Modified bismaleimide prepolymer, preparation method therefor and use thereof, and resin composition, preparation method therefor, and use thereof

Abstract

A modified bismaleimide prepolymer, a preparation method therefor and a use thereof, and a resin composition, a preparation method therefor and a use thereof. A naphthalene ring-containing modifier is selected to modify a bismaleimide resin. The obtained modified bismaleimide prepolymer has two or more naphthalene rings in the structure, so that a cured product of the modified bismaleimide prepolymer has the characteristics of a low thermal expansion coefficient, excellent high-temperature modulus retention and extremely high heat resistance. In addition, the modified bismaleimide prepolymer is rationally combined with other raw material components, to obtain a resin composition having a low thermal expansion coefficient, excellent high-temperature modulus retention, and extremely high heat resistance, without adding a large proportion of an organic filler, thereby avoiding the problems of dispersity and processability caused by the addition of a large amount of inorganic filler; furthermore, a laminated board prepared with the resin composition as a raw material has relatively excellent performance, can effectively inhibit warping when applied to a thin material of a substrate for semiconductor packaging, and has good prospects of application.

Description

Modified bismaleimide prepolymer, resin composition, preparation method and application thereof Technical Field

[0001] The present invention relates to the technical field of resin materials, and in particular to a modified bismaleimide prepolymer, a resin composition, and a preparation method and application thereof. Background Art

[0002] In recent years, as semiconductor packages have become thinner, lighter, and more multifunctional, higher requirements have been placed on them, requiring greater integration and higher-density mounting. Consequently, further reducing the coefficient of thermal expansion (CTE) of laminates used in semiconductor packages has become a key issue that needs to be addressed.

[0003] The traditional approach to reducing the thermal expansion coefficient of laminated boards is to add large amounts of inorganic fillers to the resin composition. The inorganic filler typically accounts for over 60% of the resin composition by weight. While this high percentage of fillers has some effect on reducing the thermal expansion coefficient of laminated boards, due to the inherent thermal expansion coefficient of the inorganic filler itself, further reduction in the thermal expansion coefficient of the board becomes difficult after a certain percentage of filler addition. Furthermore, the addition of large amounts of fillers can severely affect the dispersibility of the resin composition, leading to reduced processing performance, such as shortened drill bit life, and reduced processing efficiency and yield.

[0004] Summary of the Invention

[0005] Based on this, it is necessary to provide a modified bismaleimide prepolymer, a resin composition, and a preparation method and application thereof. By selecting a modifier containing multiple naphthalene rings to modify the bismaleimide resin, a modified bismaleimide prepolymer is prepared. When the modified bismaleimide prepolymer is used as a raw material to prepare a resin composition, the large amount of inorganic filler addition can be avoided, and the resin composition can have a lower thermal expansion coefficient. In addition, the resin composition can also have excellent high-temperature modulus retention and high heat resistance.

[0006] The specific technical solutions are as follows:

[0007] The first aspect of the present invention provides a modified bismaleimide prepolymer obtained by prepolymerizing a bismaleimide resin and a modifier;

[0008] The modifier includes a first modifier, and a functional group of the first modifier includes two or more naphthalene rings.

[0009] In one embodiment, the first modifier includes a tripolynaphthalene bisallyl ether compound.

[0010] In one embodiment, the tri-naphthalene bisallyl ether compound includes a compound having a structure as described in Formula I:

[0011] In one embodiment, the modifier further comprises a second modifier;

[0012] Optionally, the second modifier includes one or more of diallyl bisphenol A, diallyl bisphenol S, diallyl bisphenol F and bisphenol A bisallyl ether.

[0013] In one embodiment, the mass ratio of the bismaleimide resin to the modifier is (1-2):1.

[0014] In one embodiment, the bismaleimide resin includes one or more of N,N'-(4,4'-methylenediphenyl)bismaleimide, N,N'-(1,4-phenylene)bismaleimide, N,N'-(4-methyl-1,3-phenylene)bismaleimide, N,N'-m-phenylene bismaleimide, bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, polyphenylmethane bismaleimide and bismaleimide containing a biphenyl structure.

[0015] The second aspect of the present invention provides a method for preparing the modified bismaleimide prepolymer as described above, comprising the following steps:

[0016] The bismaleimide resin is mixed with the modifier to perform a prepolymerization reaction.

[0017] In one embodiment, the prepolymerization reaction satisfies at least one of the following conditions:

[0018] (1) The temperature of the prepolymerization reaction is 140°C-170°C;

[0019] (2) The prepolymerization reaction time is 60 min-180 min.

[0020] A third aspect of the present invention provides a resin composition, wherein the raw materials thereof comprise the following components in parts by weight:

[0021] 40-70 parts of modified bismaleimide prepolymer;

[0022] 30-80 parts of resin matrix;

[0023] Wherein, the modified bismaleimide prepolymer includes the modified bismaleimide prepolymer described above.

[0024] In one embodiment, the resin matrix comprises the following components in parts by weight:

[0025] 20-50 parts of cyanate resin;

[0026] 10-30 parts of functional resin.

[0027] In one embodiment, the resin composition further comprises 30-100 parts by weight of an inorganic filler;

[0028] Optionally, the inorganic filler accounts for less than 40% by mass in the resin composition;

[0029] Optionally, the inorganic filler includes one or more of zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, eucryptite, silica, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc, aluminum oxide, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, clay and kaolin.

[0030] In one embodiment, the cyanate ester resin includes one or more of bisphenol A cyanate ester resin, novolac cyanate ester resin, bisphenol F cyanate ester resin, bisphenol M cyanate ester resin, bisphenol E cyanate ester resin, naphthalene cyanate ester resin, biphenyl cyanate ester resin, bisphenol S cyanate ester resin and dicyclopentadiene bisphenol cyanate ester resin; and / or

[0031] The functional resin includes one or more of epoxy resin, benzoxazine resin, modified polyphenylene ether, silicone resin and hydrocarbon resin.

[0032] In one embodiment, the raw materials of the resin composition further include, by weight: 10-20 parts of flame retardant; and / or

[0033] 1-10 parts of curing accelerator; and / or

[0034] 1-5 parts of additives.

[0035] A fourth aspect of the present invention provides a prepreg comprising a reinforcing material and the resin composition as described above.

[0036] According to a fifth aspect of the present invention, there is provided a laminated board, which is produced by curing the prepreg as described above.

[0037] A sixth aspect of the present invention provides use of the modified bismaleimide prepolymer, the resin composition, the prepreg, and the laminate in a semiconductor package.

[0038] The present invention has the following beneficial effects:

[0039] The present invention selects a naphthalene ring-containing modifier to modify a bismaleimide resin to prepare a modified bismaleimide prepolymer. Since the obtained modified bismaleimide prepolymer has two or more naphthalene rings in its structure, its cured product has the characteristics of low thermal expansion coefficient, excellent high-temperature modulus retention and extremely high heat resistance. Therefore, a resin composition with a low thermal expansion coefficient can be obtained without adding a large amount of inorganic filler, thereby avoiding the problems of dispersibility and processability caused by adding a large amount of inorganic filler.

[0040] At the same time, the modified bismaleimide prepolymer is rationally matched with the remaining raw material components, and the components are matched with each other according to specific weight proportions, so that the resin composition has a low thermal expansion coefficient while also having excellent high-temperature modulus retention and extremely high heat resistance; furthermore, the laminate prepared with the above resin composition as raw material has relatively excellent performance. When applied to thin substrate materials for semiconductor packaging, it can effectively suppress the warping problem and has good application prospects. DETAILED DESCRIPTION

[0041] To make the above-mentioned objects, features, and advantages of the present invention more readily apparent, specific embodiments of the present invention are described in detail below. The following description sets forth numerous specific details to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways than those described herein, and those skilled in the art may make similar modifications without departing from the scope of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0042] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in this specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0043] Unless otherwise specified or incompatible herewith, the terms and phrases used herein shall have the following meanings:

[0044] As used herein, "one or more" refers to any one, any two, or any two or more of the listed items.

[0045] Herein, the optional scope of "and / or", "or / and", and "and / or" includes any one of two or more relevant listed items, and also includes any and all combinations of the relevant listed items, and the said any and all combinations include any two relevant listed items, any more relevant listed items, or a combination of all relevant listed items.

[0046] Herein, “further”, “further”, “particularly”, etc. are used for descriptive purposes to indicate differences in content, but should not be understood as limiting the scope of protection of the present invention.

[0047] Herein, “the first aspect”, “the second aspect”, “the third aspect”, “the fourth aspect”, etc. are used for descriptive purposes only and cannot be understood as indicating or implying relative importance or quantity, nor can they be understood as implicitly indicating the importance or quantity of the indicated technical features. In addition, “the first”, “the second”, “the third”, “the fourth”, etc. only serve the purpose of non-exhaustive enumeration and description, and should be understood as not constituting a closed limitation on quantity. Thus, the features defined as “the first” or “the second” may explicitly or implicitly include at least one of such features. In the description of the invention, “a plurality” means at least two, such as two, three, etc., unless otherwise clearly and specifically defined. In the description of the present invention, “a number” means at least one, such as one, two, etc., unless otherwise clearly and specifically defined.

[0048] In the present invention, when referring to numerical ranges, unless otherwise specified, the numerical ranges are considered continuous and include the minimum and maximum values ​​of the range, as well as every value between such minimum and maximum values. Furthermore, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe a feature or characteristic, the ranges can be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges subsumed therein.

[0049] Unless otherwise specified, the percentage contents mentioned in the present invention refer to mass percentage for solid-liquid mixture and solid-solid mixture, and refer to volume percentage for liquid-liquid mixture.

[0050] The percentage concentrations mentioned in the present invention, unless otherwise specified, refer to the final concentration, which refers to the percentage of the added component in the system after the addition of the component.

[0051] The temperature parameters in the present invention, unless otherwise specified, allow both constant temperature treatment and treatment within a certain temperature range. The constant temperature treatment allows the temperature to fluctuate within the accuracy range of instrument control. Fluctuations within the ranges of ±5°C, ±2°C, ±1°C, ±0.5°C, ±0.4°C, ±0.3°C, ±0.2°C, and ±0.1°C are permitted. Normal temperature in the present invention refers to no temperature control operation, generally 4°C to 35°C, preferably 20±5°C.

[0052] In the present invention, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0053] In recent years, with the rapid development of the electronics industry, traditional epoxy resins have struggled to meet the high-performance requirements of laminates. To accommodate the rapid growth of the semiconductor industry, a number of high-performance resin matrices have emerged, such as polyimide, one of the most comprehensive organic polymer materials. Among these, bismaleimide resins, a derivative of the polyimide resin system, are bifunctional compounds with maleimide (MI) as the active end group. They exhibit similar fluidity and moldability to epoxy resins and can be processed and molded using the same general methods as epoxy resins, overcoming the relatively low heat resistance of epoxy resins.

[0054] Therefore, bismaleimide resin (BMI) is widely used in aviation, aerospace, machinery, electronics and other industrial fields due to its excellent heat resistance, electrical insulation, wave transparency, radiation resistance, flame retardancy, good mechanical properties and dimensional stability, and molding process similar to epoxy resin. It is used as the resin matrix of advanced composite materials, high-temperature insulating materials and adhesives. However, unmodified bismaleimide resin has poor solubility, high crosslinking density, and large brittleness of the solidified product, making it difficult to use alone and must be modified with a modifier before use. Therefore, how to obtain a resin with low thermal expansion coefficient, high heat resistance and high modulus has always been a difficult problem for those skilled in the art to overcome.

[0055] During experiments, researchers at the present application unexpectedly discovered that modifying a bismaleimide resin using a terpolymer naphthalene bisallyl ether compound containing multiple highly rigid naphthalene rings as a modifier can help reduce the thermal expansion coefficient and improve the compatibility of the prepolymer with other components in the resin composition. By rationally matching the proportions of the components and regulating the reaction conditions, a modified bismaleimide prepolymer with excellent performance can be produced. Due to the presence of multiple naphthalene rings in the structure, the resulting bismaleimide prepolymer has a low thermal expansion coefficient, excellent high-temperature modulus retention, and extremely high heat resistance. Therefore, a low thermal expansion coefficient resin composition can be obtained without adding a large amount of inorganic filler, thus avoiding the dispersibility and processability issues associated with the addition of large amounts of inorganic fillers.

[0056] At the same time, the resin composition prepared using the above-mentioned modified bismaleimide prepolymer as raw material can be used to further prepare prepregs and laminates, so that the final laminate has a low thermal expansion coefficient, excellent high-temperature modulus retention and extremely high heat resistance. When used in thin substrate materials for semiconductor packaging, it can effectively suppress the warping problem.

[0057] A first aspect of the present invention provides a modified bismaleimide prepolymer obtained by prepolymerizing a bismaleimide resin and a modifier.

[0058] In one specific example, the modifier includes a first modifier.

[0059] In one specific example, the functional group of the first modifier includes two or more naphthalene rings. It is understood that the first modifier includes an organic compound with two or more naphthalene rings, and the number of naphthalene rings in the first modifier includes but is not limited to: 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0060] In one specific example, the first modifier includes a tripolynaphthalene bisallyl ether compound.

[0061] In one specific example, the tri-naphthalene bisallyl ether compound includes a compound having a structure as described in Formula I:

[0062] In one specific example, the modifier further includes a second modifier;

[0063] Optionally, the second modifier includes one or more of diallyl bisphenol A, diallyl bisphenol S, diallyl bisphenol F and bisphenol A bisallyl ether.

[0064] It can be understood that when the bismaleimide resin is modified with a modifier, the first modifier, i.e., the tripolynaphthalene bisallyl ether compound, can be used alone or in combination with a second modifier such as diallyl bisphenol A, diallyl bisphenol S, diallyl bisphenol F, or bisphenol A bisallyl ether, and the combination ratio is not limited.

[0065] Specifically, a bismaleimide resin is modified using a terpolymer naphthalene bisallyl ether modifier represented by formula (I). The resulting bismaleimide prepolymer has multiple naphthalene rings in its structure, and its cured product has the characteristics of a low thermal expansion coefficient, excellent high-temperature modulus retention and extremely high heat resistance. Therefore, a resin composition with a low thermal expansion coefficient can be obtained without adding a large amount of inorganic filler, thereby avoiding the problems of dispersibility and processability caused by adding a large amount of inorganic filler.

[0066] In one specific example, the mass ratio of the bismaleimide resin to the modifier is (1-2): 1. It is understood that the mass ratio of the bismaleimide resin to the modifier includes but is not limited to: 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1 and 2:1.

[0067] In one specific example, the bismaleimide resin includes one or more of N,N'-(4,4'-methylenediphenyl)bismaleimide, N,N'-(1,4-phenylene)bismaleimide, N,N'-(4-methyl-1,3-phenylene)bismaleimide, N,N'-m-phenylene bismaleimide, bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, polyphenylmethane bismaleimide and bismaleimide containing a biphenyl structure.

[0068] The second aspect of the present invention provides a method for preparing the modified bismaleimide prepolymer as described above, comprising the following steps:

[0069] The bismaleimide resin is mixed with the modifier to perform a prepolymerization reaction.

[0070] In one specific example, in the prepolymerization reaction, the temperature of the prepolymerization reaction is 140° C.-170° C. It can be understood that the temperature of the prepolymerization reaction includes but is not limited to: 140° C., 150° C., 160° C., and 170° C.

[0071] In one specific example, the prepolymerization reaction time is 60 min-180 min. It is understandable that the prepolymerization reaction time includes but is not limited to: 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min, 130 min, 140 min, 150 min, 160 min, 170 min and 180 min.

[0072] A third aspect of the present invention provides a resin composition, wherein the raw materials thereof comprise the following components in parts by weight:

[0073] 40-70 parts of modified bismaleimide prepolymer;

[0074] 30-80 parts of resin matrix;

[0075] The modified bismaleimide prepolymer comprises the modified bismaleimide prepolymer described above. Further, the resin composition comprises 40-60 parts by weight of the modified bismaleimide prepolymer.

[0076] In one specific example, the resin matrix includes the following components in parts by weight:

[0077] 20-50 parts of cyanate resin;

[0078] 10-30 parts of functional resin.

[0079] In one specific example, the resin composition further comprises 30-100 parts by weight of an inorganic filler. Furthermore, the resin composition further comprises 30-70 parts by weight of the inorganic filler.

[0080] In one specific example, the inorganic filler accounts for less than 40% by mass in the resin composition.

[0081] In one specific example, the inorganic filler includes one or more of zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, eucryptite, silica, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc, aluminum oxide, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, clay and kaolin.

[0082] In one specific example, the silica includes one or more of spherical silica, composite silica and fused silica.

[0083] In one specific example, the cyanate ester resin includes one or more of bisphenol A cyanate ester resin, novolac cyanate ester resin, bisphenol F cyanate ester resin, bisphenol M cyanate ester resin, bisphenol E cyanate ester resin, naphthalene cyanate ester resin, biphenyl cyanate ester resin, bisphenol S cyanate ester resin, and dicyclopentadiene bisphenol cyanate ester resin. Furthermore, the resin composition includes 20-40 parts by weight of the cyanate ester resin.

[0084] In one specific example, the functional resin includes one or more of epoxy resin, benzoxazine resin, modified polyphenylene ether, silicone resin, and hydrocarbon resin. Furthermore, the resin composition includes 10-20 parts by weight of the functional resin.

[0085] In one specific example, the epoxy resin includes one or more of naphthalene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phosphorus-containing epoxy resin, unsaturated epoxy resin, phenolic epoxy resin, o-cresol-type epoxy resin, bisphenol A phenolic epoxy resin, multifunctional epoxy resin, alicyclic epoxy resin, resorcinol epoxy resin, rubber-modified epoxy resin, biphenyl epoxy resin and dicyclopentadiene epoxy resin.

[0086] In one specific example, the benzoxazine resin includes one or more of bisphenol A benzoxazine resin, bisphenol F benzoxazine resin, main chain benzoxazine resin, phosphorus-containing benzoxazine, bisphenol S benzoxazine resin, dicyclopentadiene benzoxazine resin, biphenyl benzoxazine resin, tetraphenol ethane benzoxazine resin and naphthalene benzoxazine resin.

[0087] In one specific example, the raw materials of the resin composition include the following components in parts by weight:

[0088] Wherein, the modified bismaleimide prepolymer includes the modified bismaleimide prepolymer described above.

[0089] In one specific example, the raw materials of the resin composition include the following components in parts by weight:

[0090] Wherein, the modified bismaleimide prepolymer includes the modified bismaleimide prepolymer described above.

[0091] In one specific example, the raw materials of the resin composition further include 10-20 parts by weight of a flame retardant.

[0092] In one specific example, the raw materials of the resin composition further include 1-10 parts by weight of a curing accelerator.

[0093] In one specific example, the raw materials of the resin composition further include 1-5 parts of auxiliary agents by weight.

[0094] In one specific example, the flame retardant includes one or more of decabromodiphenylethane, tetrabromobisphenol A, brominated epoxy resin, phosphorus-containing epoxy resin, phosphorus-containing phenolic resin, phosphazene compound, phosphate ester compound and phosphorus-containing cyanate ester.

[0095] In one specific example, the curing accelerator includes one or more of a tertiary amine accelerator, an imidazole accelerator, a peroxide accelerator, an organophosphorus accelerator, and a transition metal carboxylate accelerator.

[0096] In one specific example, the auxiliary agent includes one or more of a leveling agent, a defoaming agent, a dispersant, a coupling agent, and a treating agent.

[0097] In one specific example, the raw materials of the resin composition include the following components in parts by weight:

[0098] Wherein, the modified bismaleimide prepolymer includes the modified bismaleimide prepolymer described above.

[0099] In one specific example, the raw materials of the resin composition include the following components in parts by weight:

[0100] Wherein, the modified bismaleimide prepolymer includes the modified bismaleimide prepolymer described above.

[0101] In one specific example, the raw materials for preparing the resin composition further include a solvent, and the solvent includes one or more of butanone, toluene and propylene glycol methyl ether.

[0102] A fourth aspect of the present invention provides a prepreg comprising a reinforcing material and the resin composition as described above.

[0103] A fifth aspect of the present invention provides a method for preparing the prepreg as described above, comprising the following steps:

[0104] The resin composition is covered on the surface of the reinforcing material by an impregnation method, and heated to semi-solidification to prepare a semi-cured sheet.

[0105] In one specific example, the process parameters of the semi-curing are: heating to a constant temperature of 120-230° C. for 3 minutes to 15 minutes.

[0106] In one specific example, the reinforcing material includes one or more of an inorganic fiber material and an organic fiber material. The inorganic fiber material includes one or more of glass fiber, carbon fiber, silicon carbide fiber, and asbestos fiber; and the organic fiber material includes one or more of nylon, ultra-high molecular weight polyethylene fiber, aramid fiber, polyimide fiber, polyester fiber, and cotton fiber.

[0107] According to a sixth aspect of the present invention, there is provided a laminated board, which is produced by curing the prepreg as described above.

[0108] A seventh aspect of the present invention provides a method for preparing the laminate as described above, comprising the following steps:

[0109] Several of the above-mentioned prepregs are laminated.

[0110] In one specific example, the lamination process parameters are: temperature 150℃~300℃, pressure 10kgf / cm 2 ~30kgf / cm 2 , under the condition of vacuum degree <2kPa, hot pressing is carried out for 200min~400min.

[0111] It can be understood that the “several prepregs” refer to at least one prepreg.

[0112] It is understandable that during lamination, a plurality of the prepregs, ie, a laminate, may be coated with metal copper foil on one side or both sides, and then laminated to obtain a metal copper foil-clad laminate.

[0113] In one specific example, the thickness of the metal copper foil is 3 μm to 105 μm. It is understood that the thickness of the metal copper foil includes but is not limited to: 3 μm, 5 μm, 8 μm, 10 μm, 15 μm, 18 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm and 105 μm.

[0114] An eighth aspect of the present invention provides use of the modified bismaleimide prepolymer, the resin composition, the prepreg, and the laminate in a semiconductor package.

[0115] The present invention will be further described in detail with reference to specific embodiments.

[0116] Unless otherwise specified, the raw materials, reagents, etc. used in the following examples can be purchased from commercial products. Some of the raw materials used in the examples and comparative examples of this application are as follows:

[0117] Tripolynaphthalene bisallyl ether can be purchased from Kungang New Materials;

[0118] Bismaleimide resin can be purchased from Yamato Chemical under the model number BMI-1000. The chemical formula is shown in the figure below:

[0119] Diallyl bisphenol A can be purchased from Honghu Shuangma Resin Factory under the model DABPA;

[0120] Biphenyl epoxy resin can be purchased from Nippon Kayaku, model number NC-3000H;

[0121] Bisphenol A cyanate ester can be purchased from Lonza Group under the model number BA-3000S;

[0122] The flame retardant is a phosphinothric compound, available from Otsuka Chemical under the model number SPB-100;

[0123] Spherical silica can be purchased from Yaduma, model number SO-C1;

[0124] 2-Methylimidazole can be purchased from Shikoku Chemical under the model number 2MI;

[0125] The additive is a defoaming agent, which can be purchased from BYK Chemicals under the model number BYK-1650.

[0126] For experimental parameters not specified in the following specific examples, reference should be made to the guidelines provided in this application document. Reference may also be made to experimental manuals in the art, other experimental methods known in the art, or manufacturer-recommended experimental conditions. It should be understood that the instruments and raw materials used in the following examples are relatively specific and are not limited to these in other specific examples.

[0127] Examples 1 to 6 provide a modified bismaleimide resin and a preparation method thereof, a resin composition and a preparation method thereof, a prepreg and a preparation method thereof, and a laminate and a preparation method thereof, as follows:

[0128] Example 1

[0129] (1) First, 60 parts of tert-naphthalene bisallyl ether were heated to a molten state, and then 100 parts of bismaleimide resin were added. The mixture was prepolymerized at 150° C. for 90 minutes and then cooled to room temperature to obtain a modified bismaleimide prepolymer A.

[0130] (2) 40 parts of the modified bismaleimide prepolymer A, 30 parts of bisphenol A cyanate resin, 15 parts of biphenyl epoxy resin, and 10 parts of flame retardant are dissolved in a mixed solvent of 50 parts of butanone, toluene, and propylene glycol methyl ether, wherein the butanone, toluene, and propylene glycol methyl ether are mixed uniformly in a mass ratio of 1:1:1. 30 parts of spherical silica, 1 part of an auxiliary agent, and 1 part of 2-methylimidazole are added under stirring, and stirring is continued to obtain a uniform glue solution, i.e., a modified bismaleimide prepolymer resin composition.

[0131] (3) The 2116 type glass fiber cloth was impregnated with the modified bismaleimide prepolymer resin composition and then placed in a hot air circulation oven and baked at 160° C. for 5 minutes to obtain a prepreg.

[0132] (4) Eight prepreg sheets were stacked, and a 12 μm thick electrolytic copper foil was covered on each of the upper and lower sides of the stack. The stack was placed in a programmable temperature and pressure controlled vacuum press. The pressure was 25 kgf / cm2 under vacuum. 2 Under the pressure of , after hot pressing and curing according to the procedure of 180℃★2h+220℃★2h, a copper clad laminate with a thickness of 0.8mm was made.

[0133] Example 2

[0134] (1) First, 60 parts of tert-naphthalene bisallyl ether were heated to a molten state, and then 100 parts of bismaleimide resin were added. The mixture was prepolymerized at 150° C. for 90 minutes and then cooled to room temperature to obtain a modified bismaleimide prepolymer A.

[0135] (2) 50 parts of the modified bismaleimide prepolymer A, 20 parts of bisphenol A cyanate resin, 20 parts of biphenyl epoxy resin, and 15 parts of flame retardant are dissolved in 60 parts of a mixed solvent of butanone, toluene, and propylene glycol methyl ether, wherein the butanone, toluene, and propylene glycol methyl ether are mixed uniformly in a mass ratio of 1:1:1. 50 parts of spherical silica, 3 parts of an auxiliary agent, and 5 parts of 2-methylimidazole are added under stirring, and stirring is continued to obtain a uniform glue solution, i.e., a modified bismaleimide prepolymer resin composition.

[0136] (3) The 2116 type glass fiber cloth was immersed in the above modified bismaleimide prepolymer resin composition glue solution and then placed in a hot air circulation oven and baked at 170°C for 6 minutes to form a semi-cured sheet.

[0137] (4) Eight prepreg sheets were stacked, and a 12 μm thick electrolytic copper foil was covered on each of the upper and lower sides of the stack. The stack was placed in a programmable temperature and pressure controlled vacuum press. The pressure was 25 kgf / cm2 under vacuum. 2Under the pressure of , after hot pressing and curing according to the procedure of 180℃★2h+220℃★2h, a copper clad laminate with a thickness of 0.8mm was made.

[0138] Example 3

[0139] (1) First, 60 parts of tert-naphthalene bisallyl ether were heated to a molten state, and then 100 parts of bismaleimide resin were added. The mixture was prepolymerized at 150° C. for 90 minutes and then cooled to room temperature to obtain a modified bismaleimide prepolymer A.

[0140] (2) 60 parts of the modified bismaleimide prepolymer A, 40 parts of bisphenol A cyanate resin, 10 parts of biphenyl epoxy resin, and 20 parts of flame retardant are dissolved in a mixed solvent of 60 parts of butanone, toluene, and propylene glycol methyl ether, wherein the butanone, toluene, and propylene glycol methyl ether are mixed uniformly in a mass ratio of 1:1:1. 70 parts of spherical silica, 5 parts of an auxiliary agent, and 10 parts of 2-methylimidazole are added under stirring, and stirring is continued to obtain a uniform glue solution, i.e., a modified bismaleimide prepolymer resin composition.

[0141] (3) The 2116 type glass fiber cloth was immersed in the above modified bismaleimide prepolymer resin composition glue solution and then placed in a hot air circulation oven and baked at 165° C. for 5 minutes to obtain a semi-cured sheet.

[0142] (4) Eight prepreg sheets were stacked, and a 12 μm thick electrolytic copper foil was covered on each of the upper and lower sides of the stack. The stack was placed in a programmable temperature and pressure controlled vacuum press. The pressure was 25 kgf / cm2 under vacuum. 2 Under the pressure of , after hot pressing and curing according to the procedure of 175℃★2h+220℃★2h, a copper clad laminate with a thickness of 0.8mm was made.

[0143] Example 4

[0144] (1) First, 100 parts of tert-naphthalene bisallyl ether were heated to a molten state, and then 100 parts of bismaleimide resin were added. The mixture was prepolymerized at 150° C. for 120 minutes and then cooled to room temperature to obtain a modified bismaleimide prepolymer B.

[0145] (2) 50 parts of the modified bismaleimide prepolymer B, 20 parts of bisphenol A cyanate resin, 20 parts of biphenyl epoxy resin, and 15 parts of flame retardant are dissolved in a mixed solvent of 50 parts of butanone, toluene, and propylene glycol methyl ether, wherein the butanone, toluene, and propylene glycol methyl ether are mixed uniformly in a mass ratio of 1:1:1. 50 parts of spherical silica, 3 parts of an auxiliary agent, and 5 parts of 2-methylimidazole are added under stirring, and stirring is continued to obtain a uniform glue solution, i.e., a modified bismaleimide prepolymer resin composition.

[0146] (3) The 2116 type glass fiber cloth was immersed in the above modified bismaleimide prepolymer resin composition glue solution and then placed in a hot air circulation oven and baked at 165° C. for 6 minutes to obtain a semi-cured sheet.

[0147] (4) Eight prepreg sheets were stacked, and a 12 μm thick electrolytic copper foil was covered on each of the upper and lower sides of the stack. The stack was placed in a programmable temperature and pressure controlled vacuum press. The pressure was 25 kgf / cm2 under vacuum. 2 Under the pressure of , after hot pressing and curing according to the procedure of 180℃★2h+230℃★2h, a 0.8mm thick copper clad laminate was made.

[0148] Example 5

[0149] (1) First, 80 parts of tert-naphthalene bisallyl ether were heated to a molten state, and then 100 parts of bismaleimide resin were added. The mixture was prepolymerized at 150° C. for 100 minutes and then cooled to room temperature to obtain a modified bismaleimide prepolymer C.

[0150] (2) 50 parts of the modified bismaleimide prepolymer C, 20 parts of bisphenol A cyanate resin, 20 parts of biphenyl epoxy resin, and 15 parts of flame retardant are dissolved in a mixed solvent of 50 parts of butanone, toluene, and propylene glycol methyl ether, wherein the butanone, toluene, and propylene glycol methyl ether are mixed uniformly in a mass ratio of 1:1:1. 50 parts of spherical silica, 3 parts of an auxiliary agent, and 5 parts of 2-methylimidazole are added under stirring, and stirring is continued to obtain a uniform glue solution, i.e., a modified bismaleimide prepolymer resin composition.

[0151] (3) The 2116 type glass fiber cloth was immersed in the above modified bismaleimide prepolymer resin composition glue solution and then placed in a hot air circulation oven and baked at 165° C. for 6 minutes to obtain a semi-cured sheet.

[0152] (4) Eight prepreg sheets were stacked, and a 12 μm thick electrolytic copper foil was covered on each of the upper and lower sides of the stack. The stack was placed in a programmable temperature and pressure controlled vacuum press. The pressure was 25 kgf / cm2 under vacuum. 2 Under the pressure of , after hot pressing and curing according to the procedure of 180℃★2h+220℃★2h, a copper clad laminate with a thickness of 0.8mm was made.

[0153] Example 6

[0154] (1) First, 60 parts of tripolynaphthalene bisallyl ether and 20 parts of allyl bisphenol A were heated to a molten state, and then 100 parts of bismaleimide resin were added. The mixture was prepolymerized at 150°C for 120 minutes and then cooled to room temperature to obtain a modified bismaleimide prepolymer D.

[0155] (2) 50 parts of the modified bismaleimide prepolymer D, 20 parts of bisphenol A cyanate resin, 20 parts of biphenyl epoxy resin, and 15 parts of flame retardant are dissolved in a mixed solvent of 50 parts of butanone, toluene, and propylene glycol methyl ether, wherein the butanone, toluene, and propylene glycol methyl ether are mixed uniformly in a mass ratio of 1:1:1. 50 parts of spherical silica, 3 parts of an auxiliary agent, and 5 parts of 2-methylimidazole are added under stirring, and stirring is continued to obtain a uniform glue solution, i.e., a modified bismaleimide prepolymer resin composition.

[0156] (3) The 2116 type glass fiber cloth was immersed in the above modified bismaleimide prepolymer resin composition glue solution and then placed in a hot air circulation oven and baked at 165° C. for 6 minutes to obtain a semi-cured sheet.

[0157] (4) Eight prepreg sheets were stacked, and a 12 μm thick electrolytic copper foil was covered on each of the upper and lower sides of the stack. The stack was placed in a programmable temperature and pressure controlled vacuum press. The pressure was 25 kgf / cm2 under vacuum. 2 Under the pressure of , after hot pressing and curing according to the procedure of 180℃★2h+220℃★2h, a 0.8mm thick copper clad foil was made.

[0158] Comparative Example 1

[0159] (1) First, 80 parts of allyl bisphenol A were heated to a molten state, and then 100 parts of bismaleimide resin were added. The mixture was prepolymerized at 150° C. for 120 minutes and then cooled to room temperature to obtain a modified bismaleimide prepolymer E.

[0160] (2) 50 parts of the modified bismaleimide prepolymer E, 20 parts of bisphenol A cyanate resin, 20 parts of biphenyl epoxy resin, and 15 parts of flame retardant are dissolved in a mixed solvent of 50 parts of butanone, toluene, and propylene glycol methyl ether, wherein the butanone, toluene, and propylene glycol methyl ether are mixed uniformly in a mass ratio of 1:1:1. 50 parts of spherical silica, 3 parts of an auxiliary agent, and 5 parts of 2-methylimidazole are added under stirring, and stirring is continued to obtain a uniform glue solution, i.e., a modified bismaleimide prepolymer resin composition.

[0161] (3) The 2116 type glass fiber cloth was immersed in the above modified bismaleimide prepolymer resin composition glue solution and then placed in a hot air circulation oven and baked at 165° C. for 6 minutes to obtain a semi-cured sheet.

[0162] (4) Eight prepreg sheets were stacked, and a 12 μm thick electrolytic copper foil was covered on each of the upper and lower sides of the stack. The stack was placed in a programmable temperature and pressure controlled vacuum press. The pressure was 25 kgf / cm2 under vacuum. 2Under the pressure of , after hot pressing and curing according to the procedure of 180℃★2h+220℃★2h, a copper clad laminate with a thickness of 0.8mm was made.

[0163] Comparative Example 2

[0164] (1) 50 parts of unmodified bismaleimide resin, 20 parts of bisphenol A cyanate resin, 20 parts of biphenyl epoxy resin, and 15 parts of flame retardant are dissolved in a mixed solvent of 50 parts of butanone, toluene, and propylene glycol methyl ether, wherein the butanone, toluene, and propylene glycol methyl ether are mixed uniformly in a mass ratio of 1:1:1. Under stirring conditions, 50 parts of spherical silica, 3 parts of an auxiliary agent, and 5 parts of 2-methylimidazole are added, and stirring is continued to obtain a uniform glue solution, i.e., an unmodified bismaleimide prepolymer resin composition.

[0165] (2) The 2116 type glass fiber cloth was immersed in the above modified bismaleimide prepolymer resin composition glue solution and then placed in a hot air circulation oven and baked at 165° C. for 6 minutes to obtain a semi-cured sheet.

[0166] (3) Eight prepreg sheets were stacked, and a 12 μm thick electrolytic copper foil was covered on each of the upper and lower sides of the stack. The stack was placed in a programmable temperature and pressure controlled vacuum press. The pressure was 25 kgf / cm2 under vacuum. 2 Under the pressure of , after hot pressing and curing according to the procedure of 180℃★2h+220℃★2h, a copper clad laminate with a thickness of 0.8mm was made.

[0167] The formulas and process parameters of the bismaleimide prepolymers of Examples 1 to 6 and Comparative Examples 1 to 2 are summarized in Table 1 below:

[0168] Table 1

[0169] The formulas of the resin compositions in the preparation methods of Examples 1 to 6 and Comparative Examples 1 to 2 are listed in Table 2 below:

[0170] Table 2

[0171] The resin compositions and copper-clad laminates prepared in Examples 1 to 6 and Comparative Examples 1 to 2 were subjected to performance tests. The test methods are as follows:

[0172] (1) Resin compatibility: Visual inspection, let it stand for one day, and observe whether there is precipitation and stratification;

[0173] (2) Peel strength: The test method is carried out in accordance with IPC-TM-650 2.4.8;

[0174] (3) Glass transition temperature (Tg) / high temperature modulus: tested according to IPC-TM650 2.4.25D;

[0175] (4) Coefficient of thermal expansion (XYZ-CTE): Tested according to IPC-TM650 2.4.24;

[0176] (5) Flame retardant grade: tested according to IPC-TM650 2.3.10.

[0177] The test results are shown in Table 3 below.

[0178] Table 3

[0179] From the experimental results in Table 3 above, it can be seen that the copper-clad laminates prepared from the bismaleimide prepolymer, resin composition, and prepreg provided in Examples 1 to 6 have a low thermal expansion coefficient, excellent high-temperature modulus retention, and extremely high heat resistance. At the same time, they also have better peel strength and better compatibility, and their performance is significantly improved.

[0180] It can be seen from Example 2 and Comparative Example 2 that precipitation problems occurred after the unmodified bismaleimide prepolymer was used in Comparative Example 2, and the compatibility was poor; it can be seen from Example 2 and Comparative Example 1 that the modified bismaleimide prepolymer of the present invention has a significantly lower thermal expansion coefficient and an increased glass transition temperature compared with the traditional modifier.

[0181] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0182] The above-described embodiments merely represent several implementation methods of the present invention, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art may make various modifications and improvements without departing from the spirit of the present invention, and these modifications and improvements fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be based on the appended claims, and the description may be used to interpret the content of the claims.

Claims

1. A modified bismaleimide prepolymer, characterized in that: It is obtained by prepolymerization of bismaleimide resin and a modifier; The modifier includes a first modifier, and a functional group of the first modifier includes two or more naphthalene rings.

2. The modified bismaleimide prepolymer according to claim 1, characterized in that The first modifier includes tert-naphthalene bisallyl ether compounds.

3. The modified bismaleimide prepolymer according to claim 2, characterized in that: The tripolynaphthalene bisallyl ether compounds include compounds having a structure as described in Formula I:

4. The modified bismaleimide prepolymer according to any one of claims 1 to 3, characterized in that: The modifier also includes a second modifier; Optionally, the second modifier includes one or more of diallyl bisphenol A, diallyl bisphenol S, diallyl bisphenol F and bisphenol A bisallyl ether.

5. The modified bismaleimide prepolymer according to any one of claims 1 to 3, characterized in that: The mass ratio of the bismaleimide resin to the modifier is (1-2):

1.

6. The modified bismaleimide prepolymer according to any one of claims 1 to 3, characterized in that: The bismaleimide resin includes one or more of N,N'-(4,4'-methylenediphenyl)bismaleimide, N,N'-(1,4-phenylene)bismaleimide, N,N'-(4-methyl-1,3-phenylene)bismaleimide, N,N'-m-phenylene bismaleimide, bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, polyphenylmethane bismaleimide and bismaleimide containing biphenyl structure.

7. The method for preparing the modified bismaleimide prepolymer according to any one of claims 1 to 6, characterized in that: The steps include: The bismaleimide resin is mixed with the modifier to perform a prepolymerization reaction.

8. The method for preparing the modified bismaleimide prepolymer according to claim 7, characterized in that: The prepolymerization reaction satisfies at least one of the following conditions: (1) The temperature of the prepolymerization reaction is 140°C-170°C; (2) The prepolymerization reaction time is 60min-180min.

9. A resin composition, characterized in that The raw materials include the following components by weight: 40-70 parts of modified bismaleimide prepolymer; Resin matrix 30-80 parts; Wherein, the modified bismaleimide prepolymer comprises the modified bismaleimide prepolymer according to any one of claims 1 to 6.

10. The resin composition according to claim 9, characterized in that The resin matrix includes the following components in parts by weight: 20-50 parts of cyanate resin; 10-30 parts of functional resin.

11. The resin composition according to claim 9 or 10, characterized in that The components thereof, by weight, also include 30-100 parts of inorganic filler; Optionally, the inorganic filler accounts for less than 40% by mass in the resin composition; Optionally, the inorganic filler includes one or more of zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, eucryptite, silicon dioxide, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc, aluminum oxide, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, clay and kaolin.

12. The resin composition according to claim 10, characterized in that The cyanate resin includes one or more of bisphenol A cyanate resin, phenol formaldehyde cyanate resin, bisphenol F cyanate resin, bisphenol M cyanate resin, bisphenol E cyanate resin, naphthalene cyanate resin, biphenyl cyanate resin, bisphenol S cyanate resin and dicyclopentadiene bisphenol cyanate resin; and / or The functional resin includes one or more of epoxy resin, benzoxazine resin, modified polyphenylene ether, silicone resin and hydrocarbon resin.

13. The resin composition according to claim 9 or 10, characterized in that The raw materials thereof further include, by weight: 10-20 parts of flame retardant; and / or 1-10 parts of curing accelerator; and / or 1-5 parts of additives.

14. A prepreg, characterized in that: The invention comprises a reinforcing material and the resin composition according to any one of claims 9 to 13.

15. A laminated board, characterized in that: It is obtained by curing the prepreg according to claim 15.

16. Use of the modified bismaleimide prepolymer according to any one of claims 1 to 8, the resin composition according to any one of claims 9 to 13, the prepreg according to claim 14, and the laminate according to claim 15 in a semiconductor package.

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