Modified Bismaleimide Prepolymer, Resin Composition, Preparation Method and Application Thereof

Abstract

The present invention relates to a modified bismaleimide prepolymer, a resin composition, and a preparation method and application thereof. By using a modifier containing a naphthalene ring to modify the bismaleimide resin, the obtained modified bismaleimide prepolymer has two or more naphthalene rings in its structure, and its cured product has the characteristics of a low coefficient of thermal expansion, excellent high-temperature modulus retention, and extremely high heat resistance. At the same time, by reasonably formulating the above-mentioned modified bismaleimide prepolymer with the remaining raw material components, a resin composition with a low coefficient of thermal expansion, excellent high-temperature modulus retention, and extremely high heat resistance can be prepared without adding a large proportion of inorganic fillers, avoiding the problems of dispersibility and processability caused by adding a large amount of inorganic fillers. Further, the laminate prepared from the above resin composition has excellent performance. When applied to the thin substrate material for semiconductor packaging, the problem of warping can be effectively suppressed, and it has good application prospects.

Description

Technical Field

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

[0002] In recent years, with the development of semiconductor packages towards thinner, lighter, and more multifunctional directions, higher requirements have been put forward for semiconductor packages, that is, semiconductor packages require higher integration and higher density installation. Therefore, further reducing the coefficient of thermal expansion (CTE) of the laminate for semiconductor packages has become one of the key problems to be solved urgently.

[0003] Regarding how to reduce the coefficient of thermal expansion of the laminate, the traditional method is generally to add a large amount of inorganic fillers to the resin composition. The mass percentage of the inorganic fillers in the resin composition is generally above 60%. Although the addition of a large amount of inorganic fillers has a certain effect on reducing the coefficient of thermal expansion of the laminate, due to the limitation of the expansion coefficient of the inorganic fillers themselves, when the addition amount of the inorganic fillers reaches a certain proportion, it is difficult to further reduce the coefficient of thermal expansion of the board. In addition, the addition of a large amount of fillers will also seriously affect the dispersibility of the resin composition, resulting in a decline in the processing performance of the board, such as shortening the service life of the drill bit, affecting the processing efficiency and yield, etc. Summary of the Invention

[0004] Based on this, it is necessary to provide a modified bismaleimide prepolymer, a resin composition, and a preparation method and application thereof. By using a modifier containing multiple naphthalene rings to modify the bismaleimide resin, a modified bismaleimide prepolymer is prepared. When the resin composition is prepared with this as the raw material, a large amount of inorganic fillers can be avoided, and the resin composition has a low coefficient of thermal expansion. In addition, the resin composition can also have excellent high-temperature modulus retention and high heat resistance.

[0005] The specific technical solutions are as follows:

[0006] In the first aspect of the present invention, a modified bismaleimide prepolymer is provided, which is obtained by prepolymerizing a bismaleimide resin and a modifier;

[0007] The modifier includes a first modifier, and the functional group of the first modifier includes two or more naphthalene rings.

[0008] In one embodiment, the first modifier includes a trinaphthalene diallyl ether compound.

[0009] In one embodiment, the trinaphthalene diallyl ether compound includes a compound having the structure as shown in Formula I:

[0010] (I)。

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

[0012] Optionally, the second modifier comprises one or more of diallylbisphenol A, diallylbisphenol S, diallylbisphenol F, and bisphenol A diallyl 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 comprises 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] In a second aspect of the present invention, there is provided a method for preparing the modified bismaleimide prepolymer as described above, comprising the following steps:

[0016] Mix the bismaleimide resin with the modifier and carry out 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 o °C - 170 o °C;

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

[0020] In a third aspect of the present invention, there is provided a resin composition, the raw materials of which comprise the following components by weight:

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

[0022] 30 - 80 parts of the resin matrix;

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

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

[0025] 20 - 50 parts of cyanate ester resin;

[0026] 10 - 30 parts of functional resin.

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

[0028] Optionally, the mass ratio of the inorganic filler in the resin composition is less than 40%;

[0029] Optionally, the inorganic filler includes one or more of zirconium vanadate, zirconium tungstate, hafnium tungstate, glass-ceramics, leucite, silica, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc powder, 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 type cyanate ester resin, phenolic type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol M type cyanate ester resin, bisphenol E type cyanate ester resin, naphthalene type cyanate ester resin, biphenyl type cyanate ester resin, bisphenol S type cyanate ester resin, and dicyclopentadiene bisphenol type 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: 10 - 20 parts of flame retardant; and / or

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

[0034] 1 - 5 parts of auxiliary agent.

[0035] In a fourth aspect of the present invention, a prepreg is provided, which includes a reinforcing material and the resin composition as described above.

[0036] In a fifth aspect of the present invention, a laminate is provided, which is obtained by curing the prepreg as described above.

[0037] In a sixth aspect of the present invention, an application of the modified bismaleimide prepolymer as described above, the resin composition as described above, the prepreg as described above, and the laminate as described above in a semiconductor package is provided.

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

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

[0040] Meanwhile, the above-mentioned modified bismaleimide prepolymer is rationally formulated with the remaining raw material components, and each component is matched with each other according to specific weight parts. While making the resin composition have a low coefficient of thermal expansion, it also has excellent high-temperature modulus retention and extremely high heat resistance; further, the laminate prepared from the above-mentioned resin composition has relatively excellent performance. When applied to the thin substrate material for semiconductor packaging, the problem of warping can be effectively suppressed, and it has good application prospects. Specific Embodiments

[0041] In order to make the above objects, features, and advantages of the present invention more obvious and understandable, the specific embodiments of the present invention will be described in detail below. Many specific details are set forth in the following description in order to fully understand the present invention. However, the present invention can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without departing from the connotation of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed below.

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

[0043] Unless otherwise stated or there is a contradiction, the terms or phrases used herein 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] As used herein, the optional scope of "and / or", "or / and", and "and / or" includes any one of two or more related listed items, and also includes any and all combinations of the related listed items. The said any and all combinations include any two related listed items, any more related listed items, or the combination of all related listed items.

[0046] In this text, terms such as "further", "even further", "especially", etc. are used for descriptive purposes to indicate differences in content, but should not be construed as limiting the scope of protection of the present invention.

[0047] In this text, terms such as "first aspect", "second aspect", "third aspect", "fourth aspect", etc. are only used for descriptive purposes and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. In addition, "first", "second", "third", "fourth", etc. only serve for non-exhaustive enumerative description purposes and should be understood not to constitute a closed limitation on quantity. Thus, features defined with "first" and "second" may explicitly or implicitly include at least one such feature. In the description of the invention, "a plurality" means at least two, such as two, three, etc., unless otherwise specifically defined. In the description of the present invention, "several" means at least one, such as one, two, etc., unless otherwise specifically defined.

[0048] In the present invention, regarding numerical ranges, unless otherwise specified, the above numerical ranges are considered continuous and include the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when the range refers to integers, it includes each integer between the minimum and maximum values of the range. In addition, when multiple ranges are provided to describe features or characteristics, these ranges can be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all sub-ranges subsumed therein.

[0049] In the present invention, the percentage content involved, unless otherwise specified, refers to the mass percentage for solid-liquid mixtures and solid-solid mixtures, and refers to the volume percentage for liquid-liquid mixtures.

[0050] In the present invention, the percentage concentration involved, unless otherwise specified, refers to the final concentration. The final concentration refers to the proportion of the added component in the system after adding this component.

[0051] The temperature parameters in the present invention, unless otherwise specifically limited, allow both isothermal treatment and treatment within a certain temperature range. The isothermal treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument. Fluctuation within a range such as ±5°C, ±2°C, ±1°C, ±0.5°C, ±0.4°C, ±0.3°C, ±0.2°C, ±0.1°C is allowed. Normal temperature in the present invention refers to no temperature control operation, generally referring to 4 °C to 35 °C, preferably 20 ± 5°C.

[0052] In the present invention, for technical features described in an open-ended manner, it includes a closed technical solution composed of the listed features, as well as an open technical solution containing the listed features.

[0053] In recent years, with the rapid development of the electronics industry, traditional epoxy resins have been difficult to meet the high-performance requirements of laminates. In order to adapt to the high-speed development of the semiconductor industry, many high-performance resin matrices have emerged, such as polyimide, which is one of the organic polymer materials with the best comprehensive performance. Among them, bismaleimide resin is another type of resin system derived from the polyimide resin system. It is a bifunctional compound with maleimide (MI) as the active end group. It has fluidity and moldability similar to those of epoxy resins and can be processed and formed by the same general methods as epoxy resins, overcoming the disadvantage of relatively low heat resistance of epoxy resins.

[0054] Therefore, bismaleimide resin (BMI) is widely used in industrial fields such as aviation, aerospace, machinery, and electronics due to its excellent heat resistance, electrical insulation, wave transmission, radiation resistance, flame retardancy, good mechanical properties and dimensional stability, and a molding process similar to that of epoxy resins, such as the resin matrix of advanced composites, high-temperature insulation materials, and adhesives. However, unmodified bismaleimide resin has poor solubility, too high crosslinking density, and brittle cured products, making it difficult to be used alone and requiring modification with a modifier before use. Therefore, how to obtain a resin with both a low coefficient of thermal expansion, high heat resistance, and high modulus has always been a difficult problem for those skilled in the art to overcome.

[0055] During the experiment, the researchers of this application unexpectedly found that when using a trinaphthalene diallyl ether compound with multiple highly rigid naphthalene rings in its structure as a modifier to modify bismaleimide resin, it is beneficial to reduce the coefficient of thermal expansion and improve the compatibility of the prepolymer with other components in the resin composition. By reasonably formulating the proportion of each component and controlling the reaction conditions, a modified bismaleimide prepolymer with excellent properties can be prepared. Due to the presence of multiple naphthalene rings in the structure of the prepared bismaleimide prepolymer, its cured product has the characteristics of a low coefficient of thermal expansion, excellent high-temperature modulus retention, and extremely high heat resistance. Therefore, a resin composition with a low coefficient of thermal expansion can be obtained without adding a large proportion of inorganic fillers, avoiding the problems of dispersion and processability caused by adding a large amount of inorganic fillers.

[0056] At the same time, a resin composition prepared from the above-mentioned modified bismaleimide prepolymer can be used to further prepare prepregs and laminates, making the finally prepared laminates have a low coefficient of thermal expansion, excellent high-temperature modulus retention, and extremely high heat resistance. When applied to the thin substrate material for semiconductor packaging, the problem of warping can be effectively suppressed.

[0057] In the first aspect of the present invention, a modified bismaleimide prepolymer is provided, which is obtained by prepolymerizing bismaleimide resin and a modifier.

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

[0059] In one specific example, the functional groups of the first modifier include two or more naphthalene rings. It can be understood that the first modifier is an organic compound including two or more naphthalene rings. The number of naphthalene rings of 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 trinaphthalene diallyl ether compounds.

[0061] In one specific example, the trinaphthalene diallyl ether compounds include compounds having the structure shown in Formula I:

[0062] (I).

[0063] In one specific example, the modifier further includes a second modifier;

[0064] Optionally, the second modifier includes one or more of diallyl bisphenol A, diallyl bisphenol S, diallyl bisphenol F, and bisphenol A diallyl ether.

[0065] It can be understood that when the bismaleimide resin is modified with a modifier, the first modifier, i.e., the trinaphthalene diallyl ether compound, can be used alone or in combination with a second modifier such as diallyl bisphenol A, diallyl bisphenol S, diallyl bisphenol F, and bisphenol A diallyl ether, and the mixing ratio is not limited.

[0066] Specifically, when the bismaleimide resin is modified with the trinaphthalene diallyl ether modifier shown in Formula (I), the cured product of the obtained bismaleimide prepolymer has the characteristics of a low coefficient of thermal expansion, excellent high-temperature modulus retention, and extremely high heat resistance due to the presence of multiple naphthalene rings in its structure. Therefore, a resin composition with a low coefficient of thermal expansion can be obtained without adding a large proportion of inorganic fillers, avoiding the problems of dispersibility and processability caused by adding a large amount of inorganic fillers.

[0067] In one specific example, the mass ratio of the bismaleimide resin to the modifier is (1 - 2):1. It can be 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.

[0068] 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.

[0069] In a second aspect of the present invention, there is provided a method for preparing the modified bismaleimide prepolymer as described above, comprising the following steps:

[0070] Mix the bismaleimide resin with the modifier and carry out a prepolymerization reaction.

[0071] In one specific example, in the prepolymerization reaction, the temperature of the prepolymerization reaction is 140 o °C - 170 o °C. It can be understood that the temperature of the prepolymerization reaction includes but is not limited to: 140°C, 150°C, 160°C, 170°C.

[0072] In one specific example, the time of the prepolymerization reaction is 60 min - 180 min. It can be understood that the time of the prepolymerization reaction 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.

[0073] In a third aspect of the present invention, there is provided a resin composition, the raw materials of which include the following components by weight:

[0074] Modified bismaleimide prepolymer 40 - 70 parts;

[0075] Resin matrix 30 - 80 parts;

[0076] Wherein, the modified bismaleimide prepolymer includes the modified bismaleimide prepolymer as described above. Further, the resin composition includes 40 - 60 parts of the modified bismaleimide prepolymer by weight.

[0077] In one specific example, the resin matrix includes the following components by weight:

[0078] 20 - 50 parts of cyanate ester resin;

[0079] 10 - 30 parts of functional resin.

[0080] In one specific example, the components of the resin composition, by weight parts, further include 30 - 100 parts of inorganic filler. Further, the resin composition includes 30 - 70 parts of the inorganic filler by weight parts.

[0081] In one specific example, the mass proportion of the inorganic filler in the resin composition is less than 40%.

[0082] In one specific example, the inorganic filler includes one or more of zirconium vanadate, zirconium tungstate, hafnium tungstate, glass ceramics, lithium nepheline, silicon dioxide, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc powder, 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.

[0083] In one specific example, the silicon dioxide includes one or more of spherical silicon dioxide, composite silicon dioxide, and fused silicon dioxide.

[0084] In one specific example, the cyanate ester resin includes one or more of bisphenol A cyanate ester resin, phenolic 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. Further, the resin composition includes 20 - 40 parts of the cyanate ester resin by weight parts.

[0085] In one specific example, the functional resin includes one or more of epoxy resin, benzoxazine resin, modified polyphenylene ether, silicone resin, and hydrocarbon resin. Further, the resin composition includes 10 - 20 parts of the functional resin by weight parts.

[0086] In one specific example, the epoxy resin includes one or more of naphthalene epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, unsaturated epoxy resin, phenolic epoxy resin, o-cresol novolac epoxy resin, bisphenol A phenolic epoxy resin, multi-functional epoxy resin, alicyclic epoxy resin, resorcinol epoxy resin, rubber-modified epoxy resin, biphenyl epoxy resin, and dicyclopentadiene epoxy resin.

[0087] 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-type benzoxazine resin, tetraphenylethane benzoxazine resin, and naphthalene-type benzoxazine resin.

[0088] In one specific example, the raw materials of the resin composition include the following components by weight:

[0089] Modified bismaleimide prepolymer 40 - 70 parts;

[0090] Cyanate ester resin 20 - 50 parts;

[0091] Functional resin 10 - 30 parts;

[0092] Inorganic filler 30 - 100 parts;

[0093] Among them, the modified bismaleimide prepolymer includes the modified bismaleimide prepolymer as described above.

[0094] In one specific example, the resin composition, its raw materials include the following components by weight:

[0095] Modified bismaleimide prepolymer 40 - 60 parts;

[0096] Cyanate ester resin 20 - 40 parts;

[0097] Functional resin 10 - 20 parts;

[0098] Inorganic filler 30 - 70 parts;

[0099] Among them, the modified bismaleimide prepolymer includes the modified bismaleimide prepolymer as described above.

[0100] In one specific example, the raw materials of the resin composition further include 10 - 20 parts of a flame retardant by weight.

[0101] In one specific example, the raw materials of the resin composition further include 1 - 10 parts of a curing accelerator by weight.

[0102] In one specific example, the raw materials of the resin composition further include 1 - 5 parts of an auxiliary agent by weight.

[0103] 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, phosphonitrile compound, phosphate compound, and phosphorus-containing cyanate ester.

[0104] In one specific example, the curing accelerator includes one or more of tertiary amine accelerators, imidazole accelerators, peroxide accelerators, organophosphorus accelerators, and transition metal carboxylate accelerators.

[0105] In one specific example, the additives include one or more of a leveling agent, an antifoaming agent, a dispersant, a coupling agent, and a treating agent.

[0106] In one specific example, the raw materials of the resin composition include the following components by weight parts:

[0107] Modified bismaleimide prepolymer: 40 - 70 parts;

[0108] Cyanate ester resin: 20 - 50 parts;

[0109] Functional resin: 10 - 30 parts;

[0110] Inorganic filler: 30 - 100 parts;

[0111] Flame retardant: 10 - 20 parts;

[0112] Curing accelerator: 1 - 10 parts;

[0113] Additives: 1 - 5 parts;

[0114] Among them, the modified bismaleimide prepolymer includes the modified bismaleimide prepolymer as described above.

[0115] In one specific example, the raw materials of the resin composition include the following components by weight parts:

[0116] Modified bismaleimide prepolymer: 40 - 60 parts;

[0117] Cyanate ester resin: 20 - 40 parts;

[0118] Functional resin: 10 - 20 parts;

[0119] Inorganic filler: 30 - 70 parts;

[0120] Flame retardant: 10 - 20 parts;

[0121] Curing accelerator: 1 - 10 parts;

[0122] Additives: 1 - 5 parts;

[0123] Among them, the modified bismaleimide prepolymer includes the modified bismaleimide prepolymer as described above.

[0124] In one specific example, the raw materials for preparing the resin composition further include a solvent, and the solvent includes one or more of methyl ethyl ketone, toluene, and propylene glycol methyl ether.

[0125] In a fourth aspect of the present invention, there is provided a prepreg, comprising a reinforcing material and the resin composition as described above.

[0126] In a fifth aspect of the present invention, there is provided a method for preparing a prepreg as described above, comprising the following steps:

[0127] By means of impregnation, the above resin composition is covered on the surface of the reinforcing material and heated to semi-cured state to prepare the prepreg.

[0128] In one specific example, the process parameters of the semi-curing are: heating to 120 - 230 °C and keeping constant temperature for 3 - 15 minutes.

[0129] In one specific example, the reinforcing material includes one or more of inorganic fiber materials and organic fiber materials. The inorganic fiber materials include one or more of glass fiber, carbon fiber, silicon carbide fiber, and asbestos fiber; the organic fiber materials include one or more of nylon, ultra-high molecular weight polyethylene fiber, aramid fiber, polyimide fiber, polyester fiber, and cotton fiber.

[0130] In a sixth aspect of the present invention, there is provided a laminate, which is obtained by curing the prepreg as described above.

[0131] In a seventh aspect of the present invention, there is provided a method for preparing a laminate as described above, comprising the following steps:

[0132] Laminate a plurality of the above prepregs.

[0133] In one specific example, the process parameters of the lamination are: at a temperature of 150 °C to 300 °C, a pressure of 10 kgf / cm 2 ~ 30 kgf / cm 2 , and a degree of vacuum < 2 kPa, hot press forming for 200 - 400 minutes.

[0134] It can be understood that the "a plurality of the prepregs" refers to at least one prepreg.

[0135] It can be understood that, during lamination, a metal copper foil can also be covered on one or both sides of the plurality of prepregs, that is, the laminate, and then laminated to obtain a copper-clad laminate.

[0136] In one specific example, the thickness of the metallic copper foil is 3 μm to 105 μm. It is understandable that the thickness of the metallic 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.

[0137] In the eighth aspect of the present invention, there is provided an application of the modified bismaleimide prepolymer as described above, the resin composition as described above, the semi-cured sheet as described above, and the laminate as described above in a semiconductor package.

[0138] The present invention will be further described in detail in conjunction with specific embodiments.

[0139] The raw materials, reagents, etc. used in the following examples can be purchased from commercially available products without special instructions. Some of the raw materials used in the examples and comparative examples of this application are as follows:

[0140] Tricoronene diallyl ether can be purchased from Kun Gang New Materials;

[0141] The bismaleimide resin can be purchased from Dainichi Kasei, with the model number BMI-1000, and the chemical formula is shown in the following figure:

[0142] ;

[0143] Diallyl bisphenol A can be purchased from Honghu Shuangma Resin Factory, with the model number DABPA;

[0144] Biphenyl epoxy resin can be purchased from Nippon Kayaku, with the model number NC-3000H;

[0145] Bisphenol A cyanate ester can be purchased from Lonza Group, with the model number BA-3000S;

[0146] The flame retardant is a phosphonitrile compound, which can be purchased from Otsuka Chemical, with the model number SPB-100;

[0147] Spherical silica can be purchased from Yaduma, with the model number SO-C1;

[0148] 2-Methylimidazole can be purchased from Shikoku Kasei, with the model number 2MI;

[0149] The auxiliary agent is an antifoaming agent, which can be purchased from BYK Chemie, with the model number BYK-1650.

[0150] For the experimental parameters not specified in the following specific embodiments, it is preferred to refer to the guidance given in this application document. It is also possible to refer to experimental manuals in this field or other experimental methods known in this field, or to the experimental conditions recommended by the manufacturer. It is understandable that the instruments and raw materials used in the following embodiments are relatively specific, and in other specific embodiments, this may not be limited thereto.

[0151] Examples 1 to 6 provide a modified bismaleimide resin, its preparation method, a resin composition, its preparation method, a prepreg, its preparation method, and a laminate, its preparation method, as follows:

[0152] Example 1

[0153] (1) First, heat 60 parts of trinaphthalene diallyl ether to a molten state, then add 100 parts of bismaleimide resin, react and pre-polymerize at 150 °C for 90 min, and then cool to room temperature to obtain a modified bismaleimide prepolymer A.

[0154] (2) Sequentially dissolve 40 parts of the above-mentioned modified bismaleimide prepolymer A, 30 parts of bisphenol A cyanate resin, 15 parts of biphenyl epoxy resin, and 10 parts of flame retardant in 50 parts of a mixed solvent of methyl ethyl ketone, toluene, and propylene glycol methyl ether, wherein methyl ethyl ketone, toluene, and propylene glycol methyl ether are mixed evenly according to a mass ratio of 1:1:1. Under stirring conditions, add 30 parts of spherical silica, 1 part of additive, and 1 part of 2-methylimidazole, and continue stirring to obtain a uniform adhesive solution, that is, a modified bismaleimide prepolymer resin composition.

[0155] (3) Immerse a 2116 type glass fiber cloth in the above-mentioned modified bismaleimide prepolymer resin composition, and then place it in a hot air circulation oven and bake at 160 °C for 5 min to obtain a semi-cured sheet.

[0156] (4) Stack 8 semi-cured sheets, cover each side of the stack with an electrolytic copper foil with a thickness of 12 μm, place it in a programmable temperature and pressure vacuum press, and under vacuum conditions, at a pressure of 25 kgf / cm², cure by hot pressing according to the program of 180 °C * 2 h + 220 °C * 2 h to make a copper-clad laminate with a thickness of 0.8 mm.

[0157] Example 2

[0158] (1) First, heat 60 parts of trinaphthalene diallyl ether to a molten state, then add 100 parts of bismaleimide resin, react and pre-polymerize at 150 °C for 90 min, and then cool to room temperature to obtain a modified bismaleimide prepolymer A.

[0159] (2) 50 parts of the above-mentioned modified bismaleimide prepolymer A, 20 parts of bisphenol A cyanate ester resin, 20 parts of biphenyl epoxy resin, and 15 parts of flame retardant were successively dissolved in 60 parts of a mixed solvent of methyl ethyl ketone, toluene, and propylene glycol methyl ether, wherein methyl ethyl ketone, toluene, and propylene glycol methyl ether were mixed evenly according to a mass ratio of 1:1:1. Under stirring conditions, 50 parts of spherical silica, 3 parts of additive, and 5 parts of 2-methylimidazole were added, and stirring was continued to obtain a uniform adhesive solution, namely the modified bismaleimide prepolymer resin composition.

[0160] (3) The 2116 type glass fiber cloth was impregnated with the above-mentioned modified bismaleimide prepolymer resin composition adhesive solution and then placed in a hot air circulation oven, baked at 170 °C for 6 min to obtain a semi-cured sheet.

[0161] (4) 8 semi-cured sheets were laminated, and one electrolytic copper foil with a thickness of 12 μm was covered on each of the upper and lower surfaces of the laminate, and placed in a programmable temperature and pressure vacuum press. Under vacuum conditions, at a pressure of 25 kgf / cm², after hot pressing and curing according to the procedure of 180 °C * 2 h + 220 °C * 2 h, a copper clad laminate with a thickness of 0.8 mm was made.

[0162] Example 3

[0163] (1) First, 60 parts of trinaphthalene diallyl ether were heated to a molten state, then 100 parts of bismaleimide resin were added, and after reacting and prepolymerizing at 150 °C for 90 min, it was cooled to room temperature to obtain the modified bismaleimide prepolymer A.

[0164] (2) 60 parts of the above-mentioned modified bismaleimide prepolymer A, 40 parts of bisphenol A cyanate ester resin, 10 parts of biphenyl epoxy resin, and 20 parts of flame retardant were successively dissolved in 60 parts of a mixed solvent of methyl ethyl ketone, toluene, and propylene glycol methyl ether, wherein methyl ethyl ketone, toluene, and propylene glycol methyl ether were mixed evenly according to a mass ratio of 1:1:1. Under stirring conditions, 70 parts of spherical silica, 5 parts of additive, and 10 parts of 2-methylimidazole were added, and stirring was continued to obtain a uniform adhesive solution, namely the modified bismaleimide prepolymer resin composition.

[0165] (3) The 2116 type glass fiber cloth was impregnated with the above-mentioned modified bismaleimide prepolymer resin composition adhesive solution and then placed in a hot air circulation oven, baked at 165 °C for 5 min to obtain a semi-cured sheet.

[0166] (4) 8 semi-cured sheets were laminated, and one electrolytic copper foil with a thickness of 12 μm was covered on each of the upper and lower surfaces of the laminate, and placed in a programmable temperature and pressure vacuum press. Under vacuum conditions, at a pressure of 25 kgf / cm², after hot pressing and curing according to the procedure of 175 °C * 2 h + 220 °C * 2 h, a copper clad laminate with a thickness of 0.8 mm was made.

[0167] Example 4

[0168] (1) First, heat 100 parts of trinaphthalene diallyl ether to the molten state, then add 100 parts of bismaleimide resin, react and pre-polymerize at 150 °C for 120 min, and then cool to room temperature to obtain the modified bismaleimide prepolymer B.

[0169] (2) Sequentially dissolve 50 parts of the above-mentioned modified bismaleimide prepolymer B, 20 parts of bisphenol A cyanate ester resin, 20 parts of biphenyl epoxy resin, and 15 parts of flame retardant in 50 parts of a mixed solvent of methyl ethyl ketone, toluene, and propylene glycol methyl ether, wherein methyl ethyl ketone, toluene, and propylene glycol methyl ether are mixed evenly according to a mass ratio of 1:1:1. Under stirring conditions, add 50 parts of spherical silica, 3 parts of auxiliary agent, and 5 parts of 2-methylimidazole, and continue stirring to obtain a uniform adhesive solution, that is, the modified bismaleimide prepolymer resin composition.

[0170] (3) Immerse the 2116 type glass fiber cloth in the above-mentioned modified bismaleimide prepolymer resin composition adhesive solution, and then place it in a hot air circulation oven and bake at 165 °C for 6 min to obtain a semi-cured sheet.

[0171] (4) Stack 8 semi-cured sheets, cover each of the upper and lower surfaces of the laminate with an electrolytic copper foil with a thickness of 12 μm, place it in a programmable temperature and pressure vacuum press, and under a vacuum state, at a pressure of 25 kgf / cm², cure by hot pressing according to the procedure of 180 °C * 2 h + 230 °C * 2 h to make a copper-clad laminate with a thickness of 0.8 mm.

[0172] Example 5

[0173] (1) First, heat 80 parts of trinaphthalene diallyl ether to the molten state, then add 100 parts of bismaleimide resin, react and pre-polymerize at 150 °C for 100 min, and then cool to room temperature to obtain the modified bismaleimide prepolymer C.

[0174] (2) Sequentially dissolve 50 parts of the above-mentioned modified bismaleimide prepolymer C, 20 parts of bisphenol A cyanate ester resin, 20 parts of biphenyl epoxy resin, and 15 parts of flame retardant in 50 parts of a mixed solvent of methyl ethyl ketone, toluene, and propylene glycol methyl ether, wherein methyl ethyl ketone, toluene, and propylene glycol methyl ether are mixed evenly according to a mass ratio of 1:1:1. Under stirring conditions, add 50 parts of spherical silica, 3 parts of auxiliary agent, and 5 parts of 2-methylimidazole, and continue stirring to obtain a uniform adhesive solution, that is, the modified bismaleimide prepolymer resin composition.

[0175] (3) Immerse the 2116 type glass fiber cloth in the above-mentioned modified bismaleimide prepolymer resin composition adhesive solution, and then place it in a hot air circulation oven and bake at 165 °C for 6 min to obtain a semi-cured sheet.

[0176] (4) Stack 8 prepregs, cover each side of the stack with an electrolytic copper foil with a thickness of 12 μm, place it in a programmable temperature and pressure vacuum press, and under vacuum, at a pressure of 25 kgf / cm², cure it by hot pressing according to the procedure of 180 °C * 2 h + 220 °C * 2 h to obtain a copper-clad laminate with a thickness of 0.8 mm.

[0177] Example 6

[0178] (1) First, heat 60 parts of trinaphthalene diallyl ether and 20 parts of allyl bisphenol A to the molten state, then add 100 parts of bismaleimide resin, react and pre-polymerize at 150 °C for 120 min, and then cool to room temperature to obtain a modified bismaleimide prepolymer D.

[0179] (2) Sequentially dissolve 50 parts of the above-mentioned modified bismaleimide prepolymer D, 20 parts of bisphenol A cyanate resin, 20 parts of biphenyl epoxy resin, and 15 parts of flame retardant in 50 parts of a mixed solvent of methyl ethyl ketone, toluene, and propylene glycol methyl ether, where methyl ethyl ketone, toluene, and propylene glycol methyl ether are mixed evenly according to a mass ratio of 1:1:1. Under stirring conditions, add 50 parts of spherical silica, 3 parts of additives, and 5 parts of 2-methylimidazole, and continue stirring to obtain a uniform glue solution, that is, a modified bismaleimide prepolymer resin composition.

[0180] (3) Immerse a 2116 type glass fiber cloth in the above-mentioned modified bismaleimide prepolymer resin composition glue solution, and then place it in a hot air circulation oven and bake at 165 °C for 6 min to obtain a prepreg.

[0181] (4) Stack 8 prepregs, cover each side of the stack with an electrolytic copper foil with a thickness of 12 μm, place it in a programmable temperature and pressure vacuum press, and under vacuum, at a pressure of 25 kgf / cm², cure it by hot pressing according to the procedure of 180 °C * 2 h + 220 °C * 2 h to obtain a copper-clad laminate with a thickness of 0.8 mm.

[0182] Comparative Example 1

[0183] (1) First, heat 80 parts of allyl bisphenol A to the molten state, then add 100 parts of bismaleimide resin, react and pre-polymerize at 150 °C for 120 min, and then cool to room temperature to obtain a modified bismaleimide prepolymer E.

[0184] (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 50 parts of a mixed solvent of butanone, toluene, and propylene glycol methyl ether, wherein 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., a modified bismaleimide prepolymer resin composition.

[0185] (3) The 2116 type glass fiber cloth was immersed in the 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.

[0186] (4) Stack 8 semi-cured sheets, cover the upper and lower surfaces of the stack with a 12 μm thick electrolytic copper foil, place it in a programmable temperature and pressure control vacuum press, and heat press and cure it at a pressure of 25 kgf / cm² at 180°C*2h+220°C*2h under vacuum to produce a 0.8 mm thick copper-clad laminate.

[0187] Comparative Example 2

[0188] (1) Dissolve 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 in 50 parts of a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein butanone, toluene and propylene glycol methyl ether are mixed uniformly in a mass ratio of 1:1:1. Add 50 parts of spherical silica, 3 parts of an auxiliary agent and 5 parts of 2-methylimidazole under stirring, and continue stirring to obtain a uniform glue solution, i.e., an unmodified bismaleimide prepolymer resin composition.

[0189] (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.

[0190] (3) Stack 8 semi-cured sheets, cover the upper and lower surfaces of the stack with a 12 μm thick electrolytic copper foil, place it in a programmable temperature and pressure control vacuum press, and heat-press and cure it at a pressure of 25 kgf / cm² at 180°C*2h+220°C*2h under vacuum to produce a 0.8 mm thick copper-clad laminate.

[0191] 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:

[0192] Table 1

[0193]

[0194] The formulation lists of the resin compositions in the preparation methods of Examples 1 to 6 and Comparative Examples 1 to 2 are shown in Table 2 below:

[0195] Table 2

[0196]

[0197] The resin compositions and copper-clad laminates prepared from Examples 1 to 6 and Comparative Examples 1 to 2 were subjected to performance tests. The test methods are as follows:

[0198] (1) Resin compatibility: Visually observed. After standing for one day, check whether there is precipitation and delamination;

[0199] (2) Peel strength: The test method was carried out in accordance with IPC-TM-650 2.4.8;

[0200] (3) Glass transition temperature (Tg) / high-temperature modulus: Tested according to IPC-TM650 2.4.25D;

[0201] (4) Coefficient of thermal expansion (XYZ-CTE): Tested according to IPC-TM650 2.4.24;

[0202] (5) Flame retardant rating: Tested according to IPC-TM650 2.3.10.

[0203] The test results are shown in Table 3 below.

[0204] Table 3

[0205]

[0206] It can be seen from the experimental results in Table 3 above that the copper-clad laminates prepared from the bismaleimide prepolymers, resin compositions, and prepregs provided in Examples 1 to 6 have both a low coefficient of thermal expansion, excellent high-temperature modulus retention, and extremely high heat resistance. At the same time, they also have better peel strength and better compatibility, and the performance improvement is obvious.

[0207] It can be seen from Example 2 and Comparative Example 2 that precipitation problems occurred and the compatibility was poor when the unmodified bismaleimide prepolymer was used in Comparative Example 2; it can be seen from Example 2 and Comparative Example 1 that compared with the traditional modifiers, the modified bismaleimide prepolymer of the present invention significantly reduces the coefficient of thermal expansion and simultaneously increases the glass transition temperature.

[0208] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as falling within the scope described in this specification.

[0209] The above-described embodiments only express several implementation manners of the present invention. The description is relatively specific and detailed, but it should not be construed as a limitation on the scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the invention patent shall be subject to the appended claims, and the description can be used to explain the content of the claims.

Claims

1. A modified bismaleimide prepolymer, characterized in that, It is obtained by pre-polymerizing a bismaleimide resin and a modifier; The modifier includes a first modifier, and the first modifier includes a trinaphthalene diallyl ether compound.

2. The modified bismaleimide prepolymer according to claim 1, wherein The trinaphthalene diallyl ether compound includes a compound having a structure shown in Formula I: 。 3. The modified bismaleimide prepolymer according to any one of claims 1-2, characterized in that The modifier further includes a second modifier; The second modifier includes one or more of diallyl bisphenol A, diallyl bisphenol S, diallyl bisphenol F, and bisphenol A diallyl ether.

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

1.

5. The modified bismaleimide prepolymer according to any one of claims 1-2, 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, 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 a bismaleimide containing a biphenyl structure.

6. The preparation method of the modified bismaleimide prepolymer according to any one of claims 1-5, characterized in that, It includes the following steps: Mix the bismaleimide resin with the modifier and carry out a pre-polymerization reaction.

7. The preparation method of the modified bismaleimide prepolymer according to claim 6, characterized in that, The pre-polymerization reaction satisfies at least one of the following conditions: (1) The temperature of the prepolymerization reaction is 140 o C - 170 o °C; (2) The time of the pre-polymerization reaction is 60 min - 180 min.

8. A resin composition, characterized in that, Its raw materials by weight include the following components: 40 - 70 parts of a modified bismaleimide prepolymer; 30 - 80 parts of a resin matrix; Among them, the modified bismaleimide prepolymer includes the modified bismaleimide prepolymer according to any one of claims 1 - 5.

9. The resin composition according to claim 8, wherein The resin matrix includes the following components by weight: 20 - 50 parts of a cyanate resin; 10 - 30 parts of a functional resin.

10. The resin composition according to claim 8 or 9, characterized in that, Its components by weight further include 30 - 100 parts of an inorganic filler; The mass proportion of the inorganic filler in the resin composition is less than 40%; The inorganic filler includes one or more of zirconium vanadate, zirconium tungstate, hafnium tungstate, glass-ceramics, leucite, silica, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc powder, 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.

11. The resin composition according to claim 9, characterized in that, The cyanate resin includes one or more of bisphenol A type cyanate resin, phenolic type cyanate resin, bisphenol F type cyanate resin, bisphenol M type cyanate resin, bisphenol E type cyanate resin, naphthalene type cyanate resin, biphenyl type cyanate resin, bisphenol S type cyanate resin, and dicyclopentadiene bisphenol type cyanate resin; and / or the functional resin includes one or more of epoxy resin, benzoxazine resin, modified polyphenylene ether, silicone resin, and hydrocarbon resin.

12. The resin composition according to claim 8 or 9, characterized in that, Its raw materials by weight further include: 10 - 20 parts of a flame retardant; and / or 1 - 10 parts of a curing accelerator; and / or 1-5 parts of auxiliary agent.

13. A prepreg, characterized in that, It includes a reinforcing material and the resin composition according to any one of claims 8-12.

14. A laminate, characterized in that, It is prepared by curing the prepreg according to claim 13.

15. Application of the modified bismaleimide prepolymer according to any one of claims 1-5, the resin composition according to any one of claims 8-12, the prepreg according to claim 13, and the laminate according to claim 14 in a semiconductor package.

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