Modified maleimide prepolymer, resin composition and use thereof

Abstract

The application provides a modified maleimide prepolymer, a resin composition and application thereof. The modified maleimide prepolymer is obtained by reacting a maleimide mixture, a diamino compound and a reaction aid; wherein the maleimide mixture comprises a first maleimide compound shown in structural formula (1), a second maleimide compound shown in structural formula (2) and a third maleimide compound shown in structural formula (3); structural formula (1), R is hydrogen, C1-C5 alkyl, phenyl or n is an integer of 1-10; structural formula (2), R1 and R2 are hydrogen or C1-C5 alkyl; structural formula (3).

Description

Technical Field

[0001] This application relates to the field of electronic materials technology, and in particular to a modified maleimide prepolymer and a resin composition containing the modified maleimide prepolymer, and their applications. Background Technology

[0002] Bismaleimide resin (BMI), a key resin material for high-performance packaging substrates, has attracted much attention due to its excellent heat resistance and high modulus. However, it has a significant drawback in actual processing: it is difficult to dissolve in low-boiling-point solvents such as acetone and ethanol, and can only be dissolved using highly toxic and expensive high-boiling-point polar solvents such as DMF. This not only brings environmental hazards and process challenges in the preparation of prepregs, but may also damage the quality of copper-clad laminate substrates. Therefore, improving the solubility of BMI has become a key issue restricting the green and high-performance development of the industry.

[0003] Existing technologies often employ prepolymer modification methods—such as introducing structural units like allyl groups, aromatic diamines, or cyanate esters—to enhance the resin's compatibility with common solvents. While this method alleviates processing difficulties to some extent, it is limited by the inherent chemical structure of BMI. If unreacted maleimide groups remain after curing, it will lead to increased water absorption and deterioration of dielectric properties in the composite material, thereby threatening the long-term reliability of the final product. Summary of the Invention

[0004] The purpose of this application is to provide a modified maleimide prepolymer, which is modified by mixing three maleimide compounds with different structures and reactivity, thus solving the problems of poor solubility and reactivity in the prior art.

[0005] To achieve one of the above-mentioned objectives, one embodiment of this application provides a modified maleimide prepolymer obtained by reacting a mixture of maleimides, a diamino compound, and a reaction aid. The maleimide mixture includes a first maleimide compound represented by structural formula (1), a second maleimide compound represented by structural formula (2), and a third maleimide compound represented by structural formula (3): Structural formula (1), where R is hydrogen, C1-C5 alkyl, phenyl, or... n is an integer from 1 to 10; Structural formula (2), where R1 and R2 are hydrogen or C1-C5 alkyl groups; Structural formula (3).

[0006] In one embodiment of this application, the weight ratio of the maleimide mixture, the diamino compound, and the reaction aid is 100:(5-70):(0.1-10).

[0007] In one embodiment of this application, the weight ratio of the first maleimide compound, the second maleimide compound, and the third maleimide compound is (10-60):(5-50):(5-60).

[0008] In one embodiment of this application, the diamino compound is selected from at least one of aromatic diamino compounds, aliphatic diamino compounds, and organosilicon diamino compounds.

[0009] In one embodiment of this application, the aromatic diamino compound is selected from at least one of unsubstituted phenylenediamine, methylphenylenediamine, dimethylphenylenediamine, trimethylphenylenediamine, tetramethylphenylenediamine, diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, diaminobenzophenone, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminobiphenyl, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl fluorene, and diaminodiphenyl anthraquinone. The aliphatic diamino compound is selected from dimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, diaminocyclohexane, tetramethyldisiloxanediamine, polydiamine, or diaminocyclohexylmethane. The organosilicon diamino compound has the following structural formula (4): The structure is (4), where n is an integer from 1 to 20 and m is an integer from 1 to 5.

[0010] In one embodiment of this application, the amino equivalent of the diamino compound is 400-1600 g / mol.

[0011] In one embodiment of this application, the reaction aid is aminophenol, carboxylic acid, or carboxylic anhydride.

[0012] In one embodiment of this application, the aminophenol is 4-aminophenol; the carboxylic acid is at least one selected from maleic acid, phthalic acid, succinic acid and acetic acid; and the carboxylic anhydride is at least one selected from citric anhydride, phthalic anhydride, succinic anhydride and acetic anhydride.

[0013] In one embodiment of this application, when the maleimide mixture, the diamino compound, and the reaction aid react, the third maleimide compound is first pre-reacted with the diamino compound and the reaction aid to obtain a pre-reactant. When the number average molecular weight of the pre-reactant reaches 700-1500, the first maleimide compound and the second maleimide compound are added sequentially.

[0014] One embodiment of this application also provides a resin composition comprising: The aforementioned modified maleimide prepolymer: 50-100 parts by weight; At least one of epoxy resin, polyphenylene ether resin, and cyanate ester resin; The components are: epoxy resin (5-30 parts by weight), polyphenylene ether resin (30-100 parts by weight), and cyanate ester resin (10-60 parts by weight).

[0015] In one embodiment of this application, the epoxy resin is selected from at least one of biphenyl-type epoxy resin, naphthalene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol M-type epoxy resin, bisphenol F-type epoxy resin, DCPD-type epoxy resin, and phenolic epoxy resin.

[0016] In one embodiment of this application, the polyphenylene ether resin has vinyl or methacrylate groups at its ends.

[0017] In one embodiment of this application, the cyanate resin is selected from one or more of bisphenol A cyanate resin, bisphenol F cyanate resin, bisphenol S cyanate resin, bisphenol E cyanate resin, bisphenol M cyanate resin, phosphorus-containing cyanate resin, phenolic cyanate resin, biphenyl cyanate resin, naphthalene ring cyanate resin, and dicyclopentadiene cyanate resin.

[0018] One embodiment of this application also provides the application of the aforementioned resin composition in prepreg, laminate, and circuit board.

[0019] One or more technical solutions provided in this application have at least the following technical effects or advantages: This application modifies maleimide compounds by mixing three compounds with different structures and reactivity and then reacting them with a diamino compound. This process not only maintains the high heat resistance of the maleimide compounds themselves but also effectively adjusts their solvent solubility and reactivity. The different maleimide resins maintain excellent compatibility, and the reaction with the diamino compound proceeds fully, maintaining suitable resin flowability. When the modified maleimide prepolymer provided in this application is combined with other resins and applied to circuit boards, it can significantly improve the thickness uniformity and substrate quality of the substrate material, ultimately yielding a copper-clad laminate material with high heat resistance, low CTE, high modulus, and high processability. Attached Figure Description

[0020] Figure 1 These are the rheological test data of Embodiment 1 and Comparative Example 1 of this application. Detailed Implementation

[0021] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0022] This application provides a modified maleimide prepolymer obtained by reacting a mixture of maleimides, a diamino compound, and a reaction aid. The maleimide mixture includes a first maleimide compound represented by structural formula (1), a second maleimide compound represented by structural formula (2), and a third maleimide compound represented by structural formula (3): Structural formula (1), where R is hydrogen, C1-C5 alkyl, phenyl, or... n is an integer from 1 to 10; Structural formula (2), where R1 and R2 are hydrogen or C1-C5 alkyl groups; Structural formula (3).

[0023] This application modifies maleimide compounds by mixing three compounds with different structures and reactivity and then reacting them with a diamino compound. This process not only maintains the high heat resistance of the maleimide compounds themselves but also effectively adjusts their solvent solubility and reactivity. The different maleimide resins maintain excellent compatibility, and the reaction with the diamino compound proceeds fully, maintaining suitable resin flowability. When the modified maleimide prepolymer provided in this application is combined with other resins and applied to circuit boards, it can significantly improve the thickness uniformity and substrate quality of the substrate material, ultimately yielding a copper-clad laminate material with high heat resistance, low CTE, high modulus, and high processability.

[0024] Furthermore, the weight ratio of the maleimide mixture, the diamino compound, and the reaction aid is 100:(5-70):(0.1-10).

[0025] Preferably, the weight ratio of the first maleimide compound, the second maleimide compound, and the third maleimide compound is (10-60):(5-50):(5-60).

[0026] More preferably, the weight ratio of the first maleimide compound, the second maleimide compound, and the third maleimide compound is (30-50):(10-40):(10-40).

[0027] Preferably, R1 and R2 in the structural formula (2) are hydrogen.

[0028] The first maleimide compound shown in structural formula (1) can be prepared by Nippon Kayaku Co., Ltd., with the brand name MIR-3000. The second maleimide compound shown in structural formula (2) can be prepared by KI Co., Ltd., with the brand name BMI. The third maleimide compound shown in structural formula (3) can be prepared by KI Co., Ltd., with the brand name BMI-80.

[0029] In some embodiments of this application, the diamino compound is selected from at least one of aromatic diamino compounds, aliphatic diamino compounds, and organosilicon diamino compounds.

[0030] Preferably, the aromatic diamino compound is selected from at least one of unsubstituted phenylenediamine, methylphenylenediamine, dimethylphenylenediamine, trimethylphenylenediamine, tetramethylphenylenediamine, diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, diaminobenzophenone, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminobiphenyl, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl nitrate, diaminodiphenyl fluorene, and diaminoanthraquinone.

[0031] The aliphatic diamino compound is selected from dimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, diaminocyclohexane, tetramethyldisiloxanediamine, polydiamine, or diaminocyclohexylmethane.

[0032] The organosilicon diamino compound has the following structural formula (4): The structure is (4), where n is an integer from 1 to 20 and m is an integer from 1 to 5.

[0033] The various substances listed above as diamino compounds include all isomers of the listed substances.

[0034] The organosilicon diamino compound shown in the above structural formula (4) is a diamino compound prepared by Shin-Etsu Chemical Co., Ltd. with the brand name KF8010, X-22-161A or X-22-161B, DOWSIL™ BY 16-853.

[0035] Preferably, the amino equivalent of the diamino compound is 400-1600 g / mol.

[0036] In some embodiments of this application, the reaction aid is aminophenol, carboxylic acid, or carboxylic anhydride.

[0037] Preferably, the aminophenol is 4-aminophenol; the carboxylic acid is at least one selected from maleic acid, phthalic acid, succinic acid and acetic acid; and the carboxylic anhydride is at least one selected from citric anhydride, phthalic anhydride, succinic anhydride and acetic anhydride.

[0038] In some embodiments of this application, when the maleimide mixture, the diamino compound, and the reaction aid react, the third maleimide compound is first pre-reacted with the diamino compound and the reaction aid to obtain a pre-reactant. When the number average molecular weight of the pre-reactant reaches 700-1500, the first maleimide compound and the second maleimide compound are added sequentially.

[0039] Through extensive experiments, the inventors discovered that maleimide compounds with different structures exhibit significant differences in solubility and reactivity. To ensure a thorough cross-linking reaction between the diamino compound and the maleimide compound, the slower-reacting third maleimide compound was pre-reacted with the diamino compound, followed by sequential reactions with the faster-reacting first and second maleimide compounds. This process not only resulted in a better reaction between the diamino compound and maleimide compounds with different structures but also yielded a highly homogeneous prepolymer solution. This improved resin flowability during subsequent lamination, further enhancing the uniformity of the board thickness and the quality of the substrate (residue defects such as voids and resin deficiencies).

[0040] The number-average molecular weight of the pre-reactants was calculated using gel permeation chromatography (GPC) based on the calibration curve of standard polystyrene.

[0041] In the aforementioned prepolymerization reaction, the reaction temperature is controlled at 80-150℃ and the reaction time is 0.5-6 hours.

[0042] Preferably, the reaction temperature is controlled at 100-130℃ and the reaction time is 2-5 hours.

[0043] This application also provides a resin composition comprising: The aforementioned modified maleimide prepolymer: 50-100 parts by weight; At least one of epoxy resin, polyphenylene ether resin, and cyanate ester resin; The components are: epoxy resin (5-30 parts by weight), polyphenylene ether resin (30-100 parts by weight), and cyanate ester resin (10-60 parts by weight).

[0044] That is, 5-30 parts by weight of epoxy resin can be mixed with 50-100 parts by weight of modified maleimide prepolymer, or 30-100 parts by weight of polyphenylene ether resin can be mixed with 50-100 parts by weight of modified maleimide prepolymer, or 10-60 parts by weight of cyanate ester resin can be mixed with 50-100 parts by weight of modified maleimide prepolymer, or the aforementioned two resins can be mixed with modified maleimide prepolymer in the corresponding weight parts.

[0045] In some embodiments of this application, the epoxy resin is selected from at least one of biphenyl-type epoxy resin, naphthalene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol M-type epoxy resin, bisphenol F-type epoxy resin, DCPD-type epoxy resin, and phenolic epoxy resin.

[0046] Preferably, the epoxy resin is a biphenyl-type epoxy resin, with the following structure: The structure is (5), where n is an integer from 1 to 20.

[0047] When biphenyl-type epoxy resin is selected in the resin composition, it exhibits excellent compatibility with modified maleimide prepolymer and improves the coefficient of thermal expansion of the substrate.

[0048] Biphenyl-type epoxy resin can be prepared by Nippon Kayaku, with the brand name NC3000.

[0049] In some embodiments of this application, the polyphenylene ether resin has vinyl or methacrylate groups at its ends.

[0050] Preferably, the vinyl group is vinylbenzyl ( ) or vinylphenyl ( ); methacrylate group is .

[0051] Polyphenylene ether resins with terminal vinyl benzyl groups are more conducive to improving dielectric properties and heat resistance of resin compositions. Polyphenylene ether resins with terminal vinyl benzyl groups are prepared by Mitsubishi Chemical Corporation, with grades such as OPE-2st 1200 (number average molecular weight Mn of 1200) and / or OPE-2st 2200 (number average molecular weight Mn of 2200). Polyphenylene ethers with terminal methacrylate groups are prepared by Sabiq, with the grade SA9000.

[0052] In some embodiments of this application, the cyanate resin is selected from one or more of the following: bisphenol A type cyanate resin, bisphenol F type cyanate resin, bisphenol S type cyanate resin, bisphenol E type cyanate resin, bisphenol M type cyanate resin, phosphorus-containing cyanate resin, phenolic type cyanate resin, biphenyl type cyanate resin, naphthalene ring type cyanate resin, and dicyclopentadiene type cyanate resin.

[0053] In some embodiments of this application, the resin composition further includes 30-200 parts by weight of inorganic filler, wherein the inorganic filler is spherical silica, alumina or aluminum hydroxide, more preferably spherical silica.

[0054] In some embodiments of this application, the resin composition further includes 0.001-5 parts by weight of a catalyst selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-dodecylimidazole or 1-cyanoethyl-2-methylimidazole.

[0055] In some embodiments of this application, the resin composition may also contain dyes, such as fluorescent dyes or black dyes.

[0056] Preferably, the fluorescent dye is a pyrazoline compound, and the black dye is liquid or powdered carbon black, pyridine complex, azo complex, quinone compound, zirconium nitride, titanium oxide, titanium nitride, cobalt chromium metal oxide, or azazine, etc.

[0057] This application also provides an application of the aforementioned resin composition in prepreg, laminate, and circuit board.

[0058] Specifically, this application also provides a semi-cured sheet, including a reinforcing material and the aforementioned resin composition. The preparation method of the semi-cured sheet is as follows: the resin composition is dissolved in a solvent to form an adhesive solution, and then the reinforcing material is immersed in the adhesive solution. The immersed reinforcing material is then taken out and baked at 100~180℃ for 1~15 minutes. After drying, the semi-cured sheet is obtained.

[0059] The solvent is selected from at least one of acetone, butanone, methyl isobutyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, and cyclohexane.

[0060] The reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics. Preferably, the reinforcing material is glass fiber cloth; the glass fiber cloth is preferably open-fiber cloth or flat cloth; the glass fiber cloth is preferably E glass fiber cloth, T glass fiber cloth, S glass fiber cloth, or Q glass fiber cloth.

[0061] Furthermore, when glass fiber cloth is used as the reinforcing material, it is chemically treated with a coupling agent to improve the interfacial bonding between the resin composition and the glass fiber cloth. Epoxy silane coupling agents or amino silane coupling agents are preferred to provide good water and heat resistance.

[0062] This application also provides a laminate, including a prepreg and a metal foil disposed on at least one surface of the prepreg; or including a composite sheet formed by stacking multiple prepregs and a metal foil disposed on at least one surface of the composite sheet.

[0063] The laminate is prepared by the following method: metal foil is coated onto one or both surfaces of a prepreg, or at least two prepregs are stacked to form a composite sheet, and metal foil is coated onto one or both surfaces of the composite sheet. The laminate is then hot-pressed to obtain a metal foil laminate. The hot-pressing conditions are: pressing at 0.2~2MPa and 150~250℃ for 2~6 hours.

[0064] Preferably, the metal foil is selected from copper foil or aluminum foil. The thickness of the metal foil is 5 micrometers, 8 micrometers, 12 micrometers, 18 micrometers, 35 micrometers, or 70 micrometers.

[0065] This invention also provides a circuit board, including at least one of the aforementioned prepreg and laminate.

[0066] The technical solution of this application will be further described below with reference to some specific embodiments.

[0067] Synthesis Example 1: Modified maleimide prepolymer A 15.0g of organosilicon diamino compound (Shin-Etsu Chemical, X-22-161A), 40g of maleimide compound (structural formula (3), BMI-80 manufactured by KI, Japan), 2g of 4-aminophenol, and 150g of propylene glycol monomethyl ether were added to a reaction vessel equipped with a thermometer, a stirring device, a reflux condenser, and a volume of 1L. After reacting at 120°C for 2 hours, the number-average molecular weight of the prepolymer was 910 as determined by gel permeation chromatography (GPC). Then, 30g of maleimide compound (structural formula (1), MIR-3000 manufactured by Nippon Kayaku) and 30g of maleimide compound (structural formula (2), BMI manufactured by KI, Japan) were added sequentially, and the reaction was continued at 120°C for 2 hours to obtain the final modified maleimide prepolymer A.

[0068] Synthesis Example 2: Modified Maleimide Prepolymer B 12.0 g of organosilicon diamino compound (Shin-Etsu Chemical, X-22-161B), 20 g of maleimide compound (structural formula (3), BMI-80 manufactured by KI, Japan), 2 g of 4-aminophenol, and 150 g of propylene glycol monomethyl ether were added to a reaction vessel equipped with a thermometer, a stirring device, a reflux condenser, and a volume of 1 L. After reacting at 120 °C for 2 h, the number average molecular weight of the prepolymer was 880 as determined by gel permeation chromatography (GPC). Then, 40 g of maleimide compound (structural formula (1), MIR-3000 manufactured by Nippon Kayaku) and 40 g of maleimide compound (structural formula (2), BMI manufactured by KI, Japan) were added sequentially, and the reaction was continued at 120 °C for 2 h to obtain the final modified maleimide prepolymer B.

[0069] Synthesis Example 3: Modified maleimide prepolymer C 12.0g of organosilicon diamino compound (Shin-Etsu Chemical, X-22-161B), 5g of diaminodiphenyl sulfone (DDS), 20g of maleimide compound (structural formula (3), BMI-80 manufactured by KI, Japan), 1.5g of 4-aminophenol, and 180g of propylene glycol monomethyl ether were added to a reaction vessel equipped with a thermometer, a stirring device, a reflux condenser, and a volume of 1L. After reacting at 130°C for 1.5h, the number average molecular weight of the prepolymer was 870 as determined by gel permeation chromatography (GPC). Then, 50g of maleimide compound (structural formula (1), MIR-3000 manufactured by Nippon Kayaku) and 30g of maleimide compound (structural formula (2), BMI manufactured by KI, Japan) were added sequentially, and the reaction was continued at 130°C for 2 hours to obtain the final modified maleimide prepolymer C.

[0070] Synthesis Example 4: Modified maleimide prepolymer D 25g of diaminodiphenyl sulfone (DDS), 50g of maleimide compound (structural formula (3), Japanese KI BMI-80), 2g of 4-aminophenol, and 180g of propylene glycol monomethyl ether were added to a reaction vessel equipped with a thermometer, a stirring device, a reflux condenser, and a volume of 1L. After reacting at 120°C for 2 hours, the number average molecular weight of the prepolymer was 980 as determined by gel permeation chromatography (GPC). Then, 30g of maleimide compound (structural formula (1), Japanese Kayaku Corporation MIR-3000) and 20g of maleimide compound (structural formula (2), Japanese KI BMI) were added sequentially, and the reaction was continued at 130°C for 2 hours to obtain the final modified maleimide prepolymer D.

[0071] Synthesis Example 5: Modified Maleimide Prepolymer G 15.0g of organosilicon diamino compound (Shin-Etsu Chemical, X-22-161A), 40g of maleimide compound (structural formula (1), Nippon Kayaku Corporation MIR-3000), 2g of 4-aminophenol, and 150g of propylene glycol monomethyl ether were added to a reaction vessel equipped with a thermometer, a stirring device, a reflux condenser, and a volume of 1L. After reacting at 120°C for 2 hours, the number-average molecular weight of the prepolymer was 1050 as determined by gel permeation chromatography (GPC). Then, 30g of maleimide compound (structural formula (3), Nippon KI Corporation BMI-80) and 30g of maleimide compound (structural formula (2), Nippon KI Corporation BMI) were added sequentially, and the reaction was continued at 120°C for 2 hours to obtain the final modified maleimide prepolymer G.

[0072] Synthesis Example 6: Modified Maleimide Prepolymer H 15.0g of organosilicon diamino compound (Shin-Etsu Chemical, X-22-161A), 40g of maleimide compound (structural formula (2), BMI manufactured by KI, Japan), 2g of 4-aminophenol, and 150g of propylene glycol monomethyl ether were added to a reaction vessel equipped with a thermometer, a stirring device, a reflux condenser, and a volume of 1L. After reacting at 130°C for 2.5h, the number average molecular weight of the prepolymer was 1590 as determined by gel permeation chromatography (GPC). Then, 30g of maleimide compound (structural formula (1), MIR-3000 manufactured by Nippon Kayaku) and 30g of maleimide compound (structural formula (3), BMI80 manufactured by KI, Japan) were added sequentially, and the reaction was continued at 120°C for 2 hours to obtain the final modified maleimide prepolymer H.

[0073] Comparative Synthesis Example 1: Modified Maleimide Prepolymer E 15.0g of organosilicon diamino compound (Shin-Etsu Chemical, X-22-161A), 100g of maleimide compound (structural formula (3), BMI-80, KI, Japan), 2g of 4-aminophenol, and 150g of propylene glycol monomethyl ether were added to a reaction vessel equipped with a thermometer, a stirring device, a reflux condenser, and a volume of 1L. The reaction was carried out at 120°C for 4h to obtain the final modified maleimide prepolymer E.

[0074] Comparative Synthesis Example 2: Modified Maleimide Prepolymer F 15.0g of organosilicon diamino compound (Shin-Etsu Chemical, X-22-161A), 100g of maleimide compound (structural formula (1), Nippon Kayaku Corporation MIR-3000), 2g of 4-aminophenol, and 150g of propylene glycol monomethyl ether were added to a reaction vessel equipped with a thermometer, a stirring device, a reflux condenser, and a volume of 1L. The reaction was carried out at 120°C for 4h to obtain the final modified maleimide prepolymer F.

[0075] Table 1

[0076] Note: The epoxy resin used is NC3000 manufactured by Nippon Kayaku, the polyphenylene ether resin used is SA9000 manufactured by Sabiq, the cyanate ester resin used is naphthalene ring cyanate ester resin manufactured by Tianqi, and the spherical silica used is Lianrui manufactured with a D50 of 3.0μm.

[0077] Weigh the corresponding solid substances according to the data in Table 1. Adjust the solid content of each solid substance to 65% using methyl ethyl ketone (MEK). Coat the MEK onto 2116E fiberglass cloth, soak it, and then place it in a 160℃ forced-air drying oven for 5 minutes to make a semi-cured sheet.

[0078] Two prepreg sheets obtained above were neatly stacked to form a laminate. A 12μm low-profile electrolytic copper foil was stacked on the top and bottom sides of the laminate, respectively. The laminate was then placed in a vacuum hot press and pressed at 2 MPa pressure and 220°C for 1.52 hours to obtain a laminate. Specific performance tests are shown in Table 2. The rheological test data for Example 1 and Comparative Example 1 are as follows: Figure 1 .

[0079] Table 2

[0080] The above performance testing methods are as follows: (1) Tg (DMA): The dynamic thermomechanical analysis (DMA) method was used to determine Tg according to the DMA method specified in IPC-TM-6502.4.24.4. The unit of Tg is °C. (2) Peel strength (PS): The peel strength of the sheet was tested according to the experimental conditions of “after thermal stress” in IPC-TM-650 2.4.8. The unit of peel strength is N / mm. (3) Thickness uniformity: Five samples were taken from the four corners and the middle of the board to test the thickness of the board. If the thickness of the board meets the third-level tolerance of copper clad laminate, the thickness uniformity is good. If the thickness of the board does not meet the third-level tolerance of copper clad laminate, the thickness uniformity is poor. (4) CTE: A laminate with a length of 60 mm, a width of 4 mm, and a thickness of 0.20 mm was used as the sample. The glass fiber warp direction was Y and the glass fiber weft direction was X. The sample was dried in an oven at 105℃ for 1 h and then cooled to room temperature in a desiccator. The mechanical thermal analysis (TMA) method was used for measurement. The heating rate was 10℃ / min. The temperature was increased from room temperature to 300℃ twice. After the first heating was completed and the sample was cooled to room temperature, it was put back into place for the second heating. The result was the planar thermal expansion coefficient at the second heating from 50℃ to 130℃, and the unit was ppm / ℃. (5) Modulus: Tested using IPC-TM650 2.4.24.4 method; (6) Sub-apparent quality: After the copper foil is etched away, the internal quality of the substrate is observed under a microscope. When there are no defects such as resin deficiency, white lines, voids, or dried flowers, the sub-apparent quality is good. When there are defects such as resin deficiency, white lines, voids, or dried flowers, the sub-apparent quality is poor.

[0081] It should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This way of describing the specification is only for clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

[0082] The detailed descriptions listed above are merely specific descriptions of feasible implementation methods of this application and are not intended to limit the scope of protection of this application. All equivalent implementation methods or modifications made without departing from the spirit of the art of this application should be included within the scope of protection of this application.

Claims

1. A modified maleimide prepolymer, characterized in that, It is obtained by reacting a mixture of maleimide, a diamino compound, and a reaction auxiliaries; The maleimide mixture includes a first maleimide compound represented by structural formula (1), a second maleimide compound represented by structural formula (2), and a third maleimide compound represented by structural formula (3): Structural formula (1), where R is hydrogen, C1-C5 alkyl, phenyl, or... n is an integer from 1 to 10; Structural formula (2), where R1 and R2 are hydrogen or C1-C5 alkyl groups; Structural formula (3) When maleimide mixtures, diamino compounds and reaction aids react, the third maleimide compound is first pre-reacted with the diamino compound and reaction aids to obtain a pre-reactant. When the number average molecular weight of the pre-reactant reaches 700-1500, the first maleimide compound and the second maleimide compound are added sequentially.

2. The modified maleimide prepolymer according to claim 1, characterized in that, The weight ratio of the maleimide mixture, the diamino compound, and the reaction aid is 100:(5-70):(0.1-10).

3. The modified maleimide prepolymer according to claim 2, characterized in that, The weight ratio of the first maleimide compound, the second maleimide compound, and the third maleimide compound is (10-60):(5-50):(5-60).

4. The modified maleimide prepolymer according to claim 1, characterized in that, The diamino compound is selected from at least one of aromatic diamino compounds, aliphatic diamino compounds, and organosilicon diamino compounds.

5. The modified maleimide prepolymer according to claim 4, characterized in that, The aromatic diamino compound is selected from at least one of the following: unsubstituted phenylenediamine, methylphenylenediamine, dimethylphenylenediamine, trimethylphenylenediamine, tetramethylphenylenediamine, diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, diaminobenzophenone, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminobiphenyl, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl fluorene, and diaminoanthraquinone. The aliphatic diamino compound is selected from dimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, diaminocyclohexane, tetramethyldisiloxanediamine, polydiamine, or diaminocyclohexylmethane. The organosilicon diamino compound has the following structural formula (4): The structure is (4), where n is an integer from 1 to 20 and m is an integer from 1 to 5.

6. The modified maleimide prepolymer according to claim 1, characterized in that, The amino equivalent of the diamino compound is 400-1600 g / mol.

7. The modified maleimide prepolymer according to claim 1, characterized in that, The reaction aid is aminophenol, carboxylic acid, or carboxylic anhydride.

8. The modified maleimide prepolymer according to claim 7, characterized in that, The aminophenol is 4-aminophenol; the carboxylic acid is at least one of maleic acid, phthalic acid, succinic acid and acetic acid; the carboxylic anhydride is at least one of citric anhydride, phthalic anhydride, succinic anhydride and acetic anhydride.

9. A resin composition, characterized in that, include: The modified maleimide prepolymer according to any one of claims 1 to 8: 50-100 parts by weight; At least one of epoxy resin, polyphenylene ether resin, and cyanate ester resin; The components are: epoxy resin (5-30 parts by weight), polyphenylene ether resin (30-100 parts by weight), and cyanate ester resin (10-60 parts by weight).

10. The resin composition according to claim 9, characterized in that, The epoxy resin is selected from at least one of biphenyl-type epoxy resin, naphthalene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol M-type epoxy resin, bisphenol F-type epoxy resin, DCPD-type epoxy resin, and phenolic epoxy resin.

11. The resin composition according to claim 9, characterized in that, The polyphenylene ether resin has vinyl or methacrylate groups at its ends.

12. The resin composition according to claim 9, characterized in that, The cyanate resin is selected from one or more of the following: bisphenol A type cyanate resin, bisphenol F type cyanate resin, bisphenol S type cyanate resin, bisphenol E type cyanate resin, bisphenol M type cyanate resin, phosphorus-containing cyanate resin, phenolic type cyanate resin, biphenyl type cyanate resin, naphthalene ring type cyanate resin, and dicyclopentadiene type cyanate resin.

13. The use of a resin composition as described in any one of claims 9 to 12 in prepreg, laminate, or circuit board.

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