TWI861499B - Biphenyl bismaleimide-containing resin composition - Google Patents

Abstract

A biphenyl bismaleimide-containing resin composition is provided. The biphenyl bismaleimide-containing resin composition includes unsaturated diene rubber, hydrogenated ethylene-butene copolymer, and bismaleimide resin. the bismaleimide resin includes biphenyl bismaleimide resin and modified bismaleimide resin. The weight ratio between the biphenyl bismaleimide resin and the modified bismaleimide resin is 1:2~5.

Description

Resin composition containing biphenyl type bismaleimide

The present invention relates to a resin composition, in particular to a resin composition containing biphenyl bismaleimide.

As the information and electronics industries enter the 5G era, smart terminals are also moving towards miniaturization and multi-functionality. In order to meet the needs of high-frequency and high-speed signal transmission, 5G copper clad laminates are required to have high heat resistance, low water absorption, low dielectric, good weather resistance, and green environmental protection.

At present, the base material of copper-clad laminates mostly uses relatively polar epoxy resin materials to facilitate bonding to metal surfaces such as copper foil, but the polar groups in epoxy resins also lead to higher dielectric constants and dielectric losses, which do not meet the requirements of high-frequency and high-speed transmission. On the other hand, the use of relatively non-polar resin materials such as polybutadiene and polyisoprene has better electrical performance, but the adhesion between non-polar resin materials and metal surfaces is relatively low. When low-surface roughness copper foil or ultra-low-surface roughness copper foil is used for high-speed transmission, the adhesion between the resin material and the metal surface will be seriously reduced.

In the prior art (e.g., US5629098), in order to improve the adhesion between the copper foil and the substrate, an adhesive is used between the copper foil and the substrate. An adhesive with high peel strength can effectively bond the copper foil and the substrate. However, these adhesives with high peel strength are found to have insufficient high temperature stability through a solder blister resistance test, and adhesives with high temperature stability cannot have satisfactory adhesion. In other words, the peel strength and high temperature stability of the adhesive are two mutually restrictive properties, and it is still difficult to solve the problem of poor adhesion between the resin material and the metal surface by using an adhesive.

Therefore, there is still a need to develop a substrate material that simultaneously meets the requirements of high peeling strength and low dielectric loss to overcome the above-mentioned defects, which has become one of the important issues that the industry wants to solve.

The technical problem to be solved by the present invention is to provide a resin composition containing biphenyl type bismaleimide in view of the shortcomings of the prior art, which includes unsaturated diene rubber, hydrogenated ethylene-butene copolymer and bismaleimide resin. The bismaleimide resin includes biphenyl type bismaleimide resin and modified bismaleimide resin. The weight ratio of the biphenyl type bismaleimide resin to the modified bismaleimide resin is 1:2-5.

In one embodiment of the present invention, the unsaturated diene rubber is polybutadiene rubber.

In one embodiment of the present invention, the biphenyl type bismaleimide resin has the structure of the following formula (I): Among them, n=1~5.

In one embodiment of the present invention, the modified bismaleimide resin has a structure of the following formula (II) or formula (III): Among them, n=1~5.

In one embodiment of the present invention, the resin composition of biphenyl bismaleimide further comprises a crosslinking agent, and the molecular weight of the crosslinking agent is less than or equal to 1500.

In one embodiment of the present invention, the crosslinking agent is selected from the group consisting of trimethylallyl isocyanate (TMAIC), triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), 1,2,4-trivinylcyclohexane (TVCH), diallyl isophthalate (DAIP) and 4-tert-butylstyrene (TBS).

In one embodiment of the present invention, the resin composition of biphenyl bismaleimide further comprises a crosslinking accelerator, and the crosslinking accelerator is a peroxide.

In one embodiment of the present invention, the resin composition of biphenyl bismaleimide further includes a silane coupling agent, a flame retardant and an inorganic filler.

In one embodiment of the present invention, the flame retardant is selected from phosphate compounds or nitrogen-containing phosphate compounds.

In one embodiment of the present invention, the inorganic filler is surface-treated in advance with the silane coupling agent.

One of the beneficial effects of the present invention is that the resin composition containing biphenyl type bismaleimide provided by the present invention can meet the requirements of high peel strength (for example, peel strength greater than or equal to 4.3) by means of the technical scheme of "comprising unsaturated diene rubber, hydrogenated ethylene-butene copolymer and bismaleimide resin" and "the weight ratio of biphenyl type bismaleimide resin to modified bismaleimide resin is 1:2-5". Lb/Inch) and low dielectric loss (e.g. dielectric loss less than or equal to 3.0), and is suitable as a high-end copper clad laminate material, which can be applied to resin compositions, prepregs, laminates and printed circuit boards for electronic circuits.

In order to further understand the features and technical contents of the present invention, please refer to the following detailed description of the present invention. However, the detailed description provided is only used for reference and description, and is not used to limit the present invention.

The following is an implementation method of the "resin composition containing biphenyl-type bismaleimide" disclosed in the present invention, which is described through specific concrete examples. Those skilled in the art can understand the advantages and effects of the present invention from the contents disclosed in this specification. The present invention can be implemented or applied through other different specific embodiments, and the details in this specification can also be modified and changed in various ways based on different viewpoints and applications without departing from the concept of the present invention. The following implementation method will further explain the relevant technical content of the present invention in detail, but the disclosed content is not intended to limit the scope of protection of the present invention. In addition, the term "or" used in this article may include any one or more combinations of the related listed items depending on the actual situation.

The resin composition containing biphenyl bismaleimide of the present invention includes unsaturated diene rubber, hydrogenated ethylene-butene copolymer and bismaleimide resin. Although the prior art believes that polybutadiene has poor adhesion to metal surfaces, the present invention uses unsaturated polybutadiene rubber to improve the toughness of the resin composition. In addition, the resin composition containing biphenyl bismaleimide of the present invention also includes hydrogenated ethylene-butene copolymer, which is a linear triblock copolymer prepared by hydrogenating polystyrene-polybutadiene-polystyrene (SBS) to saturate double bonds.

Specifically, in the presence of a catalyst, SBS is hydrogenated in a directional manner to convert the polybutadiene chain segments into polyethylene (E) and polybutene (B) chain segments. Therefore, the hydrogenated SBS is called SEBS, also known as saturated SBS or hydrogenated SBS. Hydrogenated SBS has good heat resistance, aging resistance and excellent electrical properties.

In one embodiment of the present invention, relative to 100 parts by weight of the unsaturated polybutadiene rubber, the content of the hydrogenated ethylene-butene copolymer is 10 to 50 parts by weight, preferably 10 to 40 parts by weight, and more preferably 12 to 40 parts by weight.

The bismaleimide resin includes biphenyl bismaleimide resin and modified bismaleimide resin. The biphenyl bismaleimide resin helps to improve the peeling strength, reduce the dielectric constant and water absorption rate, and the modified bismaleimide resin helps to reduce the dielectric constant and improve the mechanical strength. In one embodiment of the present invention, relative to 100 parts by weight of unsaturated polybutadiene rubber, the content of the bismaleimide resin is 30 to 60 parts by weight, preferably 35 to 50 parts by weight, and more preferably 35 to 45 parts by weight.

It is worth noting that in the resin composition of the present invention, the weight ratio of the biphenyl type bismaleimide resin to the modified bismaleimide resin is 1:2, 1:3, 1:4, 1:5 or any number between 1:2 and 1:5. Adding the biphenyl type bismaleimide resin and the modified bismaleimide resin to the resin composition at the same time helps to improve the glass strength between the resin composition and the metal, reduce the water absorption rate of the resin composition, and at the same time has excellent dielectric properties.

The biphenyl type bismaleimide resin undergoes polymerization reaction with the unsaturated diene rubber in the formulation. The biphenyl type bismaleimide resin has the chemical structure of the following formula (I): Among them, n=1~5.

The modified bismaleimide resin can be prepared using an aromatic amine resin as a precursor in a non-water-soluble solvent. For example, the aromatic amine resin can have a structure of the following formula (A) or formula (B), preferably a structure of formula (A) with lower crystallinity: Among them, n=1~5.

In one embodiment of the present invention, the method for preparing the modified bismaleimide resin is to dissolve the aromatic amine resin of formula (A) or formula (B) in a water-insoluble solvent, then add anhydrous maleic acid to generate acylamine, then add a catalyst, remove the azeotropic water during the reaction to the outside of the system, and return toluene to the system to carry out the maleimidization reaction.

The non-water-soluble solvent may be an aromatic solvent, an aliphatic solvent, an ether, an ester, and a ketone solvent. For example, the solvent may be aromatic toluene, xylene, etc.; the aliphatic solvent may be cyclohexane, n-hexane, etc.; the ether solvent may be diethyl ether, diisopropyl ether, etc.; the ester solvent may be ethyl acetate, butyl acetate, etc.; the ketone solvent may be methyl isobutyl ketone, cyclopentanone, etc. In addition, the non-water-soluble solvent may also be used in combination with an aprotic polar solvent, preferably in combination with an aprotic polar solvent having a higher boiling point than the non-aqueous solvent. Examples of the aprotic polar solvent that can be used include dimethyl sulfone, dimethyl sulfone, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and N-methyl-2-pyrrolidone. However, the present invention is not limited to the above examples.

In addition, acidic catalysts such as toluenesulfonic acid, hydroxy-p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, phosphoric acid, etc. can be used in the reaction. The amount of the acidic catalyst used is generally 0.1 wt % to 10 wt %, preferably 1 wt % to 5 wt % relative to the aromatic amine resin.

After the maleimidation reaction, water is added to the reaction solution to separate it into a resin solution layer and a water layer. The water layer is removed repeatedly to completely remove the excess maleic acid or maleic anhydride, the aprotic polar solvent, and the catalyst. The catalyst is added again, and the residual acylamine is subjected to a dehydration ring-closing reaction under heating reflux conditions for 1 to 5 hours, preferably 1 to 3 hours, to obtain a bismaleimide resin solution with a low acid value. After the reaction is completed, the solution is cooled and repeatedly washed with water until the washing water becomes neutral. Then, after removing water by azeotropic dehydration under heating and reduced pressure, the solvent can be distilled off, or other solvents can be added to adjust the resin solution to the desired concentration. The solvent can also be completely distilled off to take out in the form of a solid resin.

In one embodiment of the present invention, the modified bismaleimide resin is N,N'-(phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide (N,N'-(phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide), which has the following structure (II): Among them, n=1~5.

In one embodiment of the present invention, the modified bismaleimide resin is N,N'-(1,3-phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide, which has the following structure (III): Among them, n=1~5.

In one embodiment of the present invention, the resin composition containing biphenyl bismaleimide of the present invention further includes a crosslinking agent, which can be a vinyl compound with a small molecular weight, such as a vinyl compound with a molecular weight less than or equal to 1500. Preferably, the molecular weight of the vinyl compound can be between 200 and 1000. For example, the vinyl compound can be any one of trimethylallyl isocyanate (TMAIC), triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), 1,2,4-trivinylcyclohexane (TVCH), diallyl isophthalate (DAIP), 4-tert-butylstyrene (TBS) or a combination thereof. However, the present invention is not limited to the above examples.

In the resin composition of the present invention, a highly stable vinyl compound can be selected as a crosslinking agent, such as trimethylallyl isocyanate (TMAIC), which has a high thermal stability trifunctional monomer, making it have a very low homopolymerization tendency, and also has a lower vapor pressure at high temperature compared to other crosslinking agents (such as TAIC), and is very stable when exposed to water and inorganic acids. When used in polymer reactions, it can improve compression deformation, elastic modulus, aging performance and chemical resistance. Relative to 100 parts by weight of unsaturated polybutadiene rubber, the content of the crosslinking agent can be 5 to 15 parts by weight, preferably 5 to 10 parts by weight, and more preferably 8 to 10 parts by weight. When the content of the crosslinking agent is less than 5 parts by weight, a good crosslinking effect cannot be exerted. When the content of the crosslinking agent is greater than 15 parts by weight, the viscosity is easily too high and the processability is affected.

In one embodiment of the present invention, the resin composition containing biphenyl type bismaleimide of the present invention further includes a crosslinking accelerator for effectively bonding the crosslinking agent with the resin. The crosslinking accelerator can be a peroxide with a half-life of 10 hours and a temperature range of 116°C to 128°C. For example, the peroxide used in the present invention can be diisopropylbenzene peroxide, α,α'-bis(tert-butylperoxy)diisopropylbenzene and 2,5-dimethyl-2,5-bis(tert-butylperoxy)-3-hexyne. However, the present invention is not limited to the above examples. Relative to 100 parts by weight of the unsaturated polybutadiene rubber, the amount of the crosslinking promoter added may be 0.5 to 1 part by weight, preferably 0.6 to 0.9 part by weight, and more preferably 0.7 to 0.9 part by weight.

In one embodiment of the present invention, the resin composition containing biphenyl bismaleimide of the present invention further includes a silane coupling agent. The silane coupling agent helps to improve the mechanical properties and dispersibility of the resin composition, strengthen the bonding effect, etc. Since the silane coupling agent contains a relatively long bond, it can form a flexible interface layer that is conducive to stress relaxation, absorb and disperse impact energy, and obtain good impact strength and toughness. For example, the silane coupling agent can be aminosilane, vinylsilane, (meth)acrylic silane, isocyanate silane, isocyanurate silane, ethylsilane, urea silane, styryl silane, cationic silane, phenylsilane, and acid anhydride, etc. However, any silane coupling agent used for surface treatment of general inorganic substances can be used as the silane coupling agent of the present invention.

For example, the aminosilane may be 3-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3 -aminopropyl dimethoxymethyl silane, N-(2-aminoethyl)-3-aminopropyl diethoxymethyl silane, N-phenyl-3-aminopropyl trimethoxy silane, N-phenyl-3-aminopropyl triethoxy silane, [3-(6-aminohexylamino)propyl]trimethoxy silane, and [3-(N,N-dimethylamino)-propyl]trimethoxy silane, etc. The vinyl silane can be vinyl tris(2-methoxyethoxy) silane, vinyl trimethoxy silane, vinyl triethoxy silane, dimethoxymethyl vinyl silane, diethoxymethyl vinyl silane, trimethoxy(7-octen-1-yl) silane, and trimethoxy(4-vinylphenyl) silane, etc. The epoxysilane may be γ-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyldiethoxymethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, [8-(glycidoxy)-n-octyl]trimethoxysilane, or the like. (Meth)acrylic silane may be 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-methacryloxypropyl dimethoxymethyl silane, 3-methacryloxypropyl diethoxymethyl silane, methacryloxypropyl trimethoxy silane, γ-acryloxypropyl trimethoxy silane, 3-acryloxypropyl triethoxy silane, etc. Isocyanate silane may be 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl triethoxy silane, etc. Isocyanurate silane may be 3-(trimethoxysilylpropyl) isocyanurate, etc. The butyl silane may be 3-butyl propyl trimethoxy silane, 3-butyl propyl dimethoxy methyl silane, etc. The ureido silane may be 3-butyl propyl triethoxy silane, etc. The styryl silane may be p-styryl trimethoxy silane, etc. The cationic silane may be N-β-(N-vinyl benzylaminoethyl)-γ-aminopropyl trimethoxy silane hydrochloride, etc. The acid anhydride may be [3-(trimethoxysilyl)propyl] succinic anhydride, etc. The phenyl silane may be phenyl trimethoxy silane, phenyl triethoxy silane, dimethoxy methyl phenyl silane, diethoxy methyl phenyl silane, and p-tolyl trimethoxy silane, etc. The aryl silane may be trimethoxy (1-naphthyl) silane, etc. The above silane coupling agents may be used alone or in combination of two or more silane coupling agents.

In one embodiment of the present invention, KBM503 (Shin-Etsu Chemical Co., Ltd., Japan) can be used as a silane coupling agent. Relative to 100 parts by weight of unsaturated polybutadiene rubber, the amount of the silane coupling agent added can be 0.1 to 1 part by weight, preferably 0.1 to 0.5 part by weight, and more preferably 0.2 to 0.4 part by weight.

In one embodiment of the present invention, the resin composition containing biphenyl bismaleimide of the present invention further includes a flame retardant. The flame retardant may be selected from the group consisting of resorcinol dixylenylphosphate (RDXP (e.g., PX-200)), melamine polyphosphate, tri(2-carboxyethyl)phosphine (TCEP), trimethyl phosphate (TMP), tri(isopropyl chloride)phosphate, dimethyl methyl phosphonate (DMMP), bisphenol diphenyl phosphate, ammonium polyphosphate, hydroquinone bis-(diphenyl phosphate), and bisphenol A bis-(diphenyl phosphate).

In the resin composition of the present invention, the amount of the flame retardant added can be 20 to 50 parts by weight, preferably 30 to 50 parts by weight, and more preferably 30 to 40 parts by weight, relative to 100 parts by weight of the unsaturated polybutadiene rubber. When the amount of the flame retardant added is less than 20 parts by weight, a good flame retardant effect cannot be achieved. When the amount of the flame retardant added is greater than 50 parts by weight, the heat resistance of the composition may decrease and the water absorption rate may increase.

In one embodiment of the present invention, the resin composition containing biphenyl bismaleimide of the present invention further includes an inorganic filler. The inorganic filler may be surface treated in advance with a silane coupling agent to improve the dispersibility and adhesion of the inorganic filler in the resin. Preferably, the inorganic filler may be a spherical, flaky, granular, columnar, plate-like, needle-like or irregular inorganic filler. Preferably, the inorganic filler is selected from the group consisting of silicon dioxide (such as molten, non-molten, porous or hollow silicon dioxide), aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, barium sulfate, magnesium carbonate, barium carbonate, mica, talc, and graphene.

Inorganic fillers can reduce the thermal expansion coefficient of the composition, and can also reduce costs and improve mechanical strength. In the resin composition of the present invention, relative to 100 parts by weight of unsaturated polybutadiene rubber, the content of inorganic fillers is 80 to 110 parts by weight, preferably 80 to 105 parts by weight, and more preferably 90 to 105 parts by weight. When the content of inorganic fillers is less than 80 parts by weight, the dielectric properties will not meet the application requirements of communication substrates, and when the content of inorganic fillers is greater than 110 parts by weight, unnecessary manufacturing costs will be increased.

In order to make the above-mentioned objects and other objects, features and advantages of the present invention more clearly understood, several embodiments are described in detail as follows: The resin compositions of Examples 1 to 6 (E1 to E6) are listed in Table 1 below, and the resin compositions of Comparative Examples 1 to 5 (C1 to C5) are listed in Table 2 below.

Table 1 Element E1 E2 E3 E4 E5 E6 Unsaturated diene rubber 100 100 100 100 100 100 Hydrogenated ethylene-butene copolymer 40 28 17 27 19 12 Formula I bismaleimide resin 14 11 9 13 11 9 Formula II bismaleimide resin 28 33 36 - - - Formula III bismaleimide resin - - - 26 33 36 Crosslinking agent A 10 9 8 - - - Crosslinking agent B - - - 9 9 9 Flame retardant (PX200) 40 36 32 36 36 36 Crosslinking promoter 0.8 0.7 0.7 0.7 0.9 0.7 Silane coupling agent 0.31 0.28 0.26 0.28 0.27 0.26 Inorganic filler 99 94 91 90 104 84 Crosslinking agent A: Triallyl isocyanurate (TAIC) Crosslinking agent B: Trimethylallyl isocyanate (TMAIC)

Table 2 Element C1 C2 C3 C4 C5 Unsaturated diene rubber 100 100 100 100 100 Hydrogenated ethylene-butene copolymer 27 18 82 82 82 Formula I bismaleimide resin 19 27 20 14 14 Formula II bismaleimide resin - - - 84 - Formula III bismaleimide resin - - - - 84 Crosslinking agent A 20 10 15 15 - Crosslinking agent B - - - - 15 Flame retardant (PX200) 37 36 54 54 54 Crosslinking promoter 0.7 0.7 1.1 1.1 1 Silane coupling agent 0.28 0.27 0.41 0.41 0.41 Inorganic filler 93 91 135 135 135

The resin compositions of the above-mentioned embodiments E1 to E6 and comparative examples C1 to C5 are coated on glass fiber cloth respectively, and then the excess resin is scraped off by a metering roller, and then put into a gluing furnace for baking for a certain period of time to evaporate the solvent and solidify the resin to a certain degree, and then cooled and rolled to form a semi-cured film. Then, four sheets and two sheets of semi-cured films from the same batch of the semi-cured films are taken. μm copper foil was stacked in the order of copper foil, four semi-cured adhesive sheets, and copper foil. The copper foil substrate was then pressed at 220℃ for 2 hours under vacuum conditions. The four semi-cured adhesive sheets were cured to form an insulating layer between the two copper foils. The physical properties of the copper foil substrate were evaluated and the test results are recorded in Tables 3 and 4.

Table 3 Physical properties E1 E2 E3 E4 E5 E6 Peel strength Lb/Inch 4.7 4.3 4.7 4.5 4.5 4.6 Tg ℃ 198 216 207 208 213 209 D _k 10G 3.14 3.21 3.19 3.22 3.27 3.24 _D 10G 0.0032 0.0038 0.0033 0.0031 0.004 0.0037 Water absorption % PCT/121℃/1hr 0.35 0.37 0.34 0.37 0.36 0.38

Table 4 Physical properties C1 C2 C3 C4 C5 Peel strength Lb/Inch 2.3 3.6 4.1 3 2.8 Tg ℃ 202 171 186 186 186 D _k 10G 3.27 3.23 3.22 3.63 3.71 _D 10G 0.0029 0.0035 0.0023 0.0033 0.0036 Water absorption % PCT/121℃/1hr 0.42 0.4 0.45 0.44 0.46

The peel strength is based on IPC-TM650 specification, using a universal tensile tester to test the adhesion between the copper foil and the circuit board substrate in the copper foil substrate.

The glass transition temperature (Tg) is determined by differential scanning calorimetry (DSC) according to the DSC method specified in IPC-TM-6502.4.25.

The dielectric properties are tested according to IPC-TM-650 2.5.5 test specification. The dielectric constant (D _k ) represents the electronic insulation properties of the film. The lower the value, the better the electronic insulation properties. The dielectric loss (D _f ) represents the ability of a substance to absorb microwaves of a certain frequency at a certain temperature. Usually in the specifications of communication products, the dielectric loss value should be as low as possible.

The water absorption test is to place the prepared copper-clad laminate in a pressure cooker at 121°C and 1.1 kgf/cm2 for 1 hour and then measure its weight change.

As shown in Tables 1 to 4, the present invention adds hydrogenated ethylene-butene copolymer to increase toughness, but when too much hydrogenated ethylene-butene copolymer is added, the water absorption rate will increase (such as comparative example C3). Water absorption rate can also be called hygroscopicity, which is used to determine the extent to which the copper-clad substrate expands and deforms or absorbs moisture due to the temperature and humidity of the environment. When the water absorption rate increases, it means that the copper-clad substrate has a high water content and humidity, which is prone to cracking.

Bismaleimide resin helps to improve peel strength, reduce dielectric coefficient, reduce water absorption and improve dielectric strength. However, compared with using only one bismaleimide resin (such as Comparative Examples C1 to C3), using a mixture of biphenyl type bismaleimide resin and modified bismaleimide resin (such as Examples E1 to E6) can not only improve the glass strength between the resin composition and the metal, reduce the water absorption of the resin composition, but also take into account excellent dielectric properties.

It is worth noting that the above effect can not be achieved by simply mixing biphenyl type bismaleimide resin and modified bismaleimide resin. As shown in Comparative Examples C4 and C5, when the weight ratio of biphenyl type bismaleimide resin and modified bismaleimide resin is outside 1:2-5, not only the glass strength between the resin composition and the metal cannot be improved, but also the water absorption, D _k and D _f of the resin composition are increased, and even the glass transition temperature is reduced.

In addition, according to the contents shown in Tables 1 to 4, when the weight ratio of the crosslinking agent to the flame retardant is 1:4, a more stable resin composition can be obtained, and the adhesion between the copper foil and the circuit board substrate is further improved.

In summary, the resin composition containing biphenyl bismaleimide of the present invention not only adds bismaleimide to the resin composition, but also further finds that the use of a specific ratio of biphenyl bismaleimide resin and modified bismaleimide resin enables the resin composition to meet the requirements of high peel strength and low dielectric loss when applied to a copper foil substrate.

[Beneficial Effects of Embodiments]

One of the beneficial effects of the present invention is that the resin composition containing biphenyl type bismaleimide provided by the present invention can meet the requirements of high peel strength (for example, peel strength greater than or equal to 4.3) by means of the technical scheme of "comprising unsaturated diene rubber, hydrogenated ethylene-butene copolymer and bismaleimide resin" and "the weight ratio of biphenyl type bismaleimide resin to modified bismaleimide resin is 1:2-5". Lb/Inch) and low dielectric loss (e.g. dielectric loss less than or equal to 3.0), and is suitable as a high-end copper clad laminate material, which can be applied to resin compositions, prepregs, laminates and printed circuit boards for electronic circuits.

Furthermore, the resin composition containing biphenyl bismaleimide provided by the present invention can improve the glass strength between the resin composition and the metal and reduce the water absorption rate of the resin composition through the technical solution of "relative to 100 parts by weight of unsaturated polybutadiene rubber, the content of hydrogenated ethylene-butene copolymer is 10 to 50 parts by weight". It can also take into account excellent dielectric properties.

The contents disclosed above are only preferred feasible embodiments of the present invention and are not intended to limit the scope of the patent application of the present invention. Therefore, all equivalent technical changes made using the contents of the present invention specification are included in the scope of the patent application of the present invention.

without.

Claims (8)

A resin composition containing biphenyl bismaleimide, comprising: unsaturated diene rubber, hydrogenated ethylene-butene copolymer; and bismaleimide resin, wherein the bismaleimide resin comprises biphenyl bismaleimide resin and modified bismaleimide resin; wherein the weight ratio of the biphenyl bismaleimide resin to the modified bismaleimide resin is 1:2-5; wherein the content of the hydrogenated ethylene-butene copolymer is 10 to 50 parts by weight relative to 100 parts by weight of the unsaturated polybutadiene rubber; wherein the biphenyl bismaleimide resin has a structure of the following formula (I):

Wherein, n=1-5; wherein the modified bismaleimide resin has a structure of the following formula (II):

Among them, n=1~5. The resin composition containing biphenyl bismaleimide as described in claim 1, wherein the unsaturated diene rubber is polybutadiene rubber. The resin composition containing biphenyl-type bismaleimide as claimed in claim 1, wherein the modified bismaleimide resin has a structure of the following formula (III):

Among them, n=1~5. The resin composition containing biphenyl-type bismaleimide as described in claim 1 further includes a crosslinking agent, the molecular weight of the crosslinking agent is less than or equal to 1500. The resin composition containing biphenyl bismaleimide as described in claim 4, wherein the crosslinking agent is selected from the group consisting of trimethylallyl isocyanate (TMAIC), triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), 1,2,4-trivinylcyclohexane (TVCH), diallyl isophthalate (DAIP) and 4-tert-butylstyrene (TBS). The resin composition containing biphenyl bismaleimide as described in claim 1 further includes a crosslinking accelerator, and the crosslinking accelerator is a peroxide. The resin composition containing biphenyl-type bismaleimide as described in claim 1 further includes a silane coupling agent, a flame retardant and an inorganic filler, wherein the flame retardant is selected from phosphate compounds or nitrogen-containing phosphate compounds. The resin composition containing biphenyl-type bismaleimide as described in claim 7, wherein the inorganic filler is pre-surface-treated with the silane coupling agent.