CN118240341A - Thermosetting resin composition and application thereof - Google Patents

Abstract

The invention provides a thermosetting resin composition and application thereof, wherein the thermosetting resin composition comprises (A) a modified maleimide compound, (B) a polymer containing maleimide groups and (C) other thermosetting resins, and the preparation raw materials of the (A) modified maleimide compound comprise: a maleimide group-containing compound and a fluorenyl group-containing aromatic diamine compound having a structure represented by the formula I or the formula II. In the invention, the combination of (A) modified maleimide compound, (B) maleimide group-containing polymer and (C) other thermosetting resin makes the cured product have low water absorption, high glass transition temperature, excellent dielectric properties, heat resistance, moist heat resistance, low thermal expansion coefficient, strong binding force with metal foil, and low dielectric properties after water absorption.

Description

Thermosetting resin composition and application thereof

Technical Field

The invention belongs to the technical field of laminated boards, and relates to a thermosetting resin composition and application thereof.

Background

In recent years, with the rapid development of information industry, electronic products are increasingly shortened, miniaturized, thinned, high-performance and multifunctional, in order to meet the development requirements of various electronic devices, information communication devices tend to be high-speed and high-frequency in signal transmission, and integrated circuits are advanced towards high density, high precision and high integration, so that printed circuit substrate materials are required to have good dielectric properties, and meanwhile, substrates are required to have good heat resistance, dimensional stability and low thermal expansion rate, so as to meet the requirements of high reliability of printed circuit board processes. For example, in a substrate of a smart mobile phone or the like, which is being thinned and reduced in price, a material having a low relative dielectric constant is required to cope with the thinning; in devices of communication systems typified by servers, routers, mobile base stations, and the like, materials having low dielectric properties (low dielectric constant and low dielectric loss), high glass transition temperature (high T _g), and excellent reflow heat resistance are also required in order to be able to be used in higher frequency bands and to be able to use high-melting-point lead-free solders for soldering electronic components; in the package base material for a semiconductor, warpage due to a difference in thermal expansion coefficient between a chip and a substrate at the time of component mounting and package assembly is also a major research subject, and a substrate is required to have low dielectric properties and low thermal expansion coefficient while stringent requirements are put on loss during signal transmission.

Maleimide resin is a high-performance matrix resin, and the cured product of the maleimide resin has the advantages of high glass transition temperature, high heat resistance, good mechanical property, good dielectric property and the like. For example, CN105385105A discloses a bismaleimide modified epoxy resin, a preparation method and application thereof, the preparation method comprises: firstly, reacting a modifier, epoxy resin and bismaleimide to form a resin glue solution, and continuously reacting the resin glue solution with a curing agent and a curing accelerator to obtain bismaleimide modified epoxy resin; wherein the modifier is selected from allyl compounds of O-diallyl bisphenol A diglycidyl ether, bisphenol A bis allyl ether, 2-allyl phenol bisphenol S or diallyl ether. The modified epoxy resin obtained by the method can be used for preparing a copper-clad plate substrate with high temperature resistance, low loss, good moist heat resistance and good mechanical property. CN101652026a discloses a method for preparing copper-clad plate, which specifically comprises: firstly, a bismaleimide resin reacts with an allyl compound to obtain a prepolymer; then mixing the prepolymer with phosphorus-containing epoxy resin, a composite curing agent and the like to obtain a glue solution; coating the glue solution on glass fiber cloth, baking to obtain B-stage prepreg, and stacking and hot-pressing the prepreg and copper foil to obtain a copper-clad plate; the obtained copper-clad plate can meet the requirements of halogen-free flame retardance, and has excellent heat resistance, moist heat resistance, low dielectric loss and good processing toughness. Meanwhile, in order to use the electronic device even in an environment with high humidity, it is often insufficient to reduce only the water absorption of the printed wiring board, and it is also required that the printed wiring board can maintain its low dielectric characteristics even after water absorption.

However, maleimide resins are brittle in cured physical properties and poor in solubility, and are often used in combination with epoxy resins or the like after being modified or mixed with amines, diallyl compounds or the like, and the resulting network structure after reaction contains a large number of polar, water-absorbable secondary alcohol hydroxyl groups, so that the cured products are greatly reduced in dielectric properties, moist heat resistance and the like.

CN108401433a discloses a resin varnish comprising a maleimide compound, an epoxy resin, a copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride, silica treated with an aminosilane-based coupling agent, an organic solvent, and the like, a prepreg, a laminated board, and a printed wiring board, and a thermosetting resin composition material having good heat resistance and adhesion, a high glass transition temperature, a relatively low dielectric constant and low thermal expansion, and excellent moldability and plating coverage is obtained by using a maleimide compound containing an acidic substituent and a maleimide group. However, the maleimide compound used in the resin varnish contains an acidic substituent such as a hydroxyl group, a carboxyl group or a sulfonic acid group, and reacts with the epoxy resin to form a secondary alcoholic hydroxyl group which is highly polar and easily absorbs water, thereby adversely affecting the dielectric properties, water absorption rate and moist heat resistance of the cured product.

Therefore, in the art, development of materials having excellent dielectric properties, and also having excellent heat resistance, wet heat resistance, low thermal expansion coefficient, strong adhesion, and comprehensive properties such as low dielectric properties that can be maintained after water absorption, so as to meet the performance and application requirements of high-performance circuit substrates, is an important research point in the art.

Disclosure of Invention

In view of the shortcomings of the prior art, the invention aims to provide a thermosetting resin composition and application thereof.

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

In one aspect, the present invention provides a thermosetting resin composition comprising (a) a modified maleimide compound, (B) a maleimide group-containing polymer, and (C) other thermosetting resin, wherein the preparation raw materials of the (a) modified maleimide compound comprise: a maleimide group-containing compound and a fluorenyl group-containing aromatic diamine compound having a structure represented by the formula I or formula II;

Wherein each X is independently selected from a substituted or unsubstituted C6-C20 (e.g., C6, C9, C10, C12, C14, C16, C18, or C20, etc.) arylene group, -X ₁-Y-X₂ -, a substituted or unsubstituted C1-C20 (e.g., C2, C3, C4, C5, C7, C9, C10, C12, C14, C16, C18, or C20, etc.) linear or branched alkylene group, a substituted or unsubstituted C3-C20 (e.g., C3, C4, C5, C7, C9, C10, C12, C14, C16, C18, or C20, etc.) cycloalkylene group, or a single bond;

Each Z is independently selected from substituted or unsubstituted C6-C20 (e.g., C6, C9, C10, C12, C14, C16, C18, or C20, etc.) aryl, X ₃-Y-X₂ -, substituted or unsubstituted C1-C20 (e.g., C2, C3, C4, C5, C7, C9, C10, C12, C14, C16, C18, or C20, etc.) straight or branched alkyl, substituted or unsubstituted C3-C20 (e.g., C3, C4, C5, C7, C9, C10, C12, C14, C16, C18, or C20, etc.) cycloalkyl, or a hydrogen atom;

Each R is independently selected from a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, bromine, or iodine), an epoxy group, an amino group, a hydroxyl group, an acrylate group, a mercapto group, a sulfonic acid group, or a carboxyl group;

X ₁、X₂ is each independently selected from substituted or unsubstituted C6-C12 (e.g., C6, C9, C10, or C12, etc.) arylene;

X ₃ is each independently selected from substituted or unsubstituted C6-C12 (e.g., C6, C9, C10, C12, etc.) aryl;

y is each independently selected from C1-C5 (e.g., C1, C2, C3, C4, or C5) straight or branched alkylene, -O-, -S-, a single bond, a sulfone group, or a sulfoxide group;

X, Z each independently selected from C1 to C5 (e.g., C1, C2, C3, C4, or C5) straight or branched alkyl;

The total weight of the monomers of the maleimide group-containing compounds which have not reacted in the modified maleimide compound (A) is 30 to 80% (for example, 30%, 35%, 38%, 40%, 43%, 45%, 48%, 50%, 55%, 60%, 65%, 70%, 75% or 80%) of the maleimide group-containing compounds in the raw materials for production.

In the present invention, short straight lines on one side or both sides of the group structure (for example, short straight lines on both sides in-X ₁-Y-X₂ -, short straight lines on the right side in X ₃-Y-X₂ -) represent the access bond of the group, and do not represent methyl.

The preparation raw materials of the (A) modified maleimide compound provided by the invention comprise two types: a maleimide group-containing compound and a fluorenyl group-containing aromatic diamine compound; the modified maleimide compound (A) contains maleimide group and fluorenyl group, which are cooperated with each other, so that the modified maleimide compound (A) has low dielectric constant, low dielectric loss, high heat resistance and low thermal expansion coefficient, and can maintain low dielectric property after water absorption.

In the invention, the combination of (A) modified maleimide compound, (B) maleimide group-containing polymer and (C) other thermosetting resin makes the cured product have low water absorption, high glass transition temperature, excellent dielectric properties, heat resistance, moist heat resistance, low thermal expansion coefficient, strong binding force with metal foil, and low dielectric properties after water absorption.

In the present invention, the total weight of the monomers of the maleimide group-containing compounds which have not reacted in the (A) modified maleimide compound is controlled to be 30 to 80% of the total weight of the maleimide group-containing compounds in the raw materials for the preparation, and the prepared (A) modified maleimide compound has good storage stability and good compatibility with other resins. If the total weight of the monomers containing the maleimide group compounds which are not reacted is less than 30% of the total weight of the monomers containing the maleimide group compounds in the preparation raw materials, the modified maleimide compound has poor compatibility with the thermosetting resin, and a two-phase separation state is generated after the modified maleimide compound is prepared into glue; if the total weight of the monomers of the maleimide group-containing compounds which have not reacted is more than 80% of the total weight of the maleimide group-containing compounds in the raw materials for preparation, the modified maleimide compounds are rapidly crystallized and separated out during storage, and the modified maleimide compounds cannot be used for normal glue preparation.

Preferably, each X is independently selected from the group consisting of substituted or unsubstituted C1-C10 (e.g., C2, C3, C4, C5, C7, C9, or C10) straight or branched chain alkylene, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene ether;

Each Z is independently selected from substituted or unsubstituted C1-C10 (e.g., C2, C3, C4, C5, C7, C9, or C10) straight or branched alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl ether;

X, Z are each independently selected from C1-C5 (e.g., C1, C2, C3, C4, or C5) straight or branched alkyl.

In the present invention, the maleimide group-containing compound is a maleimide group-containing monomer.

Preferably, the maleimide group-containing monomer includes N, N '-ethylene bismaleimide, N' -hexamethylene bismaleimide, N '- (1, 3-phenylene) bismaleimide, N' - (1, 3- (2-methylphenyl)) bismaleimide, N '- (1, 3- (4-methylphenyl)) bismaleimide, N, N' - (1, 4-phenylene) bismaleimide, 4 '-diphenylmethane bismaleimide, bis (3-methyl-4-maleimidophenyl) methane, bis (3, 5-dimethyl-4-maleimidophenyl) methane, 3' -dimethyl-5, 5 '-diethyl-4, 4' -diphenylmethane bismaleimide, bis (3-ethyl-4-maleimidophenyl) methane, bis (3, 5-diethyl-4-maleimidophenyl) methane, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) ketone, bis (4-maleimidocyclohexyl) methane, 1, 4-bis (4-maleimidophenyl) cyclohexane, 1, 4-bis (maleimidomethyl) cyclohexane, 1, 6-bismaleimide-2, 4-trimethyl-hexane, 1, 4-bis (maleimidomethyl) benzene, 1, 3-bis (4-maleimidophenoxy) benzene, 1, 3-bis (3-maleimidophenoxy) benzene, bis (4- (3-maleimidophenoxy) phenyl) methane, bis (4- (4-maleimidophenoxy) phenyl) methane, 1-bis (4- (3-maleimidophenoxy) phenyl) ethane, 1-bis (4- (4-maleimidophenoxy) phenyl) ethane, 1, 2-bis (4- (3-maleimidophenoxy) phenyl) ethane, 1, 2-bis (4- (4-maleimidophenoxy) phenyl) ethane 2, 2-bis (4- (3-maleimidophenoxy) phenyl) propane, 2' -bis [4- (4-maleimidophenoxy) phenyl ] propane, 2-bis (4- (3-maleimidophenoxy) phenyl) butane, 2-bis (4- (4-maleimidophenoxy) phenyl) butane, 4' -bis (3-maleimidophenoxy) biphenyl, 4' -bis (4-maleimidophenoxy) biphenyl, bis (4- (3-maleimidophenoxy) phenyl) ketone, any one or a combination of at least two of bis (4- (4-maleimidophenoxy) phenyl) ketone, bis (4- (3-maleimidophenoxy) phenyl) ether or bis (4- (4-maleimidophenoxy) phenyl) ether.

Further preferably, the maleimide group-containing monomer comprises any one or a combination of at least two of 4,4' -diphenylmethane bismaleimide, N ' - (1, 3-phenylene) bismaleimide, 2' -bis [4- (4-maleimidophenoxy) phenyl ] propane, 3' -dimethyl-5, 5' -diethyl-4, 4' -diphenylmethane bismaleimide, N ' - (1, 3- (4-methylphenyl)) bismaleimide, or 1, 6-bismaleimide-2, 4-trimethyl-hexane.

Illustratively, the maleimide group-containing compound may be any one or a combination of at least two of BMI-1000、BMI-1000H、BMI-1100、BMI-1100H、BMI-3000、BMI-3000H、BMI-4000H、BMI-5000、BMI-5100、BMI-7000、BMI-7000H、BMI-70 or BMI-80; the names listed above are trade names, of which ,BMI-1000、BMI-1000H、BMI-1100、BMI-1100H、BMI-3000、BMI-3000H、BMI-4000H、BMI-5000、BMI-5100、BMI-7000、BMI-7000H is available from Japanese DAIWAKASEI, and BMI-70 and BMI-80 are available from Japanese K.I chemical company.

Preferably, the fluorenyl-containing aromatic diamine compound is used in an amount of 0.05 to 1mol, for example 0.08mol、0.1mol、0.15mol、0.2mol、0.25mol、0.3mol、0.35mol、0.4mol、0.45mol、0.5mol、0.55mol、0.6mol、0.65mol、0.7mol、0.75mol、0.8mol、0.85mol、0.9mol or 0.95mol, based on 1mol of the maleimide group in the maleimide group-containing compound, and specific point values between the above point values, are not exhaustive, and the specific point values included in the range are preferably 0.1 to 0.75mol, more preferably 0.15 to 0.5mol, for the sake of brevity and conciseness.

As a preferable embodiment of the present invention, the amount of the fluorenyl-containing aromatic diamine compound is 0.05 to 1mol based on 1mol of the maleimide group in the maleimide group-containing compound. The lower the amount of the fluorenyl-containing aromatic diamine compound is, namely, the lower the modification degree of the maleimide-containing compound is, the modified maleimide compound (A) obtained by the reaction has no obvious effect of improving the solubility in an organic solvent, and the lower the proportion of functional groups which can react with thermosetting resin in the structure is, thus having no good effect of improving the brittleness of a cured product; on the contrary, the higher the amount of the fluorenyl-containing aromatic diamine compound, the more advantageous the solubility and toughness of the resulting (A) modified maleimide compound are, although the higher the degree of modification, the great sacrifice of the advantages of the maleimide-containing compound in terms of high glass transition temperature, low expansion coefficient, etc.

In the invention, the preparation raw material also comprises a hydroxyl-containing monoamine compound with a structure shown in a formula III;

HO-A-NH₂

A formula III;

Wherein A is selected from the group consisting of substituted or unsubstituted C6-C20 (e.g., C6, C9, C10, C12, C14, C16, C18, or C20, etc.) arylene, -X ₁-Y-X₂ -, substituted or unsubstituted C1-C20 (e.g., C6, C9, C10, C12, C14, C16, C18, or C20, etc.) straight or branched alkylene, substituted or unsubstituted C3-C20 (e.g., C3, C4, C5, C7, C9, C10, C12, C14, C16, C18, or C20, etc.) cycloalkylene;

X ₁、X₂ is each independently selected from substituted or unsubstituted C6-C12 (e.g., C6, C9, C10, or C12, etc.) arylene;

Y is selected from C1-C5 (e.g. C1, C2, C3, C4 or C5) straight or branched chain alkylene, -O-, -S-, single bond, sulfone group or sulfoxide group;

The substituent groups of the substituent groups in A are selected from C1-C5 (such as C1, C2, C3, C4 or C5) straight-chain or branched alkyl groups.

As a preferable embodiment of the present invention, the hydroxyl group-containing monoamine compound is used in an amount of 0 to 0.25mol based on 1mol of maleimide groups in the maleimide group-containing compound. Such as 0mol, 0.05mol, 0.08mol, 0.1mol, 0.12mol, 0.15mol, 0.18mol, 0.2mol, 0.21mol, 0.22mol, 0.23mol or 0.24mol, as well as specific point values between the above point values, are limited in scope and for brevity, the invention is not intended to be exhaustive list of the specific point values included in the range.

Although the introduction of hydroxyl groups in the hydroxyl-containing monoamine compound partially lowers the dielectric constant, dielectric loss and water absorption of the cured product, there is a deterioration in the heat resistance and wet heat resistance. However, the introduction of hydroxyl groups in the hydroxyl-containing monoamine compound can further improve the solubility of the fluorenyl-containing aromatic diamine compound modified maleimide-based compound. Only when the solubility of the fluorenyl-containing aromatic diamine compound-modified maleimide-based compound needs to be further improved, a hydroxyl-containing monoamine compound may be appropriately added in a certain proportion. If the solubility of the fluorenyl-containing aromatic diamine compound modified maleimide-based compound is not a problem that the solubility is poor and needs to be improved, the hydroxyl-containing monoamine compound does not need to be added.

Preferably, the total amount of amine groups in the fluorenyl-containing aromatic diamine compound and the hydroxyl-containing monoamine compound is 0.05 to 1mol, such as 0.08mol、0.1mol、0.15mol、0.2mol、0.25mol、0.3mol、0.35mol、0.4mol、0.45mol、0.5mol、0.55mol、0.6mol、0.65mol、0.7mol、0.75mol、0.8mol、0.85mol、0.9mol or 0.95mol, based on 1mol of maleimide groups in the maleimide-containing compound, and specific point values between the above point values are limited in space and, for brevity, the present invention is not exhaustive to list the specific point values included in the range. The lower the amount of the fluorenyl-containing aromatic diamine compound and the hydroxyl-containing monoamine compound is, namely, the lower the modification degree of the maleimide-containing compound is, the modified maleimide compound (A) obtained by the reaction has no obvious effect of improving the solubility in an organic solvent, and the lower the proportion of functional groups which can react with thermosetting resin in the structure is, thus having no good effect of improving the brittleness of a cured product; on the contrary, the higher the amount of the fluorenyl-containing aromatic diamine compound and the hydroxyl-containing monoamine compound, the more advantageous the degree of modification is for the improvement of the solubility and toughness of the resulting (a) -modified maleimide compound, but the advantages of the maleimide-containing compound in terms of high glass transition temperature, low thermal expansion coefficient and the like are greatly sacrificed. Therefore, the total amount of amine groups in the fluorenyl-containing aromatic diamine compound and the hydroxyl-containing monoamine compound is preferably 0.1 to 0.6mol, more preferably 0.15 to 0.4mol, per 1mol of maleimide groups in the maleimide-containing compound.

As a preferred technical scheme of the invention, the preparation raw materials of the (A) modified maleimide compound comprise a combination of a maleimide group-containing compound, a fluorenyl-containing aromatic diamine compound and an optional hydroxyl-containing monoamine compound, and are prepared by carrying out addition reaction on amine groups in the fluorenyl-containing aromatic diamine compound and/or the hydroxyl-containing monoamine compound and maleimide groups in the maleimide group-containing compound. The hydroxyl group-containing monoamine compound is not used in an amount of 0 to 0.25mol based on 1mol of maleimide groups in the maleimide group-containing compound.

The preparation method of the (A) modified maleimide compound comprises the following steps: reacting the maleimide group-containing compound with a fluorenyl group-containing aromatic diamine compound having a structure shown in formula I or formula II and optionally a hydroxyl group-containing monoamine compound having a structure shown in formula III to obtain the (A) modified maleimide compound.

In the present invention, the total of the monomer weights of the maleimide-group-containing compounds which have not reacted in the modified maleimide compound (A) is a proportion of the maleimide-group-containing compounds in the raw materials for production, which is obtained by GPC (gel permeation chromatography) test during the synthesis. The specific operation is as follows: in the synthesis process of the modified maleimide compound, samples are taken at intervals, the sampled products are dissolved by Tetrahydrofuran (THF), shaken uniformly and put into GPC equipment for testing, a spectrogram is obtained, the molecular weight, the leaching area, the total molecular weight and the like of different sections are analyzed, the area proportion occupied by monomer peaks is confirmed, and the proportion of the total monomer weight of the unreacted maleimide-containing compound to the maleimide-containing compound in the preparation raw material is calculated. If the ratio is within the range of the present invention, the synthesis reaction may be terminated. The present invention is to monitor the progress of the synthesis reaction by GPC to obtain the (A) modified maleimide compound satisfying the present invention.

Preferably, the temperature of the reaction is 70 to 200 ℃, such as 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, or 195 ℃, and specific point values between the above point values, limited in space and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the range, more preferably 80 to 170 ℃.

Preferably, the reaction time is from 0.5 to 8 hours, such as 0.6h、0.8h、1h、1.2h、1.5h、1.8h、2h、2.2h、2.5h、2.8h、3h、3.2h、3.5h、3.8h、4h、4.2h、4.5h、4.8h、5.0h、5.5h、6.0h、6.5h、7.0h、7.5h or 7.8 hours, and the specific point values between the above point values are limited in space and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values included in the range.

Preferably, the reaction is carried out in a protective atmosphere, preferably nitrogen.

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

The solvent is not particularly limited, and exemplary ones include but are not limited to: any one or a combination of at least two of an alcohol solvent, an ether solvent, a ketone solvent, an aromatic hydrocarbon solvent, an ester solvent, a nitrogen-containing solvent, and a sulfur-containing solvent. Wherein the alcohol solvent comprises any one or a combination of at least two of methanol, ethanol, propanol or butanol; the ether solvent comprises any one or a combination of at least two of tetrahydrofuran, 1, 4-dioxane, methyl cellosolve, butyl cellosolve or propylene glycol monomethyl ether; the ketone solvent comprises any one or a combination of at least two of acetone, butanone, methyl isobutyl ketone and cyclohexanone; the aromatic hydrocarbon solvent comprises any one or a combination of at least two of toluene, xylene or benzene; the nitrogen-containing solvent comprises N, N-dimethylformamide and/or N, N-dimethylacetamide; the ester solvent comprises any one or a combination of at least two of ethyl acetate, butyl acetate, gamma-butyrolactone or ethoxyethyl acetate; the sulfur-containing solvent comprises dimethyl sulfoxide. From the viewpoint of solubility, any one or a combination of at least two of an alcohol solvent, a ketone solvent, an ester solvent, or a nitrogen-containing solvent is preferable; from the viewpoint of low toxicity, more preferable is any one or a combination of at least two of cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve or gamma-butyrolactone; in view of the high volatility and the fact that the solvent does not remain as a residual solvent in the post-production, any one or a combination of at least two of cyclohexanone, methyl isobutyl ketone, propylene glycol monomethyl ether, N-dimethylformamide and N, N-dimethylacetamide is further preferable.

The amount of the solvent may be appropriately adjusted according to 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. From the viewpoint of both solubility and reaction efficiency, the solvent mass is preferably 0.2 to 10 times, for example, 0.25 times, 0.3 times, 0.5 times, 0.7 times, 0.9 times, 1 times, 1.5 times, 2 times, 2.5 times, 3 times, 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, 9.5 times, or the like, more preferably 0.4 to 5 times, based on the sum of the respective raw materials.

Preferably, the (B) maleimide group-containing polymer is a polymer having a structure represented by formula iv or formula v:

In formula IV or formula V, A ₁ is selected from the group of the structure of formula (1) or formula (2), R ₆ is selected independently from the group consisting of hydrogen atoms and aliphatic hydrocarbon groups having 1 to 5 carbon atoms (e.g., 1,2, 3,4 or 5), and 1 < b.ltoreq.10 (b represents an average value of the number of repeating units contained in the polymer molecular chain, and may be an integer or a fraction, such as 1.1, 2, 2.1, 3, 3.1, 4, 4.1, 5, 5.1, 6, 6.1, 7, 7.1, 8, 8.1, 9, 9.1 or 10);

In the formula (1), R ₁ is independently selected from hydrogen atom, aliphatic hydrocarbon group with carbon number of 1-5 (such as 1,2,3, 4 or 5) or halogen atom, o is selected from integer of 0-4 (such as 0, 1,2,3 or 4);

In the formula (2), R _2a、R_2b、R_3a、R_3b is independently selected from a hydrogen atom, an aliphatic hydrocarbon group with a carbon number of 1-5 (such as 1,2,3, 4 or 5) or a halogen atom, A ₂ is selected from a single bond, a straight-chain or branched alkylene group with a carbon number of 1-5 (such as 1,2,3, 4 or 5), an ether group, a thioether group, a sulfonyl group, a ketone group or a group with a structure of the formula (2-1), and pa, pb, qa, qb is independently selected from an integer of 0-4 (such as 0, 1,2,3 or 4);

In the formula (2-1), R ₄、R₅ is independently selected from a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms (e.g., 1, 2, 3, 4 or 5), or a halogen atom, A ₃ is selected from a single bond, a straight-chain or branched alkylene group having 1 to 5 carbon atoms (e.g., 1, 2, 3, 4 or 5), an ether group, a thioether group, a sulfonyl group or a ketone group, and x and y are each independently selected from an integer of 0 to 4 (e.g., 0, 1, 2, 3 or 4).

Illustratively, the (B) maleimide-containing polymer may be any one or a combination of at least two of BMI-2000, BMI-2300, MIR-3000-70MT, MIR-5000-60T, DFE950 or DFE-958; the names listed above are trade names, wherein BMI-2000 and BMI-2300 are purchased from Japanese DAIWAKASEI, MIR-3000-70MT and MIR-5000-60T are purchased from Japanese NIPPON KAYAKU, and DFE950 and DFE-958 are purchased from Sichuan Dong materials science and technology.

In the invention, the structure of the (B) maleimide group-containing polymer contains more than 2 maleimide group functional groups, so that the problem of reduced crosslinking density after chain extension of the (A) modified maleimide compound is solved, tg (glass transition temperature) can be effectively improved, thermal expansion coefficient and dimensional change rate can be reduced, heat resistance can be improved, and the like. (A) The modified maleimide compound and the polymer (B) containing maleimide group are used together, so that the optimal effect in terms of performance can be achieved.

Preferably, the (C) other thermosetting resin includes any one or a combination of at least two of epoxy resin, phenolic resin, cyanate ester, active ester, polyphenylene ether resin, other maleimide resin, silicone resin, polybenzoxazine resin, polyimide resin, styrene-maleic anhydride resin, hydrocarbon resin, or acrylate resin.

Preferably, the epoxy resin refers to an epoxy resin having at least two epoxy groups in 1 molecule.

Preferably, the epoxy resin is selected from 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 novolac type epoxy resin, a bisphenol a type novolac epoxy resin, a dicyclopentadiene epoxy resin, a biphenyl epoxy resin, a dicyclopentadiene type novolac epoxy resin, a biphenyl novolac 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 epoxy resin, a polyethylene glycol type epoxy resin, tetraphenolethyl tetraglycidyl 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.

Preferably, in the thermosetting resin composition, the amount of the maleimide-group-containing polymer (B) is 0.1 to 300 parts by mass (for example, 0.1 part by mass, 1 part by mass, 5 parts by mass, 10 parts by mass, 50 parts by mass, 100 parts by mass, 200 parts by mass, 255 parts by mass, or 300 parts by mass), more preferably 10 to 150 parts by mass, based on 100 parts by mass of the modified maleimide compound (a); the amount of the other thermosetting resin (C) used is 0.1 to 300 parts by mass (for example, 0.1 part by mass, 1 part by mass, 5 parts by mass, 10 parts by mass, 50 parts by mass, 100 parts by mass, 200 parts by mass, 255 parts by mass or 300 parts by mass), and more preferably 10 to 150 parts by mass.

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

Preferably, in the thermosetting resin composition, the flame retardant is used in an amount of 0 to 150 parts by mass (for example, 5 parts by mass, 10 parts by mass, 50 parts by mass, 100 parts by mass, or 150 parts by mass) based on 100 parts by mass of the thermosetting resin composition; further preferably 10 to 100 parts by mass.

Preferably, the filler is used in an amount of 0 to 300 parts by mass (for example, 5 parts by mass, 10 parts by mass, 50 parts by mass, 100 parts by mass, 200 parts by mass, 255 parts by mass, or 300 parts by mass), and more preferably 10 to 150 parts by mass, based on 100 parts by mass of the thermosetting resin composition.

Preferably, the curing accelerator is used in an amount of 0 to 5 parts by mass (for example, 0.1 parts by mass, 1 part by mass, 2 parts by mass, 3 parts by mass, 4 parts by mass, or 5 parts by mass), and more preferably 0.01 to 3 parts by mass, based on 100 parts by mass of the thermosetting resin composition.

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 comprises an inorganic filler and/or an organic filler.

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 term "comprising" as used herein means that it may include, in addition to the components, other components which impart different properties to the thermosetting resin composition. In addition, the "including" of the present invention may be replaced by "being" or "consisting of … …" which are closed.

In another aspect, the present invention provides a resin dope comprising the thermosetting resin composition as described above and a solvent.

The preparation method of the resin glue solution provided by the invention comprises the following steps: firstly, putting the solid into the solvent, then adding the solvent, stirring until the solid is completely dissolved, then adding the liquid resin, the filler, the curing accelerator and the like, 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, and is preferably a ketone 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.

The present invention also relates to a cured product obtained by curing the thermosetting resin composition as described above.

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 reinforcing material, and the thermosetting resin composition as described above attached to the reinforcing material by impregnation drying.

Preferably, the reinforcing material includes any one of glass fiber cloth, organic fiber cloth, or glass fiber paper.

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 reinforcing material is not particularly limited; the thickness of the reinforcing material 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 reinforcing material is a reinforcing material 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 reinforcing 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 laminate 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 laminated substrate comprises the following steps: pressing metal foil on one side or two sides of a piece of prepreg, and curing to obtain the laminated substrate; or bonding at least two prepregs to form a laminated board, then laminating metal foils on one side or two sides of the laminated board, and curing to obtain the laminated substrate.

Preferably, the curing is performed in a hot press.

Preferably, the curing temperature is 150 to 250 ℃, for example 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃, 235 ℃, 240 ℃, 245 ℃, or the like.

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

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

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

In the invention, the combination of (A) modified maleimide compound, (B) maleimide group-containing polymer and (C) other thermosetting resin makes the cured product have low water absorption, high glass transition temperature, excellent dielectric properties, heat resistance, moist heat resistance, low thermal expansion coefficient, strong binding force with metal foil, and low dielectric properties after water absorption.

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.

Preparation example 1

A modified maleimide compound M-1 is prepared by the following steps:

Into a flask equipped with a thermometer, a reflux condenser, a stirrer and a nitrogen unit, 179.2g of 4,4 '-diphenylmethane bismaleimide (BMI, maleimide content 1mol, manufactured by K.I Co.), 34.8g of 9, 9-bis (4-aminophenyl) Fluorene (FDA) (primary amine equivalent 0.20mol, supplied by Shanghai Ala Biochemical Co., ltd.) and 142.7g of dimethylacetamide were charged, and reacted at 100℃for 4 hours to obtain a dimethylacetamide solution of the modified maleimide compound M-1, wherein the total of the unreacted 4,4' -diphenylmethane bismaleimide monomers in M-1 was 53% by weight as measured by GPC.

Preparation example 2

A modified maleimide compound M-2 is prepared by the following steps:

Into a flask equipped with a thermometer, a reflux condenser, a stirrer and a nitrogen unit, 285.3g (BMI-4000 produced by Dai chemical Co., ltd., maleimide group content: 1 mol) of 2,2 '-bis [4- (4-maleimidophenoxy) phenyl ] propane, 34.8g (available from Shanghai Ala Biotechnology Co., ltd., primary amino equivalent: 0.20 mol) of 9, 9-bis (4-aminophenyl) Fluorene (FDA) and 213.4g of dimethylacetamide were charged, and the mixture was reacted at 110℃for 5 hours to obtain a dimethylacetamide solution of the modified maleimide compound M-2, wherein the weight of the unreacted 2,2' -bis [4- (4-maleimidophenoxy) phenyl ] propane monomers in M-2 was found to be 71% by GPC.

Preparation example 3

A modified maleimide compound M-3 is prepared by the following steps:

221.3g (BMI-5100 produced by Daand chemical Co., ltd., maleimide group content: 1 mol), 42.1g (available from Shanghai Ala Biochemical Co., ltd., primary amino equivalent of 0.20 mol) of 2, 7-diamino-9, 9-di-n-octylfluorene and 175.6g of dimethylacetamide were charged into a flask equipped with a thermometer, reflux condenser, stirrer and nitrogen unit, and reacted at 110℃for 6 hours to obtain a dimethylacetamide solution of the modified maleimide compound M-3, wherein the total weight of unreacted 3,3' -dimethyl-5, 5' -diethyl-4, 4' -diphenylmethane bismaleimide monomers in M-3 was 34% as measured by GPC.

Preparation example 4

A modified maleimide compound M-4 is prepared by the following steps:

a flask equipped with a thermometer, a reflux condenser, a stirrer and a nitrogen unit was charged with 285.3g (BMI-4000 produced by Dai chemical Co., ltd., maleimide group content: 1 mol) of 2,2 '-bis [4- (4-maleimidophenoxy) phenyl ] propane, 34.8g (available from Shanghai Ala Biotechnology Co., ltd., primary amino equivalent: 0.20 mol), 5.5g (available from Shanghai Ala Biotechnology Co., ltd., primary amino equivalent: 0.05 mol) of p-aminophenol (PAP) and 217.1g of dimethylacetamide, and a dimethylacetamide solution of the modified maleimide compound M-4 was obtained by reacting at 110℃for 4.5 hours, wherein the total weight of the unreacted 2,2' -bis [4- (4-imidophenoxy) phenyl ] propane monomers in M-4 was 72% by GPC.

Preparation example 5

A modified maleimide compound M-5 is prepared by the following steps:

Into a flask equipped with a thermometer, a reflux condenser, a stirrer and a nitrogen unit, 179.2g of 4,4' -diphenylmethane bismaleimide (BMI, maleimide group content 1mol, manufactured by K.I Co.), 50.9g of 9,9' -bis (4-aminophenyl) fluorene-2, 7-disulfonic acid (primary amino equivalent 0.20mol, supplied by Shanghai Ala Biochemical technology Co., ltd.) and 153.4g of dimethylacetamide were charged, and reacted at 100℃for 4 hours to obtain a dimethylacetamide solution of the modified maleimide compound M-5, wherein the total weight of unreacted 4,4' -diphenylmethane bismaleimide monomers in M-5 was 49% as measured by GPC.

Comparative preparation example 1

A modified maleimide compound N-1 is prepared by the following steps:

Into a flask equipped with a thermometer, a reflux condenser, a stirrer and a nitrogen unit, 179.2g of 4,4 '-diphenylmethane bismaleimide (BMI produced by K.I Co., ltd., maleimide group content: 1 mol), 19.8g of 4,4' -diaminodiphenylmethane (DDM) (available from Shanghai Ala Biotech Co., ltd., primary amino equivalent of 0.20 mol) and 132.7g of dimethylacetamide were charged, and the reaction was carried out at 100℃for 4 hours to obtain a dimethylacetamide solution of the modified maleimide compound N-1, wherein the total of the weight of 4,4 '-diphenylmethane bismaleimide monomers which had not reacted in N-1 was measured by GPC was 50% based on the weight of 4,4' -diphenylmethane bismaleimide in the raw material to be produced.

Comparative preparation example 2

A modified maleimide compound N-2 is prepared by the following steps:

Into a flask equipped with a thermometer, a reflux condenser, a stirrer and a nitrogen unit, 179.2g of 4,4 '-diphenylmethane bismaleimide (BMI, maleimide content 1mol, manufactured by K.I Co.), 34.8g of 9, 9-bis (4-aminophenyl) Fluorene (FDA) (primary amine equivalent 0.20mol, supplied by Shanghai Ala Biochemical Co., ltd.) and 142.7g of dimethylacetamide were charged, and reacted at 100℃for 1 hour to obtain a dimethylacetamide solution of the modified maleimide compound N-2, wherein the total of the unreacted 4,4' -diphenylmethane bismaleimide monomers in N-2 was 84% by weight as measured by GPC.

Comparative preparation example 3

A modified maleimide compound N-3 is prepared by the following steps:

Into a flask equipped with a thermometer, a reflux condenser, a stirrer and a nitrogen unit, 179.2g of 4,4 '-diphenylmethane bismaleimide (BMI, maleimide content 1mol, manufactured by K.I Co.), 34.8g of 9, 9-bis (4-aminophenyl) Fluorene (FDA) (primary amine equivalent 0.20mol, supplied by Shanghai Ala Biochemical Co., ltd.) and 142.7g of dimethylacetamide were charged, and reacted at 105℃for 8 hours to obtain a dimethylacetamide solution of the modified maleimide compound N-3, wherein the total of the unreacted 4,4' -diphenylmethane bismaleimide monomers in N-3 was 24% by weight as measured by GPC.

Comparative preparation example 4

A modified maleimide compound N-4 is prepared by the following steps:

Into a flask equipped with a thermometer, a reflux condenser, a stirrer, and a nitrogen unit, 179.2g of 4,4' -diphenylmethane bismaleimide (BMI manufactured by K.I Co., ltd., maleimide group content: 1 mol), and 64.05g of 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl (TFMB) (available from Kabushiki Kaisha, primary amino equivalent of 0.20 mol) and 162.2g of dimethylacetamide, and reacting at 100 ℃ for 4 hours to obtain a dimethylacetamide solution of the modified maleimide compound N-4, wherein the total weight of unreacted 4,4' -diphenylmethane bismaleimide monomers in the N-4 measured by GPC is 95% of the weight of the 4,4' -diphenylmethane bismaleimide monomers in the preparation raw material.

The experimental materials used in the following examples and comparative examples of the present invention include:

(1) Maleimide group-containing polymer

B-1, polyphenyl methane maleimide, japanese DAIWAKASEI, BMI-2300;

B-2, polybiphenyl aralkyl maleimide, MIR-3000-70MT, japanese NIPPON KAYAKU company;

B-3, polyphenylene aralkyl maleimide, MIR-5000-60T, japanese NIPPON KAYAKU company;

(2) Other thermosetting resins

C-1, biphenyl type novolac epoxy resin, japanese NIPPON KAYAKU, NC-3000H;

c-2, modified polyphenylene ether resin, sabert base (SABIC), MX9000;

c-3, phenol novolac type multifunctional cyanate resin, longsha Japan, PT30;

(3) Packing material

D-1, spherical silica with a particle size of 0.5-2 microns, jiangsu-associated, DQS305;

(4) Flame retardant

E-1, 3-phenylenedi (di-2, 6-xylylene phosphate), japan Dagaku chemical, PX-200;

(5) Curing accelerator

F-1, 2-ethyl-4-methylimidazole, produced in Japan, four countries, 2E4MZ.

Example 1

A thermosetting resin composition, a prepreg and a laminated substrate containing the same, and a preparation method thereof are as follows:

(1) Uniformly mixing 40 parts by weight of polyphenyl methane maleimide B-1, 60 parts by weight of biphenyl type phenolic epoxy resin C-1, 100 parts by weight of modified maleimide compound M-1, 100 parts by weight of spherical silica D-1, 50 parts by weight of flame retardant E-1 and 0.25 part by weight of curing accelerator F-1 in a butanone (MEK) solvent to obtain a resin glue solution of the thermosetting resin composition, wherein the solid content of the resin glue solution is 70%; the above-mentioned glue solution was impregnated with 2116 glass cloth (from Shanghai Honghe), and then baked in an oven at 165℃for 5 minutes to prepare a prepreg, the thickness of which was controlled to 0.10mm.

(2) 7 Prepregs were stacked together, and on top of each other, a 35 μm HTE copper foil (from Sanin Malaysia) was stacked on each side, and a laminate substrate was produced under conditions of a curing temperature of 210℃and a curing pressure of 35Kg/cm ² and a curing time of 120 minutes.

Examples 2 to 9 and comparative examples 1 to 7

A thermosetting resin composition, and a prepreg and a laminate substrate comprising the same, the components and contents of the thermosetting resin composition are shown in tables 1 and 2, and the preparation methods of the prepreg and the laminate substrate are the same as in example 1; the parts by weight indicated in examples 1 to 9 and comparative examples 1 to 7 refer to parts by weight of a solid resin containing no solvent.

TABLE 1 resin composition of examples 1-9 (unit: parts by weight)

Table 2 resin compositions of comparative examples 1 to 7 (unit: parts by weight)

Performance test:

the laminate substrates provided in examples 1 to 9 and comparative examples 1 to 7 were subjected to performance test by the following method:

(1) Glass transition temperature (T _g): the test was performed using a TMA instrument according to the TMA test method specified in the standard IPC-TM-650.2.4.24.

(2) Coefficient of thermal expansion after Tg α2 (Z-CTE): the coefficient of thermal expansion α2 of the sample after Tg was measured by a TMA meter according to the CTE (Z-axis direction) test method specified in the standard IPC-TM-650.2.4.24.

(3) Dimensional change rate (Z-CTE): the dimensional change rate of the samples was measured at 50-260℃using TMA according to the CTE (Z-axis direction) test method specified in the standard IPC-TM-650.2.4.24.

(4) Dielectric constant D _k and dielectric dissipation factor D _f: d _k and D _f were measured at 1GHz according to the plate method specified in the standard IPC-TM-650.2.5.5.9;

Dielectric constant D _k after water absorption: a sample of the above-mentioned test dielectric constant D _k was taken, and after the water absorption treatment at 105 ℃/5h, the dielectric constant D _k,△D_k =dielectric constant D _k after water absorption-dielectric constant D _k before water absorption was measured.

(5) Thermal delamination time T300 (with copper): the measurement was performed by TMA according to the T300 (with copper) test method specified in standard IPC-TM-650.2.4.24.1.

(6) Wet heat resistance (PCT) evaluation: after 3 samples of 100X 100mm were held in a pressure cooker at 105℃and 103KPa for 5 hours, the samples were immersed in a solder bath at 288℃for 5 minutes, and observed for the occurrence of delamination bubbling or the like, the occurrence of 3 samples was marked as 3/3, the occurrence of 2 samples was marked as 2/3, the occurrence of 1 sample was marked as 1/3, and the occurrence of 0 sample was marked as 0/3.

(7) PCT water absorption: the measurement was performed according to the water absorption test method defined in the standard IPC-TM-650.2.6.2.1.

(8) Peel Strength (PS): the peel strength of the copper foil was tested according to the "accepted state" experimental conditions specified in the standard IPC-TM-650.4.8.

The specific test results are shown in table 3:

TABLE 3 physical Property test results of sheet materials

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As can be seen from the performance test data in table 3, the laminated substrates provided in examples 1 to 9 of the present invention have low dielectric constant (D _k), low dielectric loss (D _f), excellent heat resistance and wet heat resistance, and also have high glass transition temperature (T _g), low coefficient of thermal expansion (Z-CTE), low dimensional change rate (Z-CTE) and strong bonding force with metal foil, and can effectively suppress the change of Dk after water absorption; the dielectric constant is less than or equal to 3.81 (1 GHz), the dielectric loss factor is less than or equal to 0.0073 (1 GHz), the delta D _k change after water absorption is less than or equal to 0.08, the T300 (with copper) thermal delamination time is more than or equal to 60min, the glass transition temperature can reach 197-213 ℃, the thermal expansion coefficient alpha 2 after Tg is as low as 115-136 ppm/DEG C, the dimensional change rate (Z-CTE) is as low as 1.25-1.35%, the peeling strength can reach 1.19-1.26N/mm, the moisture and heat resistance can pass PCT (5 h) test, and the application requirements of the high-performance laminated board can be fully met.

The modified maleimide compound M-2 used in example 2 was left for two weeks to exhibit slight crystallization; compared with M-2, the modified maleimide compound M-4 of the embodiment 4 adopts p-aminophenol with a structure of formula III in synthesis, and the M-4 still has no crystallization after being placed for one month, so that the solubility and storage stability of the modified maleimide compound are improved.

The raw materials for preparing the modified maleimide compound used in comparative example 1, which did not contain the fluorenyl-containing aromatic diamine compound of the structure of formula I or formula II, resulted in a laminated substrate inferior to example 1 in thermal expansion coefficient, dimensional change rate, dielectric constant, dielectric loss, heat resistance, water absorption, moist heat resistance and ability to suppress Dk change after water absorption.

The total weight of the unreacted 4,4 '-diphenylmethane bismaleimide monomers in the modified maleimide compound in the comparative example 2 is 84% of the weight of the 4,4' -diphenylmethane bismaleimide in the preparation raw material, and the modified maleimide compound is severely crystallized after being placed for 4 hours, so that glue can not be prepared, and prepregs and laminated substrates can not be prepared.

The weight of the unreacted 4,4' -diphenylmethane bismaleimide monomer in the modified maleimide compound in the comparative example 3 is 24% in total, and the two phases are separated when the modified maleimide compound is compounded, so that the compound cannot be compounded, and the prepreg and the laminated substrate cannot be prepared.

The modified maleimide compound used in comparative example 4 was prepared from a low-polarity and large-volume fluorine-containing diamine TFMB, but the fluorine-containing diamine had poor reactivity, and the total weight of unreacted 4,4 '-diphenylmethane bismaleimide monomers in the modified maleimide compound was 95% based on the weight of 4,4' -diphenylmethane bismaleimide in the preparation, and the modified maleimide compound was left to stand for 1 hour to cause severe crystallization, and thus, no glue could be formulated, and no prepreg and laminate substrate could be prepared.

Comparative example 5 the maleimide group-containing polymer was not used, and the resulting laminated substrate was inferior to example 1 in terms of thermal expansion coefficient, dimensional change rate, dielectric constant, dielectric loss, heat resistance, water absorption, wet heat resistance and ability to suppress Dk change after water absorption.

Comparative example 6 the resulting laminated substrate was inferior to example 1 in terms of thermal expansion coefficient, dimensional change rate, dielectric constant, dielectric loss, heat resistance, water absorption, wet heat resistance and ability to suppress Dk change after water absorption without using a modified maleimide compound.

Comparative example 7 was free of other thermosetting resins, and the resulting laminated substrate was inferior to example 1 in terms of thermal expansion coefficient, dimensional change rate, dielectric constant, dielectric loss, heat resistance, water absorption, wet heat resistance and ability to suppress Dk change after water absorption.

The applicant states that the present invention is described by way of the above examples as to the resin composition of the present invention and its use, but the present invention is not limited to the above examples, i.e., it is not meant that the present invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (10)

1. A thermosetting resin composition, characterized in that the thermosetting resin composition comprises (a) a modified maleimide compound, (B) a maleimide group-containing polymer and (C) other thermosetting resin, wherein the preparation raw materials of the (a) modified maleimide compound comprise: a maleimide group-containing compound and a fluorenyl group-containing aromatic diamine compound having a structure represented by the formula I or formula II;

wherein X is each independently selected from substituted or unsubstituted C6-C20 arylene, -X ₁-Y-X₂ -, substituted or unsubstituted C1-C20 straight or branched alkylene, substituted or unsubstituted C3-C20 cycloalkylene, or a single bond;

Z is independently selected from substituted or unsubstituted C6-C20 aryl, X ₃-Y-X₂ -, substituted or unsubstituted C1-C20 straight or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl or hydrogen atom;

each R is independently selected from a hydrogen atom, a halogen atom, an epoxy group, an amino group, a hydroxyl group, an acrylate group, a mercapto group, a sulfonic acid group, or a carboxyl group;

X ₁、X₂ is each independently selected from substituted or unsubstituted C6-C12 arylene;

X ₃ is each independently selected from substituted or unsubstituted C6-C12 aryl;

Y is independently selected from C1-C5 straight chain or branched chain alkylene, -O-, -S-, single bond, sulfonyl or sulfoxide;

X, Z each independently selected from C1-C5 straight or branched alkyl;

The total weight of the monomer containing maleimide group which is not reacted in the modified maleimide compound (A) accounts for 30-80% of the maleimide group-containing compound in the preparation raw material.

2. The thermosetting resin composition according to claim 1, wherein each X is independently selected from the group consisting of a substituted or unsubstituted C1 to C10 linear or branched alkylene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene ether group;

Each Z is independently selected from a substituted or unsubstituted C1-C10 straight or branched alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl ether group;

X, Z each independently selected from C1-C5 straight or branched alkyl;

Preferably, the maleimide group-containing compound is a maleimide group-containing monomer;

Preferably, the maleimide group-containing monomer includes N, N '-ethylene bismaleimide, N' -hexamethylene bismaleimide, N '- (1, 3-phenylene) bismaleimide, N' - (1, 3- (2-methylphenyl)) bismaleimide, N '- (1, 3- (4-methylphenyl)) bismaleimide, N, N' - (1, 4-phenylene) bismaleimide, 4 '-diphenylmethane bismaleimide, bis (3-methyl-4-maleimidophenyl) methane, bis (3, 5-dimethyl-4-maleimidophenyl) methane, 3' -dimethyl-5, 5 '-diethyl-4, 4' -diphenylmethane bismaleimide, bis (3-ethyl-4-maleimidophenyl) methane, bis (3, 5-diethyl-4-maleimidophenyl) methane, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) ketone, bis (4-maleimidocyclohexyl) methane, 1, 4-bis (4-maleimidophenyl) cyclohexane, 1, 4-bis (maleimidomethyl) cyclohexane, 1, 6-bismaleimide-2, 4-trimethyl-hexane, 1, 4-bis (maleimidomethyl) benzene, 1, 3-bis (4-maleimidophenoxy) benzene, 1, 3-bis (3-maleimidophenoxy) benzene, bis (4- (3-maleimidophenoxy) phenyl) methane, bis (4- (4-maleimidophenoxy) phenyl) methane, 1-bis (4- (3-maleimidophenoxy) phenyl) ethane, 1-bis (4- (4-maleimidophenoxy) phenyl) ethane, 1, 2-bis (4- (3-maleimidophenoxy) phenyl) ethane, 1, 2-bis (4- (4-maleimidophenoxy) phenyl) ethane 2, 2-bis (4- (3-maleimidophenoxy) phenyl) propane, 2' -bis [4- (4-maleimidophenoxy) phenyl ] propane, 2-bis (4- (3-maleimidophenoxy) phenyl) butane, 2-bis (4- (4-maleimidophenoxy) phenyl) butane, 4' -bis (3-maleimidophenoxy) biphenyl, 4' -bis (4-maleimidophenoxy) biphenyl, bis (4- (3-maleimidophenoxy) phenyl) ketone, any one or a combination of at least two of bis (4- (4-maleimidophenoxy) phenyl) ketone, bis (4- (3-maleimidophenoxy) phenyl) ether or bis (4- (4-maleimidophenoxy) phenyl) ether;

Further preferably, the maleimide group-containing monomer comprises any one or a combination of at least two of 4,4' -diphenylmethane bismaleimide, N ' - (1, 3-phenylene) bismaleimide, 2' -bis [4- (4-maleimidophenoxy) phenyl ] propane, 3' -dimethyl-5, 5' -diethyl-4, 4' -diphenylmethane bismaleimide, N ' - (1, 3- (4-methylphenyl)) bismaleimide, or 1, 6-bismaleimide-2, 4-trimethyl-hexane.

3. The thermosetting resin composition according to claim 1 or 2, wherein the fluorenyl-containing aromatic diamine compound is used in an amount of 0.05 to 1mol, more preferably 0.1 to 0.75mol, based on 1mol of maleimide groups in the maleimide-containing compound;

preferably, the preparation raw material also comprises a hydroxyl-containing monoamine compound with a structure shown as a formula III;

HO-A-NH₂

A formula III;

wherein A is selected from substituted or unsubstituted C6-C20 arylene, -X ₁-Y-X₂ -, substituted or unsubstituted C1-C20 straight or branched alkylene, substituted or unsubstituted C3-C20 cycloalkylene;

X ₁、X₂ is each independently selected from substituted or unsubstituted C6-C12 arylene;

Y is selected from C1-C5 straight chain or branched chain alkylene, -O-, -S-, single bond, sulfonyl or sulfoxide;

the substituent group of the substituent A is selected from C1-C5 straight-chain or branched-chain alkyl;

Preferably, the hydroxyl-containing monoamine compound is used in an amount of 0 to 0.25mol based on 1mol of maleimide groups in the maleimide-containing compound;

Preferably, the total amount of amine groups in the fluorenyl-containing aromatic diamine compound and the hydroxyl-containing monoamine compound is 0.05 to 1mol, more preferably 0.1 to 0.6mol, based on 1mol of maleimide groups in the maleimide-containing compound.

4. A thermosetting resin composition according to any one of claims 1 to 3, wherein the maleimide group-containing polymer (B) is a polymer having a structure represented by formula iv or formula v:

In the formula IV or the formula V, A ₁ is selected from a group with a structure of a formula (1) or a formula (2), R ₆ is independently selected from a hydrogen atom or an aliphatic hydrocarbon group with a carbon number of 1-5, and b is more than 1 and less than or equal to 10;

In the formula (1), R ₁ is independently selected from hydrogen atom, aliphatic hydrocarbon group with 1-5 carbon atoms or halogen atom, and o is selected from integer of 0-4;

In the formula (2), R _2a、R_2b、R_3a、R_3b is independently selected from a hydrogen atom, an aliphatic hydrocarbon group with 1-5 carbon atoms or a halogen atom, A ₂ is selected from a single bond, a straight-chain or branched alkylene group with 1-5 carbon atoms, an ether group, a thioether group, a sulfonyl group, a ketone group or a group with the structure of the formula (2-1), and pa, pb, qa, qb is independently selected from an integer of 0-4;

In the formula (2-1), R ₄、R₅ is independently selected from a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, A ₃ is selected from a single bond, a straight-chain or branched-chain alkylene group having 1 to 5 carbon atoms, an ether group, a thioether group, a sulfonyl group or a ketone group, and x and y are independently selected from integers of 0 to 4.

5. The thermosetting resin composition according to any one of claims 1 to 4, wherein the (C) other thermosetting resin comprises any one or a combination of at least two of epoxy resin, phenolic resin, cyanate ester, active ester, polyphenylene ether resin, other maleimide resin, silicone resin, polybenzoxazine resin, polyimide resin, styrene-maleic anhydride resin, hydrocarbon resin, or acrylate resin;

Preferably, the epoxy resin refers to an epoxy resin having at least two epoxy groups in 1 molecule;

Preferably, the epoxy resin is selected from 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 novolac type epoxy resin, a bisphenol a type novolac epoxy resin, a dicyclopentadiene epoxy resin, a biphenyl epoxy resin, a dicyclopentadiene type novolac epoxy resin, a biphenyl novolac 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 epoxy resin, a polyethylene glycol type epoxy resin, tetraphenolethyl tetraglycidyl 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;

Preferably, the amount of the maleimide-group-containing polymer (B) used in the thermosetting resin composition is 0.1 to 300 parts by mass, more preferably 10 to 150 parts by mass, based on 100 parts by mass of the modified maleimide compound (a); the amount of the other thermosetting resin (C) is 0.1 to 300 parts by mass, more preferably 10 to 150 parts by mass;

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

6. A resin dope comprising the thermosetting resin composition according to any one of claims 1 to 5 and a solvent.

7. 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 5.

8. A prepreg comprising a reinforcing material, and the thermosetting resin composition according to any one of claims 1 to 5 attached to the reinforcing material by impregnation drying;

preferably, the reinforcing material includes any one of glass fiber cloth, organic fiber cloth, or glass fiber paper.

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

10. A laminated film comprising a reinforcing material film or a metal foil, and the thermosetting resin composition according to any one of claims 1 to 5 coated on at least one surface of the reinforcing material film or the metal foil.