Modified pre-polymerized resin as well as preparation method and application thereof

Abstract

The invention relates to modified pre-polymerized resin as well as a preparation method and application thereof. The modified prepolymerized resin is prepared by prepolymerizing oligomeric maleimide resin and cyanate ester resin, the structural formula of the oligomeric maleimide resin is shown as a formula (1) or a formula (2), and in the formula (1) and the formula (2), 0 lt; a < lt >; 5, 0lt; blt; 20, 0lt; nlt; 5, 0lt; mlt; mlt; r1, R2, R3 and R4 are respectively and independently selected from one or a combination of two or more of alkylene, an ether bond, a silicon-oxygen bond, # imgabs0, # imgabs1, # imgabs2 and # imgabs3; and R1, R2, R3 and R4 are respectively and independently selected from one or a combination of more than two of # imgabs0, # imgabs1, # imgabs2 and # imgabs3. The modified pre-polymerized resin provided by the invention has a specific structure, relatively strong solubility and relatively good compatibility with other resins, and a circuit substrate prepared from the modified pre-polymerized resin has low thermal expansion coefficient and low water absorption rate at the same time, so that the circuit substrate and a printed circuit board are effectively prevented from cracking and layering.

Description

Technical Field

[0001] The present invention relates to the technical field of the electronics industry, and particularly to a modified prepolymer resin, a preparation method thereof, and an application thereof. Background Art

[0002] With the development of electronic products towards high frequency and high speed, higher requirements are put forward for the performance of circuit boards. Especially in high-density and high multi-layer packaging, a low coefficient of thermal expansion of the circuit board is required.

[0003] In traditional technologies, maleimide prepolymer resin is usually used to reduce the coefficient of thermal expansion (CTE) of circuit boards. However, the water absorption rate of maleimide prepolymer resin is relatively high. After water absorption, it is easy to cause board explosion, resulting in the failure of circuit boards. In addition, the solubility of maleimide prepolymer resin is relatively low, and its compatibility with other resins is poor, which makes the preparation process of circuit boards difficult. Therefore, it is urgent to improve the solubility of maleimide prepolymer resin and its compatibility with other resins, and to enable the circuit boards prepared therefrom to simultaneously have a low coefficient of thermal expansion and a low water absorption rate, so as to avoid board explosion and delamination of circuit boards and printed circuit boards. Summary of the Invention

[0004] Based on this, in view of the above problems, it is necessary to provide a modified prepolymer resin, a preparation method thereof, and an application thereof. The modified prepolymer resin has a specific structure, strong solubility, and good compatibility with other resins. The circuit board prepared therefrom simultaneously has a low coefficient of thermal expansion and a low water absorption rate, effectively avoiding board explosion and delamination of circuit boards and printed circuit boards.

[0005] A modified prepolymer resin is prepared by prepolymerizing a low-molecular-weight maleimide resin and a cyanate resin. The structural formula of the low-molecular-weight maleimide resin is shown in formula (1) or formula (2),

[0006]

[0007] In formula (1) and formula (2), 0 < a < 5, 0 < b < 20, 0 < n < 5, 0 < m < 20, and R1, R2, R3, and R4 are each independently selected from alkylene, ether bond, siloxane bond,

[0008] or one or a combination of two of them.

[0009] In one application example, R1 and R3 are each independently selected from ether bond, R2 and R4 are each independently selected from or one or a combination of two of them.

[0010] In one application example, the cyanate resin is selected from at least one of a cyanate resin containing a naphthalene ring structure, a cyanate resin containing an anthracene ring structure, a cyanate resin containing a dicyclopentadiene structure, a cyanate resin containing a biphenyl structure, a cyanate resin containing a fluorene structure, a polyfunctional cyanate resin, a bisphenol A cyanate resin, a bisphenol F cyanate resin, a bisphenol M cyanate resin, a bisphenol E cyanate resin, and a phenolic cyanate resin.

[0011] In one application example, the cyanate equivalent of the cyanate resin is 150 g / mol to 2500 g / mol.

[0012] A method for preparing the modified prepolymer resin as described above, comprising the following steps:

[0013] The resin monomer is subjected to a self-polymerization reaction under the action of a self-polymerization initiator to obtain an oligomeric maleimide resin. Among them, the structural formula of the resin monomer is as shown in formula (3) or formula (4). In formula (3) and formula (4), 0 < a < 5, 0 < n < 5, and R1, R2, R3, and R4 are each independently selected from an alkylene group, an ether bond, a siloxane bond, or one or a combination of two of them. The temperature of the self-polymerization reaction is 110°C to 170°C, and the time is 1 h to 6 h.

[0014] The oligomeric maleimide resin and the cyanate resin are subjected to a prepolymerization reaction to obtain a modified prepolymer resin.

[0015] In one application example, the mass ratio of the self-polymerization initiator to the resin monomer is 0.01:100 to 0.5:100;

[0016] and / or the self-polymerization initiator is selected from at least one of organic peroxides or azo initiators.

[0017] In one application example, the mass ratio of the oligomeric maleimide resin to the cyanate resin is 1:6 to 6:1;

[0018] and / or the prepolymerization reaction system further includes a metal salt catalyst. Based on 100 parts by weight of the oligomeric maleimide resin and the cyanate resin, the amount of the metal salt catalyst used is 0.01 part by weight to 1 part by weight. The metal salt catalyst is selected from at least one of zinc octoate, cobalt octoate, cobalt acetylacetonate, and zinc acetylacetonate.

[0019] A resin composition comprising at least the modified prepolymer resin as described above.

[0020] In one application example, the resin composition further comprises an auxiliary resin, and the mass ratio of the auxiliary resin to the modified prepolymer resin is 1:60 to 5:2;

[0021] And / or, the resin composition further comprises an auxiliary resin, and the auxiliary resin is selected from at least one of polytetrafluoroethylene resin, polybutadiene resin, polypentadiene resin, polystyrene resin, butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, small molecule vinyl compound, acrylate resin, vinyl-terminated polyphenylene ether resin, vinyl-terminated maleimide resin, allyl benzoxazine resin, and styrene maleic anhydride resin.

[0022] In one application example, the auxiliary resin is selected from vinyl-terminated polyphenylene ether, and the number average molecular weight of the auxiliary resin is 500 to 3000.

[0023] In one application example, the resin composition also includes at least one of a curing agent, a catalyst, an initiator, and a filler, wherein the amount of the curing agent is 0 to 20 parts by weight, the amount of the catalyst is 0 to 0.1 parts by weight, the amount of the initiator is 0 to 0.2 parts by weight, and the amount of the filler is 0 to 600 parts by weight.

[0024] In one application example, the auxiliary resin is selected from at least one of polytetrafluoroethylene resin, polybutadiene resin, polypentadiene resin, polystyrene resin, butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, small molecule vinyl compound, acrylate resin, vinyl-terminated polyphenylene ether resin, vinyl-terminated maleimide resin, allyl benzoxazine resin, and styrene maleic anhydride resin.

[0025] In one application example, the auxiliary resin is selected from vinyl-terminated polyphenylene ether, and the number average molecular weight of the auxiliary resin is 500 to 3000.

[0026] A prepreg made from the modified prepolymer resin or resin composition described above.

[0027] A circuit substrate made of the prepreg described above.

[0028] In the modified prepolymer resin provided by the present invention, on the one hand, the oligomeric maleimide resin and the cyanate ester resin have a certain crosslinking density, effectively ensuring the low coefficient of thermal expansion of the circuit board, and at the same time making the curing rate of the modified prepolymer resin reach 5% - 70%, which is beneficial to improving the solubility of the modified prepolymer resin and enhancing the compatibility of the modified prepolymer resin with other resins. Thus, the prepolymer resin can be used together with other resins to prepare a circuit board, further improving the performance of the circuit board. On the other hand, the further curing of the oligomeric maleimide resin and the cyanate ester resin can reduce the number of hydrophilic groups in the modified prepolymer resin, effectively reducing the water absorption rate of the circuit board made of the modified prepolymer resin, and effectively preventing the circuit board and the printed circuit board from bursting and delaminating.

[0029] Therefore, the circuit board prepared by the present invention has a low coefficient of thermal expansion and a low water absorption rate. The circuit board and the printed circuit board are not prone to bursting and delaminating, effectively improving the performance and service life of the circuit board and the printed circuit board, and having high market application potential. Specific Embodiments

[0030] To facilitate the 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 application examples described herein. On the contrary, the purpose of providing these embodiments or application examples is to make the understanding of the disclosure content of the present invention more thorough and comprehensive.

[0031] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which the present invention belongs. The terms used in the description of the present invention herein are only for the purpose of describing specific embodiments or application examples and are not intended to limit the present invention. The optional range 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 the related listed items. The any and all combinations include any two related listed items, any more related listed items, or all combinations of the related listed items.

[0032] The modified prepolymer resin provided by the present invention is prepared by pre-polymerizing an oligomeric maleimide resin and a cyanate ester resin. The structural formula of the oligomeric maleimide resin is shown in Formula (1) or Formula (2),

[0033]

[0034]

[0035] In Formula (1) and Formula (2), 0 < a < 5, 0 < b < 20, 0 < n < 5, 0 < m < 20, and R1, R2, R3, and R4 are each independently selected from alkylene, ether bond, siloxane bond, or One or a combination of two or more.

[0036] It should be noted that the oligomeric maleimide resin may be an oligomer or a mixture of several oligomers having a structural formula satisfying formula (1) or formula (2). When the oligomeric maleimide resin is a mixture of several oligomers, a, b, n or m represents the average value of the degree of polymerization of the mixture of several oligomers.

[0037] On the one hand, in the above-mentioned modified prepolymer resin, the oligomeric maleimide resin and the cyanate ester resin have a certain cross-linking density, which effectively ensures the low thermal expansion coefficient of the circuit substrate, and at the same time makes the curing rate of the modified prepolymer resin reach 5% to 70%, which is beneficial to improve the solubility of the modified prepolymer resin and improve the compatibility of the modified prepolymer resin with other resins, so that the prepolymer resin can be used together with other resins to prepare a circuit substrate to further improve the performance of the circuit substrate; on the other hand, the further curing of the oligomeric maleimide resin and the cyanate ester resin can reduce the number of hydrophilic groups in the modified prepolymer resin, thereby effectively reducing the water absorption rate of the circuit substrate made of the modified prepolymer resin, and effectively preventing the circuit substrate and the printed circuit board from bursting and delamination.

[0038] Therefore, the circuit substrate prepared by the present invention has a low thermal expansion coefficient and low water absorption rate, and the circuit substrate and printed circuit board are not prone to board explosion and delamination, which effectively improves the performance and service life of the circuit substrate and printed circuit board, and has high market application potential.

[0039] In order to further improve the compatibility of the modified prepolymer resin with other resins, thereby improving the water absorption and thermal expansion coefficient of the circuit substrate, the R1 and R3 are each independently selected from ether bonds, Said R2 and R4 are each independently selected from or

[0040] In one embodiment, the cyanate resin is selected from at least one of a naphthalene ring structure-containing cyanate resin, anthracene ring structure-containing cyanate resin, a dicyclopentadiene structure-containing cyanate resin, a biphenyl structure-containing cyanate resin, a fluorene structure-containing cyanate resin, a multifunctional cyanate resin, a bisphenol A type cyanate resin, a bisphenol F type cyanate resin, a bisphenol M type cyanate resin, a bisphenol E type cyanate resin, and a phenolic type cyanate resin.

[0041] It should be noted that the multifunctional cyanate ester resin described in the present invention refers to a cyanate ester resin with multiple functionalities, that is, the cyanate ester resin has two or more cyanate groups in one molecular structure.

[0042] Preferably, the cyanate ester resin has a cyanate equivalent of 150 g / mol to 2500 g / mol. After pre-polymerization with the low molecular weight maleimide resin, the modified prepolymer resin has a certain crosslinking density, which reduces the water absorption rate of the circuit board while ensuring the low expansion of the circuit board.

[0043] More preferably, the cyanate ester resin has a cyanate equivalent of 200 g / mol to 400 g / mol.

[0044] Specifically, the cyanate ester resin is selected from naphthalene-based cyanate ester resin, dicyclopentadienyl cyanate ester resin, and biphenyl-based cyanate ester resin.

[0045] The present invention also provides a method for preparing the modified prepolymer resin as described above, comprising the following steps:

[0046] S1, subjecting the resin monomer to a self-polymerization reaction under the action of a self-polymerization initiator to obtain a low molecular weight maleimide resin, wherein the structural formula of the resin monomer is as shown in formula (3) or formula (4), In formula (3) and formula (4), 0 < a < 5, 0 < n < 5, and R1, R2, R3, and R4 are each independently selected from an alkylene group, an ether bond, a siloxane bond,

[0047] or a combination of one or two of them, and the temperature of the self-polymerization reaction is 110°C to 170°C, and the time is 1 h to 6 h;

[0048] S2, subjecting the low molecular weight maleimide resin and the cyanate ester resin to a pre-polymerization reaction to obtain a modified prepolymer resin.

[0049] The method for preparing the modified prepolymer resin provided by the present invention, by pre-polymerizing the low molecular weight maleimide resin obtained by self-polymerizing the resin monomer with the cyanate ester resin, on the one hand, effectively controls the reaction rate and crosslinking density of the low molecular weight maleimide resin and the cyanate ester resin, effectively ensures the low thermal expansion coefficient of the circuit board, and makes the curing rate of the modified prepolymer resin reach 5% to 70%, so that the prepolymer resin can be used together with other resins to prepare a circuit board to further improve the performance of the circuit board; on the other hand, reduces the hydrophilic groups in the modified prepolymer resin, thereby effectively reducing the water absorption rate of the circuit board, and further preventing the manufactured circuit board and printed circuit board from bursting and delaminating.

[0050] In one embodiment, the mass ratio of the self-polymerization initiator to the resin monomer is 0.01:100 to 0.5:100.

[0051] In one embodiment, the self-polymerization initiator is selected from at least one of an organic peroxide or an azo initiator, thereby effectively improving the activity of the self-polymerization reaction.

[0052] Specifically, the organic peroxide is selected from at least one of dibenzoyl peroxide, tert-butyl peracetate, tert-butyl perbenzoate, diisopropylbenzene peroxide, bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, dibenzoyl peroxide, tert-butyl hydroperoxide, diisopropylbenzene hydroperoxide, methyl ethyl ketone peroxide or cyclohexane peroxide.

[0053] The azo initiator is selected from at least one of 2,2'-azobis-(2-methylbutyronitrile), 2,2'-azobisisobutyronitrile or azobisisoheptanenitrile.

[0054] In one embodiment, the self-polymerization reaction system of the maleimide resin further comprises a solvent, and the solvent is selected from at least one of dimethylformamide, dimethylacetamide, dimethyl sulfoxide, toluene, propylene glycol methyl ether, butanone, and 1,4-dioxane.

[0055] In one embodiment, the mass ratio of the oligomeric maleimide resin to the cyanate ester resin is 1:6 to 6:1;

[0056] In one embodiment, the prepolymerization reaction system further includes a metal salt catalyst, and based on 100 parts by weight of the oligomeric maleimide resin and the cyanate ester resin, the amount of the metal salt catalyst is 0.01 to 1 parts by weight, and the metal salt catalyst is selected from at least one of zinc octoate, cobalt octoate, cobalt acetylacetonate and zinc acetylacetonate. In this case, the prepolymerization reaction has a higher reaction rate.

[0057] In one embodiment, the prepolymerization reaction is carried out at a temperature of 110° C. to 170° C. and for a time of 1 hour to 6 hours.

[0058] The present invention also provides a resin composition comprising at least the modified prepolymer resin described above.

[0059] In order to further improve the thermal expansion coefficient and water absorption rate of the circuit substrate, the resin composition further comprises an auxiliary resin, and the mass ratio of the auxiliary resin to the modified prepolymer resin is 1:60 to 5:2.

[0060] In one embodiment, the auxiliary resin is selected from at least one of polytetrafluoroethylene resin, polybutadiene, polypentadiene, polystyrene, butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, small molecule vinyl compound, acrylate resin, vinyl terminated polyphenylene ether, vinyl terminated maleimide resin, allyl benzoxazine resin, and styrene maleic anhydride resin.

[0061] It should be noted that the small molecule vinyl compound mentioned above refers to a vinyl compound having a molecular weight of less than or equal to 1000.

[0062] In order to further reduce the thermal expansion coefficient and water absorption rate of the circuit substrate, the auxiliary resin is preferably a vinyl-terminated polyphenylene ether, including at least one of vinyl polyphenylene ether resin, vinyl benzyl polyphenylene ether resin, vinyl benzyl-modified bisphenol A polyphenylene ether resin, dicyclopentadiene-vinyl benzyl phenylene ether resin, methacrylate polyphenylene ether resin, allyl polyphenylene ether resin, vinyl-extended polyphenylene ether resin, maleimide and maleic anhydride-modified polyphenylene ether resin.

[0063] More preferably, the number average molecular weight of the auxiliary resin is 500 to 3000, which improves the compatibility of the auxiliary resin and the modified prepolymer resin, thereby reducing the thermal expansion and water absorption of the circuit substrate.

[0064] In one embodiment, the resin composition further comprises a curing agent. Based on 100 parts by weight of the modified prepolymer resin, the amount of the curing agent is 0 to 20 parts by weight.

[0065] Specifically, the curing agent is selected from triallyl isocyanurate, triallyl cyanurate, dicyclopentadiene dimethacrylate, divinylbenzene, bis(vinylbenzyl) ether, diallyl phthalate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trivinylbenzene, etc. It is beneficial to increase the crosslinking density between the modified prepolymer resin and the auxiliary resin.

[0066] In one embodiment, the resin composition further comprises an initiator. Based on 100 parts by weight of the modified prepolymer resin, the amount of the initiator is 0 to 0.2 parts by weight.

[0067] The initiator is selected from at least one of dibenzoyl peroxide, tert-butyl peracetate, tert-butyl perbenzoate, diisopropylbenzene peroxide, bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, dibenzoyl peroxide, tert-butyl hydroperoxide, diisopropylbenzene hydroperoxide, methyl ethyl ketone peroxide, and cyclohexane peroxide, which is beneficial to improving the crosslinking reaction activity of the modified prepolymer resin and the auxiliary resin, thereby reducing the water absorption rate and thermal expansion coefficient of the circuit substrate.

[0068] In one embodiment, the resin composition further comprises a catalyst. Based on 100 parts by weight of the modified prepolymer resin, the amount of the catalyst is 0 to 0.1 parts by weight.

[0069] The catalyst is selected from imidazole, metal organic salt catalyst, acetylacetone catalyst, amine catalyst, phosphorus catalyst, pyridine, etc., including at least one of 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, zinc octoate, zinc isooctanoate, stannous octoate, dibutyltin dilaurate, zinc naphthenate, cobalt naphthenate, aluminum acetylacetonate, cobalt acetylacetonate, copper acetylacetonate, triethylamine, pyridine, tributylamine, boron trifluoride amine complex, triphenylphosphine, ethyltriphenylphosphine chloride, and 4-dimethylaminopyridine.

[0070] In one embodiment, the resin composition further comprises a filler, wherein the amount of the filler is 0 to 600 parts by weight based on 100 parts by weight of the modified prepolymer resin.

[0071] Preferably, the filler is selected from at least one of silicon dioxide, titanium dioxide, aluminum hydroxide, magnesium hydroxide, aluminum nitride, silicon nitride, talc, calcium carbonate, and glass fiber.

[0072] More preferably, the filler is selected from spherical silica treated with a silane coupling agent, and the silane coupling agent is selected from at least one of an epoxy silane coupling agent, an amino silane coupling agent, a vinyl silane coupling agent, an acrylate silane coupling agent, and an allyl silane coupling agent.

[0073] In one embodiment, when the resin composition includes an auxiliary resin, the resin composition further includes at least one of a curing agent, a catalyst, an initiator and a filler. Based on 100 parts by weight of the modified prepolymer resin and the auxiliary resin, the amount of the curing agent is 1 to 10 parts by weight, the amount of the catalyst is 0.001 to 0.05 parts by weight, the amount of the initiator is 0.001 to 0.1 parts by weight, and the amount of the filler is 100 to 300 parts by weight.

[0074] The present invention also provides a prepreg made from the modified prepolymer resin or resin composition.

[0075] The prepreg of the present invention is prepared by an existing preparation method, which is not limited in the present invention. Preferably, the prepreg is obtained by impregnating or coating the above-mentioned modified prepolymer resin or resin composition on a reinforcing material and drying it. The reinforcing material is preferably at least one of glass fiber cloth, aramid cloth or carbon fiber cloth.

[0076] The present invention also provides a circuit substrate made of the prepreg as described above. The circuit substrate has a low thermal expansion coefficient and low water absorption rate, is not prone to board bursting and delamination, effectively improves the performance and service life of the circuit substrate, and has high market application potential.

[0077] Specifically, the circuit substrate includes 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 more superimposed prepregs, and the conductive layer is preferably copper foil.

[0078] The present invention also provides a printed circuit board made of the circuit substrate, which has a low thermal expansion coefficient and low water absorption rate and is not prone to board bursting and delamination.

[0079] Preferably, the printed circuit board is made of the circuit substrate through processes such as drilling, hole filling, micro-etching, pre-preg, activation, acceleration, chemical copper and copper thickening.

[0080] Hereinafter, the modified prepolymer resin and its preparation method and application will be further described through the following specific application examples.

[0081] Synthesis example 1

[0082] Add 60 g of maleimide (structural formula as shown in Formula 3-1) and 100 g of N,N-dimethylformamide (DMF) to a flask and dissolve them, add 0.1 g of 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, and heat the reaction at 160°C for 2 hours to obtain an oligomeric maleimide resin (structural formula as shown in Formula 1-1).

[0083] 50 g of the prepared oligomeric maleimide resin (excluding the mass of the solvent), 50 g of biscyclopentadienyl cyanate resin (the equivalent weight of the cyanide group is 250 g / mol) and 0.05 g of zinc acetylacetonate were mixed and heated at 160° C. for 2 h to obtain a modified prepolymer resin.

[0084] The oligomeric maleimide resin prepared in Synthesis Example 1 was subjected to GPC testing, and it was found that the number average molecular weight of the oligomeric maleimide resin was in the range of 1800 to 4000, indicating that the structural formula of the oligomeric maleimide resin prepared in Synthesis Example 1 satisfied Formula (1).

[0085] Synthesis example 2

[0086] Add 60 g of maleimide (structural formula as shown in Formula 3-2) and 100 g of DMF to a flask for dissolution, add 0.1 g of 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, and heat the reaction at 160° C. for 2 h to obtain an oligomeric maleimide resin (structural formula as shown in Formula 1-2).

[0087] 50 g of the prepared oligomeric maleimide resin (excluding the mass of the solvent), 50 g of biscyclopentadienyl cyanate resin (the equivalent weight of the cyanide group is 250 g / mol) and 0.05 g of zinc acetylacetonate were mixed and heated at 160° C. for 2 h to obtain a modified prepolymer resin.

[0088] Synthesis example 3

[0089] Add 60 g of maleimide (structural formula as shown in Formula 3-3) and 100 g of DMF to a flask for dissolution, add 0.1 g of 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, and heat the reaction at 160° C. for 2 h to obtain an oligomeric maleimide resin (structural formula as shown in Formula 1-3).

[0090] 75 g of the prepared oligomeric maleimide resin (excluding the mass of the solvent), 25 g of biscyclopentadienyl cyanate resin (the equivalent weight of the cyanide group is 250 g / mol) and 0.067 g of zinc octoate were mixed and heated at 160° C. for 2 h to obtain a modified prepolymer resin.

[0091] Synthesis example 4

[0092] Add 60 g of maleimide (structural formula as shown in Formula 4-1) and 100 g of DMF to a flask to dissolve, add 0.1 g of 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, and heat the reaction at 160°C for 2 hours to obtain an oligomeric maleimide resin (structural formula as shown in Formula 2-1).

[0093] 25 g of the prepared oligomeric maleimide resin (excluding the mass of the solvent), 75 g of biscyclopentadienyl cyanate resin (the equivalent weight of the cyanide group is 250 g / mol) and 0.067 g of zinc octoate were mixed and heated at 160° C. for 2 h to obtain a modified prepolymer resin.

[0094] Synthesis example 5

[0095] Add 60 g of maleimide (structural formula as shown in Formula 4-2) and 100 g of DMF to a flask for dissolution, add 0.1 g of 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, and heat the reaction at 160°C for 2 hours to obtain an oligomeric maleimide resin (structural formula as shown in Formula 2-2).

[0096] 50 g of the prepared oligomeric maleimide resin (excluding the mass of the solvent), 50 g of biscyclopentadienyl cyanate resin (the equivalent weight of the cyanide group is 250 g / mol) and 0.05 g of zinc acetylacetonate were mixed and heated at 160° C. for 2 h to obtain a modified prepolymer resin.

[0097] Synthesis example 6

[0098] Add 60 g of maleimide (structural formula as shown in Formula 4-3) and 100 g of DMF to a flask for dissolution, add 0.1 g of 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, and heat the reaction at 160° C. for 2 h to obtain an oligomeric maleimide resin (structural formula as shown in Formula 2-3).

[0099] 50 g of the prepared oligomeric maleimide resin (excluding the mass of the solvent), 50 g of biscyclopentadienyl cyanate resin (the equivalent weight of the cyanide group is 250 g / mol) and 0.05 g of zinc acetylacetonate were mixed and heated at 160° C. for 2 h to obtain a modified prepolymer resin.

[0100] Synthesis Example 7

[0101] Add 60 g of maleimide (structural formula as shown in Formula 3-4) and 100 g of DMF to a flask for dissolution, add 0.1 g of 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, and heat the reaction at 160° C. for 2 h to obtain an oligomeric maleimide resin (structural formula as shown in Formula 1-4).

[0102] 50 g of the prepared oligomeric maleimide resin (excluding the mass of the solvent), 50 g of biscyclopentadienyl cyanate resin (the equivalent weight of the cyanide group is 250 g / mol) and 0.05 g of zinc acetylacetonate were mixed and heated at 160° C. for 2 h to obtain a modified prepolymer resin.

[0103] Synthesis example 8

[0104] Synthesis Example 8 is the same as Synthesis Example 7.

[0105] Synthesis example 9

[0106] Synthesis Example 9 is the same as Synthesis Example 1.

[0107] Synthesis example 10

[0108] Synthesis Example 10 is the same as Synthesis Example 1.

[0109] Synthesis Example 11

[0110] The difference between Synthesis Example 11 and Synthesis Example 1 is that 50 g of naphthol aralkyl type cyanate compound (cyano group equivalent is 261 g / mol) is used instead of 50 g of biscyclopentadienyl cyanate resin (cyano group equivalent is 250 g / mol).

[0111] Synthesis example 12

[0112] The difference between Synthesis Example 12 and Synthesis Example 1 is that 50 g of biscyclopentadienyl cyanate (the equivalent weight of cyano group is 125 g / mol) is used instead of 50 g of biscyclopentadienyl cyanate resin (the equivalent weight of cyano group is 250 g / mol).

[0113] Synthesis example 13

[0114] The difference between Synthesis Example 13 and Synthesis Example 1 is that 50 g of biscyclopentadienyl cyanate (the equivalent weight of cyano group is 2750 g / mol) is used instead of 50 g of biscyclopentadienyl cyanate resin (the equivalent weight of cyano group is 250 g / mol).

[0115] Synthesis example 14

[0116] The difference between Synthesis Example 14 and Synthesis Example 1 is that 0.05 g of 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne was used.

[0117] Synthesis Example 15

[0118] The difference between Synthesis Example 15 and Synthesis Example 1 is that 0.2 g of 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne was used.

[0119] Comparative Example 1

[0120] Add 60g of maleimide (structural formula as shown in Formula 3-1) and 100g of DMF solution, 0.1g of 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, 50g of dicyclopentadienyl cyanate resin (cyano equivalent is 250g / mol) and 0.05g of zinc acetylacetonate into a flask, mix well, and heat to react at 160°C for 2h to obtain a modified prepolymer resin.

[0121] Comparative Example 2

[0122] 60 g of maleimide (structural formula as shown in Formula 5) and 100 g of DMF were added to a flask for dissolution, 0.1 g of 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne was added, and the mixture was heated at 160° C. for 2 h to obtain an oligomeric maleimide resin.

[0123] Since the structural formula of the resin monomer of Comparative Example 2 (structural formula such as Formula 5) does not satisfy Formula (3) or Formula (4), the structural formula of the oligomeric maleimide resin prepared in Comparative Example 2 does not satisfy Formula (1) or Formula (2).

[0124] 50 g of the prepared oligomeric maleimide resin (excluding the mass of the solvent), 50 g of biscyclopentadienyl cyanate resin (the equivalent weight of the cyanide group is 250 g / mol) and 0.05 g of zinc acetylacetonate were mixed and heated at 160° C. for 2 h to obtain a modified prepolymer resin.

[0125] Comparative Example 3

[0126] Add 60 g of maleimide (structural formula as shown in Formula 3-1) and 100 g of DMF to a flask for dissolution, add 0.1 g of 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, and heat the reaction at 150° C. for 8 h to obtain an oligomeric maleimide resin (structural formula as shown in Formula 1-5).

[0127] 50 g of the prepared oligomeric maleimide resin (excluding the mass of the solvent), 50 g of biscyclopentadienyl cyanate resin (the equivalent weight of the cyanide group is 250 g / mol) and 0.05 g of zinc acetylacetonate were mixed and heated at 160° C. for 2 h to obtain a modified prepolymer resin.

[0128] Comparative Example 4

[0129] 60 g of maleimide (structural formula shown in Formula 3-1) and 100 g of DMF were added to a flask to dissolve, and heated to react at 160° C. for 2 h to obtain an oligomeric maleimide resin (structural formula shown in Formula 1-6).

[0130] 50 g of the prepared oligomeric maleimide resin (excluding the mass of the solvent), 50 g of biscyclopentadienyl cyanate resin (the equivalent weight of the cyanide group is 250 g / mol) and 0.05 g of zinc acetylacetonate were mixed and heated at 160° C. for 2 h to obtain a modified prepolymer resin.

[0131] The structural formulas of the resin monomers and oligomeric maleimide resins in all synthesis examples and comparative examples are as follows:

[0132]

[0133]

[0134]

[0135] Application Examples

[0136] The modified prepolymer resins prepared in all synthesis examples and comparative examples were used in the amounts shown in Table 1 to prepare the corresponding application examples. The corresponding amounts (all figures shown in Table 1 are solids contents) were weighed and added with butanone / DMAC to prepare a resin adhesive solution, controlling the solids content of the resin adhesive to 60%. The adhesive solution was evenly coated onto 2116 fiberglass cloth using a glue applicator and placed in a drying oven at 160°C for 4 minutes to form a prepreg. Four prepregs were stacked, each covered with a copper foil on top and bottom, and then pressed in a vacuum press at 210°C for 120 minutes to produce a circuit substrate.

[0137] Table 1 (unit: g)

[0138]

[0139] Performance tests were conducted on the modified prepolymer resins obtained in all synthesis examples and comparative examples, as well as the circuit substrates obtained in all application examples and comparative application examples. The test indicators and test methods are as follows:

[0140] (1) Curing rate of modified prepolymer resin: The reaction heat peak curves of completely uncured modified prepolymer resin and modified prepolymer resin were measured by DSC at a heating rate of 10°C / min, and the curing rate was calculated by the reaction heat (ΔH):

[0141] Curing rate = (heat released by completely uncured modified prepolymer resin ΔH - heat released by modified prepolymer resin ΔH) / heat released by completely uncured modified prepolymer resin ΔH × 100%.

[0142] (2) Water absorption rate of circuit board: refer to IPC-TM-650 2.6.2.1 for water absorption test.

[0143] (3) Circuit board CTE: Refer to IPC-TM-650 2.4.24 and use thermomechanical analysis (TMA) with a heating rate of 10°C / min to test the thermal expansion coefficient.

[0144] (5) Compatibility of resin in circuit substrate: Refer to IPC-TM-650 and observe the dispersion of resin in slices using scanning electron microscope (SEM).

[0145] (6) Circuit board cracking and delamination: Immerse a 5cm×5cm circuit board in a 288℃ tin furnace for 30 minutes and observe whether the circuit board cracking and delamination occur.

[0146] All performance test results are shown in Table 2.

[0147] Table 2

[0148]

[0149]

[0150] As can be seen from the test results in the table, under the same test conditions, the modified prepolymer resins of all synthesis examples have lower cure rates and better compatibility with other resins compared to the comparative examples. The circuit substrates prepared therefrom can simultaneously achieve low thermal expansion coefficients and low water absorption rates, and no board bursting or delamination occurs. Therefore, the modified prepolymer resins of the present invention and the preparation method thereof can simultaneously improve various performance and service life of the circuit substrate and have high market application potential.

[0151] The various technical features of the above-mentioned application examples can be combined arbitrarily. In order to make the description concise, not all possible combinations of the various technical features in the above-mentioned application examples 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.

[0152] The application examples described above merely illustrate several embodiments of the present invention, and their descriptions are relatively specific and detailed. However, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art may make various modifications and improvements without departing from the scope of the present invention, and these modifications and improvements fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be based on the appended claims.

Claims

1. A modified prepolymer resin, characterized in that, The modified prepolymer resin is prepared by prepolymerization of an oligomeric maleimide resin and a cyanate resin. The structural formula of the oligomeric maleimide resin is shown in Formula (1) or Formula (2). In formulas (1) and (2), 0 < a < 5, 0 < b < 20, 0 < n < 5, 0 < m < 20, R1, R2, R3, and R4 are each independently selected from an alkylene group, an ether bond, a siloxane bond, or one or a combination of two of them.

2. The modified prepolymer resin according to claim 1, wherein The R1 and R3 are each independently selected from ether bonds, Said R2 and R4 are each independently selected from or One or a combination of two.

3. The modified prepolymer resin according to claim 1, wherein The cyanate resin is selected from at least one of a cyanate resin containing a naphthalene ring structure, a cyanate resin containing an anthracene ring structure, a cyanate resin containing a dicyclopentadiene structure, a cyanate resin containing a biphenyl structure, a cyanate resin containing a fluorene structure, a multifunctional cyanate resin, a bisphenol A cyanate resin, a bisphenol F cyanate resin, a bisphenol M cyanate resin, a bisphenol E cyanate resin, and a phenolic cyanate resin.

4. The modified prepolymer resin according to claim 1 or 3, wherein The cyanate ester resin has a cyano equivalent weight of 150 g / mol to 2500 g / mol.

5. A method for preparing the modified prepolymer resin according to any one of claims 1 to 4, characterized in that: The following steps are involved: The resin monomer is subjected to a self-polymerization reaction under the action of a self-polymerization initiator to obtain an oligomeric maleimide resin. Among them, the structural formula of the resin monomer is shown in Formula (3) or Formula (4). In Formula (3) and Formula (4), 0 < a < 5, 0 < n < 5, and R1, R2, R3, and R4 are each independently selected from alkylene groups, ether bonds, siloxane bonds, or one or a combination of two of them, and the temperature of the self-polymerization reaction is 110°C to 170°C, and the time is 1 h to 6 h. The oligomeric maleimide resin and the cyanate resin are subjected to a prepolymerization reaction to prepare a modified prepolymer resin.

6. The preparation method of modified prepolymer resin according to claim 5, wherein The mass ratio of the self-polymerization initiator to the resin monomer is 0.01:100 to 0.5:100; And / or, the self-polymerization initiator is at least one selected from organic peroxides or azo initiators.

7. The preparation method of modified prepolymer resin according to claim 5, wherein The mass ratio of the oligomeric maleimide resin to the cyanate ester resin is 1:6 to 6:1; And / or, the prepolymerization reaction system further includes a metal salt catalyst, and based on 100 parts by weight of the oligomeric maleimide resin and the cyanate ester resin, the amount of the metal salt catalyst is 0.01 to 1 part by weight, and the metal salt catalyst is selected from at least one of zinc octoate, cobalt octoate, cobalt acetylacetonate and zinc acetylacetonate.

8. A resin composition, characterized in that The resin composition at least comprises the modified prepolymer resin according to any one of claims 1 to 4.

9. The resin composition according to claim 8, characterized in that The resin composition further comprises an auxiliary resin, wherein the mass ratio of the auxiliary resin to the modified prepolymer resin is 1:60 to 5:2; And / or, the resin composition further comprises an auxiliary resin, and the auxiliary resin is selected from at least one of polytetrafluoroethylene resin, polybutadiene resin, polypentadiene resin, polystyrene resin, butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, small molecule vinyl compound, acrylate resin, vinyl-terminated polyphenylene ether resin, vinyl-terminated maleimide resin, allyl benzoxazine resin, and styrene maleic anhydride resin.

10. The resin composition according to claim 9, characterized in that The auxiliary resin is selected from vinyl-terminated polyphenylene ether, and the number average molecular weight of the auxiliary resin is 500 to 3000.

11. The resin composition according to claim 8, characterized in that The resin composition also includes at least one of a curing agent, a catalyst, an initiator, and a filler, wherein, based on 100 parts by weight of the modified prepolymer resin, the amount of the curing agent is 0 to 20 parts by weight, the amount of the catalyst is 0 to 0.1 parts by weight, the amount of the initiator is 0 to 0.2 parts by weight, and the amount of the filler is 0 to 600 parts by weight.

12. A prepreg made from the modified prepolymer resin according to any one of claims 1 to 4 or the resin composition according to any one of claims 8 to 11.

13. A circuit substrate made of the prepreg according to claim 12.

14. A printed circuit board manufactured using the circuit substrate according to claim 12.

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