A resin composition, a prepreg, and a metal-clad laminate

Abstract

The present application provides a resin composition, a prepreg and a metal-clad laminate, the resin composition comprising triallyl cyanurate, an elastomer block copolymer and a phosphorus-containing flame retardant; the content of the triallyl cyanurate is 50-70% based on the total mass of the resin component in the resin composition being 100%. The resin composition of the present application uses triallyl cyanurate as the main component, which is combined with the elastomer block copolymer and the phosphorus-containing flame retardant, so that the board containing the same has excellent dielectric properties, heat-oxidative aging resistance, wet-heat resistance and good flame retardant properties, meeting the requirements of the high-frequency high-speed circuit board field.

Description

Technical Field

[0001] This invention belongs to the field of copper clad laminate technology, specifically relating to a resin composition, a prepreg, and a metal foil laminate. Background Technology

[0002] In recent years, with the rapid development of electronic information technology and hardware carriers, the demand for transmission capacity of electronic components and circuit materials has also increased, leading to the era of high-frequency and high-speed transmission in electronic products. Therefore, the dielectric properties of related electronic materials have become a key concern. With the trends of higher frequency and higher speed signal transmission and higher circuit board density, the requirements for low dielectric constant, low dielectric loss, and flame retardancy in electronic materials are becoming increasingly prominent.

[0003] Printed circuit boards (PCBs) are components used for electrical connections in electronic devices and electronic components, and are one of the most important electronic materials. PCBs are usually manufactured by processing copper-clad laminates through different processes. Therefore, the performance, quality, service life, and manufacturing level of a PCB largely depend on the performance of the copper-clad laminate.

[0004] Copper-clad laminates consist of copper foil, reinforcing materials, and resin materials. The properties of the resin materials directly affect the performance of the board material and the PCB. Epoxy resin is a traditional raw material for boards, possessing good adhesion, heat resistance, and processing performance, and offering significant cost advantages. However, with the application of high-speed, high-frequency circuit boards, higher dielectric loss requirements are placed on the materials. Epoxy resin has a high dielectric constant and dielectric loss (Df) value, resulting in poor dielectric performance of the board material, failing to meet application requirements.

[0005] Polyolefin materials are non-polar materials with low dielectric loss (Df), which meets the low dielectric requirements of copper-clad laminates and has attracted widespread attention in the industry. CN110605880A discloses a thermosetting hydrocarbon polymer composition, a prepreg, and a thermosetting copper-clad laminate. The preparation method includes: using polyhydroxyl-type polyaryl ether resin, hydrogenated hydroxyl-terminated polyolefin resin, polydiolefin resin, and vinyl-modified polyaryl ether resin as raw materials to prepare a polyaryl ether-polyolefin block copolymer and a thermosetting hydrocarbon polymer composition containing it; then using this composition to prepare a thermosetting copper-clad laminate. Compared with epoxy resin copper-clad laminates, the above-mentioned board containing olefin polymers has better dielectric properties. However, olefin polymers have poor resistance to heat and oxygen aging. After aging for a period of time under high temperature and oxygen conditions, the dielectric loss (Df) increases significantly, resulting in Df failing to meet the usage requirements after long-term use. Furthermore, existing hydrocarbon materials are highly flammable resins, and even with the addition of a large amount of halogen-free flame retardant, it is difficult to achieve halogen-free flame retardancy.

[0006] Therefore, in this field, there is a desire to develop a circuit material that combines excellent aging resistance, dielectric properties, bonding strength, and halogen-free flame retardant properties to meet the requirements of the high-frequency and high-speed circuit board field. Summary of the Invention

[0007] To address the shortcomings of existing technologies, the present invention aims to provide a resin composition, a prepreg, and a metal foil laminate. The resin composition of the present invention uses triallyl cyanurate as the main component, which is combined with an elastomer block copolymer and a phosphorus-containing flame retardant. This results in a board containing the resin composition exhibiting excellent dielectric properties, resistance to heat and oxygen aging, resistance to damp heat (stability of electrical properties under long-term damp heat conditions, i.e., wet bleaching performance often mentioned in the industry), and good flame retardant properties, meeting the requirements of the high-frequency and high-speed circuit board field.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] On one hand, the present invention provides a resin composition comprising triallyl cyanurate (TAC), an elastomer block copolymer, and a phosphorus-containing flame retardant;

[0010] The content of triallyl cyanurate is 50-70% based on the total mass of the resin components in the resin composition being 100%.

[0011] In the resin composition provided by this invention, triallyl cyanurate (TAC) serves as the main component, exhibiting excellent heat and oxygen aging resistance and dielectric properties. It demonstrates excellent wetting, strong adhesion, and good flowability, and has a high nitrogen content. When combined with a phosphorus-containing flame retardant, it forms a N / P synergistic flame retardant effect, achieving halogen-free flame retardancy. The elastomeric block copolymer, when compounded with TAC, helps to improve and control the adhesive viscosity, facilitating application, optimizing processability and gluing properties, and enhancing the toughness of the finished resin board. Through the synergistic effect of TAC and the elastomeric block copolymer, the resin composition exhibits low dielectric constant and dielectric loss, excellent dielectric properties, significantly improving the heat and oxygen aging resistance, dielectric stability, and board reliability of the resin composition, prepreg, and metal foil-coated laminate. Furthermore, it possesses good processability and gluing properties, fully meeting the dielectric reliability requirements of the resin composition and boards in high-frequency and high-speed applications. The resin composition of the present invention, with the combination of three components—triallyl cyanurate (TAC), elastomer block copolymer, and phosphorus-containing flame retardant—gives the sheet material excellent dielectric properties, resistance to heat and oxygen aging, resistance to damp heat, and good flame retardant properties, resulting in excellent overall performance.

[0012] In this invention, based on the total mass of the resin components in the resin composition as 100%, the content of triallyl cyanurate is 50-70%, for example, it can be 50%, 55%, 58%, 60%, 63%, 65%, 68% or 70%. If the content of triallyl cyanurate is less than 50%, it will lead to insufficient heat and oxygen aging resistance; if the content of triallyl cyanurate is higher than 70%, the board will be too brittle and have poor mechanical properties.

[0013] In this invention, the elastomeric block copolymer includes any one or a combination of at least two of styrene-butadiene copolymer, styrene-butadiene-styrene triblock copolymer, styrene-isoprene copolymer, or styrene-isoprene-styrene triblock copolymer.

[0014] Preferably, the number average molecular weight of the elastomeric block copolymer is ≥50,000, for example, it can be 50,000, 60,000, 70,000, 80,000, 100,000, 120,000, 150,000, 180,000, 200,000, 250,000 or 300,000.

[0015] In this invention, the test method for molecular weight (weight-average molecular weight, number-average molecular weight, etc.) is GB / T21863-2008, which is determined by gel permeation chromatography (GPC) based on polystyrene calibration.

[0016] In this invention, the total mass of the resin component in the resin composition is 100%, and the content of the elastomeric block copolymer is 10-30%, for example, 10%, 13%, 15%, 18%, 20%, 23%, 25%, 28%, or 30%. If the amount of elastomeric block copolymer added is too large, the adhesive viscosity will be too high, resulting in insufficient wetting of reinforcing materials such as fiberglass cloth, leading to more voids in the board, increased water absorption, poor processability, etc. If the amount of elastomeric block copolymer added is too small, the adhesive viscosity will be too low, resulting in poor curing properties.

[0017] Preferably, the phosphorus-containing flame retardant can be a reactive or additive flame retardant. A reactive phosphorus-containing flame retardant refers to one that contains reactive groups that can react with the resin components in the resin composition, while an additive phosphorus-containing flame retardant refers to one that does not contain reactive groups that can react with the resin components in the resin composition.

[0018] Preferably, the phosphorus-containing flame retardant is selected from any one or a mixture of at least two of the following: tris(2,6-dimethylphenyl)phosphine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphine, p-xylylbis(diphenylphosphine oxide), phenoxyphosphazene compounds, phosphate esters, polyphosphate esters, phosphonates, polyphosphonates, phosphonate-carbonate copolymers, or organophosphorus-containing phosphonates. Examples include SPB-100 manufactured by Otsuka Chemicals, Japan; OP-930 and OP-935 manufactured by Clariant, Germany; SP-703H manufactured by Shikoku Chemical Co., Ltd.; PQ-60 from Jinyi Chemical; and DE-295 from Jiangsu Yake. Further preference is given to organophosphorus-containing phosphonate flame retardants, which can provide superior heat resistance and electrical properties.

[0019] Preferably, the content of the phosphorus-containing flame retardant is 10-35% based on the total mass of the resin components in the resin composition as 100%, for example, 10%, 15%, 18%, 20%, 23%, 25%, 28%, 30% or 35%.

[0020] It should be noted that in the resin composition provided by the present invention, the combination of the triallyl cyanurate and the elastomer block copolymer reacts when used in prepregs and metal foil laminates. The reaction can proceed spontaneously at an appropriate temperature, or optionally by adding an initiator (or accelerator) to initiate (or promote) it.

[0021] Preferably, the resin composition further includes an initiator.

[0022] Preferably, the initiator is an organic peroxide.

[0023] Preferably, the initiator comprises any one or a combination of at least two of dicumyl peroxide, bis-tert-butyl peroxide, tert-butyl perbenzoate, or 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne.

[0024] Preferably, the initiator content is 0.1-8% based on the total mass of the resin components in the resin composition as 100%, for example, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7% or 8%.

[0025] Preferably, the resin composition further includes a polyphenylene ether resin.

[0026] Preferably, the polyphenylene ether resin is a polyphenylene ether resin containing unsaturated groups.

[0027] Preferably, the polyphenylene ether resin containing unsaturated groups is a polyphenylene ether resin with unsaturated group-terminated ends.

[0028] As a preferred embodiment of the present invention, the resin composition further includes polyphenylene ether resin containing unsaturated groups, which is compounded with TAC and elastomeric block copolymers to improve the rigidity of the resin composition, prepreg and metal foil laminate, and prevent the board from warping.

[0029] Preferably, the unsaturated group includes any one or at least a combination of two of vinyl, vinylphenyl, vinylbenzyl, or acrylate groups.

[0030] Preferably, the polyphenylene ether resin containing unsaturated groups comprises structural units as shown in Formula I:

[0031]

[0032] In Formula I, the wavy line represents the connection site of the functional group.

[0033] In Formula I, R1, R2, R1', and R2' are each independently selected from hydrogen, halogen, substituted or unsubstituted C1-C7 (C1, C2, C3, C4, C5, C6, or C7) straight-chain or branched alkyl, C1-C7 (C1, C2, C3, C4, C5, C6, or C7) aminoalkyl, C1-C7 (C1, C2, C3, C4, C5, C6, or C7) straight-chain or branched alkoxy, C2-C7 (C2, C3, C4, C5, C6, or C7) straight-chain or branched alkenyl, substituted or unsubstituted C6-C12 (C6, C9, C10, or C12, etc.) aryl, and C6-C1 (C6, C9, C10, or C12, etc.) aryloxy.

[0034] The substituents described in R1, R2, R1', and R2' are each independently selected from at least one of halogens, C1-C6 (C1, C2, C3, C4, C5, or C6) straight-chain or branched alkyl groups.

[0035] The halogen includes fluorine, chlorine, bromine or iodine, with chlorine or bromine being more preferred.

[0036] Preferably, R1 and R2 are each independently selected from any one of unsubstituted or halogenated C1-C7 (C1, C2, C3, C4, C5, C6 or C7) straight-chain or branched alkyl, C2-C5 (C2, C3, C4 or C5) straight-chain or branched alkenyl, phenyl or tolyl.

[0037] Preferably, R1' and R2' are each independently hydrogen or methyl.

[0038] Preferably, the polyphenylene ether in the polyphenylene ether resin containing unsaturated groups includes poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,3,6-trimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2,6-dipropyl-1,4-phenylene) ether, poly(2-methyl-6-allyl-1,4-phenylene) ether, poly(di-tert-butyl-dimethoxy-1,4-phenylene) ether, and poly(2,6-dichloromethyl-1,4-phenylene) ether. The poly(2,6-dibromomethyl-1,4-phenylene) ether, poly(2,6-di(2-chloroethyl)-1,4-phenylene) ether, poly(2,6-xylyl-1,4-phenylene) ether, poly(2,6-dichloro-1,4-phenylene) ether, poly(2,6-diphenyl-1,4-phenylene) ether or poly(2,5-dimethyl-1,4-phenylene) ether, or any one or at least two combinations thereof, with poly(2,6-dimethyl-1,4-phenylene) ether being more preferred.

[0039] The aforementioned exemplary types are types of polyphenylene ether body structures, which also contain unsaturated groups, preferably with end groups containing unsaturated groups, said unsaturated groups including any one or at least two combinations of vinyl, vinylphenyl, vinylbenzyl, acrylate or methacrylate.

[0040] In this invention, the polyphenylene ether containing unsaturated groups can be purchased from the market, and exemplary examples include but are not limited to: polyphenylene ether MX9000 (SABIC) containing methacrylate groups and polyphenylene ether OPE-2ST (Mitsubishi Chemical Corporation) containing vinyl benzyl groups.

[0041] Preferably, the content of the polyphenylene ether resin is 1-30% based on the total mass of the resin components in the resin composition as 100%, for example, 1%, 3%, 5%, 10%, 13%, 15%, 18%, 20%, 25%, 28% or 30%.

[0042] Preferably, the resin composition further includes fillers; the fillers have the functions of preventing sticking, improving the mechanical properties of the board, and improving the coefficient of thermal expansion (CTE).

[0043] Preferably, the filler is an inorganic filler and / or an organic filler.

[0044] Preferably, the filler is a powder filler, including any one or a combination of at least two of the following: crystalline silica, amorphous silica, spherical silica, angular silica, chemically produced silica, silica micropowder, hollow glass microspheres, titanium dioxide, strontium titanate, barium titanate, boron nitride, aluminum nitride, silicon nitride, silicon carbide, alumina, polytetrafluoroethylene, polyphenylene sulfide, or polyethersulfone.

[0045] Preferably, the filler content is 50-70% based on the total mass of the resin composition and the filler, for example, 50%, 55%, 60%, 65% or 70%.

[0046] On the other hand, the present invention provides a resin adhesive obtained by dissolving or dispersing the resin composition described above in a solvent.

[0047] The amount of solvent added is selected by those skilled in the art based on experience and process requirements, so as to achieve a suitable viscosity for the resin composition to facilitate impregnation, coating, etc. During subsequent drying, semi-curing, or full curing stages, the solvent in the resin composition will partially or completely evaporate.

[0048] The solvent used in this invention is not particularly limited, and generally can be ketones such as acetone, butanone, and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; alcohols such as methanol, ethanol, or butanol; alcohols such as ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol, or butyl carbitol; and nitrogen-containing solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, or N-methyl-2-pyrrolidone. The solvent can be used alone or in mixtures of two or more. Preferably, ketones such as acetone, butanone, and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene are used.

[0049] On the other hand, the present invention provides a resin film, the material of which comprises the resin composition described above.

[0050] Preferably, the resin film is obtained by coating the resin composition onto a release material and then drying and / or semi-curing it.

[0051] On the other hand, the present invention provides a semi-cured sheet comprising a reinforcing material and a resin composition as described above attached to the reinforcing material.

[0052] Preferably, the resin composition is attached to the reinforcing material after impregnation and drying.

[0053] Preferably, the reinforcing material includes any one or at least two combinations of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fibers; for example, glass fiber cloth, quartz glass fiber blended cloth, non-woven fabric, quartz cloth, etc.

[0054] For example, the method for preparing the prepreg is as follows: impregnate the reinforcing material with the resin solution of the resin composition, and then dry it to obtain the prepreg.

[0055] Preferably, the drying temperature is 100-160℃, such as 105℃, 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃ or 155℃.

[0056] On the other hand, the present invention provides a metal foil laminate comprising a metal foil and at least one of a resin film as described above or a prepreg as described in the third aspect.

[0057] Preferably, the metal foil is copper foil, and the metal foil laminate is copper clad laminate.

[0058] For example, the method for preparing the metal foil laminate includes: pressing a metal foil onto one or both sides of a prepreg, curing it, and obtaining the metal foil laminate; or, stacking at least two prepregs into a laminate, then pressing a metal foil onto one or both sides of the laminate, curing it, and obtaining the metal foil laminate.

[0059] Preferably, the curing is carried out in a press.

[0060] Preferably, the curing temperature is 170-280℃, such as 180℃, 190℃, 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃ or 270℃.

[0061] Preferably, the curing pressure is 1-10 MPa, such as 1.5 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa or 9 MPa.

[0062] Preferably, the curing time is 30-150 min, such as 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min, 130 min, 140 min or 145 min.

[0063] On the other hand, the present invention provides a printed circuit board, the printed circuit board comprising at least one of the resin film as described above, the prepreg as described above, or the metal foil laminate as described above.

[0064] Compared with the prior art, the present invention has the following beneficial effects:

[0065] The resin composition of this invention uses triallyl cyanurate as the main component. By combining it with an elastomer block copolymer and a phosphorus-containing flame retardant, it significantly improves the heat and oxygen aging resistance, dielectric properties, damp heat resistance, and flame retardant properties of the resin composition, prepreg, and metal foil laminate. This results in a dielectric loss of 0.0036-0.0045 at 10 GHz; a dielectric loss of 0.0050-0.0058 after 4 weeks of high-temperature heat and oxygen aging; a dielectric loss change value ≤0.0020; a Df change rate ≤52.94%; and a flame retardancy rating of V-0. It exhibits excellent dielectric properties and reliability, good processability and adhesive properties, high peel strength, and low warpage, fully meeting the performance requirements of the resin composition and laminate in the high-frequency and high-speed field. Detailed Implementation

[0066] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0067] The materials involved in the following embodiments and comparative examples of the present invention include:

[0068] (1) Main components

[0069] Triallyl cyanurate, TAC;

[0070] Triallyl isocyanurate, TAIC;

[0071] Polybutadiene resin, B-3000, Nippon Soda, number average molecular weight 4500;

[0072] (2) Elastomer block copolymer

[0073] Styrene-butadiene-styrene triblock copolymer (SBS), KRATON D-1118, weight average molecular weight 80,000, Kraton, USA;

[0074] Styrene-butadiene diblock copolymer (SB), weight average molecular weight 40,000, T171E, Dushanzi Petrochemical;

[0075] Styrene-isoprene-styrene triblock copolymer, weight average molecular weight 100,000, KRATON D-1114, Kraton, USA;

[0076] Non-block copolymer: Butadiene-styrene copolymer, number average molecular weight 4500, R100, Sartamomer;

[0077] (3) Polyphenylene ether containing unsaturated groups

[0078] Polyphenylene ether MX9000, methacrylate-terminated, SABIC Corporation;

[0079] Polyphenylene ether OPE-2ST, vinyl benzyl ether modified polyphenylene ether, Mitsubishi Chemical Corporation;

[0080] (4) Initiator

[0081] Dicumyl peroxide, DCP;

[0082] BIPB (Di-tert-butylperoxide diisopropylbenzene)

[0083] (5) Packing

[0084] Filler F1, silica, brand name Megasil 525, Sibelco;

[0085] (6) Flame retardants

[0086] Phosphorus-containing flame retardant 1: P1, aluminum diethylphosphinate, brand name OP935, Clariant.

[0087] Phosphorus-containing flame retardant 2: P2, Di-DOPO, brand name DE-295, Jiangsu Yake Technology Co., Ltd.

[0088] Phosphorus-containing flame retardant 3: P3, phenoxyphosphazene, brand name SPB-100, Otsuka Chemical Co., Ltd.

[0089] Example 1

[0090] A resin composition comprising, by weight, the following components: 50 parts triallyl cyanurate (TAC), 30 parts elastomeric block copolymer (KRATON D-1118), 20 parts polyphenylene ether (MX9000), 4 parts initiator (DCP), 200 parts filler (F1), and 10 parts phosphorus-containing flame retardant.

[0091] A prepreg and a copper-clad laminate comprising the resin composition are prepared by the following method:

[0092] (1) The resin composition is mixed with toluene according to the formula to prepare a glue solution with a solid content of 60%; glass fiber cloth is impregnated with the glue solution and then baked at 120°C for 3 minutes to obtain a semi-cured sheet;

[0093] (2) Six semi-cured sheets are stacked together, and copper foil is covered on the top and bottom sides. The sheets are then cured in a press at 240°C and 5MPa for 2 hours to obtain the copper-clad laminate.

[0094] The components of the resin composition and their mass fractions are shown in Tables 1 and 2; the mass unit for each component in Tables 1 and 2 is "parts".

[0095] Table 1 Examples

[0096]

[0097]

[0098] Table 2 Comparative Examples

[0099]

[0100]

[0101] The above resin composition was used to prepare a copper-clad laminate according to the method in Example 1, and the following performance tests were performed on it:

[0102] (1) Dielectric constant Dk and dielectric loss factor Df: The dielectric constant Dk and dielectric loss factor Df were measured using the resonant cavity method (SPDR) at a frequency of 10 GHz. The accepting state was the original state, and the state after 4 weeks of oxygen aging treatment at 153 ℃ was the state after thermo-oxidative aging. The rate of change of Df = (Df after thermo-oxidative aging - Df in the original state) / Df in the original state.

[0103] (2) Warpage height: Cut the laminate into 300mm×300mm pieces, etch copper foil on one side, place it on a horizontal platform, and measure the vertical distance between the edge of the board and the platform. This distance is the warpage height.

[0104] (3) Flame retardancy: UL94. For test methods, please refer to UL Flame Retardancy Test Methods, Chapter 8 of UL.

[0105] (4) Adhesive application process: Based on the appearance of the prepreg during the adhesive application process, observe with the naked eye whether there is obvious sagging or stickiness. If the prepreg does not sagging or stickiness at all, the adhesive application process is excellent; if the prepreg has slight sagging, the adhesive application process is good; if the prepreg has severe sagging or stickiness, the adhesive application process is poor.

[0106] (5) Formability of the board: If the board is too brittle and forms granular fragments after being slightly bent, it is considered to have poor formability; if the board cracks or breaks but does not have obvious granular fragments when bent, it is considered to have good formability; if the board does not have the above conditions, it is considered to have excellent formability.

[0107] Table 3. Changes in Df after thermo-oxidative aging treatment at 153℃

[0108]

[0109]

[0110] Table 4 Warpage / Flame Retardancy / Processability / Moldability

[0111]

[0112] Based on the data in Tables 3 and 4, this invention uses TAC as the main component. By compounding it with components such as elastomeric block copolymers, and simultaneously adding 50-70% by mass of filler and 10-35% by mass of halogen-free flame retardant, a high-frequency copper-clad laminate that achieves halogen-free V-0 flame retardancy can be prepared. The laminate also has a low dielectric loss (SPDR@10GHz), ranging from 0.0036 to 0.0045, and good resistance to thermo-oxidative aging. After 4 weeks of thermo-oxidative treatment at 153℃, the change rate of Df is 22.22%-52.94%.

[0113] Specifically, Example 4 exhibits a low initial dielectric loss. Using OPE-2ST helps reduce the initial dielectric loss to 0.0034, while using MX9000 results in a slightly higher initial dielectric loss of 0.0036. Examples 3, 5, and 6 demonstrate strong resistance to thermo-oxidative aging. After 4 weeks of thermo-oxidative aging treatment at 153°C, the dielectric loss change rates are only 28.21%, 22.22%, and 25.00%, respectively. These examples correspond to high TAC contents, ranging from 65% to 70%, which enhances resistance to thermo-oxidative aging. It can be seen that the improved flame retardancy of the embodiments of this invention is superior. Examples 1-7 all achieve V-0 halogen-free flame retardancy. With TAC as the main resin, a certain degree of N and P synergistic flame retardancy is formed with the halogen-free phosphorus-containing flame retardant. In Example 5, the low MX9000 polyphenylene ether content (5%) results in a large warpage height of 3.0 cm, which is not conducive to PCB processing. In Examples 1, 4 and 6, when the polyphenylene ether content was 20%, the warpage height was relatively low, between 1.1 and 1.3 cm.

[0114] Compared with Example 1, Comparative Example 1 replaced TAC with an equal amount of B3000. It can be seen that the initial Df of Comparative Example 1 was greatly optimized, decreasing from 0.0036 in Example 1 to 0.0032 in Comparative Example 1. However, the shortcomings are also very obvious. The flame-retardant sample of Comparative Example 1 burned to the fixture and had no flame retardancy. In addition, its resistance to heat and oxygen aging was also poor. After heat and oxygen aging treatment, the Df change rate of Comparative Example 1 was 112.50%, while that of Example 1 was only 47.22%.

[0115] Compared with Example 1, Comparative Example 2 used an equal amount of R100 styrene-butadiene copolymer to replace the elastic block copolymer. Although V-0 halogen-free flame retardancy and good thermo-oxidative aging resistance could still be achieved after the replacement, serious process problems such as sticky adhesive sheets that could not be rolled up, and brittle and easily broken sheets existed, making normal production and use impossible.

[0116] Compared with Example 1, Comparative Example 3 used 40 parts of TAC with a lower content to replace 50 parts of TAC in Example 1. The thermo-oxidative aging ability of Comparative Example 3 was worse, with a Df change rate of 66.67%, while that of Example 1 was 47.22%. The most serious effect was on the flame retardant performance, which was downgraded from V-0 flame retardant rating to V-1 flame retardant rating.

[0117] Compared with Example 6, Comparative Example 4 used a higher content of 80 parts of TAC to replace the 70 parts of TAC in Example 6. The high content of TAC resulted in very low adhesive viscosity, and the adhesive on the bonding sheet was severely dripped and could not be formed, making it impossible to produce and use normally, and also impossible to test the dielectric properties.

[0118] Compared with Example 1, Comparative Example 5 removed the phosphorus-containing flame retardant, and the corresponding flame retardant test result was V-2, which could not achieve V-0 halogen-free flame retardancy.

[0119] Compared with Example 1, Comparative Example 6 used an equal amount of TAIC to replace TAC, resulting in a decrease in heat and oxygen aging resistance, with the Df change rate increasing from 47.22% to 66.67%.

[0120] The applicant declares that the above embodiments illustrate the resin composition, prepreg, and metal foil-coated laminate of the present invention, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A resin composition, characterized in that, The resin composition includes triallyl cyanurate, an elastomer block copolymer, and a phosphorus-containing flame retardant; The elastomeric block copolymer includes any one or a combination of at least two of the following: styrene-butadiene copolymer, styrene-butadiene-styrene triblock copolymer, styrene-isoprene copolymer, or styrene-isoprene-styrene triblock copolymer. The phosphorus-containing flame retardant is selected from any one or a mixture of at least two of the following: tris(2,6-dimethylphenyl)phosphine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphine, p-xylylbis(diphenylphosphine oxide), phenoxyphosphazene compounds, phosphate esters, polyphosphate esters, phosphonates, polyphosphonates, phosphonate-carbonate copolymers, or organophosphorus phosphonates. Based on the total mass of the resin components in the resin composition being 100%, the content of the triallyl cyanurate is 50-70%; The resin composition also includes polyphenylene ether resin; The polyphenylene ether resin is a polyphenylene ether resin containing unsaturated groups.

2. The resin composition according to claim 1, characterized in that, The number-average molecular weight of the elastomeric block copolymer is ≥50,000.

3. The resin composition according to claim 1, characterized in that, The total mass of the resin components in the resin composition is 100%, and the content of the elastomer block copolymer is 10-30%.

4. The resin composition according to claim 1, characterized in that, The phosphorus-containing flame retardant is selected from phosphonates containing organophosphorus compounds.

5. The resin composition according to claim 1, characterized in that, The content of the phosphorus-containing flame retardant is 10-35% based on the total mass of the resin components in the resin composition being 100%.

6. The resin composition according to claim 1, characterized in that, The resin composition also includes an initiator.

7. The resin composition according to claim 6, characterized in that, The initiator is an organic peroxide.

8. The resin composition according to claim 7, characterized in that, The initiator includes any one or a combination of at least two of the following: dicumyl peroxide, bis-tert-butyl peroxide, tert-butyl perbenzoate, or 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne.

9. The resin composition according to claim 6, characterized in that, The initiator content is 0.1-8% based on the total mass of the resin components in the resin composition being 100%.

10. The resin composition according to claim 1, characterized in that, The polyphenylene ether resin containing unsaturated groups is a polyphenylene ether resin with unsaturated group-terminated ends.

11. The resin composition according to claim 10, characterized in that, The unsaturated group includes any one or at least a combination of two of vinyl, vinylphenyl, vinylbenzyl, or acrylate groups.

12. The resin composition according to claim 1, characterized in that, The polyphenylene ether resin containing unsaturated groups includes poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,3,6-trimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2,6-dipropyl-1,4-phenylene) ether, poly(2-methyl-6-allyl-1,4-phenylene) ether, poly(di-tert-butyl-dimethoxy-1,4-phenylene) ether, and poly(2,6-dimethyl-1,4-phenylene) ether. -Dichloromethyl-1,4-phenylene) ether, poly(2,6-dibromomethyl-1,4-phenylene) ether, poly(2,6-di(2-chloroethyl)-1,4-phenylene) ether, poly(2,6-xylyl-1,4-phenylene) ether, poly(2,6-dichloro-1,4-phenylene) ether, poly(2,6-diphenyl-1,4-phenylene) ether or poly(2,5-dimethyl-1,4-phenylene) ether, or any one or at least two combinations thereof.

13. The resin composition according to claim 12, characterized in that, The polyphenylene ether in the polyphenylene ether resin containing unsaturated groups includes poly(2,6-dimethyl-1,4-phenylene) ether.

14. The resin composition according to claim 1, characterized in that, The content of the polyphenylene ether resin is 1-30% based on the total mass of the resin components in the resin composition being 100%.

15. The resin composition according to claim 1, characterized in that, The resin composition also includes fillers.

16. The resin composition according to claim 15, characterized in that, The filler is a powder filler, including any one or a combination of at least two of the following: crystalline silica, amorphous silica, spherical silica, angular silica, chemically produced silica, silica micropowder, hollow glass microspheres, titanium dioxide, strontium titanate, barium titanate, boron nitride, aluminum nitride, silicon nitride, silicon carbide, alumina, polytetrafluoroethylene, polyphenylene sulfide, or polyethersulfone.

17. The resin composition according to claim 15, characterized in that, The filler content is 50-70% based on the total mass of the resin composition (100%).

18. A resin adhesive, characterized in that, The resin solution is obtained by dissolving or dispersing the resin composition as described in any one of claims 1-17 in a solvent.

19. A resin film, characterized in that, The material of the resin film includes the resin composition as described in any one of claims 1-17.

20. The resin film according to claim 19, characterized in that, The resin film is obtained by coating the resin composition onto a release material and then drying and / or semi-curing it.

21. A semi-cured sheet, characterized in that, The prepreg comprises a reinforcing material and a resin composition as described in any one of claims 1-17 attached to the reinforcing material.

22. The semi-cured sheet according to claim 21, characterized in that, The resin composition is attached to the reinforcing material after impregnation and drying.

23. A metal foil-coated laminate, characterized in that, The metal foil laminate includes a metal foil and at least one of the resin film as described in claim 19 or 20 or the prepreg as described in claim 21 or 22.

24. A printed circuit board, characterized in that, The printed circuit board includes at least one of the following: the resin film as described in claim 19 or 20, the prepreg as described in claim 21 or 22, or the metal foil laminate as described in claim 23.

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