Resin composition, prepreg, circuit board, and printed circuit board

Abstract

The present application relates to resin composition, prepreg, circuit board and printed circuit board. The resin composition comprises: epoxy resin, silicon modified benzoxazine resin and cyanate ester resin. In the resin composition of the present application, the reactivity of siloxy group connected to both ends of the silicon modified benzoxazine resin is large, on the basis of ensuring that the silicon modified benzoxazine has excellent ring-opening reactivity, the phenolic hydroxyl group can fully react with the organic group in the resin composition, in addition, the hydrolysis product of siloxy group can react with isocyanate group. Therefore, the present application can effectively reduce the content of water absorption group in the circuit board, thereby improving the moisture heat aging resistance of the circuit board, and further ensuring the long-term use performance of the printed circuit board in high temperature and high humidity environment.

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] In the current 5G information age, in order to maintain transmission rates and preserve the integrity of transmitted signals, circuit substrates must not only have a low dielectric constant and dielectric loss, but more importantly, have high resistance to environmental aging in high temperature and high humidity environments.

[0003] To this end, conventional resin compositions typically combine benzoxazine, epoxy resin, and cyanate esters. However, due to the heat-induced ring-opening of the benzoxazine resin's molecular structure, hydrophilic phenolic hydroxyl groups are generated. If these phenolic hydroxyl groups cannot fully react with the organic groups in the resin composition, they will become entangled within the resin's crosslinking system, causing the circuit substrate to have a certain degree of water absorption. Furthermore, the isocyanate groups of the cyanate ester are also water-absorbing. Due to the high curing reaction temperature of the cyanate group, they are not easily fully reacted, resulting in residual water-absorbing groups, which also cause the circuit substrate to have a certain degree of water absorption. As a result, the high content of water-absorbing groups in the circuit substrate leads to poor resistance to wet-heat aging, affecting the long-term use of the printed circuit board. Summary of the Invention

[0004] 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 prepared using the resin composition has excellent resistance to moisture and heat aging, thereby ensuring the long-term performance of the printed circuit board.

[0005] A resin composition comprising: an epoxy resin, a silicon-modified benzoxazine resin, and a cyanate resin;

[0006] The structure of the silicon-modified benzoxazine resin is shown in formula (I):

[0007]

[0008] In formula (I), X is an arylene group or a cycloalkylene group, R1 is selected from an alkyl group, R2 is selected from an alkyl group or an unsaturated hydrocarbon group, R3 is selected from an alkyl group, and n is a positive integer of 1-20.

[0009] In one embodiment, X is selected from phenylene, naphthylene, biphenylene, cyclohexylene, cyclopentylene or biscyclopentadienylene;

[0010] and / or, R1 is selected from a C1-C8 alkyl group;

[0011] and / or, R2 is selected from a C1-C8 alkyl group;

[0012] And / or, R3 is selected from C1-C5 alkyl.

[0013] In one embodiment, the epoxy equivalent weight of the epoxy resin is 150 g / eq-300 g / eq.

[0014] In one embodiment, the cyanate ester resin is selected from a phenolic cyanate ester resin as shown in formula (II),

[0015]

[0016] Wherein, R4 is selected from the following groups:

[0017]

[0018] R5 is selected from H, hydrocarbon or aryl;

[0019] n is a positive integer from 5 to 10.

[0020] In one embodiment, in the resin composition, based on 100 parts by weight of the epoxy resin, the amount of the silicon-modified benzoxazine resin is 150 parts by weight to 250 parts by weight, and the amount of the cyanate ester resin is 50 parts by weight to 150 parts by weight.

[0021] In one embodiment, the resin composition further comprises a curing accelerator, and the amount of the curing accelerator is less than or equal to 10 parts by weight based on 100 parts by weight of the epoxy resin;

[0022] And / or, the resin composition further comprises a filler, and the amount of the filler is 50%-150% of the total weight of the epoxy resin, the silicon-modified benzoxazine resin and the cyanate ester resin.

[0023] A prepreg comprises a reinforcing material and the resin composition described above attached to the reinforcing material. In one embodiment, the reinforcing material is a reinforcing material surface-treated with a first coupling agent, a reinforcing material subjected to a mechanical fiber opening treatment, or a reinforcing material treated with an impregnation liquid, wherein the impregnation liquid comprises a silicon-modified benzoxazine resin and a second coupling agent.

[0024] A circuit substrate comprises an insulating layer and a conductive layer arranged on at least one surface of the insulating layer, wherein the insulating layer is formed by pressing one or at least two superimposed prepregs.

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

[0026] In the resin composition of the present invention, the silanol groups attached to both ends of the silicon-modified benzoxazine resin are highly reactive. While ensuring excellent ring-opening reactivity of the silicon-modified benzoxazine, the phenolic hydroxyl groups can fully react with organic groups in the resin composition. Furthermore, the hydrolysis products of the silanol groups can react with isocyanate groups. Therefore, the present invention can effectively reduce the content of water-absorbing groups in the circuit substrate, thereby improving the circuit substrate's resistance to wet-heat aging, thereby ensuring the long-term performance of the printed circuit board in high-temperature and high-humidity environments. DETAILED DESCRIPTION

[0027] 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.

[0028] 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.

[0029] In the present invention, the arylene and aryleneoxy groups referred to herein refer to divalent groups formed by the loss of a hydrogen atom from an aryl or aryloxy group, wherein an aryl group refers to an optional functional group or substituent derived from an aromatic carbocyclic ring. An aryl group can be a monocyclic aryl group (e.g., a phenyl group) or a polycyclic aryl group. Specifically, an aryl group can be a monocyclic aryl group, a fused-ring aryl group, two or more monocyclic aryl groups conjugated via a carbon-carbon bond, a monocyclic aryl group and a fused-ring aryl group conjugated via a carbon-carbon bond, or two or more fused-ring aryl groups conjugated via a carbon-carbon bond. An aryloxy group refers to a group formed by the end of the above aryl groups being connected to an oxygen atom.

[0030] For example, in the present invention, the arylene group is selected from biphenylene, phenylene and naphthylene; and the aryleneoxy group is selected from phenyleneoxy.

[0031] The present invention provides a resin composition, which comprises: an epoxy resin, a silicon-modified benzoxazine resin and a cyanate resin;

[0032] The structure of the silicon-modified benzoxazine resin is shown in formula (I):

[0033]

[0034] In formula (I), X is arylene or cycloalkylene, R1 is selected from alkyl, R2 is selected from alkyl or unsaturated hydrocarbon group, R3 is selected from alkyl, and n is a positive integer from 1 to 20.

[0035] In the resin composition of the present application, the siloxane group at both ends of the silicon-modified benzoxazine resin has high reactivity, and the phenolic hydroxyl group can fully react with the organic group in the resin composition on the basis of ensuring excellent ring-opening reactivity of the silicon-modified benzoxazine. In addition, the hydrolysis product of the siloxane group can react with the isocyanate group. Therefore, the present application can effectively reduce the content of water-absorbing groups in the circuit board, thereby improving the moisture and heat aging resistance of the circuit board, and further ensuring the long-term use performance of the printed circuit board in a high temperature and high humidity environment.

[0036] In addition, the cross-linking and curing reaction between the silicon-modified benzoxazine epoxy resin, the epoxy resin and the cyanate ester resin in formula (1) has good reactivity, and the silicon-modified benzoxazine epoxy resin is not easy to precipitate, thereby improving the CAF failure resistance of the circuit board.

[0037] In one embodiment, X is selected from phenylene, naphthylene, biphenylene, cyclohexane alkylene, cyclopentane alkylene or bicyclopentadiene alkylene, and is further preferably phenylene, which can effectively improve the rigidity of the silicon-modified benzoxazine resin molecule, and further improve the moisture and heat aging resistance of the circuit board.

[0038] In one embodiment, R1 is selected from C1-C8 alkyl, and is further preferably methyl, ethyl, hexyl or octyl. By controlling the length of the R1 alkyl chain, on the one hand, the relationship between the cross-linking reactivity and hydrophobicity of the siloxane chain of the silicon-modified benzoxazine resin can be balanced, thereby reducing the water absorption of the circuit board prepared from the resin composition. On the other hand, the phenolic hydroxyl group generated by ring-opening can be avoided from being coated by the siloxane chain, so that the phenolic hydroxyl group can be more fully reacted.

[0039] Similarly, in one embodiment, R2 is selected from alkenyl, alkynyl or C1-C8 alkyl, and is further preferably C1-C8 alkyl such as methyl, ethyl, hexyl and octyl.

[0040] In one embodiment, R3 is selected from C1-C5 alkyl, and is specifically selected from methyl, ethyl, propyl and the like, and is preferably ethyl, so that the cross-linking and curing reaction between the epoxy resin, the silicon-modified benzoxazine resin and the cyanate ester resin in the resin composition has better reactivity, and the water absorption of the circuit board prepared from the resin composition is lower.

[0041] And when n is a positive integer of 1-5 in the silicon-modified benzoxazine resin, the cross-linking and curing reaction activity among the epoxy resin, the silicon-modified benzoxazine resin and the cyanate ester resin is higher, the cross-linking and curing reaction of the resin is more sufficient, the residual organic groups in the cross-linking and curing reaction process are effectively avoided, and the moisture and heat aging resistance of the circuit board is further improved.

[0042] In one embodiment, the silicon-modified benzoxazine resin in formula (I) can be prepared by the common silicon-hydrogen addition reaction of the benzoxazine resin shown in formula (IV) and the polysiloxane shown in formula (V):

[0043]

[0044] In formula (IV), R7 is selected from unsaturated hydrocarbon groups, and R8 is selected from H, hydroxyl, amino, unsaturated hydrocarbon groups and the like. The benzoxazine resin shown in formula (IV) and the polysiloxane shown in formula (V) can undergo silicon-hydrogen addition reaction to obtain the silicon-modified benzoxazine resin shown in formula (I).

[0045] In order to ensure that the epoxy resin can fully perform cross-linking and curing reaction with the silicon-modified benzoxazine resin and the cyanate ester resin, the epoxy equivalent of the epoxy resin is 150 g / eq-300 g / eq, preferably 170 g / eq-260 g / eq, so as to better improve the moisture and heat aging resistance of the circuit board. The type of the epoxy resin is not limited in the application. In one embodiment, the epoxy resin is selected from the epoxy resin shown in formula (III):

[0046]

[0047] In formula (III), R6 is arylene, aryloxy or cycloalkylene, and n=1-50.

[0048] In one embodiment, R6 is selected from phenylene, biphenylene, naphthylene, phenoxy, cyclohexane alkylene, cyclopentane alkylene or bicyclopentadiene alkylene.

[0049] In one embodiment, preferably, the epoxy resin is selected from biphenyl epoxy resin, phenyl epoxy resin, naphthyl epoxy resin, dicyclopentadiene-modified epoxy resin or phenoxy epoxy resin.

[0050] And when the cyanate ester resin in the resin composition is selected from the phenolic cyanate ester resin shown in formula (II), it has a synergistic effect with the silicon-modified benzoxazine resin and the epoxy resin, and can further improve the moisture and heat aging resistance of the circuit board.

[0051]

[0052] In formula (II), R4 is selected from the following groups:

[0053]

[0054] R5 is selected from H, hydrocarbon or aryl;

[0055] When n is a positive integer of 5-10, the cross-linking and curing reaction activity between the epoxy resin, silicon-modified benzoxazine resin, and cyanate resin in the resin composition is excellent, thereby reducing the water absorption rate of the circuit substrate prepared from the resin composition, and the circuit substrate has excellent resistance to wet heat aging.

[0056] Furthermore, when R4 is more preferably a biphenylene group and R5 is more preferably a methyl group, the effect is better.

[0057] In one embodiment, in the resin composition, based on 100 parts by weight of the epoxy resin, the amount of the silicon-modified benzoxazine resin is 150 parts by weight to 250 parts by weight, and the amount of the cyanate ester resin is 50 parts by weight to 150 parts by weight.

[0058] The specific weight parts of the resin composition are compounded according to the above weight parts. The epoxy resin, the silicon-modified benzoxazine resin and the cyanate resin work synergistically to effectively improve the heat and humidity aging resistance and the CAF failure resistance of the circuit substrate.

[0059] Furthermore, in order to promote better cross-linking and curing between the epoxy resin, silicon-modified benzoxazine resin, and cyanate resin in the resin composition, a curing accelerator can be added to the resin composition according to specific usage requirements. The present invention does not limit the type of curing accelerator. Optionally, the curing accelerator is selected from an imidazole curing accelerator, an azo curing accelerator, or a zinc curing accelerator. Based on 100 parts by weight of the epoxy resin, the amount of the curing accelerator is less than or equal to 10 parts by weight.

[0060] In one embodiment, the curing accelerator includes a first curing accelerator and a second curing accelerator. Based on 100 parts by weight of the epoxy resin, the amount of the first curing accelerator is 0.01 parts by weight to 5 parts by weight, and the amount of the second curing accelerator is 0.005 parts by weight to 5 parts by weight. Specifically, the first curing accelerator is selected from at least one of an imidazole curing accelerator or an azo curing accelerator, and the second curing accelerator is a zinc curing accelerator. Preferably, the imidazole curing accelerator can be selected from at least one of dimethylimidazole, diethyltetramethylimidazole, diphenylimidazole, monobenzyldiphenylimidazole, or triphenylimidazole; the azo curing accelerator is selected from at least one of azobisisobutyronitrile, azobisisoheptanoonitrile, or azobisisovaleronitrile; and the zinc curing accelerator can be selected from at least one of zinc octoate, zinc isooctanoate, or zinc naphthenate.

[0061] In one embodiment, a filler can be added to the resin composition according to specific usage requirements. The present invention does not limit the type of filler. In one embodiment, the filler is selected from at least one of crystalline silica and fused silica, and the filler is treated with a coupling agent. The amount of the filler is 50%-150% of the total weight of the epoxy resin, silicon-modified benzoxazine resin and cyanate ester resin.

[0062] In order to improve the flame retardancy of the resin composition, a halogen-free flame retardant can be added to the resin composition according to specific usage requirements. The present invention does not limit the type of halogen-free flame retardant. In one embodiment, the halogen-free flame retardant is selected from at least one of a phosphorus-based flame retardant, a nitrogen-based flame retardant, a silicon-based flame retardant and a phosphorus-nitrogen-silicon synergistic flame retardant.

[0063] The present invention also provides a prepreg, comprising a reinforcing material and a resin composition as described above attached to the reinforcing material. The present invention does not limit the specific preparation method of the prepreg from the resin composition. In one embodiment, a solvent may be added to the resin composition. The amount of solvent added is selected by a person skilled in the art based on experience and process requirements to achieve a viscosity suitable for use. The resin composition is then impregnated or coated with the reinforcing material and dried to obtain a prepreg. During the drying process, the solvent in the resin composition will partially or completely evaporate. The present invention does not limit the type of solvent, and commercially available common organic solvents, such as butanone, may be selected.

[0064] In the present invention, there is no limitation on the type of reinforcing material. In one embodiment, the reinforcing material can be selected from glass fiber cloth.

[0065] Considering that the inorganic interface of the reinforcing material and the organic interface of the resin composition cannot be fully bonded, microcracks are easily present in the circuit substrate, and there is a problem of CAF failure after printed circuit board (PCB) processing. In one embodiment of the present invention, the reinforcing material is a reinforcing material that has been surface-treated with a first coupling agent, a reinforcing material that has been mechanically fiberized, or a reinforcing material that has been impregnated with an impregnation liquid, wherein the impregnation liquid includes a silicon-modified benzoxazine resin and a second coupling agent. This can better bond the inorganic interface of the reinforcing material with the organic interface of the resin composition, thereby improving the CAF failure resistance of the PCB.

[0066] Since the silicon-modified benzoxazine resin of the present invention can bond or be similarly soluble with the coupling agent through its silicon-modified chain segment, the bonding strength at the interface between the resin base, the coupling agent, and the reinforcing material can be increased. Furthermore, since the resin composition and the impregnating liquid can fully dissolve and bond, the reinforcing material is deeply impregnated and fully coated with the resin composition, thereby further enhancing the CAF failure resistance of the PCB. Therefore, the reinforcing material is preferably a reinforcing material that has been impregnated with the impregnating liquid.

[0067] In the present invention, there is no limitation on the types of the first coupling agent and the second coupling agent. The first coupling agent and the second coupling agent may be of the same or different types. The first coupling agent and the second coupling agent may be selected from common commercially available coupling agents, for example, at least one of an epoxy coupling agent, an aminosilane coupling agent, a vinylsilane coupling agent, an aromatic silane coupling agent, or an amino coupling agent. Specifically, the epoxy coupling agent may be 3-glycidoxypropyltrimethoxysilane; an aminosilane coupling agent may be 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane; a vinylsilane coupling agent may be 3-methacryloyloxypropyltrimethoxysilane; an aromatic silane coupling agent may be N-2-(N-vinylbenzylaminoethyl)-3-aminopropyltrimethoxysilane; an amino coupling agent may be the same or different types.

[0068] In one embodiment, the second coupling agent includes an epoxy coupling agent and an aminosilane coupling agent, such as 3-glycidoxypropyltrimethoxysilane and N-2-(N-vinylbenzylaminoethyl)-3-aminopropyltrimethoxysilane, which has a better effect.

[0069] In one embodiment, the specific steps of treating the reinforcing material with an impregnation liquid include: mixing and stirring the silicon-modified benzoxazine resin, the second coupling agent and the solvent to prepare an impregnation liquid, completely immersing the reinforcing material in the impregnation liquid, taking it out and drying it to obtain the reinforcing material treated with the impregnation liquid.

[0070] The solvent of the impregnation solution can be selected from common commercial organic solvents, such as butanone and acetone, and the present invention is not limited thereto.

[0071] The present invention further provides a circuit substrate comprising an insulating layer and a conductive layer disposed on at least one surface of the insulating layer, wherein the insulating layer is formed by pressing one or at least two superimposed prepregs as described above.

[0072] In one embodiment, the conductive layer is a metal foil layer, such as copper foil.

[0073] In one of the embodiments, the pressing process is hot pressing at a temperature of 200°C or higher for 1-5 hours at a pressure of 1.5-5.0 MPa.

[0074] The present application also provides a printed circuit board made of the circuit substrate as described above. The printed circuit board made of the resin composition has excellent resistance to humid heat aging.

[0075] The printed circuit board is mainly made of the circuit substrate through the processes of drilling, hole finishing, micro-etching, pre-impregnation, activation, acceleration, chemical copper, and copper thickening.

[0076] Hereinafter, the resin composition, prepreg, circuit substrate, and printed circuit board will be further described through the following specific examples.

[0077] Example 1

[0078] 100 parts by weight of a dicyclopentadiene (DCPD) type epoxy resin (the epoxy equivalent weight of the dicyclopentadiene (DCPD) type epoxy resin is 255 g / eq), 180 parts by weight of a dimethylethoxy-modified DCPD benzoxazine resin (the structural formula of the dimethylethoxy-modified DCPD benzoxazine resin is shown in formula (I), wherein X is dicyclopentadienyl, n = 1, R1 is methyl, R2 is methyl, and R3 is ethyl), 100 parts by weight of a biphenyl phenol novolac cyanate ester resin (the structural formula of the biphenyl phenol novolac cyanate ester resin is shown in formula (II), wherein R4 is biphenylene, R5 is methyl, and n = 6), 0.5 parts by weight of diethyltetramethylimidazole, 0.5 parts by weight of zinc octoate, 400 parts by weight of fused silica, and 20 parts by weight of hexaphenoxycyclotriphosphazene were dissolved in 300 parts by weight of butanone and mixed and stirred at a stirring rate of 500 rpm for 20 h to prepare a resin composition.

[0079] 1 part by weight of a dimethylethoxy-modified DCPD benzoxazine resin (the structural formula of the dimethylethoxy-modified DCPD benzoxazine resin is shown in formula (I), wherein X is dicyclopentadienyl, n = 1, R1 is methyl, R2 is methyl, and R3 is ethyl), 0.05 parts by weight of 3-glycidyloxypropyltrimethoxysilane, and 55 parts by weight of butanone were mixed and stirred at 25°C for 2 h at a stirring rate of 300 rpm to obtain an impregnating solution. An opened glass fiber cloth was completely immersed in the impregnating solution at 50°C, and then taken out and dried at 100°C for 3 min. The resin composition was coated on the opened glass fiber cloth treated with the impregnating solution, and dried at 150°C for 3 min to remove the solvent, thereby preparing a prepreg.

[0080] Six of the above-mentioned prepregs were stacked, covered with 1 oz thick copper foil on both sides, and pressed at a pressure of 3 MPa and 200° C. for 2 hours to produce a circuit substrate.

[0081] Example 2

[0082] The difference from Example 1 is that the epoxy resin is a biphenyl epoxy resin, and the epoxy equivalent of the biphenyl epoxy resin is 290 g / eq.

[0083] Example 3

[0084] The difference from Example 1 is that the epoxy resin is a bisphenol A epoxy resin, and the epoxy equivalent of the bisphenol A epoxy resin is 420 g / eq.

[0085] Performance testing:

[0086] The performance of the circuit substrates prepared in Examples 1-3 and the printed circuit boards processed therefrom were tested. The specific test contents and standards are shown below, and the test results are shown in Table 1.

[0087] Water absorption rate: IPC-TM-650 2.6.21 standard was used to test the circuit substrates prepared in Examples 1-3.

[0088] Resistance to moist heat aging: The circuit substrates prepared in Examples 1-3 were treated at 85°C and 85% humidity for 168 hours. The water absorption of the circuit substrates before and after treatment was tested. The moist heat aging resistance was calculated as (water absorption after aging - water absorption before aging) / water absorption before aging * 100%. The test results of Examples 1-3 are shown in Table 1.

[0089] CAF resistance performance test: After processing, the circuit substrates prepared in Examples 1-3 were treated in an 85RH% / 85°C environment for 96 hours and subjected to a bias test. After 240 hours of testing, the slices at the model were marked as NG if CAF was formed and PASS if CAF was not formed. The test results of Examples 1-3 are shown in Table 1.

[0090] Table 1

[0091]

[0092] By comparing Examples 2-3 with Example 1, it can be seen that when the epoxy equivalent of the epoxy resin is preferably 150g / eq-300g / eq, the circuit substrate prepared from the resin composition has low water absorption, excellent resistance to moist heat aging, and excellent CAF resistance. When the epoxy equivalent of the epoxy resin is more preferably 170g / eq-260g / eq, the effect is better.

[0093] Example 4

[0094] The difference from Example 1 is that the benzoxazine resin is a diisopropylethoxy-modified cyclohexylbenzoxazine resin, and the structural formula of the diisopropylethoxy-modified cyclohexylbenzoxazine resin is shown in Formula (I), wherein X is a cyclohexane alkylene group, n=6, R1 is an isopropyl group, R2 is an isopropyl group, and R3 is an ethyl group.

[0095] Example 5

[0096] The difference from Example 1 is that the benzoxazine resin is a dodecylmethoxy-modified DCPD benzoxazine resin, and the structural formula of the dodecylmethoxy-modified DCPD benzoxazine resin is shown in Formula (I), wherein X is a biscyclopentadienylene group, n=1, R1 is a dodecyl group, R2 is a methyl group, and R3 is an ethyl group.

[0097] Example 6

[0098] The difference from Example 1 is that the benzoxazine resin is a vinylmethylethoxy-modified DCPD benzoxazine resin, and the structural formula of the vinylmethylethoxy-modified DCPD benzoxazine resin is shown in Formula (I), wherein X is a biscyclopentadienylene group, n=1, R1 is a methyl group, R2 is a vinyl group, and R3 is a hexyl group.

[0099] Performance testing:

[0100] The performance of the circuit substrates prepared in Examples 4-6 and the printed circuit boards processed therefrom were tested. The specific test contents and standards were the same as those in Examples 1-3. The test results are shown in Table 2.

[0101] Table 2

[0102]

[0103] As shown in Table 2, when the structure of the silicon-modified benzoxazine resin is as shown in formula (I), in formula (I), X is an arylene group or a cycloalkylene group, R1 is selected from an alkyl group, R2 is selected from an alkyl group or an unsaturated hydrocarbon group, R3 is selected from an alkyl group, and n is a positive integer of 1-20, the circuit substrate prepared from the resin composition has low water absorption, excellent resistance to wet heat aging, and excellent CAF resistance. Comparing Examples 4-6 with Example 1, it can be seen that when, in formula (1), X is preferably a phenylene group, a naphthylene group, a biphenylene group, a cyclohexylene group, a cyclopentylene group, or a biscyclopentadienylene group; and / or, R1 is preferably a C1-C8 alkyl group; and / or, R2 is preferably a C1-C8 alkyl group; and / or, R3 is preferably a C1-C5 alkyl group; and n is preferably a positive integer of 1-5, the effect is better.

[0104] Example 7

[0105] The difference from Example 1 is that the cyanate ester resin is a cresol novolac type cyanate ester resin, and the structural formula of the cresol novolac type cyanate ester resin is shown in Formula (II), wherein R4 is a methyl group, R5 is a methyl group, and n=6.

[0106] Example 8

[0107] The difference from Example 1 is that the cyanate ester resin is a biphenyl cresol novolac cyanate ester resin, and the structural formula of the biphenyl cresol novolac cyanate ester resin is shown in Formula (II), wherein R4 is a biphenylene group, R5 is a methyl group, and n=20.

[0108] Example 9

[0109] The difference from Example 1 is that the cyanate resin is a bisphenol A cyanate resin, and the structural formula of the bisphenol A cyanate resin is shown in Formula (II), wherein R4 is R5 is phenyl, n=6.

[0110] Performance testing:

[0111] The performance of the circuit substrates prepared in Examples 7-9 and the printed circuit boards processed therefrom were tested. The specific test contents and standards were the same as those in Examples 1-3. The test results are shown in Table 3.

[0112] Table 3

[0113]

[0114]

[0115] Comparing Examples 7-9 with Example 1, it can be seen that when the cyanate ester resin is preferably a phenolic cyanate ester resin as shown in formula (II), wherein R4 is selected from one of the following groups:

[0116]

[0117] R5 is selected from H, a hydrocarbon group or an aromatic group; when n is a positive integer of 5-10, the circuit substrate prepared from the resin composition has a lower water absorption rate, better resistance to moist heat aging, and excellent CAF resistance, and when R4 is more preferably a biphenylene group, R5 is more preferably a methyl group, and n is a positive integer of 5-10, the effect is better.

[0118] Example 10

[0119] The difference from Example 1 is that the weight portion of the dimethylethoxy-modified DCPD benzoxazine resin is 250, the weight portion of the biphenylcresol novolac cyanate resin is 150, and diethyltetramethylimidazole is replaced by diphenylimidazole.

[0120] Example 11

[0121] The difference from Example 1 is that the weight part of dimethylethoxy-modified DCPD benzoxazine resin is 100, the weight part of biphenylcresol novolac cyanate resin is 40, diethyltetramethylimidazole is replaced by diphenylimidazole, and zinc octoate is replaced by zinc naphthenate.

[0122] Example 12

[0123] The difference from Example 1 is that the opened glass fiber cloth is treated with a coupling agent, and the coupling agent is 1.05 parts by weight of 3-glycidoxypropyltrimethoxysilane.

[0124] Performance testing:

[0125] The performance of the circuit substrates prepared in Examples 10-12 and the printed circuit boards processed therefrom were tested. The specific test contents and standards were the same as those in Examples 1-3. The test results are shown in Table 4.

[0126] Table 4

[0127]

[0128] By comparing Examples 10-11 with Example 1, it can be seen that in the resin composition, based on 100 parts by weight of the epoxy resin, when the amount of the silicon-modified benzoxazine resin is 150 parts by weight to 250 parts by weight and the amount of the cyanate ester resin is 50 parts by weight to 150 parts by weight, the circuit substrate prepared from the resin composition has lower water absorption, better resistance to wet heat aging, and better CAF resistance.

[0129] Comparative Example 1

[0130] The difference from Example 3 is that the benzoxazine resin is a hydrogen-terminated polydimethyl-modified DCPD benzoxazine resin, and the structural formula of the hydrogen-terminated polydimethyl-modified DCPD benzoxazine is shown in Formula (I), wherein X is a biscyclopentadienylene group, n=40, R1 is a methyl group, R2 is a methyl group, and R3 is H.

[0131] Comparative Example 2

[0132] The difference from Example 1 is that the benzoxazine resin is a bisphenol A type benzoxazine resin.

[0133] Comparative Example 3

[0134] The difference from Example 1 is that the benzoxazine resin is a DCPD-type diene-modified benzoxazine resin.

[0135] Performance testing:

[0136] The performance of the circuit substrates prepared in Comparative Examples 1-3 and the printed circuit boards processed therefrom were tested. The specific test contents and standards were the same as those in Examples 1-3. The test results are shown in Table 5.

[0137] Table 5

[0138]

[0139] Comparative Example 3 and Comparative Example 1, and Comparative Example 1 and Comparative Examples 2-3, it can be seen that when the structure of the silicon-modified benzoxazine resin is as shown in formula (I), in formula (I), X is an arylene group or a cycloalkyl group, R1 is selected from an alkyl group, R2 is selected from an alkyl group or an unsaturated hydrocarbon group, R3 is selected from an alkyl group, and n is a positive integer of 1-20, the circuit substrate prepared from the resin composition has low water absorption, excellent resistance to moist heat aging, and excellent CAF resistance.

[0140] 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.

[0141] 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 resin composition comprises: epoxy resin, silicon-modified benzoxazine resin and cyanate resin; The structure of the silicon-modified benzoxazine resin is shown in formula (I): In formula (I), X is an arylene group or a cycloalkylene group, R1 is selected from an alkyl group, R2 is selected from an alkyl group or an unsaturated hydrocarbon group, R3 is selected from an alkyl group, and n is a positive integer of 1-20; In the resin composition, based on 100 parts by weight of the epoxy resin, the amount of the silicon-modified benzoxazine resin is 150 parts by weight to 250 parts by weight, and the amount of the cyanate ester resin is 50 parts by weight to 150 parts by weight.

2. The resin composition according to claim 1, wherein Said X is selected from phenylene, naphthylene, biphenylene, cyclohexylene, cyclopentylene or biscyclopentadienylene; and / or, R1 is selected from a C1-C8 alkyl group; and / or, R2 is selected from a C1-C8 alkyl group; And / or, R3 is selected from C1-C5 alkyl.

3. The resin composition according to claim 1, wherein The epoxy equivalent of the epoxy resin is 150 g / eq-300 g / eq.

4. The resin composition according to claim 1, characterized in that The cyanate resin is selected from the phenolic cyanate resin shown in formula (II), Wherein, R4 is selected from one of the following groups: R5 is selected from H or hydrocarbon; n is a positive integer from 5 to 10.

5. The resin composition according to claim 1, wherein The resin composition further comprises a curing accelerator, wherein the amount of the curing accelerator is less than or equal to 10 parts by weight based on 100 parts by weight of the epoxy resin; And / or, the resin composition further comprises a filler, and the amount of the filler is 50%-150% of the total weight of the epoxy resin, the silicon-modified benzoxazine resin and the cyanate ester resin.

6. A prepreg, characterized in that: The invention comprises a reinforcing material and the resin composition according to any one of claims 1 to 5 attached to the reinforcing material.

7. The prepreg according to claim 6, wherein: The reinforcing material is a reinforcing material surface-treated with a first coupling agent, a reinforcing material subjected to a mechanical fiber opening treatment, or a reinforcing material treated with an impregnation liquid, wherein the impregnation liquid comprises the silicon-modified benzoxazine resin and a second coupling agent.

8. A circuit substrate, characterized in that: The invention comprises an insulating layer and a conductive layer provided on at least one surface of the insulating layer, wherein the insulating layer is formed by pressing one or at least two superimposed prepregs according to any one of claims 6 to 7.

9. A printed circuit board made using the circuit substrate according to claim 8.

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