TWI657108B - Epoxy resin composition, prepreg, laminate and printed circuit board - Google Patents

Abstract

The present invention relates to an epoxy resin composition and a prepreg, a laminate, and a printed circuit board using the same. The epoxy resin composition of the present invention includes an epoxy resin (A), a maleimide compound (B) having a structure of the formula (I), and an active ester compound (C). The prepregs, laminates (including metal foil-clad laminates) and printed circuit boards made therefrom have low dielectric constant (Dk) / dielectric loss tangent value (Df), high glass transition temperature (Tg), low Characteristics of water absorption, low coefficient of thermal expansion (CTE), excellent heat resistance and moisture and heat resistance.

Description

Epoxy resin composition, prepreg, laminate and printed circuit board

The invention relates to the technical field of electronic products, in particular to an epoxy resin composition and a prepreg, a laminate and a printed circuit board using the same.

With the rapid development of the electronics industry, electronic products are developing to be light, thin, short, high-density, secure, and highly functional. Electronic components are required to have higher wiring density and high integration reliability. Metal foil-clad laminates used to make printed circuit boards have superior moisture and heat resistance, low thermal expansion coefficient, dielectric constant, and low water absorption.

Epoxy resin has excellent mechanical properties and processability. It is a commonly used matrix resin in the production of metal foil-clad laminates for high-end printed circuit boards. The prepregs and laminates produced are widely used as a modification. Raw materials are used in high-performance printed circuit board materials.

The epoxy resin composition has excellent flexibility, chemical resistance, adhesion, and the like. However, the cured product has problems of high water absorption and insufficient moisture and heat resistance, and cannot meet the performance requirements of high-end substrates.

Japanese patent application CN106103534 discloses an aromatic amine resin having a low content of diphenylamine, a maleimide resin derived therefrom, and curing using the aromatic amine resin and the maleimide resin A curable resin composition and a cured product excellent in heat resistance, low hygroscopicity, low dielectric properties, flame retardancy, and toughness obtained by curing the curable resin composition. However, it has been found in practice that these resins have the disadvantage of having a relatively large water absorption.

In view of the above shortcomings of the prior art, an object of the present invention is to provide an epoxy resin composition and a prepreg, a laminate (including a metal foil-clad laminate), and a printed circuit board made using the same, which have a low dielectric constant ( Dk) / dielectric loss angle tangent (Df), high glass transition temperature (Tg), low water absorption, low coefficient of thermal expansion (CTE), excellent heat resistance and humidity and heat resistance.

The inventors of the present application have conducted intensive studies to achieve the above-mentioned object, and found that by using a composition containing an epoxy resin, a maleimide of a specific structure, and an active ester compound, the above-mentioned object can be achieved, and the reduction in particular is significantly reduced In addition, by adding an active ester compound, the problem of poor dissolution of maleimide in the solvent used for epoxy resins and the difficulty in formulating the glue are solved, thereby avoiding the complex glue mixing process, which greatly Simplified production process and improved production efficiency.

An aspect of the present invention relates to an epoxy resin composition, characterized in that the epoxy resin composition includes an epoxy resin (A), a maleimide compound (B) having a structure of the formula (I), Ester compound (C), (I) R is Group, hydrogen atom, alkyl group having 1 to 6 carbon atoms, aryl group having 6 to 18 carbon atoms or aralkyl group having 7 to 24 carbon atoms, and R ₁ is an arylene group having 6 to 18 carbon atoms R ₂ and R ₃ are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms or an aralkyl group having 7 to 24 carbon atoms, and n is an integer of 1 to 20.

In certain embodiments, n in the maleimide compound (B) having the structure of formula (I) is an integer of 1 to 15, preferably n is an integer of 1 to 10; preferably, R is A group or a hydrogen atom; preferably, R ₁ is a phenylene group, a naphthylene group or a biphenylene group, further preferably R ₁ is a biphenylene group; preferably, R ₂ and R ₃ are hydrogen atoms.

In some embodiments, the epoxy resin (A) contains Groups, Groups, Groups, Groups, Group or A compound of a group; and / or, the active ester compound (C) contains Groups, Groups, Groups, Groups, Group or Group of compounds.

In some embodiments, the epoxy resin (A) is a novolac epoxy resin, a cresol novolac epoxy resin, a naphthol epoxy resin, a naphthol novolac epoxy resin, and an anthracene epoxy resin. Resin, dicyclopentadiene epoxy resin, dicyclopentadiene phenolic epoxy resin, phenolphthalein epoxy resin, biphenyl epoxy resin, aralkyl epoxy resin, aralkyl novolac epoxy resin Any one or a mixture of at least two epoxy resins containing an arylene ether structure in the molecule; more preferably, the epoxy resin (A) is a novolac epoxy resin, a cresol novolac epoxy resin, Naphthol type epoxy resin, naphthol novolac type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, aralkyl novolac type epoxy resin, anthracene type epoxy resin, dicyclopentadiene type Any one or a mixture of at least two of epoxy resin, dicyclopentadiene novolac epoxy resin, and epoxy resin containing arylene ether structure in the molecule; and / or, the active ester compound (C) is At least one selected from the following.

(1) An active ester obtained by reacting a phenolic compound, a difunctional carboxylic acid aromatic compound or an acid halide and a monohydroxy compound connected through an alicyclic hydrocarbon structure.

Preferably, the amount of the difunctional carboxylic aromatic compound or acid halide in the active ester (1) is 1 mol, the amount of the phenol compound connected through the alicyclic hydrocarbon structure is 0.05 to 0.75 mol, and the amount of the monohydroxy compound is 0.25. ~ 0.95 mol.

Preferably, the active ester (1) has the following structural formula: X is phenyl or naphthyl, j is 0 or 1, k is 0 or 1, and n represents a repeating unit of 0.25 to 1.25.

(2) a styrene-containing active ester, preferably, the styrene-containing active ester (2) has the following structure: Where A is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a C1-C8 alkyl group, m and n are natural numbers, and m / n = 0.8-19;

(3) fluorene imine modified active ester, preferably, the fluorene imine modified active ester (3) has a structure represented by formula (i): (I) In formula (i), R is , , , or , Z is phenyl, naphthyl, phenyl substituted by C1-C4 alkyl or naphthyl substituted by C1-C4 alkyl; X is arylene, arylene substituted by bromine compound, substituted by phosphorus compound Arylene or C1-C10 alkylene; Y is phenylene, naphthylene, phenylene substituted with C1-C4 alkyl, or naphthylene substituted with C1-C4 alkyl; n represents average polymerization Degrees, 0.05-10.

Preferably, the amidine imine-modified active ester has a structure represented by formula (ii): (Ii) In formula (ii), Z is phenyl, naphthyl, phenyl substituted with C1-C4 alkyl or naphthyl substituted with C1-C4 alkyl; X is arylene, substituted with bromine compound Arylene, arylene substituted with a phosphorus compound, or C1-C10 alkylene; Y is phenylene, naphthylene, phenylene substituted with C1-C4 alkyl, or C1-C4 alkyl Naphthylene; n represents the average degree of polymerization and is 0.05-10.

Preferably, the fluorene imine-modified active ester has a structure represented by formula (iii): (Iii) In formula (iii), R is the same or different, and is independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted C1-C8 alkyl group; n ₁ represents an average degree of polymerization and is 0.05-5.0.

(4) A double-ended polyfunctional active ester containing a PPO main chain, preferably, the double-ended polyfunctional active ester containing a PPO main chain (4) has a structure represented by the following formula: Where R ₁ is , , or ; R ₂ is , , , Substituted or unsubstituted C1-C3 linear or branched alkyl, allyl or isoallyl; R ₃ is H, allyl or isoallyl; R ₄ , R ₅ , R ₆ , R _{7 is} independently selected from H, substituted or unsubstituted C1-C3 linear or branched alkyl, allyl, isoallyl, or -OR ₈ ; R ₈ is substituted or unsubstituted C1 -C3 linear or branched alkyl or substituted or unsubstituted phenyl; n1 and n2 are positive integers greater than 0 and satisfy 4≤n1 + n2≤25; n3 and n4 are equal or different, independent Ground is 1, 2 or 3, preferably independently 2 or 3, more preferably n3, n4 are equal and are 2 or 3.

In some embodiments, the content of each component in the epoxy resin composition is as follows: based on the total amount of organic solids of the resin component in the epoxy resin composition being 100 parts by weight, the epoxy resin (A) is 20 to 60 parts by weight, maleimide compound (B) is 10 to 50 parts by weight, and active ester compound (C) is 10 to 50 parts by weight.

In some embodiments, the epoxy resin composition further includes a cyanate compound (D); preferably, in the case where the cyanate compound (D) is contained, the resin in the epoxy resin composition The total amount of organic solids of the components is 100 parts by weight, and the amount of the cyanate ester compound (D) in the epoxy resin composition is 10 to 50 parts by weight; more preferably, the active ester compound (C) and The ratio of the cyanate ester compound (D) is 1: 5 to 5: 1.

In some embodiments, the epoxy resin composition further includes an inorganic filler (E), preferably, based on 100 parts by weight of the total organic solids of the resin components in the epoxy resin composition, The amount of the inorganic filler (E) in the epoxy resin composition is 20 to 300 parts by weight.

Another aspect of the present invention relates to the use of the above-mentioned epoxy resin composition, including a prepreg using the epoxy resin composition, a laminate including the prepreg, and a printed circuit board including the prepreg.

The epoxy resin composition of the present invention and the prepregs, laminates (including metal foil-clad laminates) and printed circuit boards made using the same can have a low dielectric constant (Dk) / dielectric loss tangent value (Df), High glass transition temperature (Tg), low water absorption, low coefficient of thermal expansion (CTE), excellent heat resistance and humidity and heat resistance, etc., especially with significantly reduced water absorption.

In the epoxy resin composition of the present invention, by adding an active ester compound, the problem of poor dissolution of maleimide in a solvent used for epoxy resin is solved, and the epoxy resin composition can be formulated into a glue. This greatly simplifies the production process and improves production efficiency. In addition, by blending the active ester compound (C) and the cyanate ester compound (D), the adhesiveness with the copper foil is improved, and the water absorption thereof is reduced.

The technical solutions of the present invention will be further described below through specific embodiments.

One aspect of the present invention relates to an epoxy resin composition including an epoxy resin (A), a maleimide compound (B) having a structure of the formula (I), and an active ester compound (C). It can also include the following optional components: cyanate ester compound (D), inorganic filler (E), curing accelerator (G), solvent (H), and other additives (I). Hereinafter, each component of the epoxy resin composition of the present invention will be described in detail.

Epoxy resin (A)

The epoxy resin (A) is one of the main components of the epoxy resin composition of the present invention. The epoxy resin (A) according to the present invention is not particularly limited. It is selected from organic compounds containing at least two epoxy groups in the molecular structure, and may be selected from bisphenol A-type epoxy resin and bisphenol F-type ring. Oxygen resin, novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, tetramethyl bisphenol F epoxy resin, bisphenol M epoxy resin, bisphenol S epoxy resin Epoxy resin, bisphenol E type epoxy resin, bisphenol P type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, naphthalene Novolac epoxy resin, anthracene epoxy resin, phenolphthalein epoxy resin, phenoxy epoxy resin, norbornene epoxy resin, adamantane epoxy resin, fluorene epoxy resin, biphenyl Epoxy resin, dicyclopentadiene epoxy resin, dicyclopentadiene novolac epoxy resin, aralkyl epoxy resin, aralkyl novolac epoxy resin, Epoxy resin, alicyclic epoxy resin, polyhydric alcohol epoxy resin, silicon-containing epoxy resin, nitrogen-containing ring Resins, glycidyl amine epoxy resins, glycidyl ester epoxy resin, and introducing a halogen into these, halogen-containing, phosphorus-phosphorus compound such as epoxy resin.

In order to improve the heat resistance and flame retardancy of the epoxy resin composition and reduce the thermal expansion coefficient and dielectric characteristics of the resin composition, the epoxy resin according to the present invention is preferably an epoxy resin containing the following groups in its molecular structure: , , , , or .

Further preferred are novolac epoxy resin, cresol novolac epoxy resin, naphthol epoxy resin, naphthol novolac epoxy resin, anthracene epoxy resin, dicyclopentadiene epoxy resin, and dicyclopentadiene. Enol novolac epoxy resin, phenolphthalein epoxy resin, biphenyl epoxy resin, aralkyl epoxy resin, aralkyl novolac epoxy resin, epoxy resin containing arylene ether structure in the molecule Any one or a mixture of at least two of them.

More preferably, the epoxy resin (A) is a novolac epoxy resin, a cresol novolac epoxy resin, a naphthol epoxy resin, a naphthol novolac epoxy resin, a biphenyl epoxy resin, an arane Basic epoxy resin, aralkyl novolac epoxy resin, anthracene epoxy resin, dicyclopentadiene epoxy resin, dicyclopentadiene novolac epoxy resin, ring containing arylene ether structure in the molecule Any one of oxygen resins or a mixture of at least two of them. The epoxy resin may be used alone, or at least two epoxy resins may be mixed and used as required.

The biphenylaralkyl-type epoxy compound is not particularly limited, and may be, for example, a compound represented by the following formula (IV). By using such a biphenylaralkyl-type epoxy resin, the flame retardance and curability of a resin composition can be improved. (IV) In the formula (IV), n represents an integer of 1 or more. The upper limit value of n is usually 50, and preferably 1 to 20.

The content of the epoxy resin (A) is not particularly limited. From the viewpoints of flame retardancy, glass transition temperature, water absorption, and elastic modulus, the organic solid state of the resin component in the epoxy resin composition is considered. The total amount of the substance is 100 parts by weight, and may be 10 to 70 parts by mass, preferably 20 to 60 parts by mass, and more preferably 30 to 60 parts by mass.

Maleimide compound (B) having a structure of formula (I)

The maleimide compound (B) used in the present invention has the structure of formula (I): (I) where R is Group, hydrogen atom, alkyl group having 1 to 6 carbon atoms, aryl group having 6 to 18 carbon atoms or aralkyl group having 7 to 24 carbon atoms, and R ₁ is an arylene group having 6 to 18 carbon atoms R ₂ and R ₃ are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms or an aralkyl group having 7 to 24 carbon atoms, and n is an integer of 1 to 20.

Preferably, in the maleimide compound having the formula (I), n is an integer of 1 to 15, preferably n is an integer of 1 to 10; preferably, R is A group or a hydrogen atom; preferably, R ₁ is a phenylene group, a naphthylene group or a biphenylene group, further preferably R ₁ is a biphenylene group; preferably, R ₂ and R ₃ are hydrogen atoms.

The maleimide compound having the formula (I) can be obtained by reacting maleic anhydride with an amine compound having at least two primary amine groups in one molecule. This reaction is preferably performed in an organic solvent. As a specific example, there is MIR-3000 manufactured by Nippon Kayaku Co., Ltd. Since the compound has a biphenyl structure, the cured product is excellent in flame retardancy. At the same time, the compound has a novolac-like structure and has a large number of crosslinking points, which can effectively increase the glass transition temperature of the cured product.

The content of the maleimide compound is not particularly limited, and from the viewpoint of the glass transition temperature and water absorption, the total amount of the organic solid matter of the resin component in the epoxy resin composition is 100 parts by weight The amount of the maleimidine imine compound may be in a range of 5 to 60 parts by mass, and preferably 10 to 50 parts by mass.

Active ester compound (C)

As the active ester compound (C) that can be used in the present invention, the following active ester compounds can be selected.

(1) An active ester obtained by reacting a phenolic compound, a difunctional carboxylic acid aromatic compound or an acid halide and a monohydroxy compound connected through an alicyclic hydrocarbon structure.

Preferably, the amount of the difunctional carboxylic aromatic compound or acid halide in the active ester (1) is 1 mol, the amount of the phenol compound connected through the alicyclic hydrocarbon structure is 0.05 to 0.75 mol, and the amount of the monohydroxy compound is 0.25. ~ 0.95 mol.

Preferably, the difunctional carboxylic acid aromatic compound has one of the following structural formulas: In the formula, X is an alkylene group having 1 to 5 carbon atoms.

Preferably, the phenolic compound connected through the alicyclic hydrocarbon structure has one of the following structural formulas: In the formula, p is an integer of 1-5.

Preferably, the active ester (1) has the following structural formula: X is phenyl or naphthyl, j is 0 or 1, k is 0 or 1, and n represents a repeating unit of 0.25 to 1.25.

(2) a styrene-containing active ester, preferably, the styrene-containing active ester (2) has the following structure: Wherein A is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a C1-C8 alkyl group, m and n are natural numbers, and m / n = 0.8-19.

(3) fluorene imine modified active ester, preferably, the fluorene imine modified active ester (3) has a structure represented by formula (i): (I) In formula (i), R is , , , or , Z is phenyl, naphthyl, phenyl substituted by C1-C4 alkyl or naphthyl substituted by C1-C4 alkyl; X is arylene, arylene substituted by bromine compound, substituted by phosphorus compound Arylene or C1-C10 alkylene; Y is phenylene, naphthylene, phenylene substituted with C1-C4 alkyl, or naphthylene substituted with C1-C4 alkyl; n represents average polymerization Degrees, 0.05-10.

Preferably, the amidine imine-modified active ester has a structure represented by formula (ii): (Ii) In formula (ii), Z is phenyl, naphthyl, phenyl substituted with C1-C4 alkyl or naphthyl substituted with C1-C4 alkyl; X is arylene, substituted with bromine compound Arylene, arylene substituted with a phosphorus compound, or C1-C10 alkylene; Y is phenylene, naphthylene, phenylene substituted with C1-C4 alkyl, or C1-C4 alkyl Naphthylene; n represents the average degree of polymerization and is 0.05-10.

Preferably, the fluorene imine-modified active ester has a structure represented by formula (iii): (Iii) In formula (iii), R is the same or different, and is independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted C1-C8 alkyl group; n ₁ represents an average degree of polymerization and is 0.05-5.0.

(4) A double-ended polyfunctional active ester containing a PPO main chain, preferably, the double-ended polyfunctional active ester containing a PPO main chain (4) has a structure represented by the following formula: Where R ₁ is , , or ; R ₂ is , , , Substituted or unsubstituted C1-C3 linear or branched alkyl, allyl or isoallyl; R ₃ is H, allyl or isoallyl; R ₄ , R ₅ , R ₆ , R _{7 is} independently selected from H, substituted or unsubstituted C1-C3 linear or branched alkyl, allyl, isoallyl, or -OR ₈ ; R ₈ is substituted or unsubstituted C1 -C3 linear or branched alkyl or substituted or unsubstituted phenyl; n1 and n2 are positive integers greater than 0 and satisfy 4≤n1 + n2≤25; n3 and n4 are equal or different, independent Ground is 1, 2 or 3, preferably independently 2 or 3, more preferably n3, n4 are equal and are 2 or 3.

Preferably, the active ester compound (C) contains Groups, Groups, Groups, Groups, Group or Group of compounds.

More preferably, the active ester compound includes an active ester having the following structure: X is phenyl or naphthyl, j is 0 or 1, k is 0 or 1, and n represents a repeating unit of 0.25 to 1.25.

Due to the special structure of the active ester, rigid structures such as phenyl, naphthyl, and cyclopentadiene impart high heat resistance to the active ester. At the same time, due to the structural regularity and no secondary reaction with the epoxy resin Hydroxyl groups are generated, giving them good electrical properties and low water absorption.

The content of the active ester compound (C) is not particularly limited. From the viewpoints of flame retardancy, glass transition temperature, water absorption, and dielectric characteristics, the organic solid state of the resin component in the epoxy resin composition is considered. The total amount of the substance is 100 parts by weight, preferably 10 to 70 parts by mass, and more preferably 10 to 50 parts by mass.

Cyanate ester compound (D)

The epoxy resin composition of the present invention may further contain a cyanate ester compound (D). As specific examples of the cyanate compound (D), cyanate compounds known in the art may be listed, for example, a cyanate monomer or a cyanate prepolymer containing at least two cyanate groups in its molecular structure. , Preferably from bisphenol A type cyanate resin, bisphenol F type cyanate resin, tetramethyl bisphenol F type cyanate resin, bisphenol M type cyanate resin, bisphenol S type cyanate Resin, bisphenol E-type cyanate resin, bisphenol P-type cyanate resin, novolac-type cyanate resin, cresol novolac-type cyanate resin, naphthol-type cyanate resin, naphthol-type cyanide resin Acid ester resin, dicyclopentadiene type cyanate resin, phenolphthalein type cyanate resin, aralkyl type cyanate resin, aralkyl novolac type cyanate resin, bisphenol A type cyanate prepolymer , Bisphenol F-type cyanate prepolymer, tetramethylbisphenol F-type cyanate prepolymer, bisphenol M-type cyanate prepolymer, bisphenol S-type cyanate prepolymer, bisphenol E-type cyanate prepolymer, bisphenol P-type cyanate prepolymer, novolac cyanate prepolymer, cresol novolac cyanate prepolymer, naphthol cyanate prepolymer Naphthalene Novolac cyanate prepolymer, dicyclopentadiene cyanate prepolymer, phenolphthalein cyanate prepolymer, aralkyl cyanate prepolymer, or aralkyl phenolic cyanate prepolymer Any one or a mixture of at least two of the polymers, such as a mixture of a bisphenol A-type cyanate resin and a bisphenol F-type cyanate resin, a tetramethylbisphenol F-type cyanate resin, and a bisphenol Mixture of phenol M type cyanate resin, mixture of bisphenol S type cyanate resin and bisphenol E type cyanate resin, mixture of bisphenol P type cyanate resin and novolac cyanate resin, Mixture of phenol novolac cyanate resin and naphthol novolac cyanate resin, mixture of dicyclopentadiene cyanate resin and phenolphthalein cyanate resin, aralkyl cyanate resin and aralkyl Blend of phenolic cyanate resin, mixture of novolac cyanate resin and bisphenol A cyanate prepolymer, bisphenol A cyanate prepolymer and bisphenol F cyanate prepolymer Product mixture, mixture of tetramethylbisphenol F-cyanate prepolymer and bisphenol M-cyanate prepolymer, bisphenol S Mixture of cyanate prepolymer and bisphenol E cyanate prepolymer, mixture of bisphenol P cyanate prepolymer and novolac cyanate prepolymer, cresol novolac cyanate Mixture of prepolymer and naphthol novolac cyanate prepolymer, dicyclopentadiene cyanate prepolymer, phenolphthalein cyanate prepolymer, aralkyl cyanate prepolymer and aromatic A mixture of alkyl novolac cyanate prepolymers. In order to improve the heat resistance and flame retardancy of the cyanate resin composition, novolac cyanate resin, naphthol cyanate resin, naphthol phenolic cyanate resin, phenolphthalein cyanate resin, Aralkyl cyanate resin, aralkyl novolac cyanate resin, novolac cyanate prepolymer, naphthol cyanate prepolymer, naphthol phenol cyanate prepolymer, Any one or a mixture of at least two of a phenolphthalein type cyanate prepolymer, an aralkyl type cyanate prepolymer, or an aralkyl novolak type cyanate prepolymer. From the standpoint of better heat resistance and flame retardancy, novolac cyanate resin, naphthol novolac cyanate resin, aralkyl novolac cyanate resin, and novolac cyanate prepolymer are particularly preferred. Any one or a mixture of at least two of naphthol novolac cyanate prepolymer or aralkyl novolac cyanate prepolymer. From the viewpoint of better dielectric properties, bisphenol-based cyanate resin, aralkyl-based cyanate resin, dicyclopentadiene-based cyanate resin, bisphenol-based cyanate prepolymer, and aromatic are particularly preferred. Either one of an alkyl-type cyanate prepolymer or a dicyclopentadiene-type cyanate prepolymer or a mixture of at least two of them. These cyanate ester resins can be used alone or in combination as required.

The content of the cyanate compound (D) is not particularly limited. From the viewpoints of flame retardancy, glass transition temperature, and adhesion of the resin composition, the organic solid state of the resin component in the epoxy resin composition is considered. The total amount of the substance is 100 parts by weight, preferably 10 to 70 parts by mass, and more preferably 20 to 60 parts by mass.

In addition, in the epoxy resin composition of the present invention, the ratio of the cyanate ester compound (D) to the active ester compound (C) can be appropriately adjusted so that the comprehensive index of the epoxy resin composition includes (Tg, CTE, and water absorption). Sex) is in the preferred range. For example, the ratio of the active ester compound (C) to the cyanate ester compound (D) is 1: 5 to 5: 1, preferably 1: 5 to 3: 1.

Inorganic filler (E)

The epoxy resin composition of the present invention may further contain an inorganic filler (E). The inorganic filler (E) mainly plays the role of improving the dielectric properties, reducing the coefficient of thermal expansion, improving the thermal conductivity and reducing the cost.

The inorganic filler (E) is not particularly limited, and may be selected from the group consisting of silicon dioxide, metal hydrate, molybdenum oxide, zinc molybdate, titanium oxide, zinc oxide, strontium titanate, barium titanate, barium sulfate, boron nitride, and nitrogen. Aluminium carbide, silicon carbide, alumina, zinc borate, zinc stannate, clay, kaolin, talc, mica, composite silicon powder, E glass powder, D glass powder, L glass powder, M glass powder, S glass powder, T glass Powder, NE glass powder, Q glass powder, quartz glass powder, short glass fiber or hollow glass, or a mixture of at least two of them, preferably crystalline silica, fused silica, amorphous silica, spherical Silicon dioxide, hollow silicon dioxide, aluminum hydroxide, boehmite, magnesium hydroxide, molybdenum oxide, zinc molybdate, titanium oxide, zinc oxide, strontium titanate, barium titanate, barium sulfate, boron nitride, nitrogen Aluminium carbide, silicon carbide, alumina, zinc borate, zinc stannate, clay, kaolin, talc, mica, composite silicon powder, E glass powder, D glass powder, L glass powder, M glass powder, S glass powder, T glass Powder, NE glass powder, Q glass powder, quartz glass powder, Any one or a mixture of at least two of short glass fibers or hollow glass, such as a mixture of crystalline silica and fused silica, a mixture of amorphous silica and spherical silica, hollow dioxide A mixture of silicon and aluminum hydroxide, a mixture of boehmite and magnesium hydroxide, a mixture of molybdenum oxide and zinc molybdate, a mixture of titanium oxide, zinc oxide, strontium titanate, and barium titanate, barium sulfate, boron nitride, and nitrogen Mixture of aluminum carbide, mixture of silicon carbide, aluminum oxide, zinc borate and zinc stannate, composite silicon fine powder, E glass powder, D glass powder, L glass powder and M glass powder, S glass powder, T glass powder, A mixture of NE glass powder and quartz glass powder, a mixture of clay, kaolin, talc and mica, a mixture of short glass fibers and hollow glass, and further preferably fused silica or / and boehmite. Among them, fused silica is preferred because it has a low thermal expansion coefficient and boehmite is excellent in flame retardancy and heat resistance. Spherical fused silica is more preferred. Spherical fused silica has characteristics such as a low thermal expansion coefficient and good dielectric properties, and also has good dispersibility and fluidity, so it is preferred.

The average particle diameter (d50) of the inorganic filler (E) is not particularly limited, but from the viewpoint of dispersibility, the average particle diameter (d50) is preferably 0.1-10 microns, for example, 0.2 microns, 0.8 microns, 1.5 microns, and 2.1 microns , 2.6 microns, 3.5 microns, 4.5 microns, 5.2 microns, 5.5 microns, 6 microns, 6.5 microns, 7 microns, 7.5 microns, 8 microns, 8.5 microns, 9 microns, 9.5 microns, and more preferably 0.2-5 microns. Inorganic fillers of different types, different particle size distributions, or different average particle diameters can be used individually or in combination as required.

In order to improve the compatibility between the inorganic filler (E) and the resin composition, it may be used in combination with a surface treatment agent, a wetting agent, and a dispersant. The surface treatment agent is not particularly limited, and is selected from surface treatment agents commonly used for surface treatment of inorganic substances. It is specifically an ethyl orthosilicate compound, an organic acid compound, an aluminate compound, a titanate compound, an organosilicon oligomer, a macromolecular processing agent, a silane coupling agent, and the like. There is no particular limitation on the silane coupling agent, and it is selected from the silane coupling agents commonly used in the surface treatment of inorganic materials, and is specifically amine silane coupling agent, epoxy silane coupling agent, vinyl silane coupling agent, phenyl Silane coupling agents, cationic silane coupling agents, mercaptosilane coupling agents, etc. There is no particular limitation on the wetting agent and dispersant, and it is selected from wetting agents and dispersants commonly used in coatings. According to the present invention, different types of surface treating agents, wetting agents, and dispersing agents can be used alone or in appropriate combinations in combination.

The addition amount of the inorganic filler (E) is not particularly limited, and the total amount of the organic solids of the resin component in the epoxy resin composition is 100 parts by weight (that is, based on the components (A) to (C) The sum of the added amounts or the sum of the amounts of components (A) to (D) is 100 parts by weight), the amount of the inorganic filler (E) may be 0 to 400 parts by weight, preferably 20 to 300 parts by weight, It is more preferably 50-250 parts by weight.

The cyanate resin composition according to the present invention may further include an organic filler. The organic filler is not particularly limited, and is selected from any one or a mixture of at least two of silicone, liquid crystal polymer, thermosetting resin, thermoplastic resin, rubber, or core-shell rubber, and more preferably silicone powder or core-shell rubber. . The organic filler may be a powder or a granule. Among them, organosilicon powder is preferred because it has good flame retardancy properties and core-shell rubber has good toughening effect.

Curing accelerator (G)

The epoxy resin composition of the present invention may further contain a curing accelerator (G), which accelerates the resin curing speed. The curing accelerator is selected from curing accelerators that can accelerate the curing of cyanate resins, active ester compounds, and epoxy resins. Specifically, the curing accelerators are organic salts of metals such as copper, zinc, cobalt, nickel, and manganese, imidazole, and derivatives thereof. , Tertiary amines, etc.

Preferably, the total amount of the organic solids of the resin component in the epoxy resin composition is 100 parts by weight, and the addition amount of the curing accelerator may be 0.01 to 5 parts by weight.

Solvent (H)

An outstanding advantage of the epoxy resin composition of the present invention is that the epoxy resin composition can be formulated into a glue form by using a solvent (H). As the solvent (H) that can be used in the present invention, any resin component can be dissolved without separation when mixed, and examples thereof include methanol, ethanol, ethylene glycol, acetone, methyl ethyl ketone, and methyl ethyl methyl ester. Ketone, cyclohexanone, toluene, xylene, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, ethyl acetate, ethylene glycol methyl ester Ether (MC), propylene glycol methyl ether (PM), propylene glycol methyl ether acetate (PMA), etc. One or more solvents can be used.

Relative to 100 parts by weight of the epoxy resin composition (excluding the solvent), the amount of the solvent (H) is generally 5-50 parts by weight, such as 10-50, 20-50, 30-40 parts by weight, etc., so as to form Coating viscosity (eg 300-600 cPa·s). The solid content in the glue solution may be 60% to 70% by weight.

Other additives (I)

The epoxy resin composition of the present invention may further contain other additives (I), such as a flame retardant, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, or a lubricant. These various additives may be used alone or in combination of two or more. However, the epoxy resin composition of the present invention is preferably free of halogens or halides. The amount of other additives (I) can be arbitrarily adjusted within a range that does not lose the effects of the present invention.

The epoxy resin composition of the present invention can also be used in combination with a maleimide compound other than the maleimide compound (B) having a structure of the formula (I), as long as it does not damage the inherent properties of the cyanate resin composition. Performance is enough. They can be used alone or in combination as required.

The epoxy resin composition according to the present invention can also be used in combination with various polymers as long as it does not impair the inherent properties of the epoxy resin composition. Specific examples may include liquid crystal polymers, thermosetting resins, thermoplastic resins, different flame retardant compounds or additives. They can be used alone or in combination as required.

Another aspect of the present invention relates to a prepreg including a substrate and the above-mentioned epoxy resin composition of the present invention adhered to the substrate after being dried by impregnation.

There are no particular restrictions on the substrates that can be used in the present invention, and are usually woven fabrics, non-woven fabrics, rovings, short fibers, fiber paper, etc., and the material can be inorganic fibers (such as E glass, D glass, L glass, M glass, Glass fibers such as S glass, T glass, NE glass, quartz) or organic fibers (such as polyimide, polyimide, polyester, polyphenylene ether, liquid crystal polymer, etc.), and glass fiber cloth is preferred.

The thickness of the substrate is not particularly limited, and may be, for example, about 0.03 to 0.5 mm. In terms of heat resistance, moisture resistance, and processability, a surface-treated substrate such as a silane coupling agent or a substrate subjected to mechanical fiber opening treatment is preferred. After the resin composition is adhered to the substrate at a resin content of 20 to 90% by mass after the resin is impregnated or coated on the substrate, the resin composition is usually impregnated at a temperature of 100 to 200 ° C for 1 to 30 Heating and drying for one minute to make it semi-cured (B-staged) to obtain a prepreg (also referred to as a prepreg) of the present invention.

The invention also relates to a laminate comprising at least one prepreg as described above. For example, a laminate (metal foil-clad laminate) can be manufactured by laminating and forming 1 to 20 sheets of prepreg and using a configuration in which metal foils such as copper and aluminum are arranged on one or both sides.

The metal foil is not particularly limited as long as it is a material used for electrical insulation materials, and examples thereof include metal foils such as copper and aluminum. Among these, copper foil is preferred. In particular, electrolytic copper foil, rolled copper foil, and the like can be suitably used. The metal foil may be subjected to a known surface treatment such as nickel treatment or cobalt treatment. The thickness of the metal foil can be appropriately adjusted within a range suitable as a material for a printed circuit board, and is preferably 2 to 35 μm.

The molding conditions can be applied to laminates and multilayer boards for electrical insulation materials. For example, multi-stage stamping, multi-stage vacuum stamping, continuous molding, and autoclave molding machines can be used. The temperature is 100 to 250 ° C and the pressure is 2 to 100 kg / cm ^2. The molding is performed under the conditions of a heating time in the range of 0.1 to 5 hours.

In addition, the prepreg of the present invention and a wiring board for an inner layer may be combined and laminated to produce a multilayer board.

The invention also relates to a printed circuit board comprising at least one prepreg as described above.

The printed circuit board can be manufactured by using the prepreg (or metal foil-clad laminate) as a build-up material. Specifically, a prepreg (or a metal foil-clad laminate) is used as a build-up material, and the prepreg is surface-treated by a conventional method, and a wiring pattern (conductor layer) is formed by plating on the surface of the insulating layer. Thus, a printed circuit board of the present invention can be obtained.

The present invention may have at least one of the following advantages: (1) The epoxy resin composition of the present invention and a prepreg made therefrom, a laminate (including a metal-clad laminate), and a printed circuit board have a low dielectric constant (Dk) / dielectric loss angle tangent (Df), high glass transition temperature (Tg), low water absorption, low coefficient of thermal expansion (CTE), excellent heat resistance and humidity and heat resistance, etc., especially with significantly reduced Water absorption. (2) By adding the active ester compound, the problem of poor dissolution of maleimide in the solvent used for epoxy resin is solved, and the epoxy resin composition can be formulated into glue, which greatly simplifies the production process, Increase productivity. (3) The blending of the active ester compound (C) and the cyanate ester compound (D) can improve the adhesion to the copper foil and reduce its water absorption.

Examples

The following further describes the technical solutions of the present invention through examples, but these examples do not limit the scope of the present invention in any way.

In the following examples, unless otherwise indicated, parts by mass of the organic resin are based on parts by mass of the organic solid matter.

Examples 1-4 And comparative example 1-3

Put the epoxy resin, maleimide, active ester, curing accelerator, and filler into the container according to the formula shown in Table 1 and a suitable solvent, stir it to mix and disperse uniformly, make a glue, and adjust the solution solid with the solvent The content is 60% -70% to make a glue solution, that is, a halogen-free thermosetting resin composition glue solution is obtained. The glue is impregnated with 2116 electronic-grade glass fiber cloth and baked in an oven to form a prepreg. 4 pieces of 2116 prepreg are taken, and then double-sided. Cover with 18 μm thick electrolytic copper foil, vacuum laminate in a hot press, cure at 220 ° C / 120min, press 45 kg / cm ² to make a 0.50 mm thick copper clad sheet. The performance test results are shown in Table 2.

The components used in the examples and comparative examples are detailed as follows: (A) Epoxy resin (A-1) Biphenyl type epoxy resin: NC-3000-H (Japanese chemical) (A-2) Dicyclopentyl Ethylene type epoxy resin: HP-7200H (Japanese DIC) (B) Maleimide: (B-1) MIR-3000-70MT (Japanese chemical) (B-2) BMI-70 (KI Chemical) ( C) Active ester: (C-1) HPC-8000-65T (Japanese DIC, which conforms to the more preferred formula for active esters, X is a naphthalene ring) (C-2) HPC-8000L-65MT (Japanese DIC) (D) Cyanate: BA-3000S (Lonza, bisphenol A cyanate) (E) Filler: Spherical silica SC-2500SQ (ADMATECHS) (F) Novolac resin: HF-4M (Japan Mingwa) (G) Curing accelerator (G-1): DMAP (4-dimethylaminopyridine) (G-2): 2P4MHZ-PW (2-phenyl-4-methyl-5hydroxymethylimidazole) (G-3) : Zinc isooctanoate (G-4): 2,4,5-triphenylimidazole

Table 1. Resin composition formula (parts by weight)

Table 2. Substrate characteristic values

Examples 5-8 And comparative example 4-6

Put the epoxy resin, maleimide, active ester, cyanate ester, curing accelerator, and filler in the container according to the formula shown in Table 3 and a suitable solvent, stir to make it mix and disperse uniformly, and make a glue. The solvent adjusts the solid content of the solution to 60% -70% to make a glue solution. The halogen-free thermosetting resin composition glue solution is obtained. The glue is impregnated with 2116 electronic-grade glass fiber cloth and baked in an oven to form a prepreg. Take 4 2116 prepregs. Then, 18 μm-thick electrolytic copper foil was coated on both sides, vacuum-laminated in a hot press, cured at 220 ° C./120 min, and the press pressure was 45 kg / cm ² to make a 0.50 mm-thick copper-clad sheet. The performance test results are shown in Table 4.

Table 3. Resin composition formula (parts by weight)

Table 4. Substrate characteristic values

The test methods for the above characteristics are as follows:

(1) Dielectric constant (Dk) and tangent value of dielectric loss angle (Df): The resonance method of the strip line is used to measure the dielectric constant (Dk) and the dielectric loss angle at 1 GHz in accordance with IPC-TM-650 2.5.5.5 Tangent value (Df).

(2) Glass transition temperature (Tg): DMA (Dynamic thermomechanical analysis) test is used to measure according to the DMA test method specified in IPC-TM-650 2.4.24.

(3) Thermal Expansion Coefficient (Z-CTE): Tested with a Thermo Mechanical Analyzer (TMA) and measured in accordance with the TMA test method specified in IPC-TM-650 2.4.24.1.

(4) Water absorption: According to the test method specified in IPC-TM-650 2.6.2.1, the specific steps are as follows: 1. Sample treatment: The sample is dried in an oven at 105-110 ° C for 1 h. Put in a desiccator to cool to room temperature, weigh out immediately after removing it from the desiccator. 2. Weighing: Each dried sample is weighed and recorded as m ₁ , accurate to 0.1 mg. 3. Water immersion: The treated sample is placed in a container containing distilled water, and all edges should be completely immersed in water. The samples should be placed separately in the container, and should not overlap or contact the surface with each other. The water temperature was maintained at 23 ± 1 ° C. After 24 + 0.5 / -0 h, the sample was taken out of the water, wiped with a dry cloth to remove the surface moisture, and weighed immediately, recorded as m ₂ , accurate to 0.1 mg. 4. Calculation Calculate the water absorption of each sample according to the following formula, accurate to 0.01%. Water absorption% = (m ₂ -m ₁ ) / m ₁ × 100

(5) Moisture and heat resistance evaluation: After the copper foil on the surface of the copper-clad laminate is etched, the substrate is evaluated; the substrate is placed in a pressure cooker, treated at 120 ° C and 105KPa for 4 hours, and then immersed in a tin furnace at 288 ° C; The evaluation can be completed when no blistering or delamination occurs in the tin furnace for more than 5 minutes.

From the physical property data in Table 1 and the substrate property values in Table 2, it can be known that Example 1 is an example of the invention of this patent. After changing an epoxy resin and an active ester respectively in Example 2 and Example 3, the DK, water absorption and The key performance of Z-CTE is basically unchanged; Example 4 is the invention example after the filler is removed in Example 1. Except that the Z-CTE increases more, other key performances are basically unchanged. Comparative Example 1 uses a phenolic resin instead of an active ester as a curing agent for the epoxy resin, and its DK, water absorption and Z-CTE are all significantly increased; Comparative Example 2 after the maleimide is removed, its Tg is significantly reduced, and Z- The CTE increased significantly, the water absorption also increased, and the moisture and heat resistance could not pass. In Comparative Example 3, the maleimine imide was replaced with another structure, and it could not completely dissolve and the resin precipitated, and the laminate could not be produced. It can be seen that the epoxy / maleimine / active ester composition of the present invention has a low Dk / Df, a high glass transition temperature (Tg), a low water absorption, a low CTE, and excellent heat resistance and humidity and heat resistance. specialty.

From the physical property data in Table 3 and the substrate property values in Table 4, it can be known that Example 5 is an example of the invention in which a cyanate resin is added to the present invention. After replacing an epoxy resin and an active ester in Example 6 and Example 7, respectively, The key properties of DK, water absorption, and Z-CTE are basically unchanged. Example 8 is an example of the invention after the filler is removed in Example 5. Except that the Z-CTE increases more, other key properties are basically unchanged. Comparative Example 4 uses a phenolic resin instead of an active ester as a curing agent for the epoxy resin, and its DK, water absorption, and Z-CTE are significantly increased; Comparative Example 5 after the maleimide is removed, its Tg is significantly reduced, and Z- The CTE was significantly increased, the water absorption was also increased, and the moisture and heat resistance could not be passed. In Comparative Example 6, after the maleimide of another structure was replaced, it could not completely dissolve and the resin precipitated, and the laminate could not be produced. It can be seen that the epoxy / maleimine / active ester / cyanate composition of the present invention has lower Dk / Df, higher glass transition temperature (Tg), lower water absorption, lower CTE, and excellent Features of heat resistance and heat resistance.

In summary, compared with a general copper foil substrate, the copper-clad laminate of the present invention has a high glass transition temperature (Tg) and lower CTE, and also has outstanding performance in terms of Dk / Df and water absorption, and With excellent heat resistance and humidity and heat resistance, it can meet the requirements of substrate materials for high-density printed circuit boards.

Of course, the embodiments described above are only preferred examples of the present invention. The applicant states that the present invention illustrates the detailed composition of the present invention through the above embodiments, but the present invention is not limited to the above detailed composition, that is, it does not mean that the present invention must rely on the above detailed composition to be implemented. Those skilled in the art should know that any improvement to the present invention, equivalent replacement of the raw materials of the products of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the scope of protection and disclosure of the present invention.

Claims (23)

An epoxy resin composition, characterized in that the epoxy resin composition includes an epoxy resin (A), a maleimide compound (B) having a structure of formula (I), and an active ester compound (C). R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 18 carbon atoms, R ₁ is a biphenylene group, R ₂ and R ₃ are hydrogen atoms, and n is an integer of 1 to 20. The epoxy resin composition according to claim 1, wherein n is an integer of 1 to 15 in the maleimide compound (B) having the structure of formula (I). The epoxy resin composition according to claim 2, wherein n is an integer of 1 to 10 in the maleimide compound (B) having the structure of the formula (I). The epoxy resin composition according to claim 1, wherein the epoxy resin (A) is contained in a molecular structure Groups, Groups, Groups, Groups, Group or A compound of a group; and / or, the active ester compound (C) contains Groups, Groups, Groups, Groups, Group or Group of compounds. The epoxy resin composition according to claim 1, wherein the epoxy resin (A) is a novolac epoxy resin, a cresol novolac epoxy resin, a naphthol epoxy resin, and a naphthol novolac ring Oxygen resin, biphenyl epoxy resin, anthracene epoxy resin, dicyclopentadiene epoxy resin, dicyclopentadiene novolac epoxy resin, aralkyl epoxy resin, aralkyl novolac epoxy At least one of a resin, an epoxy resin containing an arylene ether structure in the molecule; and / or, the active ester compound (C) is at least one selected from the group consisting of: (1) connected by an alicyclic hydrocarbon structure Active esters obtained by reacting phenolic compounds, difunctional carboxylic aromatic compounds or acid halides with a monohydroxy compound; (2) active esters containing a styrene structure; (3) amidine-modified active esters ; And (4) a double-ended polyfunctional active ester containing a PPO backbone. The epoxy resin composition according to claim 5, wherein the amount of the difunctional carboxylic aromatic compound or acid halide in the active ester (1) is 1 mol, and the amount of the phenolic compound connected through the alicyclic hydrocarbon structure is 0.05 ~ 0.75mol, the amount of monohydroxy compound is 0.25 ~ 0.95mol. The epoxy resin composition according to claim 5, wherein the active ester (1) has the following structural formula: X is phenyl or naphthyl, j is 0 or 1, k is 0 or 1, and n represents a repeating unit of 0.25 to 1.25. The epoxy resin composition according to claim 5, wherein the active ester (2) containing a styrene structure has the following structure: Wherein A is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a C1-C8 alkyl group, m and n are natural numbers, and m / n = 0.8-19. The epoxy resin composition according to claim 5, wherein the fluorene imine-modified active ester (3) has a structure represented by formula (i): In formula (i), R is , , , or , Z is phenyl, naphthyl, phenyl substituted by C1-C4 alkyl or naphthyl substituted by C1-C4 alkyl; X is arylene, arylene substituted by bromine compound, substituted by phosphorus compound Arylene or C1-C10 alkylene; Y is phenylene, naphthylene, phenylene substituted with C1-C4 alkyl, or naphthylene substituted with C1-C4 alkyl; n represents average polymerization Degrees, 0.05-10. The epoxy resin composition according to claim 5, wherein the fluorene imine-modified active ester (3) has a structure represented by formula (ii): In formula (ii), Z is a phenyl group, a naphthyl group, a phenyl group substituted with a C1-C4 alkyl group, or a naphthyl group substituted with a C1-C4 alkyl group; X is an arylene group, and an arylene group substituted with a bromine compound , An arylene group or a C1-C10 alkylene group substituted with a phosphorus compound; Y is a phenylene group, a naphthylene group, a phenylene group substituted with a C1-C4 alkyl group, or a naphthylene group substituted with a C1-C4 alkyl group ; N represents the average degree of polymerization and is 0.05-10. The epoxy resin composition according to claim 5, wherein the fluorene imine-modified active ester (3) has a structure represented by formula (iii): In formula (iii), R is the same or different, and is independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted C1-C8 alkyl group; n ₁ represents an average degree of polymerization and is 0.05 to 5.0. The epoxy resin composition according to claim 5, wherein the double-ended polyfunctional active ester (4) containing a PPO main chain has a structure represented by the following formula: Where R ₁ is , , or ; R ₂ is , , , Substituted or unsubstituted C1-C3 linear or branched alkyl, allyl or isoallyl; R ₃ is H, allyl or isoallyl; R ₄ , R ₅ , R ₆ , R _{7 is} independently selected from H, substituted or unsubstituted C1-C3 linear or branched alkyl, allyl, isoallyl, or -OR ₈ ; R ₈ is substituted or unsubstituted C1 -C3 linear or branched alkyl or substituted or unsubstituted phenyl; n1, n2 are positive integers greater than 0, and satisfy 4 n1 + n2 25; n3, n4 are equal or different, independently 1, 2, or 3. The epoxy resin composition according to claim 1, wherein the total amount of the organic solids of the resin components in the epoxy resin composition is 100 parts by weight, and the content of each component is as follows: epoxy resin ( A) is 20 to 60 parts by weight, the maleimide compound (B) is 10 to 50 parts by weight, and the active ester compound (C) is 10 to 50 parts by weight. The epoxy resin composition according to claim 1, wherein the epoxy resin composition further includes a cyanate ester compound (D). The epoxy resin composition according to claim 14, wherein the cyanate ester in the epoxy resin composition is 100 parts by weight based on the total amount of the organic solid matter of the resin component in the epoxy resin composition. The amount of the compound (D) is 10 to 50 parts by weight. The epoxy resin composition according to claim 14, wherein a ratio of the active ester compound (C) to the cyanate ester compound (D) is 1: 5 to 5: 1. The epoxy resin composition according to claim 1, wherein the epoxy resin composition further includes an inorganic filler (E). The epoxy resin composition according to claim 17, wherein the inorganic filler in the epoxy resin composition (based on the total amount of organic solids of the resin component in the epoxy resin composition is 100 parts by weight) The amount of E) is 20 to 300 parts by weight. A prepreg, characterized in that the prepreg comprises a substrate and the epoxy resin composition according to any one of claims 1-18 attached to the substrate after being dried by impregnation. A laminate, wherein the laminate includes at least one prepreg according to claim 19. The laminate according to claim 20, wherein the laminate is a metal foil-clad laminate. The laminate according to claim 20, wherein the metal foil-clad laminate includes at least one prepreg according to claim 19 and a metal foil covering one or both sides of the prepreg. A printed circuit board, characterized in that the printed circuit board comprises at least one prepreg according to claim 19.