Thermosetting resin and heat-resistant resin composition containing same

Abstract

The invention discloses a thermosetting resin and a heat-resistant resin composition containing the same. The thermosetting resin comprises bismaleimide resin, allyl long-chain type macromolecular resin and fluorine-containing maleic anhydride resin. The fluorine-containing maleic anhydride resin reacts with the allyl long-chain polymer resin to form a net structure. The weight ratio of the bismaleimide to the allyl long-chain type polymer resin is (0.75: 1.25)-(1.25: 0.75). The thermosetting resin and the heat-resistant resin composition containing the thermosetting resin provided by the invention can be favorable for forming a prepreg sheet with excellent electrical property, excellent heat resistance and low expansion coefficient.

Description

Technical Field

[0001] The present invention relates to a resin composition, in particular to a thermosetting resin and a heat-resistant resin composition containing the same. Background Art

[0002] Materials used in electronics, aerospace and other fields usually require excellent electrical and mechanical properties and high heat resistance. Maleic anhydride polymers have excellent electrical properties, high heat resistance and high dimensional stability, but they are hard and brittle after cross-linking and curing, resulting in poor mechanical properties. Adding rubber or toughening agents may affect the physical properties or dielectric properties of the polymer.

[0003] Therefore, how to improve the resin composition formula to balance high heat resistance and excellent mechanical and electrical properties to further form a composite material to overcome the above-mentioned defects has become one of the important issues that this business wants to solve. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a thermosetting resin in view of the deficiencies of the prior art, which includes: bismaleimide resin, allyl long-chain polymer resin and fluorine-containing maleic anhydride resin. The fluorine-containing maleic anhydride resin reacts with the allyl long-chain polymer resin to form a network structure. The weight ratio of bismaleimide to the allyl long-chain polymer resin is 0.75:1.25 to 1.25:0.75.

[0005] Furthermore, the weight ratio of the bismaleimide to the allyl long-chain polymer resin is 0.9:1.1 to 1.1:0.9.

[0006] Furthermore, the bismaleimide is m-phenylene bismaleimide, 4,4'-bismaleimide diphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane or phenylmethane maleimide.

[0007] Furthermore, the weight ratio of the allyl long-chain polymer resin, the bismaleimide and the fluorine-containing maleic anhydride resin is 100:85:15.

[0008] Furthermore, the allyl long-chain polymer resin is allyl polybenzoxazine or allyl-modified phenolic long-chain polymer.

[0009] Furthermore, the fluorine-containing maleic anhydride resin has a structure of formula A:

[0010]

[0011] In order to solve the above-mentioned technical problems, another technical solution adopted by the present invention is to provide a heat-resistant resin composition, which includes: 15 to 25 parts by weight of epoxy resin, 10 to 20 parts by weight of benzoxazine resin and 50 to 60 parts by weight of the thermosetting resin as described in claim 1.

[0012] Furthermore, the heat-resistant resin composition further includes 2 to 6 parts by weight of a toughening agent, 2 to 6 parts by weight of a flame retardant, and 50 to 60 parts by weight of a filler.

[0013] Furthermore, the heat-resistant resin composition further includes a solvent.

[0014] Furthermore, the solvent is toluene, γ-butyrolactone, methyl ethyl ketone, cyclohexanone, butanone, acetone, xylene, methyl isobutyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or a mixture thereof.

[0015] One of the beneficial effects of the present invention is that the thermosetting resin and the heat-resistant resin composition containing the thermosetting resin provided by the present invention can form a prepreg with excellent electrical properties, excellent heat resistance and low expansion coefficient through the technical scheme of "fluorinated maleic anhydride resin reacting with the allyl long-chain polymer resin to form a network structure" and "the weight ratio of the bismaleimide to the allyl long-chain polymer resin is 0.75:1.25 to 1.25:0.75", and is suitable for applications such as HDIPCB (high-density interconnect PCB) and carrier-like boards.

[0016] To further understand the features and technical contents of the present invention, please refer to the following detailed description of the present invention. However, the detailed description provided is only for reference and illustration and is not intended to limit the present invention. DETAILED DESCRIPTION

[0017] The following is an explanation of the implementation methods of the "thermosetting resin and heat-resistant resin composition containing the same" disclosed in the present invention through specific embodiments. Those skilled in the art can understand the advantages and effects of the present invention from the contents disclosed in this specification. The present invention can be implemented or applied through other different specific embodiments, and the details in this specification can also be modified and changed in various ways based on different viewpoints and applications without departing from the concept of the present invention. The following implementation methods will further explain the relevant technical contents of the present invention in detail, but the disclosed contents are not intended to limit the scope of protection of the present invention.

[0018] It should be understood that the term "or" used herein may include any one or more combinations of the associated listed items as appropriate.

[0019] The present invention provides a thermosetting resin, which includes: bismaleimide resin, allyl long-chain polymer resin and fluorine-containing maleic anhydride resin. The bismaleimide resin can be m-phenylene-bismaleimide, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane or phenylmethane maleimide.

[0020] Specifically, the fluorinated maleic anhydride resin can react with the allyl long-chain polymer resin to form a network structure to provide high heat resistance and excellent mechanical and electrical properties. In one embodiment of the present invention, the fluorinated maleic anhydride resin can have a structure of formula A:

[0021]

[0022] Further, in one embodiment of the present invention, the synthesis method of the fluorinated maleic anhydride resin is to place 17.9 grams of 4-amino-2-fluorobenzotrifluoride (4-Amino-2-fluorobenzotrifluoride) produced by Merck and 150 grams of dimethylacetamide (Dimethylacetamide, DMAC) in a 1-liter four-mouth detachable reaction bottle equipped with a heating device, a thermometer, a stirrer, and a cooling tube, and heat it to about 60° C. and stir it evenly to make it completely dissolved. Subsequently, while maintaining the stirring state, 10 grams of maleic anhydride are gradually added within 20 minutes, and the temperature of the synthetic solution is raised to 90° C., and then 1 gram of 5-ethyl-2-methylpyridine is added. The above mixture is gradually heated to 140° C. and reacted for 1 hour. The reaction formula is shown in the following reaction formula A to obtain the fluorinated maleic anhydride resin BMI-F.

[0023]

[0024] As above, after reacting at 140° C. for 1 hour, the temperature was lowered to room temperature, and 400 g of methanol was added for precipitation. The mixture was then washed with methanol three times and dried to obtain the fluorine-containing maleic anhydride resin of formula A in this case.

[0025] On the other hand, the allyl long-chain polymer resin of the present invention can be an allyl benzoxazine resin or an allyl phenolic resin. Specifically, the allyl long-chain polymer resin of the present invention can be synthesized by the methods described in the following Synthesis Examples 1 to 5.

[0026] Synthesis Example 1 Preparation of Propylene Benzoxazine (BZ-A) Resin

[0027] 100 grams of BPA-type benzoxazine resin (BPA-BZ produced by Yuanhong) and 300 grams of toluene are added to a 1-liter four-mouth detachable reaction bottle equipped with a heating device, a thermometer, a stirrer, a cooling tube, a dripping device and a decompression recovery device to form a synthetic solution. 15 grams of potassium hydroxide (KOH) are added and the synthetic solution is heated to about 40°C and stirred evenly. While maintaining stirring, 38 grams of allyl chloride (Allyl Chloride) are gradually added to the synthetic solution within 20 minutes to react for 1 hour. At this time, the synthetic solution is gradually heated to about 90°C, and the synthetic solution is heated and maintained at a temperature of about 90°C and reacted for 1 hour. Allyl chloride is then removed at 90°C and under a reduced pressure of 90 mm Hg. Subsequently, heating and stirring were stopped, 300 g of pure water was added and the mixture was allowed to stand for about 20 minutes. After the synthetic solution was separated into two layers, the lower aqueous phase was removed and water washing was repeated three times until the water washing solution was neutral, thus obtaining a toluene solution of 410 g of propylene grafted benzoxazine (BZ-A). The reaction formula is shown in the following reaction formula 1.

[0028]

[0029] Synthesis Example 2 Preparation of Propylene Phenolic Resin (PN-A)

[0030] 100 grams of phenolic resin (Phenolic Novolac produced in Changchun) and 300 grams of toluene were added to the reactor, and 15 grams of potassium hydroxide (KOH) was added. While maintaining stirring, 38 grams of allyl chloride were gradually added to the synthetic solution within 20 minutes to react for 1 hour. Allyl chloride was then removed at 90°C and under reduced pressure at 90 mmHg. Subsequently, heating and stirring were stopped, 300 grams of pure water were added and allowed to stand for about 20 minutes. After the synthetic solution was separated into two layers, the lower aqueous phase was removed, and water washing was repeated three times until the water washing solution was neutral, and a toluene solution of 417 grams of propylene grafted phenolic (PN-A) resin was obtained. The reaction formula is shown in the following reaction formula 2.

[0031]

[0032] Synthesis Example 3 Preparation of Propylene Phenolic Resin (Nath-A) Resin 100 grams of naphthol aralkyl phenolic resin (SN-495 Nathpthlene phenolic Novolac produced by Nippon Steel, Japan) and 300 grams of toluene are added to a reactor, and 15 grams of potassium hydroxide (KOH) are added. While maintaining stirring, 38 grams of allyl chloride are gradually added to the synthetic solution within 20 minutes to react for 1 hour. Allyl chloride is then removed at 90°C and under reduced pressure at 90 mmHg. Subsequently, heating and stirring are stopped, 300 grams of pure water are added and allowed to stand for about 20 minutes. After the synthetic solution is separated into two layers, the lower aqueous phase is removed, and water washing is repeated three times until the water washing solution is neutral, i.e., a toluene solution of 421 g of proppylene grafted phenolic (Nath-A) resin is obtained. The reaction formula is shown in the following reaction formula 3.

[0033]

[0034] Synthesis Example 4 Preparation of Propylene Phenolic Resin (DCDPN-A)

[0035] 100 grams of DCDP novolac resin (ERM-6105 produced by SONGWON, South Korea) and 300 grams of toluene were added to the reactor, and 15 grams of potassium hydroxide (KOH) was added. While maintaining stirring, 38 grams of allyl chloride were gradually added to the synthetic solution within 20 minutes to react for 1 hour. Allyl chloride was then removed at 90°C and under reduced pressure at 90 mmHg. Subsequently, heating and stirring were stopped, 300 grams of pure water were added and allowed to stand for about 20 minutes. After the synthetic solution was separated into two layers, the lower aqueous phase was removed, and water washing was repeated three times until the water washing solution was neutral, and a toluene solution of 417 grams of propylene grafted DCDPN novolac resin (DCDPN-A) was obtained. The reaction formula is shown in the following reaction formula 4.

[0036]

[0037] Synthesis Example 5 Preparation of Bisphenol A Propylene Novolac Resin (BPN-A)

[0038] 100 grams of phenolic resin (4,40-diglycidyl biphenyl novolac resin (GPH-65) produced by DIC, Japan) and 300 grams of toluene were added to the reactor, and 15 grams of potassium hydroxide (KOH) were added. While maintaining stirring, 38 grams of allyl chloride were gradually added to the synthetic solution within 20 minutes to react for 1 hour. Allyl chloride was then removed at 90°C and under reduced pressure of 90 mmHg. Subsequently, heating and stirring were stopped, 300 grams of pure water were added and allowed to stand for about 20 minutes. After the synthetic solution was separated into two layers, the lower aqueous phase was removed and washed with water three times until the washed solution was neutral, thus obtaining a toluene solution of 417 grams of propylene grafted biphenyl phenolic resin (BPN-A). The reaction formula is shown in the following reaction formula 5.

[0039]

[0040] Furthermore, the preparation method of the thermosetting resin of the present invention is described in the following Examples 1 to 9. The reaction formulas of Examples 1 to 9 are roughly as shown in the following Reaction Formula 6.

[0041]

[0042] Example 1

[0043] 100 g of the benzoxazine resin (BZ-A) of Synthesis Example 1 and 200 g of methyl ethyl ketone (MEK) were added to a 1-liter four-mouth detachable reaction bottle equipped with a heating device, a thermometer, a stirrer, and a cooling tube device to form a synthetic solution, and the synthetic solution was heated to about 70°C and stirred evenly to dissolve. While maintaining stirring, 85 g of 4,4'-bismaleimidodiphenyl methane resin and 15 g of fluorinated bismaleimide resin BMI-F were gradually added to the synthetic solution within 20 minutes. At this time, the temperature of the synthetic solution rose to about 110°C, and the synthetic solution was heated and maintained at a temperature of about 110°C and reacted for 1 hour. The reaction was then stopped to obtain a brown transparent clear solution, and the obtained product was called BMBZ-1. The gel time of BMBZ-1 was 346 seconds when tested at 200°C by a gelator.

[0044] Example 2

[0045] 100 g of the benzoxazine resin (BZ-A) of Synthesis Example 1 and 200 g of butanone were added to a 1-liter four-mouth detachable reaction bottle equipped with a heating device, a thermometer, a stirrer, and a cooling tube to form a synthetic solution, and the synthetic solution was heated to about 70°C and stirred evenly to dissolve. While maintaining stirring, 85 g of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane resin (Bis

[0046] (3-ethyl-5-methyl-4-maleimido phenyl)methane) and 15 grams of fluorinated bismaleimide resin BMI-F were added to the synthetic solution. At this time, the temperature of the synthetic solution rose to about 110°C. The synthetic solution was heated and maintained at a temperature of about 110°C and reacted for 1 hour. The reaction was then stopped to obtain a brown transparent clear solution. The obtained product was called BMBZ-2. The gel time of BMBZ-2 was 365 seconds when tested at 200°C by a gelator.

[0047] Example 3

[0048] 100 g of the benzoxazine resin (BZ-A) of Synthesis Example 1 and 200 g of butanone were added to a 1-liter four-mouth detachable reaction bottle equipped with a heating device, a thermometer, a stirrer, and a cooling tube device to form a synthetic solution, and the synthetic solution was heated to about 70°C and stirred evenly to dissolve. While maintaining stirring, 85 g of benzyl maleimide (BMI-2300) and 15 g of fluorinated bismaleimide resin BMI-F were gradually added to the synthetic solution within 20 minutes. At this time, the temperature of the synthetic solution rose to about 110°C, and the synthetic solution was heated and maintained at a temperature of about 110°C and reacted for 1 hour. The reaction was then stopped to obtain a brown transparent clear solution, and the obtained product was called BMBZ-3. Tested at 200°C by a gelator, the gel time of BMBZ-3 was 355 seconds.

[0049] Example 4

[0050] 100 g of the propylene phenolic resin (PN-A) of Synthesis Example 2 and 200 g of butanone were added to a 1-liter four-mouth detachable reaction bottle equipped with a heating device, a thermometer, a stirrer, and a cooling tube device to form a synthetic solution, and the synthetic solution was heated to about 70°C and stirred evenly to dissolve. While maintaining stirring, 85 g of 4,4'-bismaleimide diphenylmethane and 15 g of fluorinated bismaleimide resin BMI-F were gradually added to the synthetic solution within 20 minutes. At this time, the temperature of the synthetic solution rose to about 110°C, and the synthetic solution was heated and maintained at a temperature of about 110°C and reacted for 1 hour. The reaction was then stopped to obtain a brown transparent clear solution, and the obtained product was called BMPN-1. Tested at 200°C by a gelator, the gel time of BMPN-1 was 346 seconds.

[0051] Example 5

[0052] 100 g of the propylene phenolic resin (PN-A) of Synthesis Example 2 and 200 g of butanone were added to a 1-liter four-mouth detachable reaction bottle equipped with a heating device, a thermometer, a stirrer, and a cooling tube device to form a synthetic solution, and the synthetic solution was heated to about 70°C and stirred evenly to dissolve. While maintaining stirring, 85 g of bis(3-ethyl-5-methyl-4-maleimide benzene)methane resin and 15 g of fluorine-containing bismaleimide resin BMI-F were gradually added to the synthetic solution within 20 minutes. At this time, the temperature of the synthetic solution rose to about 110°C, and the synthetic solution was heated and maintained at a temperature of about 110°C and reacted for 1 hour. The reaction was then stopped to obtain a brown transparent clear solution, and the obtained product was called BMPN-2. Tested at 200°C by a gelator, the gel time of BMPN-2 was 346 seconds.

[0053] Example 6

[0054] 100 grams of the propylene phenolic resin (PN-A) of Synthesis Example 2 and 200 grams of butanone were added to a 1-liter four-mouth detachable reaction bottle equipped with a heating device, a thermometer, a stirrer, and a cooling tube device to form a synthetic solution, and the synthetic solution was heated to about 70°C and stirred evenly to dissolve. While maintaining stirring, 85 grams of benzyl maleimide (BMI-2300) and 15 grams of fluorine-containing bismaleimide resin BMI-F were gradually added to the synthetic solution within 20 minutes. At this time, the temperature of the synthetic solution rose to about 110°C, and the synthetic solution was heated and maintained at a temperature of about 110°C and reacted for 1 hour. The reaction was then stopped to obtain a brown transparent clear solution, and the obtained product was called BMPN-3. Tested at 200°C by a gel machine, the gel time of BMPN-3 was 346 seconds.

[0055] Example 7

[0056] 100 grams of the acrylphenol-formaldehyde resin (Nath-A) of Synthesis Example 3 and 200 grams of butanone were added to a 1-liter four-mouth detachable reaction bottle equipped with a heating device, a thermometer, a stirrer, and a cooling tube device to form a synthetic solution, and the synthetic solution was heated to about 70°C and stirred evenly to dissolve. While maintaining stirring, 85 grams of bis(3-ethyl-5-methyl-4-maleimide benzene)methane resin and 15 grams of fluorine-containing bismaleimide resin BMI-F were gradually added to the synthetic solution within 20 minutes. At this time, the temperature of the synthetic solution rose to about 110°C, and the synthetic solution was heated and maintained at a temperature of about 110°C and reacted for 1 hour. The reaction was then stopped to obtain a brown transparent clear solution, and the obtained product was called BMNa. The gel time of BMNa was 346 seconds when tested at 200°C by a gel machine.

[0057] Example 8

[0058] 100 g of the propylene phenolic resin (DCDPN-A) of Synthesis Example 4 and 200 g of butanone were added to a 1-liter four-mouth detachable reaction bottle equipped with a heating device, a thermometer, a stirrer, and a cooling tube device to form a synthetic solution, and the synthetic solution was heated to about 70°C and stirred evenly to dissolve. While maintaining stirring, 85 g of bis(3-ethyl-5-methyl-4-maleimide benzene)methane resin and 15 g of fluorine-containing bismaleimide resin BMI-F were gradually added to the synthetic solution within 20 minutes. At this time, the temperature of the synthetic solution rose to about 110°C, and the synthetic solution was heated and maintained at a temperature of about 110°C and reacted for 1 hour. The reaction was then stopped to obtain a brown transparent clear solution, and the obtained product was called BMDC. The gel time of BMDC was 346 seconds when tested at 200°C by a gel machine.

[0059] Example 9

[0060] 100 g of the bisphenol-type acryl phenolic resin (BPN-A) of Synthesis Example 5 and 200 g of butanone were added to a 1-liter four-mouth detachable reaction bottle equipped with a heating device, a thermometer, a stirrer, and a cooling tube device to form a synthetic solution, and the synthetic solution was heated to about 70°C and stirred evenly to dissolve. While maintaining stirring, 85 g of bis(3-ethyl-5-methyl-4-maleimide benzene)methane resin and 15 g of fluorine-containing bismaleimide resin BMI-F were gradually added to the synthetic solution within 20 minutes. At this time, the temperature of the synthetic solution rose to about 110°C, and the synthetic solution was heated and maintained at a temperature of about 110°C and reacted for 1 hour. The reaction was then stopped to obtain a brown transparent clear solution, and the obtained product was called BMBPN. The gel time of BMBPN was 346 seconds when tested at 200°C by a gel machine.

[0061] The compositions and gel times of Examples 1 to 9 are shown in Table 1. In Table 1, BMI-1 is 4,4'-bismaleimidodiphenyl methane resin; BMI-2 is Bis(3-ethyl-5-methyl-4-maleimido phenyl)methane; and BMI-3 is Phenylmethane maleimide (BMI-2300) resin. BMI-1, BMI-2, and BMI-3 are all produced by ACR.

[0062] Table 1

[0063]

[0064] The heat-resistant resin composition of the present invention can be made into a varnish-like form by uniformly mixing the components of the resin composition, including BMI-modified benzoxazine, fillers, toughening agents, etc., with a homogenizer and dissolving or dispersing them in a solvent for subsequent processing. The solvent can be any inert solvent that can dissolve or disperse the components of the resin composition but does not react with the components. The solvents that can be used to dissolve or disperse the components of the resin composition include but are not limited to: toluene, γ-butyrolactone, methyl ethyl ketone, cyclohexanone, butanone, acetone, xylene, methyl isobutyl ketone, N,N-dimethylformamide (N,N-dimethylformamide, DMF), N,N-dimethylacetamide (N,N-dimethyl acetamide, DMAc), and N-methylpyrolidone (N-methyl-pyrolidone, NMP). Each solvent can be used alone or in combination. There is no special restriction on the amount of solvent used, in principle, as long as the components of the resin composition can be uniformly dissolved or dispersed therein. In a preferred embodiment of the present invention, a mixture of toluene, methyl ethyl ketone, and γ-butyrolactone is used as the solvent.

[0065] Furthermore, Table 2 shows the compositions and properties of Examples E1 to E10 and Comparative Examples C1 to C3 of the heat-resistant resin composition of the present invention.

[0066] Table 2 (unit: weight parts)

[0067]

[0068]

[0069]

[0070] Among them, ODA-BZ and Allyl-BZ are benzoxazine resins produced by Yuanhong; the filler is 10umcut SiO2 produced by Sibico; CNE epoxy resin is Changchun synthetic resin, and the long-chain epoxy resin is Huntsman PKFE; the toughening agent is styrene copolymer (SEBS) produced by Lee Changrong Company; SPB-100 is a phosphorus-based flame retardant; and the copper foil is H1 1 / 3oz produced by Nan Ya.

[0071] Adhesion strength refers to the adhesion of metal foil to the laminated prepreg. The adhesion strength test is to tear off a 1 / 8 inch wide copper foil vertically from the board surface, and the strength of the adhesion is expressed by the amount of force required.

[0072] The heat resistance test is to immerse the dried metal foil laminate in a 288°C solder bath for 100 seconds and repeat the process three times. If the appearance does not change, it means the heat resistance is excellent and is recorded as "○". If there are bubbling bulges on the appearance, it means the heat resistance is poor and is recorded as "×".

[0073] The glass transition temperature (Tg) is measured using a Thermal Mechanical Analyzer (TMA) according to IPC-TM-650 2.4.24.4.

[0074] The water absorption test is based on IPC-TM-650 2.6.2. The copper foil is completely etched off the test piece, and its size is 10cm*10cm. The test piece is first baked at 105℃ for half an hour, placed in a drying oven for cooling and weighed, and then immersed in 23℃ pure water for 24 hours, taken out, wiped dry, and weighed after standing. The weight of the test piece before and after treatment is subtracted to calculate the moisture absorption degree of the test piece.

[0075] The dielectric constant (Dk) is measured according to the IPC-TM-650 2.5.5 test specification. The dielectric constant represents the electronic insulation properties of the film. The lower the value, the better the electronic insulation properties. The dielectric loss (Df) is measured according to the IPC-TM-650 2.5.5 test specification.

[0076] The X / Y axis thermal expansion coefficient (CTE) is measured according to the IPC-TM-650-2.4.24 test specification. The thermal mechanical analyzer (TMA) is used to measure the thermal expansion coefficient (CTE) of the sample under test at a temperature below Tg. The folding resistance-MIT test (folding test) is measured according to the JISP8115 specification, where R = 1.0mm, the bending frequency of 90 degrees is 175 times / minute, and the load is 250g, to measure the number of bending times that can be endured.

[0077] Advantageous Effects of Embodiments

[0078] One of the beneficial effects of the present invention is that the thermosetting resin provided by the present invention, that is, the heat-resistant resin composition comprising the thermosetting resin, can form a prepreg having excellent electrical properties, excellent heat resistance and low expansion coefficient through the technical scheme of "fluorinated maleic anhydride resin reacting with the allyl long-chain polymer resin to form a network structure" and "the weight ratio of the bismaleimide to the allyl long-chain polymer resin is 0.75:1.25 to 1.25:0.75", and is suitable for applications such as HDIPCB (high-density interconnect PCB) and carrier-like boards.

[0079] In the resin composition of the present invention, the weight ratio of bismaleimide to the allyl long-chain polymer resin is 0.75:1.25-1.25:0.75, preferably 0.9:1.1-1.1:0.9, so as to form a prepreg with excellent electrical properties, excellent heat resistance and low expansion coefficient.

[0080] In addition, the use of fluorinated maleic anhydride resin is helpful for CTE and heat resistance. Furthermore, the present invention utilizes the low dielectric properties and low hygroscopic properties of fluorinated maleic anhydride resin to crosslink and solidify the fluorinated maleic anhydride resin and the allyl long-chain polymer resin into a resin composition with excellent thermal and electrical properties. Among them, the weight ratio of the allyl long-chain polymer resin, bismaleimide and fluorinated maleic anhydride resin is 100:85:15, which can make the allyl long-chain polymer resin react to form a network structure more efficiently. Therefore, the thermosetting resin of the present invention is used to make the resin composition into which the substrate is impregnated to make the substrate have better folding resistance.

[0081] On the other hand, the heat-resistant resin composition of the present invention includes 15 to 25 parts by weight of epoxy resin, 10 to 20 parts by weight of benzoxazine resin, and 50 to 60 parts by weight of the thermosetting resin of Examples 1 to 9. When the content of the epoxy resin is less than 15 parts by weight, the toughness of the heat-resistant resin composition is poor, and when the content of the epoxy resin is greater than 25 parts by weight, the impact resistance of the cured product of the heat-resistant resin composition is deteriorated. When the content of the benzoxazine resin is less than 10 parts by weight, the moisture absorption rate of the heat-resistant resin composition is deteriorated, and when the content of the benzoxazine resin is greater than 20 parts by weight, the cured product of the heat-resistant resin composition becomes too brittle, resulting in poor processability. When the content of the thermosetting resin is less than 50 parts by weight, the heat resistance of the heat-resistant resin composition is poor, and when the content of the thermosetting resin is greater than 60 parts by weight, the processability of the heat-resistant resin composition is affected.

[0082] Preferably, the heat-resistant resin composition of the present invention comprises 18 to 22 parts by weight of epoxy resin, 13 to 16 parts by weight of benzoxazine resin, and 53 to 56 parts by weight of the thermosetting resin of Examples 1 to 9. In a preferred embodiment of the present invention, the epoxy resin is a composition of a long-chain epoxy resin and a CNE epoxy resin in a weight ratio of 1:3, and the benzoxazine resin is a composition of Allyl-BZ and ODA-BZ in a weight ratio of 1:2, and a heat-resistant resin composition with good high-temperature insulation, arc resistance and tracking resistance can be obtained. After hardening, the heat-resistant resin composition can obtain a material with a high cross-linking density and improved flexibility, and is more suitable for the fields of electronics, aerospace, etc.

[0083] The contents disclosed above are only preferred feasible embodiments of the present invention, and are not intended to limit the protection scope of the claims of the present invention. Therefore, all equivalent technical changes made using the contents of the present invention specification are included in the protection scope of the claims of the present invention.

Claims

1. A thermosetting resin, characterized in that: The thermosetting resin comprises: Bismaleimide resin; Allyl long chain polymer resin; and The fluorine-containing maleic anhydride resin reacts with the allyl long-chain polymer resin to form a network structure: Wherein, the weight ratio of the bismaleimide to the allyl long-chain polymer resin is 0.75:1.25 to 1.25:0.

75.

2. The thermosetting resin according to claim 1, characterized in that The weight ratio of the bismaleimide to the allyl long-chain polymer resin is 0.9:1.1 to 1.1:0.

9.

3. The thermosetting resin according to claim 1, characterized in that The bismaleimide is m-phenylene bismaleimide, 4,4'-bismaleimide diphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane or phenylmethane maleimide.

4. The thermosetting resin according to claim 1, characterized in that The weight ratio of the allyl long-chain polymer resin, the bismaleimide and the fluorine-containing maleic anhydride resin is 100:85:

15.

5. The thermosetting resin according to claim 1, characterized in that The allyl long-chain polymer resin is allyl polybenzoxazine or allyl-modified phenolic long-chain polymer.

6. The thermosetting resin according to claim 1, characterized in that The fluorine-containing maleic anhydride resin has a structure of formula A:

7. A heat-resistant resin composition, characterized in that: The heat-resistant resin composition comprises: 15 to 25 parts by weight of epoxy resin; 10 to 20 parts by weight of a benzoxazine resin; and 50 to 60 parts by weight of the thermosetting resin according to claim 1.

8. The heat-resistant resin composition according to claim 7, characterized in that: The heat-resistant resin composition further includes 2 to 6 parts by weight of a toughening agent, 2 to 6 parts by weight of a flame retardant, and 50 to 60 parts by weight of a filler.

9. The heat-resistant resin composition according to claim 7, characterized in that: The heat-resistant resin composition further includes a solvent.

10. The heat-resistant resin composition according to claim 9, characterized in that The solvent is toluene, γ-butyrolactone, methyl ethyl ketone, cyclohexanone, butanone, acetone, xylene, methyl isobutyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or a mixture thereof.

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