Allyl-based flame-retardant prepolymers, resin compositions, composite resins, prepregs, and laminates

Abstract

The present invention discloses an allyl-based flame-retardant prepolymer, a resin composition, a composite resin, a prepreg, and a laminate. The allyl-based flame-retardant prepolymer according to the present invention is obtained by prepolymerizing an allyl benzoxazine compound and an allyl phosphorus-containing compound having a mass ratio of 100:(20-80). The resin composition, composite resin, prepreg, and laminate produced using the allyl-based flame-retardant prepolymer according to the present invention have strong flame retardant performance, excellent high-temperature elastic modulus performance, excellent heat resistance and water absorption, and extremely excellent dielectric properties.

Description

Technical Field

[0001] The present invention belongs to the technical field of copper-clad laminates, and specifically relates to allyl-based flame-retardant prepolymers, resin compositions, composite resins, prepregs and laminates.

Background Art

[0002] A copper foil-clad laminate (copper-clad laminate) is a plate-like material manufactured by impregnating a reinforcing material with a resin, coating copper foil on one or both sides, and heating and pressing. In a printed circuit board, the copper-clad laminate can play roles of interconnection conduction, insulation and support, and has a great influence on signal transmission speed, energy loss and characteristic impedance in the circuit. With the further development of communication technology, the requirements for copper-clad laminates have become diversified.

[0003] Bismaleimide resin (BMI) is a novel high-performance resin material with excellent heat resistance and high-temperature elastic modulus retention rate. However, when used alone, it has drawbacks such as too high curing temperature and low solubility. The modified bismaleimide (BMI) overcomes some of the above drawbacks and is widely used in the manufacture of copper-clad laminate substrates, but its flame retardancy is insufficient and it cannot reach the UL-94V0 level. In order to achieve the flame retardant performance of copper-clad laminates, generally, a resin containing flame retardant elements such as P, N, Si, etc. is added as a blending component. The most effective in terms of flame retardancy is to add a phosphorus-containing flame retardant such as a phosphorus-containing epoxy resin and a phosphazene compound. However, if the addition amount of the phosphorus-containing flame retardant is too high, it will have an adverse effect on the heat resistance and high-temperature elastic modulus retention rate of the substrate.

[0004] Patent document CN109504087A discloses a resin composition using a modified bismaleimide prepolymer as a raw material. The resulting copper-clad laminate has a certain degree of heat resistance and flame retardancy, but lacks toughness and has a low retention rate of high-temperature modulus. Patent document CN106336662A discloses a thermosetting resin composition in which an allyl-modified polyphenylene ether resin is added to the compound components. The resulting laminate has high flame retardancy, but its glass transition temperature is low (about 200°C), which is lower than the average value of BT resin substrates (200°C to 300°C), and its peel strength is not ideal.

[0005] In light of this, there is a need to provide a resin composition with excellent overall performance. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Chinese Patent Application Publication No. 109504087 Specification [Patent Document 2] Chinese Patent Application Publication No. 106336662 Specification [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] The present invention aims to provide allyl-based flame-retardant prepolymers, resin compositions, and composite resins, as well as prepregs and laminates manufactured therefrom. These laminates exhibit high flame retardancy, high peel strength, low water absorption, and high high-temperature modulus retention. [Means for solving the problem]

[0008] A first aspect of the present invention comprises 100 parts by mass of an allylbenzoxazine compound and 20 to 80 parts by mass of an allylphosphorus-containing compound. The structural formula of the allylrin-containing compound is, [ka] And, The allylbenzoxazine compound is at least one selected from the group consisting of compounds represented by the following structural formula, [ka] X is independently selected from -CHR1-, -CR2R3-, -SO2-, or -O-. R1, R2, and R3 each independently provide an allyl-based flame-retardant prepolymer selected from -H or -CH3.

[0009] In some embodiments of the present invention, the structural formula of the allylbenzoxazine compound in the allyl flame-retardant prepolymer is shown below. [ka]

[0010] In some embodiments of the present invention, the allyl-based flame retardant prepolymer further comprises 10 to 20 parts by mass of a phosphorus-free allyl compound, The phosphorus-free allyl compound is at least one selected from the group consisting of allylbisphenol A, allylbisphenol S, and allyldiphenyl ether.

[0011] In some embodiments of the present invention, the allyl-based flame-retardant prepolymer is obtained by mixing the allylbenzoxazine compound and the allyl phosphorus-containing compound and heating them at 100°C to 130°C for 1 to 3 hours.

[0012] A second aspect of the present invention provides a resin composition comprising, by mass, 10 to 30 parts by the allyl-based flame-retardant prepolymer described in the first aspect of the present invention, 50 to 100 parts by the bismaleimide resin, 30 to 80 parts by the cyanate ester resin, 5 to 30 parts by the functional resin, and 10 to 60 parts by the inorganic filler as constituent components.

[0013] In some embodiments of the present invention, in the resin composition, the bismaleimide resin is selected from organic compounds containing two or more maleimide structures in the molecular structure, and / or the cyanate ester resin is at least one selected from the group consisting of bisphenol A type cyanate ester resin, novolac type cyanate ester resin, bisphenol F type cyanate ester resin, polyfunctional type cyanate ester resin, bisphenol M type cyanate ester resin, bisphenol E type cyanate ester resin, and dicyclopentadiene bisphenol type cyanate ester resin, and / or the functional resin is at least one selected from the group consisting of epoxy resin, polyphenylene ether, and hydrocarbon resin, and / or the inorganic filler is at least one selected from the group consisting of zirconium vanadate, zirconium tungstate, hafnium tungstate, crystallized glass, eucryptite, silica, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc powder, alumina, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, clay, and kaolin.

[0014] In some embodiments of the present invention, the resin composition further contains 1 to 5 parts by mass of an auxiliary agent, and the auxiliary agent is at least one selected from the group consisting of a curing accelerator, a coupling agent, and a reinforcing agent.

[0015] A third aspect of the present invention provides a composite resin containing the allyl-based flame-retardant prepolymer according to the first aspect of the present invention or the resin composition according to the second aspect of the present invention.

[0016] A fourth aspect of the present invention provides a prepreg containing a reinforcing material and a resin material supported on the reinforcing material, wherein the resin material is the composite resin according to the third aspect of the present invention.

[0017] The fifth aspect of the present invention provides a laminated board containing the prepreg according to the fourth aspect of the present invention as a manufacturing raw material.

Advantages of the Invention

[0018] Copper-clad laminated boards with bismaleimide as the main resin material have excellent heat resistance but insufficient flame retardant performance. In order to improve their flame retardancy, pretreatment such as adding a large amount of flame retardants or inorganic fillers to the formulation components or modifying the raw material resin is often carried out. The present invention uses an allyl-based flame retardant prepolymer with an appropriate addition amount and combines it with components such as bismaleimide and other functional resins, inorganic fillers, and auxiliaries to comprehensively improve the flame retardant heat resistance of the resin composition. The laminated board (copper-clad laminated board) manufactured using this resin not only has flame retardancy but also has excellent comprehensive performance.

[0019] In the present invention, an allylbenzoxazine-based compound and an allyl phosphorus-containing compound are used for prepolymerization to obtain a flame retardant prepolymer rich in allyl groups, which is added to the bismaleimide resin to form a resin composition together with other components. By the bonding of allyl groups in the resin composition to each other, the straight chain of benzoxazine can be extended, the stress in the reaction process can be reduced, the toughness of the resin composition can be improved, and the swelling and shrinkage of the resin composition can be reduced.

[0020] In the resin composition according to the present invention, nitrogen and phosphorus elements exert a synergistic effect and can further improve its flame retardant performance. <好

[0021] The laminated board according to the present invention can reach a UL-94V0 overall flame retardant level, has a high glass transition temperature (Tg>300 °C), high peel strength, high high-temperature elastic modulus retention rate (flexural elastic modulus, storage elastic modulus), low coefficient of thermal expansion (CTE), low water absorption rate, and extremely strong dielectric properties.

Embodiments for Carrying out the Invention

[0022] The present invention will be further described below with reference to embodiments and examples. These embodiments are merely for illustrative purposes and do not limit the scope of the present invention. Furthermore, after reading the description of the present invention, those skilled in the art can make various changes and modifications to the present invention, and these equivalent forms are also included within the scope of the claims of this application.

[0023] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which the present invention pertains. The terms used herein are for illustrative purposes only and are not intended to limit the present invention.

[0024] [term] Unless otherwise stated or contradicted, terms or expressions used herein have the following meanings:

[0025] As used herein, the selection of terms “and / or,” “or / and,” and “and / or else” includes any one of two or more related enumerated items, and further includes any and all combinations of related enumerated items, the any and all combinations of any two related enumerated items, any more related enumerated items, or any combination of all related enumerated items. It goes without saying that, as can be understood, when connecting at least three items with a combination of at least two conjunctions selected from “and / or,” “or / and,” and “and / or else,” such technical means in this application include technical means connected by a “logical AND,” and further include technical means connected by a “logical OR.” For example, “A and / or B” includes three meanings: A, B, and A+B. For example, the technical means "A and / or B and / or C and / or D" includes any one of A, B, C, and D (i.e., a technical means in which all are connected by "logical OR"), any and all combinations of A, B, C, and D (i.e., any two or three combinations of A, B, C, and D), and further includes four combinations of A, B, C, and D (i.e., a technical means in which all are connected by "logical AND").

[0026] In this specification, the terms "preferably," "more preferably," and "even more preferably" are merely used to describe more effective embodiments or examples and should not be understood as limiting the scope of protection of the present invention.

[0027] In this invention, phrases such as "furthermore," "moreover," and "especially" are used to explain the purpose and indicate differences in content, but should not be understood as limiting the scope of protection of this invention.

[0028] In this application, terms such as "First Aspect," "Second Aspect," "Third Aspect," "Fourth Aspect," and "Fifth Aspect" are used solely for explanatory purposes and should not be understood as indicating or implying relative importance or quantity, nor should they be understood as implicitly indicating the importance or quantity of the technical features shown. Furthermore, it should be understood that "First," "Second," "Third," "Fourth," and "Fifth" serve only the purpose of non-exclusive enumeration and do not constitute a closed-type limitation on number.

[0029] In this invention, the technical features described in open format include both closed-type technical proposals consisting of the listed features and open-type technical proposals containing the listed features.

[0030] In the present invention, with respect to a numerical interval (i.e., a numerical range), unless otherwise specified, the selectable numerical distribution is considered to be continuous within the numerical interval and includes the two numerical endpoints of the numerical range (i.e., the minimum and maximum values) and each numerical value between the two numerical endpoints. Unless otherwise specified, if a numerical interval refers only to integers within that numerical interval, it includes the integers at the two endpoints of the numerical range and each integer between the two endpoints. Furthermore, if there are multiple ranges that describe features or characteristics, they may be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include all subranges that are contained within them.

[0031] In the present invention, "at least one type" should be understood as including the number of such types and as one or more types.

[0032] Unless otherwise specified, the temperature parameters in this invention may be constant temperature treatments or may fluctuate within a certain temperature range. It should be understood that the constant temperature treatment allows for temperature fluctuations within the accuracy range of the instrument control. For example, fluctuations within the ranges of ±5°C, ±4°C, ±3°C, ±2°C, and ±1°C are acceptable.

[0033] In the present invention, unless otherwise specified, size, particle size, and diameter generally refer to average values.

[0034] A first aspect of the present invention provides an allyl-based flame-retardant prepolymer.

[0035] In the present invention, by prepolymerizing an allylbenzoxazine compound and an allylamine phosphorus-containing compound into an allyl flame-retardant prepolymer and adding them to a resin composition, an excellent flame-retardant effect can be obtained, the toughness of the resin composition can be improved, and excellent overall performance can be achieved.

[0036] A first aspect of the present invention comprises 100 parts by mass of an allylbenzoxazine compound and 20 to 80 parts by mass of an allylphosphorus-containing compound. The structural formula of the allylrin-containing compound is, [ka] And, The allylbenzoxazine compound is at least one selected from the group consisting of compounds represented by the following structural formula, [ka] X is independently selected from -CHR1-, -CR2R3-, -SO2-, or -O-. R1, R2, and R3 each independently provide an allyl-based flame-retardant prepolymer selected from -H or -CH3.

[0037] In some embodiments of the present invention, in the allyl-based flame retardant prepolymer, the ratio of parts by mass of the allylbenzoxazine compound to the allylphosphorus-containing compound is 100:(20-80), and may also be 100:(40-60). For example, the ratio of parts by mass may be 100:20, 100:25, 100:30, 100:35, 100:40, 100:45, 100:50, 100:55, 100:60, 100:65, 100:70, 100:75, or 100:80.

[0038] In some embodiments of the present invention, the ratio of parts by mass of an allylbenzoxazine compound to an allylphosphorus-containing compound in an allyl-based flame-retardant prepolymer is 100:50.

[0039] In the present invention, in the allyl-based flame-retardant prepolymer, the allyl groups in the allylbenzoxazine compound and the allylphosphorus-containing compound bond to each other, thereby extending the linear chain of benzoxazine, reducing stress during the reaction process, improving the toughness of the resin composition, and reducing the expansion and contraction of the resin composition.

[0040] In some embodiments of the present invention, the structural formula of the allylbenzoxazine compound in the allyl flame-retardant prepolymer is shown below. [ka]

[0041] In some embodiments of the present invention, the allyl-based flame retardant prepolymer further comprises 10 to 20 parts by mass of a phosphorus-free allyl compound. In some embodiments, the phosphorus-free allyl compound is at least one selected from the group consisting of allylbisphenol A, allylbisphenol S, and allyldiphenyl ether.

[0042] In some embodiments of the present invention, the allyl-based flame retardant prepolymer further comprises 10 parts by mass of allylbisphenol A.

[0043] In some embodiments of the present invention, the amount of phosphorus-free allyl compound in the flame-retardant prepolymer is 10 to 20 parts by mass per 100 parts by mass of allylbenzoxazine compound, for example, 10, 12, 15, 18, or 20 parts.

[0044] In some embodiments of the present invention, an allylbenzoxazine compound and an allyl phosphorus-containing compound are mixed and heated at 100°C to 130°C for 1 to 3 hours to obtain an allyl-based flame-retardant prepolymer. In some examples, after mixing the allylbenzoxazine compound and the allyl phosphorus-containing compound, the mixture is heated at 100°C to 130°C. The heating temperature may be selected from 100°C to 120°C, 100°C to 110°C, 100°C to 105°C, 110°C to 120°C, 120°C to 130°C, etc., for example, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, or 130°C. In some embodiments, the heating time is 1 to 3 hours, and may be further selected from 1 to 3 hours, 1 to 2 hours, 1 to 1.5 hours, 2 to 3 hours, 2.5 to 3 hours, etc., for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours, or 3 hours.

[0045] In some embodiments of the present invention, an allylbenzoxazine compound and an allylphosphorus-containing compound are mixed and heated at 120°C for 2.5 hours to obtain the allyl-based flame-retardant prepolymer.

[0046] A second aspect of the present invention provides a resin composition (BT resin composition) that has high flame retardancy, high high-temperature modulus retention, and extremely strong dielectric properties.

[0047] A second aspect of the present invention provides a resin composition comprising, by mass, 10 to 30 parts by the allyl-based flame-retardant prepolymer described in the first aspect of the present invention, 50 to 100 parts by the bismaleimide resin, 30 to 80 parts by the cyanate ester resin, 5 to 30 parts by the functional resin, and 10 to 60 parts by the inorganic filler as constituent components.

[0048] In some embodiments of the present invention, the amount of allyl-based flame retardant prepolymer in the resin composition is 10 to 30 parts by mass per 50 to 100 parts by mass of bismaleimide resin, and may be even more than 10 to 20 parts, for example, 10, 12, 15, 18, 20, 22, 25, 28, or 30 parts.

[0049] In the present invention, the bismaleimide resin is selected from organic compounds that contain two or more maleimide structures in their molecular structure.

[0050] In some embodiments of the present invention, the bismaleimide resin is at least one selected from the group consisting of N-phenylmaleimide group, N-(2-methylphenyl)maleimide group, N-(4-methylphenyl)maleimide group, N-(2,6-dimethylphenyl)maleimide group, bis(4-maleimidophenyl)methane group, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane group, bis(3,5-dimethyl-4-maleimidophenyl)methane group, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane group, bis(3,5-diethyl-4-maleimidophenyl)methane group, polyphenylmethanebismaleimide group, and biphenyl structure-containing maleimide group.

[0051] In some embodiments of the present invention, the bismaleimide resin is N,N'-(4,4'-methylenediphenyl)bismaleimide.

[0052] In some embodiments of the present invention, the amount of bismaleimide resin in the resin composition is 50 to 100 parts by mass per 10 to 30 parts by mass of allyl-based flame retardant prepolymer, and may be further 50 to 75 parts, for example, 50, 55, 60, 65, 70, 75, 85, 90, or 100 parts.

[0053] In some embodiments of the present invention, the cyanate ester resin is at least one selected from the group consisting of bisphenol A type cyanate ester resin, novolac type cyanate ester resin, bisphenol F type cyanate ester resin, polyfunctional cyanate ester resin, bisphenol M type cyanate ester resin, bisphenol E type cyanate ester resin, and dicyclopentadienebisphenol type cyanate ester resin.

[0054] In some embodiments of the present invention, the cyanate ester resin is a bisphenol A type cyanate ester.

[0055] In some embodiments of the present invention, the amount of allyl-based flame retardant prepolymer in the resin composition is 30 to 80 parts by mass per 50 to 100 parts by mass of bismaleimide resin, and may be further 30 to 60 parts, for example, 30, 35, 40, 45, 50, 55, 60, 70, or 80 parts.

[0056] In some embodiments of the present invention, the functional resin is at least one selected from the group consisting of epoxy resins, polyphenylene ethers, and hydrocarbon resins.

[0057] In some embodiments of the present invention, the functional resin is an epoxy resin.

[0058] In some embodiments of the present invention, the amount of functional resin in the resin composition is 5 to 30 parts by mass per 50 to 100 parts by mass of bismaleimide resin, and may be further 5 to 20 parts, for example, 5, 8, 10, 12, 15, 17, 20, 25, or 30 parts.

[0059] In some embodiments of the present invention, the inorganic filler is at least one selected from the group consisting of zirconium vanadate, zirconium tungstate, hafnium tungstate, crystallized glass, eucryptite, silica, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc powder, alumina, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, clay, and kaolin.

[0060] In some embodiments of the present invention, the inorganic filler is silica.

[0061] In some embodiments of the present invention, the amount of inorganic filler in the resin composition is 10 to 60 parts by mass per 50 to 100 parts by mass of bismaleimide resin, and may be even more than 40 to 50 parts, for example, 10, 20, 30, 35, 38, 40, 42, 45, 50, 55, or 60 parts.

[0062] In the present invention, the resin composition may or may not contain an auxiliary agent.

[0063] In some embodiments of the present invention, the auxiliary agent is at least one selected from the group consisting of curing accelerators, coupling agents, and reinforcing agents.

[0064] In some embodiments of the present invention, the auxiliary agent is a curing accelerator, and the curing accelerator may be selected from imidazoles, such as 2-methylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazole, or at least one selected from the group consisting of organometallic salts, such as zinc octyolate, zinc isooctanoate, stannous octyolate, dibutyltin dilaurate, zinc naphthenate, cobalt naphthenate, aluminum acetylacetonate, cobalt acetylacetonate, and copper acetylacetonate. The coupling agent may be at least one selected from the group consisting of silane coupling agents, titanate coupling agents, aluminate coupling agents, and organochromium complex coupling agents. The reinforcing agent may be at least one selected from the group consisting of rubber, silicone resin, and polybutadiene.

[0065] In some embodiments of the present invention, the auxiliary agent is a 2-methylimidazole curing accelerator.

[0066] In some embodiments of the present invention, the amount of additive in the resin composition is 1 to 5 parts by mass per 50 to 100 parts by mass of bismaleimide resin, and may be further 2 to 5 parts, for example, 1, 2, 3, 4, 5, 6, 7, or 8 parts.

[0067] In some embodiments, the resin composition comprises, by mass, 10 to 30 parts allyl flame-retardant prepolymer, 50 to 100 parts bismaleimide resin, 30 to 80 parts cyanate ester resin, 5 to 30 parts functional resin, 10 to 60 parts inorganic filler, and 0 to 5 parts auxiliary agent. The amount of allyl flame-retardant prepolymer may be independently 10 to 30 parts, for example, 10, 12, 15, 18, 20, 25, 28, or 30 parts; the amount of bismaleimide resin may be independently 50 to 100 parts, for example, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100 parts; and the amount of cyanate ester resin may be independently 30 to 80 parts, for example, 30, 40, 50, 60, 70, or 80 parts. The parts by mass of the functional resin may be independently 5 to 30 parts, for example 5, 8, 10, 12, 15, 18, 20, 25, 28, or 30 parts; the parts by mass of the inorganic filler may be independently 10 to 60 parts, for example 10, 20, 30, 50, 50, or 60 parts; and the parts by mass of the auxiliary agent may be independently 0 to 5 parts, further 1 to 5 parts, or further 2 to 5 parts, for example 0, 1, 2, 3, 4, or 5 parts.

[0068] A third aspect of the present invention provides a composite resin comprising an allyl-based flame-retardant prepolymer according to the first aspect of the present invention, or a resin composition according to the second aspect of the present invention. The composite resin has excellent flame retardancy and heat resistance, and excellent high-temperature modulus performance.

[0069] A fourth aspect of the present invention provides a prepreg containing a composite resin according to the third aspect of the present invention.

[0070] In some embodiments of the present invention, the prepreg comprises a reinforcing material and a resin material supported on the reinforcing material, wherein the resin material may be the composite resin described above.

[0071] A fifth aspect of the present invention provides a laminate including a prepreg according to the fourth aspect of the present invention.

[0072] In this invention, the flame retardancy level of the laminate reaches UL94V0 and furthermore, it has excellent overall performance. In some examples, the glass transition temperature Tg of the laminate is >250°C, and in some cases, Tg >280°C. In some examples, the peel strength of the laminate is >5.6 lb / in. In some examples, the tin plating heat resistance of the laminate is >300 s. In some examples, the laminate passes the saturated vapor pressure test (PCT). In some examples, the storage modulus of the laminate at 200°C is >30 Gpa. In some examples, the water absorption rate of the laminate is 0.1% to 0.12%. Specific examples are shown below. [Examples]

[0073] For experimental parameters not described in the following specific examples, refer to the guide provided in this application, or to experimental manuals in the art or other known experimental methods in the art, or to experimental conditions recommended by the manufacturer.

[0074] The raw materials and reagents relating to the following specific examples are commercially available or can be manufactured by means known to those skilled in the art.

[0075] Raw materials: The bismaleimide resin is BMI-01, manufactured by Honghu Shuangma Chang. The cyanate ester resin is BA-3000S, manufactured by Lonza Group. The phosphorus-containing epoxy resin is 589K75, manufactured by Hongchang Electronics. The phosphazene compound in question is SPB100, manufactured by Otsuka Chemical Co., Ltd. The epoxy resin in question is NC3000H, manufactured by Nippon Kayaku Co., Ltd.

[0076] Production of allylphosphorus-containing compounds: In Step 1, 1 mole of 2-methylallylamine was taken and mixed with a solvent, the temperature was raised to 80°C to 120°C, 0.5 mole of terephthalaldehyde was added, and the mixture was reacted under a nitrogen atmosphere for 3 to 8 hours.

[0077] In step 2, the reaction mixture was cooled to room temperature, filtered by suction to obtain the crude product, and then recrystallized with water (4-7 times). The recrystallized product was then dried at 60°C-90°C for 24 hours to obtain the intermediate product.

[0078] In step 3, 0.5 mol of the intermediate product, 1 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), and the solvent were mixed, the temperature was raised to 100°C to 150°C, and the reaction was carried out under a nitrogen atmosphere for 5 to 7 hours. The reaction mixture was then cooled to room temperature, and recrystallization was performed with water (4 to 7 times). The recrystallized product was then dried at 60°C to 90°C for 24 hours to obtain the allyl phosphorus-containing compound.

[0079] Manufacturing of allyl-based flame-retardant prepolymer 1: 100 parts by mass of an allylbenzoxazine compound and 50 parts by mass of an allylphosphorus-containing compound were placed in a three-necked flask, an organic solvent was added and mixed, and then heated in an oil bath to 120°C and stirred continuously for 2.5 hours to obtain allyl-based flame-retardant prepolymer 1.

[0080] The structural formulas of allylbenzoxazine compounds are shown below. [ka]

[0081] Manufacturing of allyl-based flame-retardant prepolymer 2: 100 parts by mass of an allylbenzoxazine compound, 50 parts by mass of an allylphosphorus-containing compound, and 10 parts by mass of allylbisphenol A were placed in a three-necked flask, an organic solvent was added and mixed, and then heated in an oil bath to 120°C and stirred continuously for 2.5 hours to obtain allyl-based flame-retardant prepolymer 2.

[0082] The structural formulas of allylbenzoxazine compounds are shown below. [ka]

[0083] Manufacturing of allyl-based flame-retardant prepolymer 3: 100 parts by mass of an allylbenzoxazine compound and 100 parts by mass of an allylphosphorus-containing compound were placed in a three-necked flask, an organic solvent was added and mixed, and then heated in an oil bath to 120°C and stirred continuously for 2.5 hours to obtain allyl-based flame-retardant prepolymer 3.

[0084] The structural formulas of allylbenzoxazine compounds are shown below. [ka]

[0085] Prepreg manufacturing: The raw materials were uniformly mixed according to the mixing ratio of each component shown in Table 1 to obtain an emulsion solution. Then, the 2116 glass cloth was immersed in the emulsion solution and baked in an oven at 160°C for 3 minutes to obtain a prepreg with an emulsion content of 55%.

[0086] [Table 1]

[0087] Manufacturing of laminated boards: Ten prepreg sheets are laminated, and one sheet of electrolytic copper foil, each 18 μm thick, is coated on both the top and bottom surfaces of the laminate. The laminate is then placed in a vacuum press machine with programmable temperature and pressure, at 30 kgf / cm². 2 The material was cured by heating in stages under a vacuum (vacuum degree < 10 mBar), first at 180°C for 1 hour, then at 220°C for 2 hours, then at 240°C for 2 hours, and finally cooled to obtain a copper foil laminate with a thickness of 1.0 mm.

[0088] Performance testing: Performance tests were conducted on the laminates manufactured in Examples 1-3 and Comparative Examples 1-4, respectively, according to the following test criteria.

[0089] The glass transition temperature (Tg) / storage modulus was tested in accordance with IPC-TM650 2.4.25D.

[0090] Regarding peel strength, the test method was conducted in accordance with IPC-TM-650 2.4.8.

[0091] The heat resistance of the tin plating was tested in accordance with IPC-TM650 2.4.6.

[0092] The PCT was tested in accordance with IPC-TM650 2.6.23.

[0093] The flexural modulus was tested in accordance with IPC-TM650 2.4.4.

[0094] The flame retardancy level was tested in accordance with IPC-TM650 2.3.10.

[0095] The water absorption rate was tested in accordance with IPC-TM650 2.6.2.1.

[0096] The dielectric properties were tested in accordance with IPC-TM650 2.5.5.9.

[0097] The results of the above test are shown in Table 2.

[0098] [Table 2]

[0099] As can be seen from the data in Table 2, the resin composition using the allyl-based flame-retardant prepolymer according to the present invention has strong flame retardancy, can reach UL94V0 level, has high heat resistance and moisture resistance, has a low rate of change in high-temperature modulus, low water absorption, and possesses extremely strong dielectric properties.

[0100] As can be seen from the data in Table 2, changing the composition of the prepolymer reduces peel strength, increases water absorption, and affects elastic modulus performance. Adding allylbisphenol A to the compounding components can improve viscosity and peel strength, but if too much allyl-based flame retardant prepolymer is added, the high-temperature elastic modulus performance decreases significantly, water absorption increases, and the overall performance of the laminate is seriously affected. If the allyl-based flame retardant prepolymer according to the present invention is not used, or if a normal phosphorus-containing resin is used as a flame retardant additive, the water absorption increases significantly, and the elastic modulus performance and dielectric properties decrease significantly.

[0101] All documents referenced herein are incorporated herein by reference in whole, just as each document is incorporated by reference individually. To the extent that they do not conflict with the purposes and / or technical means of the present invention, any references relating to the present invention are incorporated herein by whole, and for all purposes. Where relating to a reference, the definitions in the reference, including relevant technical features, terms, nouns, and phrases, are also incorporated. Where relating to a reference, examples of relevant technical features and preferred embodiments may also be incorporated herein by reference, but only to those that enable the implementation of the present invention. Where any references conflict with the description of this application, it should be understood that they should be modified adaptively, based on or in accordance with the description of this application.

[0102] The technical features of the above embodiments and examples can be combined in any way, and for the sake of brevity, not all possible combinations of the technical features of the above embodiments and examples have been described. However, as long as these combinations of technical features are inconsistent, they should all be considered within the scope of this specification.

[0103] The above examples illustrate only some embodiments of the present invention and should not be understood as limiting the scope of the patent. Furthermore, those skilled in the art can make various modifications and improvements to the present invention as long as they do not deviate from its spirit, and these modifications and changes also fall within the scope of the present invention. Also, to ensure that it is understandable, after reading the above description of the present invention, those skilled in the art can make various changes and modifications to the present invention, and these equivalent forms are also included within the scope of protection of the present invention. It should be understood that any technical means obtained by those skilled in the art through logical analysis, reasoning, or limited experimentation based on the technical means provided by the present invention are all within the scope of the claims attached to the present invention. Therefore, the scope of patent protection of the present invention depends on the attached claims, and the specification is intended to explain the content of the claims.

Claims

1. The material comprises an allyl-based flame-retardant prepolymer, a bismaleimide resin, a cyanate ester resin, a functional resin, and an inorganic filler, with a parts-by-mass ratio of (10-30):(50-100):(30-80):(5-30):

40. The allyl-based flame-retardant prepolymer comprises an allylbenzoxazine compound and an allylphosphorus-containing compound in a parts-by-mass ratio of 100:(20-80). The structural formula of the allylrin-containing compound is, 【Chemistry 1】 And, The allylbenzoxazine compound is at least one selected from the group consisting of compounds represented by the following structural formula, 【Chemistry 2】 X is independently -CHR １ -, -CR ２ R ３ -, -SO ２ - or -O- selected, R １ , R ２ , R ３ These are, independently, -H or -CH ３ Selected from, The resin composition is characterized in that the functional resin is at least one selected from the group consisting of epoxy resins, polyphenylene ethers, and hydrocarbon resins.

2. The resin composition according to claim 1, characterized in that the structural formula of the allylbenzoxazine compound is as shown below. 【Transformation 3】

3. The allyl-based flame retardant prepolymer further comprises a phosphorus-free allyl compound, wherein the amount of the phosphorus-free allyl compound is 10 to 20 parts by mass per 100 parts by mass of the allylbenzoxazine compound. The resin composition according to claim 1, characterized in that the phosphorus-free allyl compound is at least one selected from the group consisting of allylbisphenol A, allylbisphenol S, and allyldiphenyl ether.

4. The cyanate ester resin is at least one selected from the group consisting of bisphenol A type cyanate ester resin, novolac type cyanate ester resin, bisphenol F type cyanate ester resin, polyfunctional type cyanate ester resin, bisphenol M type cyanate ester resin, bisphenol E type cyanate ester resin, and dicyclopentadiene bisphenol type cyanate ester resin, and / or The inorganic filler is at least one selected from the group consisting of zirconium vanadate, zirconium tungstate, hafnium tungstate, crystallized glass, eucryptite, silica, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc powder, alumina, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, clay, and kaolin. The resin composition according to claim 1.

5. The resin composition according to claim 1, wherein the resin composition further comprises 1 to 5 parts by mass of an auxiliary agent per 40 parts by mass of the inorganic filler, and the auxiliary agent is at least one selected from the group consisting of curing accelerators, coupling agents and reinforcing agents.

6. A composite resin characterized by comprising the resin composition described in any one of claims 1 to 5.

7. A prepreg comprising a reinforcing material and a resin material supported on the reinforcing material, wherein the resin material is the composite resin described in claim 6.

8. A laminated board characterized by containing the prepreg described in claim 7 as a manufacturing raw material.

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