Phosphorus-containing benzoxazine resin, resin composition and application

Abstract

The application discloses a phosphorus-containing benzoxazine resin, a resin composition and application, and comprises a structural formula (1): wherein Y is an epoxy resin residue; a T group is one of C1-C4 straight-chain or branched-chain alkane, substituted or unsubstituted aryl, and substituted or unsubstituted aryloxy; a Z group is direct connection, C1-C5 alkylene, substituted or unsubstituted arylene, sulfoxide group, sulfido group or C3-20 alicyclic group; and R is phenyl or substituted phenyl, naphthyl or substituted naphthyl, C1-C5 alkyl or an unsaturated double bond-containing group. The phosphorus-containing benzoxazine resin containing a phenolic hydroxyl group is adopted, the reaction crosslinking points are increased, the reaction crosslinking points are more uniformly distributed, the overall crosslinking density is further improved, the phenoxyl bond and the phosphorus-containing group are matched, the brittleness of a cured product is improved, the halogen-free flame-retardant requirement is met, when the maleimide resin is matched, excellent halogen-free flame retardancy is obtained, the heat resistance, water absorption, moisture resistance are not reduced, and the toughness is further improved, the CTE and warping are reduced.

Description

Technical Field

[0001] This invention relates to the field of electronic materials technology, and in particular to a phosphorus-containing benzoxazine resin, resin composition and its application. Background Technology

[0002] With the development of communication technology, printed circuit boards (PCBs) need to accommodate more chips and modules, requiring copper-clad laminates to have high dimensional stability, high heat resistance, and a low coefficient of thermal expansion. As electronic products become smaller and circuit designs become denser, more and more design companies are adopting HDI (High-Intensity Discharge) processes, demanding improved performance from substrate materials in terms of dimensional stability, resistance to repeated thermal shocks, and long-term thermo-oxidative aging. Traditional resin formulations can no longer meet these requirements. On the other hand, influenced by the EU's "green" regulations, the use of bromine as a flame retardant in polymer science has become a subject of intense debate. Although tetrabromobisphenol A (TBBPA) as a flame retardant has not yet been found to have significant negative environmental impacts, calls for its inclusion as a prohibited substance are growing louder. Therefore, the reliance on bromine for flame retardancy will inevitably decrease in the future.

[0003] Benzooxazine resin has a small curing shrinkage rate during high-temperature polymerization reaction, and the cured product has high heat resistance, high carbon residue, and excellent thermal stability. Therefore, it is widely used in the field of copper clad laminates. However, it has disadvantages such as poor toughness, poor rigidity, and poor dielectric properties. Furthermore, relying solely on the nitrogen atoms of benzooxazine resin is insufficient to meet the requirements for halogen-free flame retardancy.

[0004] Existing technology JP2020158705 discloses a technical solution combining maleimide resin, allyl benzoxazine resin, and polymer resin. This solution improves the toughness of the cured product to a certain extent and maintains good heat resistance. However, the polymer resin has poor compatibility with other resins and is prone to precipitating to the surface during the curing process, affecting the adhesion between the insulating resin and the copper foil, water absorption, etc. Existing technology CN109082118 discloses a technical solution combining maleimide resin, benzoxazine resin, and flame retardant. The flame retardant is a flame retardant with a thermal decomposition temperature greater than 380℃, a hypophosphite metal salt flame retardant, and decabromodiphenyl ethane, all of which are additive flame retardants. When an appropriate amount of flame retardant is added, the flame retardancy after curing can reach the UL94 V-0 level. However, the additive flame retardant affects the heat resistance and hygrothermal properties of the cured product to varying degrees.

[0005] Therefore, the present invention provides a phosphorus-containing benzoxazine resin, resin composition and application, and provides a resin material and resin composition that simultaneously meets the requirements of excellent heat resistance, low CTE, high toughness, low water absorption and good flame retardancy, which obviously has positive practical significance. Summary of the Invention

[0006] The purpose of this invention is to provide a phosphorus-containing benzoxazine resin, resin composition, and application that achieves excellent halogen-free flame retardancy without reducing heat resistance, water absorption, or moisture resistance, and further improves toughness, reduces CTE, and reduces warpage.

[0007] To achieve the above-mentioned objectives, the technical solution adopted by this invention is: a phosphorus-containing benzoxazine resin, comprising the structural formula (1):

[0008]

[0009] Where Y represents epoxy resin residues, and n is an integer from 1 to 10;

[0010] X is

[0011] The T group is one of the following: a C1-C4 straight-chain or branched alkane, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryloxy group;

[0012] Z-group can be directly linked, C1-C5 alkylene, substituted or unsubstituted arylene, sulfoxide, thionyl or C3-20 alicyclic group;

[0013] R is a phenyl or substituted phenyl, naphthyl or substituted naphthyl, C1-C5 alkyl, or a group containing an unsaturated double bond. In the above technical solution, the Y group is a ring-opening residue of the epoxy resin, such as the following groups:

[0014] R1 and R2 may be the same or different, and are selected from hydrogen, C1-C5 alkyl or unsaturated groups, respectively.

[0015] Preferably, in the structural formula (1), the R group is one of the following: a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted styryl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted acrylate group.

[0016] Preferably, in the structural formula (1), the R group is allyl, propenyl, vinyl, styrene or styrene.

[0017] Preferably, it is obtained by reacting a phosphorus-containing bisphenol compound of structural formula (2) with an epoxy resin, and then reacting it with a monoamine compound;

[0018]

[0019] Wherein, Z is a directly linked, C1-C5 alkylene group, substituted or unsubstituted arylene group, sulfoxide group, thionyl group or C3-20 alicyclic group;

[0020] The T group is one of the following: a C1-C4 straight-chain or branched alkane, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryloxy group.

[0021] Preferably, the reaction molar ratio of the phosphorus-containing bisphenol resin and the epoxy resin is 2:1.

[0022] Preferably, the reaction temperature of the phosphorus-containing bisphenol resin and the epoxy resin is 120-180℃, and the reaction time is 2h-10h.

[0023] Preferably, during the above reaction process, a catalyst is added as needed, and the catalyst is selected from at least one of alkali metal hydroxide, tertiary amine compound, quaternary ammonium compound, tertiary phosphine compound and tertiary phosphonium compound or imidazole compound.

[0024] This application also claims a resin composition comprising the phosphorus-containing benzoxazine resin described above.

[0025] Preferably, by weight, it comprises:

[0026] (A) Phosphorus-containing benzoxazine resin: 5-50 parts by weight;

[0027] (B) Maleimide resin: 30-100 parts by weight.

[0028] Preferably, by weight, it comprises:

[0029] (A) Phosphorus-containing benzoxazine resin: 5-50 parts by weight;

[0030] (B) Maleimide resin: 30-100 parts by weight;

[0031] (C) Epoxy resin: 10-100 parts by weight.

[0032] In the above technical solution, the maleimide resin is a compound whose molecular structure contains at least two maleimide groups, specifically selected from the maleimide resins shown in the following structures.

[0033]

[0034] Wherein, R2 is hydrogen, methyl, or ethyl, and R1 is methylene, ethylene, or... n is 0 or an integer from 1 to 10;

[0035]

[0036] Where n is an integer from 1 to 10;

[0037]

[0038] Where n is an integer from 1 to 10;

[0039]

[0040] Where n is an integer from 1 to 10;

[0041]

[0042] Where n is an integer from 1 to 10;

[0043]

[0044] Where n is an integer from 1 to 10;

[0045]

[0046] Where n is an integer from 1 to 10, and m is an integer from 1 to 10;

[0047]

[0048] Where n is an integer from 1 to 10, and m is an integer from 1 to 10;

[0049]

[0050] Where n is an integer from 1 to 10;

[0051]

[0052] Furthermore, the maleimide resin is selected from Yamato Chemical's BMI-2300, BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-4000, BMI-5100, KI Chemical's BMI-70, BMI-80, and Nippon Kayaku's MIR-3000 and MIR-5000.

[0053] In the above technical solution, the epoxy resin is selected from any one or a combination of at least two of the following: dicyclopentadiene epoxy resin, phosphorus-containing epoxy resin, isocyanate-modified epoxy resin, biphenyl epoxy resin, bisphenol A type epoxy resin, phenolic epoxy resin, o-cresol aldehyde type epoxy resin, epoxidized polybutadiene resin, naphthalene-containing epoxy resin, bisphenol F type epoxy resin, trifunctional epoxy resin, hydrogenated bisphenol A epoxy resin, or hydrogenated bisphenol F type epoxy resin. Typical but non-limiting combinations include: dicyclopentadiene epoxy resin and phosphorus-containing epoxy resin, biphenyl epoxy resin and bisphenol A type epoxy resin, o-cresol aldehyde type epoxy resin and epoxidized polybutadiene resin, and o-cresol aldehyde type epoxy resin and dicyclopentadiene type epoxy resin.

[0054] More preferably, the epoxy resin is selected from at least one of the following structures:

[0055]

[0056] The number of repeating units (p, n, m) in the above structures (16) to (21) are integers from 1 to 10.

[0057] More preferably, the epoxy resin is selected from DIC's HP4032, HP4032H, HP4032D, HP4032SS, HP4700, HP4710, N-690, N-695, HP7200, HP7200H, HP7200HH, EXA7311, HP6000, Nippon Kayaku's NC3000, NC7000, NC3100, and Nippon Steel Chemical's ESN475V, ESN485.

[0058] In the above technical solution, the resin composition further contains filler. The filler content is 20-200 parts by weight per 100 parts by weight of the resin composition.

[0059] The filler includes inorganic fillers, organic fillers, and composite fillers. Preferably, the filler is spherical silica, boehmite, alumina, or aluminum hydroxide, and more preferably spherical silica.

[0060] Furthermore, the filler is surface-treated with a silane coupling agent containing reactive groups, wherein the silane coupling agent is at least one of an aminosilane coupling agent, a silane coupling agent containing carbon-carbon double bonds, or an epoxysilane coupling agent. Preferably, the silane coupling agent is selected from the following structures:

[0061]

[0062] In the above technical solution, the benzoxazine resin and maleimide resin in the resin composition can be prepolymerized at a prepolymerization temperature of 100-150℃ and a prepolymerization time of 30-120min.

[0063] In the above technical solution, the resin composition also contains a flame retardant, which is 1-50 parts by weight per 100 parts by weight of the total resin composition.

[0064] The flame retardant is selected from at least one of the following: bromine-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, organosilicon flame retardants, organometallic flame retardants, and inorganic flame retardants.

[0065] Among them, bromine-based flame retardants can be decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene, or tetrabromophthalamide. Phosphorus-based flame retardants can be inorganic phosphorus, condensed phosphate compounds, phosphonic acid compounds, phosphonic acid compounds, phosphine oxide compounds, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris(2,6-dimethylphenyl)phosphine, (m is an integer from 1 to 5) Organic phosphorus-containing compounds such as phosphononitriles. Nitrogen-based flame retardants can be triazine compounds, cyanuric acid compounds, isocyanate compounds, and phenothiazine compounds. Organosilicon flame retardants can be organosilicon oils, organosilicon rubbers, and organosilicon resins. Organometallic salt flame retardants can be ferrocene, acetylacetone metal complexes, and organometallic carbonyl compounds. Inorganic flame retardants can be aluminum hydroxide, magnesium hydroxide, aluminum oxide, and barium oxide.

[0066] Of course, the types of flame retardants are not limited to this. It is understood that the added flame retardants can be selected according to the specific application field of the laminate. For example, in application fields that require halogens, non-halogen flame retardants are preferred, such as phosphorus-containing or nitrogen-containing flame retardants, and more preferably phosphazene or DOPO.

[0067] Preferably, when selecting a phosphorus-containing flame retardant, it can form a nitrogen-phosphorus synergistic flame retardant with the nitrogen element of the active ester compound in the curing agent, thereby improving the flame retardant efficiency.

[0068] Furthermore, the aforementioned resin composition also contains 0.01 to 5 parts by weight of a catalyst, which is at least one of imidazole catalysts, pyridine catalysts, and organometallic salt catalysts.

[0069] Preferably, the catalyst is at least one selected from 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole, and zinc octoate.

[0070] Preferably, the modified imidazole has the following structure:

[0071] Among them, R3, R4, R5, and R6 may be the same or different, representing methyl, ethyl, or tert-butyl, respectively, and B represents methylene, ethylene, or... Modified imidazole with the brand name P200F50 prepared by JER Corporation can be used.

[0072] Among them, R3, R4, R5, and R6 may be the same or different, representing methyl, ethyl, or tert-butyl, respectively, and A represents methylene, ethylene, or... Alternatively, an aromatic hydrocarbon group may be used, such as a modified imidazole with the brand name G8009L prepared by Daiichi Kogyo Co., Ltd.

[0073] This application also claims the use of the resin composition described above in prepregs, laminates and printed circuit boards.

[0074] When the resin composition described in this application is applied to a prepreg, the prepreg includes a reinforcing material and the aforementioned resin composition. The prepreg is prepared by dissolving the resin composition in a solvent to form a syrup, then immersing the reinforcing material in the syrup, taking out the immersed reinforcing material and baking it at 100-180°C for 1-15 minutes; after drying, a prepreg is obtained.

[0075] The solvent is selected from at least one of acetone, butanone, toluene, methyl isobutyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, and cyclohexane.

[0076] The reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics. Preferably, the reinforcing material is glass fiber cloth; the glass fiber cloth is preferably open-fiber cloth or flat cloth; the glass fiber cloth is preferably E glass fiber cloth, S glass fiber cloth, T glass fiber cloth, or Q glass fiber cloth.

[0077] Furthermore, when glass fiber cloth is used as the reinforcing material, it is chemically treated with a coupling agent to improve the interfacial bonding between the resin composition and the glass fiber cloth. Epoxy silane coupling agents or amino silane coupling agents are preferred to provide good water and heat resistance.

[0078] When the resin composition described in this application is applied to a laminate, the laminate includes a prepreg sheet and a metal foil disposed on at least one surface of the prepreg sheet; or it includes a composite sheet formed by stacking multiple prepreg sheets and a metal foil disposed on at least one surface of the composite sheet.

[0079] The laminate is prepared by the following method: metal foil is coated onto one or both surfaces of a prepreg, or at least two prepregs are stacked to form a composite sheet, and metal foil is coated onto one or both surfaces of the composite sheet. The laminate is then hot-pressed to obtain a metal foil laminate. The hot-pressing conditions are: pressing at 0.2–2 MPa and 150–250°C for 2–4 hours.

[0080] Preferably, the metal foil is selected from copper foil or aluminum foil. The thickness of the metal foil is 1 μm, 1.5 μm, 3 μm, 5 μm, 8 μm, 12 μm, 18 μm, 35 μm or 70 μm.

[0081] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art:

[0082] 1. This invention uses a phosphorus-containing benzoxazine resin containing phenolic oxygen groups, which increases the number of reaction crosslinking points and makes the reaction crosslinking points more evenly distributed, thereby further improving the overall crosslinking density. In addition, the combination of phenoxy bonds and phosphorus-containing groups improves the brittleness of the cured product while achieving the requirements of halogen-free flame retardancy. When combined with maleimide resin, it achieves excellent halogen-free flame retardancy without reducing heat resistance, water absorption, or moisture resistance, and further improves toughness, reduces CTE and warpage.

[0083] 2. The resin composition provided by the present invention has excellent comprehensive properties and has broad development and application prospects in the fields of prepreg, laminate and printed circuit board. Detailed Implementation

[0084] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0085] Synthesis Example 1: Synthesis of benzoxazine resin A

[0086] Step 1: Add 536g of phosphorus-containing bisphenol compound (shown in the following structural formula), 358g of dicyclopentadiene epoxy resin and 700g of toluene solvent to the reaction vessel, heat to 100℃ and stir evenly to dissolve, then add 0.05g of imidazole compound, continue to heat to 145℃ and keep the reaction at this temperature for 8 hours, then cool to room temperature to obtain intermediate reactant A-1.

[0087] (T represents phenyl, Z represents...) )

[0088] Step 2: Continue to add 83g of formaldehyde (36% formalin solution) and 93g of aniline compound to the above intermediate reactant A-1, then heat to 95℃ and react for 6 hours. Then, take out the reactant, dry it under reduced pressure at 130℃ for 4 hours, and pulverize it to obtain thermosetting benzoxazine resin A.

[0089] Synthesis Example 2: Synthesis of benzoxazine resin B (different from Synthesis Example 1, containing a different phosphorus resin).

[0090] Step 1: Add 505g of phosphorus-containing bisphenol compound (shown in the following structural formula), 358g of dicyclopentadiene epoxy resin and 700g of toluene solvent to the reaction vessel, heat to 100℃ and stir evenly to dissolve, then add 0.05g of imidazole compound, continue to heat to 145℃ and keep the reaction at this temperature for 8 hours, then cool to room temperature to obtain intermediate reactant B-1.

[0091] (T stands for methyl, Z stands for...) )

[0092] Step 2: Continue to add 83g of formaldehyde (36% formalin solution) and 93g of aniline compound to the above intermediate reactant A-1, then heat to 95℃ and react for 6 hours. Then, take out the reactant, dry it under reduced pressure at 130℃ for 4 hours, and pulverize it to obtain thermosetting benzoxazine resin B.

[0093] Synthesis Example 3: Synthesis of benzoxazine resin C (compared to Comparative Example 1, it contains allylbenzene at the end)

[0094] Step 1: Add 536g of phosphorus-containing bisphenol compound (shown in the following structural formula), 358g of dicyclopentadiene epoxy resin and 700g of toluene solvent to the reaction vessel, heat to 100℃ and stir evenly to dissolve, then add 0.05g of imidazole compound, continue to heat to 145℃ and keep the reaction at this temperature for 8 hours, then cool to room temperature to obtain intermediate reactant C-1.

[0095] (T represents phenyl, Z represents...) )

[0096] Step 2: 83g of formaldehyde (36% formalin solution) and 133g of allyl aniline compound were added dropwise to the above intermediate reactant A-1. The mixture was then heated to 90°C and reacted for 5 hours. The reactant was then removed, dried under reduced pressure at 130°C for 4 hours, and pulverized to obtain thermosetting benzoxazine resin C.

[0097] Synthesis Example 4: Benzooxazine-modified maleimide resin prepolymer D

[0098] Add 40g of benzoxazine resin C, 100g of maleimide resin (structural formula (6)) and 200g of toluene solvent to the reaction flask, raise the reaction temperature to 120℃, stir evenly and start the reaction for 60min to obtain phosphorus-containing benzoxazine modified maleimide resin prepolymer D.

[0099] Synthesis Example 5: Phosphorus-containing benzoxazine resin E

[0100] 505g of a phosphorus-containing bisphenol compound (shown in the following structural formula) was added to a reaction vessel, along with 166g of formaldehyde (36% formalin solution) and 186g of aniline compound. The mixture was then heated to 100°C and reacted for 8 hours. The reactant was then removed, dried under reduced pressure at 130°C for 4 hours, and pulverized to obtain thermosetting benzoxazine resin E.

[0101] (T represents phenyl, Z represents...) )

[0102] Example 1

[0103] In this embodiment, by weight, 35 parts of benzoxazine resin A, 70 parts of maleimide resin A, 0.1 parts of catalyst and 80 parts of filler are mixed with solvent to adjust the solid content of the adhesive to 60%. The adhesive is then coated onto E glass fiber cloth, soaked, and placed in a 160°C forced-air drying oven for 3-6 minutes to produce a semi-cured sheet A.

[0104] Example 2

[0105] In this embodiment, by weight, 30 parts of benzoxazine resin B, 65 parts of maleimide resin A, 5 parts of maleimide resin B, 0.1 parts of catalyst and 80 parts of filler are mixed with solvent to adjust the solid content of the adhesive to 60%. The adhesive is then coated onto E glass fiber cloth, soaked, removed and placed in a 160°C forced-air drying oven for 3-6 minutes to prepare semi-cured sheet B.

[0106] Example 3

[0107] In this embodiment, by weight, 45 parts of benzoxazine resin C, 60 parts of maleimide resin B, 20 parts of epoxy resin, 0.1 parts of catalyst and 80 parts of filler are mixed with solvent to adjust the solid content of the adhesive to 60%. The adhesive is then coated onto E glass fiber cloth, soaked, removed and placed in a 160°C forced-air drying oven for 3-6 minutes to prepare a semi-cured sheet C.

[0108] Example 4

[0109] In this embodiment, by weight, 90 parts of prepolymer D, 0.1 parts of catalyst and 80 parts of filler are mixed with solvent to adjust the adhesive solution to a solid content of 60%. The adhesive solution is coated onto E glass fiber cloth, soaked and then placed in a 160°C forced-air drying oven and baked for 3-6 minutes to produce a semi-cured sheet D.

[0110] Example 5

[0111] In this embodiment, by weight, 85 parts of prepolymer D, 20 parts of epoxy resin, 0.1 parts of catalyst and 80 parts of filler are mixed with solvent to adjust the adhesive solution to a solid content of 60%. The adhesive solution is coated onto glass fiber cloth E, soaked, and then placed in a 160°C forced-air drying oven for 3-6 minutes to produce a semi-cured sheet E.

[0112] Example 6

[0113] In this embodiment, by weight, 20 parts of benzoxazine resin A, 20 parts of benzoxazine resin B, 60 parts of maleimide resin A, 20 parts of epoxy resin, 0.1 parts of catalyst and 80 parts of filler are mixed with solvent to adjust the adhesive solution to a solid content of 60%. The adhesive solution is coated onto E glass fiber cloth, soaked, removed and placed in a 160℃ forced-air drying oven for 3-6 minutes to prepare a semi-cured sheet F.

[0114] Example 7

[0115] In this embodiment, by weight, 50 parts of benzoxazine resin B, 30 parts of maleimide resin A, 50 parts of epoxy resin, 0.1 parts of catalyst and 80 parts of filler are mixed with solvent to adjust the solid content of the adhesive to 60%. The adhesive is then coated onto E glass fiber cloth, soaked, removed and placed in a 160°C forced-air drying oven for 3-6 minutes to prepare a semi-cured sheet G.

[0116] Comparative Example 1

[0117] By weight, 35 parts of benzoxazine resin E, 70 parts of maleimide resin A, 0.1 parts of catalyst and 80 parts of filler are mixed with solvent to adjust the solid content of the adhesive to 60%. The adhesive is coated onto E glass fiber cloth, soaked, and then placed in a 160℃ forced-air drying oven for 3-6 minutes to make a semi-cured sheet H.

[0118] Comparative Example 2

[0119] By weight, 30 parts of benzoxazine resin F, 65 parts of maleimide resin A, 5 parts of maleimide resin B, 0.1 parts of catalyst and 80 parts of filler are mixed with solvent to adjust the solid content of the adhesive to 60%. The adhesive is then coated onto E glass fiber cloth, soaked, and placed in a 160℃ forced-air drying oven for 3-6 minutes to prepare semi-cured sheet I.

[0120] Comparative Example 3

[0121] By weight, 40 parts of benzoxazine resin G, 60 parts of maleimide resin A, 25 parts of epoxy resin, 5 parts of combustion improver, 0.1 parts of catalyst and 80 parts of filler are mixed with solvent to adjust the adhesive solution to a solid content of 60%. The adhesive solution is coated onto E glass fiber cloth, soaked, and then placed in a 160℃ forced-air drying oven for 3-6 minutes to make a semi-cured sheet J.

[0122] In the above, the components and their weight parts used in Examples 1-7 and Comparative Examples 1-3 are shown in Table 1, and the grades of the components are shown in Table 2.

[0123] The prepregs prepared in Examples 1-7 and Comparative Examples 1-3 were cut to 300×300mm. An electrolytic copper foil was placed on each side of the prepreg and stacked into a certain structure. The prepregs were then pressed in a vacuum press to obtain a metal foil laminate (or copper-clad laminate). The specific performance tests are shown in Table 3.

[0124] Table 1. Substances and weight parts of each component:

[0125]

[0126]

[0127] Table 2. Material Grades:

[0128]

[0129] The methods for performance testing of the copper-clad laminates prepared in all Examples 1-7 and Comparative Examples 1-2 mainly include:

[0130] 1) The glass transition temperature was determined using DMA (thermomechanical analysis) at a heating rate of 10℃ / min;

[0131] 2) PCT 2HR water absorption rate determination: Take 3 samples of 10cm×10cm thickness and 0.40mm thickness with metal foil removed on both sides, dry them at 100℃ for 2 hours, weigh them and record the weight as W1, then treat them in a pressure cooker tester at 121℃ and 2 atmospheres for 2 hours, weigh them and record the weight as W2, and determine the water absorption rate as (W2-W1) / W1×100%.

[0132] 3) Determination of X / Y coefficient of thermal expansion (CTE): TMA (thermomechanical analysis) was used, with a heating rate of 10℃ / min and a test temperature range of 30~100℃;

[0133] 4) Dk and Df: Determined at 10 GHz using the plate method according to IPC-TM-650 2.5.5.9.

[0134] 5) Curing shrinkage rate: The shrinkage rate of the cured material before and after curing was tested by TMA during a temperature cycle of room temperature - 260℃ and back to room temperature.

[0135] 6) Flame retardancy: Tested according to UL94 standard.

[0136] Table 3. Performance Test Results:

[0137]

[0138] The test results above show that the copper-clad laminates prepared in Examples 1-7 have better halogen-free flame retardancy than those in Comparative Examples 1-3, without reducing heat resistance, water absorption, or moisture resistance. They also further improve toughness, reduce CTE and warpage, and have low coefficient of thermal expansion, low dielectric constant, low dielectric loss, high adhesion, and low curing shrinkage, resulting in superior overall performance.

[0139] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A resin composition, characterized in that, By weight, including: (A) Phosphorus-containing benzoxazine resin: 5-50 parts by weight; (B) Maleimide resin: 30-100 parts by weight; The phosphorus-containing benzoxazine resin includes the structural formula (1): Structural formula (1) Where Y represents epoxy resin residues, and n is an integer from 1 to 10; X is ; The T group is either phenyl or methyl; Z-base is ; R is a phenyl group; The phosphorus-containing benzoxazine resin is obtained by reacting a phosphorus-containing bisphenol compound of structural formula (2) with a dicyclopentadiene-type epoxy resin, and then reacting it with formaldehyde and aniline. Structural formula (2) Where Z is ; The T group is either phenyl or methyl; The resin composition also contains filler, and the filler content is 20-200 parts by weight per 100 parts by weight of the resin composition; the filler is silicon dioxide.

2. The resin composition according to claim 1, characterized in that, The resin composition further comprises (C) epoxy resin: 10-100 parts by weight.

3. The resin composition according to claim 1, characterized in that, The reaction molar ratio of the phosphorus-containing bisphenol resin and the dicyclopentadiene-type epoxy resin is 2:

1.

4. The resin composition according to claim 1, characterized in that, The filler is surface-treated with a silane coupling agent containing reactive groups.

5. An application of the resin composition according to claim 1, characterized in that, It is used in prepregs, laminates and printed circuit boards.

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