Modified maleimide prepolymer and resin composition

Abstract

The invention provides a modified maleimide prepolymer, a resin composition and application of the modified maleimide prepolymer, and the modified maleimide prepolymer comprises 10-100 parts by weight of a haplotype maleimide compound as shown in a structural formula (1); 10 to 100 parts by weight of a polymerizable maleimide compound represented by a structural formula (2-1) and / or a structural formula (2-2); 5-70 parts by weight of a modifier; 0.01 to 10 parts by weight of a reaction auxiliary agent; the structural formula (1), the structural formula (2-1) and the structural formula (2-2) are shown in the specification, A and B are the same or different and are selected from C1-C5 alkylene groups, or R1 to R46 are the same or different and are selected from hydrogen or C1-C5 alkyl groups, R01 to R012 are the same or different and are C1-C5 alkylene groups or-O-, X1 and X2 are the same or different and are selected from hydrogen and C1-C5 alkyl groups, a and b are integers in the range of 0-4, m is an integer in the range of 1-20, and n is an integer in the range of 1-20. The modified maleimide prepolymer provided by the invention has relatively good reactivity and solubility.

Description

Technical Field

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

[0002] Bismaleimide resin (BMI) is a type of high-temperature resistant, high-modulus resin, and one of the indispensable main resin materials in the field of encapsulation substrates. However, bismaleimide resin is difficult to dissolve in low-boiling-point solvents such as acetone and ethanol, and can only dissolve in high-boiling-point, highly polar solvents (highly toxic and expensive), such as N-dimethylformamide (DMF). If large quantities of these solvents are used in the preparation of prepregs, it will not only cause serious environmental pollution, but also bring great difficulties to the processing technology, and even affect the quality of the copper-clad laminate substrate. Therefore, improving the solubility of bismaleimide resin has always been an important research topic both domestically and internationally. Furthermore, maleimide resin also has certain structural limitations. When unreacted maleimide groups are present in the cured product, the water absorption rate of the prepreg or copper-clad laminate increases during use, affecting the overall performance of the substrate. Summary of the Invention

[0003] The purpose of this application is to provide a modified maleimide prepolymer, which uses a mixture of monomeric maleimide compounds and polymeric maleimide compounds to adjust the solubility and reactivity of the maleimide prepolymer, thereby solving the problem of poor solubility and reactivity of maleimide resins in the prior art.

[0004] To achieve one of the aforementioned objectives, one embodiment of this application provides a modified maleimide prepolymer, comprising: The monomeric maleimide compound shown in structural formula (1): 10-100 parts by weight; Polymerizable maleimide compounds represented by structural formula (2-1) and / or structural formula (2-2): 10-100 parts by weight; Modifier: 5-70 parts by weight; Reaction aid: 0.01-10 parts by weight; Structural formula (1) Structural formula (2-1). Structural formula (2-2). Wherein, A and B may be the same or different, and are selected from C1-C5 alkylene groups. , , or R1 to R46 may be the same or different, selected from hydrogen or C1-C5 alkyl groups; R01 to R012 may be the same or different, and are unlinked, C1-C5 alkylene groups or -O- groups; X1 and X2 may be the same or different, selected from hydrogen, C1-C5 alkyl groups or... a and b are integers from 0 to 4, m is an integer from 1 to 20, and n is an integer from 1 to 20.

[0005] As a further improvement of one embodiment of this application, the absolute difference in gelation time between the monomeric maleimide compound and the polymeric maleimide compound is 100-850 seconds.

[0006] As a further improvement of one embodiment of this application, the modifier is at least one of allyl compounds, aromatic amine compounds, cyanate compounds, and amino organosilicon resins.

[0007] As a further improvement of one embodiment of this application, the allyl compound is selected from at least one of diallyl bisphenol A, diallyl bisphenol F, diallyl bisphenol S, allyl phenolic resin, allyl phenolic resin, and diallyl diphenyl ether. The aromatic amine 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 fluorene, and diaminodiphenyl anthraquinone. The cyanate compound is selected from at least one of bisphenol A cyanate compound, bisphenol F cyanate compound, bisphenol E cyanate compound, bisphenol M cyanate compound, DCPD cyanate compound, naphthyl cyanate compound, phenolic cyanate compound, and biphenyl cyanate compound; The amino silicone resin is shown in structural formula (12): The structure is (12), where n is an integer from 1 to 20 and m is an integer from 1 to 5.

[0008] As a further improvement of one embodiment of this application, the ratio of total maleimide equivalent to amino equivalent of the monomeric maleimide compound and the polymeric maleimide compound is 1.5-8.

[0009] As a further improvement of one embodiment of this application, the amino equivalent of the amino organosilicon resin is 400-1600 g / mol.

[0010] As a further improvement to one embodiment of this application, the reaction aid is aminophenol, carboxylic acid, or carboxylic anhydride.

[0011] As a further improvement of one embodiment of this application, the aminophenol is 4-aminophenol, the carboxylic acid is at least one of maleic acid, phthalic acid, succinic acid and acetic acid, and the carboxylic anhydride is at least one of citric anhydride, phthalic anhydride, succinic anhydride and acetic anhydride.

[0012] One embodiment of this application also provides a resin composition, characterized in that it comprises: The aforementioned modified maleimide prepolymer: 5-100 parts by weight; At least one of epoxy resin and polyphenylene ether resin, wherein the epoxy resin is 5-30 parts by weight and the polyphenylene ether resin is 30-100 parts by weight.

[0013] As a further improvement of one embodiment of this application, when the resin composition includes an epoxy resin, 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.

[0014] As a further improvement to one embodiment of this application, the epoxy resin is selected from at least one of structural formulas (13) to (16): The structural formula (13) is given, where n is an integer from 1 to 20; The structure is (14), where p is an integer from 1 to 20; The structure is (15), where n is an integer from 1 to 20; The structure is (16), where n is an integer from 1 to 20.

[0015] As a further improvement of one embodiment of this application, when the resin composition includes a polyphenylene ether resin, the polyphenylene ether resin includes the structure shown in (17) or / and (18): Structural formula (17). Structural formula (18); In the above polyphenylene ether resin structural formula, R1, R2, R3, R4, R5, R6, R7, and R8 are each independently selected from hydrogen or any C1-C5 alkyl group, and Y is a non-linking bond, -O-, methylene, ethylene, etc. , or n is an integer from 1 to 20, and m is an integer from 1 to 20.

[0016] As a further improvement of one embodiment of this application, the resin composition further includes 0.001-5 parts by weight of a catalyst, said catalyst being selected from at least one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-dodecylimidazole, 1-cyanoethyl-2-methylimidazole, or modified imidazoles with the following structures: Among them, R3, R4, R5, and R6 may be the same or different, and are methyl, ethyl, or tert-butyl; A is methylene, ethylene, or... , , Or aromatic hydrocarbon groups; Among them, R3, R4, R5, and R6 may be the same or different, and are methyl, ethyl, or tert-butyl; B is methylene, ethylene, or... , or .

[0017] One embodiment of this application also provides the application of the resin composition as described above in prepreg, laminate, and circuit board.

[0018] One or more technical solutions provided in this application have at least the following technical effects or advantages: The modified maleimide prepolymer provided in this application uses a mixture of monomeric maleimide compounds and polymeric maleimide compounds. The monomeric maleimide compounds are introduced into the crosslinking system of the polymeric maleimide compounds, which not only effectively adjusts the solvent solubility and reactivity of the maleimide compounds and further improves their high heat resistance, but also ensures that the reaction with the modifier is fully carried out, maintaining suitable flowability. Detailed Implementation

[0019] 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.

[0020] This application provides a modified maleimide prepolymer, comprising: The monomeric maleimide compound shown in structural formula (1): 10-100 parts by weight; Polymerizable maleimide compounds represented by structural formula (2-1) and / or structural formula (2-2): 10-100 parts by weight; Modifier: 5-70 parts by weight; Reaction aid: 0.01-10 parts by weight; Structural formula (1) Structural formula (2-1). Structural formula (2-2). Wherein, A and B may be the same or different, and are selected from C1-C5 alkylene groups. , , or R1 to R46 may be the same or different, selected from hydrogen or C1-C5 alkyl groups; R01 to R012 may be the same or different, and are unlinked, C1-C5 alkylene groups or -O- groups; X1 and X2 may be the same or different, selected from hydrogen, C1-C5 alkyl groups or... a and b are integers from 0 to 4, m is an integer from 1 to 20, and n is an integer from 1 to 20.

[0021] In this context, R01 to R012 being "no connecting bonds" specifically means that the benzene ring connected to any one of R01 to R012 is directly connected to other groups. For example, R03 has benzene rings on both sides, and the two benzene rings are directly connected without being linked by any groups. In structural formula (2-1), a and b represent the number of times the corresponding groups X2 and X1 are connected to the benzene rings they are connected to, without limiting the connection sites.

[0022] Preferably, the content of monomeric bismaleimide compound is 30-70 parts by weight, and the content of polymeric bismaleimide compound is 30-70 parts by weight.

[0023] As a further improvement of one embodiment of this application, the absolute difference in gelation time between the monomeric maleimide compound and the polymeric maleimide compound is 100-850 seconds.

[0024] The gelation time of the maleimide compound was determined by the hot plate method, as follows: Drop the adhesive solution into a 200°C hot plate and start stirring and timing. The gelation time is when the adhesive solution becomes viscous, extracts without fibers, or separates from the hot plate.

[0025] The adhesive is a mixture of maleimide compound and modifier (amino organosilicon), with a maleimide equivalent to amino equivalent ratio of 5.

[0026] Further preferably, the absolute difference in gelation time between the monomeric maleimide compound and the polymeric maleimide compound is 200-500 seconds.

[0027] This application uses a mixture of monomeric maleimide compounds and polymeric maleimide compounds with a certain range of gelation time differences. The monomeric maleimide compound is introduced into the crosslinking system of the polymeric maleimide compound, which not only effectively adjusts the solvent solubility and reactivity of the maleimide compound and further improves the high heat resistance of the maleimide compound, but also allows the reaction with the modifier to proceed fully, maintaining suitable fluidity.

[0028] When the modified maleimide prepolymer in this application is applied to electronic substrates, it can effectively improve the thickness uniformity and substrate quality of the substrate material, ultimately obtaining copper clad laminate materials with high heat resistance, low CTE, high modulus and high processability.

[0029] Preferably, the monomeric maleimide compound is at least one of structural formulas (3) to (7): Structural formula (3). Structural formula (4) Structural formula (5), Structural formula (6) Structural formula (7); Polymerized maleimide compounds are at least one of the following structural formulas (8) to (11): Structure (8), where m is an integer from 1 to 20; The structure is (9), where n is an integer from 1 to 20; The structure is (10), where n is an integer from 1 to 20; The structure is (11), where n is an integer from 1 to 20.

[0030] Among them, monomeric maleimide compounds were prepared by KI Chemicals (Japan) under the brand names BMI, BMI-70, and BMI-80, while those prepared by Yamato Chemicals (Japan) under the brand names BMI1000 and BMI3000. Polymerized maleimide compounds were prepared by Yamato Chemicals (Japan) under the brand name BMI2300, by Nippon Kayaku Co. (Japan) under the brand names MIR3000 or MIR5000, and by DIC Corporation (Japan) under the brand names X-9500 or X-470.

[0031] In some embodiments of this application, during the preparation of the modified maleimide prepolymer, the monomeric maleimide compound and the polymeric maleimide compound with the longer gelation time are added first to the reaction vessel along with the modifier and reaction aid. When the number average molecular weight of the prepolymer reaches 700-1500, the other compound with the shorter gelation time is added, and the reaction continues to obtain the final prepolymer. The prepolymerization reaction temperature is 80-150°C, and the reaction time is 0.5-6 hours.

[0032] In some embodiments of this application, the modifier is at least one of allyl compounds, aromatic amine compounds, cyanate compounds, and amino organosilicon resins.

[0033] Preferably, the allyl compound is selected from at least one of diallyl bisphenol A, diallyl bisphenol F, diallyl bisphenol S, allyl phenol-oxygen resin, allyl phenol-formaldehyde resin, and diallyl diphenyl ether. The aromatic amine 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 fluorene, and diaminoanthraquinone.

[0034] The cyanate compound is selected from at least one of the following: bisphenol A cyanate compound, bisphenol F cyanate compound, bisphenol E cyanate compound, bisphenol M cyanate compound, DCPD cyanate compound, naphthyl cyanate compound, phenolic cyanate compound, and biphenyl cyanate compound.

[0035] The amino silicone resin is shown in structural formula (12): The structure is (12), where n is an integer from 1 to 20 and m is an integer from 1 to 5.

[0036] The various substances listed above as modifiers include all isomers of the listed substances.

[0037] The modifier is preferably an amino silicone resin with the structural formula (13). The long-chain siloxane is distributed in the high-rigidity maleimide crosslinking network system, which effectively improves the toughness of the substrate material, thereby reducing the coefficient of thermal expansion and maintaining high heat resistance. It also exhibits very good compatibility with long-chain amino silicone resin, monomeric maleimide compound and polymeric maleimide compound, further improving the overall performance of the board.

[0038] In some embodiments of this application, the ratio of total maleimide equivalent to amino equivalent of the monomeric maleimide compound and the polymeric maleimide compound is 1.5-8.

[0039] Preferably, the ratio of total maleimide equivalent to amino equivalent in monomeric maleimide compounds and polymeric maleimide compounds is 2.5-5.

[0040] In some embodiments of this application, the amino equivalent of the amino organosilicon resin is 400-1600 g / mol.

[0041] The amino silicone resin shown in the above structural formula (4) is an amino silicone resin with the brand name KF8010, X-22-161A or X-22-161B, DOWSIL™ BY 16-853 prepared by Shin-Etsu Chemical Co., Ltd.

[0042] In some embodiments of this application, the reaction aid is aminophenol, carboxylic acid, or carboxylic anhydride.

[0043] 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.

[0044] This application also provides a resin composition comprising: The aforementioned modified maleimide prepolymer: 5-100 parts by weight; At least one of epoxy resin and polyphenylene ether resin, wherein the epoxy resin is 5-30 parts by weight and the polyphenylene ether resin is 30-100 parts by weight.

[0045] Preferably, when the resin composition includes an epoxy resin, 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] More preferably, the epoxy resin is selected from at least one of structural formulas (13) to (16): The structural formula (13) is given, where n is an integer from 1 to 20; The structure is (14), where p is an integer from 1 to 20; The structure is (15), where n is an integer from 1 to 20; The structure is (16), where n is an integer from 1 to 20.

[0047] The epoxy resin can be selected from at least one of the following: HP6000 prepared by DIC Corporation of Japan, NC3000, NC7000, or NC3100 prepared by Nippon Kayaku Co., Ltd., or ESN475V or ESN485 prepared by Nippon Steel Chemical Co., Ltd.

[0048] When the resin composition includes a polyphenylene ether resin, the polyphenylene ether resin comprises the structure shown in (17) or / and (18): Structural formula (17). Structural formula (18); In the above polyphenylene ether resin structural formula, R1, R2, R3, R4, R5, R6, R7, and R8 are each independently selected from hydrogen or any C1-C5 alkyl group, and Y is a non-linking bond, -O-, methylene, ethylene, etc. , or n is an integer from 1 to 20, and m is an integer from 1 to 20. Y means no connecting bond, specifically meaning that the benzene rings on the left and right sides of Y in structural formula (18) and structural formula (19) are directly connected.

[0049] In some embodiments of this application, the resin composition further includes 0.001-5 parts by weight of a catalyst, said catalyst being selected from at least one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-dodecylimidazole, 1-cyanoethyl-2-methylimidazole, or modified imidazoles with the following structures: Among them, R3, R4, R5, and R6 may be the same or different, and are methyl, ethyl, or tert-butyl; A is methylene, ethylene, or... , , Or aromatic hydrocarbon groups; Among them, R3, R4, R5, and R6 may be the same or different, and are methyl, ethyl, or tert-butyl; B is methylene, ethylene, or... , or .

[0050] In some embodiments of this application, the resin composition further includes 30-200 parts by weight of inorganic filler.

[0051] The inorganic filler is selected from at least one of the following: fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.

[0052] Preferably, the inorganic filler content is 50-150 parts by weight.

[0053] Preferably, the inorganic filler is spherical silica, alumina, or aluminum hydroxide, and more preferably spherical silica.

[0054] Furthermore, the inorganic filler is surface-treated with a silane coupling agent, which is at least one of an aminosilane coupling agent, a carbon-carbon double bond silane coupling agent, or an epoxysilane coupling agent.

[0055] Preferably, the silane coupling agent is selected from the following structures: Structural formula (19), brand name is KBM-573 prepared by Shin-Etsu Chemical Co., Ltd., and Z-6883 prepared by Dow Corning Co., Ltd. The structural formula (20) is KBM-1003 prepared by Shin-Etsu Chemical Co., Ltd. The structural formula (21) is KBM-1403 prepared by Shin-Etsu Chemical Co., Ltd.

[0056] In some embodiments of this application, the resin composition further includes 5-50 parts by weight of a flame retardant, which is selected from bromine-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, organosilicon flame retardants, organometallic salt flame retardants, etc.

[0057] Specifically, the brominated flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, styrene bromide, or tetrabromophthalamide.

[0058] Phosphorus-based flame retardants are selected from inorganic phosphorus, phosphate esters, phosphoric acid, hypophosphoric acid, phosphorus oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. (m is an integer from 1 to 5) Organophosphorus compounds including 10-phenyl-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, tris(2,6-dimethylphenyl)phosphine, phosphazenes, and modified phosphazenes. In the above structures, the DOPO group is... .

[0059] Nitrogen-based flame retardants are selected from triazine compounds, cyanuric acid compounds, isocyanate compounds, phenothiazines, etc.

[0060] Organosilicon flame retardants are selected from organosilicon oils, organosilicon rubbers, organosilicon resins, etc.

[0061] Organometallic flame retardants are selected from ferrocene, acetylacetone metal complexes, organometallic carbonyl compounds, etc.

[0062] Preferably, the flame retardant is selected from phosphazene with the brand name SPB-100 prepared by Otsuka Chemicals of Japan; and modified phosphazene with the brands BP-PZ, PP-PZ, SPCN-100, SPV-100 and SPB-100L.

[0063] This application also provides an application of the aforementioned resin composition in prepreg, laminate, and circuit board.

[0064] 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°C for 1-15 minutes. After drying, the semi-cured sheet is obtained.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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 0.2-2 MPa and 150-250℃ for 2-4 hours.

[0070] 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.

[0071] This invention also provides a circuit board, including at least one of the aforementioned prepreg and laminate.

[0072] The technical solution of this application will be further described below with reference to some specific embodiments.

[0073] Synthesis Example 1: Modified maleimide prepolymer A 15.0g of diamino silicone resin (Shin-Etsu Chemical, X-22-161A), 40g of polymeric maleimide compound (structural formula (10), BMI2300 manufactured by Nippon Chemicals, gelation time 230s), 60g of monomeric maleimide compound (structural formula (4), BMI80 manufactured by KI, Nippon Chemicals, gelation time 985s), 2g of 4-aminophenol, and 200g of propylene glycol monomethyl ether were added to a reaction vessel equipped with a thermometer, stirring device, reflux condenser, and a volume of 1L. The reaction was carried out at 120℃ for 4.5h to obtain the final modified maleimide prepolymer A.

[0074] Synthesis Example 2: Modified Maleimide Prepolymer B In a reaction vessel equipped with a thermometer, a stirring device, a reflux condenser, and a volume of 1L, 25.0g of diallyl bisphenol A compound (CAS: 1745-89-7), 60g of polymeric maleimide compound (structural formula (10), manufactured by Nippon Chemicals BMI2300, gelation time 230s), 40g of monomeric maleimide compound (structural formula (4), manufactured by KI Japan BMI80, gelation time 985s), 2g of 4-aminophenol, and 200g of DMF solvent were added. The reaction was carried out at 120℃ for 5h to obtain the final modified maleimide prepolymer B.

[0075] Synthesis Example 3: Modified maleimide prepolymer C In a reaction vessel equipped with a thermometer, a stirring device, a reflux condenser, and a volume of 1L, 40.0g of bisphenol A cyanate compound (Tenki Corporation, monomer), 60g of monomeric maleimide compound (structural formula (5), BMI70 manufactured by KI Japan, gelation time 780s), 40g of polymeric maleimide compound (structural formula (8), MIR3000 manufactured by Nippon Kayaku Corporation, gelation time 521s), 2g of 4-aminophenol, and 200g of DMF solvent were added. The reaction was carried out at 110℃ for 5.5h to obtain the final modified maleimide prepolymer C.

[0076] Synthesis Example 4: Modified maleimide prepolymer D 20g of diaminodiphenyl sulfone (DDS), 50g of monomeric maleimide compound (structural formula (4), BMI80 manufactured by KI in Japan, gelation time 985s), 50g of polymeric maleimide compound (structural formula (8), MIR3000 manufactured by Nippon Kayaku, gelation time 521s), 2.5g of 4-aminophenol and 200g 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℃ for 2h to obtain the final modified maleimide prepolymer D.

[0077] Synthesis Example 5: Modified maleimide prepolymer E (Optimal solution among different addition methods) 15.0g of diamino silicone resin (Shin-Etsu Chemical, X-22-161A), 60g of monomeric maleimide compound (structural formula (4), BMI80 manufactured by KI, Japan, gelation time 985s), 2g of 4-aminophenol and 200g of propylene glycol monomethyl ether were added to a reaction vessel equipped with a thermometer, stirring device, reflux condenser and a volume of 1L. The reaction was carried out at 120°C for 2.5h. Then, 40g of polymeric maleimide compound (structural formula (10), BMI2300 manufactured by Kasei Corporation, Japan, gelation time 521s) was added and the reaction was continued for 3h to obtain the final modified maleimide prepolymer E.

[0078] Synthesis Example 6: Modified Maleimide Prepolymer H 15.0g of diamino silicone resin (Shin-Etsu Chemical, X-22-161A), 25g of polymeric maleimide compound (structural formula (10), BMI2300 manufactured by Japan Chemicals, gelation time 230s), 75g of monomeric maleimide compound (structural formula (3), BMI1000 manufactured by Japan Daiwa Chemicals, gelation time 1205s), 2g of 4-aminophenol, and 200g of propylene glycol monomethyl ether were added to a reaction vessel equipped with a thermometer, stirring device, reflux condenser, and 1L volume. The reaction was carried out at 120℃ for 4.5h to obtain the final modified maleimide prepolymer H.

[0079] Comparative Synthesis Example 1: Modified Maleimide Prepolymer F (Compared with Example 1, only monomer type was used) 15.0g of diamino silicone resin (Shin-Etsu Chemical, X-22-161A), 100g of monomeric maleimide compound (structural formula (4), BMI80, KI, Japan), 2g of 4-aminophenol, and 200g 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 4.5h to obtain the final modified maleimide prepolymer F.

[0080] Comparative Synthesis Example 2: Modified maleimide prepolymer G (compared to Example 1, only the polymeric form was used) 15.0g of diamino silicone resin (Shin-Etsu Chemical, X-22-161A), 100g of polymeric maleimide compound (structural formula (10), Nippon Kasei BMI2300), 2g of 4-aminophenol, and 200g 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 4.5h to obtain the final modified maleimide prepolymer G.

[0081] Table 1

[0082] Note: The epoxy resin used is HP6000 manufactured by DIC, and the polyphenylene ether resin used is OPE-2St manufactured by Mitsubishi.

[0083] Weigh the corresponding solid substances according to the data in Table 1. Adjust the solid content of each solid substance to 60% using methyl ethyl ketone (MEK). Coat the adhesive onto 7628E fiberglass cloth, soak it, and then place it in a 155℃ forced-air drying oven for 5 minutes to make a semi-cured sheet.

[0084] One of the prepreg sheets obtained above is neatly stacked to form a laminate. A 18μm low profile electrolytic copper foil is stacked on the top and bottom sides of the laminate, respectively. Then, it is placed in a vacuum hot press and pressed at a pressure of 2Mpa and a temperature of 220℃ for 2 hours to obtain a laminate. The specific performance test results are shown in Table 2.

[0085] Table 2

[0086] The above performance testing methods are as follows: (1) Tg (DMA): The dynamic thermomechanical analysis (DMA) method was used to determine the Tg in accordance with the DMA method specified in IPC-TM-6502.4.24.4. The unit 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.

[0087] 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.

[0088] 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, include: The monomeric maleimide compound shown in structural formula (1): 10-100 parts by weight; Polymerizable maleimide compounds represented by structural formula (2-1) and / or structural formula (2-2): 10-100 parts by weight; Modifier: 5-70 parts by weight; Reaction aid: 0.01-10 parts by weight; Structural formula (1) Structural formula (2-1). Structural formula (2-2). Wherein, A and B may be the same or different, and are selected from C1-C5 alkylene groups. , , or R1 to R46 may be the same or different, selected from hydrogen or C1-C5 alkyl groups; R01 to R012 may be the same or different, and are unlinked, C1-C5 alkylene groups or -O- groups; X1 and X2 may be the same or different, selected from hydrogen, C1-C5 alkyl groups or... a and b are integers from 0 to 4, m is an integer from 1 to 20, and n is an integer from 1 to 20.

2. The modified maleimide prepolymer according to claim 1, characterized in that, The absolute difference in gelation time between the monomeric maleimide compound and the polymeric maleimide compound is 100-850 seconds.

3. The modified maleimide prepolymer according to claim 1, characterized in that, The modifier is at least one of allyl compounds, aromatic amine compounds, cyanate compounds, and amino organosilicon resins.

4. The modified maleimide prepolymer according to claim 3, characterized in that, The allyl compound is selected from at least one of diallyl bisphenol A, diallyl bisphenol F, diallyl bisphenol S, allyl phenolic resin, allyl phenolic resin, and diallyl diphenyl ether. The aromatic amine 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 fluorene, and diaminodiphenyl anthraquinone. The cyanate compound is selected from at least one of bisphenol A cyanate compound, bisphenol F cyanate compound, bisphenol E cyanate compound, bisphenol M cyanate compound, DCPD cyanate compound, naphthyl cyanate compound, phenolic cyanate compound, and biphenyl cyanate compound; The amino silicone resin is shown in structural formula (12): The structure is (12), where n is an integer from 1 to 20 and m is an integer from 1 to 5.

5. The modified maleimide prepolymer according to claim 3, characterized in that, The ratio of total maleimide equivalent to amino equivalent of the monomeric maleimide compound and the polymeric maleimide compound is 1.5-8.

6. The modified maleimide prepolymer according to claim 3, characterized in that, The amino equivalent of the amino organosilicon resin is 400-1600 g / mol.

7. The modified maleimide prepolymer according to claim 1, characterized in that, The reaction aids are 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, and 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 1-8: 5-100 parts by weight; At least one of epoxy resin and polyphenylene ether resin, wherein the epoxy resin is 5-30 parts by weight and the polyphenylene ether resin is 30-100 parts by weight.

10. The resin composition according to claim 9, characterized in that, When the resin composition includes an epoxy resin, 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 10, characterized in that, The epoxy resin is selected from at least one of structural formulas (13) to (16): The structural formula (13) is given, where n is an integer from 1 to 20; The structural formula (14) is given, where p is an integer from 1 to 20; The structure is (15), where n is an integer from 1 to 20; The structure is (16), where n is an integer from 1 to 20.

12. The resin composition according to claim 9, characterized in that, When the resin composition includes a polyphenylene ether resin, the polyphenylene ether resin comprises the structure shown in (17) or / and (18): Structural formula (17). Structural formula (18); In the above polyphenylene ether resin structural formula, R1, R2, R3, R4, R5, R6, R7, and R8 are each independently selected from hydrogen or any C1-C5 alkyl group, and Y is a non-linking bond, -O-, methylene, ethylene, etc. , or n is an integer from 1 to 20, and m is an integer from 1 to 20.

13. The resin composition according to claim 9, characterized in that, It also includes 0.001-5 parts by weight of a catalyst, said catalyst being selected from at least one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-dodecylimidazole, 1-cyanoethyl-2-methylimidazole, or modified imidazoles with the following structures: Among them, R3, R4, R5, and R6 may be the same or different, and are methyl, ethyl, or tert-butyl; A is methylene, ethylene, or... , , Or aromatic hydrocarbon groups; Among them, R3, R4, R5, and R6 may be the same or different, and are methyl, ethyl, or tert-butyl; B is methylene, ethylene, or... , or .

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

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