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

Abstract

The application relates to a resin composition, a preparation method thereof, a prepreg, a copper-clad plate and a printed circuit board. The resin composition comprises the following components in parts by mass: phthalonitrile-terminated polyphenyl ether 20-100 parts, amino-terminated polyetherimide 1-40 parts and inorganic filler 0-60 parts. The resin composition has the advantages of high glass transition temperature, high initial thermal decomposition temperature, low water absorption, high elastic modulus, good flame retardancy, good dielectric property and high peeling strength, and has a low curing temperature.

Description

Technical Field

[0001] This application relates to the field of communication materials technology, and in particular to a resin composition and its preparation method, a prepreg, a copper-clad laminate, and a printed circuit board. Background Technology

[0002] Copper-clad laminate (CCL) is a sheet material made by impregnating electronic fiberglass cloth or other reinforcing materials with resin, covering one or both sides with copper foil, and then hot-pressing them together. It is the core material for manufacturing printed circuit boards (PCBs), through which various electronic components on the PCB are electrically connected via the copper foil traces on the CCL. As electronic products develop towards higher frequencies and speeds, the performance requirements for CCLs are also increasing. In circuits involving high-frequency, high-speed signal transmission, CCLs with lower dielectric constants (Dk) are required to reduce signal delay and attenuation; lower dielectric loss factors help improve circuit efficiency; sufficient peel strength ensures that the copper foil does not detach from the substrate during PCB manufacturing (such as etching and drilling) and during use, ensuring the reliability of electrical connections; and high modulus and low coefficient of thermal expansion (Low-CTE) are also required. Simultaneously, as electronic products become smaller and more multifunctional, higher demands are placed on the heat resistance of CCLs.

[0003] Poly(2,6-dimethyl-1,4-phenylene ether) (PPO) is a resin with low dielectric constant and dielectric loss, low coefficient of thermal expansion, and low water absorption, making it suitable for the fabrication of high-frequency, high-speed copper-clad laminates. However, as a thermoplastic resin, PPO suffers from drawbacks such as a low glass transition temperature and insufficient initial thermal decomposition temperature, which limit its further applications.

[0004] Therefore, it is necessary to improve traditional technologies. Summary of the Invention

[0005] Based on this, this application provides a resin composition with both high glass transition temperature and high peel strength, a method for preparing the same, a prepreg, a copper-clad laminate, and a printed circuit board.

[0006] The technical solution to the above-mentioned technical problems in this application is as follows.

[0007] This application provides a resin composition comprising, by weight parts:

[0008] Phthalonil-terminated polyphenylene ether, 20 to 100 parts;

[0009] 1 to 40 parts of amino-terminated polyetherimide; and

[0010] Inorganic filler 0 to 60 parts.

[0011] In some embodiments, the resin composition comprises, by weight parts:

[0012] 20 to 50 parts of phthalonitrile-terminated polyphenylene ether;

[0013] 10 to 40 parts of amino-terminated polyetherimide; and

[0014] Inorganic filler 30 to 60 parts.

[0015] In some embodiments, the mass ratio of the phthalonitrile-terminated polyphenylene ether to the amino-terminated polyetherimide in the resin composition is 0.5 to 5:1; optionally, the mass ratio of the phthalonitrile-terminated polyphenylene ether to the amino-terminated polyetherimide is 1 to 5:1.

[0016] In some embodiments, the inorganic filler in the resin composition includes at least one selected from zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, nepheline, silica, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc, alumina, 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.

[0017] This application provides a method for preparing a resin composition, comprising the following steps:

[0018] By weight, 20 to 100 parts of phthalonitrile-terminated polyphenylene ether, 1 to 40 parts of amino-terminated polyether imide, and 0 to 60 parts of inorganic filler are mixed.

[0019] In some embodiments, the preparation of the phthalonitrile-terminated polyphenylene ether in the method for preparing the resin composition includes the following steps:

[0020] A nucleophilic substitution reaction was carried out by mixing polyphenylene ether, 4-nitrophthalonitrile and a first solvent.

[0021] In some embodiments, the preparation of the terminal amino polyetherimide in the method for preparing the resin composition includes the following steps:

[0022] A thermal imidization reaction was carried out by mixing m-phenylenediamine, bisphenol A type diether dianhydride, and a second solvent.

[0023] This application provides a resin film comprising the above-described resin composition or a resin composition prepared by the above-described preparation method.

[0024] This application provides a prepreg comprising a reinforcing material and the above-described resin composition or a resin composition prepared by the above-described preparation method attached to the reinforcing material.

[0025] This application provides a copper-clad laminate, comprising at least one of the above-mentioned resin film and the above-mentioned prepreg.

[0026] This application provides a printed circuit board, including at least one of the above-mentioned resin film, the above-mentioned prepreg, and the above-mentioned copper clad laminate.

[0027] Compared with the prior art, the resin composition of this application has the following beneficial effects:

[0028] The resin composition of this application includes phthalonitrile-terminated polyphenylene ether, amino-terminated polyetherimide, and inorganic filler. The phthalonitrile groups in the phthalonitrile-terminated polyphenylene ether react with the aromatic amine groups in the amino-terminated polyetherimide to form an isoindole ring structure. At the same time, the aromatic amine structure in the amino-terminated polyetherimide can promote the self-polymerization of phthalonitrile-terminated polyphenylene ether to form phthalocyanine ring and triazine ring structures. This makes the resin composition have a high glass transition temperature, a high initial thermal decomposition temperature, a low water absorption rate, a high elastic modulus, good flame retardancy, good dielectric properties, and high peel strength. Meanwhile, the amino-terminated polyetherimide with aromatic amine structure can effectively reduce the curing temperature of the phthalonitrile groups in the phthalonitrile-terminated polyphenylene ether, effectively improving the toughness of the resin composition. While ensuring a low dielectric constant, the curing temperature of the resin composition can be effectively reduced. Detailed Implementation

[0029] The present application will be further described in detail below with reference to the embodiments and examples. It should be understood that these embodiments and examples are only used to illustrate the present application and are not intended to limit the scope of the present application. The purpose of providing these embodiments and examples is to make the disclosure of the present application more thorough and comprehensive.

[0030] It should also be understood that this application can be implemented in many different forms and is not limited to the embodiments and examples described herein. Those skilled in the art can make various alterations or modifications without departing from the spirit of this application, and the resulting equivalent forms also fall within the protection scope of this application. For example, features described or illustrated as part of one embodiment can be combined in a suitable manner in another embodiment to produce new embodiments. Furthermore, numerous specific details are set forth in the following description to provide a fuller understanding of this application; it should be understood that this application can be implemented without one or more of these details.

[0031] 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 herein in the specification of this application is for descriptive purposes only and is not intended to be limiting of the application.

[0032] Unless otherwise stated or in case of contradiction, the terms or phrases used herein shall have the following meanings:

[0033] In this application, the terms "multiple", "various", "multiple times", etc., unless otherwise specified, refer to a quantity greater than or equal to 2. For example, "one or more" means one or more than or equal to two.

[0034] The terms “combinations of,” “any combination of,” and “any combination of” used in this article include all suitable combinations of any two or more of the listed items.

[0035] In this document, the term "suitable" as used in "suitable combination", "suitable method", "any suitable method", etc., refers to the ability to implement the technical solution of this application, solve the technical problem of this application, and achieve the expected technical effect of this application.

[0036] In this document, terms such as "preferred," "better," "more suitable," and "ideal" are merely descriptions of more effective implementation methods or embodiments, and should be understood not to limit the scope of protection of this application. If multiple "preferred" terms appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "preferred" term shall be independent.

[0037] In this application, terms such as "further," "even more," and "particularly" are used for descriptive purposes and to indicate differences in content, but should not be construed as limiting the scope of protection of this application.

[0038] In this application, "optionally," "optionally," and "optional" mean that something is optional, that is, it means that it is selected from either "with" or "without." If there are multiple "optional" entries in a technical solution, unless otherwise specified, and there are no contradictions or mutual constraints, each "optional" entry shall be independent.

[0039] In this application, the terms "first aspect," "second aspect," "third aspect," "fourth aspect," etc., are used for descriptive purposes only 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. Moreover, "first," "second," "third," "fourth," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.

[0040] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0041] In this application, when numerical intervals (i.e., numerical ranges) are mentioned, unless otherwise specified, the distribution of selectable numerical values ​​within the numerical interval is considered continuous, and includes the two endpoints of the numerical interval (i.e., the minimum and maximum values), as well as every numerical value between these two endpoints. Unless otherwise specified, when a numerical interval refers only to integers within that numerical interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints, which is equivalent to directly listing every integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be merged. In other words, unless otherwise specified, the numerical ranges disclosed herein should be understood to include any and all subranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, percentage, ratio, etc. The term "numerical interval" can be broadly included to include numerical interval types such as percentage intervals, ratio intervals, and proportion intervals.

[0042] Unless otherwise specified, the temperature parameters in this application are permitted to be either constant-temperature treatment or variations within a certain temperature range. It should be understood that the constant-temperature treatment allows temperature fluctuations within the precision range of the instrument control, such as ±5℃, ±4℃, ±3℃, ±2℃, or ±1℃.

[0043] In this application, the terms "room temperature" or "normal temperature" generally refer to 4℃ to 35℃, for example, 20℃ ± 5℃. In some embodiments of this application, "room temperature" or "normal temperature" refers to 10℃ to 30℃. In some embodiments of this application, "room temperature" or "normal temperature" refers to 20℃ to 30℃.

[0044] In this application, if the unit of a data range is only followed by the right endpoint, it indicates that the units of the left and right endpoints are the same. For example, 3~5 h means that the units of the left endpoint "3" and the right endpoint "5" are both h (hours).

[0045] All references to documents mentioned in this application are incorporated herein by reference as if each document were individually incorporated by reference. Unless they conflict with the inventive purpose and / or technical solution of this application, all cited documents are incorporated herein by reference in their entirety and for all purposes. When citing documents in this application, the definitions of relevant technical features, terms, nouns, phrases, etc., are also incorporated herein by reference. When citing documents in this application, examples and preferred embodiments of the cited technical features may also be incorporated herein by reference, but only to the extent that they enable the implementation of this application. It should be understood that when the cited content conflicts with the description in this application, this application shall prevail or modifications shall be made adaptably to the description in this application.

[0046] The mass or weight of the relevant components mentioned in the embodiments of this application can refer not only to the specific content of each component, but also to the proportional relationship of mass or weight between the components. Therefore, any scaling up or down of the content of the relevant components according to the embodiments of this application is within the scope disclosed in the embodiments of this application. Specifically, the mass or weight mentioned in the embodiments of this application can be units known in the chemical industry, such as μg, mg, g, and kg.

[0047] One embodiment of this application provides a resin composition comprising, by weight parts:

[0048] Phthalonil-terminated polyphenylene ether, 20 to 100 parts;

[0049] 1 to 40 parts of amino-terminated polyetherimide; and

[0050] Inorganic filler 0 to 60 parts.

[0051] The resin composition provided in this application includes phthalonitrile-terminated polyphenylene ether, amino-terminated polyetherimide, and inorganic filler. The phthalonitrile groups in the phthalonitrile-terminated polyphenylene ether react with the aromatic amine groups in the amino-terminated polyetherimide to form an isoindole ring structure. At the same time, the aromatic amine structure in the amino-terminated polyetherimide can promote the self-polymerization of phthalonitrile-terminated polyphenylene ether to form phthalocyanine ring and triazine ring structures. This results in the resin composition having a high glass transition temperature, a high initial thermal decomposition temperature, a low water absorption rate, a high elastic modulus, good flame retardancy, good dielectric properties, and high peel strength. In addition, the amino-terminated polyetherimide with aromatic amine structure can effectively reduce the curing temperature of the phthalonitrile groups in the phthalonitrile-terminated polyphenylene ether, effectively improving the toughness of the resin composition. While ensuring a low dielectric constant, the curing temperature of the resin composition can be effectively reduced.

[0052] It is understood that, by weight, the phthalonitrile-terminated polyphenylene ether in the resin composition 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, and 60 parts. 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100 parts by weight; the mass fractions of amino-terminated polyetherimide include, but are not limited to, 1, 2, 3, 4, 5, 6, 7, 8 parts. The quantities of inorganic filler are as follows: 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, and 40 parts by weight; The quantities of inorganic filler include, but are not limited to, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, and 17 parts by weight. 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60; in some examples, any two of these point values ​​can be used as endpoints within a range, the same applies below.

[0053] In some of these examples, the resin composition comprises, by weight parts, the following components:

[0054] 20 to 50 parts of phthalonitrile-terminated polyphenylene ether;

[0055] 10 to 40 parts of amino-terminated polyetherimide; and

[0056] Inorganic filler 30 to 60 parts.

[0057] In some of these examples, the resin composition comprises, by weight parts, the following components:

[0058] 30 to 50 parts of phthalonitrile-terminated polyphenylene ether;

[0059] 10 to 30 parts of amino-terminated polyetherimide; and

[0060] 30 to 50 parts of inorganic filler.

[0061] In some of these examples, the resin composition comprises, by weight parts, the following components:

[0062] 35 to 40 parts of phthalonitrile-terminated polyphenylene ether;

[0063] 20 to 25 parts of amino-terminated polyetherimide; and

[0064] 35 to 45 parts of inorganic filler.

[0065] In some of these examples, the mass ratio of phthalonitrile-terminated polyphenylene ether to amino-terminated polyetherimide in the resin composition is 0.5 to 5:1.

[0066] It is understood that the mass ratio of phthalonitrile-terminated polyphenylene ether to amino-terminated polyetherimide 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, etc. 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.

[0067] Optionally, the mass ratio of phthalonitrile-terminated polyphenylene ether to amino-terminated polyetherimide is 1 to 5:1.

[0068] Furthermore, the mass ratio of phthalonitrile-terminated polyphenylene ether to amino-terminated polyetherimide is 1.4~3:1.

[0069] In some of these examples, the phthalonitrile-terminated polyphenylene ether in the resin composition is prepared from polyphenylene ether (SA90, SABIC) and 4-nitrophthalonitrile as reactants.

[0070] In some of these examples, the phthalonitrile-terminated polyphenylene ether in the resin composition has the following structural formula:

[0071]

[0072] In some of these examples, the amino-terminated polyetherimide in the resin composition is prepared from m-phenylenediamine and bisphenol A diether dianhydride as reactants.

[0073] In some of these examples, the structural formula of the amino-terminated polyetherimide in the resin composition is as follows:

[0074]

[0075] It is understandable that the isoindole ring structure formed by the reaction of the phthalonitrile group in the phthalonitrile-terminated polyphenylene ether with the aromatic amine group in the amino-terminated polyetherimide is shown in formulas (a) and (b), the phthalocyanine ring formed by the self-polymerization of the phthalonitrile-terminated polyphenylene ether is shown in formula (c), and the triazine ring structure formed by the self-polymerization of the phthalonitrile-terminated polyphenylene ether is shown in formula (d).

[0076]

[0077]

[0078] In some of these examples, the inorganic filler in the resin composition includes at least one of zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, nepheline, silica (spherical, composite, or fused), quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc, alumina, 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.

[0079] In some of these examples, the resin composition also includes 40 to 100 parts by weight of a third solvent.

[0080] It is understood that the mass fractions of the third solvent in the resin composition include, but are not limited to, 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, 6 7, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100.

[0081] In some of these examples, the third solvent in the resin composition includes at least one of N-methyl-2-pyrrolidone, toluene, and N,N-dimethylformamide.

[0082] In some examples, the third solvent in the resin composition includes toluene and N,N-dimethylformamide. Further, the mass ratio of toluene to N,N-dimethylformamide is 0.5 to 2:1. Optionally, the mass ratio of toluene to N,N-dimethylformamide is 1:1.

[0083] It is understood that the resin composition provided in this application may also include additives commonly used in the art, including but not limited to at least one of curing accelerators, coupling agents and toughening agents.

[0084] The resin composition provided in this application has a high glass transition temperature, a high initial thermal decomposition temperature, a low water absorption rate, a high elastic modulus, good flame retardancy, good dielectric properties, and high peel strength, and can be applied to high-performance printed circuit boards such as integrated circuit packaging and high-frequency and high-speed circuit boards.

[0085] One embodiment of this application provides a method for preparing a resin composition, comprising the following steps:

[0086] By weight, 20 to 100 parts of phthalonitrile-terminated polyphenylene ether, 1 to 40 parts of amino-terminated polyether imide, and 0 to 60 parts of inorganic filler are mixed.

[0087] It is understood that the resin composition can be prepared by the method of preparing the resin composition, and the resin composition can be prepared by the method of preparing the resin composition. The characteristics of the resin composition and the method of preparing the resin composition are mutually applicable.

[0088] The resin composition prepared by this method has a high glass transition temperature, a high initial thermal decomposition temperature, a low water absorption rate, a high elastic modulus, good flame retardancy, and good dielectric properties; at the same time, the curing temperature is low.

[0089] In some of these examples, the preparation of phthalonitrile-terminated polyphenylene ether in the method of preparing the resin composition includes the following steps:

[0090] A nucleophilic substitution reaction was carried out by mixing polyphenylene ether, 4-nitrophthalonitrile and a first solvent.

[0091] Furthermore, the first solvent includes N,N-dimethylformamide.

[0092] Furthermore, the nucleophilic substitution reaction proceeds in the presence of a catalyst. The catalyst further includes potassium carbonate.

[0093] Furthermore, the nucleophilic substitution reaction was carried out at a temperature of 50℃~60℃ for 10 h~12 h.

[0094] Furthermore, the molar ratio of polyphenylene ether to 4-nitrophthalonitrile is 1:1 to 1.2.

[0095] In some of these examples, the preparation of the amino-terminated polyetherimide in the method of preparing the resin composition includes the following steps:

[0096] A thermal imidization reaction was carried out by mixing m-phenylenediamine, bisphenol A type diether dianhydride, and a second solvent.

[0097] Bisphenol A type diether dianhydride, also known as bisphenol A type dianhydride, BPADA, or bisphenol A dianhydride, has the molecular formula C2. 31 H 20 O8 has the following structure:

[0098]

[0099] Furthermore, the second solvent includes anhydrous N,N-dimethylformamide.

[0100] Furthermore, the temperature for the thermal imidization reaction is 160℃~250℃.

[0101] Furthermore, the molar ratio of m-phenylenediamine to bisphenol A diether dianhydride is 1:1.1~1.2.

[0102] In some of these examples, the preparation steps of the amino-terminated polyetherimide include the following steps:

[0103] After mixing bisphenol A type diether dianhydride and a second solvent, m-phenylenediamine is added in an ice-water bath to obtain a mixed solution;

[0104] The mixed solution was placed in an oven at 160℃~250℃ to remove the reaction solvent and carry out a thermal imidization reaction.

[0105] One embodiment of this application provides a resin film comprising the above-described resin composition or a resin composition prepared by the above-described preparation method.

[0106] The resin film of this application includes the above-described resin composition or the resin composition prepared by the above-described preparation method, and therefore has at least the same advantages as the above-described resin composition or the resin composition prepared by the above-described preparation method.

[0107] One embodiment of this application provides a method for preparing a resin film, comprising the following steps:

[0108] The resin composition described above or the resin composition prepared by the above preparation method is coated onto a release material and then dried and / or semi-cured.

[0109] One embodiment of this application provides a prepreg comprising a reinforcing material and the above-described resin composition or resin composition prepared by the above-described preparation method attached to the reinforcing material.

[0110] The prepreg of this application includes the above-described resin composition or the resin composition prepared by the above-described preparation method, and therefore has at least the same advantages as the above-described resin composition or the resin composition prepared by the above-described preparation method.

[0111] In some of these examples, the reinforcing material in the prepreg includes, but is not limited to, at least one of inorganic fiber materials and organic fiber materials.

[0112] Furthermore, inorganic fiber materials include, but are not limited to, at least one of glass fiber (including different types such as E, NE, D, S, T), carbon fiber, silicon carbide fiber, and asbestos fiber.

[0113] Furthermore, the organic fiber materials include, but are not limited to, at least one of nylon, ultra-high molecular weight polyethylene fiber, aramid fiber, polyimide fiber, polyester fiber, and cotton fiber.

[0114] In some of these examples, the resin composition in the prepreg accounts for 40% to 60% by mass.

[0115] It is understood that the mass percentage of the resin composition in the prepreg includes, but is not limited to, 40%, 50%, and 60%.

[0116] One embodiment of this application provides a method for preparing a prepreg, comprising the following steps:

[0117] The reinforcing material is impregnated in the above-mentioned resin composition or the resin composition prepared by the above-mentioned method, and a prepreg is obtained by semi-curing treatment.

[0118] It is understood that the resin composition described above or the resin composition prepared by the above method covers the surface of the reinforcing material.

[0119] In some of these examples, the prepreg preparation method involves a semi-curing treatment at a temperature of 150°C to 250°C for a time of 2 min to 10 min.

[0120] It is understood that the semi-curing temperature includes, but is not limited to, 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, 210℃, 220℃, 230℃, 240℃, and 250℃; and the time includes, but is not limited to, 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min, and 10 min.

[0121] One embodiment of this application provides a laminate comprising at least one of the above-described resin film and the above-described prepreg.

[0122] It is understood that the laminate contains one or both of the above-mentioned resin film and the above-mentioned prepreg, and further, the resin film and the prepreg may be one or more.

[0123] In some of these examples, the laminate has copper foil on one or both sides. This can be understood as a copper-clad laminate.

[0124] Accordingly, one embodiment of this application provides a copper-clad laminate, comprising at least one of the above-mentioned resin film and the above-mentioned prepreg.

[0125] The copper-clad laminate of this application includes at least one of the above-mentioned resin film and the above-mentioned prepreg, and thus has at least the same advantages as the above-mentioned resin film or the above-mentioned prepreg.

[0126] Furthermore, the thickness of the copper foil is 3 μm to 70 μm.

[0127] One embodiment of this application provides a method for preparing a copper-clad laminate, comprising the following steps:

[0128] After a copper foil is disposed on at least one side of at least one of the above-mentioned resin film and the above-mentioned prepreg, lamination is performed.

[0129] It is understood that the aforementioned resin film and the aforementioned prepreg can be several, and several means at least one.

[0130] In some of these examples, the lamination parameters in the copper-clad laminate fabrication method are: temperature 150℃~300℃, pressure 10 kgf / cm². 2 ~30 kgf / cm 2Under vacuum conditions < 2 kPa, hot pressing is performed for 200 min to 400 min.

[0131] It is understood that the lamination temperature includes, but is not limited to, 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, 210℃, 220℃, 230℃, 240℃, and 250℃; and the pressure includes, but is not limited to, 10 kgf / cm². 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 30 kgf / cm 2 The 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.

[0132] One embodiment of this application provides a printed circuit board, including at least one of the above-mentioned resin film, the above-mentioned prepreg, and the above-mentioned copper clad laminate.

[0133] The printed circuit board of this application includes at least one of the above-mentioned resin film, the above-mentioned prepreg and the above-mentioned copper clad laminate, and thus has at least the same advantages as the above-mentioned resin film, the above-mentioned prepreg or the above-mentioned copper clad laminate.

[0134] One embodiment of this application provides a communication device including the printed circuit board described above.

[0135] It is understood that communication devices include, but are not limited to, at least one of smartphones, tablets, smartwatches, etc.

[0136] In consumer electronics, copper-clad laminates (CCLs) are indispensable: from smartphones and tablets to smartwatches, their internal circuit boards are all made based on CCLs. In the computer field, CCLs are used to build complex circuit systems, enabling electrical connections between various chips, interfaces, and electronic components, from personal computer motherboards and graphics cards to server motherboards. In the communications field, high-performance CCLs are required for 5G base station radio frequency circuit boards and backplanes of communication equipment to meet the requirements of high-speed signal transmission and high reliability. Furthermore, CCLs play a crucial role in automotive electronics, industrial control, and aerospace.

[0137] The present application will be described in further detail below with reference to specific embodiments, but the embodiments of the present application are not limited thereto.

[0138] Raw material source:

[0139] Polyphenylene oxide, SABIC, model SA-90;

[0140] 4-Nitrophthalonitrile, Inokane, analytical grade;

[0141] Bisphenol A type diether dianhydride, Inokane, analytical grade;

[0142] m-Phenylenediamine, Inokai, analytical grade;

[0143] Spherical silica, Yadu code, model number SC6500-SXD.

[0144] Example 1

[0145] (1) Preparation of phthalonitrile-terminated polyphenylene ether resin

[0146] Weigh 0.1 mol (160 g) of polyphenylene ether SA90 into a three-necked flask, add 600 mL of N,N-dimethylformamide and stir until completely dissolved. Then add anhydrous potassium carbonate (0.1 mol, 13.82 g) and 4-nitrophthalonitrile (0.11 mol, 19.04 g), maintain oil bath heating at 50℃~60℃, and stir at high speed for 10 h~12 h. After the reaction is complete, add deionized water, filter and collect the precipitate, then wash several times with deionized water and ethyl acetate respectively. Dry the obtained product in a vacuum oven at 80℃ to obtain phthalonitrile-terminated polyphenylene ether resin.

[0147] (2) Preparation of amino-terminated polyetherimide

[0148] Under nitrogen protection, bisphenol A type diether dianhydride (0.1 mol, 52.05 g) was dissolved in 200 mL of anhydrous N,N-dimethylformamide solution. The solution was maintained at 0°C in an ice-water bath. Excess m-phenylenediamine (0.11 mol, 11.90 g, molar ratio of m-phenylenediamine to bisphenol A type diether dianhydride was 1.1:1) was added in portions with high-speed stirring. After reacting for 10 h, a polyether amic acid solution was obtained. This solution was then poured into a clean mold and placed in an oven at 160°C–250°C with a programmed temperature increase to remove the reaction solvent and perform a thermal imidization reaction, ultimately yielding an amino-terminated polyether imide with the following structural formula:

[0149] .

[0150] (3) Preparation of resin composition

[0151] By weight, 50 parts of phthalonitrile-terminated polyphenylene ether resin and 10 parts of amino-terminated polyetherimide were dissolved in a mixed solvent of 60 parts toluene and N,N-dimethylformamide, wherein toluene and N,N-dimethylformamide were mixed in a mass ratio of 1:1, and the mass ratio of phthalonitrile-terminated polyphenylene ether resin to amino-terminated polyetherimide was 5:1. Under stirring conditions, 40 parts of spherical silica were added, and stirring was continued to obtain a homogeneous adhesive solution, i.e., the resin composition.

[0152] (4) Preparation of prepreg

[0153] 2116 fiberglass cloth (basic weight 105g / m) 2 The resin is impregnated in the resin composition prepared in step (3) and baked in a hot air circulating oven at 180°C for 3 minutes to obtain a prepreg with a resin content of 50%.

[0154] (5) Preparation of copper-clad laminate

[0155] The six prepreg sheets prepared in step (4) are stacked, and an electrolytic copper foil with a thickness of 18 μm is placed on each of the top and bottom surfaces of the stack. The stack is then placed in a programmable temperature and pressure controlled vacuum press and subjected to a vacuum at 30 kgf / cm². 2 Under pressure, after curing at 260℃ for 3 hours, a copper-clad laminate with a thickness of 0.6 mm is produced.

[0156] Example 2

[0157] The two examples are basically the same as in Example 1, except that in step (3) of Example 2, the mass fraction of phthalonitrile-terminated polyphenylene ether resin is 45 parts, the mass fraction of amino-terminated polyetherimide is 15 parts, and the mass ratio of phthalonitrile-terminated polyphenylene ether resin to amino-terminated polyetherimide is 3:1.

[0158] Example 3

[0159] The example is basically the same as Example 1, except that in step (3) of Example 3, the mass fraction of phthalonitrile-terminated polyphenylene ether resin is 40 parts, the mass fraction of amino-terminated polyetherimide is 20 parts, and the mass ratio of phthalonitrile-terminated polyphenylene ether resin to amino-terminated polyetherimide is 2:1.

[0160] Example 4

[0161] The example is basically the same as Example 1, except that in step (3) of Example 4, the mass fraction of phthalonitrile-terminated polyphenylene ether resin is 35 parts, the mass fraction of amino-terminated polyetherimide is 25 parts, and the mass ratio of phthalonitrile-terminated polyphenylene ether resin to amino-terminated polyetherimide is 1.4:1.

[0162] Example 5

[0163] The example is basically the same as Example 1, except that in step (3) of Example 5, the mass fraction of phthalonitrile-terminated polyphenylene ether resin is 30 parts, the mass fraction of amino-terminated polyetherimide is 30 parts, and the mass ratio of phthalonitrile-terminated polyphenylene ether resin to amino-terminated polyetherimide is 1:1.

[0164] Example 6

[0165] The example is basically the same as Example 1, except that in step (3) of Example 6, the mass fraction of phthalonitrile-terminated polyphenylene ether resin is 20 parts, the mass fraction of amino-terminated polyetherimide is 40 parts, and the mass ratio of phthalonitrile-terminated polyphenylene ether resin to amino-terminated polyetherimide is 0.5:1.

[0166] Comparative Example 1

[0167] It is basically the same as Example 5, except that step (1) is omitted and the phthalonitrile-terminated polyphenylene ether resin in step (3) of Example 5 is replaced with an equal mass of polyphenylene ether.

[0168] Comparative Example 2

[0169] The process is basically the same as in Example 1, except that in step (2), the amount of m-phenylenediamine added is 0.102 mol, and the molar ratio of m-phenylenediamine to bisphenol A diether dianhydride is 1.02:1, ultimately yielding polyetherimide with the following structural formula:

[0170] .

[0171] The composition of the resin composition used in the copper-clad laminates prepared in each embodiment and comparative example is shown in Table 1.

[0172] Table 1

[0173]

[0174] The copper-clad laminates obtained in each embodiment and comparative example were subjected to performance tests, and the test methods are as follows:

[0175] Peel strength: The test method was performed according to IPC-TM-650 2.4.8;

[0176] Glass transition temperature (Tg): Tested according to IPC-TM650 2.4.25D;

[0177] Thermal decomposition temperature (Td): Tested according to IPC-TM650 2.4.24.6;

[0178] Elastic modulus: Tested according to GB / T 22315-2008;

[0179] Water absorption rate: Tested according to IPC-TM650 2.6.2.1;

[0180] Dk / Df: Tested according to IPC-TM650 2.5.5.2;

[0181] Flame retardancy: Tested according to IPC-TM650 2.3.10.

[0182] The results are shown in Table 2.

[0183] Table 2

[0184]

[0185] As shown in Table 2, compared to the comparative examples, the resin compositions used in each embodiment, which combine phthalonitrile-terminated polyphenylene ether with amino-terminated polyetherimide, 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. In Comparative Example 1, the combination of polyphenylene ether and amino-terminated polyetherimide significantly reduced the glass transition temperature and thermal decomposition temperature of the resulting copper-clad laminate. Similarly, in Comparative Example 2, the combination of phthalonitrile-terminated polyphenylene ether and polyetherimide resulted in a significantly lower peel strength in the resulting copper-clad laminate.

[0186] 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.

[0187] 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 in that, By mass, it includes the following components: 20 to 50 parts of phthalonitrile-terminated polyphenylene ether; 10 to 40 parts of amino-terminated polyetherimide; and Inorganic filler 0 to 60 parts.

2. The resin composition according to claim 1, characterized in that, The inorganic filler in the resin composition is 30 to 60 parts by weight.

3. The resin composition according to claim 1, characterized in that, The mass ratio of the phthalonitrile-terminated polyphenylene ether to the amino-terminated polyetherimide is 1~5:

1.

4. The resin composition according to any one of claims 1 to 3, characterized in that, The inorganic filler includes at least one of zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, nepheline, silicon dioxide, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc, aluminum oxide, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, clay, and kaolin.

5. A method for preparing a resin composition, characterized in that, Includes the following steps: By weight, 20 to 50 parts of phthalonitrile-terminated polyphenylene ether, 10 to 40 parts of amino-terminated polyetherimide, and 0 to 60 parts of inorganic filler are mixed.

6. The method for preparing the resin composition according to claim 5, characterized in that, The preparation of the phthalonitrile-terminated polyphenylene ether includes the following steps: A nucleophilic substitution reaction was carried out by mixing polyphenylene ether, 4-nitrophthalonitrile and a first solvent.

7. The method for preparing the resin composition according to any one of claims 5 to 6, characterized in that, The preparation of the terminal amino polyetherimide includes the following steps: A thermal imidization reaction was carried out by mixing m-phenylenediamine, bisphenol A type diether dianhydride, and a second solvent.

8. A resin film, characterized in that, The resin film comprises the resin composition as described in any one of claims 1 to 4 or the resin composition prepared by the preparation method as described in any one of claims 5 to 7.

9. A prepreg, characterized in that, The resin composition includes a reinforcing material and a resin composition as described in any one of claims 1 to 4 or a resin composition prepared by any one of claims 5 to 7, which is attached to the reinforcing material.

10. A copper-clad laminate, characterized in that, It includes at least one of the resin film as described in claim 8 and the prepreg as described in claim 9.

11. A printed circuit board, characterized in that, It includes at least one of the resin film as described in claim 8, the prepreg as described in claim 9, and the copper clad laminate as described in claim 10.

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