Resin composition, method for producing the same, prepreg, laminate, and printed wiring board

Abstract

The application relates to a resin composition, a preparation method thereof, a prepreg, a laminated board and a printed circuit board. The resin composition comprises the following components in parts by mass: phthalonitrile-terminated polybutadiene 20-100 parts and bismaleimide benzoxazine prepolymer 1-40 parts. The resin composition has a high glass transition temperature and a high initial thermal decomposition temperature, and also has a high peeling strength, a low water absorption, a high elastic modulus, good flame retardancy and good dielectric properties; and the curing temperature of the resin composition is low.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of communication materials, in particular to a resin composition, a preparation method thereof, a prepreg, a laminate and a printed circuit board. BACKGROUND

[0002] In recent years, with the development of electronic circuits towards miniaturization, diversification and high-density interconnection, higher requirements are put forward for the performance of copper-clad plates.

[0003] As a resin with low dielectric constant and dielectric loss and low water absorption, hydrocarbon resin can be applied to the preparation of high-frequency high-speed copper-clad plates, and the raw materials are widely available, which is an ideal material to replace existing epoxy resin-based copper-clad plates. However, in the application process, there are disadvantages such as low glass transition temperature and insufficient initial thermal decomposition temperature, which are not conducive to the application in large-scale integrated circuits.

[0004] Therefore, it is necessary to improve the traditional technology. SUMMARY

[0005] Based on this, the present application provides a resin composition with a high glass transition temperature, a preparation method thereof, a prepreg, a laminate and a printed circuit board.

[0006] The technical solution of the present application to solve the above technical problems is as follows.

[0007] In one aspect, the present application provides a resin composition, which comprises the following components by mass fraction:

[0008] phthalonitrile-terminated polybutadiene 20-100 parts; and

[0009] bismaleimide benzoxazine prepolymer 1-40 parts.

[0010] In some embodiments, the resin composition comprises the following components by mass fraction:

[0011] phthalonitrile-terminated polybutadiene 20-50 parts; and

[0012] bismaleimide benzoxazine prepolymer 10-40 parts.

[0013] In some embodiments, the mass ratio of the phthalonitrile-terminated polybutadiene to the bismaleimide benzoxazine prepolymer in the resin composition is 0.5-5:1; optionally, the mass ratio of the phthalonitrile-terminated polybutadiene to the bismaleimide benzoxazine prepolymer is 1-5:1.

[0014] In some embodiments, the raw materials for preparing the bismaleimide benzoxazine prepolymer in the resin composition include a bismaleimide resin and a benzoxazine resin; optionally, the mass ratio of the bismaleimide resin to the benzoxazine resin is 0.5-1:1.

[0015] In some embodiments, the bismaleimide benzoxazine prepolymer in the resin composition satisfies at least one of the following characteristics:

[0016] (1) the monomer of the bismaleimide resin includes at least one of N-phenyl maleimide, N-(2-methylphenyl) maleimide, N-(4-methylphenyl) maleimide, N-(2,6-dimethylphenyl) maleimide, bis(4-maleimido phenyl) methane, 2,2-bis(4-(4-maleimido phenoxy)-phenyl) propane, bis(3,5-dimethyl-4-maleimido phenyl) methane, bis(3-ethyl-5-methyl-4-maleimido phenyl) methane, bis(3,5-diethyl-4-maleimido phenyl) methane, polyphenylmethane bismaleimide, a bismaleimide containing a biphenyl structure, and a poly maleimide;

[0017] (2) the benzoxazine resin includes at least one of a bisphenol A type benzoxazine resin, a bisphenol F type benzoxazine resin, a main chain type benzoxazine resin, a phosphorus-containing benzoxazine, a bisphenol S type benzoxazine resin, a dicyclopentadiene benzoxazine resin, a biphenyl type benzoxazine resin, a tetraphenyl ethane benzoxazine resin, a naphthalene type benzoxazine resin, and an allyl type benzoxazine resin.

[0018] In some embodiments, the resin composition further includes 10-60 parts of an inorganic filler by mass fraction; optionally, the inorganic filler includes at least one of zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, lithium feldspar, 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.

[0019] In one aspect, the present application provides a preparation method of a resin composition, including the following steps:

[0020] 20-100 parts of phthalonitrile-terminated polybutadiene and 1-40 parts of bismaleimide benzoxazine prepolymer are mixed by mass fraction.

[0021] In some embodiments, the preparation of the phthalonitrile-terminated polybutadiene in the preparation method of the resin composition includes the following steps:

[0022] A nucleophilic substitution reaction is carried out by mixing a hydroxyl-terminated polybutadiene, 4-nitrophthalonitrile and a solvent.

[0023] In some embodiments, the method for preparing the resin composition, the preparation of the bismaleimide-benzoxazine prepolymer comprises the following steps:

[0024] The bismaleimide resin and the benzoxazine resin are mixed at 110°C to 160°C to carry out a prepolymerization reaction.

[0025] In one aspect, the present application provides a resin film comprising the resin composition or the resin composition prepared by the method described above.

[0026] In one aspect, the present application provides a prepreg comprising a reinforcing material and the resin composition or the resin composition prepared by the method described above attached to the reinforcing material.

[0027] In one aspect, the present application provides a laminate comprising at least one of the resin film and the prepreg described above.

[0028] In one aspect, the present application provides a printed circuit board comprising at least one of the resin film, the prepreg and the laminate described above.

[0029] Compared with the prior art, the resin composition of the present application has the following beneficial effects:

[0030] The resin composition of the present application comprises a phthalonitrile-terminated polybutadiene and a bismaleimide-benzoxazine prepolymer in a specific ratio. The benzoxazine ring-opening of the bismaleimide-benzoxazine prepolymer produces phenolic hydroxyl structures and imine structures, which can promote the self-polymerization of the phthalonitrile-terminated polybutadiene to form indole rings, phthalimine rings and triazine rings, so that the resin composition has a high glass transition temperature and a high initial thermal decomposition temperature, and also has a high peel strength, a low water absorption, a high elastic modulus, good flame retardancy and good dielectric properties. At the same time, the benzoxazine ring-opening produces phenolic hydroxyl structures and Mannich-containing imine structures, which can catalyze cyanogen curing, thereby effectively reducing the curing temperature of the resin composition. DETAILED DESCRIPTION

[0031] The present application will be further described in detail below in conjunction with the embodiments and examples. It should be understood that these embodiments and examples are only used to illustrate the present application and not to limit the scope of the present application, and the purpose of providing these embodiments and examples is to make the disclosure of the present application more thorough and comprehensive.

[0032] It is also to be understood that the application can be carried out in various ways and that the application can be implemented in numerous forms, not all of which have been described herein; it should be understood that any subsequent changes and modifications in the art will likewise be encompassed by the application and are part of the contribution of the application to the art. For example, features stated or described as being part of one embodiment can be combined with features stated or described as being part of another embodiment to produce a new embodiment. Also, structural and related features of the application can be practiced in the absence of one or more of the other features that are described herein but not previously claimed in any claim.

[0033] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description herein is for describing the embodiments and examples only and is not intended to be limiting of the application.

[0034] Unless otherwise indicated, or unless the context clearly indicates otherwise, the terms or phrases used in this application have the following meanings:

[0035] As used herein in the specification and claims, including the phrase "a plurality" and "a plurality of", "plurality" means two or more unless otherwise indicated or unless the context clearly indicates otherwise.

[0036] As used herein, "combinations thereof", "any combination thereof", "any combination" and the like include all suitable combinations of any two or more of the listed items.

[0037] As used herein, "suitable combinations", "suitably", "any suitable manner", and the like mean that the combination, manner, etc. is one that enables the technical solution of the application to be implemented, the technical problem of the application to be solved, and the intended technical effects of the application to be achieved.

[0038] As used herein, "preferably", "more preferably", "even more preferably", "suitably" and the like are merely descriptive and do not constitute limitations on the scope of the application. If there are multiple "preferably" in a technical solution, and there is no specific description or contradictory relationship, each "preferably" is independent of each other.

[0039] As used herein, "further", "even further", "in particular" and the like are used to describe purposes and indicate differences in content, but should not be understood as limiting the scope of protection of the application.

[0040] In the present application, "optionally", "optional", "option" means optional, that is, selected from "yes" or "no" two parallel schemes. If there are multiple "options" in a technical solution, unless otherwise specified, and there is no contradiction or mutual restriction, each "option" is independent.

[0041] In the present application, the terms "first", "second", "third", "fourth" and the like in the "first aspect", "second aspect", "third aspect", "fourth aspect" and the like are only for description purposes, and cannot be understood as indicating or implying relative importance or quantity, nor can it be understood as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first", "second", "third", "fourth" and the like only serve the purpose of non-exhaustive enumeration description, and should be understood as not constituting a closed limitation on the quantity.

[0042] In the present application, the technical features described in an open manner include both closed technical solutions consisting of listed features and open technical solutions containing listed features.

[0043] In the present application, with respect to the numerical interval (i.e. numerical range), unless otherwise specified, the distribution of the optional values in the numerical interval is considered to be continuous, and includes both numerical endpoints (i.e. minimum value and maximum value) of the numerical interval and every value between the two numerical endpoints. Unless otherwise specified, when the numerical interval only points to the integers in the numerical interval, including the two endpoint integers of the numerical range and every integer between the two endpoints, it is equivalent to directly listing each integer. When multiple numerical ranges are provided to describe a feature or characteristic, these numerical ranges can be combined. In other words, unless otherwise specified, the numerical range disclosed herein should be understood to include any and all sub-ranges encompassed therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. The "numerical interval" allows for a broad interpretation of numerical interval types such as percentage interval, ratio interval, and value interval.

[0044] In the present application, unless otherwise specified, the temperature parameter allows for constant temperature treatment and allows for variation within a certain temperature interval. It should be understood that the constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument. It is allowed to fluctuate within the range of, for example, ±5°C, ±4°C, ±3°C, ±2°C, ±1°C.

[0045] In the present application, the term "room temperature" or "normal temperature" generally refers to 4°C to 35°C, for example 20°C ± 5°C. In some embodiments of the present application, "room temperature" or "normal temperature" refers to 10°C to 30°C. In some embodiments of the present application, "room temperature" or "normal temperature" refers to 20°C to 30°C.

[0046] In the present application, if the unit of data range is only indicated after the right end point, it means that the units of the left end point and the right end point are the same. For example, 3~5 h means that the units of the left end point "3" and the right end point "5" are both h (hour).

[0047] All the documents mentioned in the present application are incorporated by reference into the present application as if each document was individually incorporated by reference. Unless and to the extent that the content of the documents mentioned in the present application conflicts with the content of the present application, the content of the present application is incorporated by reference in its entirety. When the present application refers to the documents mentioned, the definitions of the relevant technical features, terms, names, phrases, etc. in the documents are also incorporated by reference. When the present application refers to the documents mentioned, the examples and preferred modes of the relevant technical features are also incorporated by reference into the present application, but are limited to the implementation of the present application. It should be understood that when the content of the documents mentioned conflicts with the description in the present application, the present application is given priority or is modified according to the description in the present application.

[0048] The mass or weight of the relevant components mentioned in the present application embodiment specification can not only refer to the specific content of each component, but also represent the proportional relationship between the mass or weight of each component. Therefore, as long as the content of the relevant components in the present application embodiment specification is enlarged or reduced in proportion, it is within the scope disclosed in the present application embodiment specification. Specifically, the mass or weight described in the present application embodiment specification can be μg, mg, g, kg, etc. units well known in the chemical field.

[0049] An embodiment of the present application provides a resin composition comprising the following components by mass fraction:

[0050] phthalodinitrile-terminated polybutadiene 20 parts to 100 parts; and

[0051] bismaleimide benzoxazine prepolymer 1 part to 40 parts.

[0052] The resin composition comprises phthalodinitrile-terminated polybutadiene and bismaleimide benzoxazine prepolymer in a specific proportion. The benzoxazine ring opening in the bismaleimide benzoxazine prepolymer produces phenolic hydroxyl structure and Mannich-containing imine structure, which can promote the self-polymerization of phthalodinitrile-terminated polybutadiene to form indole ring, phthalocyanine ring and triazine ring, so that the resin composition has a high glass transition temperature and a high initial thermal decomposition temperature, and also has a high peeling strength, a low water absorption, a high elastic modulus, a good flame retardancy and a good dielectric property. At the same time, the benzoxazine ring opening produces phenolic hydroxyl structure and Mannich-containing imine structure, which can catalyze the cyan group curing, so as to effectively reduce the curing temperature of the resin composition.

[0053] The benzoxazine ring opening generates phenolic hydroxyl structure and Mannich-containing imine structure as follows:

[0054]

[0055] The indole ring, phthalim ring and triazine ring formed by the self-polymerization of phthalonitrile-terminated polybutadiene are shown as formula (a), formula (b) and formula (c) respectively:

[0056]

[0057]

[0058] The indole ring, phthalim ring and triazine ring formed by the self-polymerization of phthalonitrile-terminated polybutadiene can increase the polarity of the polymer chain and improve the bonding strength of the resin composition to meet the needs of high-density interconnection circuit boards.

[0059] The curing temperature of phthalonitrile-terminated polybutadiene is high, and the benzoxazine ring opening in the bismaleimide benzoxazine prepolymer generates phenolic hydroxyl structure and Mannich-containing imine structure, which catalyzes the cyan group curing. On the basis of ensuring a low dielectric constant, the curing temperature of the resin composition is effectively reduced.

[0060] It is found that if the raw materials of the bismaleimide benzoxazine prepolymer, bismaleimide resin and benzoxazine resin, are used to react with phthalonitrile-terminated polybutadiene, the benzoxazine ring opening has limited effect, and sufficient imine structure cannot be obtained, and the ability to promote the self-polymerization of phthalonitrile-terminated polybutadiene is limited. In addition, the bismaleimide resin and benzoxazine resin will be cured in advance, have large steric hindrance, and increase the difficulty of phthalonitrile-terminated polybutadiene contacting with them, resulting in a decrease in the glass transition temperature and elastic modulus of the resin composition.

[0061] It can be appreciated that the mass fraction of the phthalonitrile-terminated polybutadiene in the resin composition, in terms of mass parts, includes but is not limited to 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, 60 parts, 61 parts, 62 parts, 63 parts, 64 parts, 65 parts, 66 parts, 67 parts, 68 parts, 69 parts, 70 parts, 71 parts, 72 parts, 73 parts, 74 parts, 75 parts, 76 parts, 77 parts, 78 parts, 79 parts, 80 parts, 81 parts, 82 parts, 83 parts, 84 parts, 85 parts, 86 parts, 87 parts, 88 parts, 89 parts, 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts, 100 parts; the mass fraction of the bismaleimide benzoxazine prepolymer includes but is not limited to 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts; in some examples, it can be within the range constituted by any two of these point values as end values, and the same applies below.

[0062] In some examples, the resin composition includes, in terms of mass parts, the following components:

[0063] phthalonitrile-terminated polybutadiene 20 parts to 50 parts; and

[0064] bismaleimide benzoxazine prepolymer 10 parts to 40 parts.

[0065] In some examples, the resin composition includes, in terms of mass parts, the following components:

[0066] phthalonitrile-terminated polybutadiene 30 parts to 50 parts; and

[0067] bismaleimide benzoxazine prepolymer 10 parts to 30 parts.

[0068] In some examples, the resin composition includes, in terms of mass parts, the following components:

[0069] phthalonitrile-terminated polybutadiene 32 parts to 42 parts; and

[0070] Bismaleimide benzoxazine prepolymer 18-28 parts.

[0071] In some examples, the resin composition comprises, by mass fraction, the following components:

[0072] Phthalonitrile-terminated polybutadiene 35-40 parts; and

[0073] Bismaleimide benzoxazine prepolymer 20-25 parts.

[0074] In some examples, the resin composition comprises, by mass fraction, the following components:

[0075] Phthalonitrile-terminated polybutadiene 38-42 parts; and

[0076] Bismaleimide benzoxazine prepolymer 18-22 parts.

[0077] In some examples, the resin composition comprises, by mass fraction, the following components:

[0078] It can be understood that the mass ratio of the phthalonitrile-terminated polybutadiene to the bismaleimide benzoxazine prepolymer includes but is not limited to 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 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, 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, 3:1, 3.1:1, 3.2:1, 3.3:1, 3.4:1, 3.5:1, 3.6:1, 3.7:1, 3.8:1, 3.9:1, 4:1, 4.1:1, 4.2:1, 4.3:1, 4.4:1, 4.5:1, 4.6:1, 4.7:1, 4.8:1, 4.9:1, 5:1.

[0079] In some examples, the resin composition comprises, by mass fraction, the following components:

[0080] In some examples, the resin composition comprises, by mass fraction, the following components:

[0081] In some examples, the mass ratio of the phthalonitrile-terminated polybutadiene to the bismaleimide benzoxazine prepolymer in the resin composition is 1.8 to 2.2:1.

[0082] In some examples, the raw materials for preparing the bismaleimide benzoxazine prepolymer in the resin composition include a bismaleimide resin and a benzoxazine resin.

[0083] It can be understood that, in some examples, the bismaleimide benzoxazine prepolymer is obtained by prepolymerization using a bismaleimide resin and a benzoxazine as raw materials.

[0084] In some examples, the mass ratio of the bismaleimide resin to the benzoxazine resin in the resin composition is 0.5 to 1:1.

[0085] It can be understood that the mass ratio of the bismaleimide resin to the benzoxazine resin includes, but is not limited to, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, and 1:1.

[0086] It can be understood that the bismaleimide resin is an organic compound containing two or more maleimide groups in the molecular structure.

[0087] In some examples, the monomer of the bismaleimide resin in the resin composition includes at least one of N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, bis(4-maleimido-phenyl)methane, 2,2-bis(4-(4-maleimido-phenoxy)-phenyl)propane, bis(3,5-dimethyl-4-maleimido-phenyl)methane, bis(3-ethyl-5-methyl-4-maleimido-phenyl)methane, bis(3,5-diethyl-4-maleimido-phenyl)methane, polyphenylmethane bismaleimide, a bismaleimide containing a biphenyl structure, and a polymaleimide.

[0088] In some examples, the benzoxazine resin in the resin composition includes at least one of a bisphenol A type benzoxazine resin, a bisphenol F type benzoxazine resin, a main chain type benzoxazine resin, a phosphorus-containing benzoxazine, a bisphenol S type benzoxazine resin, a dicyclopentadiene benzoxazine resin, a biphenyl type benzoxazine resin, a tetraphenyl ethane benzoxazine resin, a naphthalene type benzoxazine resin, and an allyl type benzoxazine resin.

[0089] In some examples, the raw materials for preparing the phthalonitrile-terminated polybutadiene in the resin composition include a hydroxyl-terminated polybutadiene and 4-nitrophthalonitrile.

[0090] If the 3-nitrophthalonitrile-terminated polybutadiene is adopted, the steric hindrance is large, and the difficulty of curing the resin composition is increased.

[0091] It can be understood that the phthalonitrile-terminated polybutadiene is synthesized by nucleophilic substitution with hydroxyl-terminated polybutadiene and 4-nitrophthalonitrile as raw materials; further, the kind, molecular weight and hydroxyl value of the hydroxyl-terminated polybutadiene are not particularly limited, including but not limited to at least one of G-1000, G-2000 and G-3000 of Japan Zeon Corporation and the like.

[0092] In some examples, the phthalonitrile-terminated polybutadiene in the resin composition includes a compound represented by formula (I):

[0093]

[0094] In some examples, the resin composition further includes 10-60 parts by mass of inorganic fillers.

[0095] It can be understood that the mass fraction of the inorganic fillers in the resin composition includes but is not limited to 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, and 60 parts by mass.

[0096] In some examples, the inorganic fillers in the resin composition include at least one of zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, lithium feldspar, silicon dioxide (spherical, composite and fused), 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.

[0097] Optionally, the mass fraction of the inorganic fillers in the resin composition is 30-60 parts.

[0098] In some examples, the resin composition further includes 120-180 parts by mass of the first solvent.

[0099] It can be understood that the mass fraction of the first solvent in the resin composition includes but is not limited to 120 parts, 125 parts, 130 parts, 135 parts, 140 parts, 145 parts, 150 parts, 155 parts, 160 parts, 165 parts, 170 parts, 175 parts, 180 parts.

[0100] Optionally, the first solvent includes at least one of toluene and N,N-dimethylformamide. Further, the first solvent includes toluene and N,N-dimethylformamide. Further, the mass ratio of toluene to N,N-dimethylformamide is 0.5-2:1. Optionally, the mass ratio of toluene to N,N-dimethylformamide is 1:1.

[0101] It can be understood that the resin composition provided by the present application can also include additives commonly used in the art; further, the mass fraction of the additive in the resin composition is 0-10 parts; further, the additive includes but is not limited to at least one of a curing accelerator, a surfactant, a coupling agent, and a toughening agent, etc. Further, the curing accelerator includes 2-methylimidazole.

[0102] The resin composition provided by the present application has a relatively high glass transition temperature and a relatively high initial thermal decomposition temperature, and also has a relatively high peeling strength, a relatively low water absorption, a relatively high elastic modulus, a relatively good flame retardancy, and a relatively good dielectric property; and the curing temperature of the resin composition is relatively low, which can be applied to the fields of integrated circuit packaging, high-frequency high-speed, and the like high-performance printed circuit board.

[0103] An embodiment of the present application provides a preparation method of a resin composition, including the following steps:

[0104] The phthalonitrile-terminated polybutadiene 20-100 parts and the bismaleimide benzoxazine prepolymer 1-40 parts are mixed in terms of mass fraction.

[0105] It can be understood that the resin composition can be prepared by the preparation method of the resin composition, the resin composition can be prepared by the preparation method of the resin composition, and the characteristics of the resin composition and the preparation method of the resin composition can be mutually applicable.

[0106] The resin composition prepared by the preparation method has a relatively high glass transition temperature and a relatively high initial thermal decomposition temperature, and also has a relatively high peeling strength, a relatively low water absorption, a relatively high elastic modulus, a relatively good flame retardancy, and a relatively good dielectric property; and the curing temperature of the resin composition is relatively low.

[0107] In some examples, the preparation method of the resin composition, the preparation of the phthalonitrile-terminated polybutadiene includes the following steps:

[0108] The hydroxyl-terminated polybutadiene, 4-nitrophthalonitrile and a second solvent are mixed to perform a nucleophilic substitution reaction.

[0109] In some examples, the second solvent includes N,N-dimethylformamide in the method of preparing the resin composition.

[0110] Further, the nucleophilic substitution reaction is performed in the presence of a catalyst. Further, the catalyst includes potassium carbonate.

[0111] Further, the nucleophilic substitution reaction is performed at a temperature of 50-60°C for a time period of 10-12 hours.

[0112] Further, the molar ratio of the hydroxyl-terminated polybutadiene to the 4-nitrophthalonitrile is 1:1-1.2.

[0113] In some examples, the method of preparing the resin composition includes preparing the bismaleimide benzoxazine prepolymer, which includes the following steps:

[0114] The bismaleimide resin and the benzoxazine resin are mixed at a temperature of 110-160°C to perform a prepolymerization reaction.

[0115] It can be understood that the temperature of the prepolymerization reaction includes but is not limited to 110°C, 120°C, 130°C, 140°C, 150°C, and 160°C.

[0116] Further, the mixing of the bismaleimide resin and the benzoxazine resin at a temperature of 110-160°C to perform a prepolymerization reaction includes the following steps:

[0117] The bismaleimide resin is heated to a molten state, and then the benzoxazine resin is added to perform a prepolymerization reaction at a temperature of 110-160°C, and then the mixture is cooled to room temperature to obtain the bismaleimide benzoxazine prepolymer.

[0118] An embodiment of the present application provides a resin film, which includes the resin composition or the resin composition prepared by the method described above.

[0119] The resin film of the present application includes the resin composition or the resin composition prepared by the method described above, and thus has at least the same advantages as the resin composition or the resin composition prepared by the method described above.

[0120] An embodiment of the present application provides a method of preparing a resin film, which includes the following steps:

[0121] The resin composition or the resin composition prepared by the method described above is coated on a release material to be dried and / or semi-cured.

[0122] The pre-preg according to an embodiment of the present application comprises the resin composition or the resin composition prepared by the method as described above, and thus has at least the same advantages as the resin composition or the resin composition prepared by the method as described above.

[0123] The pre-preg according to an embodiment of the present application comprises the resin composition or the resin composition prepared by the method as described above, and thus has at least the same advantages as the resin composition or the resin composition prepared by the method as described above.

[0124] In some examples, the reinforcing material in the pre-preg comprises at least one of inorganic fiber material and organic fiber material, but is not limited thereto.

[0125] Further, the inorganic fiber material comprises at least one of glass fiber (including different types such as E, NE, D, S, T, etc.), carbon fiber, silicon carbide fiber, and asbestos fiber, but is not limited thereto.

[0126] Further, the organic fiber material comprises at least one of nylon, ultra-high molecular weight polyethylene fiber, aramid fiber, polyimide fiber, polyester fiber, and cotton fiber, but is not limited thereto.

[0127] In some examples, the mass percentage of the resin composition in the pre-preg is 40% to 60%.

[0128] It can be understood that the mass percentage of the resin composition in the pre-preg comprises 40%, 50%, and 60%, but is not limited thereto.

[0129] The method for preparing the pre-preg according to an embodiment of the present application comprises the following steps:

[0130] The reinforcing material is impregnated in the resin composition or the resin composition prepared by the method as described above, and then the pre-preg is obtained after semi-curing.

[0131] It can be understood that the resin composition or the resin composition prepared by the method as described above covers the surface of the reinforcing material.

[0132] In some examples, the temperature for semi-curing in the method for preparing the pre-preg is 150°C to 250°C, and the time is 2 min to 10 min.

[0133] It can be understood that the temperature for semi-curing comprises 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, and 250°C, but is not limited thereto; and the time comprises 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min, and 10 min, but is not limited thereto.

[0134] The laminated board according to an embodiment of the present application comprises at least one of the resin film and the prepreg.

[0135] The laminated board according to an embodiment of the present application comprises at least one of the resin film and the prepreg, and thus has at least the same advantages as the resin film or the prepreg.

[0136] It can be understood that the laminated board comprises one or both of the resin film and the prepreg, and further, the resin film and the prepreg can each comprise one or more.

[0137] In some examples, the laminated board is provided with a metal foil on one side or both sides of the laminated board. Further, the metal foil comprises a copper foil. It can be understood that the laminated board is a copper clad laminate. Accordingly, the copper clad laminate according to an embodiment of the present application comprises at least one of the resin film and the prepreg, and a copper foil provided on at least one side of the resin film or the prepreg. Further, the thickness of the copper foil is 3 μm to 70 μm.

[0138] The method for preparing the laminated board according to an embodiment of the present application comprises the following steps:

[0139] At least one of the resin film and the prepreg is hot-pressed.

[0140] In some examples, the method for preparing the laminated board comprises the following parameters for hot-pressing: the temperature is 150°C to 300°C, the pressure is 10 kgf / cm 2 ~30 kgf / cm 2 , the vacuum degree is less than 2 kPa, and the hot-pressing time is 200 min to 400 min.

[0141] It can be understood that the temperature for hot-pressing includes but is not limited to 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C; the pressure includes but is not limited to 10 kgf / cm 2 , 12 kgf / cm 2 , 15 kgf / cm 2 , 18 kgf / cm 2 , 20 kgf / cm 2 , 22 kgf / cm 2 , 25 kgf / cm 2 , 28 kgf / cm 2 , and 30 kgf / cm 2The hot-pressing time includes, but is not limited to, 200 min, 210 min, 220 min, 230 min, 240 min, 250 min, 260 min, 270 min, 280 min, 290 min, 300 min, 310 min, 320 min, 330 min, 340 min, 350 min, 360 min, 370 min, 380 min, 390 min, and 400 min.

[0142] It can be understood that the resin film and the prepreg in the preparation method of the laminated board can be independent of each other, and the plurality of refers to at least one; further, the plurality of are stacked.

[0143] In some examples, the preparation method of the laminated board further comprises the step of arranging a metal foil on at least one side of at least one of the resin film and the prepreg before the hot-pressing step.

[0144] It can be understood that the metal foil is arranged on the outer side of the resin film and the prepreg; that is, the single side or both sides of the laminated board obtained by laminating finally are provided with the metal foil.

[0145] An embodiment of the present application provides a printed circuit board, which comprises at least one of the resin film, the prepreg, the laminated board, and the laminated board prepared by the preparation method of the laminated board.

[0146] The printed circuit board of the present application comprises at least one of the resin film, the prepreg, the laminated board, and the laminated board prepared by the preparation method of the laminated board, and thus has at least the same advantages as the resin film, the prepreg, the laminated board, and the laminated board prepared by the preparation method of the laminated board.

[0147] An embodiment of the present application provides a communication device comprising the printed circuit board.

[0148] It can be understood that the communication device includes, but is not limited to, at least one of a smart phone, a tablet computer, a smart watch, and the like.

[0149] In the field of consumer electronics, copper-clad boards are indispensable for electronic products: from smart phones, tablet computers to smart watches, the internal circuit boards are all made based on copper-clad boards. In the field of computers: from the motherboard of personal computers, graphics cards to the motherboard of servers, copper-clad boards are used to build complex circuit systems to realize electrical connections between various chips, interfaces and electronic components. In the field of communication: the radio frequency circuit board of the 5G base station and the backboard of the communication device all need to use high-performance copper-clad boards to meet the requirements of high-speed signal transmission and high reliability. In addition, in the fields of automotive electronics, industrial control, aerospace, etc., copper-clad boards also play a crucial role.

[0150] The application will be described in further detail below with reference to specific embodiments. The embodiments of the present application are not limited to this.

[0151] The sources of some raw materials used in the examples and comparative examples are as follows:

[0152] Hydroxyl-terminated polybutadiene: DuPont, model G-1000;

[0153] 1,2-polybutadiene: DuPont, model B-1000;

[0154] Bismaleimide: KI, model BMI-80;

[0155] DCPD-type benzoxazine: Huntsman, model LPY 11051;

[0156] Spherical silica: Yudao, model SC6500-SXD;

[0157] 2-methylimidazole: Shikoku Chemicals.

[0158] Example 1

[0159] (1) Preparation of phthalonitrile-terminated polybutadiene resin

[0160] Hydroxyl-terminated polybutadiene G-1000 (0.1 mol, 140 g) was weighed into a three-necked flask, 600 mL of N,N-dimethylformamide was added and stirred to completely dissolve it, then anhydrous potassium carbonate (0.1 mol, 13.82 g) and 4-nitrophthalonitrile (0.11 mol, 19.04 g) were added, the oil bath was heated to 50-60°C, and high-speed stirring was carried out for 10-12 h. After the reaction was completed, deionized water was added to collect the precipitate by filtration, then the precipitate was washed several times with deionized water and ethyl acetate, respectively, and the obtained product was dried in a vacuum oven at 80°C to obtain a phthalonitrile-terminated polybutadiene resin.

[0161] (2) Preparation of bismaleimide / benzoxazine prepolymer

[0162] According to the mass fraction, 70 parts of bismaleimide resin was heated to a molten state, then 100 parts of benzoxazine resin (the mass ratio of bismaleimide resin to benzoxazine resin was about 0.7:1) was added, and a prepolymerization reaction was carried out at 150°C for 2 h, then the mixture was cooled to room temperature to obtain a bismaleimide / benzoxazine prepolymer.

[0163] (3) Preparation of resin composition

[0164] 50 parts of phthalonitrile-terminated polybutadiene resin and 10 parts of bismaleimide / benzoxazine prepolymer were dissolved in 140 parts of mixed solvent, wherein the mixed solvent included toluene and N,N-dimethylformamide in a mass ratio of 1:1, and the mass ratio of the phthalonitrile-terminated polybutadiene resin to the bismaleimide / benzoxazine prepolymer was 5:1; 40 parts of spherical silica and 5 parts of 2-methylimidazole were added under stirring, and uniform glue liquid, i.e., the resin composition, was obtained by continuing stirring.

[0165] (4) Preparation of prepreg

[0166] 2116 glass fiber cloth (basis weight 105 g / m 2 ) was impregnated in the resin composition prepared in step (3), and baked in a hot air circulating oven at 180°C for 3 min to obtain a prepreg with a resin content of 50%.

[0167] (5) Preparation of copper-clad plate

[0168] Six pieces of the prepreg prepared in step (4) were laminated, and one electrolytic copper foil with a thickness of 18 μm was covered on the upper and lower surfaces of the lamination, respectively, and placed in a programmable temperature and pressure controlled vacuum press, and cured at 260°C for 3 h under a vacuum state at a pressure of 30 kgf / cm 2 to prepare a copper-clad laminate plate with a thickness of 0.6 mm.

[0169] Example 2

[0170] The same as example 1, except that in step (3) of example 2, the mass fraction of the phthalonitrile-terminated polybutadiene resin was 45 parts, and the mass fraction of the bismaleimide / benzoxazine prepolymer was 15 parts; the mass ratio of the phthalonitrile-terminated polybutadiene resin to the bismaleimide / benzoxazine prepolymer was 3:1.

[0171] Example 3

[0172] The same as example 1, except that in step (3) of example 3, the mass fraction of the phthalonitrile-terminated polybutadiene resin was 40 parts, and the mass fraction of the bismaleimide / benzoxazine prepolymer was 20 parts; the mass ratio of the phthalonitrile-terminated polybutadiene resin to the bismaleimide / benzoxazine prepolymer was 2:1.

[0173] Example 4

[0174] The same as example 1, except that in step (3) of example 4, the mass fraction of phthalonitrile-terminated polybutadiene resin is 35 parts, and the mass fraction of bismaleimide / benzoxazine prepolymer is 25 parts; the mass ratio of phthalonitrile-terminated polybutadiene resin to bismaleimide / benzoxazine prepolymer is 1.4:1.

[0175] Example 5

[0176] The same as example 1, except that in step (3) of example 5, the mass fraction of phthalonitrile-terminated polybutadiene resin is 30 parts, and the mass fraction of bismaleimide / benzoxazine prepolymer is 30 parts; the mass ratio of phthalonitrile-terminated polybutadiene resin to bismaleimide / benzoxazine prepolymer is 1:1.

[0177] Example 6

[0178] The same as example 1, except that in step (3) of example 6, the mass fraction of phthalonitrile-terminated polybutadiene resin is 20 parts, and the mass fraction of bismaleimide / benzoxazine prepolymer is 40 parts; the mass ratio of phthalonitrile-terminated polybutadiene resin to bismaleimide / benzoxazine prepolymer is 0.5:1.

[0179] Comparative example 1

[0180] The same as example 1, except that step (1) is omitted, and in the step of preparing the resin composition, the phthalonitrile-terminated polybutadiene in example 1 is replaced with an equal mass of hydroxyl-terminated polybutadiene resin (G-1000, Nippon Zeon Co., Ltd.).

[0181] Comparative example 2

[0182] The same as example 1, except that step (1) is omitted, and in the step of preparing the resin composition, the phthalonitrile-terminated polybutadiene in example 1 is replaced with an equal mass of 1,2-polybutadiene resin (B-1000, Nippon Zeon Co., Ltd.).

[0183] Comparative example 3

[0184] The same as example 1, except that step (2) is omitted, and the step of preparing the resin composition is as follows:

[0185] The bismaleimide resin and the benzoxazine resin with a mass ratio of 0.7:1 and the phthalonitrile-terminated polybutadiene resin were dissolved in a mixed solvent, wherein the mass ratio of the total mass of the bismaleimide resin and the benzoxazine resin to the mass of the phthalonitrile-terminated polybutadiene resin was 1:5, and the mixed solvent included toluene and N,N-dimethylformamide with a mass ratio of 1:1; 40 parts of spherical silica and 5 parts of 2-methylimidazole were further added under stirring, and uniform glue liquid, i.e., the resin composition, was obtained by continuing stirring.

[0186] The components and mass parts of the resin composition used in the copper-clad laminate prepared in each example and comparative example are shown in Table 1.

[0187] Table 1

[0188]

[0189] The copper-clad laminates prepared in each example and comparative example were subjected to performance tests, and the test methods were as follows:

[0190] Peeling strength: the test method was performed according to IPC-TM-650 2.4.8;

[0191] Glass transition temperature (Tg): tested according to IPC-TM650 2.4.25D;

[0192] Thermal decomposition temperature (Td): tested according to IPC-TM650 2.4.24.6;

[0193] Elastic modulus: tested according to GB / T 22315-2008;

[0194] Water absorption: tested according to IPC-TM650 2.6.2.1;

[0195] Dk / Df: tested according to IPC-TM650 2.5.5.2;

[0196] Flame retardance: tested according to IPC-TM650 2.3.10.

[0197] The results are shown in Table 2.

[0198] Table 2

[0199]

[0200] As shown in Table 2, compared to the comparative examples, the resin compositions used in each embodiment, which combined phthalonitrile-terminated polybutadiene and bismaleimide benzoxazine prepolymer, resulted in copper-clad laminates with better overall performance in terms of glass transition temperature, initial thermal decomposition temperature, water absorption, elastic modulus, flame retardancy, dielectric properties, and peel strength. However, Comparative Example 1, which combined hydroxyl-terminated polybutadiene resin with bismaleimide benzoxazine prepolymer, Comparative Example 2, which combined 1,2-polybutadiene resin with bismaleimide benzoxazine prepolymer, and Comparative Example 3, which directly combined bismaleimide resin and benzoxazine resin with phthalonitrile-terminated polybutadiene resin, resulted in copper-clad laminates with significantly lower glass transition temperature and thermal decomposition temperature, and lower peel strength.

[0201] The technical features of the above embodiments can be combined in any way. For the sake of brevity, 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, they should be considered to be within the scope of this specification.

[0202] The embodiments described above are merely illustrative of several implementation methods of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. It should be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification can be used to interpret the content of the claims.

Claims

1. A resin composition, characterized by comprising: by mass, comprising: phthalonitrile-terminated polybutadiene 20-100 parts; and bismaleimide benzoxazine prepolymer 1-40 parts; the preparation of the phthalonitrile-terminated polybutadiene comprises the following steps: mixing hydroxyl-terminated polybutadiene, 4-nitrophthalonitrile and solvent to perform nucleophilic substitution reaction; the preparation of the bismaleimide benzoxazine prepolymer comprises the following steps: mixing bismaleimide resin and benzoxazine resin at 150-160°C to perform prepolymerization.

2. The resin composition according to claim 1, characterized by by mass, comprising: phthalonitrile-terminated polybutadiene 20-100 parts; and bismaleimide benzoxazine prepolymer 1-40 parts; 3. The resin composition according to claim 1, wherein the mass ratio of the phthalonitrile-terminated polybutadiene to the bismaleimide benzoxazine prepolymer is 0.5-5:

1.

4. The resin composition according to Claim 3, wherein the mass ratio of the phthalonitrile-terminated polybutadiene to the bismaleimide benzoxazine prepolymer is 1-5:

1.

5. The resin composition according to any one of claims 1 to 4, wherein the mass ratio of the bismaleimide resin to the benzoxazine resin is 0.5-1:

1.

6. The resin composition according to any one of claims 1 to 4, wherein the bismaleimide benzoxazine prepolymer satisfies at least one of the following characteristics: (1) the monomer of the bismaleimide resin comprises at least one of bis(4-maleimide phenyl) methane, 2,2-bis(4-(4-maleimide phenoxy)-phenyl) propane, bis(3,5-dimethyl-4-maleimide phenyl) methane, bis(3-ethyl-5-methyl-4-maleimide phenyl) methane, bis(3,5-diethyl-4-maleimide phenyl) methane, polyphenyl methane bismaleimide and bismaleimide containing biphenyl structure; (2) the benzoxazine resin comprises at least one of bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, main chain type benzoxazine resin, phosphorus-containing benzoxazine, bisphenol S type benzoxazine resin, dicyclopentadiene benzoxazine resin, biphenyl type benzoxazine resin, tetraphenyl ethane benzoxazine resin, naphthalene type benzoxazine resin and allyl type benzoxazine resin.

7. The resin composition according to any one of claims 1 to 4, wherein by mass, the resin composition further comprises inorganic filler 10-60 parts.

8. The resin composition according to Claim 7, wherein the inorganic filler comprises at least one of zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, lithium feldspar, 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 and kaolin.

9. A method for producing a resin composition, characterized by comprising the steps of, comprises the following steps: by mass, mixing phthalonitrile-terminated polybutadiene 20-100 parts and bismaleimide benzoxazine prepolymer 1-40 parts; the preparation of the phthalonitrile-terminated polybutadiene comprises the following steps: mixing hydroxyl-terminated polybutadiene, 4-nitrophthalonitrile and solvent to perform nucleophilic substitution reaction; the preparation of the bismaleimide benzoxazine prepolymer comprises the following steps: mixing bismaleimide resin and benzoxazine resin at 150-160°C to perform prepolymerization.

10. A resin film, characterized by, The resin film includes the resin composition according to any one of claims 1 to 8 or the resin composition prepared by the production method according to claim 9.

11. A prepreg, characterized by, The prepreg includes the resin composition according to any one of claims 1 to 8 or the resin composition prepared by the production method according to claim 9 attached to the reinforcing material.

12. A laminate characterized by comprising: At least one of the resin film according to claim 10 and the prepreg according to claim 11.

13. A printed circuit board, characterized by At least one of the resin film according to claim 10, the prepreg according to claim 11, and the laminate according to claim 12.

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