Resin composition, composite material and preparation method therefor, and build-up film

Abstract

The present application relates to a resin composition, a composite material and a preparation method therefor, and a build-up film. A functional resin is at least one selected from an epoxy resin, a benzoxazine resin, a bismaleimide resin, and a hydrocarbon resin. Starting materials for preparing a modified polyphenylene ether resin prepolymer comprise a functionalized polyphenylene ether resin represented by formula I and a vinyl fluorene compound represented by formula II. The resin composition is prepared on the basis of the cooperation among the modified polyphenylene ether resin prepolymer prepared from the functionalized polyphenylene ether resin having a specific structure and the vinyl fluorene compound, the functional resin having specific composition, an inorganic filler and a curing agent component, so that the polymer composite material obtained after curing has the advantages of low coefficient of thermal expansion, good heat resistance and good dielectric property.

Description

Resin compositions, composite materials and preparation methods, and thickening films Technical Field

[0001] This application relates to the field of polymer composite materials, and in particular to a resin composition, a composite material and its preparation method, and a layered film. Background Technology

[0002] Flip Chip Ball Grid Array (FCBGA) substrate technology is an advanced packaging technology that involves flipping and mounting chips onto a substrate, connecting the chips and the substrate via solder balls to achieve electrical connections and signal transmission. FCBGA substrate technology offers advantages in high speed, high density, and high reliability, and is widely used in fields such as computers, communications, consumer electronics, medical devices, and industrial control.

[0003] The build-up film is one of the core materials in the semi-additive manufacturing process of FCBGA substrates. Once fully cured, the build-up film provides the substrate with more signal transmission path options, optimizes signal routing, reduces signal reflection and crosstalk, and improves signal transmission performance. Furthermore, the cured film can act as a reinforcing layer in the FCBGA substrate, enhancing its mechanical strength.

[0004] However, commercially available extension films, once fully cured, suffer from insufficient coefficient of thermal expansion, poor heat resistance, and suboptimal dielectric properties, limiting further improvements in FCBGA substrate performance. Effectively reducing the coefficient of thermal expansion of fully cured extension films and improving their heat resistance and dielectric properties has become a pressing issue for the industry. Summary of the Invention

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

[0006] Furthermore, a polymer composite material, its preparation method, and a layered film are provided.

[0007] The first aspect of this application provides a resin composition comprising a modified polyphenylene ether resin prepolymer, a functional resin, an inorganic filler, and a curing agent.

[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 formula I and a vinyl fluorene compound having 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 one of the following: hydrogen atom, substituted or unsubstituted C1-C9 alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, and halogen.

[0015] The above-mentioned resin composition includes a modified polyphenylene ether resin prepolymer, a functional resin, an inorganic filler, and a curing agent. The modified polyphenylene ether resin prepolymer prepared by functionalized polyphenylene ether resin with a specific structure and vinyl fluorene compounds, the functional resin with specific components, the inorganic filler, and the curing agent components work synergistically to obtain a polymer composite material after curing, which has the advantages of low coefficient of thermal expansion, good heat resistance, and good dielectric properties.

[0016] Furthermore, the extension film prepared using this resin component has a low coefficient of thermal expansion, good heat resistance, and good dielectric properties. When this extension film is used in flip chip ball grid array carriers, it can significantly improve the electrical performance, mechanical strength, and thermal stability of the flip chip ball grid array carriers.

[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 each independently selected from one of the following: hydrogen atom, substituted or unsubstituted C1 to C7 alkyl group, substituted or unsubstituted benzene ring, substituted or unsubstituted naphthalene ring, substituted or unsubstituted anthracene ring, and halogen.

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

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

[0022] (1) The epoxy resin is selected from one or more of the following: 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;

[0023] (2) The benzoxazine resin is selected from one or more of the following: 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 whose molecular structure contains two or more maleimide structures;

[0025] (4) The hydrocarbon resin is selected from one or more of the copolymer of butadiene and styrene and polybutadiene;

[0026] (5) The inorganic filler is selected from one or more of zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, nepheline, 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 curing agent is selected from one or more of acid anhydride curing agents, cyanate ester curing agents and active ester curing agents.

[0029] In some embodiments, the resin composition further includes at least one of a curing accelerator and an additive.

[0030] In some embodiments, the resin composition satisfies at least one of the following conditions:

[0031] (1) The curing accelerator is 1 to 10 parts by mass;

[0032] (2) The curing accelerator is selected from one or more of tertiary amine accelerators, imidazole accelerators, peroxide accelerators, organophosphorus accelerators and transition metal carboxylates;

[0033] (3) The mass fraction of the additive is 1 to 10 parts;

[0034] (4) The additives are one or more of the following: dispersant, leveling agent, defoamer, thickener and coupling agent.

[0035] The second aspect of this application provides a method for preparing a resin composition, comprising the following steps: mixing a modified polyphenylene ether resin prepolymer, a functional resin, an inorganic filler, and a curing agent;

[0036] The functional resin is selected from at least one of epoxy resin, benzoxazine resin, bismaleimide resin, and hydrocarbon resin.

[0037] The raw materials for preparing the modified polyphenylene ether resin prepolymer include a functionalized polyphenylene ether resin having Formula I and a vinyl fluorene compound having Formula II.

[0038]

[0039] I

[0040]

[0041] II;

[0042] Wherein, m and n are both positive integers, the sum of m and n is 5 to 60, Y is a C1 to C9 alkylene group or a single bond; R1 and R2 are independently selected from one of the following: hydrogen atom, substituted or unsubstituted C1 to C9 alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, and halogen.

[0043] In some embodiments, the method further includes a step of preparing the modified polyphenylene ether resin prepolymer;

[0044] The preparation steps of the modified polyphenylene ether resin prepolymer include:

[0045] The vinyl fluorene compound is heated to a molten state, and then the functionalized polyphenylene ether resin is added. The prepolymerization reaction is carried out at 100°C to 180°C for 60 min to 200 min.

[0046] In some embodiments, the mass ratio of the vinyl fluorene compound to the functionalized polyphenylene ether resin is (1-2):1.

[0047] A third aspect of this application provides a polymer composite material, the raw materials for which include the resin composition described in the first aspect.

[0048] The fourth aspect of this application provides a method for preparing a polymer composite material, comprising the following preparation steps:

[0049] 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.

[0050] The fifth aspect of this application provides a layering film, the raw materials for which include the resin composition described in the first aspect; or the polymer composite material described in the third aspect. Detailed Implementation

[0051] The technical solution of this application will be further described in detail below with reference to specific embodiments. This application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this application.

[0052] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0053] the term

[0054] Unless otherwise stated or in case of contradiction, the terms or phrases used herein shall have the following meanings:

[0055] The term "alkyl" refers to a saturated hydrocarbon containing a primary (normal) carbon atom, or a secondary carbon atom, or a tertiary carbon atom, or a quaternary carbon atom, or a combination thereof. Phrases containing this term, such as "C1-C9 alkyl," refer to alkyl groups containing 1 to 9 carbon atoms, and each occurrence can independently be 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( CH3)CH2CH3), 4-methyl-2-pentyl (-CH(CH3)CH2CH(CH3)2), 3-methyl-3-pentyl (-C(CH3)(CH2CH3)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).

[0056] "Alkylene" refers to a hydrocarbon group derived from an alkyl group by removing one hydrogen atom, forming a group with two monovalent centers. It can be a saturated branched alkyl group or a saturated straight-chain alkyl group. For example, "C1-C9 alkylene" refers to an alkyl moiety containing 1-9 carbon atoms, and each occurrence can be independently C1, C2, C3, C4, C5, C6, C7, C8, 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-).

[0057] "Aryl" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing one hydrogen atom. It can be a monocyclic aryl, a fused-ring aryl, or a polycyclic aryl. For polycyclic compounds, at least one ring must be an aromatic ring system. For example, "C5~C5..." 20 "Aryl" refers to an aryl group containing 5 to 20 carbon atoms. Each time it appears, it can independently be C5 aryl, C6 aryl, C7 aryl, C8 aryl, C9 ... 10 Aryl, C 14 Aryl, C 18 Aryl or C 20 Aryl groups. Suitable examples include, but are not limited to: benzene, biphenyl, naphthalene, anthracene, phenanthrene, dinaphthalene, triphenylene and their derivatives.

[0058] "Heteroaryl" refers to an aryl group in which at least one carbon atom is replaced by a non-carbon atom, which can be a nitrogen atom, an oxygen atom, a sulfur atom, etc. For example, "C3~C 10 "Heteroaryl" refers to a heteroaryl group containing 3 to 10 carbon atoms, which can be independently C3, C4, C5, C6, C7, or C8 heteroaryl each time it appears. Suitable examples include, but are not limited to: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazolium, indole, carbazole, pyrroloimidazol, pyrrolopyrrole, thiophenolopyrrole, thiophenolothiophene, furanolopyrrole, furanolofuran, thiophenolofuran, benzoisoxazole, benzoisothiazolium, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-diazonyl, quinoxaline, phenanthridine, primidine, quinazoline, and quinazolineone.

[0059] "Halogen" or "halogen group" refers to F, Cl, Br or I.

[0060] "Multiple" in this application can refer to two or more.

[0061] In this application, "substituted or unsubstituted" means that the defined group may or may not be substituted. When the defined group is substituted, it should be understood that it may be substituted by a group acceptable in the art, including but not limited to: C1 to C30 alkyl, heterocyclic group containing 3 to 20 cyclic atoms, aryl group containing 5 to 20 cyclic atoms, heteroaryl group containing 5 to 20 cyclic atoms, and one or more combinations of halogens.

[0062] One embodiment of this application provides a resin composition comprising a modified polyphenylene ether resin prepolymer, a functional resin, an inorganic filler, and a curing agent.

[0063] The functional resin is selected from at least one of epoxy resin, benzoxazine resin, bismaleimide resin, and hydrocarbon resin.

[0064] The raw materials for preparing modified polyphenylene ether resin prepolymers include functionalized polyphenylene ether resins having formula I and vinyl fluorene compounds having formula II.

[0065]

[0066] I

[0067]

[0068] II;

[0069] 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 one of the following: hydrogen atom, substituted or unsubstituted C1-C9 alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, and halogen.

[0070] The above-mentioned resin composition includes a modified polyphenylene ether resin prepolymer, a functional resin, an inorganic filler, and a curing agent. The modified polyphenylene ether resin prepolymer prepared by functionalized polyphenylene ether resin with a specific structure and vinyl fluorene compounds, the functional resin with specific components, the inorganic filler, and the curing agent components work synergistically to obtain a polymer composite material after curing, which has the advantages of low coefficient of thermal expansion, good heat resistance, and good dielectric properties.

[0071] Furthermore, the extension film prepared using this resin component has a low coefficient of thermal expansion, good heat resistance, and good dielectric properties. When this extension film is used in flip chip ball grid array carriers, it can significantly improve the electrical performance, mechanical strength, and thermal stability of the flip chip ball grid array carriers.

[0072] 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.

[0073] As an example, when Y is a single bond, it means that Y does not represent any functional group, and the two adjacent benzene rings are directly bonded together. This also indicates that functionalized polyphenylene ether resins include those according to Formula III:

[0074]

[0075] III.

[0076] In some embodiments, Y is a C1-C3 alkylene group or a single bond.

[0077] In some embodiments, R1 and R2 are each independently selected from one of the following: hydrogen atom, substituted or unsubstituted C1-C7 alkyl group, substituted or unsubstituted benzene ring, substituted or unsubstituted naphthalene ring, substituted or unsubstituted anthracene ring, and halogen.

[0078] Furthermore, R1 and R2 are each independently selected from one of the following: hydrogen atom, unsubstituted C1-C7 alkyl group, unsubstituted benzene ring, unsubstituted naphthalene ring, unsubstituted anthracene ring, and halogen.

[0079] In some embodiments, each of the above-mentioned substituents is independently selected from one or more combinations of C1 to C30 alkyl groups, heterocyclic groups containing 3 to 20 cyclic atoms, aryl groups containing 5 to 20 cyclic atoms, heteroaryl groups containing 5 to 20 cyclic atoms, and halogens.

[0080] In some embodiments, the epoxy resin is not limited to a specific type; including but not limited to one or more of the following: 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.

[0081] In some embodiments, the benzoxazine resin is not limited to a specific type; including but not limited to one or more of the following: 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.

[0082] In some embodiments, the bismaleimide resin is selected from organic compounds containing two or more maleimide structures in their molecular structure. Further, the bismaleimide resin may be one or more of the following: di(4-maleimide-phenyl)methane, 2,2-di(4-(4-maleimide-phenoxy)-phenyl)propane, di(3,5-dimethyl-4-maleimide-phenyl)methane, di(3-ethyl-5-methyl-4-maleimide-phenyl)methane, di(3,5-diethyl-4-maleimide-phenyl)methane, polyphenylmethane bismaleimide, bismaleimide containing a biphenyl structure, bismaleimide containing a phosphorus structure, bismaleimide containing a naphthalene ring structure, bismaleimide containing an anthracene ring structure, and hyperbranched bismaleimide.

[0083] In some embodiments, the hydrocarbon resin is selected from one or more of butadiene-styrene copolymers and polybutadiene.

[0084] In some embodiments, the type of inorganic filler is not particularly limited and may be selected from one or more of zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, nepheline, silica, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc, 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.

[0085] 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. More specifically, the average particle size of the inorganic filler can be a range of values ​​defined by any two of the above points as endpoints.

[0086] In some embodiments, the inorganic filler is spherical particles.

[0087] Furthermore, the inorganic filler is selected from at least one of spherical silica and spherical alumina.

[0088] Preferably, the inorganic filler is selected from modified spherical silica and modified spherical alumina. 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. 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.

[0089] In some embodiments, the curing agent is selected from one or more of acid anhydride curing agents, cyanate ester curing agents, and reactive ester curing agents.

[0090] In some embodiments, the resin composition comprises, by weight parts, 10 to 60 parts of modified polyphenylene ether resin prepolymer, 20 to 60 parts of functional resin, 100 to 300 parts of inorganic filler, and 10 to 50 parts of curing agent.

[0091] As an example, the mass fraction of the modified polyphenylene ether resin prepolymer in the resin composition can be 10 parts, 15 parts, 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 modified polyphenylene ether resin prepolymer can be a range defined by any two of the above points as endpoints. Preferably, the mass fraction of the modified polyphenylene ether resin prepolymer in the resin composition can be between 10 and 50 parts.

[0092] As an example, the mass fraction of the functional resin in the resin composition 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 of values ​​formed by using any two of the above-mentioned point values ​​as endpoints.

[0093] As an example, the mass fraction of the inorganic filler in the resin composition can be 100 parts, 125 parts, 150 parts, 175 parts, 200 parts, 225 parts, 250 parts, 275 parts, 300 parts, 325 parts, 350 parts, 375 parts, or 400 parts. Further, the mass fraction of the inorganic filler can be a range of values ​​defined by any two of the above points as endpoints.

[0094] As an example, the mass fraction of the curing agent in the resin composition 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 of values ​​formed by using any two of the above points as endpoints.

[0095] In some embodiments, the resin composition comprises, by weight parts, 10 to 50 parts of modified polyphenylene ether resin prepolymer, 20 to 60 parts of functional resin, 100 to 300 parts of inorganic filler, and 10 to 50 parts of curing agent.

[0096] In some embodiments, the resin composition further includes at least one of a curing accelerator and an additive.

[0097] In some embodiments, the resin composition comprises, by weight parts, 10 to 50 parts of modified polyphenylene ether resin prepolymer, 20 to 60 parts of functional resin, 100 to 300 parts of inorganic filler, and 10 to 50 parts of curing agent; it also comprises 1 to 10 parts of curing accelerator and / or 1 to 10 parts of additives.

[0098] In some embodiments, the curing accelerator is selected from one or more of tertiary amine accelerators, imidazole accelerators, peroxide accelerators, organophosphorus accelerators, and transition metal carboxylate accelerators.

[0099] In some embodiments, the additive may be one or more of the following: dispersant, leveling agent, defoamer, thickener, and coupling agent.

[0100] In some embodiments, the additive is a leveling agent.

[0101] In some embodiments, the leveling agent can be a commercially available conventional leveling agent. As an example, it can be FC-4432.

[0102] Another embodiment of this application provides a method for preparing a resin composition, comprising the following steps:

[0103] The modified polyphenylene ether resin prepolymer, functional resin, inorganic filler and curing agent are mixed.

[0104] The functional resin is selected from at least one of epoxy resin, benzoxazine resin, bismaleimide resin, and hydrocarbon resin.

[0105] The raw materials for preparing modified polyphenylene ether resin prepolymers include functionalized polyphenylene ether resins having formula I and vinyl fluorene compounds having formula II.

[0106]

[0107] I

[0108]

[0109] II;

[0110] Wherein, m and n are both positive integers, the sum of m and n is 5 to 60, Y is a C1 to C9 alkylene group or a single bond; R1 and R2 are independently selected from one of the following: hydrogen atom, substituted or unsubstituted C1 to C9 alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, and halogen.

[0111] In some embodiments, the above preparation method further includes a step of preparing a modified polyphenylene ether resin prepolymer.

[0112] In some embodiments, the preparation steps of the modified polyphenylene ether resin prepolymer include:

[0113] The vinyl fluorene compound was heated to a molten state, and then polyphenylene ether resin was added. The prepolymerization reaction was carried out at 100℃~180℃ for 60min~200min.

[0114] As an example, the above prepolymerization reaction can be carried out at 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, or 180°C. Furthermore, the prepolymerization reaction can be carried out at temperatures within a range defined by any two of the above point values ​​as endpoints.

[0115] As an example, the time for the prepolymerization reaction described above can be 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min, 130 min, 140 min, 150 min, 160 min, 170 min, 180 min, 190 min, or 200 min. Furthermore, the time for the prepolymerization reaction can be a range of values ​​defined by any two of the above point values ​​as endpoints.

[0116] In some embodiments, the mass ratio of the vinyl fluorene compound to the functionalized polyphenylene ether resin is (1–2):1. As an example, the mass ratio of the vinyl fluorene 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 ranges are also possible.

[0117] In another embodiment of this application, a polymer composite material is provided, the raw materials for which the above-mentioned resin composition is included.

[0118] In some embodiments, the raw materials for preparing the above-mentioned polymer composite material further include a solvent.

[0119] In some embodiments, the mass ratio of the resin composition to the solvent in the raw materials for preparing the above-mentioned polymer composite material is (1-10):1. Further, the mass ratio of the resin composition to the solvent is (1-5):1.

[0120] In some embodiments, the solvent is an organic solvent.

[0121] In some embodiments, the organic solvent includes at least one of butanone, toluene, and propylene glycol methyl ether.

[0122] In some embodiments, the organic solvent includes butanone, toluene, and propylene glycol methyl ether in a mass ratio of 1:1:1.

[0123] In another embodiment of this application, a method for preparing a polymer composite material is provided, comprising the following steps:

[0124] The above resin composition was subjected to a semi-curing reaction to obtain a polymer composite material.

[0125] The temperature of the semi-curing reaction is 70℃~200℃; the time of the semi-curing reaction is 2min~15min.

[0126] As an example, the temperature of the semi-curing reaction can be 70℃, 80℃, 90℃, 100℃, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃, 180℃, 190℃, or 200℃. Furthermore, the temperature of the semi-curing reaction can be a range of values ​​defined by any two of the above point values ​​as endpoints.

[0127] In some embodiments, the semi-curing reaction time is 2 min to 15 min. As an example, the curing reaction time 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 above semi-curing reaction time can be a range of values ​​formed by using any two of the above point values ​​as endpoints.

[0128] In some embodiments, the method for preparing the above-mentioned polymer composite material further includes the following preparation steps:

[0129] After the above resin components undergo a semi-curing reaction, a complete curing reaction is carried out.

[0130] In some embodiments, the above-mentioned complete curing reaction is at 5 kgf / cm². 2 ~15kgf / cm 2 It is carried out under pressure conditions.

[0131] In some embodiments, the temperature for complete curing is 100°C to 200°C.

[0132] In some embodiments, the temperature and time for complete curing reaction are 150 min to 200 min.

[0133] In some embodiments, the complete curing reaction step includes:

[0134] React at 100℃~120℃ for 20min~40min; then at 150℃~180℃ for 20min~40min; then at 190℃~200℃ for 100min~140min.

[0135] In another embodiment of this application, an extension film is provided, which includes the aforementioned polymer composite material. It is understood that the extension film is a semi-cured product.

[0136] In another embodiment of this application, a layering film is provided, the raw materials for preparing the layering film including the above-mentioned resin composition.

[0137] In some embodiments, the thickness of the extension film can be from 5 μm to 150 μm. For example, the thickness of the extension film can 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 extension film can be a range of values ​​defined by any two of the above point values ​​as endpoints.

[0138] Another embodiment of this application provides a method for preparing an extended film, comprising the following steps:

[0139] The above resin composition is dispersed in a solvent to form a coating material;

[0140] The coating material is applied to the surface of the support to form a resin composition coating.

[0141] Then a semi-curing reaction is carried out to obtain the thickened film.

[0142] It is understood that the laminated film obtained by the above method refers to the resin film layer formed after the resin composition undergoes a semi-curing reaction, excluding the support.

[0143] In some embodiments, the support is selected from one or more of plastic films and metal films.

[0144] In some embodiments, the plastic film includes, but is not limited to, polyethylene terephthalate (PET), polycarbonate (PC), and polymethyl methacrylate (PMMA).

[0145] In some embodiments, the metal film may be copper foil or aluminum foil.

[0146] In some embodiments, the thickness of the support is preferably, but not limited to, 3 μm to 105 μm.

[0147] In some embodiments, the coating thickness of the resin composition is preferably, but not limited to, 5 μm to 150 μm.

[0148] To make the objectives, technical solutions, and advantages of this application clearer and more concise, the following specific embodiments are used for illustration, but this application is by no means limited to these embodiments. The embodiments described below are merely preferred embodiments of this application and can be used to describe this application, but should not be construed as limiting the scope of this application. It should be noted that any modifications, equivalent substitutions, and improvements made within the spirit and principles of this application should be included within the protection scope of this application.

[0149] To better illustrate this application, the following description, in conjunction with specific embodiments, further explains its content. The following are specific embodiments.

[0150] The sources of some components in the embodiments and comparative examples of this application are as follows:

[0151] Vinylfluorene compounds were purchased from Kungang New Materials, CAS No: 142494-81-3;

[0152] Functionalized polyphenylene ether resin: SABIC SA9000;

[0153] Naphthalene-type epoxy resin: DIC Chemical HP-5000;

[0154] Reactive ester curing agent: DIC Chemical HPC-8000-65T;

[0155] Imidazole accelerator: Shikoku Kasei 2MI;

[0156] Vinyl spherical silica: Yaduma SO-C1, D50 particle size 0.4μm;

[0157] Leveling agent: 3M FC-4432;

[0158] PET film: Toray LUMIRROR R80 from Japan, with a thickness of 38μm.

[0159] Example of synthesis of modified polyphenylene ether resin prepolymer:

[0160] Example 1 of synthesis of modified polyphenylene ether resin prepolymer:

[0161] First, heat 50 parts of vinyl fluorene compound to a molten state, then add 100 parts of functionalized polyphenylene ether resin, react and prepolymerize at 160°C for 100 min, and then cool to room temperature to obtain modified polyphenylene ether resin prepolymer A.

[0162] Example 2 of synthesis of modified polyphenylene ether resin prepolymer:

[0163] First, 75 parts of vinyl fluorene compound were heated to a molten state, then 100 parts of functionalized polyphenylene ether resin were added, and the mixture was prepolymerized at 160°C for 120 min and then cooled to room temperature to obtain modified polyphenylene ether resin prepolymer B.

[0164] Example 3 of synthesis of modified polyphenylene ether resin prepolymer:

[0165] First, 100 parts of vinyl fluorene compound were heated to a molten state, and then 100 parts of functionalized polyphenylene ether resin were added. The mixture was reacted and prepolymerized at 160°C for 130 min and then cooled to room temperature to obtain modified polyphenylene ether resin prepolymer C.

[0166] The following are application examples of modified polyphenylene ether resin prepolymers:

[0167] Example 1

[0168] By weight, 10 parts of modified polyphenylene ether resin prepolymer A, 30 parts of naphthalene ring epoxy resin, 25 parts of reactive ester curing agent, 3 parts of imidazole accelerator, 100 parts of spherical silica, and 1 part of additives were dissolved in 50 parts of mixed solvent; wherein the mixed solvent was prepared by mixing methyl ethyl ketone, toluene, and propylene glycol methyl ether in a mass ratio of 1:1:1. After thorough mixing, the mixture was sprayed onto the PET surface and then baked at 120℃ for 3 minutes to obtain a laminated film with a thickness of 80 μm (this thickness does not include the thickness of the PET).

[0169] Example 2

[0170] By weight, 20 parts of modified polyphenylene ether resin prepolymer A, 40 parts of naphthalene ring epoxy resin, 40 parts of reactive ester curing agent, 5 parts of imidazole accelerator, 250 parts of spherical silica, and 5 parts of additives were dissolved in 90 parts of mixed solvent; wherein the mixed solvent was prepared by mixing methyl ethyl ketone, toluene, and propylene glycol methyl ether in a mass ratio of 1:1:1. After thorough mixing, the mixture was sprayed onto the PET surface and then baked at 125℃ for 3 minutes to obtain a laminated film with a thickness of 80 μm (this thickness does not include the thickness of the PET).

[0171] Example 3

[0172] By weight, 30 parts of modified polyphenylene ether resin prepolymer A, 20 parts of naphthalene ring epoxy resin, 10 parts of reactive ester curing agent, 1 part of imidazole accelerator, 175 parts of spherical silica, and 3 parts of additives were dissolved in 60 parts of mixed solvent; wherein the mixed solvent was composed of butanone, toluene, and propylene glycol methyl ether in a mass ratio of 1:1:1. After thorough mixing, the mixture was sprayed onto the PET surface and then baked at 120℃ for 3 minutes to obtain a laminated film with a thickness of 80 μm (this thickness does not include the thickness of the PET).

[0173] Example 4

[0174] By weight, 20 parts of modified polyphenylene ether resin prepolymer B, 40 parts of naphthalene ring epoxy resin, 40 parts of reactive ester curing agent, 5 parts of imidazole accelerator, 250 parts of spherical silica, and 5 parts of additives were dissolved in 90 parts of mixed solvent; wherein the mixed solvent was prepared by mixing methyl ethyl ketone, toluene, and propylene glycol methyl ether in a mass ratio of 1:1:1. After thorough mixing, the mixture was sprayed onto the PET surface and then baked at 125℃ for 3 minutes to obtain a laminated film with a thickness of 80 μm (this thickness does not include the thickness of the PET).

[0175] Example 5

[0176] By weight, 20 parts of modified polyphenylene ether resin prepolymer C, 40 parts of naphthalene ring epoxy resin, 40 parts of reactive ester curing agent, 5 parts of imidazole accelerator, 250 parts of spherical silica, and 5 parts of additives were dissolved in 90 parts of mixed solvent; wherein the mixed solvent was composed of methyl ethyl ketone, toluene, and propylene glycol methyl ether in a mass ratio of 1:1:1. After thorough mixing, the mixture was sprayed onto the PET surface and then baked at 125℃ for 3 minutes to obtain a laminated film with a thickness of 80 μm (this thickness does not include the thickness of the PET).

[0177] Example 6

[0178] By weight, 60 parts of modified polyphenylene ether resin prepolymer A, 40 parts of naphthalene ring epoxy resin, 40 parts of reactive ester curing agent, 5 parts of imidazole accelerator, 250 parts of spherical silica, and 5 parts of additives were dissolved in 90 parts of mixed solvent; wherein the mixed solvent was prepared by mixing methyl ethyl ketone, toluene, and propylene glycol methyl ether in a mass ratio of 1:1:1. After thorough mixing, the mixture was sprayed onto the PET surface and then baked at 125℃ for 3 minutes to obtain a laminated film with a thickness of 80 μm (this thickness does not include the thickness of the PET).

[0179] Comparative Example 1

[0180] By weight, 20 parts of functionalized polyphenylene ether resin, 40 parts of naphthalene ring epoxy resin, 40 parts of reactive ester curing agent, 5 parts of imidazole accelerator, 250 parts of spherical silica, and 5 parts of additives were dissolved in 90 parts of a mixed solvent; wherein the mixed solvent was prepared by mixing methyl ethyl ketone, toluene, and propylene glycol methyl ether in a mass ratio of 1:1:1. After thorough mixing, the mixture was sprayed onto the PET surface and then baked at 125°C for 3 minutes to obtain a laminated film with a thickness of 80 μm (this thickness does not include the thickness of the PET).

[0181] The composition of the resin compositions prepared in each embodiment and comparative example is shown in Table 1 below.

[0182] Table 1

[0183]

[0184] The laminated films (the side away from the PET film) obtained in the above embodiments and comparative examples were laminated onto a 12μm thick copper foil using a laminator. After removing the PET film, a 12μm thick copper foil was then applied over the laminated film. The laminated film was then placed in a programmable temperature and pressure controlled vacuum press and subjected to a vacuum condition (vacuum parameter <10mBar) at 8kgf / cm². 2 Under pressure, the film was completely cured at 100℃ for 30 min, then 170℃ for 30 min, and finally 190℃ for 120 min. The copper foil was then removed, and the fully cured laminated film was subjected to the following tests:

[0185] 1. Coefficient of thermal expansion (CTE) test: Tested according to IPC-TM-650 2.4.24.5;

[0186] 2. Glass transition temperature (Tg) test: Tested according to IPC-TM-650 2.4.24.2;

[0187] 3. Electrical performance testing: Tested according to IPC-TM-650 2.5.5.2;

[0188] 4. Water absorption rate: Tested according to IPC-TM650 2.6.2.1;

[0189] The performance test data of the products after curing the laminated films prepared in each embodiment and comparative example are shown in Table 2.

[0190] Table 2

[0191]

[0192] Note: In the table, "CTE / (ppm / ℃)Before TG" represents the coefficient of thermal expansion under conditions where the temperature is below the glass transition temperature; "CTE / (ppm / ℃)After TG" represents the coefficient of thermal expansion under conditions where the temperature is above the glass transition temperature.

[0193] “Dk(10G)” represents the dielectric constant of the material at a frequency of 10GHz.

[0194] “Df(10G)” indicates the loss tangent of the material at a frequency of 10GHz.

[0195] As shown in Table 2, after complete curing, the laminated films prepared in Examples 1-6 of this application have glass transition temperatures ranging from 175°C to 195°C. Their coefficients of thermal expansion (CTE) below the glass transition temperature are 18 ppm / °C to 31 ppm / °C, and above the glass transition temperature are 55 ppm / °C to 82 ppm / °C. The values ​​of Dk (10G) are 3.31 to 3.52, Df (10G) are 0.0041 to 0.0066, and the water absorption rate is 0.08% to 0.55%. Therefore, the laminated films prepared using the technical methods of this application exhibit good heat resistance, low coefficients of thermal expansion, and good dielectric properties.

[0196] Comparative Example 1 did not modify the polyphenylene ether resin. After complete curing, the glass transition temperature of its laminated film was 152°C. Its coefficient of thermal expansion (CTE) was 40 ppm / °C below the glass transition temperature and 90 ppm / °C above the glass transition temperature. Its Dk(G) value was 3.7, Df(10G) value was 0.078, and its water absorption rate was 1.21%. Its performance was significantly inferior to Examples 1-6.

[0197] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above 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.

[0198] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

1. A resin composition, characterized in that, Its components include modified polyphenylene ether resin prepolymer, functional resin, inorganic filler, and curing agent; 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 functionalized polyphenylene ether resin having formula I and vinyl fluorene compounds having formula II. Wherein, m and n are both positive integers, the sum of m and n is 5 to 60, Y is a C1 to C9 alkylene group or a single bond; R1 and R2 are independently selected from one of the following: hydrogen atom, substituted or unsubstituted C1 to C9 alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, and 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 each independently selected from one of the following: hydrogen atom, substituted or unsubstituted C1 to C7 alkyl group, substituted or unsubstituted benzene ring, substituted or unsubstituted naphthalene ring, substituted or unsubstituted anthracene ring, and halogen.

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

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 one or more of the following: 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; (2) The benzoxazine resin is selected from one or more of the following: 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 whose molecular structure contains two or more maleimide structures; (4) The hydrocarbon resin is selected from one or more of butadiene-styrene copolymers and polybutadiene; (5) The inorganic filler is selected from one or more of zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, nepheline, 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 curing agent is selected from one or more of acid anhydride curing agents, cyanate ester curing agents and active ester curing agents.

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

6. The resin composition according to claim 5, characterized in that, The resin composition satisfies at least one of the following conditions: (1) The curing accelerator is 1 to 10 parts by mass; (2) The curing accelerator is selected from one or more of tertiary amine accelerators, imidazole accelerators, peroxide accelerators, organophosphorus accelerators and transition metal carboxylate accelerators; (3) The mass fraction of the additive is 1 to 10 parts; (4) The additives are one or more of the following: dispersant, leveling agent, defoamer, thickener and coupling agent.

7. A method for preparing a resin composition, characterized in that, The process includes the following steps: mixing modified polyphenylene ether resin prepolymer, functional resin, inorganic filler and curing agent; 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 Formula I and a vinyl fluorene compound having Formula II. Wherein, m and n are both positive integers, the sum of m and n is 5 to 60, Y is a C1 to C9 alkylene group or a single bond; R1 and R2 are independently selected from one of the following: hydrogen atom, substituted or unsubstituted C1 to C9 alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, and halogen.

8. The preparation method according to claim 7, characterized in that, It also includes the preparation step of the modified polyphenylene ether resin prepolymer; The preparation steps of the modified polyphenylene ether resin prepolymer include: The vinyl fluorene compound is heated to a molten state, and then the functionalized polyphenylene ether resin is added. The prepolymerization reaction is carried out at 100°C to 180°C for 60 min to 200 min.

9. The preparation method according to claim 8, characterized in that, The mass ratio of the vinyl fluorene 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 preparation steps include the following: 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 layering film, characterized in that, The raw materials for its preparation include the resin composition as described in any one of claims 1 to 6; Or it may include the polymer composite material as described in claim 10.

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