Resin composition, prepreg, and printed circuit board

Abstract

The present application relates to the field of polymer materials, and in particular to a resin composition, a prepreg, and a printed circuit board. The resin composition provided in the present application comprises the following components: 40-80 parts of a prepolymer, 10-50 parts of a curing agent, 30-70 parts of an epoxy resin, 1-10 parts of an imidazole compound, and 50-150 parts of a filler; wherein raw materials for preparing the prepolymer comprise a maleimide resin and an amino-containing fluorene compound; the maleimide resin comprises one or more of compounds having a structure represented by formula (I); and the amino-containing fluorene compound comprises one or more of compounds having a structure represented by formula (II). The resin composition provided by the present application uses a maleimide resin-modified prepolymer, which has good compatibility with an epoxy resin, thereby effectively reducing the addition of a filler, ensuring the processability of the resin composition; in addition, the resin composition provided by the present application has excellent heat resistance.

Description

Resin composition, prepreg, printed circuit board

[0001] Related applications

[0002] This application claims priority to Chinese Patent Application No. 2024118438368, filed on December 14, 2024, entitled "Resin Composition, Prepreg, Printed Circuit Board", the entire contents of which are incorporated herein by reference. Technical Field

[0003] This application belongs to the field of polymer materials, specifically relating to a resin composition, a prepreg, and a printed circuit board. Background Technology

[0004] In recent years, diversification, multifunctionality, portability, and thinness have become the goals pursued in electronic products. Printed Circuit Boards (PCBs) are a core component of electronic products. They complete the electrical connections of electronic products by printing or etching conductive metal paths on an insulating substrate and soldering electronic components. Copper-clad laminates, as the substrate of printed circuit boards, also require excellent thermal stability to meet the thermal shock requirements of impedance design and manufacturing processes during the printed circuit board design process.

[0005] The resin composition plays a decisive role in the performance of copper-clad laminates. Most resin compositions are prepared using epoxy resin as the primary dielectric material. However, resin compositions including epoxy resin have insufficient heat resistance and a high coefficient of thermal expansion, leading to problems such as circuit board warping. Currently, to reduce the thermal expansion of the resin composition, a large amount of inorganic filler with a low coefficient of thermal expansion is usually added. While this can significantly reduce the coefficient of thermal expansion, the negative effects cannot be ignored, such as excessive viscosity of the resin composition, resulting in significantly poorer processing performance. Summary of the Invention

[0006] Based on this, this application provides a resin composition, a prepreg, and a printed circuit board. The resin composition provided in this application uses a maleimide-modified prepolymer, which has good compatibility with epoxy resin and can achieve excellent heat resistance, effectively reducing the addition of fillers and thus ensuring its processing performance.

[0007] A first aspect of this application provides a resin composition comprising the following components:

[0008] The raw materials for preparing the prepolymer include maleimide resin and amino-containing fluorene compounds;

[0009] The maleimide resin includes one or more compounds having the structure shown in formula (I);

[0010] In equation (I), Ar1 and Ar2 are each independent of each other being non-existent. C6-C6 that are unsubstituted or substituted by at least one R′ 20 Aromaticyl group, and at least one of Ar1 and Ar2 is C6-C6 that are unsubstituted or substituted by at least one R′ 20 Aromaticyl group; L1 is absent, -O-, C1-C6 alkylene group, C1-C6 haloalkylene group, C6-C 20 Aromatic groups, *-OL 13 -O-* or *-OL 14 -AL 15 -O-*,L 11 L 12 L 13 L 14 and L 15 Each is independently an unsubstituted or at least substituted C6-C. 20 Aromatic group, A is a C1 to C6 alkylene group; each time R′ appears, it is independently a halogen or a C1 to C3 alkylene group; q is any integer from 1 to 6;

[0011] The amino-containing fluorenyl compounds include one or more compounds having the structure shown in formula (II);

[0012] In equation (II), each time Cy appears, it is independently represented by C6 to C6. 20 Aromatic group; each time R1 appears, it is independently H, halogen, amino, C1-C6 alkyl, C1-C6 haloalkyl, or C6-C6. 20 Aromatic group; n is any integer from 0 to 3.

[0013] In one embodiment, the raw materials for preparing the prepolymer further include unsaturated phenolic compounds; the unsaturated phenolic compounds have one or more of the following characteristics:

[0014] (1) The unsaturated phenolic compounds include one or more compounds having the structure shown in formula (III);

[0015] In formula (III), X is selected from -CH2-, -C(CH3)2- or S(=O)2, and each time R2 appears, it is independently a C2-C6 alkenyl or C2-C6 alkynyl.

[0016] (2) The mass ratio of the unsaturated phenolic compound to the maleimide resin is (0.5-1.5):4.

[0017] In one embodiment, the maleimide resin comprises One or more of the following; each time R′ appears, it is independently a halogen or a C1-C3 alkylene group; m is any integer from 0 to 4.

[0018] In one embodiment, the amino-containing fluorene compound includes One or more of the following; each time R1 appears, it is independently H, amino or C1 to C3 alkyl; n is any integer from 0 to 3.

[0019] In one embodiment, the prepolymer has one or more of the following characteristics:

[0020] (1) The mass ratio of the maleimide resin to the amino-containing fluorenyl compound is (1-4):4;

[0021] (2) The preparation steps of the prepolymer include: heating the amino-containing fluorenyl compound to a molten state, then adding other preparation raw materials, and performing a polymerization reaction at the polymerization temperature to prepare the prepolymer; optionally, the polymerization temperature is 100℃~180℃.

[0022] In one embodiment, the imidazole compound includes one or more compounds having the structure shown in formula (IV); In formula (IV), R3 is a C1 to C6 alkyl group.

[0023] In one embodiment, the resin composition has one or more of the following characteristics:

[0024] (1) The curing agent includes one or more of cyanate ester resin and benzoxazine resin;

[0025] (2) The epoxy resin includes one or more of the following: naphthalene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol S-type epoxy resin, bisphenol F-type epoxy resin, phosphorus-containing epoxy resin, unsaturated epoxy resin, o-cresol-formaldehyde epoxy resin, bisphenol A phenolic epoxy resin, multifunctional epoxy resin, alicyclic epoxy resin, resorcinol epoxy resin, rubber-modified epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, anthracene-type epoxy resin, and organosilicon-modified epoxy resin;

[0026] (3) In the resin composition, the filler has a mass percentage of 30% to 42%.

[0027] In one embodiment, the resin composition further includes functional additives;

[0028] Optionally, the functional additive is 1 to 5 parts by weight; the functional additive includes one or more of dispersants, leveling agents, defoamers and coupling agents.

[0029] A second aspect of this application provides a prepreg comprising a reinforcing material and a resin layer loaded on the surface of the reinforcing material, the resin layer being formed by drying the resin composition described in any embodiment of the first aspect of this application.

[0030] A third aspect of this application provides a printed circuit board, the printed circuit board comprising the prepreg described in the second aspect of this application.

[0031] The resin composition provided in this application has at least the following beneficial effects:

[0032] The resin composition provided in this application uses maleimide resin and an amino-containing fluorene compound as raw materials for prepolymer preparation. The maleimide ring in the maleimide resin has high bond energy and stability, and it can also generate steric hindrance, hindering excessive proximity and interaction of molecular chains to restrict their free movement and reduce the problem of decreased heat resistance caused by chain motion. In the amino-containing fluorene compound, the fluorene group has a large, rigid planar structure of a conjugated system, which effectively prevents chain motion at high temperatures. Furthermore, the amino group can react with the maleimide group in the maleimide resin to form a cross-linked structure. This tight cross-linked network effectively resists the thermal motion of the molecular chains, thereby reducing the coefficient of thermal expansion.

[0033] Furthermore, the combined action of the curing agent, epoxy resin, and imidazole compounds enables the resin composition of this application to form a highly cross-linked network structure during the curing process. This is beneficial for improving the thermal stability of the material and also helps to maintain a low coefficient of thermal expansion, allowing the resin composition to possess excellent heat resistance with the addition of a low amount of filler. Detailed Implementation

[0034] The resin composition, prepreg, and printed circuit board of this application are 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. Of course, they are merely examples and are not intended to limit this application.

[0035] When a numerical range is disclosed herein, the range is considered continuous and includes the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0036] 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 in the specification of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. Unless otherwise stated or in case of conflict, the terms or phrases used herein have the following meanings:

[0037] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0038] In this application, percentage content refers to mass percentage for solid-liquid mixtures and solid-phase-solid mixtures, and volume percentage for liquid-phase-liquid mixtures, unless otherwise specified.

[0039] In this application, unless otherwise specified, percentage concentrations refer to final concentrations. The final concentration refers to the percentage of the added component in the system after its addition.

[0040] In this application, "*" indicates a connection site.

[0041] In this application, when no linking site is specified in the group, it means that any linkable site in the group is selected as the linking site.

[0042] In this application, the single bonds connecting the substituents extend through the corresponding ring, indicating that the substituent can be connected to any position on the ring, for example... R is attached to any substituted site on the benzene ring.

[0043] In this application, "absent" means the absence of this group, where other adjacent groups are directly bonded. For example, In the case where Ar1 does not exist, equation (I) is:

[0044] In this application, "aromatic group" 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 rings, at least one is an aromatic ring system. Phrases containing this term include, for example, "C6-C6...". 20"Aryl" refers to an aryl group containing 6 to 20 carbon atoms. Each time it appears, it can independently be a C6 aryl, C6 aryl, C6 aryl, or C6 aryl. 10 Aryl, C 14 Aryl, C 18 Aryl, C 20 Aryl groups. Suitable examples include, but are not limited to: benzene, biphenyl, naphthalene, anthracene, phenanthrene, dinaphthalene, triphenylene and their derivatives.

[0045] In this application, "aromatic group" refers to an aromatic hydrocarbon group derived by removing one hydrogen atom from an aromatic group.

[0046] In this application, "alkyl" refers to a saturated hydrocarbon group 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-C6 alkyl," refer to alkyl groups containing 1 to 6 carbon atoms, and each occurrence can independently be C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, or C6 alkyl. Suitable examples include, but are not limited to: methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1-propyl (n-propyl, n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (i-Pr, i-propyl, -CH(CH3)2), 1-butyl (n-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), tert-butyl (1,1-dimethylethyl, 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH3)3), 1-pentyl (n-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).

[0047] "Alkylene" refers to a hydrocarbon group derived from an alkyl group by removing one hydrogen atom, forming a group with two monovalent groups. It can be a saturated branched alkyl group or a saturated straight-chain alkyl group. For example, "C1-C6 alkylene" means that the alkyl part contains 1-6 carbon atoms, and each occurrence can be independently C1 alkylene, C4 alkylene, C5 alkylene, or C6 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-).

[0048] In this application, "halogen" refers to F, Cl, Br, or I.

[0049] In this application, "haloalkyl" refers to a group formed by replacing hydrogen atoms with halogen atoms on the basis of an alkyl group. For example, "C1 to C6 haloalkyl" includes, but is not limited to, CH2F, -CF2CF3, or -CF2CF2CF3.

[0050] In this application, "halogenated alkylene" refers to a group formed by replacing hydrogen atoms with halogen atoms on the basis of a haloalkyl group. For example, "C1 to C6 haloalkylene" includes, but is not limited to, -CHF, -CF2CF2- or -CF2CF2CF2-.

[0051] In this application, "alkenyl" refers to a group containing at least one unsaturated site, i.e., carbon-carbon sp. 2 Hydrocarbons with a double bond consisting of a positive, secondary, tertiary, or cyclic carbon atom. Phrases containing this term, such as "C2–C6 alkenyl," refer to alkenyl groups containing 2–6 carbon atoms, which, each time appearing, can independently be C2-alkenyl, C3-alkenyl, C4-alkenyl, C5-alkenyl, or C6-alkenyl. Suitable examples include, but are not limited to: vinyl (-CH=CH2), allyl (-CH2CH=CH2), cyclopentenyl (-C5H7), and 5-hexenyl (-CH2CH2CH2CH2CH=CH2).

[0052] In this application, "alkynyl" refers to a hydrocarbon containing at least one unsaturated carbon atom, i.e., a carbon-carbon sp triple bond, or a cyclic carbon atom. Phrases containing this term, such as "C2-C6 alkynyl," refer to alkynyl groups containing 2 to 6 carbon atoms, and each occurrence can be independently C2-alkynyl, C3-alkynyl, C4-alkynyl, C5-alkynyl, or C6-alkynyl. Suitable examples include, but are not limited to, ethynyl (-C≡CH) and propynyl (-CH2C≡CH).

[0053] A first aspect of this application provides a resin composition comprising the following components:

[0054] The raw materials for preparing the prepolymer include maleimide resin and an amino-containing fluorene compound. The maleimide ring in the maleimide resin has high bond energy and stability, and it can also generate steric hindrance, hindering excessive proximity and interaction of molecular chains, thus limiting the free movement of molecular chains and reducing the problem of decreased heat resistance caused by molecular chain movement. In the amino-containing fluorene compound, the fluorene group has a large, rigid planar structure of a conjugated system, and the amino group can participate in the formation of intramolecular or intermolecular hydrogen bonds to enhance intermolecular interactions and improve the heat resistance of the resin composition. Furthermore, as a reactive site, the amino group can also chemically react with other functional groups in the resin, such as maleimide groups, to regulate the crosslinking density and curing reaction rate. Understandably, the weight percentage of the prepolymer can be selected from any value between 40 and 80 parts. For example, the weight parts of the prepolymer include, but are not limited to, 40, 43, 45, 48, 50, 52, 55, 58, 60, 62, 65, 68, 70, 75, 78 or 80 parts, or any two of the above point values ​​as endpoint values.

[0055] The curing agent forms a highly cross-linked network structure during the curing process to further enhance the heat resistance of the resin composition. Understandably, the weight parts of the curing agent can be selected from any value between 10 and 50 parts. For example, the weight parts of the curing agent include, but are not limited to, 10, 13, 15, 18, 20, 22, 25, 28, 30, 32, 35, 38, 40, 42, 45, 48, or 50 parts, or any two of the above values ​​as endpoints.

[0056] Epoxy resin works synergistically with other components. During the curing process, the molecular chains of epoxy resin cross-link with other resin molecules to form a stable three-dimensional network structure, thereby improving the overall heat resistance of the resin composition. For example, the weight parts of epoxy resin include, but are not limited to, 30 parts, 33 parts, 35 parts, 38 parts, 40 parts, 43 parts, 45 parts, 48 ​​parts, 50 parts, 53 parts, 55 parts, 58 parts, 60 parts, 63 parts, 65 parts, 68 parts, or 70 parts, or any two of the above values ​​as endpoints.

[0057] Imidazole compounds can catalyze cross-linking reactions between resin molecules, making the curing process more thorough and uniform, and ensuring that the resin composition forms a more complete cross-linked structure after curing. In this application, the weight parts of imidazole compounds include, but are not limited to, 1 part, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts, or any two of the above points as endpoint values ​​within the range.

[0058] Understandably, the weight percentage of the packing material can be selected from any value between 50 and 120 parts. For example, the weight percentage of the packing material includes, but is not limited to, 50, 60, 70, 80, 90, 100, 110, or 120 parts, or any two of the above values ​​as endpoints.

[0059] In one example, the filler comprises 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.

[0060] The resin composition provided in this application, through the combined action of prepolymer, curing agent, epoxy resin and imidazole compound, enables the resin composition of this application to form a highly cross-linked network structure during the curing process. This is beneficial to improving the thermal stability of the material and reducing the thermal stability of the resin composition.

[0061] In one example, the maleimide resin comprises one or more compounds having the structure shown in formula (I);

[0062] In equation (I), Ar1 and Ar2 are each independent of each other being non-existent. C6-C6 that are unsubstituted or substituted by at least one R′ 20 Aromaticyl group, and at least one of Ar1 and Ar2 is C6-C6 that are unsubstituted or substituted by at least one R′ 20 Aromatic group. Each R′ is independently a halogen or a C1-C3 alkylene group. q is any integer from 1 to 6. q is 1, 2, 3, 4, 5, or 6.

[0063] For example, Ar1 and Ar2 are each independently... Each time R′ appears, it is independently a halogen, methyl, or ethyl.

[0064] L1 represents non-existent, -O-, C1-C6 alkylene, C1-C6 haloalkylene, C6-C 20 Aromatic groups, *-OL 13 -O-* or *-OL 14 -AL 15 -O-*。 L 11 L 12 L 13 L 14 and L 15 Each is independently an unsubstituted or at least substituted C6-C. 20 The aromatic group and A are C1 to C6 alkylene groups. Each time R′ appears, it is independently a halogen or a C1 to C3 alkylene group.

[0065] Furthermore, L1 represents the absence of, -O-, methyl, ethyl, propyl, and C6-C6 groups. 20 Aromatic groups, or *-OL 14 -AL 15 -O-*。 L 14 and L 15 Each is independently an unsubstituted or at least substituted C6-C. 20 The aromatic group and A are C1-C3 alkylene groups. Each time R′ appears, it is independently either a halogen or a C1-C3 alkylene group.

[0066] Furthermore, L1 is absent, -O-, methyl, ethyl, propyl, or A is a C1-C3 alkylene group. Each time R′ appears, it is independently either a halogen or a C1-C3 alkylene group.

[0067] In one example, the maleimide resin includes One or more of the following; each time R′ appears, it is independently a halogen or a C1-C3 alkylene group; m is any integer from 0 to 4.

[0068] Furthermore, the maleimide resin comprises N,N'-m-phenylenebismaleimide. bis(4-maleimidephenyl)methane 2,2-Bis(4-(4-maleimide phenoxy)-phenyl)propane bis(3,5-dimethyl-4-maleimidephenyl)methane bis(3-ethyl-5-methyl-4-maleimide-phenyl)methane bis(3,5-diethyl-4-maleimide-phenyl)methane and phosphorus-containing bismaleimide One or more of them.

[0069] The aforementioned maleimide has multiple maleimide groups, which can provide more reaction sites during the curing process to chemically react with epoxy resin, curing agent, etc., to form more crosslinking points and improve the heat resistance of the resin composition.

[0070] In one example, the amino-containing fluorenyl compound includes one or more compounds having the structure shown in formula (II);

[0071] In equation (II), each time Cy appears, it is independently represented by C6 to C6. 20 Aromatic group.

[0072] Furthermore, each time Cy appears, it independently...

[0073] Each time R1 appears, it is independently H, halogen, amino, C1-C6 alkyl, C1-C6 haloalkyl, or C6-C6. 20 Aromatic group. n is any integer from 0 to 3. n can be 0, 1, 2 or 3.

[0074] In one example, the amino-containing fluorene compound includes One or more of the following. Each time R1 appears, it is independently H, amino, or C1-C3 alkyl; n is any integer from 0 to 3. Further, each time R1 appears, it is independently H, methyl, or ethyl.

[0075] Furthermore, the amino-containing fluorene compound includes One or more of them.

[0076] In the aforementioned amino-containing fluorenyl compounds, π electrons are delocalized and distributed throughout the fluorenyl structure, forming a relatively stable electron cloud structure. When exposed to high temperatures, higher energy is required to disrupt this stable electron cloud structure and chemical bonds, thus giving the amino-containing fluorenyl compounds good thermal stability. Furthermore, the presence of the amino group not only enables cross-linking reactions with active groups such as maleimide, increasing the cross-linking density, but also allows the formation of intermolecular hydrogen bonds between compounds. This helps to enhance intermolecular interactions and make the molecular chains more tightly bonded. Consequently, under high-temperature environments, it can prevent the material from softening or decomposing due to excessive molecular chain movement, further improving the heat resistance of the resin composition.

[0077] In one example, the raw materials for preparing the prepolymer also include unsaturated phenolic compounds.

[0078] Unsaturated phenolic compounds can participate in cross-linking reactions during polymerization, forming more complex and stable network structures to prevent molecular chain slippage and breakage at high temperatures, further enhancing the material's heat resistance. Simultaneously, the benzene ring structure in phenolic compounds also possesses a certain degree of thermal stability, enabling the material to maintain its physical and chemical properties at high temperatures. Furthermore, functional groups such as phenolic hydroxyl groups can adjust the charge distribution within the molecule, reducing energy loss under an electric field and improving the material's electrical insulation properties, thus meeting the requirements of electronic devices with high dielectric performance requirements.

[0079] In one example, the unsaturated phenolic compound includes one or more compounds having the structure shown in formula (III);

[0080] In formula (III), X is selected from -CH2-, -C(CH3)2- or S(=O)2, and each time R2 appears, it is independently C2-C6 alkenyl or C2-C6 alkynyl.

[0081] Furthermore, the unsaturated phenolic compound includes one or more of diallyl bisphenol A, diallyl bisphenol S, diallyl bisphenol F, and bisphenol A diallyl ether.

[0082] For example, the unsaturated phenolic compounds include One or more of them.

[0083] The cyclic structure of maleimide resin itself provides a good basis for thermal stability, while the unsaturated bonds in the unsaturated phenolic compound can undergo cross-linking reactions with the maleimide resin. This cross-linking structure can restrict the movement of molecular chains at high temperatures, preventing the material from softening, deforming, or decomposing due to the thermal movement of the molecular chains, thereby significantly improving the material's heat resistance. In one example, the mass ratio of the unsaturated phenolic compound to the maleimide resin is (0.5–1.5):4. For example, the mass ratio of the unsaturated phenolic compound to the maleimide resin includes, but is not limited to, 0.5:4, 0.8:4, 0.9:4, 1:4, 1.1:4, 1.3:4, or 1.5:4, or any two of the above values ​​as endpoints.

[0084] In one example, the mass ratio of the maleimide resin to the amino-containing fluorene compound is (1–4):4. This specific mass ratio of maleimide resin to amino-containing fluorene compound effectively resists molecular chain movement and decomposition caused by high temperatures; it also helps optimize cohesive energy and stress distribution, improving heat resistance. For example, the mass ratio of the maleimide resin to the amino-containing fluorene compound includes, but is not limited to, 0.5:4, 0.8:4, 0.9:4, 1:4, 1.1:4, 1.3:4, or 1.5:4, or any two of these values ​​within a range defined by endpoints.

[0085] In one example, the preparation steps of the prepolymer include: polymerizing the raw materials at a polymerization temperature to prepare the prepolymer.

[0086] In one example, the polymerization temperature is 100°C to 180°C. A polymerization temperature between 100°C and 180°C effectively improves production efficiency, helps control the molecular weight and distribution of the prepolymer to balance material properties, and reduces side reactions. For example, the polymerization temperature includes, but is not limited to, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, or 180°C, or any two of the above values ​​as endpoints within a range.

[0087] In one example, the polymerization process parameters further include a polymerization time of 60 min to 200 min. For example, the polymerization time includes, but is not limited to, 60 min, 70 min, 80 min, 90 min, 100 min, 120 min, 140 min, 160 min, 180 min, or 200 min, or any two of the above values ​​as endpoints.

[0088] Further, the preparation steps of the prepolymer include: heating the amino-containing fluorenyl compound to a molten state, adding maleimide resin according to the mass ratio, polymerizing at 100℃~180℃ for 60min~200min, and cooling to room temperature to prepare the prepolymer.

[0089] Further, the preparation steps of the prepolymer include: heating the amino-containing fluorenyl compound and the unsaturated phenolic compound to a molten state, adding maleimide resin according to the mass ratio, polymerizing at 100℃~180℃ for 60min~200min, and cooling to room temperature to prepare the prepolymer.

[0090] This application employs a melt method to prepare the prepolymer. This method eliminates the need for additional organic solvents, avoiding the solvent addition and complex subsequent removal processes inherent in solvent-based methods, resulting in a simpler and more efficient operation. Furthermore, since this method does not require solvent recovery, it offers significant process advantages. Additionally, the absence of solvent interference in the melt method allows for better chemical bonding between bismaleimide and amino-containing fluorene compounds, thereby optimizing the prepolymer's chemical structure. This leads to more stable chemical bonds within the resin composition, reducing the likelihood of bond breakage at high temperatures and thus exhibiting superior heat resistance.

[0091] In one example, the imidazole compounds include one or more compounds having the structure shown in formula (IV); In formula (IV), R3 is a C1 to C6 alkyl group.

[0092] In one example, the imidazole compound includes One or more of them.

[0093] In one example, the curing agent includes one or more of cyanate ester resins and benzoxazine resins.

[0094] In one example, the cyanate resin includes one or more of the following: bisphenol A cyanate resin, phenolic cyanate resin, bisphenol F cyanate resin, bisphenol M cyanate resin, bisphenol E cyanate resin, naphthalene cyanate resin, biphenyl cyanate resin, phosphorus-containing cyanate resin, bisphenol S cyanate resin, and dicyclopentadiene bisphenol cyanate resin.

[0095] In one example, the benzoxazine resin includes one or more of the following: allyl benzoxazine resin, bisphenol A benzoxazine resin, bisphenol F benzoxazine resin, main-chain benzoxazine resin, phosphorus-containing benzoxazine resin, bisphenol S benzoxazine resin, dicyclopentadiene benzoxazine resin, biphenyl benzoxazine resin, tetraphenol ethane benzoxazine resin, and naphthyl benzoxazine resin.

[0096] In one example, the epoxy resin includes one or more of the following: naphthalene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol S-type epoxy resin, bisphenol F-type epoxy resin, phosphorus-containing epoxy resin, unsaturated epoxy resin, o-cresol-type epoxy resin, bisphenol A-type phenolic epoxy resin, multifunctional epoxy resin, alicyclic epoxy resin, resorcinol epoxy resin, rubber-modified epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, anthracene-type epoxy resin, and organosilicon-modified epoxy resin.

[0097] Furthermore, the filler is silicon dioxide. Even further, the filler is spherical silicon dioxide.

[0098] When used as a filler, silica facilitates heat dissipation and inhibits thermal expansion in resin compositions, thus ensuring chemical stability. Simultaneously, silica enhances the mechanical properties and thermal stability of the resin composition. Spherical silica exhibits superior flowability and dispersibility, demonstrating good compatibility with resin matrices such as polyphenylene ether resins, prepolymers, and functional resins, effectively preventing resin matrix agglomeration.

[0099] In one example, the filler in the resin composition comprises 30% to 42% by mass. For example, the filler by mass percentage includes, but is not limited to, 30%, 31%, 32%, 32.5%, 33%, 33.5%, 34%, 34.5%, 35%, 35.5%, 36%, 37%, 38%, 39%, 40%, 41%, or 42%, or a range formed by any two of the above points as endpoints.

[0100] In one example, the resin composition also includes functional additives.

[0101] In one example, the resin composition further includes 1 to 5 parts by weight of an additive. For example, the number of parts by weight of the additive includes, but is not limited to, 1, 2, 3, 4, or 5 parts.

[0102] For example, the additives include one or more of dispersants, leveling agents, defoamers, and coupling agents.

[0103] A second aspect of this application provides a prepreg comprising a reinforcing material and a resin layer loaded on the surface of the reinforcing material, the resin layer being formed by drying the resin composition described in any example of the first aspect of this application.

[0104] This application also provides a method for preparing a prepreg, comprising the following steps:

[0105] The components of the resin composition are mixed in a solvent to prepare a coating solution;

[0106] The coating liquid is applied to the surface of the substrate, and a first heat treatment is performed to prepare the semi-cured sheet.

[0107] Understandably, this application does not limit the method of mixing the components in the solvent, as long as the components can be mixed in any way. For example, the components that are soluble in the organic solvent can be added to the organic solvent first and allowed to dissolve completely. Heating can be performed at this time if necessary. Then, the components that are insoluble in the organic solvent, such as flame retardants and inorganic fillers, are added and mixed using a ball mill, bead mill, planetary mixer, roller mill, etc.

[0108] This application does not limit the method by which the coating liquid is loaded onto the substrate. Examples include impregnation, coating, and spraying. Furthermore, as a method for manufacturing prepreg, it includes steps of loading the resin composition onto the substrate followed by drying and heating. Additionally, the impregnation, coating, and spraying steps in this application can be repeated multiple times as needed. Furthermore, various thermosetting resin compositions with different compositions and solid content can be used for repeated impregnation to adjust the final composition and resin content.

[0109] In one example, the process parameters for the first heat treatment include a heating temperature of 100°C to 200°C. For example, the heating temperature includes, but is not limited to, 100°C, 120°C, 150°C, 180°C, or 200°C, or any two of the above values ​​as endpoints.

[0110] In one example, the process parameters for the first heat treatment further include a heating time of 2 min to 20 min. For example, the heating time includes, but is not limited to, 2 min, 5 min, 10 min, 15 min, 18 min, or 20 min, or any two of the above values ​​as endpoints.

[0111] In one example, the substrate comprises one or more of inorganic fiber materials and organic fiber materials. For example, the inorganic fiber material comprises one or more of glass fiber, carbon fiber, silicon carbide fiber, and asbestos fiber. The organic fiber material comprises one or more of nylon, ultra-high molecular weight polyethylene fiber, aramid fiber, polyimide fiber, polyester fiber, and cotton fiber.

[0112] This application also provides the use of a prepreg in the preparation of laminates, copper-clad laminates, or wiring boards.

[0113] This application also provides a laminate comprising the prepreg described in the above embodiments.

[0114] This application also provides a method for preparing a laminate, comprising the following steps:

[0115] One or more prepreg sheets are selected and laminated to prepare the laminate.

[0116] In one example, the lamination process parameters include: a temperature set to 150℃~300℃ and a pressure set to 10kgf / cm². 2 ~40kgf / cm 2 Vacuum degree <2kPa, hot pressing for 200min~400min.

[0117] This application also provides a copper-clad laminate, which includes the prepreg described in the above embodiments and a metal foil covering one or both sides of the laminated prepreg.

[0118] In one example, the thickness of the metal foil is 3 μm to 105 μm.

[0119] A third aspect of this application provides a printed circuit board, the printed circuit board comprising the prepreg described in the second aspect of this application.

[0120] To make the objectives and advantages of this invention clearer, the following detailed description is provided in conjunction with specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and should not be construed as limiting the invention. Unless otherwise specified, the following embodiments do not include components other than unavoidable impurities. Unless otherwise specified, the drugs and instruments used in the embodiments are conventionally chosen in the art. Experimental methods not specifying specific conditions in the embodiments are implemented under conventional conditions, such as those described in literature, books, or methods recommended by the manufacturer.

[0121] The raw materials used in the following embodiments and comparative examples are as follows:

[0122] [Amino-containing fluorene compounds]

[0123] Amino-containing fluorenyl compound A, structure CAS: 15499-84-0; Purchased from: Tianjin Zotye.

[0124] [Maleimide resin]

[0125] Bismaleimide resin, structure Purchased from: Yamato Kasei, model BMI-2300.

[0126] [Unsaturated phenolic compounds]

[0127] Diallyl bisphenol A, purchased from Honghu Shuangma Resin Factory.

[0128] [Epoxy Resin]

[0129] Naphthalene-type epoxy resin, purchased from Nippon Kayaku, model NC-7000H.

[0130] [Curing agent]

[0131] Bisphenol A cyanate, purchased from Lonza Group, model BA-3000S.

[0132] [Functional Resins]

[0133] Polyphenylene ether resin: purchased from SABIC, model SA-9000.

[0134] [filler]

[0135] Spherical silica, purchased from Yaduma, model SO-C4.

[0136] [Imidazole compounds]

[0137] 2-Methylimidazole, purchased from Shikoku Kasei.

[0138] [Additives]

[0139] Dispersant, purchased from BYK Chemicals, model BYK-1650 defoamer.

[0140] Preparation Example 1

[0141] 50 parts of amino-containing fluorenyl compound A were heated to a molten state, and then 100 parts of bismaleimide resin were added. The mixture was reacted and prepolymerized at 150°C for 90 min and then cooled to room temperature to prepare modified maleimide prepolymer A.

[0142] Preparation Example 2

[0143] 75 parts of amino-containing fluorenyl compound A were heated to a molten state, and then 100 parts of bismaleimide resin were added. The mixture was reacted and prepolymerized at 150°C for 120 min and then cooled to room temperature to prepare modified maleimide prepolymer B.

[0144] Preparation Example 3

[0145] 100 parts of amino-containing fluorenyl compound A were heated to a molten state, and then 100 parts of bismaleimide resin were added. The mixture was reacted and prepolymerized at 160°C for 100 min and then cooled to room temperature to prepare modified maleimide prepolymer C.

[0146] Preparation Example 4

[0147] First, 50 parts of amino-containing fluorenyl compound A and 25 parts of allyl bisphenol A were heated to a molten state, and then 100 parts of bismaleimide resin were added. After reacting and prepolymerizing at 160°C for 120 min, the mixture was cooled to room temperature to prepare modified maleimide prepolymer D.

[0148] Preparation Example 5

[0149] 75 parts of allyl bisphenol A were heated to a molten state, and then 100 parts of bismaleimide resin were added. The mixture was prepolymerized at 150°C for 130 min and then cooled to room temperature to prepare modified maleimide prepolymer E.

[0150] The compositions of the resin compositions provided in the examples and comparative examples are shown in Tables 1 and 2 below:

[0151] Table 1

[0152] Table 2

[0153] The preparation process of the resin compositions in the examples and comparative examples is as follows:

[0154] Modified maleimide prepolymer or maleimide resin, along with other resins, are mixed in a solvent comprising butanone, cyclohexanone, and propylene glycol methyl ether in a mass ratio of 3:2:1. Under stirring conditions, fillers, imidazole compounds, and additives are added, and stirring continues to prepare the resin composition.

[0155] The preparation process of the prepreg in the examples and comparative examples is as follows:

[0156] After impregnating the 2116 type glass fiber cloth with the resin composition prepared in the above examples and comparative examples, the mixture was placed in a hot air circulating oven, the temperature was set to 165°C, and heated for 6 minutes to prepare a semi-cured sheet.

[0157] The specific preparation process of the copper-clad laminates in the examples and comparative examples is as follows:

[0158] Eight semi-cured sheets prepared in each of the various embodiments and comparative examples were stacked together, with a 18μm electrolytic copper foil placed on each side. These were then placed in a programmable temperature and pressure controlled vacuum press, where a pressure of 20 kgf / cm² was applied under vacuum. 2 The copper-clad laminate with a thickness of about 0.85 mm was prepared by heating and pressing at 180℃ for 1 hour, and then heating and pressing at 220℃ for 2 hours.

[0159] Performance testing of copper-clad laminates in examples and comparative cases

[0160] 1. Resin composition compatibility: After the resin composition has stood for 24 hours, visually inspect for any layering. If no layering occurs, mark it as "OK"; if layering occurs, mark it as "precipitation".

[0161] 2. Peel strength: Tested using a universal tensile testing machine, according to IPC-TM-650 2.4.8.

[0162] 3. Glass transition temperature (Tg): The glass transition temperature (Tg) was measured using a dynamic mechanical analyzer (DMA) (DMA850 manufactured by TA Instruments); the test specification used was the IPC-TM650 2.4.25D test method.

[0163] 4. Thermal expansion coefficient test and X / Y / Z axis expansion rate: Tested according to IPC-TM650 2.4.24.

[0164] 5. Flame retardant performance measurement: Tested according to IPC-TM650 2.3.10.

[0165] The test results of the copper-clad laminates of the above embodiments and comparative examples are shown in Tables 3 and 4 below:

[0166] Table 3

[0167] Table 4

[0168] As shown in Tables 3 and 4, Comparative Example 1 used only allyl bisphenol A-modified bismaleimide resin, which had a high coefficient of thermal expansion, poor flame retardancy, and poor heat resistance. Comparative Example 2 used unmodified bismaleimide resin, and Comparative Example 3 had a high prepolymer content, both of which led to an increase in the coefficient of thermal expansion and a decrease in heat resistance. Comparative Example 4 was basically the same as Example 1, the main difference being that Comparative Example 4 used only polyphenylene ether resin, which had worse heat resistance and flame retardancy than Example 1. Comparative Example 5 included only epoxy resin and did not include cyanate ester resin, resulting in a high coefficient of thermal expansion and poor heat resistance in Comparative Example 5.

[0169] 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.

[0170] The embodiments described above are merely illustrative of several implementation methods of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of the invention patent. 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 scope of protection of this application. It should be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification can be used to interpret the content of the claims.

Claims

1. A resin composition, characterized in that, Includes the following components: The raw materials for preparing the prepolymer include maleimide resin and amino-containing fluorene compounds; The maleimide resin includes one or more compounds having the structure shown in formula (I); In equation (I), Ar1 and Ar2 are each independent of each other being non-existent. C6-C6 that are unsubstituted or substituted by at least one R′ 20 Aromaticyl group, and at least one of Ar1 and Ar2 is C6-C6 that are unsubstituted or substituted by at least one R′ 20 Aromaticyl group; L1 is absent, -O-, C1-C6 alkylene group, C1-C6 haloalkylene group, C6-C 20 Aromatic groups, *-OL 13 -O-* or *-OL 14 -AL 15 -O-*,L 11 L 12 L 13 L 14 and L 15 Each is independently an unsubstituted or at least substituted C6-C. 20 Aromatic group, A is a C1 to C6 alkylene group; each time R′ appears, it is independently a halogen or a C1 to C3 alkylene group; q is any integer from 1 to 6; The amino-containing fluorenyl compounds include one or more compounds having the structure shown in formula (II); In equation (II), each time Cy appears, it is independently represented by C6 to C6. 20 Aromatic group; each time R1 appears, it is independently H, halogen, amino, C1-C6 alkyl, C1-C6 haloalkyl, or C6-C6. 20 Aromatic group; n is any integer from 0 to 3.

2. The resin composition according to claim 1, characterized in that, The raw materials for preparing the prepolymer also include unsaturated phenolic compounds; the unsaturated phenolic compounds have one or more of the following characteristics: (1) The unsaturated phenolic compounds include one or more compounds having the structure shown in formula (III); In formula (III), X is selected from -CH2-, -C(CH3)2- or S(=O)2, and each time R2 appears, it is independently a C2-C6 alkenyl or C2-C6 alkynyl. (2) The mass ratio of the unsaturated phenolic compound to the maleimide resin is (0.5-1.5):

4.

3. The resin composition according to claim 1 or 2, characterized in that, The maleimide resin includes One or more of the following; each time R′ appears, it is independently a halogen or a C1-C3 alkylene group; m is any integer from 0 to 4.

4. The resin composition according to claim 1 or 2, characterized in that, The amino-containing fluorene compound includes One or more of the following; each time R1 appears, it is independently H, amino or C1 to C3 alkyl; n is any integer from 0 to 3.

5. The resin composition according to claim 1 or 2, characterized in that, The prepolymer has one or more of the following characteristics: (1) The mass ratio of the maleimide resin to the amino-containing fluorenyl compound is (1-4):4; (2) The preparation steps of the prepolymer include: heating the amino-containing fluorenyl compound to a molten state, then adding other preparation raw materials, and carrying out a polymerization reaction at the polymerization temperature to prepare the prepolymer; Optionally, the polymerization temperature is 100℃~180℃.

6. The resin composition according to claim 1 or 2, characterized in that, The imidazole compounds include one or more compounds having the structure shown in formula (IV); In formula (IV), R3 is a C1 to C6 alkyl group.

7. The resin composition according to claim 1 or 2, characterized in that, The resin composition has one or more of the following characteristics: (1) The curing agent includes one or more of cyanate ester resin and benzoxazine resin; (2) The epoxy resin includes one or more of the following: naphthalene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol S-type epoxy resin, bisphenol F-type epoxy resin, phosphorus-containing epoxy resin, unsaturated epoxy resin, o-cresol-formaldehyde epoxy resin, bisphenol A phenolic epoxy resin, multifunctional epoxy resin, alicyclic epoxy resin, resorcinol epoxy resin, rubber-modified epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, anthracene-type epoxy resin, and organosilicon-modified epoxy resin; (3) In the resin composition, the filler has a mass percentage of 30% to 42%.

8. The resin composition according to claim 1 or 2, characterized in that, The resin composition also includes functional additives; Optionally, the functional additive is 1 to 5 parts by weight; the functional additive includes one or more of dispersants, leveling agents, defoamers and coupling agents.

9. A semi-cured sheet, characterized in that, It includes a reinforcing material and a resin layer loaded on the surface of the reinforcing material, the resin layer being formed by drying the resin composition according to any one of claims 1 to 8.

10. A printed circuit board, characterized in that, The printed circuit board includes the prepreg as described in claim 9.

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