CN114479012A

CN114479012A - Double-end cyano-group active ester, thermosetting resin composition, preparation method and application thereof

Info

Publication number: CN114479012A
Application number: CN202011164382.3A
Authority: CN
Inventors: 林伟; 黄天辉; 游江; 范华勇
Original assignee: Shengyi Technology Co Ltd
Current assignee: Shengyi Technology Co Ltd
Priority date: 2020-10-27
Filing date: 2020-10-27
Publication date: 2022-05-13
Anticipated expiration: 2040-10-27
Also published as: CN114479012B

Abstract

The invention provides a double-end cyano active ester, a thermosetting resin composition, a preparation method and an application thereof, wherein the double-end cyano active ester has a structure shown as a formula I, and has higher reaction crosslinking site, low dielectric loss, low dielectric constant and low dielectric constant through the introduction of a terminal cyano group and the synergistic cooperation of the terminal cyano group and an active ester functional groupThe water absorption rate of (2) can be used as a curing agent to perform a curing reaction with the epoxy resin, and the obtained cured product has excellent dielectric property, heat resistance, moist heat resistance and low thermal expansion coefficient. Thermosetting resin compositions containing said dicyano-terminated active ester have a high T_gThe composite material has excellent heat resistance, mechanical property and adhesive property, and good dielectric property and processing property, and can be widely applied to semiconductor sealing materials, prepreg, circuit substrates or laminated films.

Description

Double-end cyano-group active ester, thermosetting resin composition, preparation method and application thereof

Technical Field

The invention belongs to the technical field of copper-clad plates, and particularly relates to a dicyano-terminated active ester, a thermosetting resin composition, and a preparation method and application thereof.

Background

In recent years, with the rapid development of electronic information technologies such as communication networks, data centers, cloud computing and the like and hardware carriers such as application end mobile phones, base stations, internet of things, automobiles and the like, electronic materials, electronic components and the like are required to have functions of high-frequency, high-speed and large-capacity storage and signal transmission; meanwhile, the trend of miniaturization and densification of electronic device installation puts higher demands on various properties of electronic materials, especially dielectric properties, heat resistance, dimensional stability and the like.

Electronic materials such as copper clad laminates and circuit boards generally comprise a base material having a reinforcing effect and a resin composition, and the improvement of the performance of the electronic materials depends greatly on the selection of the resin composition. The resin composition that is currently most widely used in electronic materials is an epoxy resin system. In the prior art, a cured product of an epoxy resin composition taking an epoxy resin and a curing agent thereof as essential components shows good heat resistance and insulation, and has very excellent processability and cost advantage. However, the epoxy resin itself has a high dielectric constant (D)_k) And dielectric loss (D)_f) When the epoxy resin is cured by using a conventional curing agent such as amine or phenolic resin, a cured product of the epoxy resin generates a large amount of secondary hydroxyl, so that the water absorption rate is increased, and the dielectric property and the damp-heat resistance are reduced.

The cyanate ester resin has good caking property and processing property, high glass transition temperature, lower dielectric constant and low dielectric loss, thereby having good application potential in the preparation of metal-clad laminates for high-end printed circuit boards. For example, CN102924865A discloses a cyanate ester resin composition, and a prepreg, a laminate and a metal foil-clad laminate made from the cyanate ester resin composition, wherein the cyanate ester resin composition comprises a cyanate ester resin, a halogen-free epoxy resin and an inorganic filler, and has good flame retardancy and a low thermal expansion coefficient. However, cyanate ester resin is easy to absorb water, and the humidity resistance after curing is poor, so that the wide application of cyanate ester resin in copper clad laminates is limited.

With the intensive research on resin compositions in electronic materials, it has been found that active esters contain higher-activity ester groups, which can be used as curing agents to perform transesterification with epoxy resins, and the resulting network structure after the reaction does not contain secondary hydroxyl groups, so that the cured products have low dielectric loss, low water absorption and lower dielectric constant. For example, JP2009235165 discloses an epoxy resin composition using a reactive ester compound having the following structure:

wherein X is a benzene ring or a naphthalene ring, and k represents 0 or 1. The epoxy resin composition has both high heat resistance and low dielectric tangent, and the viscosity is sufficiently low when the epoxy resin composition is dissolved in an organic solvent, so that the epoxy resin composition is beneficial to later-stage processing application. However, since the active ester-cured epoxy resin represented by the above active ester compound has a large molecular weight of the active ester reactive group and the chemical reaction mechanism with the epoxy group is an ester exchange reaction, the cured product thereof has a low cross-linking density and exhibits a glass transition temperature (T) as compared with an aromatic amine, a phenol resin, a cyanate resin, a bismaleimide resin or the like_g) The application of the material in the base material of the high-performance printed circuit board is limited to a great extent due to the defects of low thermal expansion coefficient, high thermal expansion coefficient and the like.

Therefore, it is important to develop a curing material and a resin composition having high crosslinking density, low dielectric loss, high heat resistance and moist heat resistance to meet the performance and application requirements of high performance circuit substrates.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a dicyano-terminated active ester, a thermosetting resin composition, a preparation method and an application thereof. The dicyanate-terminated active ester is used as a curing agent of epoxy resin, can endow the epoxy resin composition with excellent dielectric property, heat resistance, moist heat resistance and low thermal expansion coefficient, and enables the resin composition to fully meet the application requirements of high-performance circuit substrates.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the present invention provides a dicyano-terminated active ester, which has a structure represented by formula I:

in the formula I, Ar is a substituted or unsubstituted C6-C150 divalent aromatic group; the substituted substituent in Ar is selected from fluorine, C1-C5 straight chain or branched chain alkyl, C6-C18 aryl, C2-C5 straight chain or branched chain alkylene and a group containing an aryl phosphorus oxygen structure.

In the present invention, the "divalent aromatic group" means a group having 2 bonding sites containing an aryl group, including an arylene group, and a substituent formed by connecting at least 2 aryl groups to each other through a linking group (e.g., -O-, -S-, a carbonyl group, a sulfone group, an alkylene group, a cycloalkylene group, an arylenealkyl group, etc.). The same description is hereinafter referred to with the same meaning.

The C1-C5 straight chain or branched chain alkyl group comprises a C1, C2, C3, C4 or C5 straight chain or branched chain alkyl group, and exemplarily comprises but is not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and the like. The same description is hereinafter referred to with the same meaning.

The C6-C18 aryl group includes C6, C8, C9, C10, C12, C14, C16, C18 and the like, and exemplarily includes but is not limited to: phenyl, biphenyl, terphenyl, or naphthyl, and the like. The same description is hereinafter referred to with the same meaning.

The C2-C5 linear or branched alkenyl group includes C2, C3, C4 or C5 linear or branched alkenyl groups, which illustratively include but are not limited to: vinyl, propenyl, or allyl, and the like. The same description is hereinafter referred to with the same meaning.

In the formula I, X is selected from substituted or unsubstituted C6-C30 divalent aromatic group, substituted or unsubstituted C1-C30 (such as C1, C2, C3, C4, C5, C6, C8, C10, C12, C15, C18, C20, C22, C25, C28 or C29) straight-chain or branched alkylene group, substituted or unsubstituted C3-C20 (such as C3, C4, C5, C6, C8, C10, C12, C15, C18 or C20) cycloalkylene group; the substituents for X are each independently selected from fluorine, C1-C5 (e.g., C1, C2, C3, C4, or C5) straight or branched chain alkyl.

In formula I, n is an average value of the number of repeating units and is selected from 1 to 15, such as 1, 1.2, 1.5, 1.8, 2, 2.2, 2.5, 2.8, 3, 3.3, 3.5, 3.7, 4, 4.2, 4.5, 4.7, 5, 5.3, 5.5, 5.8, 6, 6.2, 6.5, 6.8, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14 or 14.5, and specific values therebetween are not exhaustive, and are not limited to the breadth and for brevity, and the invention is not exhaustive.

In the dicyano-terminated active ester provided by the invention, through introduction of a dicyano-terminated group and cooperation of the dicyano-terminated active ester and an active ester functional group, the dicyano-terminated active ester is endowed with a high reaction crosslinking site, low dielectric loss, low dielectric constant and low water absorption rate, can be used as a curing agent to perform curing reaction with epoxy resin, and the obtained cured product has excellent dielectric property, heat resistance, wet heat resistance and low thermal expansion coefficient.

In the active ester having a cyano group at a lower proportion of the cyano group as the average value n of the number of repeating units is larger, the performance of a cured product formed by the reaction with an epoxy resin tends to be more excellent than that of a general active ester, that is, the dielectric property is slightly excellent, and the dielectric property is slightly excellent at T_gAnd a deficiency in the coefficient of thermal expansion; and the larger the value of n, the larger the corresponding molecular weight, which isThe poorer the solubility in the organic solvent, the fewer the organic solvents can be selected, which can increase the process difficulty in the synthetic process, even cause local implosion to generate the phenomenon of 'gel', and can also increase the process difficulty in the application of the resin.

Preferably, Ar is selected from

Ar₁Is selected from

Ar₂Is selected from

R₁、R₂Each independently selected from fluorine, C1-C5 (e.g., C1, C2, C3, C4, or C5) straight or branched chain alkyl, C1-C5 (e.g., C1, C2, C3, C4, or C5) straight or branched chain alkenyl, or mixtures thereof,

R₃Is a C1-C5 (e.g., C1, C2, C3, C4, or C5) straight or branched chain alkylene.

n₁、n₃Each independently selected from an integer of 0 to 4, such as 0, 1, 2, 3 or 4.

n₂Is selected from integers of 0 to 6, such as 0, 1, 2, 3, 4, 5 or 6.

Y₁、Y₂Each independently selected from-O-, -S-, carbonyl, sulfone, substituted or unsubstituted C1-C20 (e.g. C1, C2, C3, C4, C5, C6, C8, C10, C12, C14, C16, C18 or C20) straight chain or branched chain alkylene, substituted or unsubstituted C3-C30 (e.g. C3, C4, C5, C6, C8, C10, C12, C15, C18, C20, C22, C25, C28 or C29) cycloalkylene, substituted or unsubstitutedC6 to C30 (e.g., C6, C7, C8, C9, C10, C12, C15, C18, C20, C22, C25, C28, C29, etc.) aralkylene; the substituted substituents are independently selected from fluorine, C1-C5 (e.g. C1, C2, C3, C4 or C5) straight chain or branched chain alkyl, C6-C18 (e.g. C6, C8, C9, C10, C12, C14, C16 or C18) aryl.

m is selected from 0 to 10, such as 0.2, 0.5, 0.8, 1, 1.2, 1.5, 1.8, 2, 2.2, 2.5, 2.8, 3, 3.3, 3.5, 3.7, 4, 4.2, 4.5, 4.7, 5, 5.3, 5.5, 5.8, 6, 6.2, 6.5, 6.8, 7, 7.5, 8, 8.5, 9, 9.5 or 10, and specific point values between the above point values are limited in space and for the sake of brevity, and the invention is not exhaustive of the specific point values included in the ranges.

In the present invention, short straight lines on one or both sides of the radical structure (e.g. short straight lines on one or both sides of the radical structure)

Short straight lines on both sides of the middle benzene ring) represent the access bond of the group and do not represent a methyl group.

Further preferably, said Y is₁、Y₂Each independently selected from-O-, -S-, substituted or unsubstituted C1-C10 (e.g. C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) straight or branched alkylene, substituted or unsubstituted C3-C8 (e.g. C3, C4, C5, C6, C7 or C8) cycloalkylene or C8

Preferably, X is selected from the group consisting of substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene ether

Substituted or unsubstituted C1 to C10 (e.g., C1, C2, C3, C4, C5, C6, C8, C9, or C10) straight or branched alkylene, substituted or unsubstituted C3 to C10 (e.g., C3, C4, C5, C6, C8, C9, or C10) cycloalkylene; the substituted substituents are each independently selected from fluorine, C1-C5 (e.g., C1, C2, C3, C4, or C5) straight chain orA branched alkyl group.

As a further preferred embodiment of the present invention, the dicyano-terminated reactive ester has the following structure:

in another aspect, the present invention provides a method for preparing a dicyano-terminated active ester as described above, which is prepared by the following preparation method I or preparation method II.

The preparation method I comprises the following steps: reacting a phenolic compound with a structure shown as a formula A1, a dicarboxylic halide compound with a structure shown as a formula A2 and a cyanogen compound with a structure shown as a formula A3 to obtain the dicyandiamide active ester.

The preparation method II comprises the following steps: and (3) reacting the compound with the structure shown as the formula B1 with a cyanogen compound with the structure shown as the formula A3 to obtain the dicyano-terminated active ester.

HO-Ar-OH formula A1;

Z₁-C ≡ N formula a 3;

wherein Ar, X, n each independently have the same limitations as in formula I;

X₁、Z₁each independently selected from halogen;

Z₂selected from hydrogen and Na⁺、Ka⁺Or Li⁺。

Preferably, said X₁、Z₁Each independently selected from chlorine, bromine or iodine.

In the preparation method I, the molar ratio of the phenolic compound to the dicarboxylic halide compound is preferably 1 (0.5-0.95), such as 1:0.55, 1:0.6, 1:0.65, 1:0.7, 1:0.75, 1:0.8, 1:0.85, 1:0.9 or 1: 0.93.

In the process I, at least the cyanogenic compound having the structure represented by the formula A3 is reacted with the residual phenolic hydroxyl groups in the phenolic compound in an equimolar ratio, i.e., the molar amount of the cyanogenic compound is allowed to be in an equimolar ratio or in an excess amount with respect to the residual phenolic hydroxyl groups in the phenolic compound (excluding the part in an equimolar ratio with the dicarboxylic halide compound).

Preferably, the reaction described in preparation process I is carried out in the presence of a basic catalyst.

Preferably, the basic catalyst comprises an inorganic basic compound and/or an organic base; the inorganic alkaline compound comprises any one or the combination of at least two of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, sodium bicarbonate or potassium bicarbonate; the organic base comprises any one or the combination of at least two of triethylamine, pyridine, 4-dimethylaminopyridine, tributylamine, N-diisopropylethylamine, benzyltriethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride or tetradecyltrimethylammonium chloride.

Preferably, the reaction in preparation method I is carried out in the presence of a solvent, which is not particularly limited as long as it does not interfere with the reaction, and exemplarily includes, but is not limited to: tetrahydrofuran, dioxane, benzene, toluene, xylene, methylene chloride, dichloroethane, butanone, methyl isobutyl ketone, cyclohexanone, 1, 4-butyrolactone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, or N-methylpyrrolidone, or a combination of at least two thereof. The amount of the solvent is preferably 3 to 15 times, for example, 3.5 times, 4 times, 4.5 times, 5 times, 5.5 times, 6 times, 6.5 times, 7 times, 7.5 times, 8 times, 8.5 times, 9 times, 10 times, 11 times, 12 times, 13 times, 14 times, or the like of the sum of the raw materials.

Preferably, the reaction in preparation process I is carried out in a protective atmosphere, which is preferably nitrogen or argon.

Preferably, the reaction described in preparation process I is carried out at a low temperature, preferably at a temperature of-30 ℃ to 50 ℃, e.g., -28 ℃, -25 ℃, -22 ℃, -20 ℃, -18 ℃, -15 ℃, -13 ℃, -10 ℃, -8 ℃, -5 ℃, -2 ℃, -0 ℃, 2 ℃,5 ℃, 8 ℃, 10 ℃, 12 ℃, 15 ℃, 18 ℃, 20 ℃, 22 ℃, 25 ℃, 28 ℃, 30 ℃, 32 ℃, 35 ℃, 38 ℃, 40 ℃, 42 ℃, 45 ℃ or 48 ℃ and the like.

Preferably, after the reaction in preparation process I is completed, the resulting bicyano active ester can be isolated and purified by optional filtration, washing with water, concentration, extraction, recrystallization, or column chromatography.

Preferably, the reaction in preparation method II is carried out at a low temperature, and the temperature of the reaction is preferably-30 to 20 ℃, for example, -28 ℃, -25 ℃, -22 ℃, -20 ℃, -18 ℃, -15 ℃, -13 ℃, -10 ℃, -8 ℃, -5 ℃, -2 ℃, -0 ℃, 1 ℃, 2 ℃,5 ℃, 8 ℃, 10 ℃, 12 ℃, 15 ℃, 16 ℃ or 18 ℃.

Preferably, Z is₂The reaction described in preparation II is carried out in the presence of a basic catalyst for hydrogen.

Preferably, Z is₂Selected from Na⁺、Ka⁺Or Li⁺The reaction described in preparation Process II is carried out in the presence of a phase transfer catalyst.

As a preferred embodiment of the present invention, Z is₂Selected from Na⁺、Ka⁺Or Li⁺The compound having the structure represented by formula B1 is a basic phenoxide compound, and a phase transfer catalyst soluble in a water phase and an organic solvent phase is added during the reaction described in preparation process II.

Preferably, the phase transfer catalyst comprises any one of benzyltriethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, polyethylene glycol dimethyl ether, crown ether, triethylamine hydrochloride, triethylamine, pyridine, 4-dimethylaminopyridine, tributylamine or N, N-diisopropylethylamine or a combination of at least two thereof.

Preferably, the reaction in preparation process II is carried out in the presence of a solvent, which is not particularly limited as long as it does not interfere with the reaction, and exemplarily includes, but is not limited to: tetrahydrofuran, dioxane, benzene, toluene, xylene, methylene chloride, dichloroethane, butanone, methyl isobutyl ketone, cyclohexanone, 1, 4-butyrolactone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, methanol, ethanol, isopropanol or water, or a combination of at least two thereof. The amount of the solvent may be appropriately adjusted according to the solubility of the raw materials and the product, so that each raw material and the product can be dissolved in the solvent, and is preferably 5 to 15 times, for example, 5.5 times, 6 times, 6.5 times, 7 times, 7.5 times, 8 times, 8.5 times, 9 times, 10 times, 11 times, 12 times, 13 times, 14 times, or the like of the sum of the mass of each raw material.

Preferably, the reaction in preparation process II is carried out in a protective atmosphere, which is preferably nitrogen or argon.

Preferably, after the reaction described in preparation Process II is completed, the resulting dicyanobenzoyl-active ester may be isolated and purified by optional filtration, washing with water, concentration, extraction, recrystallization, or column chromatography.

In another aspect, the present invention provides a thermosetting resin composition comprising an epoxy resin and a dicyandiamide active ester as described above.

In the thermosetting resin composition provided by the invention, the molecular structure of the dicyano-terminated active ester contains both aryl ester group and cyano group, and has more reactive sites, when the dicyano-terminated active ester is used as a curing agent to react with epoxy resin, on one hand, strong polar secondary hydroxyl groups are not generated when the aryl ester group reacts with the epoxy resin, so that the cured product has low dielectric loss, low water absorption and lower dielectric constant; on the other hand, cyano groups can be polymerized to form a high-rigidity six-membered triazine ring structure and can also react with epoxy groups to form a five-membered oxazoline heterocyclic structure, and polar groups such as hydroxyl groups or amino groups are not generated in the reaction process, so that excellent heat resistance (high T) is endowed to the thermosetting resin composition after curing_g) And mechanical properties, as well as good dielectric properties and processability.

Preferably, the epoxy resin refers to an epoxy resin having at least two epoxy groups in 1 molecule, exemplary including but not limited to: any one or a combination of at least two of bifunctional bisphenol a type epoxy resin, bifunctional bisphenol F type epoxy resin, bifunctional bisphenol S type epoxy resin, phenol formaldehyde type epoxy resin, methylphenol novolac type epoxy resin, bisphenol a type novolac epoxy resin, dicyclopentadiene (DCPD) epoxy resin, biphenyl epoxy resin, resorcinol type epoxy resin, naphthalene type epoxy resin, phosphorus-containing epoxy resin, silicon-containing epoxy resin, glycidylamine type epoxy resin, alicyclic type epoxy resin, polyethylene glycol type epoxy resin, tetraphenolethane tetraglycidyl ether, triphenolylmethane type epoxy resin, condensate of bifunctional cyanate ester and epoxy resin, or condensate of bifunctional isocyanate and epoxy resin; exemplary combinations include: a combination of a bifunctional bisphenol a type epoxy resin and a bifunctional bisphenol F type epoxy resin, a combination of a bifunctional bisphenol S type epoxy resin and a phenol formaldehyde type epoxy resin, a combination of a resorcinol type epoxy resin and a naphthalene type epoxy resin, and a combination of an alicyclic type epoxy resin and a polyethylene glycol type epoxy resin.

Preferably, any one or a combination of at least two of other curing agents, flame retardants, inorganic fillers, organic fillers or curing accelerators is also included in the thermosetting resin composition.

Preferably, the other curing agent is selected from any one of an amine curing agent, a phenol curing agent, a benzoxazine curing agent, a cyanate curing agent, an anhydride curing agent or an amine-modified maleimide curing agent, or a combination of at least two thereof.

Preferably, the flame retardant is selected from any one of or a combination of at least two of a halogen-based organic flame retardant, a phosphorus-based organic flame retardant, a nitrogen-based organic flame retardant or a silicon-containing organic flame retardant.

Preferably, the inorganic filler comprises any one of or a combination of at least two of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate or inorganic phosphorus; further preferred is any one or a combination of at least two of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, and mica.

Preferably, the organic filler comprises any one of polytetrafluoroethylene powder, polyphenylene sulfide powder or polyether sulfone powder or a combination of at least two of the foregoing.

Preferably, the curing accelerator comprises any one or a combination of at least two of imidazole compounds, imidazole compound derivatives, piperidine compounds, pyridine compounds, organic metal salt Lewis acid or triphenylphosphine.

The preparation method of the thermosetting resin composition can comprise the following steps: firstly, putting the solid into the reactor, then adding the solvent, stirring until the solid is completely dissolved, then adding the liquid resin and the curing accelerator, and continuously stirring uniformly.

The solvent is not particularly limited, and includes any one of an alcohol solvent, an ether solvent, an aromatic hydrocarbon solvent, an ester solvent, a ketone solvent, or a nitrogen-containing solvent, or a combination of at least two thereof. Wherein, the alcohol solvent comprises any one of methanol, ethanol or butanol or the combination of at least two of the methanol, the ethanol and the butanol; the ether solvent comprises any one or the combination of at least two of ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol and butyl carbitol; the aromatic hydrocarbon solvent comprises any one or a combination of at least two of benzene, toluene or xylene; the ester solvent comprises any one or the combination of at least two of ethyl acetate, butyl acetate or ethoxy ethyl acetate; the ketone solvent comprises any one or the combination of at least two of acetone, butanone, methyl ethyl ketone or cyclohexanone; the nitrogen-containing solvent comprises N, N-dimethylformamide and/or N, N-dimethylacetamide.

The amount of the solvent can be adjusted according to actual processing and application requirements.

In another aspect, the present invention provides a semiconductor sealing material whose raw material comprises the thermosetting resin composition as described above.

In another aspect, the present invention provides a prepreg comprising a substrate and a thermosetting resin composition as described above attached to the substrate by impregnation drying.

Preferably, the substrate comprises any one of glass fiber cloth, non-woven cloth or quartz cloth or a combination of at least two of the glass fiber cloth, the non-woven cloth and the quartz cloth.

The glass fiber cloth can be E-glass fiber cloth, D-glass fiber cloth, S-glass fiber cloth, T-glass fiber cloth, NE-glass fiber cloth or the like.

The thickness of the substrate is not particularly limited; the thickness of the substrate is preferably 0.01 to 0.2mm, for example, 0.02mm, 0.05mm, 0.08mm, 0.1mm, 0.12mm, 0.15mm, 0.17mm, 0.19mm, or the like, from the viewpoint of good dimensional stability.

Preferably, the substrate is a substrate subjected to fiber opening treatment and/or surface treatment with a silane coupling agent. In order to provide good water resistance and heat resistance, the silane coupling agent is preferably any one of an epoxy silane coupling agent, an aminosilane coupling agent or a vinylsilane coupling agent, or a combination of at least two thereof.

Illustratively, the preparation method of the prepreg comprises the following steps: and soaking a base material in the resin glue solution of the thermosetting resin composition, taking out the base material and drying to obtain the prepreg.

Preferably, the drying temperature is 100-250 deg.C, such as 105 deg.C, 110 deg.C, 115 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, 150 deg.C, 160 deg.C, 170 deg.C, 180 deg.C, 190 deg.C, 200 deg.C, 210 deg.C, 220 deg.C, 230 deg.C, 240 deg.C or 245 deg.C.

Preferably, the drying time is 1-15 min, such as 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min or 14 min.

In another aspect, the invention provides a circuit substrate, which includes at least one prepreg as described above, and a metal foil disposed on one or both sides of the prepreg.

The material of the metal foil is not particularly limited; preferably, the metal foil includes a copper foil, a nickel foil, an aluminum foil, or a SUS foil.

Illustratively, the preparation method of the circuit substrate comprises the following steps: pressing metal foils on one side or two sides of a piece of prepreg, and curing to obtain the circuit substrate; or bonding at least two prepregs to form a laminated board, then laminating metal foils on one side or two sides of the laminated board, and curing to obtain the circuit substrate.

Preferably, the curing is performed in a hot press.

Preferably, the curing temperature is 100 to 250 ℃, such as 105 ℃, 110 ℃, 115 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ or 245 ℃, etc.

Preferably, the curing pressure is 10-60 kg/cm²E.g. 15kg/cm²、20kg/cm²、25kg/cm²、30kg/cm²、35kg/cm²、40kg/cm²、45kg/cm²、50kg/cm²Or 55kg/cm²And the like.

In another aspect, the present invention provides a laminated film comprising a base film or a metal foil, and the thermosetting resin composition as described above applied to at least one surface of the base film or the metal foil.

Compared with the prior art, the invention has the following beneficial effects:

(1) the dicyano-terminated active ester provided by the invention contains cyano and aromatic ester groups, has more reaction crosslinking sites, low dielectric loss, low dielectric constant and low water absorption rate through the special design of a molecular structure, can be used as a curing agent to carry out curing reaction with epoxy resin, and the obtained cured product has excellent dielectric property, heat resistance, wet heat resistance and low thermal expansion coefficient.

(2) The thermosetting resin composition provided by the invention leads the obtained cured product to have high T through the introduction of the dicyan-terminated active ester with high crosslinking sites_gExcellent heat resistance, mechanical property and adhesive property, and good dielectric property and processing property. On one hand, when the aryl ester group in the double-end cyano active ester reacts with epoxy resin, strong-polarity secondary hydroxyl groups are not generated, so that the obtained cured product has low dielectric loss, low dielectric constant and low water absorption rate; on the other hand, the cyano group in the active ester with the double-end cyano group can be polymerized to form a six-membered triazine ring structure with high rigidity, and can also react with an epoxy group to form a five-membered oxazoline heterocyclic ring structure, and polar groups such as hydroxyl or amino are not generated in the reaction process, so that the cured product has excellent humidity resistance and dielectric property.

(3) The thermosetting resin composition containing the dicyanate-terminated active ester and the circuit substrate thereof have low thermal expansion coefficient, low water absorption rate, low dielectric constant and dielectric loss, show excellent dielectric property, heat resistance, wet heat resistance and adhesive strength, and can meet the high performance requirement of the circuit substrate.

Drawings

FIG. 1 is an infrared spectrum of a dicyanobenzoyl reactive ester provided in example 1;

FIG. 2 is an ultra-efficient polymer chromatogram of a dicyano-terminated active ester provided in example 1.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

Example 1

A bi-end cyano active ester K-1 has the following structure:

the preparation method comprises the following steps:

165g (hydroxyl equivalent: 165g/eq.) of a dicyclopentadiene and phenol addition polymerization resin, 50.8g (0.25mol) of isophthaloyl dichloride and 1725g of toluene were put into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer, and the inside of the system was replaced with nitrogen under reduced pressure and dissolved with stirring; controlling the reaction system below 50 ℃, dropwise adding 50.6g (0.5mol) of triethylamine for 2 hours, and stirring for 1 hour after dropwise adding; the temperature of the system is reduced to below minus 10 ℃, 36.9g (0.6mol) of cyanogen chloride is added, 65.8g (0.65mol) of triethylamine is added dropwise in 2 hours, the temperature of the reaction system is controlled to be below 0 ℃, and the stirring is carried out for 1 hour after the dropwise addition is finished. After the reaction is finished, adding deionized water, stirring for 10min, removing a water layer by standing and separating liquid, and repeatedly washing the obtained toluene layer until the pH value of the water layer is 7; and finally, heating and decompressing to concentrate toluene, and then adding butanone to prepare a resin solution to obtain the liquid resin of the dicyan-terminated active ester K-1.

The calculated and measured values according to the charging ratio show that the ester group equivalent of the double-end active ester K-1 provided by the embodiment is 420g/eq, and the calculated cyano group equivalent is 420g/eq.

Example 2

A bi-end cyano active ester K-2 has the following structure:

the preparation method comprises the following steps:

into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer were charged 200g of a double-terminal hydroxyl active ester V-575 (Unitika, Japan, number average molecular weight M)_nIs 3900 and has the structural formula

The ester group equivalent was 210g/eq., and the hydroxyl group equivalent was about 1000g/eq.) and 3000g of toluene were dissolved by stirring while replacing the system with nitrogen under reduced pressure. The reaction system was controlled to-10 ℃ or lower, 14.8g (0.24mol) of cyanogen chloride was added, 30.4g (0.3mol) of triethylamine was added dropwise over 2 hours, the reaction system was controlled to 0 ℃ or lower, and stirring was carried out for 1 hour after the completion of the dropwise addition. After the reaction, deionized water was added and stirred for 10min, and the aqueous layer was removed by standing and separating, and the water-washing operation was repeated for the obtained toluene layer until the pH of the aqueous layer was 7. And finally, heating and decompressing to concentrate toluene, and then adding butanone to prepare a resin solution to obtain the liquid resin of the dicyan-terminated active ester K-2.

The ester group equivalent of the double-end active ester K-2 provided by the embodiment is 225g/eq and the cyano group equivalent is 1025g/eq, calculated and measured according to the charging ratio.

Example 3

A bi-end cyano active ester K-3 has the following structure:

the preparation method comprises the following steps:

a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer was charged with 160g of diallylbisphenol A (hydroxyl equivalent: 160g/eq.), 71.1g (0.35mol) of isophthaloyl dichloride and 1160g of methylene chloride, and the inside of the system was replaced with nitrogen under reduced pressure and dissolved with stirring. After 0.5g of tetrabutylammonium bromide was added to the reaction system while controlling the temperature of the reaction system to 30 ℃ or lower, 140g (0.7mol) of a 20% aqueous solution of sodium hydroxide was added dropwise over 2 hours, and the mixture was stirred for 1 hour after the completion of the addition. After the aqueous layer was removed by standing and liquid separation, the temperature of the methylene chloride layer system was lowered to-10 ℃ or lower, 24.6g (0.4mol) of cyanogen chloride was added, 45.5g (0.45mol) of triethylamine was added dropwise over 2 hours, the reaction system was controlled to 0 ℃ or lower, and the mixture was stirred for 1 hour after the completion of the dropwise addition. After the reaction, deionized water was added and stirred for 10min, and the water layer was removed by standing and separating, and the washing operation was repeated until the pH of the water layer was 7. And finally, heating and decompressing to concentrate dichloromethane, and then adding butanone to prepare a resin solution to obtain the liquid resin of the dicyan-terminated active ester K-3.

The ester group equivalent of the double-end active ester K-3 provided by the embodiment is 304g/eq and the cyano group equivalent is 710g/eq, which are calculated and measured according to the charging ratio.

Example 4

A bi-end cyano active ester K-4 has the following structure:

the preparation method comprises the following steps:

in a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer, 162g (hydroxyl equivalent: 162g/eq.) of 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, 45.8g (0.25 mol.) of adipoyl chloride and 2150g of methylene chloride were charged, and the inside of the system was replaced with nitrogen under reduced pressure and dissolved with stirring. Then, the reaction system was controlled at-10 ℃ or lower, 36.9g (0.6mol) of cyanogen chloride was added, and then 121.5g (1.2mol) of triethylamine was added dropwise over 3 hours, the reaction system was controlled at 5 ℃ or lower, and after completion of the dropwise addition, the mixture was stirred for 2 hours. After the reaction, deionized water was added and stirred for 10min, and the water layer was removed by standing and separating, and the washing operation was repeated until the pH of the water layer was 7. And finally, heating and decompressing to concentrate dichloromethane, and then adding butanone to prepare a resin solution to obtain the liquid resin of the dicyan-terminated active ester K-4.

The calculated and measured values according to the charging ratio show that the ester group equivalent of the double-end active ester K-4 provided by the embodiment is 404g/eq and the cyano group equivalent is 404g/eq.

Example 5

A bi-end cyano active ester K-5 has the following structure:

the preparation method comprises the following steps:

188g (hydroxyl equivalent: 188g/eq.) of a polycondensation resin of 4,4 '-biphenyldicarboxaldehyde and phenol, 73.8g (0.25 mol.) of 4,4' -diacyl diphenyl ether and 2050g of methylene chloride were put into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer, and the inside of the system was replaced with nitrogen under reduced pressure and dissolved with stirring. The reaction system was controlled to 30 ℃ or lower, 50.6g (0.5mol) of triethylamine was added dropwise over 2 hours, and the mixture was stirred for 1 hour after the completion of the addition. Then, the temperature of the system was lowered to-10 ℃ or lower, 36.9g (0.6mol) of cyanogen chloride was added thereto, 65.8g (0.65mol) of triethylamine was added dropwise over 2 hours, the temperature of the reaction system was controlled to 0 ℃ or lower, and the mixture was stirred for 1 hour after the completion of the dropwise addition. After the reaction, deionized water was added and stirred for 10min, and the aqueous layer was removed by standing and separating, and the water-washing operation was repeated for the obtained toluene layer until the pH of the aqueous layer was 7. And finally, heating and decompressing to concentrate toluene, and then adding butanone to prepare a resin solution to obtain the liquid resin of the dicyan-terminated active ester K-5.

The calculated and measured ratio of the charge ratio, the ester equivalent of the double-end active ester K-5 provided by the embodiment is 512g/eq, and the calculated cyano equivalent is 512g/eq.

Example 6

A bi-end cyano active ester K-6 has the following structure:

the preparation method comprises the following steps:

80.1g (hydroxyl equivalent: 80.1g/eq.) of 1, 5-dihydroxynaphthalene, 52.3g (0.25 mol.) of 1, 4-cyclohexanedicarboxylic acid chloride and 1200g of methylene chloride were placed in a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer, and the inside of the system was replaced with nitrogen under reduced pressure and dissolved with stirring. The reaction system was controlled to 30 ℃ or lower, 50.6g (0.5mol) of triethylamine was added dropwise over 2 hours, and the mixture was stirred for 1 hour after the completion of the addition. Then, the temperature of the system was lowered to-10 ℃ or lower, 36.9g (0.6mol) of cyanogen chloride was added thereto, 65.8g (0.65mol) of triethylamine was added dropwise over 2 hours, the temperature of the reaction system was controlled to 0 ℃ or lower, and the mixture was stirred for 1 hour after the completion of the dropwise addition. After the reaction, deionized water was added and stirred for 10min, and the aqueous layer was removed by standing and separating, and the water-washing operation was repeated for the obtained toluene layer until the pH of the aqueous layer was 7. And finally, heating and decompressing to concentrate toluene, and then adding butanone to prepare a resin solution to obtain the liquid resin of the dicyan-terminated active ester K-6.

The calculated and measured ratio of the charge ratio, the ester group equivalent of the double-end active ester K-6 provided by the embodiment is 253.2g/eq, and the calculated cyano group equivalent is 253.2g/eq.

Performance testing of the Dicyanoactive esters

(1) Structural characterization: infrared testing characterization was performed on the dicyanobenzoyl reactive esters provided in examples 1-6 using a Fourier Infrared Spectroscopy (FT-IR).

An exemplary infrared spectrum of the cyano-terminated active ester K-1 provided in example 1 is shown in FIG. 1, and it can be seen from FIG. 1 that the cyano-terminated active ester K-1 has a wavenumber of 1739.8cm^-1The characteristic absorption peak of the ester group of the active ester appears at a wave number of 2261.0cm^-1The characteristic absorption peak of the cyano group of the cyanate appears, and the peak is at 3400cm^-1No strong absorption peak of phenolic hydroxyl group appears nearby, which indicates that the phenolic hydroxyl group is esterified or cyanolated.

(2) And (3) testing molecular weight: the weight average molecular weight M of the dicyanodide-activated esters provided in examples 1 to 6 was determined by ultra-efficient Polymer chromatography (APC) from Waters_w。

An exemplary ultra-efficient polymer chromatogram (APC diagram) of the dicyano-terminated active ester K-1 provided in example 1 is shown in FIG. 2, and it can be seen from FIG. 2 that the weight average molecular weight M of the dicyano-terminated active ester K-1_wWas 2950.

The experimental materials used in the following application examples and comparative examples of the present invention are shown in Table 1.

TABLE 1

Application example 1

A thermosetting resin composition, and a prepreg and a circuit substrate containing the thermosetting resin composition are prepared by the following steps:

(1) uniformly mixing 57 parts by weight of diphenol aldehyde epoxy resin A-1, 43 parts by weight of dicyanodide K-1 and 0.1 part by weight of 4-dimethylamino pyridine (curing accelerator D-1) in a solvent to obtain a resin glue solution of the thermosetting resin composition, wherein the solid content of the resin glue solution is 65%; dipping the glue solution by 2116 glass fiber cloth, controlling the proper thickness, and then baking for 10min in a baking oven at 160 ℃ to prepare a prepreg;

(2) stacking 6 sheets of prepreg, laminating 1Oz RTF copper foil on the upper and lower surfaces of the prepreg, and curing at 200 deg.C and 45kg/cm under pressure²And curing for 120min to obtain the circuit substrate.

Application example 2

A thermosetting resin composition, a prepreg and a circuit substrate containing the thermosetting resin composition are prepared by the following steps:

(1) uniformly mixing 56.5 parts by weight of diphenol aldehyde epoxy resin A-1, 43.5 parts by weight of dicyanodide K-2 and 0.1 part by weight of 4-dimethylamino pyridine (curing accelerator D-1) in a solvent to obtain a resin glue solution of the thermosetting resin composition, wherein the solid content of the resin glue solution is 65%; dipping the glue solution by 2116 glass fiber cloth, controlling the proper thickness, and then baking for 15min in an oven at 145 ℃ to prepare a prepreg;

(2) stacking 6 sheets of prepreg, laminating 1Oz RTF copper foil on the upper and lower surfaces of the prepreg, and curing at 190 deg.C under 60kg/cm²Curing for 90min to obtain the circuit substrate。

Application example 3

(1) uniformly mixing 57.5 parts by weight of diphenol aldehyde epoxy resin A-1, 42.5 parts by weight of dicyanodide K-3 and 0.1 part by weight of 4-dimethylaminopyridine (curing accelerator D-1) in a solvent to obtain a resin glue solution of the thermosetting resin composition, wherein the solid content of the resin glue solution is 65%; soaking the glue solution in 2116 glass fiber cloth, controlling the thickness to be proper, and then baking in an oven at 175 ℃ for 2min to prepare a prepreg;

(2) stacking 6 sheets of prepreg, laminating 1Oz RTF copper foil on the upper and lower surfaces of the prepreg, and curing at 220 deg.C under 30kg/cm²And curing for 150min to obtain the circuit substrate.

Application examples 4 to 7 and comparative examples 1 to 4

A thermosetting resin composition and a prepreg and a circuit substrate containing the same are provided, wherein the components and the content of the thermosetting resin composition are shown in Table 2, and the preparation method of the prepreg and the circuit substrate is the same as that in application example 1.

TABLE 2

Performance testing

The thermosetting resin compositions provided in examples 1 to 7 and comparative examples 1 to 4 and the circuit substrates comprising the thermosetting resin compositions were subjected to performance tests by the following methods:

(1) glass transition temperature (T)_g): measured using DSC measurements according to the DSC measurements specified in the standard IPC-TM-6502.4.24;

(2) coefficient of thermal expansion CTE (Z-axis): measuring the coefficient of thermal expansion between 50 and 260 ℃ by using a TMA (mechanical analysis) instrument according to a CTE (Z-axis) test method specified in the IPC-TM-6502.4.24 standard;

(3) dielectric constant D_kAnd dielectric dissipation factor D_f: d at 10GHz was determined according to the SPDR method specified in Standard IEC61189-2-721_kAnd D_f；

(4) Thermal stratification time T300 (with copper): measured by TMA according to the T300 (with copper) test method specified in the IPC-TM-6502.4.24.1 standard;

(5) evaluation of Wet Heat resistance (PCT): keeping 3 100 × 100mm samples in a pressure cooking device at 180 deg.C and 105KPa for 2h, soaking in a solder bath at 288 deg.C for 5min, and observing whether the samples have stratified bubbling, wherein 3 blocks have no stratified bubbling 3/3, 2 blocks have no stratified bubbling 2/3, 1 block have no stratified bubbling 1/3, and 0 block have no stratified bubbling 0/3;

(6) PCT water absorption: taking a sample pretreated under the PCT test conditions of the test method (5), and measuring according to a water absorption test method specified in the IPC-TM-6502.6.2.1;

(7) peel Strength (PS): the peel strength of the metal cap was tested according to the "as received" experimental conditions specified in the standard IPC-TM-6502.4.8.

The specific test results are shown in table 3:

TABLE 3

As is clear from the results of the performance tests in Table 3, in the circuit substrates provided in application examples 1 to 7 of the present invention, the thermosetting resin composition used in the circuit substrates provided in application examples 1 to 4 of the present invention has a high glass transition temperature (T) using the dicyanelectricity bicide active ester provided in the present invention as a curing component, as compared with comparative examples 1 to 4_g) And a low coefficient of thermal expansion (Z-CTE), while having a low dielectric constant and low dielectric loss, excellent heat resistance, moist heat resistance, low hygroscopicity, and good bond strength with metals; wherein the glass transition temperature is more than 200 ℃, the Z-CTE is 2.3-3.1%, the dielectric constant is less than 4.10(10GHz), and the dielectric loss factorLess than 0.010(10GHz), T300 (with copper)>60min, the water absorption is as low as 0.25-0.36%, the peel strength (1Oz copper foil) reaches 1.2-1.3N/mm, and the wet heat resistance test of PCT (2h) can be passed.

As can be seen by comparing application example 1 with comparative example 1, application example 1 has a higher T_gAnd lower Z-CTE performance, and proves that the system containing the dicyanate-terminated active ester is equivalent to an active ester system in the prior art, has better glass transition temperature, crosslinking density and lower thermal expansion, and has improved bonding performance with metal.

Comparing application example 1 with comparative example 3, it can be seen that the epoxy system containing the dicyanate-terminated active ester of the present invention has a higher glass transition temperature and a lower thermal expansion coefficient than the existing epoxy resin system cured by the combination of active ester and cyanate ester, and the water absorption rate and peel strength are slightly better than those of comparative example 3.

Comparing application example 2 with comparative example 2, and application example 7 with comparative example 4, it can be seen that the epoxy resin system with dicyanelectricity bicide ester as curing agent and the circuit board thereof all have higher T than the epoxy system cured by dicyanelectricity bicide ester in the prior art_gAnd lower Z-CTE performance.

The applicant states that the present invention is illustrated by the above examples to provide a dicyanelectricity-both end active ester, a thermosetting resin composition, a preparation method and applications thereof, but the present invention is not limited to the above process steps, i.e., it is not meant that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.

Claims

1. A dicyano-terminated active ester, wherein the dicyano-terminated active ester has a structure represented by formula I:

wherein Ar is a substituted or unsubstituted C6-C150 divalent aromatic group; the substituted substituent in Ar is selected from fluorine, C1-C5 linear chain or branched chain alkyl, C6-C18 aryl, C2-C5 linear chain or branched chain alkylene and a group containing an aryl phosphorus-oxygen structure;

x is selected from substituted or unsubstituted C6-C30 divalent aromatic group, substituted or unsubstituted C1-C30 straight chain or branched chain alkylene group, and substituted or unsubstituted C3-C20 cycloalkylene group; the substituted substituents in X are respectively and independently selected from fluorine, C1-C5 straight chain or branched chain alkyl;

n is 1-15.

2. The active ester of claim 1, wherein Ar is selected from the group consisting of

Ar₁Is selected from

Ar₂Is selected from

R₁、R₂Each independently selected from fluorine, C1-C5 linear or branched alkyl, C2-C5 linear or branched alkenyl,

R₃Is a C1-C5 straight chain or branched chain alkylene;

n₁、n₃each independently selected from integers of 0 to 4;

n₂an integer selected from 0 to 6;

Y₁、Y₂each independently selected from the group consisting of-O-, -S-, carbonyl, sulfone, substituted or unsubstituted C1 to C20 straight or branched alkylene, substituted or unsubstituted C3 to C30 cycloalkylene, substituted or unsubstituted C6 to C30 aralkylene; the substituted substituents are respectively and independently selected from fluorine, C1-C5 straight chain or branched chain alkyl and C6-C18 aryl;

m is 0-10.

3. The active ester of claim 1 or 2, wherein X is selected from the group consisting of substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene ether, substituted or unsubstituted C1-C10 linear or branched alkylene, substituted or unsubstituted C3-C10 cycloalkylene; the substituted substituents are respectively and independently selected from fluorine, C1-C5 straight chain or branched chain alkyl;

preferably, n is selected from 1-10.

4. A process for the preparation of a dicyano-terminated active ester according to any of claims 1 to 3, wherein the dicyano-terminated active ester is prepared by process I or process II;

the preparation method I comprises the following steps: reacting a phenolic compound with a structure shown as a formula A1, a dicarboxylic halide compound with a structure shown as a formula A2 and a cyanogen compound with a structure shown as a formula A3 to obtain the dicyano-terminated active ester;

the preparation method II comprises the following steps: reacting a compound with a structure shown as a formula B1 with a cyanogen compound with a structure shown as a formula A3 to obtain the dicyano-terminated active ester;

HO-Ar-OH formula A1;

Z₁-C ≡ N formula a 3;

wherein Ar, X, n each independently have the same limitations as in formula I;

X₁、Z₁each independently selected from halogen;

Z₂selected from hydrogen and Na⁺、Ka⁺Or Li⁺。

5. The method according to claim 4, wherein X is₁、Z₁Each independently selected from chlorine, bromine or iodine;

preferably, in the preparation method I, the molar ratio of the phenolic compound to the dicarboxylic halide compound is 1 (0.5-0.95);

preferably, the reaction described in preparation process I is carried out in the presence of a basic catalyst;

preferably, the reaction temperature in the preparation method I is-30 ℃ to 50 ℃;

preferably, Z is₂For hydrogen, the reaction described in preparation II is carried out in the presence of a basic catalyst;

preferably, the reaction temperature in preparation method II is-30-20 ℃;

6. A thermosetting resin composition comprising an epoxy resin and the dicyanobenzyl reactive ester according to any one of claims 1 to 3;

7. A semiconductor sealing material characterized in that a raw material for the semiconductor sealing material comprises the thermosetting resin composition as recited in claim 6.

8. A prepreg comprising a substrate and the thermosetting resin composition of claim 6 attached to the substrate by impregnation drying;

9. A circuit substrate comprising at least one prepreg according to claim 8 and a metal foil disposed on one or both sides of the prepreg.

10. A laminated film comprising a base film or a metal foil and the thermosetting resin composition according to claim 6 applied to at least one surface of the base film or the metal foil.