Resin composition, prepreg, circuit board and printed circuit board

Abstract

The invention relates to a resin composition, a prepreg, a circuit substrate and a printed circuit board, the resin composition comprises maleimide resin, cyanate ester, polyphenyl ether resin and a filler, at least one terminal of a molecular chain of the polyphenyl ether resin is terminated by a reactive group, and the reactive group is a reactive group. The molecular structural formula of the cyanate ester comprises a biphenyl structure or a cyclopentene structure or an indane structure and has more than two cyano group substituted aromatic rings, the molecular structural formula of the maleimide resin is shown as a formula (I), n is more than or equal to 0 and less than 1000, R1 and R2 are respectively and independently selected from alkane, an ether bond, a naphthalene ring, a fluorene ring, a formula (II), a formula (III) or a formula (IV), and n is more than or equal to 0 and less than 1000. And R3-R9 are respectively and independently selected from carbonyl, ester group, alkyl or alkenyl. The circuit substrate prepared from the resin composition has a low thermal expansion coefficient and excellent dielectric properties.

Description

Technical Field

[0001] The present invention relates to the technical field of electronic industry, in particular to a resin composition, a prepreg, a circuit substrate and a printed circuit board. Background Art

[0002] With the continuous update of AI and the significant increase in computing power requirements, the IC industry is developing rapidly. As printed circuit boards are increasingly required to be thinner and multilayered, the requirements for circuit substrates are gradually increasing. Not only are they required to have a low coefficient of thermal expansion (CTE), but they are also required to have lower dielectric loss (Df) to meet the development needs of existing technologies. Therefore, there is an urgent need to develop a new generation of resin compositions so that the circuit substrates made with the resin compositions have low coefficients of thermal expansion and low dielectric loss, which are suitable for the technical requirements of high-performance printed circuit boards in the fields of high-density interconnection, high-frequency and high-speed, and even packaging of integrated circuits. Summary of the Invention

[0003] Based on this, it is necessary to provide a resin composition, a prepreg, a circuit substrate and a printed circuit board to address the above problems. The circuit substrate made of the resin composition has a low thermal expansion coefficient and excellent dielectric properties.

[0004] A resin composition includes a maleimide resin, a cyanate ester, a polyphenylene ether resin, and a filler, wherein the molecular structure of the cyanate ester includes a biphenyl structure, a cyclopentene structure, or an indane structure and has two or more cyano-substituted aromatic rings, and the molecular structure of the maleimide resin is shown in formula (I):

[0005]

[0006] Wherein, 0≤n<1000, R1 and R2 are independently selected from alkanes, alkenes, ether bonds, naphthalene rings, fluorene rings, formula (II), formula (III) or formula (IV):

[0007]

[0008] Wherein, R3-R9 are independently selected from carbonyl, ester, alkyl or alkenyl.

[0009] In one embodiment, at least one of said R1 and said R2 is selected from formula (II), formula (III) or formula (IV).

[0010] In one embodiment, the R1 is selected from an alkane structure, the R2 is selected from formula (II), formula (III), formula (IV), a naphthalene ring or a fluorene ring, and 0≤n<600.

[0011] In one embodiment, in the molecular structure of the maleimide resin, the ratio of the number of rigid groups to the number of maleimide groups is 1:1-3:1.

[0012] In one embodiment, the cyanate ester is selected from at least one of a naphthyl ether type cyanate ester compound, an adamantane skeleton type cyanate ester compound, a dicyclopentadiene type cyanate ester, a bisphenol A type cyanate ester, a phenolic type cyanate ester, a biphenyl type cyanate ester, a naphthalene type cyanate ester, and a naphthol aralkyl type cyanate ester.

[0013] In one embodiment, the molecular structure of the cyanate ester is shown in formula (V):

[0014]

[0015] Wherein, R is selected from a cyclopentadiene structure, a bisphenol A structure, a phenolic structure or an indane structure, and 1≤n<200.

[0016] In one embodiment, the molecular weight of the polyphenylene ether resin is 1000-5000.

[0017] In one embodiment, the molecular weight of the reactive group is less than 20% of the molecular weight of the polyphenylene ether resin.

[0018] In one embodiment, the reactive group is selected from at least one of vinyl, vinylbenzyl, acrylic, propenyl, hydroxyl, and methacrylate.

[0019] In one embodiment, the polyphenylene ether resin is selected from vinyl terminated polyphenylene ether resin, and the molecular structure is shown in formula (VI) or formula (VII):

[0020]

[0021] Among them, R 10 、R 11 Independently selected from ether bonds, alkanes or alkenes, 1≤n≤100, 1≤m≤100.

[0022] In one embodiment, based on 100 parts by weight of the maleimide resin, the amount of the cyanate ester is 120 parts by weight to 200 parts by weight, the amount of the polyphenylene ether resin is 20 parts by weight to 50 parts by weight, and the amount of the filler is 300 parts by weight to 450 parts by weight.

[0023] In one embodiment, the resin composition further comprises an organic metal salt catalyst.

[0024] A prepreg made from the resin composition described above.

[0025] A circuit substrate made of the prepreg described above.

[0026] A printed circuit board made of the circuit substrate described above.

[0027] The resin composition of the present invention comprises a polyphenylene ether resin, a maleimide resin, and a cyanate ester with a specific structure. The maleimide resin has a highly rigid group and a highly symmetrical structure. The combination of the polyphenylene ether resin having a reactive group at the end and the cyanate ester having a large steric hindrance group in the molecular structure allows the cross-linked network generated by the reaction to have highly rigid groups and a symmetrical structure. As a result, a circuit substrate made from the resin composition has a low coefficient of thermal expansion and excellent dielectric properties. The circuit substrate is then used to prepare a printed circuit board, which can effectively reduce the CTE of the printed circuit board and improve its dielectric properties. DETAILED DESCRIPTION

[0028] To facilitate understanding of the present invention, the present invention will be described in more detail below. However, it should be understood that the present invention can be implemented in many different forms and is not limited to the embodiments or examples described herein. On the contrary, the purpose of providing these embodiments or examples is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art of the technical field of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments or embodiments and are not intended to limit the present invention. The optional scope of the term "and / or" used herein includes any one of two or more related listed items, and also includes any and all combinations of related listed items, including any two related listed items, any more related listed items, or the combination of all related listed items.

[0030] The present invention provides a resin composition comprising a maleimide resin, a cyanate ester, a polyphenylene ether resin, and a filler, wherein at least one end of the molecular chain of the polyphenylene ether resin is capped with a reactive group, the molecular structure of the cyanate ester comprises a biphenyl structure, a cyclopentene structure, or an indane structure, and has two or more cyano-substituted aromatic rings, and the molecular structure of the maleimide resin is as shown in formula (I):

[0031]

[0032] Wherein, 0≤n<1000, R1 and R2 are independently selected from alkanes, alkenes, ether bonds, naphthalene rings, fluorene rings, formula (II), formula (III) or formula (IV):

[0033]

[0034] Wherein, R3-R9 are independently selected from carbonyl, ester, alkyl and alkenyl.

[0035] The maleimide resin of the present invention has a rigid group, which is a cyclic structure, such as an aliphatic ring, an aromatic ring, or an aromatic heterocycle. Furthermore, the molecular structure of the maleimide resin is highly symmetrical. Therefore, on the one hand, when the maleimide resin forms a cross-linked network with a cyanate ester or a polyphenylene ether resin, the rigid group causes the cross-linked network to have a large steric hindrance. As a result, a circuit substrate prepared using the resin composition has a low coefficient of thermal expansion, and a printed circuit board further prepared using the circuit substrate has a low CTE. Furthermore, the highly symmetrical structure is beneficial for reducing the polarity of the maleimide resin, thereby effectively improving the dielectric properties of the circuit substrate.

[0036] Specifically, the maleimide resin can be selected from at least one of 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, phenylmethanemaleimide, metaphenyl bismaleimide, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 4,4-diphenylacetyl bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, and a maleimide polymer containing multiple imide rings.

[0037] Optionally, at least one of R1 and R2 is preferably selected from formula (II), formula (III) or formula (IV). Further, R1 is preferably an alkane structure, and R2 is preferably an aromatic group, and 0≤n<600. Further, R1 can be preferably a methylene group, an alkenyl group or a vinylbenzyl group; R2 can be preferably a group of formula (II), formula (III), formula (IV), a naphthalene ring or a fluorene ring, thereby further improving the CTE and dielectric properties of the circuit substrate.

[0038] Optionally, in the molecular structure of the maleimide resin, the ratio of the number of rigid groups to maleimide groups is preferably 1:1-3:1, so as to ensure that the maleimide resin has appropriate rigidity while further ensuring the cross-linking density of the cross-linked network formed with the cyanate ester and polyphenylene ether resin, thereby reducing the CTE of the circuit substrate and improving the dielectric properties and appearance of the circuit substrate. It should be explained that the ratio of the number of rigid groups to maleimide groups in the present invention refers to the ratio of the number of cyclic structures as functional groups to the number of maleimide groups in the maleimide resin. For example, when R2 in the maleimide resin is selected from formula (II), R1 is selected from an ether bond and n is 1, the rigid groups are naphthalene rings and phenyl groups, and the ratio of the number of rigid groups to maleimide groups in the maleimide resin is 2:1; when R2 in the maleimide resin is selected from formula (III), R1 is selected from an ether bond and n is 1, the rigid group is phenyl groups, and the ratio of the number of rigid groups to maleimide groups in the maleimide resin is 3:1; when R2 in the maleimide resin is selected from formula (IV), R1 is selected from an ether bond and n is 1, the rigid groups are biphenyl and phenyl groups, and the ratio of the number of rigid groups to maleimide groups in the maleimide resin is 2:1.

[0039] The present invention can use XPS and infrared spectroscopy detection methods to detect the characteristic peak intensity of rigid groups such as phenyl, naphthalene ring, and biphenyl structure and the characteristic peak intensity of maleimide group. By comparing the characteristic peak intensities, the quantitative ratio of rigid groups to maleimide groups can be roughly calculated.

[0040] The molecular structure of the cyanate ester of the present invention includes a biphenyl structure, a cyclopentene structure, or an indane structure, and has two or more cyano-substituted aromatic rings, so that the resin system can further form a cross-linked network with a symmetrical structure and steric hindrance, thereby enabling the manufactured circuit substrate to have a low CTE and excellent dielectric properties.

[0041] Specifically, the cyanate ester is preferably at least one of a naphthyl ether type cyanate ester compound, an adamantane skeleton type cyanate ester compound, a dicyclopentadiene type cyanate ester, a bisphenol A type cyanate ester, a phenol formaldehyde type cyanate ester, a biphenyl type cyanate ester, a naphthalene type cyanate ester, and a naphthol aralkyl type cyanate ester.

[0042] Optionally, the molecular structure of the cyanate ester is further preferably as shown in formula (V), wherein R is preferably a cyclopentadiene structure, a bisphenol A type structure, a phenolic type structure or an indane structure, and 1≤n<200. Thus, the structure of formula (V) is conducive to providing more cyclic structures, so that the cyanate ester has a large steric hindrance, and thus occupies a larger spatial area in the cross-linked network formed with the maleimide resin and the polyphenylene ether resin, further effectively improving the dielectric properties and CTE of the circuit substrate.

[0043]

[0044] At least one end of the polyphenylene ether resin molecular chain of the present invention is capped with a reactive group, so that during the reaction of the maleimide resin, cyanate ester and polyphenylene ether resin, the overall reactivity of the resin system can be further controlled, thereby improving the appearance of the circuit substrate, such as the resin grain or dried flower problem.

[0045] Optionally, the molecular weight of the polyphenylene ether resin is preferably 1000-5000, so as to further control the reactivity of the resin system, which is beneficial for obtaining a circuit substrate with excellent appearance, and is also beneficial for improving the CTE and dielectric properties of the circuit substrate.

[0046] Optionally, the molecular weight of the reactive group is less than 20% of the molecular weight of the polyphenylene ether resin, more preferably less than 10%, thereby improving the overall reactivity of the resin system, improving the CTE and dielectric properties of the circuit substrate, and optimizing the appearance of the circuit substrate.

[0047] Optionally, the reactive group of the present invention is a group that can react with maleimide resin or cyanate ester, preferably at least one of vinyl, vinylbenzyl, acrylic, propenyl, hydroxyl, and methacrylate, and more preferably vinyl.

[0048] Specifically, when the reactive group is preferably a vinyl group, the molecular structure of the polyphenylene ether resin is preferably Formula (VI) or Formula (VII), wherein R 10 、R 11 Independently selected from ether bonds, alkanes or alkenes, 1≤n≤100, 1≤m≤100, and further preferably, 1≤n+m≤100.

[0049] The molecular weight of the vinyl group is preferably less than 20% of the molecular weight of the polyphenylene ether resin, and more preferably less than 10%. As a result, the reaction enthalpy of the vinyl group is higher and the reactivity with the resin system is stronger. In addition, the appropriate vinyl content in the polyphenylene ether resin can be cross-linked with the maleimide resin and the cyanate ester, which is beneficial to further improve the overall reactivity of the resin system, improve the CTE and dielectric properties of the circuit substrate, and optimize the appearance of the circuit substrate.

[0050]

[0051] The filler of the present invention can be selected from conventional fillers, such as at least one of silica, alumina, aluminum nitride, boron nitride, boehmite, molybdenum oxide, and titanium oxide. In order to further enhance the compatibility of the filler with the components in the resin system, the surface of the filler can also be treated with a modifier.

[0052] To further ensure that the circuit substrate prepared using the resin composition has excellent CTE, dielectric properties and surface appearance, based on 100 parts by weight of the maleimide resin, the amount of the cyanate ester is preferably 120 parts by weight to 200 parts by weight, the amount of the polyphenylene ether resin is preferably 20 parts by weight to 50 parts by weight, and the amount of the filler is preferably 300 parts by weight to 450 parts by weight.

[0053] Optionally, the resin composition further includes an organic metal salt catalyst, which is preferably at least one of a zinc catalyst, a cobalt catalyst, and an imidazole, and is further preferably an organic zinc catalyst, such as zinc isocyanate. Based on 100 parts by weight of the maleimide resin, the amount of zinc isocyanate is preferably 2 parts by weight to 10 parts by weight, thereby further effectively controlling the reactivity of the resin system and thereby improving the appearance, CTE and dielectric properties of the circuit substrate.

[0054] In one embodiment, the resin composition further includes a solvent. The present invention does not limit the type of the solvent, and the solvent may be a common commercially available organic solvent, such as butanone, toluene, and the like.

[0055] The present invention also provides a prepreg made using the resin composition. The present invention does not limit the specific method for preparing the prepreg using the resin composition. Preferably, the prepreg is obtained by impregnating or coating a reinforcing material with the resin composition and drying it. The type of the reinforcing material is not limited, but is preferably at least one of glass fiber cloth, aramid cloth, or carbon fiber cloth.

[0056] The present invention also provides a circuit substrate made using the prepreg. Preferably, the circuit substrate comprises a dielectric layer and a conductive layer disposed on at least one surface of the dielectric layer, the dielectric layer comprising one or more stacked prepregs, and the conductive layer is preferably copper foil.

[0057] The invention also provides a printed circuit board made of the circuit substrate.

[0058] The printed circuit board is preferably manufactured by subjecting the circuit substrate to processes such as drilling, hole filling, micro-etching, pre-preg, activation, acceleration, chemical copper and copper thickening.

[0059] Hereinafter, the resin composition, prepreg, circuit substrate and printed circuit board will be further described through the following specific examples.

[0060] Example 1

[0061] 100 parts by weight of a maleimide resin having a molecular structure such as formula (I) is provided, wherein R1 is selected from methylidene, R2 is selected from formula (III), and R5 and R7 are selected from alkyl carbon chains with a carbon chain length of less than 6, R6 is selected from methylene, n is 500, and in the maleimide resin, the ratio of the number of rigid groups to the number of maleimide groups is 3:1; 200 parts by weight of a dicyclopentadiene cyanate having a molecular structure such as formula (V), wherein R is selected from a cyclopentadiene structure and n is 100; 50 parts by weight of a polyphenylene ether resin having a molecular structure such as formula (VI), wherein R 10 The invention relates to a polyphenylene ether resin comprising a methylene group, wherein n is 5 and m is 5, wherein the molecular weight of the polyphenylene ether resin is 1324 and the molecular weight of the vinyl group at the end of the molecular chain is 4.1% of the molecular weight of the polyphenylene ether resin; 0.6 parts by weight of zinc isocyanate, 0.3 parts by weight of imidazole, and 450 parts by weight of surface-modified silicon oxide. The above substances are uniformly mixed and added into toluene and butanone to be uniformly dispersed and dissolved to form a resin composition.

[0062] Then, the resin composition was impregnated into glass fiber cloth, and heated and dried at 130° C. for 5 minutes to obtain a prepreg.

[0063] Eight prepregs were stacked, and electrolytic copper foils were covered on the upper and lower surfaces thereof. The prepregs were cured in a high-temperature press at 220° C. for 4 hours to obtain a circuit substrate.

[0064] The performance test of the circuit substrate was carried out, and the results are shown in Table 1.

[0065] Example 2

[0066] 80 parts by weight of a maleimide resin having a molecular structure such as formula (I) is provided, wherein R1 is selected from methylene, R2 is selected from formula (III), and R5 is selected from an alkyl carbon chain with a carbon chain length of less than 6, R6 is selected from methylene, R7 is selected from an alkyl carbon chain with a carbon chain length of less than 6, and n is 200. In the maleimide resin, the ratio of the number of rigid groups to the number of maleimide groups is 3:1; 200 parts by weight of a dicyclopentadiene cyanate having a molecular structure such as formula (V), wherein R is selected from a cyclopentadiene structure and n is 50; 50 parts by weight of a polyphenylene ether resin having a molecular structure such as formula (VI), wherein R 10 The invention relates to a polyphenylene ether resin comprising a methylene group with n being 15 and m being 15, wherein the molecular weight of the polyphenylene ether resin is 3164 and the molecular weight of the vinyl group at the end of the molecular chain is 1.7% of the molecular weight of the polyphenylene ether resin; 0.6 parts by weight of zinc isoacetate, 0.3 parts by weight of cobalt acetylacetonate, and 360 parts by weight of surface-modified silicon oxide. The above substances are uniformly mixed, added to toluene and butanone, and dispersed and dissolved to form a resin composition.

[0067] Then, the resin composition was impregnated into glass fiber cloth, and heated and dried at 130° C. for 5 minutes to obtain a prepreg.

[0068] Eight prepregs were stacked, and electrolytic copper foils were covered on the upper and lower surfaces thereof. The prepregs were cured in a high-temperature press at 220° C. for 4 hours to obtain a circuit substrate.

[0069] The performance test of the circuit substrate was carried out, and the results are shown in Table 1.

[0070] Example 3

[0071] 80 parts by weight of a maleimide resin having a molecular structure such as formula (I), wherein R1 is selected from methylene, R2 is selected from formula (IV), R8 is selected from methyl, R9 is selected from methylene, n is 500, and in the maleimide resin, the ratio of the number of rigid groups to the number of maleimide groups is 2:1; 160 parts by weight of a bisphenol A type cyanate having a molecular structure such as formula (V), wherein R is selected from a bisphenol A structure and n is 1; 50 parts by weight of a polyphenylene ether resin having a molecular structure such as formula (VI), wherein R 10 The invention relates to a polyphenylene ether resin having an ether bond, n being 20, m being 20, a molecular weight of 4086, and a molecular weight of the vinyl group at the end of the molecular chain being 1.3% of the molecular weight of the polyphenylene ether resin; 0.3 parts by weight of imidazole, 0.3 parts by weight of cobalt acetylacetonate, and 360 parts by weight of surface-modified silicon oxide. The above substances are uniformly mixed, added to toluene and butanone, and dispersed and dissolved to form a resin composition.

[0072] Then, the resin composition was impregnated into glass fiber cloth, and heated and dried at 130° C. for 5 minutes to obtain a prepreg.

[0073] Eight prepregs were stacked, and electrolytic copper foils were covered on the upper and lower surfaces thereof. The prepregs were cured in a high-temperature press at 220° C. for 4 hours to obtain a circuit substrate.

[0074] The performance test of the circuit substrate was carried out, and the results are shown in Table 1.

[0075] Example 4

[0076] 100 parts by weight of a maleimide resin having a molecular structure such as formula (I), wherein R1 is selected from a long chain alkyl structure with a chain length of 6 carbon atoms, R2 is selected from formula (II), R3 is selected from a methylene group, R4 is selected from a vinyl group, n is 100, and in the maleimide resin, the ratio of the number of rigid groups to the number of maleimide groups is 3:1; 200 parts by weight of a phenolic cyanate having a molecular structure such as formula (V), wherein R is selected from a phenolic structure and n is 90; 60 parts by weight of a polyphenylene ether resin having a molecular structure such as formula (VII), wherein R 11A methylene group with n being 30 and m being 10, the molecular weight of the polyphenylene ether resin being 3990, and the molecular weight of the vinyl group at the end of the molecular chain being 1.35% of the molecular weight of the polyphenylene ether resin; 0.6 parts by weight of cobalt acetylacetonate and 450 parts by weight of silicon oxide without surface treatment, the above substances are mixed uniformly, added to toluene and butanone, dispersed uniformly and dissolved to form a resin composition.

[0077] Then, the resin composition was impregnated into glass fiber cloth, and heated and dried at 130° C. for 5 minutes to obtain a prepreg.

[0078] Eight prepregs were stacked, and electrolytic copper foils were covered on the upper and lower surfaces thereof. The prepregs were cured in a high-temperature press at 220° C. for 4 hours to obtain a circuit substrate.

[0079] The performance test of the circuit substrate was carried out, and the results are shown in Table 1.

[0080] Example 5

[0081] 100 parts by weight of a maleimide resin having a molecular structure such as formula (I), wherein R1 is selected from vinylbenzyl, R2 is selected from formula (II), and R3 and R4 are both selected from alkane structures with a carbon chain length of less than 6, n is 300, and in the maleimide resin, the ratio of the number of rigid groups to the number of maleimide groups is 3:1; 200 parts by weight of a dicyclopentadiene cyanate ester having a molecular structure such as formula (V), wherein R is selected from a cyclopentadiene structure and n is 10; 50 parts by weight of a polyphenylene ether resin having a molecular structure such as formula (VII), wherein R 11 The invention relates to a polyphenylene ether resin comprising an ether bond, wherein n is 10, m is 10, the molecular weight of the polyphenylene ether resin is 2230, and the molecular weight of the vinyl group at the end of the molecular chain is 2.4% of the molecular weight of the polyphenylene ether resin; and 450 parts by weight of surface-modified silicon oxide. The above substances are mixed uniformly, added to toluene and butanone, dispersed uniformly, and dissolved to form a resin composition.

[0082] Then, the resin composition was impregnated into glass fiber cloth, and heated and dried at 130° C. for 5 minutes to obtain a prepreg.

[0083] Eight prepregs were stacked, and electrolytic copper foils were covered on the upper and lower surfaces thereof. The prepregs were cured in a high-temperature press at 220° C. for 4 hours to obtain a circuit substrate.

[0084] The performance test of the circuit substrate was carried out, and the results are shown in Table 1.

[0085] Table 1

[0086] CTE (ppm / ℃) Df Appearance Example 1 8.5 0.0028 good Example 2 8.8 0.0030 good Example 3 9.2 0.0034 good Example 4 11 0.0042 Slight resin texture Example 5 11.3 0.0040 Slight resin texture

[0087] Example 6

[0088] The difference between Example 6 and Example 1 is that the molecular structure of the maleimide resin is as shown in Formula (I), wherein R1 is selected from an ether bond, R2 is selected from a methyl group, n is 0, and in the maleimide resin, the ratio of the number of rigid groups to maleimide groups is 1:1.

[0089] The performance test of the circuit substrate was carried out, and the results are shown in Table 2.

[0090] Example 7

[0091] The difference between Example 7 and Example 1 is that the molecular structure of the maleimide resin is as shown in Formula (I), wherein R1 is selected from methylene, R2 is selected from Formula (III), and R5 and R7 are selected from alkyl carbon chains with a carbon chain length of less than 6, R6 is selected from methylene, n is 900, and in the maleimide resin, the ratio of the number of rigid groups to maleimide groups is 3:1.

[0092] The performance test of the circuit substrate was carried out, and the results are shown in Table 2.

[0093] Example 8

[0094] The difference between Example 8 and Example 1 is that the molecular structure of the maleimide resin is as shown in Formula (I), wherein R1 is selected from Formula (IV), R2 is selected from Formula (III), and R5 and R6 are selected from methylene, R7 is selected from methyl, R8 and R9 are selected from methylene, n is 1, and in the maleimide resin, the ratio of the number of rigid groups to maleimide groups is 11:3.

[0095] The performance test of the circuit substrate was carried out, and the results are shown in Table 2.

[0096] Table 2

[0097] CTE (ppm / ℃) Df Appearance Example 6 11.4 0.0032 good Example 7 9.6 0.0036 good Example 8 10.5 0.0036 Slight resin texture

[0098] Example 9

[0099] The difference between Example 9 and Example 1 is that the molecular structure of the cyanate ester is as shown in Formula (V), wherein R is selected from a biphenyl structure and n is 500.

[0100] The performance test of the circuit substrate was carried out, and the results are shown in Table 3.

[0101] Example 10

[0102] The difference between Example 10 and Example 1 is that the molecular structure of the cyanate ester is as shown in Formula (V), wherein R is selected from the bisphenol A structure and n is 1000.

[0103] The performance test of the circuit substrate was carried out, and the results are shown in Table 3.

[0104] Table 3

[0105] CTE (ppm / ℃) Df Appearance Example 9 10.6 0.0036 good Example 10 11.2 0.0034 good

[0106] Example 11

[0107] The difference between Example 11 and Example 1 is that the molecular structure of the polyphenylene ether resin is as shown in Formula (VI), wherein R 10 The polyphenylene ether resin is selected from methylene, wherein n is 1, m is 1, the molecular weight of the polyphenylene ether resin is 588, and the molecular weight of the vinyl group at the end of the molecular chain is 9.2% of the molecular weight of the polyphenylene ether resin.

[0108] The performance test of the circuit substrate was carried out, and the results are shown in Table 4.

[0109] Example 12

[0110] The difference between Example 12 and Example 1 is that the molecular structure of the polyphenylene ether resin is as shown in Formula (VI), wherein R 10 The polyphenylene ether resin is selected from methylene, wherein n is 120, m is 120, the molecular weight of the polyphenylene ether resin is 22484, and the molecular weight of the vinyl group at the end of the molecular chain is 0.24% of the molecular weight of the polyphenylene ether resin.

[0111] The performance test of the circuit substrate was carried out, and the results are shown in Table 4.

[0112] Example 13

[0113] The difference between Example 13 and Example 1 is that the molecular structure of the polyphenylene ether resin is as shown in Formula (VII), wherein R 11 The polyphenylene ether resin is selected from vinyl groups, wherein n is 1, m is 0, the molecular weight of the polyphenylene ether resin is 460, and the molecular weight of the vinyl group at the end of the molecular chain is 17.4% of the molecular weight of the polyphenylene ether resin.

[0114] The performance test of the circuit substrate was carried out, and the results are shown in Table 4.

[0115] Example 14

[0116] The difference between Example 14 and Example 1 is that the molecular structure of the polyphenylene ether resin is as shown in Formula (VII), wherein R 11 The polyphenylene ether resin is selected from vinyl groups, wherein n is 3, m is 3, the molecular weight of the polyphenylene ether resin is 1002, and the molecular weight of the vinyl groups at the end of the molecular chain is 21.0% of the molecular weight of the polyphenylene ether resin.

[0117] The performance test of the circuit substrate was carried out, and the results are shown in Table 4.

[0118] Example 15

[0119] The difference between Example 15 and Example 1 is that the molecular structure of the polyphenylene ether resin is dihydroxy-terminated polyphenylene ether, the molecular weight of the polyphenylene ether resin is 2000, and the molecular weight of the terminal hydroxyl group of the molecular chain is 1.7% of the molecular weight of the polyphenylene ether resin.

[0120] The performance test of the circuit substrate was carried out, and the results are shown in Table 4.

[0121] Table 4

[0122] CTE (ppm / ℃) Df Appearance Example 11 10.4 0.0036 Slight resin texture Example 12 10.2 0.0034 Slight resin texture Example 13 10.8 0.0039 Slight resin texture Example 14 11.1 0.0034 Slight resin texture Example 15 10.5 0.0050 Slight resin texture

[0123] Comparative Example 1

[0124] The difference between Comparative Example 1 and Example 1 is that the maleimide resin is selected from bis(3-ethyl-5-methyl-4-maleimidophenyl)methane.

[0125] The performance test of the circuit substrate was carried out, and the results are shown in Table 5.

[0126] Comparative Example 2

[0127] The difference between Comparative Example 2 and Example 1 is that the cyanate ester is selected from 1-naphthyl cyanate.

[0128] The performance test of the circuit substrate was carried out, and the results are shown in Table 5.

[0129] Comparative Example 3

[0130] The difference between Comparative Example 3 and Example 1 is that the polyphenylene ether resin is selected from methyl-terminated polyphenylene ether resin.

[0131] The performance test of the circuit substrate was carried out, and the results are shown in Table 5.

[0132] Table 5

[0133] CTE (ppm / ℃) Df Appearance Comparative Example 1 13.5 0.0042 Slight resin texture Comparative Example 2 13.2 0.0040 Slight resin texture Comparative Example 3 11.4 0.0058 Obvious resin marks

[0134] The circuit substrate prepared in the above embodiment has a CTE of 8 PPm / °C-12 PPm / °C, Df≤0.005, a low thermal expansion coefficient, and excellent dielectric properties. When it is prepared into a printed circuit board, the printed circuit board also has a low thermal expansion coefficient and excellent dielectric properties, and the circuit substrate has a good appearance.

[0135] The performance testing method of the circuit substrate in the above embodiment and comparative example is as follows:

[0136] Coefficient of thermal expansion (CTE): Tested in accordance with IPC-TM-6502.4.41.1 method.

[0137] Dielectric loss tangent (Df): Measured in accordance with IEC61189-2-721-2015 at 10 GHz using a cavity resonator.

[0138] Appearance: Mainly through visual observation, to see whether there are obvious streaks.

[0139] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0140] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. A resin composition, characterized in that The invention comprises a maleimide resin, a cyanate ester, a polyphenylene ether resin and a filler, wherein at least one end of the molecular chain of the polyphenylene ether resin is capped with a reactive group, the molecular structure of the cyanate ester includes a biphenyl structure, a cyclopentene structure or an indane structure, and has an aromatic ring substituted with two or more cyano groups, and the molecular structure of the maleimide resin is shown in formula (I): Wherein, 0≤n<1000, R1 and R2 are independently selected from alkanes, alkenes, ether bonds, naphthalene rings, fluorene rings, formula (II), formula (III) or formula (IV): Wherein, R3-R9 are independently selected from carbonyl, ester, alkyl or alkenyl.

2. The resin composition according to claim 1, wherein At least one of said R1 and said R2 is selected from formula (II), formula (III) or formula (IV).

3. The resin composition according to claim 2, characterized in that The R1 is selected from an alkane structure, the R2 is selected from formula (II), formula (III), formula (IV), a naphthalene ring or a fluorene ring, and 0≤n<600.

4. The resin composition according to claim 1, characterized in that In the molecular structure of the maleimide resin, the ratio of the rigid groups to the maleimide groups is 1:1-3:

1.

5. The resin composition according to claim 1, wherein The cyanate ester is selected from at least one of naphthyl ether type cyanate ester compounds, adamantane skeleton type cyanate ester compounds, dicyclopentadiene type cyanate ester, bisphenol A type cyanate ester, phenol formaldehyde type cyanate ester, biphenyl type cyanate ester, naphthalene type cyanate ester, and naphthol aralkyl type cyanate ester.

6. The resin composition according to claim 5, characterized in that The molecular structure of the cyanate ester is shown in formula (V): Wherein, R is selected from a cyclopentadiene structure, a bisphenol A structure, a phenolic structure or an indane structure, and 1≤n<200.

7. The resin composition according to claim 1, characterized in that The molecular weight of the polyphenylene ether resin is 1000-5000.

8. The resin composition according to claim 1, wherein The molecular weight of the reactive group is less than 20% of the molecular weight of the polyphenylene ether resin.

9. The resin composition according to claim 1, characterized in that The reactive group is selected from at least one of vinyl, vinylbenzyl, acrylic, propenyl, hydroxyl, and methacrylate groups.

10. The resin composition according to claim 9, characterized in that The polyphenylene ether resin is selected from vinyl-terminated polyphenylene ether resins, and the molecular structure is as shown in formula (VI) or formula (VII): Among them, R 10 、R 11 Independently selected from ether bonds, alkanes or alkenes, 1≤n≤100, 1≤m≤100.

11. The resin composition according to claim 1, characterized in that Based on 100 parts by weight of the maleimide resin, the cyanate ester is used in an amount of 120 to 200 parts by weight, the polyphenylene ether resin is used in an amount of 20 to 50 parts by weight, and the filler is used in an amount of 300 to 450 parts by weight.

12. The resin composition according to claim 1, characterized in that The resin composition further comprises an organic metal salt catalyst.

13. A prepreg made from the resin composition according to any one of claims 1 to 12.

14. A circuit substrate manufactured using the prepreg according to claim 13.

15. A printed circuit board manufactured using the circuit substrate according to claim 14.

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