Modified maleimide prepolymer, resin composition and application thereof

Abstract

The invention discloses a modified maleimide prepolymer, a resin composition and application thereof, the modified maleimide prepolymer is an amine compound modified maleimide prepolymer and is generated by a prepolymerization reaction of maleimide resin and an amine compound, and the weight ratio of the maleimide resin to the amine compound is 100: (1-120); according to the invention, the maleimide resin is modified by a compound containing a special aliphatic ring and aromatic amine structure, and due to the existence of the aliphatic ring or olefin structure, the dielectric property, the water absorption rate and the like of bismaleimide can be reduced; the structure has an excellent thermal expansion coefficient and can meet the requirement of high-order packaging; according to the present invention, the product has characteristics of high temperature resistance, no volatile low molecular substance generation during the reaction process, stable molecular structure and high thermal decomposition temperature, can completely meet the multi-chip assembly manufacturing process requirements in the large-scale integrated circuit, and can obtain the cured product with characteristics of high heat resistance, high toughness, low CTE, low dielectric property and low water absorption rate, and the obtained cured product has characteristics of high heat resistance, high toughness, low CTE, low dielectric property and low water absorption.

Description

Technical Field

[0001] The invention relates to the technical field of copper clad laminates, and in particular to a modified maleimide prepolymer, a resin composition and applications thereof. Background Art

[0002] In recent years, as electronic signal transmission methods develop towards 5G, and electronic equipment, communication devices, personal computers, etc. are becoming more functional and miniaturized, the circuit boards used are also developing towards multi-layering, high-density wiring, and high-speed signal transmission, which puts higher requirements on the comprehensive performance of circuit substrates such as copper clad laminates. In order to avoid deformation of copper clad laminates caused by the use of high-temperature processes during product processing, which in turn causes defects in subsequent products and causes abnormal signal transmission, it is necessary to develop copper clad laminate materials with a lower thermal expansion coefficient.

[0003] Bismaleimide resin has excellent heat resistance, high modulus, low CTE, and is therefore widely used in high performance printed circuit boards. However, there are problems such as high curing temperature, large water absorption, large brittleness in bismaleimide resin. In order to improve the above-mentioned shortcomings of maleimide resin, diamine or allyl compound modification is generally used at present, wherein, the product after modified bismaleimide with aromatic diamine compounds is all improved to a certain extent in solubility and toughness, but the aromatic diamine toxicity is larger, and the modified product can only be dissolved in high boiling point polar solvents (such as DMF, NMP etc.), and it still has a large improvement space in toughness, heat resistance, dielectricity and water absorption. For example, the prior art JP2004359599A discloses a method for producing triptylenediamine, a method for preparing triptylenediamine, which comprises nitrating a triptylenediamine derivative and then reducing the obtained nitro-substituted triptylenediamine; the prior art CN108291028 discloses ortho-substituted triptylenediamines, monomers and polymers based on triptylenes, preparation methods and uses thereof, including 3,6-dimethyl-2,7-diaminotriptylenediamine derivatives.

[0004] Therefore, the present invention provides a modified maleimide prepolymer, a resin composition and applications thereof to obtain a cured product with high heat resistance, high toughness, low CTE, low dielectric properties and low water absorption, thereby obtaining a cured product with relatively excellent comprehensive performance. Summary of the invention

[0005] The purpose of the present invention is to provide a modified maleimide prepolymer, a resin composition and applications thereof, so as to obtain a cured product with high heat resistance, high toughness, low CTE, low dielectric properties and low water absorption, thereby obtaining a cured product with excellent comprehensive performance.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] A modified maleimide prepolymer, wherein the modified maleimide prepolymer is an amine compound modified maleimide prepolymer, and the modified maleimide prepolymer is generated by prepolymerizing a maleimide resin and an amine compound, wherein the weight ratio of the maleimide resin to the amine compound is 100:1 to 120; and the amine compound contains an aromatic amine compound represented by structural formula (1);

[0008]

[0009] Among them, Ar is

[0010] Preferably, the Ar group in the structural formula (1) contains at least

[0011] More preferably, the Ar group in the structural formula (1) is

[0012] When the Ar group is selected from benzocyclobutene, the dielectric properties are effectively improved while maintaining good heat resistance and modulus, especially the Dk value after moisture absorption treatment is significantly reduced.

[0013] Preferably, the prepolymerization reaction temperature is 60° C. to 180° C., and the reaction time is 0.5 to 5 hours.

[0014] More preferably, the prepolymerization reaction temperature is 100-130° C., and the reaction time is 1 hour, 2 hours, 3 hours, 4 hours or 5 hours.

[0015] The method of the prepolymerization reaction is not particularly limited. The aromatic amine compound and the maleimide resin are dissolved and dispersed in an appropriate amount of an organic solvent, heated to 60° C. to 180° C. under nitrogen protection and kept reacting under stirring conditions for 0.5 to 5 hours to obtain an amine-modified bismaleimide prepolymer.

[0016] Preferably, the organic solvent is selected from at least one of acetone, butanone, toluene, methyl isobutyl ketone, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene and cyclohexane.

[0017] Preferably, the amine compound further contains other aromatic diamine compounds other than those of structural formula (1), and the other aromatic diamine compounds are selected from at least one of unsubstituted phenylenediamine, methylphenylenediamine, dimethylphenylenediamine, trimethylphenylenediamine, tetramethylphenylenediamine, xylene diamine, diaminopyridine, diaminodiphenylmethane, substituted diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, diaminobenzophenone, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminobiphenyl, diaminodiphenyl sulfide, diaminobinaphthyl, diaminodiphenylfluorene, and diaminoanthraquinone; in parts by weight, based on 100 parts of the amine compound, the content of the other aromatic diamine compounds is 5 to 80 parts.

[0018] More preferably, the aromatic diamine compound is diaminodiphenyl ether, diaminodiphenyl sulfone or diaminodiphenylmethane.

[0019] When the aromatic amine compound shown in structural formula (1) is mixed with other diamine compounds, it can improve heat resistance, dielectric properties and water absorption while meeting good compatibility and controlling costs, and can effectively improve the problem of reaction crosslinking degree caused by steric hindrance.

[0020] Preferably, the amine compound modified maleimide prepolymer is produced by prepolymerization of maleimide resin, amine compound and aminophenol compound.

[0021] Further preferably, an aminophenol compound is added during the prepolymerization of the maleimide resin and the amine compound to control the overall reaction rate, improve the processability, and improve the overall properties of the cured product.

[0022] Preferably, the content of the aminophenol compound is 0.5 to 5 parts by weight based on 100 parts of the total amount of the maleimide resin and the amine compound.

[0023] The aminophenol is preferably 4-aminophenol.

[0024] The prepolymerization method comprises dissolving and dispersing an amine compound, a maleimide resin and an aminophenol in an appropriate amount of an organic solvent, heating to 60° C. to 180° C. under nitrogen protection and reacting for 0.5 to 5 hours under stirring conditions to obtain an amine-modified bismaleimide prepolymer.

[0025] In the above technical solution, the maleimide resin is selected from at least one of the following structures:

[0026]

[0027]

[0028] R2 is hydrogen, methyl or ethyl, R1 is methylene, ethylene or, n is an integer from 1 to 10;

[0029]

[0030] n is an integer from 1 to 10;

[0031] n is an integer from 1 to 10;

[0032] n is an integer from 1 to 10;

[0033]

[0034] R is hydrogen, methyl or ethyl, and n is an integer of 1-10.

[0035] R is a methyl group, and n is an integer of 1-20.

[0036] For further example, the maleimide resin is selected from BMI-1000, BMI-2300, BMI-5100 or BMI-TMH manufactured by Yamato Chemical; BMI, BMI-70 or BMI-80 manufactured by KI Chemical; X9-470, X9-450 or X-9500 manufactured by DIC; MIR-3000 or MIR-5000 manufactured by Nippon Kayaku.

[0037] The present application also claims protection for a resin composition, wherein the resin composition contains the modified maleimide prepolymer.

[0038] Preferably, the resin composition comprises, by weight:

[0039] Modified maleimide prepolymer: 100 parts;

[0040] Cyanate compound: 1 to 80 parts;

[0041] Epoxy resin: 0-50 parts;

[0042] Polyphenylene ether resin: 1-70 parts;

[0043] Cross-linking agent: 10-70 parts.

[0044] In the above technical scheme, the cyanate ester compound is selected from at least one of bisphenol A type cyanate ester compounds, bisphenol F type cyanate ester compounds, bisphenol E type cyanate ester compounds, bisphenol M type cyanate ester compounds, DCPD type cyanate ester compounds, naphthalene type cyanate ester compounds, biphenyl type cyanate ester compounds, and triphenyl type cyanate ester compounds.

[0045] The cyanate compound is a monomer, a prepolymer or a mixture thereof.

[0046] In the above technical scheme, the epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol E epoxy resin, phosphorus-containing epoxy resin, o-cresol epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl linear phenolic epoxy resin, alicyclic epoxy resin, glycidyl amine epoxy resin, glycidyl ether epoxy resin, and glycidyl ester epoxy resin.

[0047] In the above technical solution, the polyphenylene ether resin is represented by structural formula (13):

[0048]

[0049] Among them, X is or / and R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are hydrogen or C1-C5 alkyl, B is C1-C20 alkylene or oxy; Y is R 21 , R 22 , R 23 and R 24 are hydrogen or C1-C5 alkyl.

[0050] Specifically, the polyphenylene ether resin is selected from OPE-2ST series products manufactured by Mitsubishi Gas.

[0051] In the above technical solution, the cross-linking agent is at least one of triallyl isocyanate monomer, triallyl isocyanate prepolymer, butadiene monomer, styrene monomer, pentadiene monomer, dicyclopentadiene dimethacrylate monomer, norbornene monomer, and cyclopentadiene monomer.

[0052] Preferably, the crosslinking agent is triallyl isocyanurate monomer (TAIC), dicyclopentadiene dimethacrylate monomer (DCP) or a combination thereof.

[0053] Among them, the structural formula of triallyl isocyanurate monomer (TAIC) is:

[0054]

[0055] The structural formula of dicyclopentadiene dimethacrylate monomer (DCP) is:

[0056]

[0057] Specifically, the triallyl isocyanurate monomer (TAIC) can be TAIC manufactured by Mitsubishi Chemical, TAIC manufactured by Evonik, or TAIC manufactured by Nippon Chemical; the dicyclopentadiene dimethacrylate monomer (DCP) can be A-DCP manufactured by Shin-Nakamura Chemical or DCP-A manufactured by Kyoeisha Chemical.

[0058] Preferably, the resin composition further comprises an inorganic filler in an amount of 30 to 200 parts by weight.

[0059] The inorganic filler is selected from one of non-metallic oxides, metal nitrides, non-metallic nitrides, inorganic hydrates, inorganic salts, metal hydrates or inorganic phosphorus, or a mixture of any of them.

[0060] Preferably, the inorganic filler is selected from at least one 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, mica, and glass fiber powder.

[0061] More preferably, the inorganic filler is silicon dioxide.

[0062] More preferably, the inorganic filler is surface-treated spherical silica.

[0063] The surface treatment agent is a silane coupling agent, such as a silane coupling agent containing an epoxy group, an amino group, a vinyl group, an acrylate group or an allyl group.

[0064] Preferably, the median particle size of the inorganic filler is 1 to 15 microns, for example, 1 micron, 2 microns, 5 microns, 8 microns, 10 microns, 11 microns, 12 microns, 13 microns, 14 microns.

[0065] More preferably, the median particle size of the filler is 1 to 10 microns.

[0066] In the above technical solution, the resin composition further comprises a catalyst, and its content is 0.01 to 8 parts by weight.

[0067] Preferably, the catalyst is selected from at least one of imidazoles, pyridines, organophosphorus or metal salts.

[0068] Preferably, the imidazole is selected from at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole and zinc octanoate.

[0069] In the above technical solution, the resin composition also includes a flame retardant in an amount of 5 to 60 parts by weight.

[0070] Preferably, the flame retardant is selected from at least one of a bromine flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, an organosilicon flame retardant, and an organometallic salt flame retardant.

[0071] Preferably, the brominated flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or tetrabromophthalamide;

[0072] Preferably, the phosphorus flame retardant is selected from inorganic phosphorus, condensed phosphate, phosphoric acid, hypophosphite, phosphorus oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ), (m is an integer from 1 to 5), At least one of 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris(2,6-dimethylphenyl)phosphine, phosphazene, and modified phosphazene, wherein the DOPO group in the above structure is

[0073] Preferably, the flame retardant is a condensed phosphate ester, a hypophosphite or a bis-DOPO compound.

[0074] The present application also claims to protect the application of a resin composition, which is the application of the above-mentioned resin composition in prepregs, laminates, insulating films, insulating boards, copper-clad boards, circuit substrates and electronic devices.

[0075] Specifically, the prepreg comprises a reinforcing material and the above-mentioned resin composition attached to the surface of the reinforcing material.

[0076] Preferably, the preparation method of the prepreg is:

[0077] Dissolving the resin composition with a solvent to prepare a resin composition glue solution;

[0078] The reinforcing material is immersed in the resin composition glue solution, and the immersed reinforcing material is taken out and baked at a temperature of 100 to 180° C. for 1 to 15 minutes, and the semi-cured sheet can be obtained after drying.

[0079] Preferably, 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.

[0080] Preferably, 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, and the glass fiber cloth is preferably open fiber cloth or flat cloth. More preferably, the glass fiber cloth is E glass fiber cloth, S glass fiber cloth, T glass fiber cloth or Q glass fiber cloth.

[0081] In addition, when the reinforcing material is glass fiber cloth, the glass fiber cloth generally needs to be chemically treated to improve the bonding between the resin composition and the interface of the glass fiber cloth. The main method of the chemical treatment is coupling agent treatment. The coupling agent used is preferably an epoxy silane coupling agent or an amino silane coupling agent, so that the reinforcing material has good water resistance and heat resistance.

[0082] Preferably, the laminate comprises a piece of the above-mentioned prepreg and a metal foil arranged on at least one side of the prepreg, or the laminate comprises a composite sheet formed by overlapping a plurality of the above-mentioned prepregs and a metal foil arranged on at least one side of the composite sheet.

[0083] Preferably, the method for preparing the laminate is:

[0084] The laminated board can be obtained by coating one or both sides of the prepreg with metal foil, or by stacking at least two prepregs to form a composite sheet, coating one or both sides of the composite sheet with metal foil, and hot pressing.

[0085] The hot pressing conditions are: pressing for 2 to 4 hours at a pressure of 0.2 to 2 MPa and a temperature of 150 to 250°C.

[0086] Preferably, the metal foil is selected from copper foil or aluminum foil, and the thickness of the metal foil is not particularly limited, such as 5 μm, 8 μm, 12 μm, 18 μm, 35 μm or 70 μm.

[0087] Preferably, the insulating plate includes at least one prepreg sheet mentioned above.

[0088] Preferably, the insulating film comprises a carrier film and the above-mentioned resin composition attached to the surface of the carrier film, and the heat resistance of the insulating film is significantly improved.

[0089] Preferably, the method for preparing the insulating film is:

[0090] Dissolving the resin composition with a solvent to prepare a resin composition glue solution;

[0091] The insulating film can be obtained by coating the resin composition glue on the carrier film and heating and drying the carrier film coated with the resin composition glue.

[0092] Preferably, 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.

[0093] Preferably, the carrier film is selected from at least one of PET film, PP film, PE film and PVC film.

[0094] Preferably, the circuit substrate includes at least one of the prepreg and the laminate.

[0095] Preferably, the method for preparing the circuit substrate is a conventional technical means in the art and will not be described in detail here.

[0096] Preferably, the electronic device comprises the above-mentioned circuit substrate.

[0097] Preferably, the method for preparing the electronic device is a conventional technical means in the art and will not be described in detail here.

[0098] Due to the application of the above technical solution, the present invention has the following beneficial effects compared with the prior art:

[0099] 1. The present invention uses a compound containing a special aliphatic ring and an aromatic amine structure to modify the maleimide resin, wherein the presence of the aliphatic ring or the olefin structure can reduce the dielectric properties and water absorption rate of the bismaleimide;

[0100] 2. The structure adopted by the present invention has an excellent thermal expansion coefficient and can meet the requirements of high-order packaging; and no volatile low-molecular substances are generated during the reaction process, the molecular structure is very stable, and the thermal decomposition temperature is high, which can fully meet the production process requirements of multi-chip components in large-scale integrated circuits, and obtain a cured product with high heat resistance, high toughness, low CTE, low dielectric properties, and low water absorption, thereby obtaining a cured product with relatively excellent comprehensive performance, which is conducive to its large-scale application. DETAILED DESCRIPTION

[0101] In order to have a clearer understanding of the technical features, purposes and effects of the present invention, a specific implementation scheme is now described in detail.

[0102] The present invention is further described below in conjunction with the examples, but the present invention is not limited to the following examples. The implementation conditions used in the examples can be further adjusted according to the different requirements of specific use, and the implementation conditions not indicated are conventional conditions in the industry. The technical features involved in each embodiment of the present invention can be combined with each other as long as they do not conflict with each other.

[0103] Synthesis Example 1: Prepolymer A;

[0104] Add 40g of amine compound (Ar group in structural formula 1 is ), 100 g of maleimide resin (BMI-2300, manufactured by Yamato Chemical Industry Co., Ltd.), and 2 g of p-aminophenol were reacted at 160°C for 100 min to obtain prepolymer A.

[0105] Synthesis Example 2: Prepolymer B;

[0106] Add 40g of amine compound (Ar group in structural formula 1 is ), 100 g of maleimide resin (BMI-2300, manufactured by Yamato Chemical Industry Co., Ltd.), and 2 g of p-aminophenol were reacted at 160° C. for 100 min to obtain prepolymer B.

[0107] Synthesis Example 3: Prepolymer C;

[0108] Add 50g of amine compound (Ar group in structural formula 1 is ), 20g 4,4'-diaminodiphenylmethane, 100g maleimide resin (made by Nippon Kayaku, MIR-3000), and 2.5g p-aminophenol were reacted at 120°C for 100min to obtain prepolymer C.

[0109] Synthesis Example 4: Prepolymer D;

[0110] 100 g of maleimide resin (BMI-2300 manufactured by Yamato Chemical Industry Co., Ltd.) and 2 g of p-aminophenol were added to a beaker and reacted at 110°C for 60 min. After the temperature was raised to 120°C, 40 g of an amine compound (Ar in the structural formula 1 is ) The reaction was continued for 60 min to obtain prepolymer D.

[0111] Comparative Synthesis Example 1: Prepolymer E;

[0112] 40 g of 4,4'-diaminodiphenylmethane, 100 g of maleimide resin (BMI-2300 manufactured by Yamato Chemical Industry Co., Ltd.) and 2 g of p-aminophenol were added to a beaker and reacted at 120°C for 100 min to obtain a prepolymer E.

[0113] The amine compound used in Comparative Synthesis Example 1 is different from that in Synthesis Example 1, and the amine compound in Comparative Synthesis Example 1 does not contain an ether bond.

[0114] Comparative Synthesis Example 2: Prepolymer F;

[0115] 40 g of 4,4'-diaminodiphenyl ether, 100 g of maleimide resin (BMI-2300 manufactured by Yamato Chemical Industry Co., Ltd.) and 2 g of p-aminophenol were added to a beaker and reacted at 120°C for 100 min to obtain a prepolymer F.

[0116] The ether bond-containing aromatic amine compound used in Comparative Synthesis Example 2 is different from that in Synthesis Example 1. The aromatic amine compound in Comparative Synthesis Example 2 contains only one ether bond.

[0117] Example 1

[0118] This embodiment is a resin composition, which includes, by weight: 100 parts of prepolymer A, 30 parts of cyanate ester, 20 parts of epoxy resin, 150 parts of inorganic filler, and 0.5 parts of catalyst.

[0119] Example 2

[0120] This embodiment is a resin composition, which includes, by weight: 100 parts of prepolymer B, 20 parts of cyanate ester, 30 parts of epoxy resin, 150 parts of inorganic filler, and 0.5 parts of catalyst.

[0121] Example 3

[0122] This embodiment is a resin composition, which includes, by weight: 100 parts of prepolymer C, 15 parts of cyanate ester, 10 parts of epoxy resin, 125 parts of inorganic filler, and 0.5 parts of catalyst.

[0123] Example 4

[0124] This embodiment is a resin composition, which includes, by weight: 100 parts of prepolymer D, 60 parts of polyphenylene ether resin, 20 parts of cross-linking agent, 180 parts of inorganic filler, and 0.5 parts of catalyst.

[0125] Comparative Example 1

[0126] This embodiment is a resin composition, which includes, by weight: 100 parts of prepolymer E, 30 parts of cyanate ester, 20 parts of epoxy resin, 150 parts of inorganic filler, and 0.5 parts of catalyst.

[0127] Comparative Example 2

[0128] This embodiment is a resin composition, which includes, by weight: 100 parts of prepolymer F, 20 parts of cyanate ester, 30 parts of epoxy resin, 150 parts of inorganic filler, and 0.5 parts of catalyst.

[0129] Comparative Example 3

[0130] This embodiment is a resin composition, which includes, by weight: 100 parts of prepolymer F, 60 parts of polyphenylene ether resin, 20 parts of cross-linking agent, 180 parts of inorganic filler, and 0.5 parts of catalyst.

[0131] The components and addition amounts of Examples 1-4 and Comparative Examples 1-3 are shown in Table 1 below.

[0132] Table 1

[0133] Components Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Prepolymer A 100 Prepolymer B 100 Prepolymer C 100 Prepolymer D 100 Prepolymer E 100 Prepolymer F 100 100 Cyanate 30 20 15 30 20 Epoxy resin 20 30 10 20 30 Polyphenylene ether resin 60 60 Crosslinking agent 20 20 Inorganic fillers 150 150 125 180 150 150 180 catalyst 0.5 0.5 0.5 0.5 0.5 0.5 0.5

[0134] The raw material manufacturers and brands of each component used in Examples 1-4 and Comparative Examples 1-3 are shown in Table 2 below.

[0135] Table 2

[0136] Components Manufacturer and brand Cyanate Made by Tianqi, bisphenol A Epoxy resin DIC, HP-6000 Polyphenylene ether resin Made by Mitsubishi, OPE-2St Crosslinking agent TAIC Inorganic fillers Silicon dioxide catalyst 2-Methylimidazole

[0137] Mixing of glue:

[0138] According to the formula in Table 1, all the components in the formula are prepared into a thermosetting resin composition glue solution with a solid content of 65%;

[0139] Then a laminate was made under the following conditions:

[0140] Reinforcement material: ordinary electronic grade 2116 glass fiber cloth;

[0141] Metal foil: 18 microns, electrolytic copper foil;

[0142] Number of layers: 6;

[0143] Thickness of sheet after forming: 0.7mm;

[0144] Pre-impregnation semi-curing conditions: 170℃ / 5min;

[0145] Curing conditions: 150℃ / 60min+220℃ / 180min.

[0146] The performance tests were carried out on the above-mentioned embodiments 1-4 and comparative examples 1-3 respectively, and the test results are shown in Table 3 below.

[0147] Table 3

[0148] Test items Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Glass transition temperature (DMA / ℃) 255 248 251 254 234 237 226 PCT water absorption % 0.26 0.28 0.24 0.22 0.45 0.48 0.45 CTE (X / Y axis) (ppm / ℃) 6.8 6.6 6.4 6.5 11.0 9.9 11.1 Peel strength (N / mm) 1.1 1.03 1.11 0.98 1.0 0.92 0.89 Dielectric constant (10GHz) 3.35 3.31 3.37 3.10 3.79 3.67 3.34 Dielectric loss (10GHz) 0.0035 0.0036 0.0038 0.0025 0.0071 0.0065 0.0030 Elastic modulus(GPa) 29 29 31 32 23 25 24

[0149] The performance of the above-mentioned Examples 1-4 and Comparative Examples 1-3 was tested as follows:

[0150] (1) Glass transition temperature (Tg): dynamic mechanical properties tester (TADMAQ800, USA) was used with a heating rate of 10 °C / min and a nitrogen atmosphere;

[0151] (2) Dk and Df: measured at 10 GHz using the flat plate method in accordance with IPC-TM-6502.5.5.9;

[0152] (3) CTE (X / Y) determination: TMA (thermomechanical analysis) was used, with a heating rate of 10°C / min and a test temperature range of 30 to 100°C;

[0153] (4) PCT water absorption rate: Take 3 samples of 10 cm × 10 cm, 0.80 mm thick, with metal foil removed from both sides, dry them at 120°C for 2 hours, weigh them, and record the weight as W1. Then use a pressure cooker tester to treat them at 121°C and 2 atmospheres for 12 hours. After absorbing the free water on the surface, put them in a desiccator and cool them down. Then weigh them as W2. The water absorption rate of the board is calculated based on the weight before and after.

[0154] (5) Peel strength (PS): The peel strength of the metal cover layer was tested using a laminate according to the “after thermal stress” test conditions in the IPC-TM-650 method.

[0155] (6) Elastic modulus: measured according to the DMA method specified in IPC-TM-6502.4.24.4;

[0156] (7) Appearance quality: Visually inspect the appearance of the CCL substrate. A substrate without obvious glue deficiency or pinholes has a good appearance. A substrate with glue deficiency or pinholes has a fair appearance.

[0157] In summary, the present invention adopts a compound containing a special aliphatic ring and an aromatic amine structure to modify the maleimide resin, wherein the presence of the aliphatic ring or the olefin structure can reduce the dielectric properties, water absorption, etc. of the bismaleimide; the structure has an excellent thermal expansion coefficient and can meet the requirements of high-order packaging; and no volatile low-molecular substances are generated during the reaction process, the molecular structure is very stable, and the thermal decomposition temperature is high, which can fully meet the manufacturing process requirements of multi-chip components in large-scale integrated circuits, and obtain a cured product with high heat resistance, high toughness, low CTE, low dielectric properties, and low water absorption, thereby obtaining a cured product with relatively excellent comprehensive performance, which is conducive to its large-scale application.

[0158] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A modified maleimide prepolymer, characterized in that: The modified maleimide prepolymer is an amine compound modified maleimide prepolymer, which is generated by prepolymerizing a maleimide resin and an amine compound, wherein the weight ratio of the maleimide resin to the amine compound is 100:1-120; the amine compound contains an aromatic amine compound represented by structural formula (1); Among them, Ar is 2. The modified maleimide prepolymer according to claim 1, characterized in that The Ar group in the structural formula (1) contains at least 3. The modified maleimide prepolymer according to claim 1, characterized in that: The amine compound further contains other aromatic diamine compounds other than those of structural formula (1), wherein the other aromatic diamine compounds are selected from at least one of unsubstituted phenylenediamine, methylphenylenediamine, dimethylphenylenediamine, trimethylphenylenediamine, tetramethylphenylenediamine, xylene diamine, diaminopyridine, diaminodiphenylmethane, substituted diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, diaminobenzophenone, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminobiphenyl, diaminodiphenyl sulfide, diaminobinaphthyl, diaminodiphenylfluorene, and diaminoanthraquinone; and the content of the other aromatic diamine compounds is 5 to 80 parts by weight based on 100 parts of the amine compound.

4. The modified maleimide prepolymer according to claim 1, characterized in that The amine compound modified maleimide prepolymer is produced by prepolymerization of maleimide resin, amine compound and aminophenol compound.

5. The modified maleimide prepolymer according to claim 4, characterized in that: In parts by weight, based on 100 parts of the total amount of the maleimide resin and the amine compound, the content of the aminophenol compound is 0.5 to 5 parts.

6. A resin composition, characterized in that The resin composition contains the modified maleimide prepolymer according to any one of claims 1 to 5.

7. The resin composition according to claim 6, characterized in that By weight, including: Modified maleimide prepolymer: 100 parts; Cyanate compound: 1 to 80 parts; Epoxy resin: 0-50 parts; Polyphenylene ether resin: 1-70 parts; Cross-linking agent: 10-70 parts.

8. The resin composition according to any one of claims 6 to 7, characterized in that The resin composition also includes inorganic filler in an amount of 30 to 200 parts by weight.

9. The resin composition according to any one of claims 6 to 7, characterized in that The resin composition also includes a flame retardant in an amount of 5 to 60 parts by weight.

10. Use of the resin composition according to any one of claims 6 to 9 in prepregs, laminates, insulating films, insulating boards, copper-clad boards, circuit substrates and electronic devices.

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