CN114479012B - Double-end cyano active ester, thermosetting resin composition, and preparation method and application thereof - Google Patents
Double-end cyano active ester, thermosetting resin composition, and preparation method and application thereof Download PDFInfo
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
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- H05K1/0326—Organic insulating material consisting of one material containing O
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention provides a double-end cyano active ester, a thermosetting resin composition, a preparation method and application, wherein the double-end cyano active ester has a structure shown in a formula I, and has higher reactive crosslinking sites, low dielectric loss, low dielectric constant and low water absorption rate through introduction of a terminal cyano group and cooperative matching of the terminal cyano group and an active ester functional group, and 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, moist heat resistance and low thermal expansion coefficient. Thermosetting resin compositions comprising the double-ended cyano active esters have a high T g The 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, prepregs, circuit substrates or laminated films.
Description
Technical Field
The invention belongs to the technical field of copper-clad plates, and particularly relates to double-end cyano 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 hardware carriers such as application-side 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 high density of electronic equipment installation has put higher demands on various properties of electronic materials, in particular, dielectric properties, heat resistance, dimensional stability and the like.
Electronic materials such as copper-clad plates and circuit substrates generally comprise a base material with reinforcing effect and a resin composition, and the improvement of the performance of the electronic materials is greatly dependent on the selection of the resin composition. The most widely used resin compositions in electronic materials today are epoxy resin systems. In the prior art, cured products of epoxy resin compositions containing an epoxy resin and a curing agent thereof as essential components exhibit good heat resistance and insulation properties, and have excellent processability and cost advantages. However, the epoxy resin itself has a relatively high dielectric constant (D k ) And dielectric loss (D) f ) The curing is carried out by using traditional curing agents such as amine or phenolic resin, and the cured product can generate a large amount of secondary hydroxyl groups, so that the water absorption rate is increased, and the dielectric property and the damp-heat resistance are reduced.
The cyanate resin has good cohesiveness and processing property, high glass transition temperature, low dielectric constant and low dielectric loss, and therefore has good application potential in the preparation of metal foil-clad laminated plates for high-end printed circuit boards. For example, CN102924865a discloses a cyanate resin composition comprising a cyanate resin, a halogen-free epoxy resin and an inorganic filler, and a prepreg, a laminate and a metal foil-clad laminate manufactured using the same, which have good flame retardancy and a low thermal expansion coefficient. However, the cyanate resin is easy to absorb water and has poor wet heat resistance after curing, so that the cyanate resin is limited to be widely applied to copper-clad plates.
With the continuous intensive research on resin compositions in electronic materials, it is found that active esters contain ester groups with higher activity, which can be used as curing agents to perform transesterification reaction with epoxy resins, and the network structure formed after the reaction does not contain secondary alcohol hydroxyl groups, so that the cured product has low dielectric loss, low water absorption and lower dielectric constant. For example, JP2009235165 discloses an epoxy resin composition using an active ester compound having the following structure:
Wherein X is a benzene ring or naphthalene ring, and k represents 0 or 1. The epoxy resin composition has high heat resistance and low dielectric tangent, and has low viscosity when dissolved in an organic solvent, thereby being beneficial to later processing application. However, the active ester-cured epoxy resin represented by the above active ester compound has a relatively high molecular weight of the active ester-reactive group and a chemical reaction mechanism with the epoxy group is an ester exchange reaction, and therefore the cured product thereof has a low crosslinking density and exhibits a glass transition temperature (T) g ) The defects of low thermal expansion coefficient, high thermal expansion coefficient and the like limit the application of the high-performance printed circuit board substrate to a great extent.
Therefore, development of a curing raw material and a resin composition having a high crosslinking density, low dielectric loss, high heat resistance and wet heat resistance to meet the performance and application requirements of high-performance circuit boards is an important research point in the art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a double-end cyano active ester, a thermosetting resin composition, a preparation method and application thereof, wherein the double-end cyano active ester has higher reactive crosslinking sites under the premise of low dielectric loss, low dielectric constant and low water absorption through introduction of a terminal cyano group and cooperative coordination of the terminal cyano group and an active ester functional group. The double-end cyano active ester is used as a curing agent of the epoxy resin, can endow the epoxy resin composition with excellent dielectric property, heat resistance, moist heat resistance and low thermal expansion coefficient, and can fully meet the application requirements of high-performance circuit substrates.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a double-ended cyano active ester having a structure as shown in formula I:
in the formula I, ar is a substituted or unsubstituted C6-C150 divalent aromatic group; the substituent groups of Ar are selected from fluorine, C1-C5 straight-chain or branched-chain alkyl, C6-C18 aryl, C2-C5 straight-chain or branched-chain alkenyl and groups containing aryl phosphorus oxygen structures.
In the present invention, the term "divalent aromatic group" means a group having 2 bonding sites containing an aryl group, and includes arylene groups, and substituents formed by linking at least 2 aryl groups through a linking group (e.g., -O-, -S-, carbonyl, sulfone, alkylene, cycloalkylene, or arylalkylene groups, etc.). The same meaning is given below when referring to the same description.
The C1-C5 linear or branched alkyl group includes a C1, C2, C3, C4, or C5 linear or branched alkyl group, exemplary including but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl or isopentyl, and the like. The same meaning is given below when referring to the same description.
The C6-C18 aryl group includes C6, C8, C9, C10, C12, C14, C16, C18, etc., and exemplary includes but is not limited to: phenyl, biphenyl, terphenyl, naphthyl, and the like. The same meaning is given below when referring to the same description.
The C2-C5 linear or branched olefinic groups include C2, C3, C4, or C5 linear or branched olefinic groups, exemplary including but not limited to: ethenyl, propenyl, allyl, and the like. The same meaning is given below when referring to the same description.
In the formula I, X is selected from substituted or unsubstituted C6-C30 divalent aromatic groups, substituted or unsubstituted C1-C30 (such as C1, C2, C3, C4, C5, C6, C8, C10, C12, C15, C18, C20, C22, C25, C28 or C29 and the like) straight-chain or branched-chain alkylene groups, substituted or unsubstituted C3-C20 (such as C3, C4, C5, C6, C8, C10, C12, C15, C18 or C20 and the like) cycloalkylene groups; the substituents mentioned for the substitution in X are each independently selected from fluorine, C1-C5 (e.g. C1, C2, C3, C4 or C5) straight-chain or branched 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 the specific point values between the above point values are limited in length and for brevity, and the invention is not intended to be exhaustive of the specific point values included in the range.
According to the double-end cyano active ester, the double-end cyano active ester is provided with a high reaction crosslinking site, low dielectric loss, low dielectric constant and low water absorption rate through the introduction of the end cyano group and the cooperation of the end cyano group and the active ester functional group, and can be used as a curing agent to perform a curing reaction with epoxy resin, so that the obtained cured product has excellent dielectric property, heat resistance, moist heat resistance and low thermal expansion coefficient.
In the double-ended cyano active ester, the larger the average value n of the number of repeating units is, the lower the proportion of cyano groups is, the more the performance of a cured product formed by the reaction of the double-ended cyano active ester and epoxy resin tends to be that of a general active ester, namely, the dielectric performance is slightly excellent, and the performance of the cured product is shown in T g And a deficiency in the coefficient of thermal expansion; the larger the n value is, the larger the corresponding molecular weight is, the poorer the solubility of the n in an organic solvent is, and the less the organic solvent can be selected, so that on one hand, the process difficulty in the synthesis process can be increased, even the local explosion polymerization is caused to generate a gel phenomenon, and on the other hand, the process difficulty in the application of the resin can be increased.
Preferably, the Ar is selected from
Ar 1 Selected from the group consisting of
Ar 2 Selected from the group consisting of
R 1 、R 2 Each independently selected from fluorine, C1-C5 (e.g., C1, C2, C3, C4, or C5) straight or branched alkyl, C1-C5 (e.g., C1, C2, C3, C4, or C5) straight or branched alkenyl,
R 3 Is a C1-C5 (e.g., C1, C2, C3, C4 or C5) straight or branched alkylene group.
n 1 、n 3 Each independently selected from integers of 0 to 4, for example 0, 1, 2, 3 or 4.
n 2 An integer selected from 0 to 6, for example 0, 1, 2, 3, 4, 5 or 6.
Y 1 、Y 2 Each independently selected from-O-, -S-, carbonyl, sulfone group, substituted or unsubstituted C1-C20 (e.g., C1, C2, C3, C4, C5, C6, C8, C10, C12, C14, C16, C18, or C20, etc.), straight 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, etc.), cycloalkylene, substituted or unsubstituted C6-C30 (e.g., C6, C7, C8, C9, C10, C12, C15, C18, C20, C22, C25, C28, or C29, etc.), aralkylene; the substituted substituents are each independently selected from fluorine, C1-C5 (e.g., C1, C2, C3, C4, or C5) straight or branched alkyl, C6-C18 (e.g., C6, C8, C9, C10, C12, C14, C16, or C18, etc.) aryl.
m is selected from 0 to 10, e.g., 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 to the spread and for brevity, the invention is not intended to exhaustively list the specific point values included in the range.
In the present invention, a short straight line on one or both sides of the radical structure (e.gShort straight lines on both sides of the middle benzene ring) represent access bonds of the group, and do not represent methyl.
Further preferably, the Y 1 、Y 2 Each independently selected from-O-, -S-, a substituted or unsubstituted C1-C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10) straight or branched alkylene, a substituted or unsubstituted C3-C8 (e.g., C3, C4, C5, C6, C7, or C8) cycloalkylene, or
Preferably, the X is selected from the group consisting of substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene etherA substituted or unsubstituted C1-C10 (e.g., C1, C2, C3, C4, C5, C6, C8, C9, or C10) linear or branched alkylene, a substituted or unsubstituted C3-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 or branched alkyl.
As a further preferred embodiment of the present invention, the double-ended cyano active ester has the structure shown below:
in another aspect, the present invention provides a method for preparing a double-ended cyano active ester as described above, prepared by preparation method I or preparation method II as follows.
The preparation method I is as follows: the phenol compound with the structure shown in the formula A1, the diacylhalide compound with the structure shown in the formula A2 and the cyano compound with the structure shown in the formula A3 react to obtain the double-end cyano active ester.
The preparation method II comprises the following steps: and (3) reacting the compound with the structure shown in the formula B1 with a cyanide compound with the structure shown in the formula A3 to obtain the double-end cyano active ester.
HO-Ar-OH formula A1;
Z 1 -c≡n formula A3;
wherein Ar, X, n each independently have the same defined ranges as in formula I;
X 1 、Z 1 each independently selected from halogen;
Z 2 selected from hydrogen, na + 、Ka + Or Li (lithium) + 。
Preferably, the X 1 、Z 1 Each independently selected from chlorine, bromine or iodine.
Preferably, the molar ratio of phenolic compound to diacid halide compound in preparation I is 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, etc.
In the preparation method I, at least an equimolar ratio of the cyano compound having the structure shown in formula A3 is used to react with the remaining phenolic hydroxyl groups in the phenolic compound, i.e., the molar amount of the cyano compound may be equal to or excessive relative to the remaining phenolic hydroxyl groups in the phenolic compound (excluding the equimolar ratio with respect to the dihalide compound).
Preferably, the reaction in preparation method 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 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 comprises any one or a combination of at least two of triethylamine, pyridine, 4-dimethylaminopyridine, tributylamine, N-diisopropylethylamine, benzyl triethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bisulfate, trioctylmethyl ammonium chloride, dodecyl trimethyl ammonium chloride or tetradecyl trimethyl ammonium chloride.
Preferably, the reaction in the production 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 exemplary includes without limitation: tetrahydrofuran, dioxane, benzene, toluene, xylene, methylene chloride, dichloroethane, butanone, methyl isobutyl ketone, cyclohexanone, 1, 4-butyrolactone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone. The amount of the solvent to be used 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, based on the sum of the mass of the respective raw materials.
Preferably, the reaction in preparation method I is carried out in a protective atmosphere, preferably nitrogen or argon.
Preferably, the reaction in preparation method I is carried out at low temperature, the temperature of the reaction is preferably-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 ℃, 48 ℃, etc.
Preferably, after the reaction in preparation method I is completed, the obtained double-ended cyano active ester may be separated and purified by an optional filtration, washing with water, concentration, extraction, recrystallization, column chromatography or the like.
Preferably, the reaction in preparation method II is carried out at low temperature, the temperature of the reaction preferably being-30 to 20 ℃, e.g. -28 ℃, -25 ℃, -22 ℃, -20 ℃, -18 ℃, -15 ℃, -13 ℃, -10 ℃, -8 ℃, -5 ℃, -2 ℃, -0 ℃, 1 ℃, 2 ℃, 5 ℃, 8 ℃, 10 ℃, 12 ℃, 15 ℃, 16 ℃ or 18 ℃ and the like.
Preferably, said Z 2 In the presence of a basic catalyst, the reaction in preparation II is carried out as hydrogen.
Preferably, the basic catalyst comprises an inorganic basic compound and/or an organic base; the inorganic alkaline compound comprises 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 comprises any one or a combination of at least two of triethylamine, pyridine, 4-dimethylaminopyridine, tributylamine, N-diisopropylethylamine, benzyl triethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bisulfate, trioctylmethyl ammonium chloride, dodecyl trimethyl ammonium chloride or tetradecyl trimethyl ammonium chloride.
Preferably, said Z 2 Selected from Na + 、Ka + Or Li (lithium) + The reaction in preparation method II is carried out in the presence of a phase transfer catalyst.
As a preferable technical scheme of the invention, the Z 2 Selected from Na + 、Ka + Or Li (lithium) + The compound with the structure shown in the formula B1 is an alkaline phenolate compound, and a phase transfer catalyst which is soluble in an aqueous phase and an organic solvent phase is added in the process of the reaction in the preparation method II.
Preferably, the phase transfer catalyst comprises any one or a combination of at least two of benzyltriethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bisulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, polyethylene glycol dimethyl ether, crown ether, triethylamine hydrochloride, triethylamine, pyridine, 4-dimethylaminopyridine, tributylamine, or N, N-diisopropylethylamine.
Preferably, the reaction in the production method 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 exemplary includes without limitation: tetrahydrofuran, dioxane, benzene, toluene, xylene, methylene chloride, dichloroethane, butanone, methyl isobutyl ketone, cyclohexanone, 1, 4-butyrolactone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, methanol, ethanol, isopropanol or a combination of at least two thereof. The amount of the solvent may be appropriately adjusted depending on the different solubilities of the raw materials and the products so that each of the raw materials and the products can be dissolved in the solvent, 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, the sum of the masses of each of the raw materials.
Preferably, the reaction in preparation method II is carried out in a protective atmosphere, preferably nitrogen or argon.
Preferably, after the reaction in preparation method II is completed, the obtained double-ended cyano active ester may be isolated and purified by an optional filtration, washing with water, concentration, extraction, recrystallization, column chromatography or the like.
In another aspect, the present invention provides a thermosetting resin composition comprising an epoxy resin and a double-ended cyano active ester as described above.
In the thermosetting resin composition provided by the invention, the molecular structure of the double-end cyano active ester contains aryl ester groups and cyano groups at the same time, and has more reactive sites, and when the double-end cyano active ester is used as a curing agent to react with epoxy resin, on one hand, the aryl ester groups cannot react with the epoxy resinGenerating secondary hydroxyl groups with strong polarity, thereby enabling the cured product to have low dielectric loss, low water absorption and low dielectric constant; on the other hand, cyano groups can be self-polymerized to form a high-rigidity six-membered triazine ring structure or can be reacted with epoxy groups to form a five-membered oxazoline heterocyclic structure, and polar groups such as hydroxyl groups, amino groups and the like are not generated in the reaction process, so that the thermosetting resin composition is endowed with excellent heat resistance (high T) 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, and exemplary includes, but is not limited to: any one or a combination of at least two of a difunctional bisphenol a type epoxy resin, a difunctional bisphenol F type epoxy resin, a difunctional bisphenol S type epoxy resin, a phenol formaldehyde type epoxy resin, a methylphenol phenolic type epoxy resin, a bisphenol a type phenolic epoxy resin, a dicyclopentadiene (DCPD) epoxy resin, a biphenyl epoxy resin, a resorcinol type epoxy resin, a naphthalene type epoxy resin, a phosphorus-containing epoxy resin, a silicon-containing epoxy resin, a glycidylamine type epoxy resin, an alicyclic type epoxy resin, a polyethylene glycol type epoxy resin, tetraphenolethylenetetraglycidyl ether, a triphenol methane type epoxy resin, a condensate of difunctional cyanate ester and epoxy resin, or a condensate of difunctional isocyanate and epoxy resin; exemplary combinations include: a combination of a difunctional bisphenol a type epoxy resin and a difunctional bisphenol F type epoxy resin, a combination of a difunctional 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 or a combination of at least two of amine curing agents, phenolic curing agents, benzoxazine curing agents, cyanate ester curing agents, anhydride curing agents or amine modified maleimide curing agents.
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 inorganic filler comprises any one or a combination of at least two of a non-metal oxide, a metal nitride, a non-metal nitride, an inorganic hydrate, an inorganic salt, a metal hydrate or an inorganic phosphorus; further preferred are any one or a combination of at least two of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, or mica.
Preferably, the organic filler comprises any one or a combination of at least two of polytetrafluoroethylene powder, polyphenylene sulfide powder or polyethersulfone powder.
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 acids or triphenylphosphine.
The preparation method of the thermosetting resin composition of the invention can be as follows: firstly, putting the solid into the solvent, then adding the solvent, stirring until the solid is completely dissolved, then adding the liquid resin and the curing accelerator, and continuing to stir uniformly.
The solvent is not particularly limited and includes any one or a combination of at least two of an alcohol solvent, an ether solvent, an aromatic hydrocarbon solvent, an ester solvent, a ketone solvent, and a nitrogen-containing solvent. Wherein the alcohol solvent comprises any one or a combination of at least two of methanol, ethanol and butanol; the ether solvent comprises any one or a combination of at least two of ethyl cellosolve, butyl cellosolve, ethylene glycol methyl ether, carbitol or 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 a combination of at least two of ethyl acetate, butyl acetate or ethoxyethyl acetate; the ketone solvent comprises any one or a combination of at least two of acetone, butanone, methyl ethyl ketone and cyclohexanone; the nitrogen-containing solvent comprises N, N-dimethylformamide and/or N, N-dimethylacetamide.
The amount of solvent used can be adjusted according to the actual processing and application requirements.
In another aspect, the present invention provides a semiconductor sealing material, the raw material of which comprises the thermosetting resin composition as described above.
In another aspect, the present invention provides a prepreg comprising a substrate, and the thermosetting resin composition as described above attached to the substrate by impregnation drying.
Preferably, the substrate comprises any one or a combination of at least two of glass cloth, non-woven cloth or 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 base material 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 or 0.19mm, etc. from the viewpoint of good dimensional stability.
Preferably, the substrate is a substrate subjected to a fiber opening treatment and/or a 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 or a combination of at least two of an epoxy silane coupling agent, an amino silane coupling agent, or a vinyl silane coupling agent.
Illustratively, the method of preparing the prepreg is: and immersing the base material in the resin glue solution of the thermosetting resin composition, taking out and drying to obtain the prepreg.
Preferably, the drying temperature is 100 to 250 ℃, for example 105 ℃, 110 ℃, 115 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 245 ℃, or the like.
Preferably, the drying time is 1 to 15min, for example, 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min or 14min, etc.
In another aspect, the present invention provides a circuit substrate comprising 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 copper foil, nickel foil, aluminum foil or SUS foil.
The preparation method of the circuit substrate comprises the following steps: pressing metal foil 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 pressing 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 ℃, for example 105 ℃, 110 ℃, 115 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 245 ℃, or the like.
Preferably, the curing pressure is 10 to 60kg/cm 2 For example 15kg/cm 2 、20kg/cm 2 、25kg/cm 2 、30kg/cm 2 、35kg/cm 2 、40kg/cm 2 、45kg/cm 2 、50kg/cm 2 Or 55kg/cm 2 Etc.
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 coated on 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 double-end cyano active ester provided by the invention contains cyano and aromatic ester groups, and has more reaction crosslinking sites, low dielectric loss, low dielectric constant and low water absorption rate through the special design of a molecular structure, and can be used as a curing agent to perform curing reaction with epoxy resin, so that the obtained cured product has excellent dielectric property, heat resistance, moist 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 double-end cyano active ester with high crosslinking site g Excellent heat resistance, mechanical property and adhesive property, and good dielectric property and processability. On the one hand, the aryl ester group in the double-end cyano active ester does not generate secondary hydroxyl with strong polarity when reacting with epoxy resin, so that the obtained cured product has low dielectric loss, low dielectric constant and low water absorption; on the other hand, cyano groups in the double-end cyano active ester can be self-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, amino groups and the like are not generated in the reaction process, so that the cured product has excellent wet heat resistance and dielectric properties.
(3) The thermosetting resin composition containing the double-ended cyano active ester and the circuit substrate thereof have low thermal expansion coefficient, low water absorption, low dielectric constant and dielectric loss, show excellent dielectric property, heat resistance, moist heat resistance and bonding strength, and can meet the high-performance requirement of the circuit substrate.
Drawings
FIG. 1 is an infrared spectrum of a double-ended cyano active ester provided in example 1;
FIG. 2 is a chromatogram of an ultra-high performance polymer of a double-ended cyano active ester provided in example 1.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
A double-end cyano active ester K-1 has the following structure:
the preparation method comprises the following steps:
165g (hydroxyl equivalent: 165 g/eq.) of a resin for addition polymerization of dicyclopentadiene and phenol, 50.8g (0.25 mol) of isophthaloyl chloride 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 subjected to nitrogen substitution under reduced pressure and dissolved by stirring; 50.6g (0.5 mol) of triethylamine is dripped into the reaction system for 2 hours at the temperature of below 50 ℃, and the reaction system is stirred for 1 hour after the dripping is finished; the temperature of the reaction system was lowered to-10℃or lower, 36.9g (0.6 mol) of cyanogen chloride was added thereto, and then 65.8g (0.65 mol) of triethylamine was added dropwise over 2 hours, and the reaction system was controlled to 0℃or lower, followed by stirring for 1 hour after completion of the dropwise addition. After the reaction is finished, adding deionized water, stirring for 10min, standing and separating to remove a water layer, and repeatedly washing the obtained toluene layer until the pH value of the water layer is 7; finally, toluene is concentrated under reduced pressure by heating, butanone is added to prepare resin solution, and the liquid resin of the double-end cyano active ester K-1 is obtained.
The double-ended active ester K-1 provided in this example was calculated and measured according to the feed ratio and had an ester group equivalent of 420g/eq and a cyano equivalent of 420g/eq.
Example 2
A double-end cyano active ester K-2 has the following structure:
the preparation method comprises the following steps:
200g of double-ended hydroxyl active ester V-575 (Japanese Unitika, number average molecular weight M) was charged into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer n 3900 of the formulaThe equivalent weight of the ester group is 210g/eqThe base equivalent weight was about 1000 g/eq.) and 3000g of toluene, and the system was subjected to nitrogen substitution under reduced pressure and dissolved with stirring. 14.8g (0.24 mol) of cyanogen chloride was added to the reaction system at-10℃or below, 30.4g (0.3 mol) of triethylamine was added dropwise over 2 hours, the reaction system was at-0℃or below, and the mixture was stirred for 1 hour after the completion of the dropwise addition. After the reaction was completed, deionized water was added and stirred for 10 minutes, and the aqueous layer was removed by standing and separating, and the obtained toluene layer was repeatedly subjected to water washing until the pH of the aqueous layer was 7. Finally, toluene is concentrated under reduced pressure by heating, butanone is added to prepare resin solution, and the liquid resin of the double-end cyano active ester K-2 is obtained.
Calculated and measured according to the feed ratio, the double-ended active ester K-2 provided in this example had an ester group equivalent of 225g/eq and a cyano group equivalent of 1025g/eq.
Example 3
A double-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 diallyl bisphenol A (hydroxyl equivalent: 160 g/eq.) and 71.1g (0.35 mol) of isophthaloyl chloride and 1160g of methylene chloride, and the inside of the system was subjected to nitrogen substitution under reduced pressure and stirred for dissolution. The reaction system was controlled at 30℃or lower, 0.5g of tetrabutylammonium bromide was added thereto, 140g (0.7 mol) of a 20% aqueous sodium hydroxide solution was then added dropwise thereto over 2 hours, and the mixture was stirred for 1 hour after completion of the dropwise addition. The aqueous layer was removed by standing and separating, the system temperature of the methylene chloride layer was lowered to-10℃or lower, 24.6g (0.4 mol) of cyanogen chloride was added thereto, 45.5g (0.45 mol) of triethylamine was then added dropwise over 2 hours, the reaction system was kept at 0℃or lower, and the mixture was stirred for 1 hour after the completion of the dropwise addition. After the reaction was completed, deionized water was added and stirred for 10 minutes, and the aqueous layer was removed by standing and separating, and the resulting dichloromethane layer was repeatedly subjected to water washing until the pH of the aqueous layer was 7. Finally, concentrating dichloromethane under reduced pressure by heating, and adding butanone to prepare a resin solution, thereby obtaining the liquid resin of the double-end cyano active ester K-3.
Calculated and measured according to the feed ratio, the double-ended active ester K-3 provided in this example had an ester group equivalent of 304g/eq and a cyano equivalent of 710g/eq.
Example 4
A double-end cyano active ester K-4 has the following structure:
the preparation method comprises the following steps:
162g (hydroxyl equivalent: 162 g/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 into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer, and the system was dissolved by stirring under reduced pressure with nitrogen substitution. Subsequently, 36.9g (0.6 mol) of cyanogen chloride was added to the reaction system at-10℃or lower, and 121.5g (1.2 mol) of triethylamine was then added dropwise over 3 hours, and the reaction system was controlled at 5℃or lower, followed by stirring for 2 hours after the completion of the dropwise addition. After the reaction was completed, deionized water was added and stirred for 10 minutes, and the aqueous layer was removed by standing and separating, and the resulting dichloromethane layer was repeatedly subjected to water washing until the pH of the aqueous layer was 7. Finally, concentrating dichloromethane under reduced pressure by heating, and adding butanone to prepare a resin solution, thereby obtaining the liquid resin of the double-end cyano active ester K-4.
The double-ended active ester K-4 provided in this example had an ester group equivalent of 404g/eq and a cyano group equivalent of 404g/eq, calculated and measured according to the feed ratio.
Example 5
A double-end cyano active ester K-5 has the following structure:
the preparation method comprises the following steps:
188g (hydroxy equivalent: 188 g/eq.) of a polycondensation resin of 4,4 '-biphenyldicarboxaldehyde and phenol, 73.8g (0.25 mol) of 4,4' -diacyl chloride diphenyl ether and 2050g of methylene chloride were charged 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 subjected to nitrogen substitution under reduced pressure while stirring and dissolution. The reaction system was controlled at 30℃or lower, 50.6g (0.5 mol) of triethylamine was added dropwise over 2 hours, and the mixture was stirred for 1 hour after completion of the addition. Next, the temperature of the system was lowered to-10℃or lower, 36.9g (0.6 mol) of cyanogen chloride was added thereto, and then 65.8g (0.65 mol) of triethylamine was added dropwise over 2 hours, and the reaction system was controlled to 0℃or lower, followed by stirring for 1 hour after completion of the dropwise addition. After the reaction was completed, deionized water was added and stirred for 10 minutes, and the aqueous layer was removed by standing and separating, and the obtained toluene layer was repeatedly subjected to water washing until the pH of the aqueous layer was 7. Finally, toluene is concentrated under reduced pressure by heating, butanone is added to prepare resin solution, and the liquid resin of the double-end cyano active ester K-5 is obtained.
The double-ended active ester K-5 provided in this example was calculated and measured according to the feed ratio and had an ester group equivalent of 512g/eq and a cyano equivalent of 512g/eq.
Example 6
A double-end cyano active ester K-6 has the following structure:
the preparation method comprises the following steps:
80.1g (hydroxyl equivalent: 80.1 g/eq.) of 1, 5-dihydroxynaphthalene, 52.3g (0.25 mol) of 1, 4-cyclohexanedicarboxylic acid chloride and 1200g of methylene chloride were charged into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer, and the system was dissolved by stirring under reduced pressure with nitrogen substitution. The reaction system was controlled at 30℃or lower, 50.6g (0.5 mol) of triethylamine was added dropwise over 2 hours, and the mixture was stirred for 1 hour after completion of the addition. Next, the temperature of the system was lowered to-10℃or lower, 36.9g (0.6 mol) of cyanogen chloride was added thereto, and then 65.8g (0.65 mol) of triethylamine was added dropwise over 2 hours, and the reaction system was controlled to 0℃or lower, followed by stirring for 1 hour after completion of the dropwise addition. After the reaction was completed, deionized water was added and stirred for 10 minutes, and the aqueous layer was removed by standing and separating, and the obtained toluene layer was repeatedly subjected to water washing until the pH of the aqueous layer was 7. Finally, toluene is concentrated under reduced pressure by heating, butanone is added to prepare resin solution, and the liquid resin of the double-end cyano active ester K-6 is obtained.
The double-ended active ester K-6 provided in this example was calculated and measured according to the feed ratio and had an ester group equivalent of 253.2g/eq and a cyano equivalent of 253.2g/eq.
Performance testing of the double-ended cyano active esters
(1) Structural characterization: the double-ended cyano active esters provided in examples 1 to 6 were characterized by infrared testing using a fourier infrared spectrometer (FT-IR).
An exemplary IR spectrum of a double-ended cyano active ester K-1 as provided in example 1 is shown in FIG. 1, and it can be seen from FIG. 1 that the double-ended cyano active ester K-1 has a wavenumber of 1739.8cm -1 The characteristic absorption peak of the ester group of the active ester appears at the wavenumber of 2261.0cm -1 The cyano characteristic absorption peak of cyanate appears at 3400cm -1 A strong absorption peak of the phenolic hydroxyl group did not appear nearby, indicating that the phenolic hydroxyl group had undergone esterification or cyanation.
(2) Molecular weight testing: determination of the weight average molecular weight M of the double-ended cyanoactive esters provided in examples 1 to 6 by means of the ultra-high Performance Polymer chromatography System (APC) from Waters company w 。
Exemplary, the ultra-efficient Polymer chromatogram (APC map) of double-ended cyano active ester K-1 provided in example 1 is shown in FIG. 2, from which FIG. 2 it can be seen that the double-ended cyano active ester K-1 has a weight average molecular weight M w 2950.
The experimental materials used in the following application examples and comparative examples of the present invention are shown in table 1.
TABLE 1
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Application example 1
A thermosetting resin composition, a prepreg and a circuit board containing the same, and a preparation method thereof are as follows:
(1) Uniformly mixing 57 parts by weight of biphenyl novolac epoxy resin A-1, 43 parts by weight of double-end cyano active ester K-1 and 0.1 part by weight of 4-dimethylaminopyridine (curing accelerator D-1) in a solvent to obtain a resin glue solution of a thermosetting resin composition, wherein the solid content of the resin glue solution is 65%; dipping the glue solution by using 2116 glass fiber cloth, controlling the proper thickness, and then baking in a 160 ℃ oven for 10min to prepare prepreg;
(2) 6 prepregs were stacked together, and 1Oz of RTF copper foil was stacked on both sides of the prepreg at a curing temperature of 200℃and a curing pressure of 45kg/cm 2 And preparing the circuit substrate under the condition that the curing time is 120 min.
Application example 2
A thermosetting resin composition, a prepreg and a circuit board containing the same, and a preparation method thereof are as follows:
(1) Uniformly mixing 56.5 parts by weight of biphenyl novolac epoxy resin A-1, 43.5 parts by weight of double-end cyano active ester K-2 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%; dipping the glue solution by using 2116 glass fiber cloth, controlling the proper thickness, and then baking in an oven at 145 ℃ for 15min to prepare prepreg;
(2) 6 prepregs were stacked together, and 1Oz of RTF copper foil was laminated on both sides, and the curing pressure was 60kg/cm at a curing temperature of 190 ℃ 2 And preparing the circuit substrate under the condition that the curing time is 90 min.
Application example 3
A thermosetting resin composition, a prepreg and a circuit board containing the same, and a preparation method thereof are as follows:
(1) Uniformly mixing 57.5 parts by weight of biphenyl novolac epoxy resin A-1, 42.5 parts by weight of double-end cyano active ester 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%; dipping the glue solution by using 2116 glass fiber cloth, controlling the proper thickness, and then baking in an oven at 175 ℃ for 2min to prepare prepreg;
(2) 6 prepregs were stacked together, and 1Oz of RTF copper foil was laminated on both sides thereof at a curing temperature of 220℃and a curing pressure of 30kg/cm 2 And preparing the circuit substrate under the condition that the curing time is 150 min.
Application examples 4 to 7, comparative examples 1 to 4
A thermosetting resin composition, and a prepreg and a circuit board comprising the same, wherein the components and the contents of the thermosetting resin composition are shown in Table 2, and the prepreg and the circuit board are prepared in the same manner as in application example 1.
TABLE 2
Performance testing
The thermosetting resin compositions provided in application examples 1 to 7 and comparative examples 1 to 4 and the circuit board comprising the same were subjected to performance test by the following methods:
(1) Glass transition temperature (T) g ): using the DSC test, the measurements were made according to the DSC test method specified in standard IPC-TM-650.2.4.24;
(2) Coefficient of thermal expansion CTE (Z-axis): the coefficient of thermal expansion between 50 and 260℃was determined by TMA according to the CTE (Z-axis) test method specified in the standard IPC-TM-650.2.4.24;
(3) Dielectric constant D k And dielectric loss factor D f : d at 10GHz was determined according to SPDR method specified in standard IEC61189-2-721 k And D f ；
(4) Thermal delamination time T300 (with copper): the measurement was performed by TMA according to the T300 (with copper) test method specified in the standard IPC-TM-650.2.4.24.1;
(5) Wet heat resistance (PCT) evaluation: after 3 samples with the thickness of 100 multiplied by 100mm are kept in a pressure cooking treatment device with the temperature of 180 ℃ and 105KPa for 2 hours, the samples are immersed in a soldering tin groove with the temperature of 288 ℃ for 5 minutes, whether the samples are subject to layering bubbling or not is observed, wherein 3 samples are marked as 3/3 when layering bubbling does not occur, 2 samples are marked as 2/3 when layering bubbling does not occur, 1 sample is marked as 1/3 when layering bubbling does not occur, and 0 sample is marked as 0/3 when layering bubbling does not occur;
(6) PCT water absorption: taking a sample pretreated under PCT test conditions of the test method (5), and measuring according to a water absorption test method specified in the standard IPC-TM-650.2.6.2.1;
(7) Peel Strength (PS): the peel strength of the metal cap layer was tested according to the "as received" experimental conditions specified in standard IPC-TM-650.4.8.
The specific test results are shown in table 3:
TABLE 3 Table 3
As is clear from the results of the performance test in Table 3, the thermosetting resin compositions used in the circuit boards according to application examples 1 to 7 of the present invention, which were cured with the double-ended cyano active ester according to the present invention, had high glass transition temperatures (T) g ) And a low coefficient of thermal expansion (Z-CTE), while having a low dielectric constant and low dielectric loss, excellent heat resistance, wet heat resistance, low hygroscopicity, and good adhesion strength to metals; wherein the glass transition temperature reaches more than 200 ℃, the Z-CTE is 2.3-3.1%, the dielectric constant is lower than 4.10 (10 GHz), the dielectric loss factor is lower than 0.010 (10 GHz), and T300 (with copper)>60min, the water absorption is as low as 0.25-0.36%, the peeling strength (1 Oz copper foil) reaches 1.2-1.3N/mm, and the moisture and heat resistance test of PCT (2 h) can be passed.
As can be seen from comparing application example 1 with comparative example 1, application example 1 has a higher T g And lower Z-CTE performance, demonstrating that systems comprising the double-ended cyano active esters of the present invention are equivalent to the activities of the prior artThe ester system has better glass transition temperature, crosslinking density and lower thermal expansibility, and the bonding performance with metal is also improved.
As can be seen from a comparison of application example 1 and comparative example 3, the epoxy system comprising the double-ended cyano-activated ester of the present invention has a higher glass transition temperature and a lower coefficient of thermal expansion than the epoxy resin system cured by the prior-art activated ester+cyanate ester combination, and is slightly superior to comparative example 3 in terms of water absorption and peel strength.
As can be seen from comparison of application example 2 and comparative example 2, application example 7 and comparative example 4, the epoxy resin system and the circuit board thereof using the double-ended cyano active ester as the curing agent have a higher T than the epoxy system cured by the double-ended cyano active ester in the prior art g And lower Z-CTE performance.
The applicant states that the present invention illustrates a double-ended cyano active ester, a thermosetting resin composition, and a method of preparation and use of the present invention by the above examples, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must be carried out depending on the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (18)
1. A thermosetting resin composition comprising an epoxy resin and a double-ended cyano active ester, the double-ended cyano active ester having a structure according to formula I:
wherein Ar is a substituted or unsubstituted C6-C150 divalent aromatic group; the substituent groups of Ar are selected from fluorine, C1-C5 straight-chain or branched-chain alkyl, C6-C18 aryl, C2-C5 straight-chain or branched-chain alkenyl and groups containing aryl phosphorus oxygen structures;
x is selected from a substituted or unsubstituted C6-C30 divalent aromatic group, a substituted or unsubstituted C1-C6 linear or branched alkylene group, a substituted or unsubstituted C3-C10 cycloalkylene group; the substituents in X are each independently selected from fluorine, C1-C5 straight or branched alkyl;
n is selected from 1 to 15.
2. The thermosetting resin composition of claim 1, wherein Ar is selected from the group consisting of
Ar 1 Selected from the group consisting of
Ar 2 Selected from the group consisting of
R 1 、R 2 Each independently selected from fluorine, C1-C5 linear or branched alkyl, C2-C5 linear or branched alkenyl,
R 3 Is C1-C5 straight chain or branched chain alkylene;
n 1 、n 3 each independently selected from integers from 0 to 4;
n 2 an integer selected from 0 to 6;
Y 1 、Y 2 each independently selected from the group consisting of-O-, -S-, carbonyl, sulfone group, substituted or unsubstituted C1-C20 straight or branched alkylene, substituted or unsubstituted C3-C30 cycloalkylene, and substituted or unsubstituted C6-C30 aralkylene; the substituted substituents are each independently selected from fluorine, C1-C5 linear or branched alkyl, C6-C18 aryl;
m is selected from 0 to 10.
3. The thermosetting resin composition according to 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 to C6 linear or branched alkylene, substituted or unsubstituted C3 to C10 cycloalkylene; the substituted substituents are each independently selected from fluorine, C1-C5 straight or branched alkyl.
4. The thermosetting resin composition according to claim 1 or 2, wherein n is selected from 1 to 10.
5. The thermosetting resin composition according to claim 1, wherein the double-ended cyano active ester is prepared by the following preparation method I or preparation method II;
the preparation method I is as follows: reacting a phenolic compound with a structure shown in a formula A1, a diacylhalide compound with a structure shown in a formula A2 and a cyano compound with a structure shown in a formula A3 to obtain the double-end cyano active ester;
the preparation method II comprises the following steps: reacting a compound with a structure shown in a formula B1 with a cyanide compound with a structure shown in a formula A3 to obtain the double-end cyano active ester;
HO-Ar-OH formula A1;
Z 1 -c≡n formula A3;
wherein Ar, X, n each independently have the same defined ranges as in formula I;
X 1 、Z 1 each independently selected from halogen;
Z 2 selected from hydrogen, na + 、Ka + Or Li (lithium) + 。
6. The thermosetting resin composition of claim 5, wherein X is 1 、Z 1 Each independently selected from chlorine, bromine or iodine.
7. The thermosetting resin composition according to claim 5, wherein the molar ratio of the phenolic compound to the dihalide compound in the production method I is 1 (0.5 to 0.95).
8. The thermosetting resin composition according to claim 5, wherein the reaction in the preparation method I is carried out in the presence of a basic catalyst.
9. The thermosetting resin composition according to claim 5, wherein the temperature of the reaction in the production method I is-30℃to 50 ℃.
10. The thermosetting resin composition of claim 5, wherein Z 2 In the presence of a basic catalyst, the reaction in preparation II is carried out as hydrogen.
11. The thermosetting resin composition according to claim 5, wherein the temperature of the reaction in preparation method II is-30℃to 20 ℃.
12. The thermosetting resin composition of claim 5, wherein Z 2 Selected from Na + 、Ka + Or Li (lithium) + The reaction in preparation method II is carried out in the presence of a phase transfer catalyst.
13. The thermosetting resin composition according to claim 1, further comprising any one or a combination of at least two of other curing agents, flame retardants, inorganic fillers, organic fillers, or curing accelerators.
14. A semiconductor sealing material, wherein a raw material of the semiconductor sealing material comprises the thermosetting resin composition according to any one of claims 1 to 13.
15. A prepreg comprising a substrate and the thermosetting resin composition of any one of claims 1 to 13 attached to the substrate by impregnation drying.
16. The prepreg of claim 15, wherein the substrate comprises any one or a combination of at least two of fiberglass cloth, non-woven cloth, or quartz cloth.
17. A circuit substrate comprising at least one prepreg according to claim 15 or 16, and a metal foil provided on one or both sides of the prepreg.
18. A laminated film comprising a base film or a metal foil, and the thermosetting resin composition according to any one of claims 1 to 13 coated on at least one surface of the base film or the metal foil.
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