Active polyester compound and thermosetting resin composition and application thereof

Abstract

The invention provides an active polyester compound as well as a thermosetting resin composition and application thereof. The active polyester compound is prepared from the following raw materials: a diol compound with a lipid-containing naphthenic structure as shown in a formula A1, a diacyl compound with a structure as shown in a formula A2 and a monophenol compound with a structure as shown in a formula A3. The active polyester compound provided by the invention has excellent dielectric properties, toughness is improved, low CTE performance is achieved at the same time, and the thermosetting resin composition containing the active polyester compound shows excellent dielectric properties, heat resistance, humidity and heat resistance and cohesiveness after being cured. And the application requirements of high-performance circuit substrates or laminated adhesive films can be fully met.

Description

Technical Field

[0001] The present invention belongs to the technical fields of semiconductor sealing materials, prepregs, circuit boards, and laminated films, and relates to an active polyester compound, a thermosetting resin composition thereof, and applications thereof. Background Art

[0002] Thermosetting resin compositions containing epoxy resins and their curing agents are widely used in insulating materials such as printed circuit boards, semiconductor sealants, and laminated films because their cured products exhibit excellent heat resistance, insulation, adhesion, processability, etc.

[0003] With the continuous development of electronic devices towards miniaturization and high performance, as well as technological innovations such as high-speed and high-frequency signals in electronic devices, it is required that the substrate material has a lower dielectric constant (D k ), dielectric loss (D f ), and at the same time has high heat resistance, heat and humidity resistance, and other properties.

[0004] JP2009235165 discloses an epoxy resin composition and its cured product, and an active ester compound having the following structure is used in the epoxy resin composition:

[0005]

[0006] Wherein, X is a benzene ring or a naphthalene ring, k represents 0 or 1, and n is from 0.25 to 1.5. This active ester and its resin composition have high heat resistance and good dielectric loss performance. However, with the development of technology, it is expected to develop materials with lower dielectric loss and good processability (toughness, flexibility).

[0007] CN115210213A discloses an active ester, the general structural formula of which is shown in the following formula (1), wherein A is a straight-chain or branched alkylene chain, or a straight-chain or branched alkylene ether chain, Q is an aromatic ring, x is an average repeat number of 0.01 or more, and Ar is a substituted or unsubstituted naphthalene ring or benzene ring. The active ester resin with this structure has excellent dielectric properties and good toughness, but its middle chain segment is a flexible alkyl chain or alkyl ether chain. On the one hand, the molecular structure itself has a relatively high coefficient of thermal expansion (CTE), and its alkyl ester structure cannot crosslink with epoxy groups, that is, only the aromatic ester groups at both ends of the active ester disclosed in this patent can crosslink with epoxy groups, resulting in a lower Tg of its resin cured product and an unsatisfactory CTE performance.

[0008]

[0009] Patent CN114671764A discloses an ester compound (A) represented by the following general formula (1), wherein Ar 1Each independently may be an aryl group which may have substituents; Ar 2 Each independently may be an arylene group which may have substituents; R 1 is an aliphatic hydrocarbon group having 4 to 20 carbon atoms. The aliphatic hydrocarbon group may be either linear or branched and may have an unsaturated bond in the structure. This ester compound is mainly used in combination with a maleimide compound. For example, when it is applied to cure an epoxy resin, there is also a problem that the intermediate flexible alkyl ester chain segment does not react with the epoxy group, the thermal expansion coefficient is large, and only the aromatic ester groups at both ends can crosslink with the epoxy group, resulting in a low Tg of the resin cured product and poor CTE performance.

[0010]

[0011] Therefore, in the art, there is a desire to develop an active polyester compound that enables the cured product to have low dielectric loss and combines good toughness, heat resistance, moisture heat resistance, CTE, and adhesiveness. Summary of the Invention

[0012] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide an active polyester compound, a thermosetting resin composition thereof, and applications.

[0013] To achieve the purpose of this invention, the following technical solutions are adopted by the present invention:

[0014] On the one hand, the present invention provides an active polyester compound, and the raw materials for preparing the active polyester compound include: a diol compound having an alicyclic structure-containing structure shown in Formula A1, a diacyl compound having a structure shown in Formula A2, and a monophenol compound having a structure shown in Formula A3;

[0015] HO-X1-OH

[0016] Formula A1;

[0017] Wherein, X1 is a substituted or unsubstituted divalent monocycloalkyl group having 3 to 30 carbon atoms (such as C3, C4, C5, C6, C8, C10, C12, C15, C18, C20, C25, or C30), a substituted or unsubstituted divalent polycycloalkyl group having 6 to 50 carbon atoms (such as C6, C7, C8, C10, C12, C15, C18, C20, C25, C30, C35, C40, C45, or C50), and the substituents of the substituted group are selected from halogen, linear or branched alkyl groups having 1 to 5 carbon atoms (such as C1, C2, C3, C4, or C5);

[0018] Examples of the divalent monocycloalkyl group may include: etc.;

[0019] Examples of the divalent polycycloalkyl group may include: etc.

[0020] In the present invention, the short straight lines on one or both sides of the group structure represent the bonding keys of the group and do not represent methyl groups. When the same description is involved hereinafter, it shall have the same meaning.

[0021]

[0022] Wherein, Y is a substituted or unsubstituted divalent aromatic group of C6-C18 (such as C6, C7, C8, C10, C12, C14, C15, C16 or C18), a substituted or unsubstituted divalent alkyl group of C1-C20 (such as C1, C2, C3, C4, C6, C8, C10, C12, C15, C18 or C20), or a substituted or unsubstituted divalent cycloalkyl group of C3-C30 (such as C3, C4, C6, C8, C10, C15, C20, C25 or C30); the substituents of the substituted Y are selected from halogen, and straight-chain or branched-chain alkyl groups of C1-C5 (such as C1, C2, C3, C4 or C5);

[0023] Y1 is selected from halogen or hydroxyl;

[0024] In the present invention, the "divalent aromatic group" means a group containing an aryl group and having 2 bonding sites, including arylene, and substituents formed by connecting at least 2 aryl groups through a linking group (such as -O-, -S-, carbonyl, sulfone, alkylene, cycloalkylene or arylalkyl, etc.). When the same description is involved hereinafter, it shall have the same meaning.

[0025] The C1-C5 straight-chain or branched-chain alkyl groups include straight-chain or branched-chain alkyl groups of C1, C2, C3, C4 or C5, and exemplarily include but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, etc. When the same description is involved hereinafter, it shall have the same meaning.

[0026] Ar-OH

[0027] Formula A3;

[0028] Wherein, Ar is a substituted or unsubstituted arylene of C6-C30 (such as C6, C8, C10, C12, C15, C18, C20, C25 or C30); the substituents of the substituted Ar are selected from halogen, straight-chain or branched-chain alkyl groups of C1-C5 (such as C1, C2, C3, C4 or C5), straight-chain or branched-chain alkenyl groups of C2-C5 (such as C2, C3, C4 or C5), straight-chain or branched-chain alkynyl groups of C2-C5 (such as C2, C3, C4 or C5),

[0029]

[0030] Wherein R1 and R2 are independently selected from halogen, linear or branched alkyl groups having 1 to 5 carbon atoms (such as C1, C2, C3, C4 or C5), linear or branched alkenyl groups having 2 to 5 carbon atoms (such as C2, C3, C4 or C5), and linear or branched alkynyl groups having 2 to 5 carbon atoms (such as C2, C3, C4 or C5).

[0031] In the present invention, the molar ratio of the diacyl compound to the diol compound containing an alicyclic structure is 1:(0.5 - 0.95), such as 1:0.52, 1:0.55, 1:0.58, 1:0.6, 1:0.62, 1:0.65, 1:0.68, 1:0.7, 1:0.72, 1:0.75, 1:0.78, 1:0.8, 1:0.82, 1:0.85, 1:0.87, 1:0.89, 1:0.9, 1:0.92 or 1:0.95, etc.; the molar ratio of the diacyl compound to the diol compound containing an alicyclic structure is preferably 1:(0.55 - 0.8), such as 1:0.55, 1:0.58, 1:0.6, 1:0.62, 1:0.65, 1:0.68, 1:0.7, 1:0.72, 1:0.75, 1:0.78 or 1:0.8.

[0032] In the present invention, the molar ratio of the diacyl compound to the monophenol compound is 1:(0.1 - 1), such as 1:0.1, 1:0.12, 1:0.15, 1:0.18, 1:0.2, 1:0.22, 1:0.25, 1:0.28, 1:0.3, 1:0.32, 1:0.35, 1:0.38, 1:0.4, 1:0.42, 1:0.45, 1:0.48, 1:0.5, 1:0.52, 1:0.55, 1:0.58, 1:0.6, 1:0.62, 1:0.65, 1:0.68, 1:0.7, 1:0.72, 1:0.75, 1:0.78, 1:0.8, 1:0.82, 1:0.85, 1:0.88, 1:0.9, 1:0.92, 1:0.95, 1:0.98 or 1:1, etc.; the molar ratio of the diacyl compound to the monophenol compound is preferably 1:(0.4 - 0.9), such as 1:0.4, 1:0.42, 1:0.45, 1:0.48, 1:0.5, 1:0.52, 1:0.55, 1:0.58, 1:0.6, 1:0.62, 1:0.65, 1:0.68, 1:0.7, 1:0.72, 1:0.75, 1:0.78, 1:0.8, 1:0.82, 1:0.85, 1:0.88 or 1:0.9.

[0033] In the present invention, based on 1 mol of the diacyl compound, theoretically, the sum of the hydroxyl groups in the diol compound containing an alicyclic structure and the monophenol compound is 2 mol. Among them, the diacyl compound is in excess relative to the diol compound containing an alicyclic structure. The reaction between the diol compound containing an alicyclic structure and the diacyl compound plays a role in chain growth, while the monophenol compound is a capping agent and plays a role in terminating chain growth. Through research by the inventors, In the ester group structure, if O-R is an aryloxy structure, the formed aryl ester group can undergo a crosslinking reaction with an epoxy group. On the contrary, if O-R is an alkoxy structure, the formed alkyl ester group cannot undergo a crosslinking reaction with an epoxy group. Introducing a straight-chain or branched-chain alkyl ester group into the active polyester compound has a significant effect on reducing the dielectric properties of the resin and improving toughness. However, the introduction of flexible chain segments causes obvious deterioration in aspects such as the Tg, CTE, and heat resistance of the cured product, and no reactive crosslinking points can be formed, further exacerbating this deterioration situation. The active polyester compound provided by the present invention effectively reduces the dielectric loss of the resin by introducing an alicyclic structure with a certain rigidity into the molecular structure. Compared with introducing a straight-chain or branched-chain alkyl group into the structure, the active polyester compound of the present invention can avoid a significant decrease in the Tg of the cured product and the deterioration of CTE while toughening.

[0034] The preparation raw materials of the active polyester compound described in the present invention may further include a diphenol compound having a structure shown in Formula A4:

[0035] HO-X2-OH

[0036] Formula A4;

[0037] wherein, X2 is a divalent aromatic group selected from The divalent aromatic group may further have substituents, and the substituents are selected from halogen, a straight-chain or branched-chain alkyl group of C1-C5 (such as C1, C2, C3, C4, or C5), a straight-chain or branched-chain alkenyl group of C2-C5 (such as C2, C3, C4, or C5), and a straight-chain or branched-chain alkynyl group of C2-C5 (such as C2, C3, C4, or C5).

[0038] In the present invention, the molar ratio of the diacyl compound to the dihydroxy compound (a diol compound containing an alicyclic structure + a diphenol compound) is 1:(0.5 to 0.95), such as 1:0.52, 1:0.55, 1:0.58, 1:0.6, 1:0.62, 1:0.65, 1:0.68, 1:0.7, 1:0.72, 1:0.75, 1:0.78, 1:0.8, 1:0.82, 1:0.85, 1:0.87, 1:0.89, 1:0.9, 1:0.92 or 1:0.95, etc.; the molar ratio of the diacyl compound to the dihydroxy compound (a diol compound containing an alicyclic structure + a diphenol compound) is preferably 1:(0.55 to 0.8), such as 1:0.55, 1:0.58, 1:0.6, 1:0.62, 1:0.65, 1:0.68, 1:0.7, 1:0.72, 1:0.75, 1:0.78 or 1:0.8.

[0039] The introduction of the diphenol compound can form an aryl ester group in the middle unit of the resin structure, that is, a crosslinking point reactive with an epoxy group is introduced into the middle chain segment of the resin, which can further improve the problem of large coefficient of thermal expansion (CTE) caused by the lack of a reaction crosslinking point with an epoxy group in the middle chain segment. The present invention has no particular limitation on the molar ratio of the diol compound to the diphenol compound. For example, considering obtaining lower dielectric properties or toughening, the proportion of the diphenol compound should not be too high. Preferably, the molar ratio of the diphenol compound to the diol compound is 1:(1 to 20), such as 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, 1:3, 1:4, 1:5, 1:8, 1:10, 1:12, 1:15, 1:18, 1:19 or 1:20, etc.

[0040] In the present invention, through the combination of a diol compound containing an alicyclic structure as shown in formula A1, a diphenol compound with a structure as shown in formula A4, a diacyl compound with a structure as shown in formula A2, and a monophenol compound with a structure as shown in formula A3, the prepared active polyester compound has excellent dielectric properties and toughness, and at the same time balances the performance in terms of Tg and CTE. The thermosetting resin composition containing the active polyester compound exhibits excellent dielectric properties, heat resistance, moisture and heat resistance, and adhesiveness after curing, and can fully meet the application requirements of high-performance circuit boards or laminated films.

[0041] In the present invention, the number range of carbon atoms is defined in the group, and the defined number range of carbon atoms represents that the number of carbon atoms in the group can be any integer within the defined number range of carbon atoms. For example, C3-C30 represents that the number of carbon atoms can be 3, 6, 8, 10, 12, 15, 18, 20, 25, 30, etc.; C6-C18 represents that the number of carbon atoms can be 6, 8, 10, 12, 14, 15, 16, 18, etc.; C1-C5 represents that the number of carbon atoms can be 1, 2, 3, 4, or 5; C1-C30 represents that the number of carbon atoms can be 1, 3, 6, 8, 10, 12, 15, 18, 20, 25, 30, etc.; and so on.

[0042] The active polyester compound of the present invention comprises a component having a structure as shown in formula A5:

[0043]

[0044] Wherein, m is an integer from 1 to 20 (such as 1, 2, 5, 8, 10, 12, 15, 18, or 20), and n is an integer from 0 to 20 (such as 1, 2, 5, 8, 10, 12, 15, 18, or 20); X1, X2, Y, and Ar each independently have the same meaning as described above.

[0045] On the other hand, the present invention provides a method for preparing the active polyester compound as described above, the preparation method comprising: reacting a diol compound having an alicyclic structure as shown in formula A1, a diacyl compound having a structure as shown in formula A2, and a monophenol compound having a structure as shown in formula A3 to obtain the active polyester compound.

[0046] The method for preparing the active polyester compound of the present invention may further comprise: reacting a diol compound having an alicyclic structure as shown in formula A1, a diphenol compound having a structure as shown in formula A4, a diacyl compound having a structure as shown in formula A2, and a monophenol compound having a structure as shown in formula A3 to obtain the active polyester compound.

[0047] Preferably, the temperature of the reaction is -10 to 65 °C, such as -10 °C, -8 °C, -5 °C, -2 °C, -0 °C, 2 °C, 5 °C, 8 °C, 10 °C, 12 °C, 15 °C, 18 °C, 20 °C, 22 °C, 25 °C, 28 °C, 30 °C, 32 °C, 35 °C, 38 °C, 40 °C, 42 °C, 45 °C, 48 °C, 50 °C, 52 °C, 55 °C, 58 °C, 60 °C, 62 °C, or 65 °C, and the specific point values between the above point values. For the sake of brevity and limited space, the present invention does not exhaustively list the specific point values included in the range.

[0048] Preferably, the reaction is carried out in the presence of a basic catalyst.

[0049] Preferably, the basic catalyst includes an inorganic basic compound and / or an organic base; the inorganic basic compound includes any one or a 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 includes any one or a combination of at least two of triethylamine, pyridine, 4-dimethylaminopyridine, tributylamine, N,N-diisopropylethylamine, benzyltriethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogensulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride or tetradecyltrimethylammonium chloride.

[0050] Preferably, the reaction is carried out in a protective atmosphere, and the protective atmosphere is preferably nitrogen or argon.

[0051] Preferably, the reaction is carried out in the presence of a solvent.

[0052] Preferably, the reaction is carried out in the presence of a solvent. The solvent is not particularly limited as long as it does not hinder the reaction. Exemplarily, it includes but is not limited to: any one or a combination of at least two of tetrahydrofuran, dioxane, benzene, toluene, xylene, dichloromethane, dichloroethane, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 1,4-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone. The amount of the solvent can be appropriately adjusted according to the different solubilities of the raw materials and the product, so that each raw material and product can be dissolved in the solvent, and is preferably 3 to 15 times the sum of the masses of the raw materials, such as 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 or 14 times, etc.

[0053] Preferably, after the reaction is completed, post-treatment of the product is further included.

[0054] Preferably, the post-treatment method includes filtration, washing with water, concentration, extraction, recrystallization or column chromatography, etc., to achieve the separation and purification of the active ester.

[0055] On the other hand, the present invention provides a thermosetting resin composition, and the thermosetting resin composition includes an epoxy resin and a curing agent, and the curing agent includes the active polyester compound as described above.

[0056] Preferably, the epoxy resin refers to an epoxy resin having at least two epoxy groups in one molecule, and examples include but are not limited to: bifunctional bisphenol A epoxy resin, bifunctional bisphenol F epoxy resin, bifunctional bisphenol S epoxy resin, phenol-formaldehyde epoxy resin, methylphenol novolac epoxy resin, bisphenol A novolac epoxy resin, dicyclopentadiene (DCPD) epoxy resin, biphenyl epoxy resin, DCPD novolac epoxy resin, biphenyl novolac epoxy resin, resorcinol epoxy resin, naphthalene epoxy resin, phosphorus-containing epoxy resin, silicon-containing epoxy resin, glycidylamine epoxy resin, alicyclic epoxy resin, polyethylene glycol epoxy resin, tetraphenylethane tetraglycidyl ether, triphenylmethane epoxy resin, condensate of bifunctional cyanate ester and epoxy resin or condensate of bifunctional isocyanate and epoxy resin; exemplary combinations include: combination of bifunctional bisphenol A epoxy resin and bifunctional bisphenol F epoxy resin, combination of bifunctional bisphenol S epoxy resin and phenol-formaldehyde epoxy resin, combination of resorcinol epoxy resin and naphthalene epoxy resin, combination of alicyclic epoxy resin and polyethylene glycol epoxy resin.

[0057] Preferably, in the thermosetting resin composition, based on 100 parts by weight of the epoxy resin, the content of the active polyester compound is 10 to 200 parts by weight, more preferably 20 to 100 parts by weight, such as 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight or 90 parts by weight.

[0058] Preferably, the curing agent further includes other curing agents.

[0059] Preferably, the other curing agents are selected from any one or a combination of at least two of amine curing agents, phenolic curing agents, benzoxazine curing agents, cyanate ester curing agents, other active ester curing agents (different from the active polyester compound of the present invention), anhydride curing agents or maleimide compounds.

[0060] Preferably, the thermosetting resin composition further includes any one or a combination of at least two of a flame retardant, a filler or a curing accelerator.

[0061] Preferably, the flame retardant is selected from any one or a combination of at least two of halogen-based organic flame retardants, phosphorus-based organic flame retardants, nitrogen-based organic flame retardants or silicon-containing organic flame retardants.

[0062] Preferably, the filler includes inorganic filler and / or organic filler.

[0063] Preferably, in the thermosetting resin composition, based on 100 parts by weight of the epoxy resin, the content of the filler is 10 to 500 parts by weight, such as 20 parts by weight, 50 parts by weight, 100 parts by weight, 150 parts by weight, 200 parts by weight, 250 parts by weight, 300 parts by weight, 350 parts by weight, 400 parts by weight, 450 parts by weight or 500 parts by weight.

[0064] Preferably, the inorganic filler includes any one or a combination of at least two of non-metal oxides, metal nitrides, non-metal nitrides, inorganic hydrates, inorganic salts, metal hydrates or inorganic phosphorus; more preferably, it is any one or a combination of at least two of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc powder, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate or mica.

[0065] Preferably, the organic filler includes any one or a combination of at least two of polytetrafluoroethylene powder, polyphenylene sulfide powder or polyethersulfone powder.

[0066] Preferably, the curing accelerator includes any one or a combination of at least two of imidazole compounds, derivatives of imidazole compounds, piperidine compounds, pyridine compounds, organometallic salt Lewis acids or triphenylphosphine.

[0067] In the present invention, the term "comprising" means that in addition to the components, other components may also be included, and these other components endow the thermosetting resin composition with different properties. In addition, the term "comprising" in the present invention may also be replaced by the closed "consisting of" or "consisting of...".

[0068] On the other hand, the present invention provides a resin solution, which comprises the thermosetting resin composition and a solvent as described above.

[0069] The preparation method of the resin solution of the present invention may be: first put the solid substance, then add the solvent, stir until the solid substance is completely dissolved, and then add the liquid resin and the curing accelerator, and continue to stir evenly.

[0070] The solvent is not particularly limited and includes any one or a combination of at least two of alcohol solvents, ether solvents, aromatic hydrocarbon solvents, ester solvents, ketone solvents or nitrogen-containing solvents, preferably ketone solvents. Among them, the alcohol solvents include any one or a combination of at least two of methanol, ethanol or butanol; the ether solvents include any one or a combination of at least two of ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol or butyl carbitol; the aromatic hydrocarbon solvents include any one or a combination of at least two of benzene, toluene or xylene; the ester solvents include any one or a combination of at least two of ethyl acetate, butyl acetate or ethoxyethyl acetate; the ketone solvents include any one or a combination of at least two of acetone, butanone, methyl ethyl ketone or cyclohexanone; the nitrogen-containing solvents include N,N-dimethylformamide and / or N,N-dimethylacetamide.

[0071] The amount of the solvent can be adjusted according to actual processing and application requirements.

[0072] The present invention also relates to a cured product, which is prepared by curing the thermosetting resin composition as described above.

[0073] On the other hand, the present invention provides a semiconductor encapsulating material, and the raw materials of the semiconductor encapsulating material include the thermosetting resin composition or resin sizing solution as described above.

[0074] On the other hand, the present invention provides a prepreg, which includes a reinforcing material and the thermosetting resin composition as described above attached to the reinforcing material by impregnation and drying.

[0075] Preferably, the reinforcing material includes any one or a combination of at least two of glass fiber cloth, non-woven fabric or quartz cloth.

[0076] The glass fiber cloth can be E-glass fiber cloth, D-glass fiber cloth, S-glass fiber cloth, T glass fiber cloth or NE-glass fiber cloth, etc.

[0077] The thickness of the reinforcing material is not particularly limited; for the consideration of good dimensional stability, the thickness of the reinforcing material is preferably 0.01 - 0.2 mm, such as 0.02 mm, 0.05 mm, 0.08 mm, 0.1 mm, 0.12 mm, 0.15 mm, 0.17 mm or 0.19 mm, etc.

[0078] Preferably, the reinforcing material is a reinforcing material that has been fibrillated and / or surface-treated with a silane coupling agent. In order to provide good water resistance and heat resistance, the silane coupling agent is preferably any one or a combination of at least two of epoxy silane coupling agents, amino silane coupling agents or vinyl silane coupling agents.

[0079] Exemplarily, the method for preparing the prepreg is as follows: Immerse the reinforcing material in the resin solution of the thermosetting resin composition, take it out and dry it to obtain the prepreg.

[0080] Preferably, the drying temperature is 100 - 250 °C, such as 105 °C, 110 °C, 115 °C, 120 °C, 130 °C, 140 °C, 150 °C, 160 °C, 170 °C, 180 °C, 190 °C, 200 °C, 210 °C, 220 °C, 230 °C, 240 °C or 245 °C, etc.

[0081] Preferably, the drying time is 1 - 15 min, such as 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min or 14 min, etc.

[0082] On the other hand, the present invention provides a circuit board, which includes at least one prepreg as described above, and metal foils disposed on one side or both sides of the prepreg.

[0083] There is no special limitation on the material of the metal foil; preferably, the metal foil includes copper foil, nickel foil, aluminum foil or SUS foil.

[0084] Exemplarily, the method for preparing the circuit board is as follows: Press and bond the metal foil on one side or both sides of a prepreg, and cure it to obtain the circuit board; or, bond at least two prepregs to form a laminate, and then press and bond the metal foil on one side or both sides of the laminate, and cure it to obtain the circuit board.

[0085] Preferably, the curing is carried out in a hot press.

[0086] Preferably, the curing temperature is 150 - 250 °C, such as 150 °C, 155 °C, 160 °C, 165 °C, 170 °C, 175 °C, 180 °C, 185 °C, 190 °C, 195 °C, 200 °C, 205 °C, 210 °C, 215 °C, 220 °C, 225 °C, 230 °C, 235 °C, 240 °C or 245 °C, etc.

[0087] Preferably, the curing pressure is 10 - 60 kg / cm 2 , such as 15 kg / cm 2 , 20 kg / cm 2 , 25 kg / cm 2 , 30 kg / cm 2 , 35 kg / cm 2 , 40 kg / cm 2 , 45 kg / cm 2 , 50 kg / cm2 or 55 kg / cm 2 etc.

[0088] On the other hand, the present invention provides a laminated film, which comprises a base film or a metal foil, and the thermosetting resin composition as described above coated on at least one surface of the base film or the metal foil.

[0089] Compared with the prior art, the present invention has the following beneficial effects:

[0090] In the present invention, the active polyester compound prepared by the combination of the diol compound containing an alicyclic structure represented by the formula A1 (and the diphenol compound represented by the formula A4), the diacyl compound represented by the formula A2 and the monophenol compound represented by the formula A3 has excellent dielectric properties and toughness, and at the same time balances the performance in terms of Tg and CTE. The thermosetting resin composition containing the active polyester compound exhibits excellent dielectric properties, heat resistance, moisture and heat resistance and adhesiveness after curing, and can fully meet the application requirements of high-performance circuit boards or laminated adhesive films. Description of the Drawings

[0091] Figure 1 Infrared spectrum of the active polyester compound provided for Example 1;

[0092] Figure 2 Ultra-high performance polymer chromatogram of the active polyester compound provided for Example 1;

[0093] Figure 3 Infrared spectrum of the active polyester compound provided for Example 2;

[0094] Figure 4 Ultra-high performance polymer chromatogram of the active polyester compound provided for Example 2. Detailed Embodiments

[0095] The technical solutions of the present invention will be further described below by specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be construed as specific limitations of the present invention.

[0096] Example 1

[0097] An active polyester compound K-1, the preparation method comprising the following steps:

[0098] Into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating column and a stirrer, 58.1 g (0.5 mol) of 1,4-cyclohexanediol, 203 g (1.0 mol) of isophthaloyl chloride, 144.2 g (1.0 mol) of 1-naphthol and 2100 g of dichloromethane were added. The system was purged with nitrogen under reduced pressure and stirred for dissolution. The reaction system was controlled below 30 °C, and then 232.3 g (2.3 mol) of triethylamine was added dropwise over 3 h. After the addition was completed, stirring was continued for 2 h. After the reaction was completed, deionized water was added and stirred for 15 min. The aqueous layer was removed by standing and separation, and the dichloromethane layer obtained was repeatedly washed with water until the pH of the aqueous layer was 7. Finally, the active polyester compound K-1 was obtained by drying under reduced pressure by heating.

[0099] Calculated and measured according to the feed ratio, the active ester group equivalent of the active polyester compound K-1 provided in this example was 332 g / eq.

[0100] Example 2

[0101] A method for preparing an active polyester compound K-2 includes the following steps:

[0102] Into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating column and a stirrer, 72.1 g of hydrogenated bisphenol A (0.3 mol), 132 g of a diphenol compound obtained by the polyaddition reaction of dicyclopentadiene and phenol (0.4 mol, hydroxyl equivalent 165 g / eq.), 203 g (1.0 mol) of isophthaloyl chloride, 86.5 g (0.6 mol) of 1-naphthol and 1730 g of dichloromethane were added. The system was purged with nitrogen under reduced pressure and stirred for dissolution. The reaction system was controlled below 35 °C, and then 222.2 g (2.2 mol) of triethylamine was added dropwise over 3 h. After the addition was completed, stirring was continued for 2 h. After the reaction was completed, deionized water was added and stirred for 15 min. The aqueous layer was removed by standing and separation, and the dichloromethane layer obtained was repeatedly washed with water until the pH of the aqueous layer was 7. Finally, the active polyester compound K-2 was obtained by drying under reduced pressure by heating.

[0103] Calculated and measured according to the feed ratio, the active ester group equivalent of the active polyester compound K-2 provided in this example was 300 g / eq.

[0104] Example 3

[0105] A method for preparing an active polyester compound K-3 includes the following steps:

[0106] Into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating column and a stirrer, 192.3 g of bisphenol A hydride (0.8 mol), 203 g of isophthaloyl chloride (1.0 mol) and 4500 g of dichloromethane were charged. The system was purged with nitrogen under reduced pressure while stirring for dissolution. The reaction system was controlled below 35 °C, and then 242.4 g (2.4 mol) of triethylamine was added dropwise over 4 h. After the addition was completed, stirring was continued for 0.5 h, then 75.7 g (0.4 mol) of 4-maleimidophenyl was added, and stirring was continued for reaction for 2 h. After the reaction was completed, deionized water was added and stirred for 15 min. The aqueous layer was removed by standing and liquid separation, and the dichloromethane layer obtained was repeatedly washed with water until the pH of the aqueous layer was 7. Finally, the active polyester compound K-2 was obtained by drying under reduced pressure by heating.

[0107] Calculated and measured according to the feed ratio, the active ester group equivalent of the active polyester compound K-3 provided in this example is 995 g / eq.

[0108] Example 4

[0109] An active polyester compound K-4, the preparation method comprising the following steps:

[0110] Into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating column and a stirrer, 11.6 g (0.1 mol) of 1,4-cyclohexanediol, 154.2 g of diallylbisphenol A (0.5 mol), 203 g of isophthaloyl chloride (1.0 mol), 115.4 g (0.8 mol) of 1-naphthol and 3000 g of toluene were charged. The system was purged with nitrogen under reduced pressure while stirring for dissolution. The reaction system was controlled below 60 °C, and 460 g (2.3 mol) of 20% aqueous sodium hydroxide solution was added dropwise over 3 h. After the addition was completed, stirring was continued for 1 h. After the reaction was completed, the aqueous layer was removed by standing and liquid separation. Deionized water was added to the toluene layer obtained and stirred for 15 min. The aqueous layer was removed by standing and liquid separation, and the toluene layer obtained was repeatedly washed with water until the pH of the aqueous layer was 7. Finally, the active polyester compound K-4 was obtained by drying under reduced pressure by heating.

[0111] Calculated and measured according to the feed ratio, the active ester group equivalent of the active polyester compound K-4 provided in this example is 228 g / eq.

[0112] Example 5

[0113] An active polyester compound K-5, the preparation method comprising the following steps:

[0114] Into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer, 48.1 g of bisphenol A hydride (0.2 mol), 124.2 g of 2,5-dihydroxyphenyldiphenylphosphine oxide (0.4 mol), 183 g of adipoyl chloride (1.0 mol), 115.4 g of 1-naphthol (0.8 mol) and 2850 g of dichloromethane were added. The system was purged with nitrogen under reduced pressure and stirred to dissolve. The reaction system was controlled below 35 °C, and then 232.3 g (2.3 mol) of triethylamine was added dropwise over 3 h. After the addition was completed, stirring was continued for 2 h. After the reaction was completed, deionized water was added and stirred for 15 min. The aqueous layer was removed by standing and liquid separation, and the dichloromethane layer obtained was repeatedly washed with water until the pH of the aqueous layer was 7. Finally, the active polyester compound K-5 was obtained by drying under reduced pressure by heating.

[0115] Calculated and measured according to the feed ratio, the active ester group equivalent of the active polyester compound K-5 provided in this example is 249 g / eq.

[0116] Comparative Example 1

[0117] An active polyester compound L-1, the preparation method of which comprises the following steps:

[0118] Into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer, 165 g (0.5 mol, hydroxyl equivalent 165 g / eq.) of a diphenol compound obtained by the polyaddition reaction of dicyclopentadiene and phenol, 203 g (1.0 mol) of isophthaloyl chloride, 144.2 g (1.0 mol) of 1-naphthol and 1800 g of dichloromethane were added. The system was purged with nitrogen under reduced pressure and stirred to dissolve. The reaction system was controlled below 30 °C, and then 232.3 g (2.3 mol) of triethylamine was added dropwise over 3 h. After the addition was completed, stirring was continued for 2 h. After the reaction was completed, deionized water was added and stirred for 15 min. The aqueous layer was removed by standing and liquid separation, and the dichloromethane layer obtained was repeatedly washed with water until the pH of the aqueous layer was 7. Finally, the active polyester compound L-1 was obtained by drying under reduced pressure by heating.

[0119] Calculated and measured according to the feed ratio, the active ester group equivalent of the active polyester compound L-1 provided in this comparative example is 220 g / eq.

[0120] Comparative Example 2

[0121] An active ester L-2, the preparation method of which refers to Synthesis Example 1 and Example 1 in Patent CN115210213A, the structural general formula is as shown in Formula A6, and the active ester group equivalent is 319 g / eq.

[0122]

[0123] Performance Testing of Active Polyester Compounds or Active Esters:

[0124] (1) Structural Characterization: Fourier transform infrared spectroscopy (FT-IR) was used to perform infrared test characterization on the active polyester compounds provided in Examples 1-5.

[0125] Exemplarily, the infrared spectrum of the active polyester compound K-1 provided in Example 1 is as shown in Figure 1 From Figure 1 it can be seen that the active polyester compound K-1 has a strong characteristic absorption peak of the alcohol ester group at a wave number of 1715 cm -1 and a characteristic absorption peak of the phenolic ester group at 1735 cm -1 , and there is no strong absorption peak of the alcohol hydroxyl group or phenolic hydroxyl group near 3400 cm -1 , indicating that the alcohol hydroxyl group and phenolic hydroxyl group have undergone esterification; the infrared spectrum of the active polyester compound K-2 provided in Example 2 is as shown in Figure 3 From Figure 3 it can be seen that the active polyester compound K-2 has strong characteristic absorption peaks of the alcohol ester group and phenolic ester group at wave numbers of 1716 cm -1 and 1736.5 cm -1 respectively, and the absorption peaks of the alcohol hydroxyl group or phenolic hydroxyl group near 3400 cm -1 basically disappear, indicating that the alcohol hydroxyl group and phenolic hydroxyl group have undergone esterification.

[0126] (2) Molecular Weight Testing: The weight-average molecular weight M w of the active polyester compounds provided in Examples 1-5 was determined using the ultra-high performance polymer chromatography system (APC) of Waters.

[0127] Exemplarily, the ultra-high performance polymer chromatogram (APC chromatogram) of the active polyester compound K-1 provided in Example 1 is as shown in Figure 2 From Figure 2 it can be seen that the weight-average molecular weight M w of the active polyester compound K-1 is 1881; the ultra-high performance polymer chromatogram (APC chromatogram) of the active polyester compound K-2 provided in Example 2 is as shown in Figure 4 From Figure 4 it can be seen that the weight-average molecular weight M w of the active polyester compound K-2 is 2307.

[0128] The experimental materials used in the following application examples and comparative examples of the present invention are shown in Table 1.

[0129] Table 1

[0130]

[0131]

[0132] Application Example 6

[0133] A thermosetting resin composition, a prepreg and a circuit board containing the same are prepared as follows:

[0134] (1) 46.0 parts by weight (based on solvent-free solid) of epoxy resin A, 54.0 parts by weight of reactive polyester compound K-1, 45.0 parts by weight of spherical silica, and 0.1 part by weight of 4-dimethylaminopyridine are mixed uniformly in an organic solvent to obtain a resin solution of the thermosetting resin composition, and the solid content of the resin solution is 65%; the 2116 fiberglass cloth is impregnated with the above-mentioned solution, the thickness is controlled at 0.10 mm, and then it is baked in an oven at 160 °C for 5 min to make a prepreg;

[0135] (2) 6 or 4 prepregs are stacked together respectively, and 35-μm RTF copper foils are stacked on the upper and lower surfaces thereof, and a circuit board is made under the conditions of a curing temperature of 200 °C, a curing pressure of 45 Kg / cm 2 and a curing time of 120 min.

[0136] Application Examples 7 to 10, Comparative Application Examples 3 to 4

[0137] A thermosetting resin composition, a prepreg and a circuit board containing the same, the components and contents of the thermosetting resin composition are shown in Table 2, and the preparation methods of the prepreg and the circuit board are the same as those in Application Example 6.

[0138] Table 2

[0139]

[0140]

[0141] Performance Test

[0142] The thermosetting resin compositions and the circuit boards containing the same provided in Application Examples 6 to 10 and Comparative Application Examples 3 to 4 are subjected to performance tests as follows:

[0143] (1) Glass transition temperature (T g ): Measured using DSC according to the DSC test method specified in standard IPC-TM-650 2.4.24;

[0144] (2) Dielectric constant D k and dielectric loss factor D f : D k and D f at 10 GHz are measured according to the SPDR method specified in standard IEC61189-2-721;

[0145] (3) Coefficient of thermal expansion CTE (Z-axis): Using a TMA instrument, measure the coefficient of thermal expansion between 50 and 260 °C according to the CTE (Z-axis) test method specified in the standard IPC-TM-650 2.4.24;

[0146] (4) Thermal delamination time T320 (with copper): Using a TMA instrument, measure according to the T320 (with copper) test method specified in the standard IPC-TM-650 2.4.24.1;

[0147] (5) Evaluation of damp heat resistance (PCT): After keeping 3 samples of 100×100 mm in a pressure cooking treatment device at 180 °C and 105 KPa for 6 h, immerse them in a solder bath at 288 °C for 5 min, and observe whether phenomena such as delamination and bubbling occur on the samples. If none of the 3 samples show delamination and bubbling, it is recorded as 3 / 3; if 2 samples do not show delamination and bubbling, it is recorded as 2 / 3; if 1 sample does not show delamination and bubbling, it is recorded as 1 / 3; if 0 samples do not show delamination and bubbling, it is recorded as 0 / 3;

[0148] (6) Peel strength (PS): Test the peel strength of the metal foil according to the "as received" experimental conditions specified in the standard IPC-TM-650 2.4.8;

[0149] (7) Elongation at break: After removing the copper foil from the circuit board, make sample strips of 250 mm ╳ 25 mm at a 45° angle to the warp and weft directions, with the number of samples not less than 3. Fix the sample strips on a material testing machine with clamps and run at a stable rate of 12.5 mm / min to test the elongation at break when the sample is broken.

[0150] The specific test results are shown in Table 3:

[0151] Table 3

[0152]

[0153] *Note: The test specimen configuration for elongation at break is 2116×4 sheets, and the specimen configurations for the other test items are 2116×6 sheets.

[0154] The active polyester compound of the present invention has excellent dielectric properties, and has a relatively low CTE performance while improving toughness. The thermosetting resin composition containing the active polyester compound exhibits excellent dielectric properties, heat resistance, damp heat resistance, and adhesiveness after curing, and can fully meet the application requirements of high-performance circuit boards or laminated films.

[0155] Among the circuit boards provided in Application Examples 6 to 10 of the present invention, the thermosetting resin composition used takes the active polyester compound provided by the present invention as the curing component, and thus has excellent low dielectric constant (D k) and low dielectric loss (D f ), while improving toughness, it also has a good thermal expansion coefficient (Z-CTE), excellent moisture and heat resistance, heat resistance, and good bonding strength with metal foil; wherein, the glass transition temperature reaches above 150°C, the elongation at break is greater than 7.8%, the Z-CTE is less than 3.45%, the dielectric constant is less than 4.0 (10GHz), the dielectric loss is less than 0.0080 (10GHz), the T320 (with copper) is greater than 60min, the peel strength is greater than 1.15N / mm, and it can pass the moisture and heat resistance test of PCT (6h). Among them, compared with Application Example 6, the active polyester compound in Application Examples 7, 9 and 10 uses a diol compound and a diphenol compound containing a cycloalkane structure, and the circuit substrate obtained has better performance in Tg and CTE.

[0156] According to the performance test data in Table 3, it can be seen from the comparison between Application Examples 6 to 10 and Comparative Application Example 3 that the thermosetting resin composition and circuit substrate cured by the active polyester compound of the present invention are superior to the active ester synthesized from dicyclopentadiene-type diphenol in terms of dielectric constant, dielectric loss and toughness, and the performance of glass transition temperature and thermal expansion coefficient will not be greatly weakened, and may even be improved; it can be seen from the comparison between Application Examples 6 to 10 and Comparative Application Example 4 that the thermosetting resin composition and circuit substrate cured by the active polyester compound of the present invention have obvious advantages in terms of glass transition temperature, thermal expansion coefficient, moisture and heat resistance and heat resistance.

[0157] The applicant declares that the present invention uses the above embodiments to illustrate the reactive polyester compound and the thermosetting resin composition and application thereof, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of the raw materials selected by the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. An active polyester compound, characterized in that, The raw materials for preparing the active polyester compound include: a diol compound having an alicyclic structure as shown in Formula A1, a diacyl compound having a structure as shown in Formula A2, and a monophenol compound having a structure as shown in Formula A3; HO—X1-OH Formula A1; Wherein, X1 is a substituted or unsubstituted divalent monocycloalkyl group having 3 to 30 carbon atoms, or a substituted or unsubstituted divalent polycycloalkyl group having 6 to 50 carbon atoms with two or more rings, and the substituents of the substituted group are selected from halogen, and linear or branched alkyl groups having 1 to 5 carbon atoms; Wherein, Y is a substituted or unsubstituted divalent aromatic group having 6 to 18 carbon atoms, a substituted or unsubstituted divalent alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted divalent cycloalkyl group having 3 to 30 carbon atoms; the substituents of the substituted group in Y are selected from halogen, and linear or branched alkyl groups having 1 to 5 carbon atoms; Y1 is selected from halogen or hydroxyl; Ar-OH Formula A3; Wherein, Ar is a substituted or unsubstituted C6-C30 arylene group; the substituents of the substituted Ar are selected from halogen, C1-C5 straight-chain or branched-chain alkyl groups, C2-C5 straight-chain or branched-chain alkenyl groups, C2-C5 straight-chain or branched-chain alkynyl groups, phenyl groups, naphthyl groups, wherein R1 and R2 are independently selected from halogen, C1-C5 straight-chain or branched-chain alkyl groups.

2. The active polyester compound according to claim 1, characterized in that, The divalent monocycloalkyl group described above is selected from Preferably, the divalent polycycloalkyl group is selected from Preferably, the molar ratio of the diacyl compound to the diol compound having an alicyclic structure is 1:(0.5 to 0.95); preferably 1:(0.55 to 0.8); Preferably, the molar ratio of the diacyl compound to the monophenol compound is 1:(0.1 to 1), preferably 1:(0.4 to 0.9); Preferably, the raw materials for preparing the active polyester compound may further include a diphenol compound having a structure as shown in Formula A4: HO—X2-OH Formula A4; Among them, X2 is a substituted or unsubstituted divalent aromatic group, selected from one or a combination of two or more thereof, and the substituents of the substitution are selected from halogen, C1-C5 straight-chain or branched-chain alkyl groups, C2-C5 straight-chain or branched-chain alkenyl groups, and C2-C5 straight-chain or branched-chain alkynyl groups.

3. The active polyester compound according to claims 1-2, characterized in that, The active polyester compound contains a component having a structure as shown in Formula A5: Wherein, m is an integer from 1 to 20, and n is an integer from 0 to 20; X1, X2, Y, and Ar each independently have the same defined range as in Claim 1 or 2; Preferably, the molar ratio of the diphenol compound to the diol compound is 1:(1 to 20).

4. The method for preparing the active polyester compound according to any one of claims 1-3, characterized in that, The preparation method includes the following steps: The diol compound having an alicyclic structure as shown in Formula A1, the diacyl compound having a structure as shown in Formula A2, and the monophenol compound having a structure as shown in Formula A3 are reacted to obtain the active polyester compound; Preferably, the temperature of the reaction is -10 to 65 °C; Preferably, the reaction is carried out in the presence of a basic catalyst; Preferably, the basic catalyst includes an inorganic basic compound and / or an organic base; Preferably, the inorganic basic compound includes any one or a 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; Preferably, the organic base includes any one or a combination of at least two of triethylamine, pyridine, 4-dimethylaminopyridine, tributylamine, N,N-diisopropylethylamine, benzyltriethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogensulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, or tetradecyltrimethylammonium chloride; Preferably, the reaction is carried out in a protective atmosphere, and the protective atmosphere is preferably nitrogen or argon; Preferably, the reaction is carried out in the presence of a solvent; Preferably, the reaction is carried out in the presence of a solvent selected from any one or a combination of at least two of tetrahydrofuran, dioxane, benzene, toluene, xylene, dichloromethane, dichloroethane, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 1,4-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone.

5. A thermosetting resin composition comprising an epoxy resin and an active polyester compound as described in any one of claims 1-3; Preferably, based on 100 parts by weight of the epoxy resin in the thermosetting resin composition, the content of the active polyester compound is 10-200 parts by weight, more preferably 20-100 parts by weight; Preferably, the curing agent further includes other curing agents; Preferably, the other curing agents are selected from any one or a combination of at least two of amine curing agents, phenolic curing agents, benzoxazine curing agents, cyanate ester curing agents, other active ester curing agents, acid anhydride curing agents or maleimide compounds; Preferably, the thermosetting resin composition further includes any one or a combination of at least two of a flame retardant, a filler or a curing accelerator; Preferably, the flame retardant is selected from any one or a combination of at least two of halogen-based organic flame retardants, phosphorus-based organic flame retardants, nitrogen-based organic flame retardants or silicon-containing organic flame retardants; Preferably, the filler includes inorganic filler and / or organic filler; Preferably, based on 100 parts by weight of the epoxy resin in the thermosetting resin composition, the content of the filler is 10-500 parts by weight; Preferably, the inorganic filler includes any one or a combination of at least two of non-metal oxides, metal nitrides, non-metal nitrides, inorganic hydrates, inorganic salts, metal hydrates or inorganic phosphorus; more preferably any one or a combination of at least two of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc powder, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate or mica; Preferably, the organic filler includes any one or a combination of at least two of polytetrafluoroethylene powder, polyphenylene sulfide powder or polyethersulfone powder; Preferably, the curing accelerator includes any one or a combination of at least two of imidazole compounds, derivatives of imidazole compounds, piperidine compounds, pyridine compounds, organometallic salt Lewis acids or triphenylphosphine.

6. A resin solution comprising the thermosetting resin composition as described in claim 5 and a solvent.

7. A semiconductor sealing material, characterized in that, The raw materials of the semiconductor encapsulating material include the thermosetting resin composition as described in claim 5 or the resin solution as described in claim 6.

8. A prepreg, characterized in that, The prepreg includes a reinforcing material and the thermosetting resin composition as described in claim 5 or the resin solution as described in claim 6 attached to the reinforcing material by impregnation and drying; Preferably, the reinforcing material includes any one or a combination of at least two of glass fiber cloth, non-woven fabric or quartz cloth.

9. A circuit board, characterized in that, The circuit board includes at least one prepreg as described in claim 8, and metal foils disposed on one or both sides of the prepreg.

10. A laminated film, characterized in that, The laminated film includes a base film or a metal foil, and a thermosetting resin composition as described in claim 5 or a resin sizing agent as described in claim 6 coated on at least one surface of the base film or the metal foil.

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