Resin composition and use thereof

Abstract

The present invention provides a resin composition and a use thereof. In parts by weight, the resin composition comprises: 10-70 parts of benzoxazine resin containing unsaturated double bonds; 20-100 parts of maleimide resin and / or maleimide prepolymer; and 1-30 parts of an organosilicon compound containing double bonds.

Description

Resin composition and application thereof Technical Field

[0001] The present invention relates to the technical field of electronic materials, and in particular to a resin composition and application thereof. Background Art

[0002] In recent years, the trend toward miniaturization and higher performance in electronic devices has led to a continuous increase in wiring density and high concentration in printed circuit boards (PCBs). This has placed higher demands on the heat resistance and reliability of copper-clad laminates. In semiconductor packaging substrates, in particular, the difference in thermal expansion between the chip and the organic substrate during package assembly can easily lead to warping.

[0003] Bismaleimide resins, due to their excellent heat resistance, high modulus, and low CTE, are widely used in high-performance printed circuit boards. However, bismaleimide resins suffer from high curing temperatures, high water absorption, and brittleness. To address these shortcomings, diamine or allyl compound modifications, or the addition of thermoplastic elastomers or liquid crystal polymers, are currently common. While these methods improve toughness and other issues to a certain extent, they often result in reduced heat resistance in the resulting resin composition.

[0004] Benzoxazine resin has a small curing shrinkage rate during the polymerization reaction at high temperature, and the cured product has high heat resistance, high carbon residue rate and excellent thermal stability. Therefore, it is widely used in the field of copper clad laminates. However, benzoxazine resin has disadvantages such as poor toughness, poor rigidity and poor dielectric properties.

[0005] Prior art CN 113045896 discloses the addition of a tough resin to a maleimide resin and benzoxazine resin system. The tough resin, such as styrene-butadiene rubber, core-shell rubber, carboxyl-terminated nitrile rubber, polyacrylate rubber, polyethersulfone, or thermoplastic polyester elastomer, addresses the brittleness of conventional bismaleimide, imparting excellent impact toughness to the resulting resin composition while maintaining the low dielectric properties of bismaleimide and improving the heat resistance of the composition. However, the tough resin has poor compatibility with other resins and is easily precipitated onto the surface during curing, thereby affecting adhesion to the copper foil and water absorption.

[0006] Summary of the Invention

[0007] The purpose of the present invention is to provide a resin composition and application thereof.

[0008] To achieve the above-mentioned object, the present invention adopts the following technical solution: a resin composition, which comprises, by weight:

[0009] Benzoxazine resin containing unsaturated double bonds: 10 parts by weight to 70 parts by weight;

[0010] Maleimide resin and / or maleimide prepolymer: 20 parts by weight to 100 parts by weight;

[0011] Double bond-containing organosilicon compound: 1 part by weight to 30 parts by weight.

[0012] As a further improvement of the present invention, the benzoxazine resin containing unsaturated double bonds, the maleimide resin or maleimide prepolymer, and the organosilicon compound containing double bonds undergo a prepolymerization reaction to form a prepolymer, and the reaction temperature of the prepolymerization reaction is lower than the ring-opening temperature of the benzoxazine resin containing unsaturated double bonds.

[0013] As a further improvement of the present invention, the reaction temperature of the prepolymerization reaction is 50° C.-135° C., and / or the reaction time of the prepolymerization reaction is 30 min-200 min.

[0014] As a further improvement of the present invention, the double bond in the double-bond-containing organosilicon compound is a vinyl group, an allyl group, a propenyl group, a methacrylate group, an acrylate group, a styryl group, a phenylallyl group or a phenylpropenyl group.

[0015] As a further improvement of the present invention, the double bond-containing organosilicon compound is at least one of structural formulas (1) to (4):

[0016] Wherein, R1 and R2 are the same or different and are respectively selected from C1-C5 alkyl groups, and R3 is a C1-C5 alkylene group;

[0017] Wherein, the R group in structural formula (2) is a C1-C5 alkyl group;

[0018] Wherein, the R group in structural formula (3) is a C1-C5 alkyl group, and n is an integer of 0-5;

[0019] Wherein, in the structural formula (4), the R group is a C1-C5 alkyl group, n is an integer of 1-20, m is an integer of 1-10, and s is an integer of 1-6.

[0020] As a further improvement of the present invention, the unsaturated double bond-containing benzoxazine resin is at least one of the following structures:

[0021] Wherein, T is vinyl, allyl, propenyl, styryl, phenylallyl or phenylpropenyl; R4 is C1-C5 alkyl, C6-C 20Aromatic or alicyclic group; A is methylene, ethylene, isopropylene, dicyclopentadienyl, sulfide, sulfoxide, oxyethylene,

[0022] As a further improvement of the present invention, the maleimide resin has the following structural units Wherein, R is hydrogen or C1-C5 alkyl.

[0023] As a further improvement of the present invention, the maleimide prepolymer is selected from any one or a combination of at least two of a prepolymer of a diallyl compound and a maleimide compound, a prepolymer of a diamine and a maleimide compound, a prepolymer of a polyfunctional amine and a maleimide compound, or a prepolymer of an acidic phenol compound and a maleimide compound.

[0024] As a further improvement of the present invention, the resin composition further comprises at least one of 10-50 parts by weight of epoxy resin, 5-45 parts by weight of cyanate resin, 1-50 parts by weight of hydrocarbon resin, and 5-60 parts by weight of polyphenylene ether resin.

[0025] As a further improvement of the present invention, the resin composition further comprises a flame retardant, and / or 0.01-5 parts by weight of a catalyst, and / or a filler, and / or a dispersant, and / or a coupling agent; wherein, based on 100 parts by weight of the total of the benzoxazine resin containing unsaturated double bonds and the maleimide resin and / or maleimide prepolymer, the flame retardant is 1-50 parts by weight; based on 100 parts by weight of the resin composition, the filler is 20-250 parts by weight, the dispersant is 0.001-5 parts by weight, and the coupling agent is 0.001-10 parts by weight.

[0026] To achieve the above object of the invention, the present invention also provides a use of the above resin composition in prepregs, laminates and printed circuit boards.

[0027] Beneficial effects: Compared with the prior art, the present invention has the following advantages:

[0028] In the resin composition of the present invention, a double-bond-containing organosilicon compound is added to a double-bond-containing benzoxazine resin and a maleimide resin / maleimide prepolymer system, thereby increasing Si-O bonds and more hydrocarbon groups in the cured cross-linked structure. Due to the large Si-O bond angle, the free rotation is easy and the flexibility is good, thus giving the final resin composition excellent toughness. Simultaneously, the final resin composition is given a low water absorption rate. Thus, while maintaining excellent heat resistance and high modulus, the final resin composition can have excellent toughness, low water absorption rate, low dielectric constant and low dielectric loss, and reduced thermal expansion coefficient and warpage. DETAILED DESCRIPTION

[0029] The following is a specific implementation of the embodiment of the present invention. It should be noted that for ordinary technicians in this field, several improvements and modifications can be made without departing from the principles of the embodiment of the present invention. These improvements and modifications are also considered to be within the scope of protection of the embodiment of the present invention.

[0030] In this specification, “comprising” and “containing” mean that in addition to the components mentioned above, other components may be included, and these other components can impart different properties to the resin composition.

[0031] In this specification, "based on 100 parts by weight of the resin composition" refers to 100 parts by weight of the total amount of the components participating in the reaction in the resin composition, excluding flame retardants, catalysts, fillers, dispersants, and coupling agents. Of course, this is not limiting. It is understood that when the flame retardant is a reactive flame retardant, "based on 100 parts by weight of the resin composition" refers to 100 parts by weight of the total amount of the resin participating in the reaction and the flame retardant in the resin composition.

[0032] The present invention provides a resin composition, which comprises, by weight:

[0033] Benzoxazine resin containing unsaturated double bonds: 10 parts by weight to 70 parts by weight;

[0034] Maleimide resin and / or maleimide prepolymer: 20 parts by weight to 100 parts by weight;

[0035] Double bond-containing organosilicon compound: 1 part by weight to 30 parts by weight.

[0036] The resin composition of the present invention adds a double-bond organosilicon compound to a double-bond benzoxazine resin and a maleimide resin / maleimide prepolymer system, thereby increasing Si-O bonds and more hydrocarbon groups in the cured cross-linked structure. The large Si-O bond angle allows for easy free rotation and good flexibility, giving the final resin composition excellent toughness and low water absorption. Consequently, while maintaining excellent heat resistance and high modulus, the final resin composition exhibits excellent toughness, low water absorption, a low dielectric constant, and low dielectric loss, and reduces thermal expansion coefficient and warpage. This results in a cured product with excellent overall performance.

[0037] It should be noted that the cured product in the present invention can be understood as a prepreg, a laminate, a printed circuit board, etc.

[0038] In one embodiment, the resin composition comprises, by weight:

[0039] Benzoxazine resin containing unsaturated double bonds: 15-55 parts by weight;

[0040] Maleimide resin: 30-70 parts by weight;

[0041] Double bond-containing silicone resin: 5 to 20 parts by weight;

[0042] Preferably, the content of the double bond-containing silicone resin is 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, or 20 parts by weight. Of course, this is not limited to this.

[0043] Furthermore, the benzoxazine resin containing unsaturated double bonds, the maleimide resin / maleimide prepolymer, and the organosilicon compound containing double bonds undergo a prepolymerization reaction to form a prepolymer, and the reaction temperature of the prepolymerization reaction is lower than the ring-opening temperature of the benzoxazine resin containing unsaturated double bonds. During the prepolymerization reaction of the benzoxazine resin containing unsaturated double bonds, the maleimide resin / maleimide prepolymer, and the organosilicon compound containing double bonds, free radical polymerization occurs between the double bonds, allowing the organosilicon groups to be better incorporated into the cross-linked network structure, thus imparting excellent toughness to the final resin composition. When the temperature is higher than the ring-opening temperature of the benzoxazine resin containing unsaturated double bonds, the benzoxazine ring opens and then further reacts with the hydroxyl groups to form a denser cross-linked structure, which helps reduce the thermal expansion coefficient and water absorption rate of the final resin composition and improves the chemical resistance of the resin composition.

[0044] Specifically, the reaction temperature of the prepolymerization reaction is 50° C. to 135° C., and the reaction time of the prepolymerization reaction is 30 min to 200 min. When the temperature is higher than the ring-opening temperature of the benzoxazine resin containing unsaturated double bonds, specifically higher than 150° C., the benzoxazine ring opens and further reacts with the hydroxyl groups to form a denser cross-linked structure.

[0045] Preferably, the reaction temperature of the prepolymerization reaction is 60-110°C.

[0046] Furthermore, the double bond in the double-bond-containing organosilicon compound is a vinyl group, an allyl group, a propenyl group, a methacrylate group, an acrylate group, a styryl group, a phenylallyl group or a phenylpropenyl group.

[0047] Preferably, the double bond-containing organosilicon compound is at least one of structural formula (1) to structural formula (4):

[0048] Wherein, R1 and R2 are the same or different and are respectively selected from C1-C5 alkyl groups, and R3 is a C1-C5 alkylene group;

[0049] Wherein, the R group in structural formula (2) is a C1-C5 alkyl group;

[0050] Wherein, the R group in structural formula (3) is a C1-C5 alkyl group, and n is an integer of 0-5;

[0051] In the structural formula (4), the R group is a C1-C5 alkyl group, n is an integer of 1-20, m is an integer of 1-10, and s is an integer of 1-6.

[0052] In one embodiment, the organosilicon compound containing a double bond is an organosilicon compound containing a methacrylate group.

[0053] Furthermore, the above-mentioned benzoxazine resin containing unsaturated double bonds is at least one of the following structures:

[0054] Wherein, T is vinyl, allyl, propenyl, styryl, phenylallyl or phenylpropenyl; R4 is C1-C5 alkyl, C6-C 20 Aromatic or alicyclic group; A is methylene, ethylene, isopropylene, dicyclopentadienyl, sulfide, sulfoxide, oxyethylene,

[0055] Specifically, the unsaturated double bond-containing benzoxazine resin is preferably at least one of the following structures:

[0056] Furthermore, the maleimide resin contains the following structural units:

[0057] Structural formula (15); wherein R is hydrogen or C1-C5 alkyl.

[0058] Preferably, the maleimide resin is selected from any one of 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 2,3-dimethylbenzene maleimide, 2,6-dimethylbenzene maleimide, N-phenylmaleimide, maleimide containing an aliphatic long chain structure, allyl compound modified maleimide, amine modified maleimide or acidic phenol compound modified maleimide, or a combination of at least two thereof.

[0059] Furthermore, the maleimide prepolymer is selected from any one or a combination of at least two of a prepolymer of a diallyl compound and a maleimide compound, a prepolymer of a diamine and a maleimide compound, a prepolymer of a polyfunctional amine and a maleimide compound, or a prepolymer of an acidic phenol compound and a maleimide compound.

[0060] Specifically, the maleimide compound can be BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, BMI-4000H, BMI-5000, BMI-5100, BMI-7000 and BMI-7000H manufactured by Yamato Chemical Industry Co., Ltd.; BMI, BMI-70, BMI-80, etc. manufactured by KI Chemical Industry Co., Ltd. of Japan; MIR-3000, MIR-5000, etc. manufactured by Nippon Kayaku Co., Ltd.; X9-450, X9-470, etc. manufactured by DIC Corporation of Japan; D936, D937, D939, D950, etc. manufactured by Sichuan Dongcai Co., Ltd.

[0061] Preferably, the maleimide compound can be selected from BMI-2300 manufactured by Yamato Chemical Industry Co., Ltd., BMI-70 and BMI-80 manufactured by KI Chemical Industry Co., Ltd., and MIR-3000 manufactured by Nippon Kayaku Co., Ltd.

[0062] Furthermore, the resin composition further comprises at least one of epoxy resin, cyanate resin, hydrocarbon resin, and polyphenylene ether resin.

[0063] Specifically, when the resin composition includes epoxy resin, the content of the epoxy resin is 10-50 parts by weight.

[0064] The epoxy resin is selected from at least one of structural formulas (16) to (20):

[0065] Wherein, the number of repeating units p, n, and m in the above structures (16) to (20) is an integer of 1-10.

[0066] Specifically, when the resin composition includes a cyanate ester resin, the content of the cyanate ester resin is 5-45 parts by weight.

[0067] The cyanate ester resin contains at least one of the following structures:

[0068] The number of repeating units n in the structural formula (21) to the structural formula (26) is an integer of 1-10.

[0069] When the resin composition includes hydrocarbon resin, the content of the hydrocarbon resin is 1-50 parts by weight.

[0070] Specifically, the hydrocarbon resin is selected from at least one of polybutadiene, modified polybutadiene, polypentadiene, modified polypentadiene, polyisoprene, modified polyisoprene, polystyrene, butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, hydrogenated diene-butadiene-styrene copolymer, maleated diene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-butadiene-divinylbenzene copolymer, maleated styrene-butadiene copolymer, styrene-pentadiene copolymer, butadiene-cyclopentadiene copolymer, ethylene-cyclopentadiene copolymer, norbornene polymer, and modified norbornene polymer.

[0071] When the resin composition includes polyphenylene ether resin, the content of the polyphenylene ether resin is 5-60 parts by weight.

[0072] Furthermore, the polyphenylene ether resin is a polyphenylene ether resin containing unsaturated double bonds.

[0073] Specifically, the polyphenylene ether resin contains styrene double bonds or methacrylate groups, and can be OPE-2St manufactured by Mitsubishi Gas or SA9000 manufactured by SABIC.

[0074] Furthermore, the resin composition further comprises a flame retardant in an amount of 1-50 parts by weight based on 100 parts by weight of the combined unsaturated double-bond benzoxazine resin and maleimide resin and / or maleimide prepolymer. This flame retardant can improve the flame retardancy of the resulting cured product, which can be understood as a prepreg, laminate, printed circuit board, or the like.

[0075] Specifically, the flame retardant is at least one selected from the group consisting of brominated flame retardants, phosphorus flame retardants, nitrogen flame retardants, organosilicon flame retardants, organometallic flame retardants, and inorganic flame retardants.

[0076] Among them, the brominated flame retardant can be decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or tetrabromophthalamide. The phosphorus flame retardant can be inorganic phosphorus, condensed phosphate compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris(2,6-dimethylphenyl)phosphine, (m is an integer from 1 to 5), Phosphazene and other organic phosphorus-containing compounds. Nitrogen-based flame retardants include triazine compounds, cyanuric acid compounds, isocyanate compounds, and phenothiazines. Silicone flame retardants include silicone oils, silicone rubbers, and silicone resins. Organometallic salt flame retardants include ferrocene, acetylacetone metal complexes, and organometallic carbonyl compounds. Inorganic flame retardants include aluminum hydroxide, magnesium hydroxide, aluminum oxide, and barium oxide.

[0077] Of course, the type of flame retardant is not limited to this. It is understood that the added flame retardant can be selected based on the specific application of the final cured product, such as a laminate. For example, for applications requiring halogen, non-halogen flame retardants are preferred, such as phosphorus- or nitrogen-containing flame retardants, and more preferably phosphazene or bis-DOPO.

[0078] Furthermore, the resin composition further contains 0.01-5 parts by weight of a catalyst, which is at least one of an imidazole catalyst, a pyridine catalyst, and an organic metal salt catalyst.

[0079] Preferably, the catalyst is at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole and zinc octoate.

[0080] Furthermore, the resin composition further comprises a filler, and the content of the filler is 20-250 parts by weight based on 100 parts by weight of the resin composition.

[0081] Specifically, the filler includes inorganic filler, organic filler, and composite filler.

[0082] Preferably, the filler is spherical silica, alumina or aluminum hydroxide. More preferably, the filler is spherical silica.

[0083] Furthermore, the filler is a filler surface-treated with a silane coupling agent, and the silane coupling agent is at least one of an aminosilane coupling agent, a carbon-carbon double bond-containing silane coupling agent, or an epoxy silane coupling agent.

[0084] Furthermore, the resin composition further comprises a dispersant and a coupling agent. Based on 100 parts by weight of the resin composition, the content of the dispersant is 0.001-5 parts by weight, and the content of the coupling agent is 0.001-10 parts by weight.

[0085] Specifically, the dispersant may be BYK-161 or / and BYK-111 manufactured by BYK. The coupling agent may be KBM-402, KBM-403, KBM-502, KBE-503, KBM-603, KBM-903, KBM-573, KBM-602, KBM-1003, etc. manufactured by Shin-Etsu Chemical.

[0086] Furthermore, the present invention also provides a use of the resin composition in prepregs, laminates and printed circuit boards.

[0087] Specifically, the prepreg includes a reinforcing material and the above-mentioned resin composition attached to the surface of the reinforcing material.

[0088] The reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics. Preferably, the reinforcing material is glass fiber cloth, and the glass fiber cloth is preferably open fiber cloth or flat cloth. More preferably, the glass fiber cloth is E glass fiber cloth, S glass fiber cloth, T glass fiber cloth, or Q glass fiber cloth.

[0089] In addition, when glass fiber cloth is used as the reinforcing material, the glass fiber cloth generally needs to be chemically treated to improve the bonding between the resin composition and the glass fiber cloth. The main method of chemical treatment is treatment with a coupling agent, preferably an epoxy silane coupling agent or an amino silane coupling agent, to provide good water resistance and heat resistance.

[0090] The preparation method of the prepreg is as follows:

[0091] dissolving the resin composition in a solvent to prepare a resin composition glue solution;

[0092] The reinforcing material is immersed in the above-mentioned resin composition glue solution, and then the immersed reinforcing material is taken out and heated and dried to obtain the prepreg.

[0093] In a specific embodiment, the impregnated reinforcement material is baked at 100° C.-180° C. for 1 min-15 min, and the prepreg is obtained after drying.

[0094] Specifically, the solvent can be selected from one or a combination of acetone, butanone, toluene, methyl isobutyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, and cyclohexane.

[0095] The amount of solvent used in the present invention is not specifically limited. The amount of solvent added is selected by those skilled in the art based on their own experience, as long as the obtained resin composition glue reaches a viscosity suitable for use.

[0096] The laminate includes at least one of the above-mentioned prepregs and a metal foil formed on at least one side of the prepreg.

[0097] In an embodiment where the laminate comprises at least two of the aforementioned prepregs, the at least two prepregs are stacked and bonded together by heating and pressurizing, and then metal foil is bonded to one or both sides of the bonded prepregs by heating and pressurizing to form the laminate.

[0098] Specifically, the preparation steps of the laminate are as follows: coating one or both sides of the above-mentioned prepreg with metal foil, or stacking at least two of the above-mentioned prepregs, coating one or both sides with metal foil, and hot pressing to obtain a laminate.

[0099] The pressing conditions of the above laminated board are: pressing at a pressure of 0.2 to 2 MPa and a temperature of 150° C. to 250° C. for 2 to 4 hours.

[0100] Specifically, the number of the prepregs can be determined according to the thickness of the required laminate, and one or more prepregs can be used.

[0101] The metal foil can be copper foil or aluminum foil, and its material is not limited; the thickness of the metal foil is not particularly limited, such as 5μm, 8μm, 12μm, 18μm, 35μm or 70μm.

[0102] The printed wiring board includes at least one of the prepregs mentioned above, or the printed wiring board includes at least one of the laminates mentioned above.

[0103] The method for preparing the printed circuit board can adopt existing processes and will not be described in detail here.

[0104] The present invention will be described in detail below with reference to specific embodiments. Of course, it will be understood that the present invention is not limited to these embodiments.

[0105] Examples 1-6 and Comparative Examples 1-4:

[0106] The components and contents of the resin compositions of Examples 1-6 and Comparative Examples 1-4 are shown in Table 1 below:

[0107] Table 1

[0108] Wherein, the preparation of prepolymer A is as follows:

[0109] To the reaction flask, 40 g of allyl benzoxazine resin (DFE-148, manufactured by Tosai), 60 g of maleimide resin (BMI-2300, manufactured by Yamato Chemical), and 15 g of methacrylate-containing silicone resin (X-22-164A, manufactured by Shin-Etsu Chemical) were added, and 100 g of toluene was added. The temperature was raised to 90°C and the reaction was maintained at this temperature for 60 minutes to obtain liquid prepolymer A.

[0110] Prepolymer B was prepared as follows:

[0111] To the reaction flask, 40 g of allyl benzoxazine resin (DFE-148, manufactured by Tosai), 60 g of maleimide resin (BMI-2300, manufactured by Yamato Chemical), and 15 g of methacrylate-containing silicone resin (X-22-164, manufactured by Shin-Etsu Chemical) were added, and 100 g of toluene was added. The temperature was raised to 140°C and the reaction was maintained at this temperature for 30 minutes to obtain liquid prepolymer B.

[0112] It can be seen that both prepolymers A and B are produced by prepolymerization of the aforementioned unsaturated double-bond-containing benzoxazine resin, maleimide resin / maleimide prepolymer, and double-bond-containing organosilicon compound. Prepolymer A differs from prepolymer B in that the prepolymerization temperature of prepolymer A is lower, at 90°C, within the range of 50°C-135°C, while the prepolymer temperature of prepolymer B is higher, at 140°C, exceeding the range of 50°C-135°C.

[0113] Specifically, the information of each component involved in Table 1 above is shown in Table 2 below:

[0114] Table 2

[0115] The preparation method of the resin composition in Examples 1-6 and Comparative Examples 1-4 adopts a conventional preparation method, specifically: mixing with an appropriate amount of solvent according to the components and corresponding contents in Table 1, emulsifying with a high-speed emulsifier, and dispersing and mixing evenly to obtain a resin composition glue with a solid content of 60%, wherein the solid content of 60% is calculated by weight.

[0116] The obtained resin composition glue of Examples 1-6 and Comparative Examples 1-4 was coated on T-glass fiber cloth, taken out after soaking, placed in a 160° C. forced air drying oven, and baked for 3-6 minutes to prepare a prepreg.

[0117] Preparation of sample laminates for performance evaluation:

[0118] (1) Preparation of laminate

[0119] The prepregs prepared in Examples 1-6 and Comparative Examples 1-4 were cut into 300×300 mm, respectively. A piece of metal foil was placed on opposite sides of the prepregs, and the prepregs were pressed in a vacuum hot press to obtain laminated boards.

[0120] Performance evaluation method:

[0121] (1) Dielectric constant (Dk) / dielectric loss (Df): measured at 10 GHz using the flat plate method in accordance with IPC-TM-650 2.5.5.9;

[0122] (2) Glass transition temperature (Tg): tested using a dynamic mechanical analyzer (DMA) with a heating rate of 10°C / min. This can be used to analyze whether the system has phase separation. Generally, the presence of two or more Tgs indicates poor system compatibility and phase separation.

[0123] (3) PCT 2HR water absorption: Take three samples of 10 cm × 10 cm, 0.40 mm thick, with the metal foil removed from both sides, dry them at 100°C for 2 hours, weigh them, and record the weight as W1. Then, cook them in a pressure cooker at 121°C and 2 atmospheres for 2 hours, weigh them, and record the weight as W2. The water absorption is determined as (W2-W1) / W1×100%.

[0124] (4) X / Y thermal expansion coefficient (CTE) determination: TMA (thermomechanical analysis) was used, with a heating rate of 10°C / min and a test temperature range of 30-100°C;

[0125] (5) Hot and cold shock cycle: cool down from room temperature to -40°C at a rate of 5°C / min, then heat up to 120°C at a rate of 5°C / min, hold for 10 minutes, and then cool down to room temperature at a rate of 5°C / min. If the above operation is repeated more than 1000 times, it is considered "passed"; if it is repeated less than 1000 times, it is considered "failed".

[0126] The properties of the laminates obtained using the prepregs in Examples 1-6 and Comparative Examples 1-4 are shown in Table 3 below.

[0127] Table 3

[0128] As shown in Table 3, the laminated board obtained by using the resin composition of the present invention has a higher glass transition temperature, better heat resistance and toughness, lower dielectric constant, low dielectric loss, low water absorption and low expansion coefficient.

[0129] In particular, when Example 1 and Comparative Example 1 are compared in parallel, the resin composition in Example 1 adds a double-bond organosilicon compound compared to the resin composition in Comparative Example 1. The comparison shows that the laminate prepared from the resin composition in Example 1 has a higher glass transition temperature, better heat resistance, toughness, lower low dielectric constant, low dielectric loss, low water absorption rate, and low expansion coefficient. When Example 1 and Example 2 are compared in parallel, compared to Example 1, the allyl benzoxazine resin, maleimide resin, and methacrylate-containing organosilicon resin in Example 2 first undergo a prepolymerization reaction to form a prepolymer. The comparison shows that the laminate prepared from the resin composition in Example 2 has a higher glass transition temperature, better heat resistance, lower low dielectric constant, low dielectric loss, low water absorption rate, and low expansion coefficient. Comparing Example 3 and Comparative Example 2 in parallel, the silicone resin content in Comparative Example 2 is 40 parts by weight, which is higher than 1-30 parts by weight, while the silicone resin content in Example 3 is 20 parts by weight, which is between 1-30 parts by weight. The comparison shows that the laminate prepared from the resin composition in Example 3 has a higher glass transition temperature, better heat resistance and toughness, lower low dielectric constant, low dielectric loss, low water absorption rate, and low expansion coefficient. Comparing Example 2 and Comparative Example 4 in parallel, the prepolymer prepolymerization temperature in Example 2 is lower, while the prepolymer prepolymer prepolymer temperature in Comparative Example 4 is higher. The comparison shows that the laminate prepared from the resin composition in Example 2 has a higher glass transition temperature, better heat resistance and toughness, lower low dielectric constant, low dielectric loss, low water absorption rate, and low expansion coefficient.

[0130] It should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each implementation method can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

[0131] The series of detailed descriptions listed above are only specific descriptions of feasible implementation methods of the present invention. They are not intended to limit the scope of protection of the present invention. Any equivalent implementation methods or changes that do not deviate from the technical spirit of the present invention should be included in the scope of protection of the present invention.

Claims

1. A resin composition, characterized in that By weight, the resin composition comprises: Benzoxazine resin containing unsaturated double bonds: 10 parts by weight to 70 parts by weight; Maleimide resin and / or maleimide prepolymer: 20 parts by weight to 100 parts by weight; Double bond-containing organosilicon compound: 1 part by weight to 30 parts by weight.

2. The resin composition according to claim 1, characterized in that: The unsaturated double bond-containing benzoxazine resin, maleimide resin or maleimide prepolymer, and double bond-containing organosilicon compound undergo prepolymerization to generate a prepolymer, and the reaction temperature of the prepolymerization is lower than the ring-opening temperature of the unsaturated double bond-containing benzoxazine resin.

3. The resin composition according to claim 2, characterized in that: The reaction temperature of the prepolymerization reaction is 50° C.-135° C., and / or the reaction time of the prepolymerization reaction is 30 min-200 min.

4. The resin composition according to claim 1, characterized in that: The double bonds in the double-bond-containing organosilicon compound are vinyl, allyl, propenyl, methacrylate, acrylate, styrene, phenylallyl or phenylpropenyl.

5. The resin composition according to claim 1, characterized in that: The double bond-containing organosilicon compound is at least one of the structural formulas (1) to (4): Wherein, R1 and R2 are the same or different and are respectively selected from C1-C5 alkyl groups, and R3 is C1-C5 alkylene groups; Wherein, the R group in the structural formula (2) is a C1-C5 alkyl group; Wherein, the R group in the structural formula (3) is a C1-C5 alkyl group, and n is an integer of 0-5; Wherein, in the structural formula (4), the R group is a C1-C5 alkyl group, n is an integer of 1-20, m is an integer of 1-10, and s is an integer of 1-6.

6. The resin composition according to claim 1, characterized in that: The unsaturated double bond-containing benzoxazine resin is at least one of the following structures: Wherein, T is vinyl, allyl, propenyl, styryl, phenylallyl or phenylpropenyl; R4 is C1-C5 alkyl, C6-C 20 Aromatic or alicyclic group; A is methylene, ethylene, isopropylene, dicyclopentadienyl, sulfide, sulfoxide, oxy, 7. The resin composition according to claim 1, characterized in that: The maleimide resin has the following structural units Wherein, R is hydrogen or C1-C5 alkyl.

8. The resin composition according to claim 1, characterized in that: The maleimide prepolymer is selected from any one or a combination of at least two of a prepolymer of a diallyl compound and a maleimide compound, a prepolymer of a diamine and a maleimide compound, a prepolymer of a multifunctional amine and a maleimide compound, or a prepolymer of an acidic phenol compound and a maleimide compound.

9. The resin composition according to claim 1, characterized in that: The resin composition further comprises at least one of 10-50 parts by weight of epoxy resin, 5-45 parts by weight of cyanate resin, 1-50 parts by weight of hydrocarbon resin, and 5-60 parts by weight of polyphenylene ether resin.

10. The resin composition according to claim 1, characterized in that: The resin composition further comprises a flame retardant, and / or 0.01-5 parts by weight of a catalyst, and / or a filler, and / or a dispersant, and / or a coupling agent; wherein, based on 100 parts by weight of the benzoxazine resin containing unsaturated double bonds and the maleimide resin and / or the maleimide prepolymer, the flame retardant is 1-50 parts by weight; based on 100 parts by weight of the resin composition, the filler is 20-250 parts by weight, the dispersant is 0.001-5 parts by weight, and the coupling agent is 0.001-10 parts by weight.

11. Use of the resin composition according to claim 1 in prepregs, laminates and printed circuit boards.

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