CN108715666B

CN108715666B - Thermosetting resin composition, prepreg, laminate, and printed wiring board

Info

Publication number: CN108715666B
Application number: CN201810396597.4A
Authority: CN
Inventors: 邢燕侠; 柴颂刚
Original assignee: Shengyi Technology Co Ltd
Current assignee: Shengyi Technology Co Ltd
Priority date: 2018-04-27
Filing date: 2018-04-27
Publication date: 2021-03-02
Anticipated expiration: 2038-04-27
Also published as: CN108715666A

Abstract

The present disclosure provides a thermosetting resin composition, a prepreg, a laminate, and a printed circuit board. The thermosetting resin composition includes: a brominated epoxy resin, a hardener, and a manganese oxide, wherein the manganese oxide is a mixture of two or more of manganese monoxide, manganese dioxide, manganese sesquioxide, and manganese tetraoxide, wherein the molar number of divalent manganese ions in the manganese oxide: the sum of the number of moles of trivalent manganese ions and the number of moles of tetravalent manganese ions is 1: 1 to 10: 1. By including the defined manganese oxide in the thermosetting resin composition, the thermal decomposition temperature of the thermosetting resin composition is significantly increased, so that the heat resistance thereof is significantly improved. In addition, the copper-clad laminate made of the high-heat-resistance thermosetting resin composition has good comprehensive performance and high heat resistance, and meets the requirements in processing and assembling of printed circuit boards.

Description

Thermosetting resin composition, prepreg, laminate, and printed wiring board

Technical Field

The present disclosure relates to a thermosetting resin composition and a prepreg. In particular, the present disclosure relates to a thermosetting resin composition, a prepreg, a laminate and a printed circuit board.

Background

With the rapid development of electronic products in the aspects of miniaturization, multi-functionalization, high performance and high reliability, printed circuit boards are rapidly developed in the directions of high precision, high density, high performance, microporosity, thinning and multilayering, and have wider and wider application range, and rapidly enter civil electric appliances and related products from industrial large-scale electronic computers, communication instruments, electrical measurement, national defense, aviation, aerospace and other departments. The base material largely determines the performance of the printed circuit board, so that the development of a new generation of base material is urgently needed. The substrate material as a future new generation must have high heat resistance, low thermal expansion coefficient, and excellent chemical stability and mechanical properties.

Brominated epoxy resins have been widely used for the production of laminates for printed circuits because of their good flame retardancy. The copper clad laminate is required to have good heat resistance in response to the requirements for processing and assembling of the printed circuit board. The temperature at which the sheet loses 5% weight in the TGA test (also known as the thermal decomposition temperature) is commonly used in the industry to characterize the heat resistance of the sheet, the higher the thermal decomposition temperature, the better the heat resistance of the sheet.

At present, the methods for improving the heat resistance of the plate in the copper-clad plate industry comprise the following steps:

1. the use of high heat-resistant hardeners, such as phenolic resins, instead of dicyandiamide, however, this method causes problems of difficult curing and poor sheet processability; and

2. highly heat-resistant epoxy resins such as biphenyl type epoxy resins, DCPD (dicyclopentadiene) type epoxy resins, phenol type polyfunctional epoxy resins are used, but these highly heat-resistant epoxy resins are used in large amounts and are expensive.

Disclosure of Invention

Accordingly, there is a need for a high heat resistant thermosetting resin composition comprising an epoxy resin that can improve the thermal stability of the epoxy resin without significantly adversely affecting other properties of the composition.

There is also a need to provide a copper clad laminate manufactured using the above thermosetting resin composition having high heat resistance, which has good overall properties and high heat resistance, and meets the requirements in the processing and assembly of printed circuit boards.

In one aspect, the present disclosure provides a thermosetting resin composition comprising:

a brominated epoxy resin, which is a brominated epoxy resin,

a hardener, and

an oxide of manganese, which is a metal oxide,

wherein the manganese oxide is a mixture of two or more of manganese monoxide, manganese dioxide, manganese sesquioxide and manganomanganic oxide, wherein the molar number of divalent manganese ions in the manganese oxide is: the sum of the number of moles of trivalent manganese ions and the number of moles of tetravalent manganese ions is 1: 1 to 10: 1.

According to one embodiment of the present disclosure, the content of the manganese oxide in the thermosetting resin composition is 0.1 to 20% by weight.

According to another embodiment of the present disclosure, the radium oxide has a particle size less than 50 μm.

According to another embodiment of the present disclosure, the surface of the manganese oxide has an organic coating layer or an inorganic coating layer. The organic coating layer is a silane coupling agent coating layer, or the inorganic coating layer is a silicon dioxide, aluminum oxide or magnesium oxide coating layer.

According to another embodiment of the present disclosure, the brominated epoxy resin includes one or a combination of two or more of a tetrabromobisphenol a type epoxy resin, a high bromine type epoxy resin, a bromine-containing diphenylmethane diisocyanate modified epoxy resin, and a brominated phenol epoxy resin.

According to another embodiment of the present disclosure, the hardener is one or a combination of two or more of an amine type hardener, an anhydride type hardener, a phenolic resin type hardener, a reactive ester type hardener, a benzoxazine type hardener, and a cyanate ester type hardener.

According to another embodiment of the present disclosure, in the thermosetting resin composition, the brominated epoxy resin is contained in an amount of 20 to 98% by weight, and the hardener is contained in an amount of 1 to 30% by weight.

According to another embodiment of the present disclosure, the thermosetting resin composition further comprises an accelerator, wherein the accelerator is present in an amount of less than or equal to 10 wt% of the thermosetting resin composition. The accelerator is one or the combination of two or more of imidazole compounds, tertiary amine compounds, metal compounds and pyridine compounds.

According to another embodiment of the present disclosure, the thermosetting resin composition further comprises an inorganic filler different from the manganese oxide, wherein the content of the inorganic filler in the thermosetting resin composition is less than or equal to 60% by weight.

According to another embodiment of the present disclosure, the inorganic filler is one or a combination of two or more of crystalline silica micropowder, fused silica micropowder, spherical silica micropowder, titanium dioxide, aluminum hydroxide, magnesium hydroxide, talc, kaolin, calcium carbonate, mullite, calcium silicate, alumina, zinc oxide, and glass fiber.

According to another embodiment of the present disclosure, the thermosetting resin composition further comprises a solvent that is one or a combination of two or more of ketones, hydrocarbons, ethers, esters, or aprotic solvents.

In another aspect of the present disclosure, there is provided a prepreg comprising a reinforcing material and a thermosetting resin composition as described in any one of the above attached thereto after drying by impregnation.

In a further aspect of the present disclosure there is provided a laminate comprising at least one prepreg as described above.

In a further aspect of the present disclosure, there is provided a printed circuit board containing at least one prepreg as described above.

According to the present disclosure, by including the defined manganese oxide in the thermosetting resin composition, the thermal decomposition temperature of the thermosetting resin composition is significantly increased, so that the heat resistance thereof is significantly improved. In addition, the copper-clad laminate made of the high-heat-resistance thermosetting resin composition has good comprehensive performance and high heat resistance, and meets the requirements in processing and assembling of printed circuit boards.

Detailed Description

The technical solutions in the examples of the present disclosure will be clearly and completely described below in connection with the specific embodiments of the present disclosure, and it is obvious that the described embodiments and/or examples are only a part of the embodiments and/or examples of the present disclosure, and not all embodiments and/or examples. All other embodiments and/or all other examples that can be obtained by one of ordinary skill in the art without making any inventive step based on the embodiments and/or examples in the present disclosure are within the scope of the present disclosure.

In the present disclosure, all numerical features are meant to be within the error of measurement, for example within ± 10%, or within ± 5%, or within ± 1% of the defined numerical value.

The term "comprising", "including" or "containing" as used in this disclosure means that it may have, in addition to the recited components, other components which impart different properties to the prepreg. In addition, the terms "comprising," including, "or" containing "as used in this disclosure may also include" consisting essentially of, and may instead be "or" consisting of.

In the present disclosure, amounts, ratios, etc., are by weight if not specifically indicated.

In the present disclosure, the content of the component in the thermosetting resin composition means the content of the component in the thermosetting resin composition excluding the solvent.

As described above, the present disclosure may provide a thermosetting resin composition including: a thermosetting resin composition comprising:

a brominated epoxy resin, which is a brominated epoxy resin,

a hardener, and

an oxide of manganese, which is a metal oxide,

wherein the manganese oxide is a mixture of two or more of manganese monoxide, manganese dicyanide, manganese sesquioxide and manganomanganic oxide, wherein the molar number of divalent manganese ions in the manganese oxide is: the sum of the number of moles of trivalent manganese ions and the number of moles of tetravalent manganese ions is about 1: 1 to 10: 1.

The inventors of the present disclosure found through research that: the manganese ions having electrophilic properties are bonded to the electron-rich halogen to form a transition state, thereby protecting C — Br bonds and further playing a role in improving the heat resistance of a product (hereinafter, also referred to as a cured product) obtained after curing the thermosetting resin composition, but the C — Br bonds are not easily broken and rather deteriorate the flame retardancy of the cured product. The valence of the manganese ion is different, the electrophilic ability is different, and the protection ability for C-Br bond is different. Therefore, when the number of moles of the divalent manganese ion in the manganese oxide: when the sum of the number of moles of trivalent manganese ions and the number of moles of tetravalent manganese ions is less than 1: 1, the cured product obtained by curing the thermosetting resin composition will have poor flame retardancy. When the mole number of the divalent manganese ions in the manganese oxide: when the sum of the number of moles of trivalent manganese ions and the number of moles of tetravalent manganese ions is more than 10: 1, the heat resistance of the cured product is not significantly improved.

Preferably, the molar number of the divalent manganese ion in the manganese oxide is: the sum of the moles of trivalent manganese ions and the moles of tetravalent manganese ions is from about 1: 1 to about 7: 1.

The particle size of the manganese oxide is less than 50 mu m. Preferably, the particle size of the manganese oxide is less than 20 μm. By setting the average particle size of the inorganic filler to 50 μm or less, the probability of mixing coarse particles can be reduced and the occurrence of defects in the coarse particles can be suppressed.

In the thermosetting resin composition, the content of the manganese oxide is 0.1 to 20% by weight, preferably 0.5 to 5% by weight. If the content is less than 0.1% by weight based on the total weight of the resin composition, no significant effect is produced, and if the content is more than 20% by weight based on the total weight of the resin composition, the original overall properties of the resin composition are impaired.

The surface of the manganese oxide has an organic or inorganic coating layer. The organic or inorganic coating layer can improve the compatibility between the manganese oxide and the resin matrix, thereby improving the dispersibility of the manganese oxide.

The organic coating layer is a silane coupling agent coating layer, and the silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for the surface treatment of the inorganic strips. Specific examples thereof include an aminosilane-based material such as γ -aminopropyltriethoxysilane and N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane, an alkoxysilane-based material such as γ -glycidoxypropyltrimethoxysilane, a vinylsilane-based material such as γ -methacryloxypropyltrimethoxysilane, an anionic silane-based material such as N- β - (N-vinylphenylamidoethyl) - γ -aminopropyltrimethoxysilane hydrochloride, and a phenylsilane-based material, and 1 or at least 2 of these materials may be used in appropriate combination.

The inorganic coating layer is one or more of silicon dioxide, aluminum oxide and magnesium oxide.

The brominated epoxy resin may comprise from about 20 wt% to about 98 wt%, preferably from about 25 wt% to about 95 wt%, and more preferably from about 30 wt% to about 90 wt% of the total weight of the thermosetting resin composition. The mass percent of the thermosetting resin relative to the total weight of the thermosetting resin composition can be, for example, about 23 wt%, about 26 wt%, about 31 wt%, about 35 wt%, about 39 wt%, about 43 wt%, about 47 wt%, about 51 wt%, about 55 wt%, about 59 wt%, about 63 wt%, about 67 wt%, about 70 wt%, about 75 wt%, about 80 wt%, about 85 wt%, about 90 wt%, about 95 wt%, about 96 wt%, or about 98 wt%, and any range therebetween, such as, for example, about 23 wt%, about 26 wt%, about 31 wt%, about 35 wt%, or about 39 wt% to about 43 wt%, about 47 wt%, about 51 wt%, about 55 wt%, about 59 wt%, about 63 wt%, about 67 wt%, about 70 wt%, about 75 wt%, about 80 wt%, or any range therebetween, such as, for example, about 23 wt%, about 26 wt%, about 31 wt%, about 35 wt%, or about 39 wt% to about 43 wt%, about 47 wt%, about 51 wt%, about 55 wt%, about 59 wt%, about 63 wt%, about 67 wt%, about 85 wt%, about 90 wt%, about 95 wt%, about 96 wt%, or about 98 wt%.

Examples of amine hardeners may include: dicyandiamide and diaminodiphenyl sulfone.

Examples of the acid anhydride-based hardener may include: styrene maleic anhydride.

Examples of the phenolic resin-based hardener may include: phenol-type phenol resins, o-cresol-type phenol resins, and linear bisphenol a phenol resins.

Examples of active ester hardeners may include: dicyclopentadiene phenol type active ester.

Examples of the benzoxazine-based hardener may include: bisphenol a type benzoxazine, bisphenol F type benzoxazine and MDA type benzoxazine.

Examples of cyanate ester type hardeners may include: bisphenol A cyanate ester.

The hardener can comprise about 1 wt% to about 30 wt%, preferably about 4 wt% to about 25 wt%, more preferably about 10 wt% to about 20 wt%, such as about 2 wt%, about 5 wt%, about 8 wt%, about 11 wt%, about 14 wt%, about 17 wt%, about 19 wt%, about 22 wt%, about 26 wt%, or about 28 wt% and any range therebetween, such as about 2 wt%, about 5 wt%, about 8 wt%, about 11 wt%, or about 14 wt% to about 17 wt%, about 19 wt%, about 22 wt%, about 26 wt%, or about 28 wt%, based on the total weight of the thermosetting resin composition.

According to another embodiment of the present disclosure, the thermosetting resin composition may further include an accelerator. The accelerator is one or the combination of two or more of imidazole compounds, tertiary amine compounds, metal compounds and pyridine compounds.

Examples of imidazole compounds may include: 2-methylimidazole, 2-ethylimidazole and 4-methylimidazole.

Examples of the tertiary amine compound may include: n-alkyl marines, N-alkyl alkanolamines, N, N-dialkyl cyclohexylamines, and alkylamines, wherein alkyl is methyl, ethyl, propyl, butyl and isomeric forms thereof, and heterocyclic amines.

Examples of the metal compound may include: zinc isooctoate and cobalt acetylacetonate.

Examples of the pyridine compound may include: 4-Dimethylaminopyridine (DMAP).

The accelerator may be present in the thermosetting resin composition in an amount greater than 0 and less than or equal to about 10 wt%, preferably in an amount ranging from about 1 wt% to about 10 wt%, and more preferably in an amount ranging from about 2 wt% to about 8 wt%, such as about 0.5 wt%, about 1.5 wt%, about 2.5 wt%, about 3.5 wt%, about 4.5 wt%, about 5.5 wt%, about 6.5 wt%, about 7.5 wt%, about 8.5 wt%, or about 9.5 wt%, and any range therebetween, such as about 0.5 wt%, about 1.5 wt%, about 2.5 wt%, about 3.5 wt%, or about 4.5 wt% to about 5.5 wt%, about 6.5 wt%, about 7.5 wt%, about 8.5 wt%, or about 9.5 wt%.

The inorganic filler is one or the combination of two or more of crystalline silica micropowder, fused silica micropowder, spherical silica micropowder, titanium dioxide, aluminum hydroxide, magnesium hydroxide, talcum powder, kaolin, calcium carbonate, mullite, calcium silicate, alumina, zinc oxide and glass fiber.

According to another embodiment of the present disclosure, the thermosetting resin composition further comprises an inorganic filler different from the manganese oxide. The inorganic filler may be present in an amount of about 10 wt% to about 80 wt%, preferably about 20 wt% to about 60 wt%, such as about 23 wt%, about 28 wt%, about 32 wt%, about 37 wt%, about 42 wt%, about 47 wt%, about 52 wt%, about 57 wt%, about 62 wt%, about 67 wt%, about 72 wt%, about 76 wt%, or about 78 wt% and any range therebetween, such as about 23 wt%, about 28 wt%, about 32 wt%, about 37 wt%, or about 42 wt% to about 47 wt%, about 52 wt%, about 57 wt%, about 62 wt%, about 67 wt%, about 72 wt%, about 76 wt%, or about 78 wt%, based on the total weight of the thermosetting resin composition.

By setting the content of the inorganic filler within the range, the moldability and low thermal expansion of the thermosetting resin composition can be well maintained.

According to another embodiment of the present disclosure, the inorganic filler may be selected from: any one or a mixture of at least two of crystalline silica micropowder, fused silica micropowder, spherical silica micropowder, titanium dioxide, aluminum hydroxide, magnesium hydroxide, talcum powder, kaolin, calcium carbonate, mullite, calcium silicate, alumina, zinc oxide and glass fiber.

According to another embodiment of the present disclosure, the inorganic filler may have an average particle diameter of about 0.1 μm to about 100 μm, preferably about 0.5 μm to about 20 μm. When the average particle diameter of the inorganic filler is within the above range, the flowability of the thermosetting resin composition at the time of high-level filling can be favorably maintained, and the probability of mixing coarse particles can be reduced and the occurrence of defects in the coarse particles can be suppressed. Here, the average particle diameter refers to a particle diameter corresponding to a point of 50% by volume when a cumulative power distribution curve based on the particle diameter is obtained with the total volume of the particles as 100%, and can be measured by a particle size distribution using a laser diffraction scattering method.

According to another embodiment of the present disclosure, the thermosetting resin composition further comprises a solvent.

The present disclosure may also provide a prepreg comprising a reinforcing material and a thermosetting resin composition as described in any one of the above attached thereto by impregnation drying.

Examples of the reinforcing material may include glass cloth. In the following description, the glass cloth reinforcing material and the glass cloth may be used interchangeably.

The thermosetting resin composition may further include a silane coupling agent or/and a wetting dispersant. The silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for the surface treatment of the inorganic textured surface. Specific examples thereof include an aminosilane-based material such as γ -aminopropyltriethoxysilane and N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane, an alkoxysilane-based material such as γ -glycidoxypropyltrimethoxysilane, a vinylsilane-based material such as γ -methacryloxypropyltrimethoxysilane, an anionic silane-based material such as N- β - (N-vinylphenylamidoethyl) - γ -aminopropyltrimethoxysilane hydrochloride, and a phenylsilane-based material, and 1 or at least 2 of these materials may be used in appropriate combination. The wetting dispersant is not particularly limited as long as it is used in the thermosetting resin composition. Examples thereof include wetting dispersants such as Disperbyk-110, 111, 180, 161, BYK-W996, W9010 and W903 manufactured by BYKChemie Japan.

The thermosetting resin composition may further contain various additives, and specific examples thereof include a flame retardant, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, and the like. These various additives may be used alone or in combination of two or more.

The thermosetting resin composition of the present disclosure can be prepared by a known method such as compounding, stirring, mixing the brominated epoxy resin, the hardener, and the manganese oxide, and optionally various additives.

The solvent in the present disclosure is not particularly limited, and specific examples thereof include one or a combination of two or more of ketones, hydrocarbons, ethers, esters, or aprotic solvents, and preferably one or a mixture of at least two of acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, methanol, ethanol, primary alcohol, ethylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethyl acetate, N-dimethylformamide, and N, N-diethylformamide. The amount of the solvent to be used can be selected by those skilled in the art according to their own experience, so that the obtained resin glue solution has a viscosity suitable for use.

Specifically, the thermosetting resin composition is prepared into glue solution by mechanical stirring, emulsification or ball milling dispersion, then the glass fiber cloth is soaked by the glue solution, and the prepreg is obtained by drying. The prepreg and a metal foil such as a copper foil are hot-pressed in a vacuum press to prepare a laminate.

The present disclosure may also provide a laminate and a printed circuit board.

The laminate may contain at least one prepreg as described in any one of the above.

The printed circuit board may contain at least one prepreg as described in any one of the above.

Examples

The technical solution of the present disclosure is further explained by the following embodiments.

The manganese oxides used in the examples and comparative examples are as follows:

manganese monoxide (MnO), Aladdin, D50 ═ 1.2 μm

Manganese sesquioxide (Mn)₂O₃) Alatin, D50 ═ 1 μm

Manganese dioxide (MnO)₂) Alatin, D50 ═ 1.5 μm

Mangano manganic oxide (Mn)₃O₄) Alatin, D50 ═ 0.6 μm

Glass fiber cloth: e type 2116 glass fiber cloth, Ridong textile

Copper foil: futian (a kind of food)

D50: the term "average particle diameter" means a particle diameter corresponding to a point of 50% by volume when a cumulative power distribution curve based on the particle diameter is obtained with the total volume of the particles as 100%, and is measured by a particle size distribution measurement using a laser diffraction scattering method.

In the following examples and comparative examples, the 65 wt% resin dope means a resin dope having a content of a solvent (e.g., N-dimethylformamide or acetone) of (100-65) wt%.

The evaluation method comprises the following steps:

1) thermal decomposition temperature Td

The copper-clad laminates obtained in examples and comparative examples were measured by IPC-TM-6502.4.26 method

2) Thermal stratification time T260/T288

The copper-clad laminates obtained in examples and comparative examples were measured by IPC-TM-6502.4.24.1 method.

3) Flame retardancy test

With respect to the copper-clad laminates obtained in examples and comparative examples, the evaluation was made in accordance with UL94 method

4) Prepreg appearance

The prepreg was visually observed for its smoothness, presence of streaks and particle agglomeration.

Please describe the compounding of oxides of manganese used in the examples

Preparation of manganese oxide A (wherein the sum of the number of moles of divalent manganese ions: the number of moles of trivalent manganese ions and the number of moles of tetravalent manganese ions is 1: 1)

71g MnO and 17.4g MnO were weighed₂、63.2g Mn₂O₃Putting into a bottle, screwing the bottle cap, putting the bottle cap on a swing machine, and swinging for 4 hours to obtain the uniformly mixed manganese oxide A.

Preparation of manganese oxide B (wherein the sum of the number of moles of divalent manganese ions: the number of moles of trivalent manganese ions and the number of moles of tetravalent manganese ions is 5: 1)

71g of MnO and 3.48g of Mn0 were weighed₂、12.64g Mn₂O₃Putting into a bottle, screwing the bottle cap, putting the bottle cap on a swing machine, and swinging for 4 hours to obtain the uniformly mixed manganese oxide B.

Preparation of manganese oxide C (wherein the sum of the number of moles of divalent manganese ions: the number of moles of trivalent manganese ions and the number of moles of tetravalent manganese ions is 10: 1).

71g of MnO and 1.74g of MnO were weighed₂、6.32g Mn₂O₃Putting into a bottle, screwing the bottle cap, putting the bottle cap on a swing machine, and swinging for 4 hours to obtain the evenly mixed manganese oxide C.

Preparation of manganese oxide D (wherein the sum of the number of moles of divalent manganese ions: the number of moles of trivalent manganese ions and the number of moles of tetravalent manganese ions is 0.5: 1)

35.5g of MnO and 17.4g of Mn0 were weighed₂、63.2g Mn₂0₃Putting into a bottle, screwing the bottle cap, putting the bottle cap on a swing machine, and swinging for 4 hours to obtain the uniformly mixed manganese oxide D.

Preparation of manganese oxide E (wherein the sum of the number of moles of divalent manganese ions: the number of moles of trivalent manganese ions and the number of moles of tetravalent manganese ions is 15: 1)

1065g of MnO and 17.4g of Mn0 were weighed₂、63.2g Mn₂O₃Putting into a bottle, screwing the bottle cap, putting the bottle cap on a swing machine, and swinging for 4 hours to obtain the evenly mixed manganese oxide E.

Example 1

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 3 parts by weight of dicyandiamide, 0.05 part by weight of 2-methylimidazole (formed by four countries) and 1 part by weight of manganese oxide A were dissolved in N, N-dimethylformamide to prepare 65% by weight of a resin sol. And (3) uniformly soaking the resin glue solution in E-type glass fiber cloth with the size of 2116, which is flat and smooth, at room temperature, and baking the glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper and lower parts of the prepreg, and pressing the prepreg for 60min in a vacuum hot press under the pressure of 3MPa and the temperature of 180 ℃ to obtain the copper-clad laminated board.

Example 2

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 3 parts by weight of dicyandiamide, 0.05 part by weight of 2-methylimidazole (formed by four countries) and 1 part by weight of manganese oxide B were dissolved in N, N-dimethylformamide to prepare 65% by weight of a resin adhesive solution. And uniformly soaking the E-type glass fiber cloth which is flat, smooth and clean and has the model of 2116 in the resin glue solution at room temperature, and baking the E-type glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m of copper on the prepreg for extrusion, and pressing the prepreg for 60min in a vacuum hot press under the pressure of 3MPa and the temperature of 180 ℃ to obtain the copper-clad laminated board.

Example 3

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 3 parts by weight of dicyandiamide, 0.05 part by weight of 2-methylimidazole (formed by four countries) and 1 part by weight of manganese oxide C were dissolved in N, N-dimethylformamide to prepare 65% by weight of a resin adhesive solution. And uniformly soaking the E-type glass fiber cloth which is flat, smooth and clean and has the model of 2116 in the resin glue solution at room temperature, and baking the E-type glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper and lower parts of the prepreg, and pressing the prepreg for 60min in a vacuum hot press under the pressure of 3MPa and the temperature of 180 ℃ to obtain the copper-clad laminated board.

Example 4

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 3 parts by weight of dicyandiamide, 0.05 part by weight of 2-methylimidazole (formed by four nations) and 0.5 part by weight of manganese oxide B were dissolved in N, N-dimethylformamide to prepare a 65% by weight resin cement. And (3) uniformly soaking the resin glue solution in E-type glass fiber cloth with the size of 2116, which is flat and smooth, at room temperature, and baking the glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper and lower parts of the prepreg, and pressing the prepreg for 60min in a vacuum hot press under the pressure of 3MPa and the temperature of 180 ℃ to obtain the copper-clad laminated board.

Example 5

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 3 parts by weight of dicyandiamide, 0.05 part by weight of 2-methylimidazole (formed by four countries) and 10 parts by weight of manganese oxide B were dissolved in N, N-dimethylformamide to prepare 65% by weight of a resin cement. And uniformly soaking the E-type glass fiber cloth which is flat, smooth and clean and has the model of 2116 in the resin glue solution at room temperature, and baking the E-type glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper and lower parts of the prepreg, and pressing the prepreg for 60min in a vacuum hot press under the pressure of 3MPa and the temperature of 180 ℃ to obtain the copper-clad laminated board.

Example 6

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 3 parts by weight of dicyandiamide, 0.05 part by weight of 2-methylimidazole (formed by four countries) and 20 parts by weight of manganese oxide B were dissolved in N, N-dimethylformamide to prepare 65% by weight of a resin adhesive solution. And uniformly soaking the E-type glass fiber cloth which is flat, smooth and clean and has the model of 2116 in the resin glue solution at room temperature, and baking the E-type glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper and lower parts of the prepreg, and pressing the prepreg for 60min in a vacuum hot press under the pressure of 3MPa and the temperature of 180 ℃ to obtain the copper-clad laminated board.

Comparative example 1

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 3 parts by weight of dicyandiamide and 0.05 part by weight of 2-methylimidazole (formed by Siguo Co., Ltd.) were dissolved in N, N-dimethylformamide to prepare a 65% by weight resin cement. And uniformly soaking the E-type glass fiber cloth which is flat, smooth and clean and has the model of 2116 in the resin glue solution at room temperature, and baking the E-type glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper and lower parts of the prepreg, and pressing the prepreg for 60min in a vacuum hot press under the pressure of 3MPa and the temperature of 180 ℃ to obtain the copper-clad laminated board.

Comparative example 2

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 3 parts by weight of dicyandiamide, 0.05 part by weight of 2-methylimidazole (formed by four nations) and 1 part by weight of manganese monoxide (avastin) were dissolved in N, N-dimethylformamide to prepare a 65% by weight resin cement. And uniformly soaking the E-type glass fiber cloth which is flat, smooth and clean and has the model of 2116 in the resin glue solution at room temperature, and baking the E-type glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper and lower parts of the prepreg, and pressing the prepreg for 60min in a vacuum hot press under the pressure of 3MPa and the temperature of 180 ℃ to obtain the copper-clad laminated board.

Comparative example 3

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 3 parts by weight of dicyandiamide, 0.05 part by weight of 2-methylimidazole (formed by four nations) and 1 part by weight of manganese sesquioxide (avastin) were dissolved in N, N-dimethylformamide to prepare a 65% by weight resin cement. And (3) uniformly soaking the resin glue solution in E-type glass fiber cloth with the size of 2116, which is flat and smooth, at room temperature, and baking the glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the prepreg, and pressing the prepreg for 60min in a vacuum hot press under the pressure of 3MPa and the temperature of 180 ℃ to obtain the copper-clad laminated board. .

Comparative example 4

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 3 parts by weight of dicyandiamide, 0.05 part by weight of 2-methylimidazole (formed by four nations) and 1 part by weight of manganese dioxide (alatin) were dissolved in N, N-dimethylformamide to prepare a 65% by weight resin cement. And uniformly soaking the E-type glass fiber cloth which is flat, smooth and clean and has the model of 2116 in the resin glue solution at room temperature, and baking the E-type glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper and lower parts of the prepreg, and pressing the prepreg for 60min in a vacuum hot press under the pressure of 3MPa and the temperature of 180 ℃ to obtain the copper-clad laminated board.

Comparative example 5

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 3 parts by weight of dicyandiamide, 0.05 part by weight of 2-methylimidazole (formed by four countries) and 1 part by weight of manganese oxide D were dissolved in N, N-dimethylformamide to prepare 65% by weight of a resin adhesive solution. And (3) uniformly soaking the resin glue solution in E-type glass fiber cloth with the size of 2116, which is flat and smooth, at room temperature, and baking the glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper and lower parts of the prepreg, and pressing the prepreg for 60min in a vacuum hot press under the pressure of 3MPa and the temperature of 180 ℃ to obtain the copper-clad laminated board.

Comparative example 6

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 3 parts by weight of dicyandiamide, 0.05 part by weight of 2-methylimidazole (formed by four countries) and 1 part by weight of manganese oxide E were dissolved in N, N-dimethylformamide to prepare 65% by weight of a resin sol. And uniformly soaking the E-type glass fiber cloth which is flat, smooth and clean and has the model of 2116 in the resin glue solution at room temperature, and baking the E-type glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper and lower parts of the prepreg, and pressing the prepreg for 60min in a vacuum hot press under the pressure of 3MPa and the temperature of 180 ℃ to obtain the copper-clad laminated board.

Comparative example 7

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 3 parts by weight of dicyandiamide, 0.05 part by weight of 2-methylimidazole (formed by four nations) and 0.05 part by weight of manganese oxide B were dissolved in N, N-dimethylformamide to prepare a 65% by weight resin cement. And uniformly soaking the E-type glass fiber cloth which is flat, smooth and clean and has the model of 2116 in the resin glue solution at room temperature, and baking the E-type glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper and lower parts of the prepreg, and pressing the prepreg for 60min in a vacuum hot press under the pressure of 3MPa and the temperature of 180 ℃ to obtain the copper-clad laminated board.

Comparative example 8

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 3 parts by weight of dicyandiamide, 0.05 part by weight of 2v methylimidazole (formed by four nations) and 25 parts by weight of manganese oxide B were dissolved in N, N-dimethylformamide to prepare a 65% by weight resin cement. And (3) uniformly soaking the resin glue solution in E-type glass fiber cloth with the size of 2116, which is flat and smooth, at room temperature, and baking the glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper and lower parts of the prepreg, and pressing the prepreg for 60min in a vacuum hot press under the pressure of 3MPa and the temperature of 180 ℃ to obtain the copper-clad laminated board.

The prepregs of examples 1-6 and comparative examples 1-8 were tested for performance. The results are shown in Table 1.

From example 2 and comparative example 1, it is seen that the addition of manganese oxide increases the Td and T260 of the amine cured brominated epoxy system. From the comparison of examples 1 to 6 and comparative examples 2 to 8, it can be seen that the molar number of the divalent manganese ions in the manganese oxide formulated with the manganese oxide: when the sum of the mole number of the trivalent manganese ions and the mole number of the tetravalent manganese ions is 1: 1 to 10: 1, a cured product with good heat resistance and excellent flame retardancy can be obtained.

In addition, under the same dosage of manganese oxide, manganese oxide is adopted for compounding, and the mole number of divalent manganese ions in the manganese oxide is as follows: when the sum of the number of moles of trivalent manganese ions and the number of moles of tetravalent manganese ions is 1: 1 to 10: 1, a cured product having better heat resistance and more excellent flame retardancy can be obtained.

Example 7

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 24 parts by weight of phenol novolac resin (Nipponbare, hydroxyl equivalent 105, product name TD2090), 0.05 part by weight of 2-methylimidazole, 1 part by weight of manganese oxide A dissolved in acetone, to prepare a 65% by weight resin cement. And uniformly soaking the E-type glass fiber cloth which is flat, smooth and clean and has the model of 2116 in the resin glue solution at room temperature, and baking the E-type glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper part and the lower part of the prepreg, and pressing the prepreg for 90min in a vacuum hot press under the pressure of 3MPa and the temperature of 190 ℃ to obtain the copper-clad laminated board.

Example 8

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 24 parts by weight of phenol novolac resin (Nipponbare, hydroxyl equivalent 105, product name TD2090), 0.05 part by weight of 2-methylimidazole, 1 part by weight of manganese oxide B dissolved in acetone, to prepare a 65% by weight resin cement. And (3) uniformly soaking the resin glue solution in E-type glass fiber cloth with the size of 2116, which is flat and smooth, at room temperature, and baking the glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper part and the lower part of the prepreg, and pressing the prepreg for 90min in a vacuum hot press under the pressure of 3MPa and the temperature of 190 ℃ to obtain the copper-clad laminated board.

Example 9

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 24 parts by weight of phenol novolac resin (Kogyourong, hydroxyl equivalent 105, product name TD2090), 0.05 part by weight of 2-methylimidazole and 1 part by weight of manganese oxide C dissolved in acetone to prepare 65% by weight of resin adhesive solution. And uniformly soaking the E-type glass fiber cloth which is flat, smooth and clean and has the model of 2116 in the resin glue solution at room temperature, and baking the E-type glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper part and the lower part of the prepreg, and pressing the prepreg for 90min in a vacuum hot press under the pressure of 3MPa and the temperature of 190 ℃ to obtain the copper-clad laminated board.

Example 10

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 24 parts by weight of phenol novolac resin (Nipponbare, hydroxyl equivalent 105, product name TD2090), 0.05 part by weight of 2-methylimidazole and 0.5 part by weight of manganese oxide B were dissolved in acetone to prepare a 65% by weight resin sol. And uniformly soaking the E-type glass fiber cloth which is flat, smooth and clean and has the model of 2116 in the resin glue solution at room temperature, and baking the E-type glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper part and the lower part of the prepreg, and pressing the prepreg for 90min in a vacuum hot press under the pressure of 3MPa and the temperature of 190 ℃ to obtain the copper-clad laminated board.

Example 11

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 24 parts by weight of phenol novolac resin (Nipponbare, hydroxyl equivalent 105, product name TD2090), 0.05 part by weight of 2-methylimidazole and 10 parts by weight of manganese oxide B were dissolved in acetone to prepare a 65% by weight resin cement. And uniformly soaking the E-type glass fiber cloth which is flat, smooth and clean and has the model of 2116 in the resin glue solution at room temperature, and baking the E-type glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper part and the lower part of the prepreg, and pressing the prepreg for 90min in a vacuum hot press under the pressure of 3MPa and the temperature of 190 ℃ to obtain the copper-clad laminated board.

Example 12

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 24 parts by weight of phenol novolac resin (Kogyourong, hydroxyl equivalent 105, product name TD2090), 0.05 part by weight of 2-methylimidazole and 20 parts by weight of manganese oxide B dissolved in acetone to prepare 65% by weight of resin adhesive solution. And uniformly soaking the E-type glass fiber cloth which is flat, smooth and clean and has the model of 2116 in the resin glue solution at room temperature, and baking the E-type glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper part and the lower part of the prepreg, and pressing the prepreg for 90min in a vacuum hot press under the pressure of 3MPa and the temperature of 190 ℃ to obtain the copper-clad laminated board.

Comparative example 9

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 24 parts by weight of phenol novolac resin (Nipponbare, hydroxyl equivalent 105, product name TD2090) and 0.05 part by weight of 2-methylimidazole were dissolved in acetone to prepare a 65% by weight resin cement. And uniformly soaking the E-type glass fiber cloth which is flat, smooth and clean and has the model of 2116 in the resin glue solution at room temperature, and baking the E-type glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper part and the lower part of the prepreg, and pressing the prepreg for 90min in a vacuum hot press under the pressure of 3MPa and the temperature of 190 ℃ to obtain the copper-clad laminated board.

Comparative example 10

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 24 parts by weight of phenol novolac resin (Nipponbare, hydroxyl equivalent 105, product name TD2090), 0.05 part by weight of 2-methylimidazole and 1 part by weight of manganese monoxide were dissolved in acetone to prepare a 65% by weight resin cement. And (3) uniformly soaking the resin glue solution in E-type glass fiber cloth with the size of 2116, which is flat and smooth, at room temperature, and baking the glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper part and the lower part of the prepreg, and pressing the prepreg for 90min in a vacuum hot press under the pressure of 3MPa and the temperature of 190 ℃ to obtain the copper-clad laminated board.

Comparative example 11

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 24 parts by weight of phenol novolac resin (Kogyourong, hydroxyl equivalent 105, product name TD2090), 0.05 part by weight of 2-methylimidazole and 1 part by weight of manganese sesquioxide dissolved in acetone to prepare 65% by weight of resin glue solution. And uniformly soaking the E-type glass fiber cloth which is flat, smooth and clean and has the model of 2116 in the resin glue solution at room temperature, and baking the E-type glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper part and the lower part of the prepreg, and pressing the prepreg for 90min in a vacuum hot press under the pressure of 3MPa and the temperature of 190 ℃ to obtain the copper-clad laminated board.

Comparative example 12

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 24 parts by weight of phenol novolac resin (Nipponbare, hydroxyl equivalent 105, product name TD2090), 0.05 part by weight of 2-methylimidazole and 1 part by weight of manganese dioxide were dissolved in acetone to prepare a 65% by weight resin sol. And (3) uniformly soaking the E-type glass fiber cloth which is flat, smooth and clean and has the model of 2116 at room temperature, and baking the resin glue solution in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper part and the lower part of the prepreg, and pressing the prepreg for 90min in a vacuum hot press under the pressure of 3MPa and the temperature of 190 ℃ to obtain the copper-clad laminated board.

Comparative example 13

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 24 parts by weight of phenol novolac resin (Nipponbare, hydroxyl equivalent 105, product name TD2090), 0.05 part by weight of 2-methylimidazole and 1 part by weight of manganese oxide D were dissolved in acetone to prepare a 65% by weight resin cement. And (3) uniformly soaking the resin glue solution in E-type glass fiber cloth with the size of 2116, which is flat and smooth, at room temperature, and baking the glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper part and the lower part of the prepreg, and pressing the prepreg for 90min in a vacuum hot press under the pressure of 3MPa and the temperature of 190 ℃ to obtain the copper-clad laminated board.

Comparative example 14

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 24 parts by weight of phenol novolac resin (Nipponbare, hydroxyl equivalent 105, product name TD2090), 0.05 part by weight of 2-methylimidazole and 1 part by weight of manganese oxide E were dissolved in acetone to prepare a 65% by weight resin cement. And uniformly soaking the E-type glass fiber cloth which is flat, smooth and clean and has the model of 2116 in the resin glue solution at room temperature, and baking the E-type glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper part and the lower part of the prepreg, and pressing the prepreg for 90min in a vacuum hot press under the pressure of 3MPa and the temperature of 190 ℃ to obtain the copper-clad laminated board.

Comparative example 15

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 24 parts by weight of phenol novolac resin (Nipponbare, hydroxyl equivalent 105, product name TD2090), 0.05 part by weight of 2-methylimidazole and 0.05 part by weight of manganese oxide B were dissolved in acetone to prepare a 65% by weight resin sol. And uniformly soaking the E-type glass fiber cloth which is flat, smooth and clean and has the model of 2116 in the resin glue solution at room temperature, and baking the E-type glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper part and the lower part of the prepreg, and pressing the prepreg for 90min in a vacuum hot press under the pressure of 3MPa and the temperature of 190 ℃ to obtain the copper-clad laminated board.

Comparative example 16

100 parts by weight of brominated bisphenol A type epoxy resin (Dow chemical, epoxy resin equivalent 435, bromine content 19%, product name DER530), 24 parts by weight of phenol novolac resin (Nipponbare, hydroxyl equivalent 105, product name TD2090), 0.05 part by weight of 2-methylimidazole and 25 parts by weight of manganese oxide B were dissolved in acetone to prepare a 65% by weight resin cement. And uniformly soaking the E-type glass fiber cloth which is flat, smooth and clean and has the model of 2116 in the resin glue solution at room temperature, and baking the E-type glass fiber cloth in a blast oven at 155 ℃ for 6min to obtain the prepreg for the printed circuit. And overlapping 8 pieces of the prepreg for the printed circuit, covering 35 mu m copper foils on the upper part and the lower part of the prepreg, and pressing the prepreg for 90min in a vacuum hot press under the pressure of 3MPa and the temperature of 190 ℃ to obtain the copper-clad laminated board.

The prepregs of examples 7-12 and comparative examples 9-16 were tested for performance. The results are shown in Table 2.

From example 8 and comparative example 9, it can be seen that the addition of manganese oxide increases the Td, T288 of the novolac cured brominated epoxy system. From examples 7 to 12 and comparative examples 10 to 16, it can be seen that the molar number of divalent manganese ions in the manganese oxide formulated with the manganese oxide: when the sum of the mole number of the trivalent manganese ions and the mole number of the tetravalent manganese ions is 1: 1 to 10: 1, a cured product with good heat resistance and excellent flame retardancy can be obtained.

It will be apparent to those skilled in the art that various changes and modifications may be made in the embodiments of the disclosure without departing from the spirit and scope of the disclosure. Thus, if such modifications and variations of the present disclosure fall within the scope of the claims of the present disclosure and their equivalents, the present disclosure is intended to include such modifications and variations as well.

Claims

1. A thermosetting resin composition comprising:

a brominated epoxy resin, which is a brominated epoxy resin,

a hardener, and

an oxide of manganese, which is a metal oxide,

wherein the manganese oxide is a mixture of two or more of manganese monoxide, manganese dioxide, manganese sesquioxide and manganomanganic oxide, wherein the molar number of divalent manganese ions in the manganese oxide is: the sum of the number of moles of trivalent manganese ions and the number of moles of tetravalent manganese ions is 1: 1 to 10: 1, and

in the thermosetting resin composition, the content of the manganese oxide is 0.1 to 20% by weight.

2. The thermosetting resin composition according to claim 1, wherein the content of the manganese oxide in the thermosetting resin composition is 0.5 to 5% by weight.

3. The thermosetting resin composition of claim 1, wherein the particle size of said manganese oxide is less than 50 μm.

4. The thermosetting resin composition according to claim 1, wherein the surface of the manganese oxide has an organic coating layer or an inorganic coating layer.

5. The thermosetting resin composition of claim 4, wherein the organic coating layer is a silane coupling agent coating layer or the inorganic coating layer is a silica, alumina or magnesia coating layer.

6. The thermosetting resin composition of claim 1, wherein the brominated epoxy resin comprises one or a combination of two or more of a tetrabromobisphenol a type epoxy resin, a high bromine type epoxy resin, a bromine-containing diphenylmethane diisocyanate-modified epoxy resin, and a brominated phenol epoxy resin.

7. The thermosetting resin composition of claim 1, wherein the hardener is one or a combination of two or more of an amine type hardener, an anhydride type hardener, a phenolic resin type hardener, a reactive ester type hardener, a benzoxazine type hardener, and a cyanate ester type hardener.

8. The thermosetting resin composition according to claim 1, wherein in the thermosetting resin composition, the brominated epoxy resin is contained in an amount of 20 to 98% by weight, and the hardener is contained in an amount of 1 to 30% by weight.

9. The thermosetting resin composition of claim 1, further comprising an accelerator, wherein the accelerator is present in an amount of 10 wt% or less in the thermosetting resin composition.

10. The thermosetting resin composition of claim 9, wherein said accelerator is one or a combination of two or more of an imidazole-based compound, a tertiary amine-based compound, a metal compound, and a pyridine-based compound.

11. The thermosetting resin composition of claim 1, further comprising an inorganic filler different from the manganese oxide, wherein the content of the inorganic filler in the thermosetting resin composition is less than or equal to 60% by weight.

12. The thermosetting resin composition claimed in claim 11, wherein the inorganic filler is one or a combination of two or more of crystalline fine silica powder, molten fine silica powder, spherical fine silica powder, titanium dioxide, aluminum hydroxide, magnesium hydroxide, talc, kaolin, calcium carbonate, mullite, calcium silicate, alumina, zinc oxide and glass fiber.

13. The thermosetting resin composition of claim 1, further comprising a solvent, the solvent being an aprotic solvent.

14. The thermosetting resin composition of claim 1, further comprising a solvent that is one or a combination of two or more of ketones, hydrocarbons, ethers, or esters.

15. A prepreg comprising a reinforcing material and a thermosetting resin composition as claimed in any one of claims 1 to 12 attached thereto after drying by impregnation.

16. A laminate comprising at least one prepreg according to claim 15.

17. A printed circuit board containing at least one prepreg according to claim 15.