Resin composition and preparation method thereof, prepreg, copper-clad plate and printed circuit board

Abstract

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

Description

Technical Field

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

[0002] Copper-clad laminate (CCL) is a plate-shaped material made by impregnating electronic fiberglass cloth or other reinforcing materials with resin, covering one or both sides with copper foil and hot pressing. It is the core material for making printed circuit boards (PCBs). Various electronic components on printed circuit boards are electrically connected through copper foil lines on copper-clad laminates. As electronic products develop towards high frequency and high speed, the performance requirements for copper-clad laminates are getting higher and higher. In circuits with high frequency and high speed signal transmission, copper-clad laminates with low dielectric constants (Dk) are required to reduce signal delay and attenuation; low dielectric loss factor helps improve circuit efficiency; sufficient peel strength can ensure that the copper foil will not fall off the substrate during the circuit board manufacturing process (such as etching, drilling, etc.) and use, ensuring the reliability of electrical connections; and high modulus and low thermal expansion coefficient (Low-CTE) are required. At the same time, as electronic products develop towards miniaturization and multi-functionality, higher requirements are also placed on the heat resistance of copper-clad laminates.

[0003] Poly (2,6-dimethyl-1,4-phenylene oxide) (PPO) is a resin with low dielectric constant and dielectric loss, low thermal expansion coefficient, and low water absorption, and can be used to prepare high-frequency and high-speed copper-clad laminates. However, as a thermoplastic resin, PPO has disadvantages such as low glass transition temperature and insufficient initial thermal decomposition temperature, which limits its further application.

[0004] Therefore, it is necessary to improve the traditional technology. Summary of the invention

[0005] Based on this, the present application provides a resin composition having both a relatively high glass transition temperature and a relatively high peel strength, and a preparation method thereof, a prepreg, a copper clad laminate and a printed circuit board.

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

[0007] On the one hand, the present application provides a resin composition, which comprises the following components by weight:

[0008] 20 to 100 parts of phthalonitrile-terminated polyphenylene ether;

[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 the following components in parts by mass:

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

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

[0014] 30~60 parts of inorganic filler.

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

[0016] In some of the embodiments, in the resin composition, the inorganic filler includes at least one of zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, eucryptite, silica, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc, aluminum oxide, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, clay and kaolin.

[0017] On the one hand, the present application provides a method for preparing a resin composition, comprising the following steps:

[0018] Mix 20 to 100 parts of phthalonitrile-terminated polyphenylene ether, 1 to 40 parts of amino-terminated polyetherimide and 0 to 60 parts of inorganic filler by weight.

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

[0020] The polyphenylene ether, 4-nitrophthalonitrile and a first solvent are mixed to carry out a nucleophilic substitution reaction.

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

[0022] m-phenylenediamine, bisphenol A diether dianhydride and a second solvent are mixed to carry out a thermal imidization reaction.

[0023] In one aspect, the present application provides a resin film, which includes the above-mentioned resin composition or the resin composition prepared by the above-mentioned preparation method.

[0024] On one hand, the present application provides a prepreg, comprising a reinforcing material and the above-mentioned resin composition attached to the reinforcing material or the resin composition prepared by the above-mentioned preparation method.

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

[0026] On one hand, the present application provides a printed circuit board, comprising 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 the present application has the following beneficial effects:

[0028] The resin composition of the present application comprises phthalonitrile-terminated polyphenylene ether, amino-terminated polyetherimide and inorganic filler. The phthalonitrile group in the phthalonitrile-terminated polyphenylene ether reacts with the aromatic amine group in the amino-terminated polyetherimide to form an isoindole ring structure. Meanwhile, the aromatic amine structure in the amino-terminated polyetherimide can promote the self-polymerization of the phthalonitrile-terminated polyphenylene ether to form phthalocyanine ring and triazine ring structure, so that the resin composition has a higher glass transition temperature, a higher initial thermal decomposition temperature, a lower water absorption rate, a higher elastic modulus, better flame retardancy, better dielectric properties and higher peel strength. Meanwhile, the amino-terminated polyetherimide having an aromatic amine structure can effectively reduce the curing temperature of the phthalonitrile group in the phthalonitrile-terminated polyphenylene ether, effectively improve the toughness of the resin composition, and effectively reduce the curing temperature of the resin composition on the basis of ensuring a low dielectric constant. DETAILED DESCRIPTION

[0029] 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 are not used to limit the scope of the present application. The purpose of providing these embodiments and examples is to make the understanding of the disclosure of the present application more thorough and comprehensive.

[0030] It should also be understood that the present 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 changes or modifications without violating the connotation of the present application, and the equivalent forms obtained also fall within the scope of protection of the present application. For example, the features illustrated or described as part of one embodiment can be combined in another embodiment in a suitable manner to produce a new embodiment. In addition, in the description below, a large number of specific details are given in order to provide a more comprehensive understanding of the present application. It should be understood that the present 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 those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing implementation modes and embodiments and are not intended to limit this application.

[0032] Unless otherwise specified or incompatible herewith, the terms and phrases used herein shall have the following meanings:

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

[0034] As used herein, "combination thereof", "any combination thereof", "any combination thereof" etc. include all suitable combinations of any two or more of the listed items.

[0035] Herein, the “suitable” mentioned in “suitable combination”, “suitable method”, “any suitable method”, etc., shall be based on the ability to implement the technical solution of this application, solve the technical problems of this application, and achieve the expected technical effects of this application.

[0036] Herein, "preferred", "better", "more preferred", and "suitable" are only used to describe implementation methods or examples with better effects, and it should be understood that they do not constitute a limitation on the scope of protection of this application. If multiple "preferred" items appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "preferred" item is independent.

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

[0038] In this application, "optionally", "optional", and "optional" mean optional or dispensable, that is, any one of the two parallel schemes of "yes" or "no". If multiple "options" appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" is independent.

[0039] In the present application, the terms "first", "second", "third", "fourth", etc. in "the first aspect", "the second aspect", "the third aspect", "the fourth aspect", etc. are used only for descriptive purposes and cannot be understood as indicating or implying relative importance or quantity, nor can they be understood as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first", "second", "third", "fourth", etc. only serve the purpose of non-exhaustive enumeration and description, and it should be understood that they do not constitute a closed limitation on quantity.

[0040] In the present application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0041] In the present application, when it comes to a numerical interval (i.e., a numerical range), unless otherwise specified, the distribution of the optional numerical values ​​in the numerical interval is considered to be continuous, and includes the two numerical endpoints (i.e., the minimum value and the maximum value) of the numerical interval, and each numerical value between the two numerical endpoints. Unless otherwise specified, when the numerical interval only refers to the integers in the numerical interval, it includes the two endpoint integers of the numerical range, and each integer between the two endpoints, which is equivalent to directly listing each integer. When multiple numerical ranges are provided to describe features or characteristics, 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 included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. "Numerical interval" allows broadly including numerical interval types such as percentage intervals, ratio intervals, and ratio intervals.

[0042] The temperature parameters in this application, unless otherwise specified, are allowed to be either constant temperature treatment or to vary within a certain temperature range. It should be understood that the constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument. Fluctuations within the range of ±5°C, ±4°C, ±3°C, ±2°C, and ±1°C are allowed.

[0043] In this 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 this application, "room temperature" or "normal temperature" refers to 10°C to 30°C. In some embodiments of this application, "room temperature" or "normal temperature" refers to 20°C to 30°C.

[0044] In this application, when referring to the unit of a data range, if there is a unit only after the right endpoint, it means 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 documents mentioned in this application are cited as references in this application, just as each document is cited as reference separately. Unless they conflict with the invention purpose and / or technical solution of this application, the cited documents involved in this application are cited with all contents and all purposes. When the cited documents are involved in this application, the definitions of relevant technical features, terms, nouns, phrases, etc. in the cited documents are also cited. When the cited documents are involved in this application, the examples and preferred methods of the cited relevant technical features can also be incorporated into this application as references, but are limited to the implementation of this application. It should be understood that when the cited content conflicts with the description in this application, the present application shall prevail or be modified adaptively according to the description of this application.

[0046] The mass or weight of the relevant components mentioned in the specification of the embodiments of the present application may not only refer to the specific content of each component, but also indicate the proportional relationship of the mass or weight between the components. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the specification of the embodiments of the present application, it is within the scope disclosed in the specification of the embodiments of the present application. Specifically, the mass or weight described in the specification of the embodiments of the present application may be units known in the chemical industry such as μg, mg, g, and kg.

[0047] An embodiment of the present application provides a resin composition, which comprises the following components in parts by mass:

[0048] 20 to 100 parts of phthalonitrile-terminated polyphenylene ether;

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

[0050] Inorganic filler 0 to 60 parts.

[0051] The resin composition provided by the present application comprises a phthalonitrile-terminated polyphenylene ether, an amino-terminated polyetherimide and an inorganic filler. The phthalonitrile group in the phthalonitrile-terminated polyphenylene ether reacts with the aromatic amine group in the amino-terminated polyetherimide to form an isoindole ring structure. Meanwhile, the aromatic amine structure in the amino-terminated polyetherimide can promote the self-polymerization of the phthalonitrile-terminated polyphenylene ether to form a phthalocyanine ring and a triazine ring structure, so that the resin composition has a higher glass transition temperature, a higher initial thermal decomposition temperature, a lower water absorption rate, a higher elastic modulus, better flame retardancy, better dielectric properties and higher peel strength. Meanwhile, the amino-terminated polyetherimide having an aromatic amine structure can effectively reduce the curing temperature of the phthalonitrile group in the phthalonitrile-terminated polyphenylene ether, effectively improve the toughness of the resin composition, and effectively reduce the curing temperature of the resin composition while ensuring a low dielectric constant.

[0052] It can be understood that in the resin composition, the mass fraction of phthalonitrile-terminated polyphenylene ether is, by mass, but is not limited to, 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 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 parts of the amino-terminated polyetherimide include but are not limited to 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts , 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, 40 parts; the mass fractions of inorganic fillers include but are not limited to 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 parts , 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, and 60 parts; in some examples, any two of these point values ​​can be used as the end values ​​within the range, the same below.

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

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

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

[0056] 30~60 parts of inorganic filler.

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

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

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

[0060] 30~50 parts of inorganic filler.

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

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

[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, 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 the phthalonitrile-terminated polyphenylene ether to the amino-terminated polyetherimide is 1 to 5:1.

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

[0069] In some of the examples, in the resin composition, the phthalonitrile-terminated polyphenylene ether is prepared by using polyphenylene ether (SA90, SABIC) and 4-nitrophthalonitrile as reaction raw materials.

[0070] In some of the examples, in the resin composition, the structural formula of the phthalonitrile-terminated polyphenylene ether is as follows:

[0071]

[0072] In some of the examples, in the resin composition, the amino-terminated polyetherimide is prepared by using m-phenylenediamine and bisphenol A diether dianhydride as reaction raw materials.

[0073] In some of the examples, in the resin composition, the amino-terminated polyetherimide has the following structural formula:

[0074]

[0075] It can be understood 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 as shown in formula (a) and formula (b), the phthalocyanine ring formed by the self-polymerization of the phthalonitrile-terminated polyphenylene ether is as shown in formula (c), and the triazine ring structure formed by the self-polymerization of the phthalonitrile-terminated polyphenylene ether is as shown in formula (d):

[0076]

[0077]

[0078] In some of the examples, in the resin composition, the inorganic filler includes at least one of zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, eucryptite, silica (spherical, composite or fused), 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.

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

[0080] It can be understood that in the resin composition, the mass fraction of the third solvent is 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, 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 7 portions, 68 portions, 69 portions, 70 portions, 71 portions, 72 portions, 73 portions, 74 portions, 75 portions, 76 portions, 77 portions, 78 portions, 79 portions, 80 portions, 81 portions, 82 portions, 83 portions, 84 portions, 85 portions, 86 portions, 87 portions, 88 portions, 89 portions, 90 portions, 91 portions, 92 portions, 93 portions, 94 portions, 95 portions, 96 portions, 97 portions, 98 portions, 99 portions, and 100 portions.

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

[0082] In some examples, in the resin composition, the third 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.

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

[0084] The resin composition provided in the present 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 board fields such as integrated circuit packaging, high frequency and high speed.

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

[0086] Mix 20 to 100 parts of phthalonitrile-terminated polyphenylene ether, 1 to 40 parts of amino-terminated polyetherimide and 0 to 60 parts of inorganic filler by weight.

[0087] It can be understood that the preparation method of the resin composition can produce the above-mentioned resin composition, the above-mentioned resin composition can be produced by the preparation method of the resin composition, and the characteristics between the above-mentioned resin composition and the preparation method of the resin composition can be mutually applicable.

[0088] The resin composition prepared by the preparation 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 the examples, in the method for preparing the resin composition, the preparation of the phthalonitrile-terminated polyphenylene ether comprises the following steps:

[0090] The polyphenylene ether, 4-nitrophthalonitrile and a first solvent are mixed to carry out a nucleophilic substitution reaction.

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

[0092] Further, the nucleophilic substitution reaction is carried out under the action of a catalyst. Further, the catalyst comprises potassium carbonate.

[0093] Furthermore, the temperature of the nucleophilic substitution reaction is 50°C~60°C, and the time is 10 h~12 h.

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

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

[0096] m-phenylenediamine, bisphenol A diether dianhydride and a second solvent are mixed to carry out a thermal imidization reaction.

[0097] Bisphenol A diether dianhydride, also known as bisphenol A dianhydride, BPADA, bisphenol A dianhydride, its molecular formula is C 31 H 20 O 8 , the structure is as follows:

[0098]

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

[0100] Furthermore, the temperature of the thermal imidization reaction is 160°C to 250°C.

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

[0102] In some 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 is placed in an oven at 160°C to 250°C to remove the reaction solvent and perform a thermal imidization reaction.

[0105] One embodiment of the present application provides a resin film, which includes the above-mentioned resin composition or the resin composition prepared by the above-mentioned preparation method.

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

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

[0108] The resin composition or the resin composition obtained by the preparation method is coated on a release material and then dried and / or semi-cured to obtain the release material.

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

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

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

[0112] Furthermore, the inorganic fiber material includes but is not limited to 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.

[0113] Furthermore, the organic fiber material includes but is 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 accounts for 40% to 60% by weight of the prepreg.

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

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

[0117] The reinforcing material is impregnated into the resin composition or the resin composition obtained by the preparation method, and the prepreg is obtained by semi-curing treatment.

[0118] It can be understood that the above resin composition or the resin composition obtained by the above preparation method covers the surface of the reinforcing material.

[0119] In some of the examples, in the method for preparing the prepreg, the semi-curing treatment is performed at a temperature of 150°C to 250°C and for a time of 2 min to 10 min.

[0120] It will be understood that the semi-curing temperature 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, and 250°C; 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 the present application provides a laminate, comprising at least one of the above-mentioned resin film and the above-mentioned prepreg.

[0122] It can be understood that the laminate includes one or two of the above-mentioned resin film and the above-mentioned prepreg. Furthermore, the resin film and the prepreg can be one or more.

[0123] In some of the examples, in the laminate, one side or both sides of the laminate are copper foils, which can be understood as copper clad laminates.

[0124] Accordingly, one embodiment of the present 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 the present application includes 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.

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

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

[0128] After providing a metal copper foil on at least one side of at least one of the resin film and the prepreg, lamination is performed.

[0129] It can be understood that there may be a plurality of the resin films and the prepregs, and a plurality means at least one.

[0130] In some of the examples, in the preparation method of copper clad laminate, the lamination parameters are: temperature 150℃~300℃, pressure 10 kgf / cm 2 ~30 kgf / cm 2 , under the condition of vacuum degree <2kPa, hot pressing is carried out for 200min~400min.

[0131] It is understood that the lamination temperature 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 、30 kgf / cm 2 The time for hot pressing includes but is not limited to 200min, 210min, 220min, 230min, 240min, 250min, 260min, 270min, 280min, 290min, 300min, 310min, 320min, 330min, 340min, 350min, 360min, 370min, 380min, 390min, and 400min.

[0132] An embodiment of the present application provides a printed circuit board, comprising 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 the present 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] An embodiment of the present application provides a communication device, including the above-mentioned printed circuit board.

[0135] It is understood that the communication device includes but is not limited to at least one of a smart phone, a tablet computer, a smart watch, etc.

[0136] In the field of consumer electronics, electronic products cannot do without copper clad laminates: from smartphones, tablets to smart watches, the circuit boards inside are all made based on copper clad laminates. In the computer field: from the motherboards and graphics cards of personal computers to the motherboards of servers, copper clad laminates are used to build complex circuit systems to achieve electrical connections between various chips, interfaces and electronic components. In the field of communications: the RF circuit boards of 5G base stations, the backplanes of communication equipment, etc. all require the use of high-performance copper clad laminates to meet the requirements of high-speed signal transmission and high reliability. In addition, copper clad laminates also play a vital role in the fields of automotive electronics, industrial control, aerospace, etc.

[0137] The present application is further described in detail below in conjunction with specific implementation methods, but the implementation methods of the present application are not limited thereto.

[0138] Source of raw materials:

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

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

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

[0142] m-phenylenediamine, Inokane, analytical grade;

[0143] Spherical silica, Yaduma, model SC6500-SXD.

[0144] Example 1

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

[0146] Weigh polyphenylene ether SA90 (0.1 mol, 160 g) into a three-necked flask, add 600 mL N,N-dimethylformamide and stir to completely dissolve it, then add anhydrous potassium carbonate (0.1 mol, 13.82 g) and 4-nitrophthalonitrile (0.11 mol, 19.04 g), keep the oil bath heated at 50℃~60℃, and stir at high speed to react for 10 h~12 h; after the reaction, add deionized water and filter to collect the precipitate, then wash it with deionized water and ethyl acetate several times respectively, and 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 diether dianhydride (0.1 mol, 52.05 g) was dissolved in 200 mL of anhydrous N,N-dimethylformamide solution, and an ice-water bath was maintained at 0°C. Excess m-phenylenediamine (0.11 mol, 11.90 g, the molar ratio of m-phenylenediamine to bisphenol A diether dianhydride was 1.1:1) was added in batches under high-speed stirring. After reacting for 10 h, a polyetheramic acid solution was obtained. The solution was then poured into a clean mold and placed in an oven at 160°C~250°C for programmed heating to remove the reaction solvent and perform thermal imidization reaction, and finally an amino-terminated polyetherimide was obtained, the structural formula of which is as follows:

[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 are dissolved in a mixed solvent of 60 parts of toluene and N,N-dimethylformamide, wherein toluene and N,N-dimethylformamide are mixed in a mass ratio of 1:1, and the mass ratio of phthalonitrile-terminated polyphenylene ether resin to amino-terminated polyetherimide is 5:1. Under stirring conditions, 40 parts of spherical silica are added, and stirring is continued to obtain a uniform glue solution, i.e., a resin composition.

[0152] (4) Preparation of prepreg

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

[0154] (5) Preparation of copper clad laminate

[0155] The six prepregs prepared in step (4) were stacked, and a 18 μm thick electrolytic copper foil was covered on each of the upper and lower surfaces of the stacked body. The stacked body was placed in a programmable temperature and pressure controlled vacuum press and heated to 30 kgf / cm2 in a vacuum state. 2 Under pressure, a 0.6 mm thick copper-clad laminate was produced after curing at 260°C for 3 hours.

[0156] Example 2

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

[0158] Example 3

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

[0160] Example 4

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

[0162] Example 5

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

[0164] Example 6

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

[0166] Comparative Example 1

[0167] The method 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 by an equal mass of polyphenylene ether.

[0168] Comparative Example 2

[0169] The method is basically the same as 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. Finally, polyetherimide is obtained, and the structural formula is as follows:

[0170] .

[0171] The components of the resin composition used in the copper-clad laminates prepared in the examples and comparative examples are shown in Table 1.

[0172] Table 1

[0173]

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

[0175] Peel strength: The test method is carried out in accordance with 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: Tested according to IPC-TM650 2.6.2.1;

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

[0181] Flame retardant: tested according to IPC-TM650 2.3.10.

[0182] The results are shown in Table 2.

[0183] Table 2

[0184]

[0185] As can be seen from Table 2, compared with the comparative example, the resin composition used in each embodiment cooperates the phthalonitrile-terminated polyphenylene ether with the amino-terminated polyetherimide, and the glass transition temperature, initial thermal decomposition temperature, water absorption, elastic modulus, flame retardancy, dielectric properties and peel strength comprehensive performance of the copper-clad laminate finally obtained are better. In comparative example 1, the glass transition temperature and thermal decomposition temperature of the copper-clad laminate finally obtained by cooperating the polyphenylene ether with the amino-terminated polyetherimide are significantly reduced, and the thermal decomposition temperature is reduced; in comparative example 2, the phthalonitrile-terminated polyphenylene ether is cooperated with the polyetherimide, and the peel strength of the copper-clad laminate finally obtained is significantly reduced.

[0186] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described 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 above-described embodiments only express several implementation methods of the present application, which is convenient for understanding the technical solution of the present application in detail, but it cannot be understood as limiting the scope of protection of the invention patent. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present application, several modifications and improvements can be made, which all belong to the scope of protection of the present application. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided in the present application are all within the scope of protection of the claims attached to the present application. Therefore, the scope of protection of the patent of this application shall be based on the content of the attached claims, and the description 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 100 parts of phthalonitrile-terminated polyphenylene ether; 1 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 resin composition comprises the following components in parts by mass: 20 to 50 parts of phthalonitrile-terminated polyphenylene ether; 10 to 40 parts of amino-terminated polyetherimide; and 30~60 parts of inorganic filler.

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 0.5-5:1; optionally, 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, eucryptite, silicon dioxide, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc, aluminum oxide, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, clay and kaolin.

5. A method for preparing a resin composition, characterized in that: The following steps are involved: Mix 20 to 100 parts of phthalonitrile-terminated polyphenylene ether, 1 to 40 parts of amino-terminated polyetherimide and 0 to 60 parts of inorganic filler by weight.

6. The method for preparing the resin composition according to claim 5, wherein The preparation of the phthalonitrile-terminated polyphenylene ether comprises the following steps: The polyphenylene ether, 4-nitrophthalonitrile and a first solvent are mixed to carry out a nucleophilic substitution reaction.

7. The method for preparing a resin composition according to any one of claims 5 to 6, wherein: The preparation of the amino-terminated polyetherimide comprises the following steps: m-phenylenediamine, bisphenol A diether dianhydride and a second solvent are mixed to carry out a thermal imidization reaction.

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

9. A prepreg, characterized in that: The invention comprises a reinforcing material and a resin composition as claimed in any one of claims 1 to 4 or a resin composition prepared by the preparation method as claimed in any one of claims 5 to 7 attached to the reinforcing material.

10. A copper clad laminate, characterized in that: The method comprises at least one of the resin film according to claim 8 and the prepreg according to claim 9.

11. A printed circuit board, characterized in that: The method comprises at least one of the resin film according to claim 8, the prepreg according to claim 9 and the copper clad laminate according to claim 10.

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