resistance (glass transition temperature)]

[0149] The glass transition temperature was evaluated using a viscoelasticity measuring apparatus (DMA: Rheometrics RSAII solid viscoelasticity measuring apparatus, rectangular tension method; frequency 1 Hz, heating rate 3 °C / min), with the temperature at which the tensile modulus change was the largest (tanδ maximum).

[0150] [Dielectric loss tangent]

[0151] According to JIS-C-6481, using the Impedance Material Analyzer "HP4291B" manufactured by Agilent Technologies, Inc., the dielectric loss tangent of the test piece after being oven-dried and stored indoors at 23°C and 50% humidity for 24 hours was determined at 1 GHz. The cured epoxy resin composition of Example 1 exhibits a dielectric loss tangent of less than 0.0020°, resulting in a cured product with excellent dielectric properties.

[0152] [Table 1]

[0153]

[0154] *Phenol-biphenyl aryl type epoxy resin

[0155] [Example 2]

[0156] After measuring the epoxy resin (A-2) and reactive ester resin (C-2) according to the formulation shown in Table 2, the non-volatile components were adjusted to 60% with methyl ethyl ketone (MEK), and dissolved using a rotary mixer. The N,N-dimethyl-4-aminopyridine catalyst was adjusted to a gelation time of 5-7 minutes and mixed, and then glass cloth laminates were prepared under the conditions described below.

[0157] (Conditions for manufacturing laminated boards)

[0158] Substrate: Nitto Boshoku Co., Ltd. glass cloth "#2116" (210×280mm)

[0159] Copper foil: JTC foil (18μm) manufactured by JX Nippon Minerals & Metals Co., Ltd.

[0160] Number of floors: 6

[0161] Prepreg conditions: 160℃

[0162] Curing conditions: 200℃, 40kg / cm² 2 Next 1.5 hours

[0163] Thickness of the formed plate: 0.8mm

[0164] [Compare Examples 5 and 6]

[0165] Except for the formulation in Table 2, the laminate was made in the same manner as in Example 2.

[0166] <Evaluation>

[0167] [Peel strength]

[0168] For the laminates of the embodiments and comparative examples, according to JIS-6911, the previously obtained laminates were cut into dimensions of 10 mm in width and 200 mm in length, and used as test pieces to determine the peel strength of the copper foil. The results are shown in Table 2. The laminates of the embodiments have peel strength equal to or better than that of the conventional laminates.

[0169] [Table 2]

[0170] Example 2 Comparative Example 5 Comparative Example 6 Epoxy Resin (A-2) quality% 59.3 Epoxy Resin (B-2) quality% 55.1 Epoxy resin (B-6) quality% 61.6 Reactive ester resin (C-2) quality% 40.7 44.9 38.4 Copper foil peel strength <![CDATA[kN / m 2 ]]> 1.0 1.0 0.8 .

Claims

1. An epoxy resin composition comprising an α-naphthol biphenyl aralkyl type epoxy resin and a curing agent, wherein the curing agent is composed of an active ester resin, and the active ester resin has an esterification equivalent of 150~400 g / eq. The α-naphthol biphenyl aryl epoxy resin has the structure shown in formula (1): In equation (1), R 1 Represents a hydrogen atom, allyl, alkyl, alkoxy, or aryl group, where n is an integer from 1 to 20. The curing agent has the structure shown in formula (2): In formula (2), X represents a monovalent compound residue containing a phenolic hydroxyl group, Y represents a divalent compound residue containing a phenolic hydroxyl group, and n is an integer from 0 to 20. The curing agent is an active ester resin that uses compounds having two or more phenolic hydroxyl groups and aromatic monocarboxylic acids or their acyl halides as essential reaction raw materials.

2. The epoxy resin composition according to claim 1, further comprising a curing accelerator.

3. The cured product of the epoxy resin composition according to claim 1 or 2.

4. A printed circuit board using the epoxy resin composition of claim 1 or 2.

5. A semiconductor sealing material using the epoxy resin composition of claim 1 or 2.

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