Resin composition, composite material, preparation method and layer-adding film

Abstract

The invention relates to a resin composition, a composite material, a preparation method and a layer-adding film. The resin composition comprises the following components: a modified polyphenyl ether resin prepolymer, functional resin, a curing agent, an inorganic filler and an organic filler, the preparation raw materials of the modified polyphenyl ether resin prepolymer comprise functionalized polyphenyl ether resin with a formula I and an amido fluorene compound with a formula II. Wherein the amino fluorene compound has a Cardo ring, and the heat resistance of the resin composition can be obviously improved due to the unique structure of the amino fluorene compound; furthermore, a modified polyphenyl ether resin prepolymer is prepared from the functionalized polyphenyl ether resin with a specific structure, and then the modified polyphenyl ether resin prepolymer is cooperated with functional resin, a curing agent, inorganic filler and organic filler, so that the polymer composite material obtained after curing has the advantages of relatively low thermal expansion coefficient, relatively good heat resistance and relatively good dielectric property; and the composite material has good anti-warping performance.

Description

Technical Field

[0001] The present application relates to the field of polymer composite materials, and in particular to a resin composition, a composite material and a preparation method, and a build-up film. Background Art

[0002] Flip chip ball grid array (FCBGA) substrate technology is an advanced packaging technology, which is a technology that flips the chip upside down and attaches it to the substrate, connects the chip and the substrate through solder balls, and realizes electrical connection and signal transmission. FCBGA substrate technology has advantages in high speed, high density and high reliability, and is widely used in computer, communication, consumer electronics, medical, industrial control and other fields.

[0003] The build-up film is one of the core materials of the semi-additive manufacturing process of FCBGA substrates. After being fully cured, the build-up film can provide more signal transmission path options for the substrate, optimize the signal wiring method, thereby reducing signal reflection and crosstalk, and improving signal transmission performance; and the build-up film can be used as a strengthening layer in the FCBGA substrate to improve the mechanical strength of the FCBGA substrate.

[0004] However, the fully cured films currently on the market have problems such as insufficient thermal expansion coefficient, poor heat resistance and poor dielectric properties, which limits the further improvement of FCBGA substrate performance. How to effectively reduce the thermal expansion coefficient of the fully cured build-up film and improve its heat resistance and dielectric properties has become an urgent problem to be solved in the industry. Summary of the invention

[0005] Based on this, it is necessary to provide a resin composition and a preparation method thereof, wherein the polymer composite material obtained by the resin composition has the advantages of low thermal expansion coefficient, good heat resistance and good dielectric properties.

[0006] Furthermore, a polymer composite material, a preparation method thereof and a build-up film are provided.

[0007] The first aspect of the present application provides a resin composition, the components of which include a modified polyphenylene ether resin prepolymer, a functional resin, a curing agent, an inorganic filler and an organic filler;

[0008] The functional resin is selected from at least one of epoxy resin, benzoxazine resin, bismaleimide resin and hydrocarbon resin;

[0009] The raw materials for preparing the modified polyphenylene ether resin prepolymer include a functionalized polyphenylene ether resin having a formula I and an aminofluorene compound having a formula II;

[0010]

[0011] I

[0012]

[0013] II;

[0014] Wherein, m and n are both positive integers, the sum of m and n is 5-60, Y is a C1-C9 alkylene group or a single bond; R1 and R2 are independently selected from a hydrogen atom, a substituted or unsubstituted C1-C9 alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group and a halogen.

[0015] The resin composition comprises a modified polyphenylene ether resin prepolymer, a functional resin, an inorganic filler and a curing agent; wherein the aminofluorene compound has a Cardo ring (i.e., a fluorene ring), which can significantly improve the heat resistance of the resin composition due to its unique structure; further, the modified polyphenylene ether resin prepolymer prepared from the functionalized polyphenylene ether resin with a specific structure and the vinylfluorene compound, the functional resin of a specific component, the curing agent, the inorganic filler and the organic filler cooperate with each other, and the polymer composite material obtained after curing has the advantages of a low thermal expansion coefficient, good heat resistance and good dielectric properties; and the composite material has good anti-warping performance.

[0016] Furthermore, the build-up layer film prepared using the resin component has a low thermal expansion coefficient, good heat resistance and good dielectric properties. When the build-up layer film is used for a flip-chip ball grid array carrier, the electrical performance, mechanical strength and thermal stability of the flip-chip ball grid array carrier can be significantly improved.

[0017] In some embodiments, the resin composition satisfies at least one of the following conditions:

[0018] (1) Y is a C1~C3 alkylene group or a single bond;

[0019] (2) R1 and R2 are independently selected from a hydrogen atom, a substituted or unsubstituted C1-C7 alkyl group, a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring and a halogen.

[0020] In some embodiments, the components include, by weight, 10 to 50 parts of the modified polyphenylene ether resin prepolymer, 20 to 60 parts of the functional resin, 10 to 50 parts of the curing agent, 100 to 300 parts of the inorganic filler, and 10 to 50 parts of the organic filler.

[0021] In some embodiments, the resin composition satisfies at least one of the following conditions:

[0022] (1) The epoxy resin is selected from at least one of naphthalene epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, unsaturated epoxy resin, novolac epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, multifunctional epoxy resin, alicyclic epoxy resin, resorcinol epoxy resin, rubber-modified epoxy resin, biphenyl epoxy resin and dicyclopentadiene epoxy resin;

[0023] (2) The benzoxazine resin is at least one selected from bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, main chain type benzoxazine resin, phosphorus-containing benzoxazine, bisphenol S type benzoxazine resin, dicyclopentadiene benzoxazine resin, biphenyl type benzoxazine resin, tetraphenol ethane benzoxazine resin and naphthalene type benzoxazine resin;

[0024] (3) The bismaleimide resin is selected from organic compounds containing two or more maleimide structures in the molecular structure;

[0025] (4) The hydrocarbon resin is selected from at least one of a copolymer of butadiene and styrene and polybutadiene;

[0026] (5) The inorganic filler is selected from at least one of zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, eucryptite, silicon dioxide, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc, aluminum oxide, 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;

[0027] (6) The average particle size D50 of the inorganic filler is 0.01 μm to 10 μm;

[0028] (7) The organic filler is at least one selected from silicone particles, core-shell rubber particles, and olefin elastomer particles;

[0029] (8) The average particle size D50 of the organic filler is 10 nm to 1000 nm;

[0030] (9) The curing agent is at least one selected from anhydride curing agent, cyanate curing agent and active ester curing agent.

[0031] In some embodiments, the resin composition further includes at least one of a curing accelerator, an auxiliary agent, and a solvent.

[0032] In some embodiments, the resin composition satisfies at least one of the following conditions:

[0033] (1) The mass fraction of the curing accelerator is 1 part to 10 parts;

[0034] (2) The curing accelerator is at least one selected from tertiary amine accelerators, imidazole accelerators, peroxide accelerators, organophosphorus accelerators and transition metal carboxylate accelerators;

[0035] (3) The mass fraction of the auxiliary agent is 1 to 10 parts;

[0036] (4) The auxiliary agent is at least one of a dispersant, a leveling agent, a defoamer, a thickener and a coupling agent;

[0037] (5) The mass fraction of the solvent is 50 to 100 parts;

[0038] (6) The solvent is at least one selected from acetone, butanone, cyclohexanone, toluene, xylene, propylene glycol methyl ether, ethylene glycol methyl ether and DMF.

[0039] The second aspect of the present application provides a method for preparing a resin composition, comprising the following steps: mixing a modified polyphenylene ether resin prepolymer, a functional resin, a curing agent, an inorganic filler and an organic filler;

[0040] Wherein, the functional resin is selected from at least one of epoxy resin, benzoxazine resin, bismaleimide resin and hydrocarbon resin;

[0041] The raw materials for preparing the modified polyphenylene ether resin prepolymer include a functionalized polyphenylene ether resin having a formula I and an aminofluorene compound having a formula II;

[0042]

[0043] I

[0044]

[0045] II;

[0046] Wherein, m and n are both positive integers, the sum of m and n is 5-60, Y is a C1-C9 alkylene group or a single bond; R1 and R2 are independently selected from a hydrogen atom, a substituted or unsubstituted C1-C9 alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group and a halogen.

[0047] In some embodiments, the step of preparing the modified polyphenylene ether resin prepolymer is also included;

[0048] The preparation steps of the modified polyphenylene ether resin prepolymer include:

[0049] The aminofluorene compound is heated to a molten state, and then the functionalized polyphenylene ether resin is added to carry out a prepolymerization reaction at 100° C. to 200° C. for 100 min to 200 min.

[0050] In some embodiments, the mass ratio of the aminofluorene compound to the functionalized polyphenylene ether resin is (1-2):1.

[0051] The third aspect of the present application provides a polymer composite material, the raw materials for preparing the polymer composite material include the resin composition described in the first aspect.

[0052] A fourth aspect of the present application provides a method for preparing a polymer composite material, comprising the following preparation steps:

[0053] The resin composition described in the first aspect is subjected to a semi-curing reaction; the temperature of the semi-curing reaction is 70° C. to 200° C.; and the time of the semi-curing reaction is 2 min to 15 min.

[0054] A fifth aspect of the present application provides a build-up film, the raw materials for preparing the build-up film include the resin composition described in the first aspect; or include the polymer composite material described in the third aspect. DETAILED DESCRIPTION

[0055] The technical solution of the present application is further described in detail below in conjunction with specific embodiments. The present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present application more thorough and comprehensive.

[0056] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0057] the term

[0058] Unless otherwise specified or incompatible herewith, the terms and phrases used herein shall have the following meanings:

[0059] The term "alkyl" refers to a saturated hydrocarbon containing primary (normal) carbon atoms, or secondary carbon atoms, or tertiary carbon atoms, or quaternary carbon atoms, or a combination thereof. A phrase containing the term, for example, "C1-C9 alkyl" refers to an alkyl containing 1 to 9 carbon atoms, and each occurrence may be independently C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl or C9 alkyl. Suitable examples include, but are not limited to, methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1-propyl (n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (i-Pr, i-propyl, -CH(CH3)2), 1-butyl (n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-1-propyl (i-Bu, i-butyl, -CH2CH(CH3)2), 2-butyl (s-Bu, s-butyl, -CH(C H3)CH2CH3), 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH3)3), 1-pentyl (n-pentyl, -CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2), 3-methyl-1-butyl (- CH2CH2CH(CH3)2), 2-methyl-1-butyl (-CH2CH(CH3)CH2CH3), 1-hexyl (-CH2CH2CH2CH2CH2CH3), 2-hexyl (-CH(CH3)CH2CH2CH2CH3), 3-hexyl (-CH(CH2CH3)(CH2CH2CH3)), 2-methyl-2-pentyl (-C(CH3)2CH2CH2CH3), 3-methyl-2-pentyl (-CH(CH3)CH( 2), 2-methyl-3-pentyl (-CH(CH2CH3)CH(CH3)2), 2,3-dimethyl-2-butyl (-C(CH3)2CH(CH3)2), 3,3-dimethyl-2-butyl (-CH(CH3)C(CH3)3 and octyl (-(CH2)7CH3).

[0060] "Alkylene" refers to a hydrocarbon group with two monovalent radical centers derived from an alkyl group by removing a hydrogen atom, which can be a saturated branched alkyl group or a saturated straight-chain alkyl group. For example, "C1-C9 alkylene" means that the alkyl portion contains 1 to 9 carbon atoms, and each occurrence can be independently C1 alkylene, C4 alkylene, C5 alkylene, C6 alkylene, C7 alkylene, C8 alkylene or C9 alkylene. Suitable examples include, but are not limited to, methylene (-CH2-), 1,1-ethyl (-CH(CH3)-), 1,2-ethyl (-CH2CH2-), 1,1-propyl (-CH(CH2CH3)-), 1,2-propyl (-CH2CH(CH3)-), 1,3-propyl (-CH2CH2CH2-) and 1,4-butyl (-CH2CH2CH2CH2-).

[0061] "Aryl" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing a hydrogen atom. It can be a monocyclic aromatic group, a condensed aromatic group, or a polycyclic aromatic group. For polycyclic rings, at least one is an aromatic ring system. For example, "C5~C 20 "Aryl" refers to an aromatic group containing 5 to 20 carbon atoms, and each occurrence can be independently C5 aromatic group, C6 aromatic group, C 10 Aryl, C 14 Aryl, C 18 Aryl or C 20 Suitable examples include, but are not limited to, benzene, biphenyl, naphthalene, anthracene, phenanthrene, perylene, triphenylene, and derivatives thereof.

[0062] "Heteroaryl" means that at least one carbon atom in an aryl group is replaced by a non-carbon atom, such as an N atom, an O atom, or an S atom. For example, "C3~C 10 The term "heteroaryl" refers to a heteroaryl group containing 3 to 10 carbon atoms, which may be independently C3 heteroaryl, C4 heteroaryl, C5 heteroaryl, C6 heteroaryl, C7 heteroaryl or C8 heteroaryl at each occurrence. Suitable examples include, but are not limited to, furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-naphthyridine, quinoxaline, phenanthridine, primary idine, quinazoline and quinazolinone.

[0063] "Halogen" or "halo" refers to F, Cl, Br or I.

[0064] In the present application, "substituted or unsubstituted" means that the defined group may be substituted or unsubstituted. When the defined group is substituted, it should be understood that it is optionally substituted by a group acceptable in the art, including but not limited to: C1~C30 alkyl, heterocyclic group containing 3-20 ring atoms, aryl containing 5~20 ring atoms, heteroaryl containing 5~20 ring atoms, halogen, or a combination of one or more thereof.

[0065] In one embodiment of the present application, a resin composition is provided, the components of which include a modified polyphenylene ether resin prepolymer, a functional resin, a curing agent, an inorganic filler and an organic filler.

[0066] The functional resin is selected from at least one of epoxy resin, benzoxazine resin, bismaleimide resin and hydrocarbon resin.

[0067] The raw materials for preparing the modified polyphenylene ether resin prepolymer include a functionalized polyphenylene ether resin having a formula I and an aminofluorene compound having a formula II;

[0068]

[0069] I

[0070]

[0071] II;

[0072] Wherein, m and n are both positive integers, the sum of m and n is 5-60, Y is a C1-C9 alkylene group or a single bond; R1 and R2 are independently selected from a hydrogen atom, a substituted or unsubstituted C1-C9 alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group and a halogen.

[0073] The resin composition comprises a modified polyphenylene ether resin prepolymer, a functional resin, an inorganic filler and a curing agent; wherein the aminofluorene compound has a Cardo ring, which can significantly improve the heat resistance of the resin composition due to its unique structure; further, the modified polyphenylene ether resin prepolymer prepared from the functionalized polyphenylene ether resin with a specific structure and the vinylfluorene compound, the functional resin of a specific component, the curing agent, the inorganic filler and the organic filler cooperate with each other, and the polymer composite material obtained after curing has the advantages of a low thermal expansion coefficient, good heat resistance and good dielectric properties; and the composite material has good anti-warping performance.

[0074] Furthermore, the build-up layer film prepared using the resin component has a low thermal expansion coefficient, good heat resistance and good dielectric properties. When the build-up layer film is used for a flip-chip ball grid array carrier, the electrical performance, mechanical strength and thermal stability of the flip-chip ball grid array carrier can be significantly improved.

[0075] As an example, the sum of m and n can be 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 or 60, or any other integer value between 5 and 60.

[0076] As an example, when Y is a single bond, it means that Y does not represent any group, and two adjacent benzene rings are directly bonded. That is, the functionalized polyphenylene ether resin includes the following formula III:

[0077]

[0078] III.

[0079] In some embodiments, Y is a C1-C3 alkylene group or a single bond.

[0080] In some embodiments, R1 and R2 are independently selected from a hydrogen atom, a substituted or unsubstituted C1-C7 alkyl group, a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring and a halogen.

[0081] Furthermore, R1 and R2 are independently selected from one of a hydrogen atom, an unsubstituted C1-C7 alkyl group, an unsubstituted benzene ring, an unsubstituted naphthalene ring, an unsubstituted anthracene ring and a halogen.

[0082] In some embodiments, the epoxy resin is not limited to a specific type; including but not limited to at least one of naphthalene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phosphorus-containing epoxy resin, unsaturated epoxy resin, phenolic epoxy resin, o-cresol-type epoxy resin, bisphenol A phenolic epoxy resin, multifunctional epoxy resin, alicyclic epoxy resin, resorcinol epoxy resin, rubber-modified epoxy resin, biphenyl epoxy resin and dicyclopentadiene epoxy resin.

[0083] In some embodiments, the benzoxazine resin is not limited to a specific type; including but not limited to at least one of bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, main chain type benzoxazine resin, phosphorus-containing benzoxazine, bisphenol S type benzoxazine resin, dicyclopentadiene benzoxazine resin, biphenyl type benzoxazine resin, tetraphenol ethane benzoxazine resin and naphthalene type benzoxazine resin.

[0084] In certain embodiments, the bismaleimide resin is selected from organic compounds containing two or more maleimide structures in the molecular structure. Further, the bismaleimide resin can be at least one of bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, polyphenylmethane bismaleimide, bismaleimide containing biphenyl structure, bismaleimide containing phosphorus structure, bismaleimide containing naphthalene ring structure, bismaleimide containing anthracene ring structure and hyperbranched bismaleimide.

[0085] In some embodiments, the hydrocarbon resin is selected from at least one of a copolymer of butadiene and styrene and polybutadiene.

[0086] In some embodiments, the type of inorganic filler is not particularly limited, and can be at least one selected from zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, eucryptite, silica, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc, aluminum oxide, 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.

[0087] In some embodiments, the curing agent is selected from at least one of an anhydride curing agent, a cyanate curing agent, and an active ester curing agent.

[0088] In some embodiments, the inorganic filler is granular. Further, the average particle size D50 of the inorganic filler is 0.01 μm to 10 μm. As an example, the average particle size D50 of the inorganic filler can be 0.01 μm, 0.05 μm, 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1.0 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm. Furthermore, the average particle size of the inorganic filler can be a range value consisting of any two of the above point values ​​as end values.

[0089] In some embodiments, the inorganic filler is a spherical particle.

[0090] Furthermore, the inorganic filler is selected from at least one of spherical silica and spherical alumina.

[0091] Preferably, the inorganic filler is selected from modified spherical silica and modified spherical alumina. Among them, the modified spherical silica includes but is not limited to epoxy-modified spherical silica, aniline-modified spherical silica, vinyl-modified spherical silica, hollow spherical silica, acrylic-modified spherical silica, fluoroalkyl-modified spherical silica and molybdate-modified spherical silica. The modified spherical alumina includes but is not limited to epoxy-modified spherical alumina, aniline-modified spherical alumina, vinyl-modified spherical alumina, hollow spherical alumina, acrylic-modified spherical alumina, fluoroalkyl-modified spherical alumina and molybdate-modified spherical alumina.

[0092] In some embodiments, the organic filler is selected from at least one of silicone particles, core-shell rubber particles, and olefin elastomer particles. Further adding an organic filler to the above composition can help the system form an island structure and increase flexibility. If only a large amount of inorganic fillers are added, the layered film is too brittle and is not conducive to winding during production.

[0093] In some embodiments, the organic filler is olefin elastomer particles. Preferably, the organic filler is XT-100.

[0094] In some embodiments, the organic filler is in particulate form.

[0095] In some embodiments, the average particle size D50 of the organic filler is 10 nm to 1000 nm. As an example, the average particle size D50 of the organic filler can be 10 nm, 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm or 500 nm. Further, the average particle size D50 of the organic filler can be a range value consisting of any two of the above point values ​​as end values. Preferably, the average particle size D50 of the organic filler is 100 nm to 200 nm.

[0096] In some embodiments, the components of the above-mentioned resin composition include, by weight, 10 to 50 parts of modified polyphenylene ether resin prepolymer, 20 to 60 parts of functional resin, 10 to 50 parts of curing agent, 100 to 300 parts of inorganic filler and 10 to 50 parts of organic filler.

[0097] As an example, in the resin composition, the mass fraction of the modified polyphenylene ether resin prepolymer can be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts or 50 parts. Further, the mass fraction of the modified polyphenylene ether resin prepolymer can be a range value consisting of any two of the above point values ​​as end values. Preferably, in the resin composition, the mass fraction of the modified polyphenylene ether resin prepolymer can be 10 parts to 40 parts.

[0098] As an example, in the resin composition, the mass fraction of the functional resin can be 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts or 60 parts. Further, the mass fraction of the functional resin can be a range value consisting of any two of the above point values ​​as end values. Preferably, in the resin composition, the mass fraction of the functional resin can be 20 parts to 50 parts.

[0099] As an example, in the resin composition, the mass fraction of the curing agent can be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts or 50 parts. Further, the mass fraction of the curing agent can be a range value consisting of any two of the above point values ​​as end values. Preferably, in the resin composition, the mass fraction of the curing agent can be 10 parts to 30 parts.

[0100] As an example, in the resin composition, the mass fraction of the inorganic filler can be 100 parts, 125 parts, 150 parts, 175 parts, 200 parts, 225 parts, 250 parts, 275 parts or 300 parts. Further, the mass fraction of the inorganic filler can be a range value consisting of any two of the above point values ​​as end values. Preferably, in the resin composition, the mass fraction of the inorganic filler can be 100 parts to 250 parts.

[0101] As an example, in the resin composition, the mass fraction of the organic filler can be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts or 50 parts. Further, the mass fraction of the organic filler can be a range value consisting of any two of the above point values ​​as end values.

[0102] In some embodiments, the resin composition further includes at least one of a curing accelerator, an auxiliary agent, and a solvent.

[0103] In some embodiments, the curing accelerator is selected from at least one of a tertiary amine accelerator, an imidazole accelerator, a peroxide accelerator, an organic phosphorus accelerator, and a transition metal carboxylate accelerator.

[0104] In some embodiments, the solvent may be an organic solvent. The components of the organic solvent are not particularly limited. For example, the organic solvent may be selected from at least one of acetone, butanone, cyclohexanone, toluene, xylene, propylene glycol methyl ether, ethylene glycol methyl ether, and N,N-dimethylformamide (DMF). Furthermore, the organic solvent includes butanone, toluene, and propylene glycol methyl ether in a mass ratio of 1:1:1. Adding a solvent to the resin composition can make the resin composition in a slurry state, and then it can be made into a film layer with a relatively uniform texture.

[0105] In some embodiments, the auxiliary agent may be at least one of a dispersant, a leveling agent, a defoamer, a thickener, and a coupling agent. Preferably, the auxiliary agent is a leveling agent.

[0106] Furthermore, the leveling agent may be a conventional leveling agent available on the market, for example, FC-4432.

[0107] In some embodiments, the components of the resin composition include, by weight, 10 to 50 parts of a modified polyphenylene ether resin prepolymer, 20 to 60 parts of a functional resin, 10 to 50 parts of a curing agent, 100 to 300 parts of an inorganic filler, and 10 to 50 parts of an organic filler; and also include 1 to 10 parts of a curing accelerator, 1 to 10 parts of an auxiliary agent, and at least one of 50 to 100 parts of a solvent.

[0108] In another embodiment of the present application, a method for preparing a resin composition is provided, comprising the following steps:

[0109] The modified polyphenylene ether resin prepolymer, the functional resin, the curing agent, the inorganic filler and the organic filler are mixed.

[0110] The functional resin is selected from at least one of epoxy resin, benzoxazine resin, bismaleimide resin and hydrocarbon resin.

[0111] The raw materials for preparing the modified polyphenylene ether resin prepolymer include a functionalized polyphenylene ether resin having a formula I and an aminofluorene compound having a formula II;

[0112]

[0113] I

[0114]

[0115] II;

[0116] Wherein, m and n are both positive integers, the sum of m and n is 5-60, Y is a C1-C9 alkylene group or a single bond; R1 and R2 are independently selected from a hydrogen atom, a substituted or unsubstituted C1-C9 alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group and a halogen.

[0117] In some embodiments, the above preparation method further includes: a step of preparing a modified polyphenylene ether resin prepolymer.

[0118] In some embodiments, the preparation steps of the modified polyphenylene ether resin prepolymer include:

[0119] The aminofluorene compound is heated to a molten state, and then the polyphenylene ether resin is added to carry out a prepolymerization reaction at 100° C. to 200° C. for 100 min to 200 min.

[0120] As an example, the prepolymerization reaction can be carried out at 100° C., 110° C., 120° C., 130° C., 140° C., 150° C., 160° C., 170° C., 180° C. or 200° C. Further, the prepolymerization reaction can be carried out under the temperature condition of a range value consisting of any two of the above point values ​​as end values.

[0121] As an example, the time of the prepolymerization reaction can be 100 min, 110 min, 120 min, 130 min, 140 min, 150 min, 160 min, 170 min, 180 min, 190 min or 200 min. Further, the time of the prepolymerization reaction can be a range value consisting of any two of the above point values ​​as end values.

[0122] In some embodiments, the mass ratio of the aminofluorene compound to the functionalized polyphenylene ether resin is (1-2): 1. As an example, the mass ratio of the aminofluorene compound to the functionalized polyphenylene ether resin can be 1: 1, 1.1: 1, 1.2: 1, 1.3: 1, 1.4: 1, 1.5: 1, 1.6: 1, 1.7: 1, 1.8: 1, 1.9: 1 or 2: 1. Other ratios within the above range may also be used.

[0123] In another embodiment of the present application, a polymer composite material is provided, and the raw materials for preparing the polymer composite material include the above-mentioned resin composition.

[0124] In another embodiment of the present application, a method for preparing a polymer composite material is provided, comprising the following steps:

[0125] The resin composition is subjected to a semi-curing reaction to obtain a polymer composite material.

[0126] The temperature of the semi-curing reaction is 70°C to 200°C; the time of the semi-curing reaction is 2min to 15min.

[0127] As an example, the temperature of the semi-curing reaction may be 70° C., 80° C., 90° C., 100° C., 120° C., 130° C., 140° C., 150° C., 160° C., 170° C., 180° C., 190° C. or 200° C. Further, the temperature of the semi-curing reaction may be a range value consisting of any two of the above point values ​​as end values.

[0128] In some embodiments, the time of the semi-curing reaction is 2 min to 15 min. As an example, the time of the semi-curing reaction can be 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min or 15 min. Further, the time of the semi-curing reaction can be a range value consisting of any two of the above point values ​​as end values.

[0129] In some embodiments, the method for preparing the above polymer composite material further comprises the following preparation steps:

[0130] After the above resin components are subjected to a semi-curing reaction, a complete curing reaction is performed.

[0131] In some embodiments, the complete curing reaction is performed under a pressure of 5kgf / cm² to 15kgf / cm².

[0132] In some embodiments, the temperature of the complete curing reaction is 100°C to 200°C.

[0133] In some embodiments, the temperature time for the complete curing reaction is 150 min to 200 min.

[0134] In some embodiments, the step of fully curing the reaction comprises:

[0135] React at 100℃~120℃ for 20min~40min; then react at 150℃~180℃ for 20min~40min; then react at 190℃~200℃ for 100min~140min.

[0136] In another embodiment of the present application, a build-up film is provided, the build-up film comprising the above-mentioned polymer composite material. It can be understood that the build-up film is a semi-cured product.

[0137] In another embodiment of the present application, a build-up film is provided, and raw materials for preparing the build-up film include the above-mentioned resin composition.

[0138] In some embodiments, the thickness of the build-up film may be 5 μm to 150 μm. As an example, the thickness of the build-up film may be 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm or 150 μm. Further, the thickness of the build-up film may be a range value formed by any two of the above point values ​​as end values.

[0139] In another embodiment of the present application, a method for preparing a build-up film is provided, comprising the following steps:

[0140] Dispersing the resin composition in a solvent to form a coating material;

[0141] Applying a coating material on the surface of the support to form a resin composition coating;

[0142] Then a semi-curing reaction is carried out to obtain a build-up film.

[0143] It can be understood that the build-up film obtained by the above method refers to the resin film layer formed after the resin composition undergoes a semi-curing reaction, and does not include a support body.

[0144] In some embodiments, the support is selected from at least one of a plastic film and a metal film.

[0145] In some embodiments, the plastic film includes, but is not limited to, polyethylene terephthalate (PET), polycarbonate (PC), and polymethyl methacrylate (PMMA).

[0146] In some embodiments, the metal film may be a copper foil or an aluminum foil.

[0147] In some embodiments, the thickness of the support is preferably, but not limited to, 3 μm to 105 μm.

[0148] In some embodiments, the thickness of the resin composition coating is preferably, but not limited to, 5 μm to 150 μm.

[0149] In order to make the purpose, technical solutions and advantages of the present application more concise and clear, the present application is described with the following specific embodiments, but the present application is by no means limited to these embodiments. The embodiments described below are only preferred embodiments of the present application and can be used to describe the present application, and cannot be understood as limiting the scope of the present application. It should be pointed out that any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application should be included in the protection scope of the present application.

[0150] In order to better illustrate the present application, the present application is further described below in conjunction with the embodiments. The following are specific embodiments.

[0151] Among them, the sources of some components in each embodiment and comparative example of the present application are as follows:

[0152] Aminofluorene compounds were purchased from Tianjin Zotye, CAS No: 15499-84-0;

[0153] Functionalized polyphenylene ether resin: Sabic SA9000;

[0154] Naphthalene type epoxy resin: DIC Chemical HP-5000;

[0155] Cyanate curing agent: Lonza Group BA-230S;

[0156] Imidazole accelerator: Shikoku Chemical 2MI;

[0157] Vinyl-treated spherical silica: Yaduma SO-C1, D50 particle size 0.4 μm;

[0158] Olefin elastomer particles: Arkema XT-100, D50 particle size 180nm;

[0159] Additive: 3M FC-4432;

[0160] PET film: Japan Toray LUMIRROR R80, thickness 38μm.

[0161] The following is an example of the synthesis of modified polyphenylene ether resin prepolymer:

[0162] Modified polyphenylene ether resin prepolymer synthesis example 1:

[0163] First, 50 parts of aminofluorene compounds were heated to a molten state, and then 100 parts of functionalized polyphenylene ether resin were added, and the mixture was prepolymerized at 150° C. for 120 minutes and then cooled to room temperature to obtain modified polyphenylene ether resin prepolymer A.

[0164] Modified polyphenylene ether resin prepolymer synthesis example 2:

[0165] First, 75 parts of aminofluorene compounds were heated to a molten state, and then 100 parts of functionalized polyphenylene ether resin were added, and the mixture was prepolymerized at 155° C. for 120 minutes and then cooled to room temperature to obtain a modified polyphenylene ether resin prepolymer B.

[0166] Modified polyphenylene ether resin prepolymer synthesis example 3:

[0167] First, 100 parts of aminofluorene compounds were heated to a molten state, and then 100 parts of functionalized polyphenylene ether resin were added, and the mixture was prepolymerized at 160° C. for 120 minutes and then cooled to room temperature to obtain a modified polyphenylene ether resin prepolymer C.

[0168] The following are examples of applications of modified polyphenylene ether resin prepolymers:

[0169] Embodiment 1:

[0170] Calculated by weight, 10 parts of modified polyphenylene ether resin prepolymer A, 35 parts of naphthalene epoxy resin, 20 parts of cyanate curing agent, 3 parts of imidazole accelerator, 100 parts of spherical silica, 10 parts of olefin elastomer particles and 1 part of auxiliary agent are dissolved in 80 parts of a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein butanone, toluene and propylene glycol methyl ether are mixed in a mass ratio of 1:1:1, stirred thoroughly and evenly, sprayed on the surface of PET, and then baked at 120°C for 3 minutes to obtain a build-up film with a thickness of 80 μm (this thickness does not include the thickness of PET).

[0171] Embodiment 2:

[0172] Calculated by weight, 20 parts of modified polyphenylene ether resin prepolymer A, 50 parts of naphthalene epoxy resin, 30 parts of cyanate curing agent, 5 parts of imidazole accelerator, 250 parts of spherical silica, 20 parts of olefin elastomer particles and 5 parts of additives are dissolved in 100 parts of a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein butanone, toluene and propylene glycol methyl ether are mixed in a mass ratio of 1:1:1, stirred thoroughly and evenly, sprayed on the surface of PET, and then baked at 120°C for 3 minutes to obtain a build-up film with a thickness of 80 μm (this thickness does not include the thickness of PET).

[0173] Embodiment 3:

[0174] Calculated by weight, 30 parts of modified polyphenylene ether resin prepolymer A, 20 parts of naphthalene epoxy resin, 10 parts of cyanate curing agent, 3 parts of imidazole accelerator, 175 parts of spherical silica, 30 parts of olefin elastomer particles and 3 parts of additives are dissolved in 100 parts of a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein butanone, toluene and propylene glycol methyl ether are mixed in a mass ratio of 1:1:1, stirred thoroughly and evenly, sprayed on the surface of PET, and then baked at 120°C for 3 minutes to obtain a build-up film with a thickness of 80 μm (this thickness does not include the thickness of PET).

[0175] Embodiment 4:

[0176] Calculated by weight, 20 parts of modified polyphenylene ether resin prepolymer B, 50 parts of naphthalene epoxy resin, 30 parts of cyanate curing agent, 5 parts of imidazole accelerator, 250 parts of spherical silica, 20 parts of olefin elastomer particles and 5 parts of additives are dissolved in 100 parts of a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein butanone, toluene and propylene glycol methyl ether are mixed in a mass ratio of 1:1:1, stirred thoroughly and evenly, sprayed on the surface of PET, and then baked at 120°C for 3 minutes to obtain a build-up film with a thickness of 80μm (this thickness does not include the thickness of PET).

[0177] Embodiment 5:

[0178] Calculated by weight, 20 parts of modified polyphenylene ether resin prepolymer C, 50 parts of naphthalene epoxy resin, 30 parts of cyanate curing agent, 5 parts of imidazole accelerator, 250 parts of spherical silica, 20 parts of olefin elastomer particles and 5 parts of additives are dissolved in 100 parts of a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein butanone, toluene and propylene glycol methyl ether are mixed in a mass ratio of 1:1:1, stirred thoroughly and evenly, sprayed on the surface of PET, and then baked at 120°C for 3 minutes to obtain a build-up film with a thickness of 80 μm (this thickness does not include the thickness of PET).

[0179] Embodiment 6:

[0180] Calculated by weight, 50 parts of modified polyphenylene ether resin prepolymer A, 50 parts of naphthalene epoxy resin, 30 parts of cyanate curing agent, 5 parts of imidazole accelerator, 250 parts of spherical silica, 20 parts of olefin elastomer particles and 5 parts of additives are dissolved in 100 parts of a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein butanone, toluene and propylene glycol methyl ether are mixed in a mass ratio of 1:1:1, stirred thoroughly and evenly, sprayed on the surface of PET, and then baked at 120°C for 3 minutes to obtain a build-up film with a thickness of 80 μm (this thickness does not include the thickness of PET).

[0181] Comparative Example 1

[0182] Calculated by weight, 50 parts of naphthalene epoxy resin, 30 parts of cyanate curing agent, 5 parts of imidazole accelerator, 250 parts of spherical silica, 20 parts of olefin elastomer particles and 5 parts of additives are dissolved in 100 parts of a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein butanone, toluene and propylene glycol methyl ether are mixed in a mass ratio of 1:1:1, stirred thoroughly and evenly, sprayed on the surface of PET, and then baked at 120°C for 3 minutes to obtain a build-up film with a thickness of 80 μm (this thickness does not include the thickness of PET).

[0183] The components of the resin compositions prepared in the examples and comparative examples are shown in Table 1 below.

[0184] Table 1

[0185]

[0186] The build-up films (the side away from the PET film) prepared in the above embodiments and comparative examples were bonded to a copper foil with a thickness of 12 μm by a bonding machine, and then the PET film was removed and then covered with a copper foil with a thickness of 12 μm, and placed in a vacuum press with programmable temperature and pressure control, and cured completely at 100℃*30min+170℃*30min+190℃*120min under a vacuum state (vacuum parameters <10 mBar) and a pressure of 8kgf / cm². The copper foil was then removed, and the following tests were performed on the fully cured build-up films:

[0187] 1. Coefficient of thermal expansion (CTE) test: Tested according to IPC-TM-650 2.4.24.5;

[0188] 2. Glass transition temperature (Tg) test: tested according to IPC-TM-650 2.4.24.2;

[0189] 3. Electrical performance test: Tested according to IPC-TM-650 2.5.5.2;

[0190] 4. Water absorption: Tested according to IPC-TM650 2.6.2.1;

[0191] The performance test data of the products after curing the build-up films prepared in the embodiments and comparative examples are shown in Table 2.

[0192] Table 2

[0193]

[0194] Note: In the table, "CTE / (ppm / ℃)Before TG" indicates the thermal expansion coefficient at a temperature below the glass transition temperature; "CTE / (ppm / ℃)After TG" indicates the thermal expansion coefficient at a temperature above the glass transition temperature.

[0195] "Dk (10G)" indicates the dielectric constant value of the material at a frequency of 10 GHz.

[0196] "Df(10G)" indicates the dielectric loss tangent of the material at a frequency of 10 GHz.

[0197] From Table 2, it can be seen that after the build-up films prepared in Examples 1 to 6 of the present application are completely cured, the glass transition temperature is 174°C to 195°C, the coefficient of thermal expansion (CTE) value is 20ppm / °C to 36ppm / °C under conditions below the glass transition temperature, the coefficient of thermal expansion (CTE) value is 58ppm / °C to 85ppm / °C under conditions above the glass transition temperature, the value of Dk (10G) is 3.55 to 3.44, and the value of Df (10G) is 0.0048 to 0.0064. It can be seen that the build-up film prepared by the technical method of the present application has good heat resistance, low expansion coefficient and dielectric properties.

[0198] In Comparative Example 1, no modified polyphenylene ether resin prepolymer was added, but functionalized polyphenylene ether resin was directly added. After the prepared build-up layer film was completely cured, the glass transition temperature was 150°C, the coefficient of thermal expansion (CTE) value was 45ppm / °C under conditions below the glass transition temperature, and the coefficient of thermal expansion (CTE) value was 91ppm / °C under conditions above the glass transition temperature. The value of Dk (G) was 3.78, the value of Df (10G) was 0.079, and the water absorption rate was 1.24%. Its performance was significantly inferior to that of Examples 1 to 6.

[0199] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0200] The above-described embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be construed as limiting the scope of the patent application. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent application shall be subject to the attached claims.

Claims

1. A resin composition, characterized in that Its components include modified polyphenylene ether resin prepolymer, functional resin, curing agent, inorganic filler and organic filler; The functional resin is selected from at least one of epoxy resin, benzoxazine resin, bismaleimide resin and hydrocarbon resin; The raw materials for preparing the modified polyphenylene ether resin prepolymer include a functionalized polyphenylene ether resin having a formula I and an aminofluorene compound having a formula II; I II; Wherein, m and n are both positive integers, the sum of m and n is 5-60, Y is a C1-C9 alkylene group or a single bond; R1 and R2 are independently selected from a hydrogen atom, a substituted or unsubstituted C1-C9 alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group and a halogen.

2. The resin composition according to claim 1, characterized in that The resin composition satisfies at least one of the following conditions: (1) Y is a C1~C3 alkylene group or a single bond; (2) R1 and R2 are independently selected from a hydrogen atom, a substituted or unsubstituted C1-C7 alkyl group, a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring and a halogen.

3. The resin composition according to claim 1, characterized in that The components include, by weight, 10 to 50 parts of the modified polyphenylene ether resin prepolymer, 20 to 60 parts of the functional resin, 10 to 50 parts of the curing agent, 100 to 300 parts of the inorganic filler and 10 to 50 parts of the organic filler.

4. The resin composition according to any one of claims 1 to 3, characterized in that The resin composition satisfies at least one of the following conditions: (1) The epoxy resin is selected from at least one of naphthalene epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, unsaturated epoxy resin, novolac epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, multifunctional epoxy resin, alicyclic epoxy resin, resorcinol epoxy resin, rubber-modified epoxy resin, biphenyl epoxy resin and dicyclopentadiene epoxy resin; (2) The benzoxazine resin is at least one selected from bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, main chain type benzoxazine resin, phosphorus-containing benzoxazine, bisphenol S type benzoxazine resin, dicyclopentadiene benzoxazine resin, biphenyl type benzoxazine resin, tetraphenol ethane benzoxazine resin and naphthalene type benzoxazine resin; (3) The bismaleimide resin is selected from organic compounds containing two or more maleimide structures in the molecular structure; (4) The hydrocarbon resin is selected from at least one of a copolymer of butadiene and styrene and polybutadiene; (5) The inorganic filler is selected from at least one of zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, eucryptite, silicon dioxide, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc, aluminum oxide, 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; (6) The average particle size D50 of the inorganic filler is 0.01 μm to 10 μm; (7) The organic filler is at least one selected from silicone particles, core-shell rubber particles, and olefin elastomer particles; (8) The average particle size D50 of the organic filler is 10 nm to 1000 nm; (9) The curing agent is at least one selected from anhydride curing agent, cyanate curing agent and active ester curing agent.

5. The resin composition according to any one of claims 1 to 3, characterized in that The resin composition further comprises at least one of a curing accelerator, an auxiliary agent and a solvent.

6. The resin composition according to claim 5, characterized in that The resin composition satisfies at least one of the following conditions: (1) The mass fraction of the curing accelerator is 1 part to 10 parts; (2) The curing accelerator is at least one selected from tertiary amine accelerators, imidazole accelerators, peroxide accelerators, organophosphorus accelerators and transition metal carboxylate accelerators; (3) The mass fraction of the auxiliary agent is 1 to 10 parts; (4) The auxiliary agent is at least one of a dispersant, a leveling agent, a defoamer, a thickener and a coupling agent; (5) The mass fraction of the solvent is 50 to 100 parts; (6) The solvent is at least one selected from acetone, butanone, cyclohexanone, toluene, xylene, propylene glycol methyl ether, ethylene glycol methyl ether and DMF.

7. A method for preparing a resin composition, characterized in that: The method comprises the following steps: mixing a modified polyphenylene ether resin prepolymer, a functional resin, a curing agent, an inorganic filler and an organic filler; Wherein, the functional resin is selected from at least one of epoxy resin, benzoxazine resin, bismaleimide resin and hydrocarbon resin; The raw materials for preparing the modified polyphenylene ether resin prepolymer include a functionalized polyphenylene ether resin having a formula I and an aminofluorene compound having a formula II; I II; Wherein, m and n are both positive integers, the sum of m and n is 5-60, Y is a C1-C9 alkylene group or a single bond; R1 and R2 are independently selected from a hydrogen atom, a substituted or unsubstituted C1-C9 alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group and a halogen.

8. The preparation method according to claim 7, characterized in that: The method also includes the step of preparing the modified polyphenylene ether resin prepolymer; The preparation steps of the modified polyphenylene ether resin prepolymer include: The aminofluorene compound is heated to a molten state, and then the functionalized polyphenylene ether resin is added to carry out a prepolymerization reaction at 100° C. to 200° C. for 100 min to 200 min.

9. The preparation method according to claim 8, characterized in that: The mass ratio of the aminofluorene compound to the functionalized polyphenylene ether resin is (1-2):

1.

10. A polymer composite material, characterized in that: The raw materials for its preparation include the resin composition as described in any one of claims 1 to 6.

11. A method for preparing a polymer composite material, characterized in that: The method comprises the following preparation steps: The resin composition according to any one of claims 1 to 6 is subjected to a semi-curing reaction; the temperature of the semi-curing reaction is 70° C. to 200° C.; and the time of the semi-curing reaction is 2 min to 15 min.

12. A build-up film, characterized in that: The raw materials for preparing the same include the resin composition as described in any one of claims 1 to 6; or include the polymer composite material as described in claim 10.

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