Hydrocarbon resin polymers, methods for producing the same, resin compositions, curable composite materials, cured resin bodies, and resin products

Abstract

The present invention provides a hydrocarbon resin polymer having high solubility and / or good processability, and a method for producing the same. [Solution] The hydrocarbon resin polymer comprises a structural unit (A) represented by the following formula (I) or formula (II); a structural unit (B) derived from a monovinyl aromatic compound; and a structural unit (C) derived from a divinyl aromatic compound. TIFF2026143373000049.tif49136 (In equations (I) and (II), R1 is C 1-4 Alkyl or C 1-4 (This is an alkoxy group, where n is an integer selected from 0 to 3, and * represents a linking site to another group or unit.)

Description

Technical Field

[0001] Cross-reference to Related Applications This application claims the benefit of U.S. Provisional Patent Application No. 63 / 763,442, filed on February 26, 2025, which is incorporated herein by reference in its entirety.

[0002] This application claims the priority of Taiwan Patent Application No. 115104802, filed on February 6, 2026, which is incorporated herein by reference in its entirety.

[0003] The present disclosure relates to a resin polymer, a method for producing the same, a resin composition, a curable composite material, a cured resin body, and a resin product comprising the same, and more particularly to a hydrocarbon resin polymer, a method for producing the same, a resin composition, a curable composite material, a cured resin body, and a resin product comprising the same.

Background Art

[0004] Fifth-generation mobile communication technology (fifth-generation wireless communication system or 5G) is the latest generation of mobile communication technology. 5G mobile communication technology has the characteristics of high-speed transmission, wide-area connection, and low latency. There are three types of 5G mobile communication technology according to the frequency bands used: high-frequency 5G, intermediate-frequency 5G, and low-frequency 5G. High-frequency 5G can provide ultra-high connection speeds.

[0005] However, in the transmission process, high-frequency 5G can be affected by signal transmission and reception due to high-frequency path loss, conductor loss, and dielectric loss. Therefore, it is necessary to develop materials for copper-clad laminates (CCL) with low dielectric loss to reduce the dielectric loss of high-frequency 5G during the transmission process, thereby improving the quality of signal transmission and reception.

[0006] To manufacture copper-clad laminates, a resin polymer with high solubility and good processability is required. This ensures that the resin polymer exhibits suitable fluidity and processability during the CCL manufacturing process. This improves process stability and manufacturing yield, and helps to achieve copper-clad laminates with uniform thickness, good interlayer adhesion, and consistent quality. [Overview of the project] [Problems that the invention aims to solve]

[0007] In view of the above issues, this disclosure provides a hydrocarbon resin polymer having high solubility and / or good processability, as well as a method for producing the same. Resin compositions containing the hydrocarbon resin polymer of this disclosure may also have high solubility and / or good processability. Furthermore, in some embodiments, the hydrocarbon resin polymer of this disclosure has good electrical properties. Resin compositions, curable composite materials, cured resin bodies, and resin products containing the hydrocarbon resin polymer of this disclosure may also have good electrical properties. In another embodiment, the hydrocarbon resin polymer of this disclosure has good thermal properties. Resin compositions, curable composite materials, cured resin bodies, and resin products containing the hydrocarbon resin polymer of this disclosure may also have good thermal properties. In yet another embodiment, a resin composition containing the hydrocarbon resin polymer of this disclosure can form a cured resin body with good peel strength, thus increasing the reliability of resin products containing the cured resin body.

[0008] In some embodiments, the present disclosure relates to a structure represented by the following formula (I) or formula (II). The present invention provides a hydrocarbon resin polymer comprising a unit (A), a structural unit (B) derived from a monovinyl aromatic compound, and a structural unit (C) derived from a divinyl aromatic compound.

[0009] [ka]

[0010] In equations (I) and (II), R1 is C1-4 Alkyl or C 1-4 It is an alkoxy group, where n is an integer selected from 0 to 3, and * represents a linking site to another group or unit.

[0011] In some embodiments, the present disclosure provides a method for producing a hydrocarbon resin polymer, comprising a polymerization process to form a hydrocarbon resin polymer from a mixture, wherein the mixture comprises a monovinyl aromatic compound, a divinyl aromatic compound, and a compound represented by the following formula (III).

[0012] [ka]

[0013] In equation (III), R1 is C 1-4 Alkyl or C 1-4 It is an alkoxy group, and n is an integer selected from 0 to 3.

[0014] In some embodiments, the present disclosure provides resin compositions comprising the hydrocarbon resin polymer described above.

[0015] In some embodiments, the present disclosure provides a curable composite material comprising the hydrocarbon resin polymer described above.

[0016] In some embodiments, the present disclosure provides a cured resin body formed from the hydrocarbon resin polymer described above.

[0017] In some embodiments, the present disclosure provides resin products comprising the cured resin body. [Brief explanation of the drawing]

[0018] [Figure 1] This is the 1H-NMR spectrum of a hydrocarbon resin polymer according to an embodiment of the present disclosure. [Figure 2]This is the 13C-NMR spectrum of a hydrocarbon resin polymer according to an embodiment of the present disclosure. [Figure 3] This is the 1H-NMR spectrum of a hydrocarbon resin polymer according to an embodiment of the present disclosure. [Figure 4] This is the 13C-NMR spectrum of a hydrocarbon resin polymer according to an embodiment of the present disclosure. [Figure 5] This is the 1H-NMR spectrum of a hydrocarbon resin polymer according to an embodiment of the present disclosure. [Figure 6] This is the 13C-NMR spectrum of a hydrocarbon resin polymer according to an embodiment of the present disclosure. [Figure 7] This is the 19F-NMR spectrum of a hydrocarbon resin polymer according to an embodiment of the present disclosure. [Modes for carrying out the invention]

[0019] The present invention can be better understood by referring to the attached drawings and reading the following detailed description and examples.

[0020] Where “contains” and / or “includes” are used herein, they specifically refer to the presence of the described features, integers, steps, operations, elements, components, and / or groups thereof, but do not exclude one or more other features, integers, steps, operations, elements, components, and / or their presence or addition. Where the singular “a” and “an” are used herein, they are intended to include the plural unless the context clearly indicates otherwise.

[0021] In this specification, terms such as "first," "second," etc., may be used to describe various steps, elements, components, areas, layers, and / or parts, but it should be understood that these steps, elements, components, areas, layers, and / or parts should not be limited by these terms. These terms are used solely to distinguish one step, element, component, area, layer, or part from another step, element, component, area, layer, or part.

[0022] It should be understood that the terms “about,” “approximately,” and “substantially” as used herein generally refer to a value or range that is within 20%, preferably 10%, more preferably 5%, or 3%, or 2%, or 1%, or 0.5% of a given value or range. The quantities specified herein are approximations, meaning that even without explicit mention of “about,” “approximately,” or “substantially,” the meanings of “about,” “approximately,” or “substantially” are still implicitly included. Furthermore, numerical values ​​expressed in this disclosure may include stated values ​​and deviations within a range acceptable to those skilled in the art. It should be understood that the expressions “a to b” or “a ~ b” used herein to express a particular range of numerical values ​​are defined as “≥ a and ≤ b.”

[0023] Unless otherwise defined, technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art to which this disclosure belongs. These terms, for example, those defined in commonly used dictionaries, should be interpreted in a way that is consistent with the relevant art and the background or context of this disclosure, unless specifically defined in embodiments of this disclosure, and should not be interpreted in an idealized or overly formal manner. Descriptions that could unnecessarily obscure known features and structures of this disclosure are omitted below.

[0024] When used herein, "C1-4 Alkoxy" refers to -O-C 1-4 alkyl or -C 1-4 alkyl-O structure. As used herein, "C 1-4 alkyl" refers to a monovalent group of linear, branched, or cyclic aliphatic hydrocarbon having 1 to 4 carbon atoms on the main carbon chain. C 1-4 Examples of alkyl may include methyl, ethyl, propyl, isobutyl, sec-butyl, and tert-butyl, but the present disclosure is not limited thereto.

[0025] As used herein, "C 1-20 alkyl" refers to a monovalent group of linear, branched, or cyclic aliphatic hydrocarbon having 1 to 20 carbon atoms on the main carbon chain. C 1-20 Examples of alkyl may include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, decyl, dodecyl, cyclohexyl, cyclooctyl, and cyclododecyl, but the present disclosure is not limited thereto.

[0026] As used herein, "C 2-60 alkenyl" refers to a monovalent group of linear, branched, or cyclic aliphatic hydrocarbon having 2 to 60 carbon atoms on the main carbon chain and at least one carbon-carbon double bond. As used herein, "C 2-20 alkenyl" refers to a monovalent group of linear, branched, or cyclic aliphatic hydrocarbon having 2 to 20 carbon atoms on the main carbon chain and at least one carbon-carbon double bond. C 2-60Examples of alkenyls may include, but are not limited to, vinyl, propenyl, isobutenyl, sec-butenyl, tert-butenyl, pentenyl, isopentenyl, hexenyl, decenyl, dodecenyl, pentadecenyl, cyclohexenyl, cyclooctenyl, cyclopentenyl, cyclopentadienyl, cyclopentadecenyl, 1,2-dihydronaphthalene, bicyclodecene, norbornene, and dicyclopentadiene.

[0027] Some embodiments of the present disclosure provide hydrocarbon resin polymers comprising structural units (A) represented by the following formula (I) or formula (II), structural units (B) derived from monovinyl aromatic compounds, and structural units (C) derived from divinyl aromatic compounds.

[0028] [ka]

[0029] In equations (I) and (II), R1 is C 1-4 Alkyl or C 1-4 It is an alkoxy group, where n is an integer selected from 0 to 3, and * represents a linking site to which another group or unit is attached. In some embodiments, R1 in formulas (I) and (II) is selected from the group consisting of methyl, ethyl, isopropyl, tert-butyl, methoxy, and ethoxy. In some embodiments, R1 in formulas (I) and (II) is C 1-4 It is an alkyl group.

[0030] In some embodiments, formulas (I) and (II) are derived from aromatic compounds having a dielectric constant of less than 4. That is, in some embodiments, structural unit (A) may be derived from aromatic compounds having a dielectric constant of less than 4. In such embodiments, the hydrocarbon resin polymers of the Disclosure may have enhanced electrical performance. In some embodiments, formulas (I) and (II) are derived from compounds represented by formula (III), but the Disclosure is not limited thereto.

[0031] [ka]

[0032] In equation (III), R1 is C 1-4 Alkyl or C 1-4 It is an alkoxy group, and n is an integer selected from 0 to 3. In some embodiments, R1 in formula (III) is C 1-4 It is an alkyl group. In some embodiments, the compound represented by formula (III) may be selected from the group consisting of benzene, toluene, xylene, ethylbenzene, methoxybenzene, isopropylbenzene, tert-butylbenzene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, and 1,3,5-trimethylbenzene (mesitylene), but the disclosure is not limited thereto.

[0033] [ka]

[0034] In some embodiments, with the total amount of all units in the hydrocarbon resin polymer being 100 mol%, the content of structural unit (A) is 0.01 to 10 mol%. The content of structural unit (A) described herein is: 1 HNMR and 13This can be calculated by CNMR. Within the above content range, structural unit (A) is derived from aromatic compounds, and the aromatic structure introduced thereby can provide a hydrocarbon resin polymer with good compatibility with commonly used organic solvents, thereby increasing the solubility of the hydrocarbon resin polymer in solvents and improving the fluidity and processability of the resin composition in the manufacturing process. In addition, the aromatic structure introduced by structural unit (A) also helps to adjust the polarity and electronic structure distribution of the hydrocarbon resin polymer, thereby enabling the hydrocarbon resin polymer to exhibit good dielectric properties. When the content of structural unit (A) is within the above range, structural unit (A), together with other structural units (e.g., structural unit (B) and structural unit (C)) in the overall formulation, can contribute to the hydrocarbon resin polymer having excellent electrical properties, thermal properties, solubility, and processability. Furthermore, resin compositions containing it can form cured resin bodies with good peel strength. In some embodiments, with the total amount of all units in the hydrocarbon resin polymer being 100 mol%, the content of structural unit (A) may be 0.05 to 10 mol%, 0.1 to 10 mol%, 0.1 to 6.5 mol%, 0.1 to 5 mol%, 0.8 to 10 mol%, or 0.2 to 3 mol%. Preferably, in some embodiments, with the total amount of all units in the hydrocarbon resin polymer being 100 mol%, the content of structural unit (A) may be <5 mol%, <4 mol%, or <3 mol%, for example, 0.3 mol%, 0.4 mol%, 0.5 mol%, 2 mol%, or 3 mol%. In some embodiments, when the content of structural unit (A) is within the above preferred range, the content of structural unit (A) is not excessively high to affect the contribution of other structural units, so that the hydrocarbon resin polymer can be given, for example, excellent electrical properties, thermal properties, solubility, and / or processability.

[0035] As used herein, a monovinyl aromatic compound refers to a compound comprising a carbocyclic aromatic structure in which one hydrogen atom on the ring-forming carbon atoms of the carbocyclic aromatic structure is substituted with a vinyl group. In some embodiments, the vinyl group may be unsubstituted. In some embodiments, at least one hydrogen atom on the vinyl group is C 1-20 It may be substituted with an alkyl group. In some embodiments, the carbocyclic aromatic structure may contain 6 to 60 or 6 to 20 ring-forming carbon atoms. In some embodiments, at least one other hydrogen on the ring-forming carbon atoms in the carbocyclic aromatic structure is C 1-20 They may be substituted with alkyl groups. Examples of monovinyl aromatic compounds may include, but are not limited to, styrene, methylstyrene, α-methylstyrene, or ethylstyrene.

[0036] [ka]

[0037] In some embodiments, structural unit (B) derived from a monovinyl aromatic compound includes a carbocyclic aromatic structure derived from the monovinyl aromatic compound. For example, in some embodiments, structural unit (B) may have the following structure, but is not limited to this disclosure.

[0038] [ka]

[0039] In the structure above, "*" represents a linking point that connects to another base or unit.

[0040] In some embodiments, with the total amount of all units in the hydrocarbon resin polymer being 100 mol%, the content of structural unit (B) is 15 to 95 mol%. The content of structural unit (B) described herein is 1 HNMR and 13This can be calculated by 14C NMR. Structural unit (B) has a carbocyclic aromatic structure, and the aromatic skeleton introduced thereby can provide a hydrocarbon resin polymer with good compatibility with organic solvents, thereby increasing the solubility of the hydrocarbon resin polymer in solvents and contributing to the dispersibility and processability of the resin composition during the manufacturing process. When the content of structural unit (B) is within the above range, structural unit (B) is composed together with other structural units, thereby enabling the hydrocarbon resin polymer of this disclosure to have good electrical performance, good thermal performance, high solubility, and / or good processability. Furthermore, a resin composition containing this can form a cured resin body with good peel strength. In some embodiments, with the total amount of all units in the hydrocarbon resin polymer being 100 mol%, the content of structural unit (B) may be 16.5 to 94.5 mol%, 30 to 94 mol%, 40 to 93 mol%, or 50 to 90 mol%. In some embodiments, with the total amount of all units in the hydrocarbon resin polymer being 100 mol%, the content of structural unit (B) may be 16 mol%, 17 mol%, 18 mol%, 20 mol%, 80 mol%, 75 mol%, 70 mol%, or 65 mol%.

[0041] As used herein, a divinyl aromatic compound means a compound comprising at least one carbocyclic aromatic structure and having at least two vinyl substituents in all molecules. The vinyl substituents are linked to one or more ring-forming carbon atoms of the carbocyclic aromatic structure. In some embodiments, the vinyl group may be unsubstituted. In some embodiments, at least one hydrogen on the vinyl group is C 1-20 It may be substituted with an alkyl group. In some embodiments, the carbocyclic aromatic structure may contain 6 to 60 or 6 to 20 ring-forming carbon atoms. In some embodiments, at least one other hydrogen on the ring-forming carbon atoms of the carbocyclic aromatic structure is C 1-20The alkyl groups may be substituted. Examples of divinyl aromatic compounds may include, but are not limited to, divinylbenzene (DVB), 1,3-diisopropenylbenzene, 1,2-bis(4-vinylphenyl)ethane (BVPE), and p-isopropenyl-α-methylstyrene (IPAMS).

[0042] [ka]

[0043] In some embodiments, the structural unit (C) derived from the divinyl aromatic compound includes a carbocyclic aromatic structure derived from the divinyl aromatic compound. In some embodiments, the structural unit (C) may include a crosslinkable structural unit (C1) and a crosslinked structural unit (C2).

[0044] [ka]

[0045] R2, R3, R4, and R5 in the crosslinkable structural unit (C1) and the crosslinked structural unit (C2) are each independently H or C 1-20 The alkyl group is such that Ar1 and Ar2 are each divalent groups having a carbocyclic aromatic structure, such as phenylene, biphenylene, or divalent aromatic groups formed by crosslinking an aromatic ring with an alkylene group, and * represents a linkage site of a crosslinkable structural unit (C1) and / or a crosslinked structural unit (C2) linked to another group or unit. In some embodiments, the crosslinkable structural unit (C1) may include, but is not limited to, the following structures.

[0046] [ka]

[0047] In some embodiments, the crosslinked structural unit (C2) may include, but is not limited to, the following structures.

[0048] [ka]

[0049] In some embodiments, with the total amount of all units in the hydrocarbon resin polymer being 100 mol%, the content of structural unit (C) is 1 to 80 mol%. The content of structural unit (C) described herein is: 1 HNMR and 13 This can be calculated by 14C NMR. When the content of structural units (C) is within the above range, a hydrocarbon resin polymer with a desired degree of crosslinking is provided. In this configuration, the crosslinked structure formed by structural units (C) promotes improvements in the thermal performance, thermal stability, and electrical performance of the hydrocarbon resin polymer while maintaining the solubility and processability of the resin required in the manufacturing process. Furthermore, a resin composition containing this can form a cured resin body with excellent peel strength. In some embodiments, with the total amount of all units in the hydrocarbon resin polymer being 100 mol%, the content of structural units (C) may be 3 to 70 mol%, 5 to 60 mol%, or 10 to 50 mol%. In some embodiments, with the total amount of all units in the hydrocarbon resin polymer being 100 mol%, the content of structural units (C) may be 1.5 mol%, 2 mol%, 4 mol%, 8 mol%, 12 mol%, 15 mol%, 18 mol%, 20 mol%, 25 mol%, 35 mol%, or 45 mol%.

[0050] In some embodiments, with the total amount of all units in the hydrocarbon polymer being 100 mol%, the hydrocarbon polymer may contain 1 to 30 mol% of crosslinkable structural units (C1). When the content of crosslinkable structural units (C1) in the hydrocarbon polymer is within the above range, the hydrocarbon polymer may have good thermal performance, electrical performance, and / or processability. In some embodiments, with the total amount of all units in the hydrocarbon polymer being 100 mol%, the hydrocarbon polymer may contain 3 to 28 mol%, 5 to 25 mol%, or 6 to 22 mol% of crosslinkable structural units (C1). In some embodiments, with the total amount of all units in the hydrocarbon polymer being 100 mol%, the content of crosslinkable structural units (C1) may be 1.5 mol%, 2 mol%, 2.5 mol%, 4 mol%, 7 mol%, 8 mol%, 10 mol%, 15 mol%, 18 mol%, 26 mol%, or 29 mol%.

[0051] In some embodiments, the hydrocarbon resin polymer of the present disclosure may further include structural unit (D), which is a first structural unit (D1) and / or a second structural unit (D2). The first structural unit (D1) is derived from a cyclic olefin compound or a non-alkenyl-substituted aromatic compound. The second structural unit (D2) is derived from a linear olefin compound or a branched olefin compound.

[0052] As used herein, a non-alkenyl-substituted aromatic compound means a compound containing a carbocyclic aromatic structure. As used herein, a non-alkenyl-substituted aromatic compound means an aromatic compound whose substituent is not an alkenyl group. A non-alkenyl-substituted aromatic compound may be a substituted or unsubstituted aromatic compound, provided that its substituent is not an alkenyl group. In some embodiments, a non-alkenyl-substituted aromatic compound may be a polycyclic aromatic compound, such as a carbocyclic aromatic compound containing two or more fused aromatic rings. In some embodiments, a non-alkenyl-substituted aromatic compound has at least one hydrogen atom on the ring-forming carbon atoms of the carbocyclic aromatic structure that is C 1-20 The aromatic compounds may be alkyl-substituted. In some embodiments, the carbocyclic aromatic structure may contain 6 to 60 or 6 to 20 ring-forming carbon atoms. Examples of non-alkenyl-substituted aromatic compounds may include, but are not limited to, indene, methylindene, naphthalene, or methylnaphthalene.

[0053] Cyclic olefin compounds are C 3-60 It may be an alkenyl compound. A cyclic olefin compound is a hydrocarbon compound in which carbon atoms are linked to each other to form a closed non-aromatic carbocyclic structure, and the non-aromatic carbocyclic structure contains at least one carbon-carbon double bond (C=C). In some embodiments, the non-aromatic carbocyclic structure may include a polycyclic structure or a bridged ring structure. In some embodiments, at least one other hydrogen on the ring-forming carbon atoms of the carbocyclic structure is C 1-20 Alkyl or C 2-20 They may be substituted with alkenyls. Examples of cyclic olefin compounds may include, but are not limited to, cyclopentene, cyclohexene, dicyclopentadiene, norbornene, ethylidene norbornene (ENB), vinyl norbornene, or norbornadiene.

[0054] In some embodiments, the first structural unit (D1) may have the following structure, but the disclosure is not limited thereto.

[0055] [ka]

[0056] In the structure described above, * represents a linkage site connected to another group or unit. Compared to the second structural unit (D2), the first structural unit (D1) is more rigid, which can increase the glass transition temperature of the hydrocarbon polymer or improve the thermal performance of the hydrocarbon polymer.

[0057] Linear olefin compounds are C 2-60 It may be an alkenyl compound. A linear olefin compound is a hydrocarbon compound having a carbon back chain that is not connected end-to-end and is arranged linearly (without branching), and the carbon back chain contains at least one carbon-carbon double bond. In some embodiments, at least one other hydrogen on the carbon back chain of the linear olefin compound is C 1-20 Alkyl or C 2-20 They may be substituted with alkenyls. Examples of linear olefin compounds may include, but are not limited to, ethylene, propylene, 1-butene, and butadiene.

[0058] Branched olefin compounds C 2-60 It may be an alkenyl compound. A branched olefin compound is a hydrocarbon compound that comprises a linearly arranged carbon back chain and one or more side chain carbon chains, and which contains a carbon-carbon double bond, with the carbon atoms not connected at their ends. In some embodiments, at least one other hydrogen on the carbon back chain and / or side chain carbon chain of the branched olefin compound is C 1-20 Alkyl or C 2-20They may be substituted with alkenyls. Examples of branched olefin compounds may include, but are not limited to, isobutylene, isoprene, and 2-methylhexene.

[0059] In some embodiments, with the total amount of all units in the hydrocarbon resin polymer being 100 mol%, the content of structural unit (D) may be 0.1 to 80 mol%. The content of structural unit (D) described herein is 1 HNMR and 13 This can be calculated by 14C NMR. As mentioned above, structural unit (D) may include structural unit (D1) and structural unit (D2). Structural unit (D1) is derived from a more rigid cyclic olefin compound or a non-alkenyl-substituted aromatic compound, and since it can introduce a relatively rigid molecular structure, it helps to improve the glass transition temperature and overall thermal performance of the hydrocarbon resin polymer. On the other hand, structural unit (D2) is derived from a linear olefin compound or a branched olefin compound, and the aliphatic structure introduced thereby makes it easier to adjust the electrical performance of the hydrocarbon resin polymer. When the content of structural unit (D) is within the above range, structural unit (D1) and structural unit (D2) can be present in the hydrocarbon resin polymer in an appropriate ratio, which can result in a hydrocarbon resin polymer with better thermal performance, glass transition temperature, and electrical performance, and lower manufacturing costs. Furthermore, resin compositions containing this can form cured resin bodies with good peel strength. In some embodiments, with the total amount of all units in the hydrocarbon resin polymer being 100 mol%, the content of structural unit (D), first structural unit (D1), and / or second structural unit (D2) may be 0.15 to 50 mol%, 0.5 to 30 mol%, or 1 to 15 mol%. In some embodiments, with the total amount of all units in the hydrocarbon resin polymer being 100 mol%, the content of structural unit (D), first structural unit (D1), and / or second structural unit (D2) may be 2 mol%, 3 mol%, 4 mol%, 5 mol%, 6 mol%, 7 mol%, 8 mol%, 60 mol%, 75 mol%, 78 mol%, or 79 mol%.

[0060] In some embodiments, when structural units (C) and (D) are contained in a suitable content within the hydrocarbon polymer, better thermal performance and / or thermal stability of the hydrocarbon polymer may be provided. In some embodiments, with the total amount of all units in the hydrocarbon polymer being 100 mol%, the total content of structural units (C) and (D) in the hydrocarbon polymer may be 5 mol% or more. In some embodiments, with the total amount of all units in the hydrocarbon polymer being 100 mol%, the total content of structural units (C) and (D) in the hydrocarbon polymer may be 10 mol% or more, 13 mol% or more, 20 mol% or more, or 30 mol% or more. In some embodiments, with the total amount of all units in the hydrocarbon polymer being 100 mol%, the total content of structural units (C) and (D) in the hydrocarbon polymer may be 85 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol%, or 50 mol%.

[0061] In some embodiments, the hydrocarbon resin polymer may contain reactive double bonds. As used herein, “reactive double bond” means a double bond in a structural unit (C) or structural unit (D) that can react with another compound or polymer. For example, in some embodiments, the reactive double bond includes, but is not limited to, a double bond in the following first structural unit (D1) or a double bond in the following crosslinkable structural unit (C1).

[0062] [ka]

[0063] In some embodiments, the hydrogen atom content in the reactive double bonds of the hydrocarbon resin polymer may be less than 10%. In some embodiments, the hydrogen atom content in the reactive double bonds of the hydrocarbon resin polymer may be greater than 0.2%. When the hydrogen atom content in the reactive double bonds of the hydrocarbon resin polymer is less than 10%, the hydrocarbon resin polymer is less susceptible to oxidation during the thermosetting process, or the crosslinking reaction is more easily completed before oxidation, thus maintaining the good electrical properties of the hydrocarbon resin polymer. When the hydrogen atom content in the reactive double bonds of the hydrocarbon resin polymer is greater than 0.2%, the resin composition containing it can form a cured resin body with good peel strength. In some embodiments, the hydrogen atom content in the reactive double bonds of the hydrocarbon resin polymer may be 0.2% to 10%, 0.3% to 9%, 0.5% to 8%, 1% to 7%, or 3% to 7%. In some embodiments, the hydrogen atom content in the reactive double bond of the hydrocarbon resin polymer may be 2.0%, 2.5%, 3.0%, 3.5%, 8.5%, 9.0%, or 9.5%.

[0064] In some embodiments, the number-average molecular weight (Mn) of the hydrocarbon resin polymer may be 200 to 25,000 g / mol. Having the number-average molecular weight of the hydrocarbon resin polymer within the above range can result in good solubility of the hydrocarbon resin polymer. In some embodiments, the number-average molecular weight (Mn) of the hydrocarbon resin polymer may be 300 to 140,000 g / mol, 500 to 130,000 g / mol, 700 to 120,000 g / mol, or 900 to 110,000 g / mol. In some embodiments, the number-average molecular weight (Mn) of the hydrocarbon resin polymer may be 2,000 g / mol, 2,500 g / mol, 3,000 g / mol, 3,500 g / mol, 4,000 g / mol, 16,000 g / mol, 17,000 g / mol, 18,000 g / mol, or 20,000 g / mol.

[0065] In some embodiments, the weight-average molecular weight (Mw) of the hydrocarbon polymer may be 10,000 to 150,000 g / mol. When the weight-average molecular weight of the hydrocarbon polymer falls within the above range, the hydrocarbon polymer may exhibit good solubility, better processability, and / or good film-forming properties. In some embodiments, the weight-average molecular weight (Mw) of the hydrocarbon polymer may be 20,000 to 140,000 g / mol, 30,000 to 130,000 g / mol, 40,000 to 120,000 g / mol, or 50,000 to 110,000 g / mol. In some embodiments, the weight-average molecular weight (Mw) of the hydrocarbon polymer may be 25,000 g / mol, 35,000 g / mol, 145,000 g / mol, or 135,000 g / mol.

[0066] In some embodiments, the polymer dispersion index (PDI) of the hydrocarbon resin polymer may be from 1 to 50. The PDI is the ratio (Mw / Mn) of the weight-average molecular weight (Mw) of the hydrocarbon resin polymer to the number-average molecular weight (Mn). In some embodiments, the PDI of the hydrocarbon resin polymer may be 1, 3, 5, 11, 13, 15, 17, 21, 25, or 27.

[0067] In some embodiments, the hydrocarbon resin polymer may have molecular weight distribution characteristics within a specific range. To illustrate the degree of molecular weight distribution, the parameter Fp is defined here as an auxiliary indicator. Fp is calculated by the following formula, and the PDI is as described above.

[0068]

number

[0069] In some embodiments, the Fp of the hydrocarbon polymer may be 0.02 to 1.0. When the Fp of the hydrocarbon polymer is within the above range, the hydrocarbon polymer may have good solubility and / or better processability. In some embodiments, the Fp of the hydrocarbon polymer may be less than 1.5. In some embodiments, the Fp of the hydrocarbon polymer may be 0.1 to 1.0, 0.5 to 1.0, or 0.8 to 1.0. In some embodiments, the Fp of the hydrocarbon polymer may be 0.05, 0.06, 0.07, 0.08, or 0.15.

[0070] To characterize the structural configuration state related to stiffness and thermal properties, the parameter Rh is further defined here as an index indicating the configuration state of structural units related to stiffness and thermal performance in hydrocarbon resin polymers. Rh is calculated by the following formula.

[0071]

number

[0072] In the formula, H, C1, and D1 are numerical values ​​expressed as H%, C1%, and D1%, respectively, and the percentage values ​​are used directly in the calculation without being converted to decimals. The Rh obtained after substituting these proportional values ​​into the above formula is a calculated index value used to reflect the relative differences between different structural configurations. Of these, H% is the hydrogen atom content in the reactive double bond of the hydrocarbon resin polymer, C1% is the content of crosslinkable structural units (C1) when the total amount of all units in the hydrocarbon resin polymer is set to 100 mol%, and D1% is the content of the first structural unit (D1) when the total amount of all units in the hydrocarbon resin polymer is set to 100 mol%.

[0073] For example, when the hydrogen atom content (H%) in the reactive double bonds of a hydrocarbon resin polymer is 3.24%, the content of crosslinkable structural units (C1%) is 11 mol%, and the content of first structural units (D1%) is 4 mol%. In this embodiment, after substituting the numerical values ​​3.24, 11, and 4 corresponding to H, C1, and D1, respectively, into the above equation, an Rh value of approximately 4.42 can be obtained.

[0074] In some embodiments, the Rh of the hydrocarbon polymer may be 0.5 to 15. When the Rh of the hydrocarbon polymer is within the above range, the hydrocarbon polymer may have good thermal performance and / or thermal stability. In some embodiments, the Rh of the hydrocarbon polymer may be greater than 3. In some embodiments, the Rh of the hydrocarbon polymer may be 1 to 15, 2 to 12, or 3 to 10. In some embodiments, the Rh of the hydrocarbon polymer may be 4, 5, 6, 7, or 8.

[0075] To characterize the structural configuration state related to electrical performance, the parameter Ed is further defined here as an index indicating the configuration state of structural units related to electrical performance in hydrocarbon resin polymers. Ed is calculated by the following formula, where Fp is as described above.

[0076]

number

[0077] In the formula, Ms is calculated by the following formula.

[0078]

number

[0079] In the formula, A, B, and D2 are numerical values ​​expressed as A%, B%, and D2%, respectively, and the percentage values ​​are used directly in the calculation without being converted to decimals. The Ms and Ed obtained after substituting these proportional values ​​into the above formula are calculated index values ​​used to reflect the relative differences between different structural configurations. A% represents the content of structural unit (A) when the total amount of all units in the hydrocarbon resin polymer is set to 100 mol%; B% represents the content of structural unit (B) when the total amount of all units in the hydrocarbon resin polymer is set to 100 mol%; and D2% represents the content of the second structural unit (D2) when the total amount of all units in the hydrocarbon resin polymer is set to 100 mol%.

[0080] For example, when the Fp of a hydrocarbon resin polymer is 0.1984, the content of structural unit (A) (A%) is 1 mol%, the content of structural unit (B) (B%) is 77 mol%, and the content of the second structural unit (D2) (D2%) is 0 mol%. In this embodiment, A, B, and D2 are expressed in the form of percentages, using the corresponding numerical values ​​1, 77, and 0, respectively. Substituting these into the above formula for calculating Ms, Ms can be obtained as (1 + 77 + 3 × 0) / 1,000 = 0.078. Furthermore, by substituting Fp and Ms into the above formula for calculating Ed, the value of Ed can be obtained as approximately 0.1864.

[0081] In some embodiments, the Ed of the hydrocarbon polymer may be 0.02 to 0.3. When the Ed of the hydrocarbon polymer is within the above range, the hydrocarbon polymer can have good electrical performance. In some embodiments, the Ed of the hydrocarbon polymer may be 0.025 to 0.25, 0.03 to 0.2, or 0.04 to 0.16. In some embodiments, the Ed of the hydrocarbon polymer may be 0.07, 0.08, 0.1, or 0.15.

[0082] To characterize the structural configuration state related to peel strength performance, the parameter PL is further defined here as an index indicating the configuration state of the structural parameter related to peel strength performance in the hydrocarbon resin polymer. PL is calculated by the following formula, where Mn is the number-average molecular weight of the hydrocarbon resin polymer, and PDI and H are as described above.

[0083]

number

[0084] Mn, PDI, and H are used as input parameters for the calculation. H is a numerical value expressed as H%, and the percentage value is used directly in the calculation without being converted to a decimal. The PL obtained by substituting these parameters into the above formula is a calculated index value that reflects the relative differences between different structural configuration states.

[0085] For example, in one embodiment, the number-average molecular weight (Mn) of the hydrocarbon resin polymer is 7,787 g / mol, the dispersion index (PDI) is 5.04, and the hydrogen atom content (H%) in reactive double-bonded water is 3.24%. In this embodiment, after substituting Mn as the numerical value 7,787, PDI as the numerical value 5.04, and H as the numerical value 3.24 corresponding to its percentage form into the PL calculation formula, the PL value obtained is 7,787 × 5.04 × 3.24 / 100 = 1,271.59.

[0086] In some embodiments, the PL of the hydrocarbon resin polymer may be 200 to 10,000. Having the PL of the hydrocarbon resin polymer within the above range can promote improved peel strength performance of the cured resin body formed from the hydrocarbon resin polymer. In some embodiments, the PL of the hydrocarbon resin polymer may be 300 to 8,000, 400 to 7,000, or 500 to 6,000. In some embodiments, the PL of the hydrocarbon resin polymer may be 400, 500, 600, 1,000, 2,000, 3,000, or 4,000.

[0087] To simultaneously maintain a balance of various properties of hydrocarbon resin polymers, including rigidity, thermal performance, electrical performance, processability, and peel strength, this disclosure further characterizes the relative constituent relationships between these properties by utilizing ratios of various parameters. These ratios can be used to reflect whether these properties are maintained in a reasonable balance under various structural designs, thus helping to avoid situations where excessive improvement in one property leads to deterioration of others.

[0088] In some embodiments, the ratio of Rh, an index relating to the stiffness and thermal performance of a hydrocarbon resin polymer, to Fp, an index relating to the molecular weight distribution (Rh / Fp), may be from 5 to 250, preferably from 10 to 200. When Rh / Fp is within the above range, the hydrocarbon resin polymer can maintain good solubility and processability while retaining a certain degree of stiffness and thermal performance. In some embodiments, Rh / Fp may be 20, 30, 40, 50, 60, 90, 120, or 150.

[0089] In some embodiments, the ratio of the index Rh for stiffness and thermal performance in a hydrocarbon polymer to the index Ed for electrical performance (Rh / Ed) may be between 5 and 250, preferably between 10 and 200. When Rh / Ed is within the above range, the hydrocarbon polymer can maintain good dielectric properties while also meeting the requirements for both thermal performance and stiffness. In some embodiments, Rh / Ed may be 20, 30, 40, 50, 60, 90, 120, or 150.

[0090] In some embodiments, the ratio of PL, an index for peel strength in a hydrocarbon resin polymer, to Rh, an index for stiffness and thermal performance (PL / Rh), may be between 80 and 1,750, preferably between 290 and 1,300. When PL / Rh is within the above range, the cured resin body formed from the hydrocarbon resin polymer can maintain the required structural stiffness and thermal stability while having good peel strength. In some embodiments, PL / Rh may be between 200, 300, 400, 500, 600, 700, 900, or 1,000.

[0091] In some embodiments, the ratio of the peel strength index PL to the electrical performance index Ed (PL / Ed) in a hydrocarbon resin polymer may be 700 to 250,000, preferably 6,000 to 140,000. When PL / Ed is within the above range, the cured resin formed from the hydrocarbon resin polymer can simultaneously exhibit good peel strength and electrical performance. In some embodiments, PL / Ed may be 7,000, 10,000, 15,000, 20,000, 30,000, 40,000, 50,000, 60,000, or 70,000.

[0092] In some embodiments, the hydrocarbon resin polymer may satisfy at least one of (I) to (IV) below, where Rh, Fp, Ed, and PL are as described above. (I) Rh / Fp = 5 to 250, (II) Rh / Ed = 5 to 250, (III) PL / Rh = 80 to 1,750, and (IV) PL / Ed = 700 to 250,000

[0093] If a hydrocarbon polymer satisfies any of (I) through (IV), it can achieve an excellent balance between forming a cured resin body with electrical properties (dielectric properties), thermal properties, processability, and / or good peel strength, thereby meeting the stringent requirements of applications such as high-speed and high-frequency circuit boards, copper-clad laminates (CCLs), and resin-coated copper (RCCs).

[0094] In summary, the hydrocarbon polymers according to this disclosure may possess good electrical properties, good thermal properties, high solubility, and / or good processability. In some embodiments, the hydrocarbon polymers according to this disclosure may further form cured resin bodies having good peel strength. In some embodiments, the hydrocarbon polymers according to this disclosure may achieve an excellent balance between electrical properties (dielectric properties), thermal properties, processability, and / or the formation of cured resin bodies having good peel strength.

[0095] This disclosure also provides a method for producing hydrocarbon resin polymers. The hydrocarbon resin polymer produced by the method for producing hydrocarbon resin polymers of this disclosure may be the above-mentioned hydrocarbon resin polymer, and therefore its details will not be repeated here.

[0096] The present disclosure provides a method for producing a hydrocarbon resin polymer, comprising a polymerization process to form a hydrocarbon resin polymer from a mixture, wherein the mixture comprises a monovinyl aromatic compound, a divinyl aromatic compound, and a compound represented by the following formula (III).

[0097] [ka]

[0098] In equation (III), R1 is C 1-4 Alkyl or C 1-4 It is an alkoxy group, and n is an integer selected from 0 to 3.

[0099] In some embodiments, examples of monovinyl aromatic compounds may include, but are not limited to, styrene, methylstyrene, α-methylstyrene, or ethylstyrene.

[0100] In some embodiments, examples of divinyl aromatic compounds may include, but are not limited to, divinylbenzene, 1,3-diisopropenylbenzene, 1,2-bis(4-vinylphenyl)ethane, or p-isopropenyl-α-methylstyrene.

[0101] In some embodiments, R1 in formula (III) is C 1-4 Alkyl or C 1-4 It is an alkoxy group, and n is an integer selected from 0 to 3. In some embodiments, R1 in formula (III) is C 1-4 It is an alkyl group. In some embodiments, the compound represented by formula (III) may be selected from the group consisting of benzene, toluene, xylene, ethylbenzene, anisole, isopropylbenzene, tert-butylbenzene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, and 1,3,5-trimethylbenzene, but the disclosure is not limited thereto.

[0102] In some embodiments, the content of the monovinyl aromatic compound may be 5 to 80 mol%, with the total amount of all components in the mixture being 100 mol%. In some embodiments, the content of the monovinyl aromatic compound may be 12 to 70 mol%, 10 to 60 mol%, or 15 to 55 mol%, with the total amount of all components in the mixture being 100 mol%. In some embodiments, the content of the divinyl aromatic compound may be 1 to 20 mol%, with the total amount of all components in the mixture being 100 mol%. In some embodiments, the content of the divinyl aromatic compound may be 5 to 15 mol%, 4 to 12 mol%, or 3 to 10 mol%, with the total amount of all components in the mixture being 100 mol%. In some embodiments, the content of the compound represented by formula (III) may be 20 to 80 mol%, with the total amount of all components in the mixture being 100 mol%. In some embodiments, the content of the compound represented by formula (III) may be 25 to 77 mol%, 30 to 75 mol%, or 35 to 73 mol%, with the total amount of all components in the mixture being 100 mol%.

[0103] In some embodiments, the mixture may further comprise cyclic olefin compounds, linear olefin compounds, branched olefin compounds, and / or non-alkenyl-substituted aromatic compounds. Examples of cyclic olefin compounds may include, but are not limited to, cyclopentene, cyclohexene, dicyclopentadiene, norbornene, ethylidene norbornene, vinyl norbornene, or norbornadiene. Examples of linear olefin compounds may include, but are not limited to, ethylene, propylene, 1-butene, 1-hexene, and butadiene. Examples of branched olefin compounds may include, but are not limited to, isobutylene, isoprene, and 2-methylhexene. Examples of non-alkenyl-substituted aromatic compounds may include, but are not limited to, indene, methylindene, naphthalene, or methylnaphthalene.

[0104] In some embodiments, with the total amount of all components in the mixture being 100 mol%, the total content of cyclic olefin compounds, linear olefin compounds, branched olefin compounds, and / or non-alkenyl-substituted aromatic compounds may be 0 to 20 mol%. In some embodiments, with the total amount of all components in the mixture being 100 mol%, the total content of cyclic olefin compounds, linear olefin compounds, branched olefin compounds, and / or non-alkenyl-substituted aromatic compounds may be 1 to 17 mol%, 3 to 15 mol%, or 5 to 12 mol%.

[0105] In some embodiments, the polymerization process may include adding a catalyst to the mixture. The catalyst may include titanium tetrachloride and / or boron trifluoride complexes. Examples of boron trifluoride complexes may include, but are not limited to, boron trifluoride tetrahydrofuran complex (BF3-THF), boron trifluoride methanol complex (BF3-MeOH), boron trifluoride hydrate (BF3-H2O), boron trifluoride diethyl ether complex (BF3-OEt2), boron trifluoride anisole complex (BF3-PhOMe), boron trifluoride acetate complex (BF3-AcOH), or any combination thereof. In some embodiments, the molar ratio of catalyst to mixture may be from 0.1 to 7:100. In some embodiments, the molar ratio of catalyst to mixture may be 0.2 to 6:100, 0.3 to 5:100, or 0.4 to 4.5:100, but the disclosure is not limited thereto.

[0106] In some embodiments, the reaction temperature, reaction time, and raw material-to-catalyst ratio of the polymerization process may affect the distribution of various structural units (e.g., structural unit (A), structural unit (B), structural unit (C), structural unit (D), etc.) in the formed hydrocarbon resin polymer. In some embodiments, the polymerization process may include reaction temperatures from 0 to 100°C. In some embodiments, the polymerization process may include reaction temperatures from 0 to 80°C, 0 to 60°C, 0 to 40°C, or 0 to 20°C. In some embodiments, higher reaction temperatures promote the formation of structural unit (A). Conversely, excessively low reaction temperatures may result in less formation of structural unit (A) or make it difficult for structural unit (A) to form. In some embodiments, the polymerization process may include reaction temperatures from 60 to 80°C, 40 to 60°C, or 30 to 40°C. In some embodiments, the polymerization process may include reaction times from 0.5 to 10 hours. In some embodiments, the polymerization process may include reaction times of 0.8 to 10 hours, 1 to 7 hours, or 1 to 5 hours. In some embodiments, longer reaction times promote the formation of structural units (A). Conversely, relatively short reaction times may result in less formation of structural units (A) or make it difficult for structural units (A) to form. In some embodiments, higher amounts of catalyst added promote the formation of structural units (A). Conversely, relatively low amounts of catalyst added may result in less formation of structural units (A) or make it difficult for structural units (A) to form.

[0107] The specific structure of the hydrocarbon polymer obtained by the method for producing the hydrocarbon polymer of this disclosure is as described above and will not be repeated here. The hydrocarbon polymer obtained by the method for producing the hydrocarbon polymer of this disclosure may have good electrical properties, good thermal properties, high solubility, and / or good processability. In some embodiments, the hydrocarbon polymer obtained by the method for producing the hydrocarbon polymer of this disclosure can further form a cured resin body having good peel strength. In some embodiments, the hydrocarbon polymer obtained by the method for producing the hydrocarbon polymer of this disclosure can achieve an excellent balance between properties such as electrical properties (dielectric properties), thermal properties, processability, and the formation of a cured resin body with good peel strength.

[0108] Some embodiments of the present disclosure provide resin compositions comprising the hydrocarbon resin polymer described above. In some embodiments, the resin composition is in the form of a varnish and is suitable for electronic materials applications, such as in impregnation or coating processes of fibrous substrates.

[0109] In some embodiments, the resin composition may further contain a solvent. The solvent may be an aromatic solvent, an aliphatic solvent, an alicyclic solvent, a halogenated hydrocarbon solvent, an ether solvent, an ester solvent, a ketone solvent, or a mixture thereof. Examples of solvents, but not limited to, may include toluene, xylene, mesitylene, ethylbenzene, isopropylbenzene, trifluoromethylbenzene, fluorobenzene, chlorobenzene, bromobenzene, iodobenzene, dichloroethane, chloroform, cyclohexane, methylcyclohexane, n-hexane, heptane, p-menthane, tetrahydrofuran, ethyl acetate, anisole, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate (PGMEA), or any combination thereof. In some embodiments, with 100 parts by weight of the hydrocarbon resin polymer in the resin composition, the resin composition of the present disclosure may contain 5 to 350 parts by weight of an organic solvent. In some embodiments, the resin composition of the present disclosure may further optionally contain a photoinitiator, a reaction inhibitor, a crosslinking agent, a leveling agent, or a combination thereof.

[0110] Resin compositions comprising the hydrocarbon resin polymer of this disclosure may have good solubility, improved processability, good film-forming properties, good electrical and thermal properties, and / or may form cured resin bodies having good peel strength.

[0111] Some embodiments of the present disclosure provide a curable composite material comprising the hydrocarbon resin polymer described above. In some embodiments, the curable composite material may comprise a fibrous substrate and a hydrocarbon resin polymer formed on the fibrous substrate. In some embodiments, the curable composite material may be in the form of a prepreg.

[0112] In some embodiments, a method for producing a curable composite material may include the steps of: preparing a resin composition comprising a hydrocarbon resin polymer of the present disclosure; impregnating a fibrous substrate with the resin composition to form a curable material; and heating the curable material under required heating conditions (e.g., heating at about 100°C to about 180°C for about 1 to about 15 minutes) to partially cure the resin composition on the fibrous substrate and obtain a partially cured curable composite material.

[0113] Examples of fibrous substrates may include, but are not limited to, glass fiber cloth, aramid cloth, polyester cloth, glass fiber nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, pulp paper, printer paper, other suitable materials, or any combination thereof. In some embodiments, the fibrous substrate may be a glass fiber cloth having a dielectric loss tangent (Df) of 0.0030 or less, which is measured at a frequency of approximately 28 GHz (Df@28 GHz).

[0114] In some embodiments, the curable composite material of the present disclosure may have a dielectric loss tangent (Df@28GHz) of less than 0.01. In some embodiments, the curable composite material of the present disclosure may have a dielectric loss tangent (Df@28GHz) of 0.00250 or less, 0.00220 or less, 0.00200 or less, 0.00180 or less, or 0.00170 or less.

[0115] Some embodiments of the present disclosure provide cured resin bodies formed from the hydrocarbon resin polymer described above. In some embodiments, the cured resin body is a copper-clad laminate (CCL) which can be formed from the curable composite material by a hot pressing process.

[0116] Specifically, in some embodiments, the cured resin body is manufactured by laminating the above-mentioned curable composite material (i.e., a semi-cured sheet) with copper foil, and then heating it to 210°C by a hot press process to produce a cured resin body.

[0117] Some embodiments of this disclosure provide another cured resin body and a resin product comprising the cured resin body. In some embodiments, the resin product is resin-coated copper foil (RCC).

[0118] In some embodiments, the resin product may include a base film and a cured resin body formed on the base film. In some embodiments, the resin product may include one or more base films and a cured resin body formed on at least one surface of at least one base film. In some embodiments, the resin product can be obtained by applying the resin composition onto at least one base film to form a curable resin layer, and curing the resin composition under necessary heating conditions to form a cured resin body.

[0119] In some embodiments, the resin product (e.g., resin-coated metal foil) may be further laminated with one or more material layers, thereby forming another resin product by a hot-pressing process. In some embodiments, the base film may include metal foil. In some embodiments, the metal foil may include copper foil.

[0120] There are no specific limitations on the method of applying the resin composition to at least one surface of a metal foil. Specifically, the application method includes introducing the resin composition into an application apparatus and applying the resin composition to at least one surface of the metal foil to a desired thickness. Examples of application apparatus include, but are not limited to, comma coaters, knife coaters, lip coaters, roll coaters, extrusion coaters, reverse coaters, transfer roll coaters, gravure coaters, spray coaters, and the like.

[0121] The hot pressing conditions in the hot pressing process can be appropriately set based on the thickness of the metal foil laminate being manufactured and the type of resin composition used in the prepreg or resin-coated copper foil. For example, the hot pressing conditions can be set to a temperature of 180 to 210°C, a pressure of 1.0 to 3.0 MPa, and a time of 60 to 180 minutes.

[0122] Curable composite materials, cured resin bodies, and / or resin products containing hydrocarbon resin polymers of this disclosure may have good electrical and / or thermal properties. Furthermore, layers or films containing hydrocarbon polymers in curable composite materials, cured resin bodies, and / or resin products have good peel strength, thus increasing the reliability of curable composite materials, cured resin bodies, and / or resin products.

[0123] One or more embodiments of the present disclosure will be described in detail with reference to the following examples. However, these examples are used solely to illustrate embodiments of the present disclosure and are not intended to limit the scope of embodiments of the present disclosure.

[0124] [Preparation of hydrocarbon resin polymers 1 to 20]

[0125] Polymerization process

[0126] The raw materials listed in Table 1 (Table 1-1, Table 1-2) were added under nitrogen to a 1 L four-neck straight-jacketed reactor equipped with a single-stage four-blade flat-paddle. The raw materials were then stirred using the four-blade flat-paddle at a stirring speed of 400 rpm to form a mixture. At the temperature shown in Table 1, the amount of catalyst shown in Table 1 was added to the mixture at a rate of 0.25 mL / min using a syringe pump. After the addition of the catalyst was complete, the reaction was allowed to proceed for the reaction time shown in Table 1, and then the reaction was stopped by adding isopropanol to obtain the polymer mother liquor. The polymer mother liquor ultimately became colorless.

[0127] Purification process

[0128] First, the polymer mother liquor was filtered to remove impurities and insoluble matter. The polymer mother liquor was washed using a mechanical stirrer at a rotation speed of 500 rpm. Under mechanical stirring at 500 rpm, the polymer mother liquor was slowly added dropwise to 5 times its weight of isopropanol using a dropping funnel to obtain a white crude resin product. Solid-liquid separation was performed using a suction filter to obtain a white solid. This white solid was redissolved in tetrahydrofuran to create a new mother liquor, and precipitation was performed again with isopropanol (the weight ratio of mother liquor to isopropanol was 1:5). After filtration, a white resin solid of higher purity was obtained. Finally, the solid was washed with methanol to remove impurities and residual isopropanol, and the solvent was removed by heating with stirring under vacuum, thereby obtaining the white powdered hydrocarbon resin polymers 1 to 20 of the present disclosure.

[0129] Table 1 below shows the raw materials, reaction temperatures, reaction times, and amounts of catalyst used to form hydrocarbon polymers 1 to 20 of this disclosure. Except for the catalyst used for hydrocarbon polymer 16, which is titanium tetrachloride, the catalysts used for hydrocarbon polymers 1 to 15 and 17 to 20 are all boron trifluoride complexes. The mol% of each raw material listed in Table 1 refers to the content of each component when the total amount of all components (excluding catalysts) in the mixture is set to 100 mol%. The mol% of the catalyst listed in Table 1 refers to the amount of catalyst relative to the mixture when the total amount of the mixture is set to 100 mol%. The xylene mixture listed in Table 1 refers to a mixture containing 40 to 65 wt.% m-xylene, 15 to 20 wt.% o-xylene, less than 20 wt.% p-xylene, and 15 to 20 wt.% ethylbenzene.

[0130] [Table 1-1] [Table 1-2]

[0131] [Measurement of the dielectric constant of compounds represented by formula (III)]

[0132] The measurement equipment included a high-precision LCR meter, a cell for measuring the dielectric constant of liquid, a constant-temperature water bath (set to 25°C), and a syringe for injecting the sample.

[0133] A parallel plate capacitor can be used to measure the dielectric constant (ε) of the compound represented by equation (III). The capacitance (C) when filled with liquid was compared with the capacitance (C0) when filled with air or in a vacuum, where ε = C / C0. Specifically, C0 was obtained by first measuring the capacitance with air (ε ≈ 1) and calibrating the capacitor. Subsequently, a high-purity liquid sample (e.g., HPLC grade) was injected into a liquid dielectric constant measurement cell, ensuring that no air bubbles were present. While maintaining a constant temperature, the capacitance C was measured within a frequency range from 1 kHz to 1 MHz, and the dielectric constant ε was calculated based on this. To improve the accuracy of the measurement, the measurement was repeated multiple times and the average value was taken. The dielectric constant measurement results of the compound represented by equation (III) used to manufacture hydrocarbon resin polymers 1 to 20, and their comparative compounds, are shown in Table 2 below.

[0134] [Table 2]

[0135] [Measurement of physical / chemical properties of hydrocarbon resin polymers 1 to 20]

[0136] [Measurement of hydrogen atom content in reactive double bonds]

[0137] Hydrocarbon resin polymers 1 to 20 were each dissolved in deuterated chloroform (CDCl3). The hydrogen atom content in the double bonds and reactive double bonds of hydrocarbon resin polymers 1 to 20 was measured using NMR (JEOL, JNM-ECZ400S / L1). Specifically, the hydrogen atom content in the reactive double bonds was calculated by dividing the sum of the integral values ​​of hydrogen in the reactive double bonds by the sum of the integral values ​​of all hydrogen, thereby obtaining the hydrogen atom content in the reactive double bonds of hydrocarbon resin polymers 1 to 20.

[0138] [Measurement of number-average molecular weight (Mn) and polymer dispersion index (PDI)]

[0139] Polystyrene was used as a standard. The number-average molecular weight (Mn) and polymer dispersion index (PDI) of hydrocarbon resin polymers 1 to 20 were measured by gel permeation chromatography (GPC) (Waters APC; column: Waters Acquity XT 900).

[0140] Specifically, 5 mL of tetrahydrofuran (THF) was added to 0.01 g each of hydrocarbon polymers 1 to 20 to prepare hydrocarbon polymer samples 1 to 20. After filtering the hydrocarbon polymer samples 1 to 20 through a 0.22 μm filter, instrumental analysis was performed to obtain the number-average molecular weight (Mn) and polymer dispersion index (PDI) of hydrocarbon polymers 1 to 20. PDI is the ratio (Mw / Mn) of the weight-average molecular weight (Mw) of the hydrocarbon polymer to the number-average molecular weight (Mn). The weight-average molecular weight (Mw) can be calculated from the PDI and number-average molecular weight (Mn). The measurement results for the dispersion index (PDI), number-average molecular weight (Mn), and hydrogen atom content in the reactive double bond of hydrocarbon polymers 1 to 20 are shown in Table 3-1 below.

[0141] [Table 3-1]

[0142] [Structural Analysis of Hydrocarbon Polymers 1 to 20]

[0143] 0.05 g each of hydrocarbon resin polymers 1 to 20 was weighed out, and 1.0 g of deuterated chloroform (CDCl3) was added to prepare samples 1 to 20. Subsequently, using a nuclear magnetic resonance spectrometer (NMR; JEOL, JNM-ECZ400S), samples 1 to 10 and 12 to 20 were analyzed at 25°C. 13 C-NMR and 1 H-NMR, and of sample 11 19 F-NMR was measured. 13 C-NMR, 1 H-NMR, and 19 The structural compositions of hydrocarbon polymers 1 to 20 were determined based on 1F-NMR. The results indicate that hydrocarbon polymers 1 to 20 contain structural units derived from compounds represented by formula (III) (A), structural units derived from monovinyl aromatic compounds (B), structural units derived from divinyl aromatic compounds (C), and structural units derived from cyclic olefin compounds, linear olefin compounds, branched olefin compounds, and / or non-alkenyl-substituted aromatic compounds (D).

[0144] The following explains how to calculate the content of structural units (A) through (D), using structural unit (A) of hydrocarbon resin polymer 2 as an example. Figure 1 shows the hydrocarbon resin polymer 2 1 This is the 1H-NMR spectrum. Figure 2 shows the hydrocarbon resin polymer 2. 13This is a 1C-NMR spectrum. The method for calculating the content of structural units (A) to (D) in the following hydrocarbon resin polymer 2 is explained by using structural units derived from ethylstyrene (EVB) as an example to illustrate the calculation of structural units derived from toluene. This is only one specific embodiment of the quantitative process used in this disclosure and is used to illustrate one viable quantitative analytical method. It is not intended that the technical solution of this application must include ethylstyrene as the monomer source, nor is it intended that subsequent calculations or analyses of units derived from toluene and other structural units must use structural units derived from ethylstyrene (EVB) as the sole criterion. The quantitative concepts and methods disclosed herein are not limited to specific monomers or specific structural units.

[0145] In fact, a person skilled in the art would determine the corresponding based on the type of monomer actually used (e.g., vinyl aromatic compounds, divinyl aromatic compounds, or combinations thereof). 1 H-NMR or 13 By selecting characteristic chemical shift peaks in 1C-NMR and performing integral analysis, the relative or absolute content of each structural unit can be quantified.

[0146] For example, if structural units derived from different sources in a hydrocarbon resin polymer are defined as unit A, unit B, unit C, and unit D, a person skilled in the art can perform signal integration based on the position of the characteristic peak corresponding to each structural unit in the NMR spectrum to calculate the content of each unit (e.g., a, b, c, and d), and if necessary, normalize the obtained values ​​so that the total amount of structural units is 100 mol%.

[0147] First, Figure 1 ( 1Using 1H-NMR spectra, the relative ratios of structural units derived from dicyclopentadiene, styrene, ethylstyrene, and divinylbenzene in the entire hydrocarbon resin polymer 2 were calculated. Subsequently, Figure 2( 13 Using 1C-NMR, the signals at 15.0 to 16.5 ppm (representing structural units derived from ethylstyrene) and 19.6 to 20.4 ppm (representing structural units derived from toluene) were integrated. The ratio of these two integral values ​​was used to obtain the relative ratio of structural units derived from ethylstyrene and structural units derived from toluene in hydrocarbon resin polymer 2. Furthermore, based on the above relative ratio relationship, the content of all structural units was normalized so that the total content was 100 mol%, thereby obtaining the content of each structural unit.

[0148] Specifically, Figure 1 of hydrocarbon resin polymer 2 ( 1 Based on calculations using 1H-NMR spectroscopy, if the total content of structural units derived from dicyclopentadiene, styrene, ethylstyrene, and divinylbenzene in the hydrocarbon resin is set to 100 mol%, then the content of structural units derived from ethylstyrene was 11 mol%. Next, Figure 2( 13 According to 13C-NMR, the ratio of structural units derived from toluene to those derived from ethylstyrene was 10.11:89.89. Therefore, after normalizing the content of all structural units, the content of units derived from toluene was calculated to be 1.24 mol% (11 mol% × 10.11 ÷ 89.89).

[0149] The following explains how to calculate the content of structural units (A) through (D), using structural unit (A) of hydrocarbon resin polymer 7 as an example. Figure 3 shows the hydrocarbon resin polymer 7. 1 Figure 4 shows the H-NMR spectrum of hydrocarbon resin polymer 7. 13 This is a 1C-NMR spectrum.

[0150] First, Figure 3 ( 1 Using 1H-NMR spectra, the relative ratios of structural units derived from dicyclopentadiene, styrene, ethylstyrene, and divinylbenzene in the entire hydrocarbon resin polymer 7 were calculated. Subsequently, Figure 4( 13 Using 13C-NMR, the signals at 15.0 to 16.5 ppm (representing structural units derived from ethylstyrene) and 19.1 to 20.1 ppm and 20.6 to 21.6 ppm (representing structural units derived from xylene) were integrated. Using the ratio of these integrals, the relative ratio of structural units derived from ethylstyrene and structural units derived from xylene in the hydrocarbon resin polymer 7 was obtained. Specifically, Figure 3( 1 Based on calculations using 1H-NMR spectra, if the total content of structural units derived from dicyclopentadiene, styrene, ethylstyrene, and divinylbenzene is assumed to be 100 mol%, then the content of structural units derived from ethylstyrene was 14 mol%. Next, Figure 4( 13 According to 13C-NMR, the ratio of structural units derived from xylene to structural units derived from ethylstyrene was (23.66 + 31.91):44.43. Therefore, after normalizing the content of all structural units, the content of structural units derived from xylene was calculated to be 8.7% (14% × 55.57 ÷ (44.43 × 2)).

[0151] The following explains how to calculate the content of structural units (A) through (D) of hydrocarbon resin polymer 10, using structural unit (A) as an example. Figure 5 shows the hydrocarbon resin polymer 10. 1 Figure 6 shows the H-NMR spectrum of hydrocarbon resin polymer 10. 13 This is a 1C-NMR spectrum.

[0152] First, Figure 5 ( 1Using 1H-NMR spectra, the relative ratios of structural units derived from dicyclopentadiene, styrene, ethylstyrene, and divinylbenzene in the entire hydrocarbon resin polymer 10 were calculated. Subsequently, Figure 6( 13 Using 13C-NMR, integration was performed on the signals at 15.0 to 16.5 ppm (representing structural units derived from ethylstyrene) and 20.0 to 21.7 ppm (representing structural units derived from mesitylene). The ratio of these two integral values ​​was used to obtain the relative ratio of structural units derived from ethylstyrene and structural units derived from mesitylene in the hydrocarbon resin polymer 10. Furthermore, based on the above relative ratio relationship, the content of all structural units was normalized so that the total content was 100 mol%, thereby obtaining the content of each structural unit.

[0153] Specifically, Figure 5 shows the hydrocarbon resin polymer 10. 1 Based on calculations using 1H-NMR spectra, if the total content of structural units derived from dicyclopentadiene, styrene, ethylstyrene, and divinylbenzene is assumed to be 100 mol%, then the content of structural units derived from ethylstyrene was 11 mol%. Next, Figure 6( 13 According to 13C-NMR, the ratio of structural units derived from mesitylene to those derived from ethylstyrene was 21.26:78.74. Therefore, after normalizing the content of all structural units, the content of structural units derived from mesitylene was calculated to be 0.99 mol% (11 mol% × 21.26 ÷ (78.74 × 3)).

[0154] Figure 7 shows the hydrocarbon resin polymer 11. 19 This is the F-NMR spectrum. As can be seen from Figure 7, the content of structural unit (A) in the hydrocarbon resin polymer 11 is 0 mol%.

[0155] The following describes how to calculate the content of structural units (A) through (D), using hydrocarbon resin polymer 12 as an example of structural unit (A). Structural unit (A) of hydrocarbon resin polymer 12 is derived from anisole. In this disclosure, the content of structural unit (A) derived from anisole was quantified using GC-FID (gas chromatography-flame ionization detector).

[0156] Specifically, the raw material mixture used in the polymerization process to form the hydrocarbon resin polymer 12 was first diluted 10-fold with isopropanol (IPA) and filtered to create a "pre-reaction raw material sample." Next, this "pre-reaction raw material sample" was analyzed under the following GC conditions to determine the ratio of each component. GC conditions: Injection volume: 1 μL; Split ratio: 10:1; Injector temperature: 210°C; Column oven heating conditions: Hold at 40°C for 1 minute, heat up to 200°C at 10°C / min and hold for 1 minute, then heat up to 250°C at 20°C / min and hold for 1 minute; Column: DB-ALC2, 30m × 530 μm × 2.0 μm; Detector: FID; Detector temperature: 250°C. As described above, after the reaction of the raw material mixture in the polymerization process, a polymer mother liquor was formed. The polymer mother liquor contained the hydrocarbon resin polymer 12 and residual raw materials. Next, the polymer mother liquor was taken, diluted 10-fold with isopropanol (IPA), and filtered to form a "post-reaction residual raw material sample." This sample was then analyzed under the same GC conditions to determine the proportion of each component. The conversion rate of each component in the hydrocarbon resin polymer 12 was calculated using the proportions of each component in the "pre-reaction raw material sample" and the "post-reaction residual raw material sample" used to form the hydrocarbon resin polymer 12 of this disclosure. The results are shown in the table below. For example, the anisole content in the pre-reaction raw material sample was 37.89583075 wt%, and in the post-reaction residual raw material sample it was 6.399680 wt%. Therefore, the conversion rate was 83.11% ((37.896 wt% - 6.400 wt%) / 37.896 wt% * 100%).

[0157] [Table 3-2]

[0158] Based on the conversion rates listed in the table above and the amounts of each raw material for hydrocarbon resin polymer 12 in Table 1-1, it was possible to calculate that hydrocarbon resin polymer 12 contains 40.33 mol% structural units derived from anisole, 41.43 mol% structural units derived from styrene, 10.39 mol% structural units derived from dicyclopentadiene, 4.91 mol% structural units derived from divinylbenzene, and 2.94 mol% structural units derived from ethylstyrene.

[0159] [Measurement of crosslinkable structural unit content (C1)]

[0160] By analyzing the structures of hydrocarbon resin polymers 1 to 20 using NMR (JEOL, JNM-ECZ400S / L1) and GPC (Waters), the content of crosslinkable structural units (C1) in hydrocarbon resin polymers 1 to 20 was measured using CDCl3 as the solvent and the CDCl3 resonance line as the internal standard.

[0161] The content of structural units (A), structural units (B), structural units (C), structural units (D), crosslinkable structural units (C1), crosslinked structural units (C2), first structural unit (D1), second structural unit (D2), and the total content of structural units (C) and structural units (D) in hydrocarbon resin polymers 1 to 20 are shown in Tables 4 to 6 below.

[0162] [Table 4]

[0163] [Table 5]

[0164] [Table 6]

[0165] Tables 3-1 to 6 and the following formula were used to calculate Fp, Rh, Ed, PL, Rh / Fp, Rh / Ed, PL / Rh, and PL / Ed for hydrocarbon resin polymers 1 to 20. The calculation results are shown in Tables 7 to 10 below.

[0166]

number

[0167] [Table 7]

[0168] [Table 8]

[0169] [Table 9]

[0170] [Table 10]

[0171] [Solubility Test of Hydrocarbon Polymers 1 to 20]

[0172] Hydrocarbon resin polymers 1 to 20 were dissolved in toluene or methyl ethyl ketone (MEK), respectively, to form solutions with a viscosity of less than 1,000 cP. The maximum content of the hydrocarbon resin polymer that formed a solution with a viscosity of less than 1,000 cP was measured. When the hydrocarbon resin polymer content in the solution was greater than 65 wt%, the hydrocarbon resin polymer showed excellent solubility; when the hydrocarbon resin polymer content in the solution was between 45 and 65 wt%, the hydrocarbon resin polymer showed good solubility; and when the hydrocarbon resin polymer content in the solution was less than 45 wt%, the hydrocarbon resin polymer showed poor solubility. The results of the solubility tests for hydrocarbon resin polymers 1 to 20 are shown in Table 11 below.

[0173] [Table 11]

[0174] [Electrical performance testing of hydrocarbon polymers 1 to 20]

[0175] Mixtures were prepared by dissolving 15 g each of hydrocarbon resin polymers 1 to 20 in 15 g of toluene. These mixtures were stirred until the hydrocarbon resin polymers were completely dissolved to form resin compositions 1 to 20, and their clarity was observed. Glass fiber cloth (Asahi 2116, Dk / Df at 28 GHz = 3.3 / 0.0030) was immersed in each of resin compositions 1 to 20 for approximately 16 hours to form curable composite materials 1 to 20. These curable composite materials 1 to 20 were baked at 170°C for 10 minutes to form cured resin bodies 1 to 20. The dielectric constant / loss coefficient (Dk / Df) and RC% of cured resin bodies 1 to 20 at 28 GHz were measured using network analyzer software (Network analyzer Keysight P5007A, SCR). The measurement results are shown in Table 12 below.

[0176]

number

[0177] [Table 12]

[0178] Resin solutions 1 to 20 were prepared by mixing 100 parts by weight each of hydrocarbon resin polymers 1 to 20 with 100 parts by weight of toluene, 15 parts by weight of a reinforcing agent, 9 parts by weight of DVB, 0.27 parts by weight of a peroxide, and 30 parts by weight of a filler, and polishing with zirconia beads until the filler was uniformly dispersed. Ricon 100 was used as the reinforcing agent. The filler could be SVC purchased from Admatch or SS-10 purchased from Tokuyama. The peroxide could be perbutyl P purchased from NOF CORPORATION.

[0179] Glass fiber cloth (Asahi 2116, Dk / Df at 28 GHz = 3.3 / 0.0030) was impregnated with resin solutions 1 to 20, respectively, and then baked at 160°C for 7 minutes to obtain prepregs 1 to 20. Two prepregs were laminated with copper foil (RTF, Hoz (18 μm), Rz: 3.5 μm), silane adhesive (KBM503) was applied between the copper foil and the prepreg, and then pressed at 210°C for 3 hours to obtain substrate samples 1 to 20. The following property measurements were performed on substrate samples 1 to 20.

[0180] [Measurement of glass transition temperature (Tg)]

[0181] Substrate samples 1 to 20 were heated from 25°C to 270°C at a rate of 3°C / min. The glass transition temperature (Tg) of cured resin bodies 1 to 20 was measured by dynamic mechanical analysis (DMA, TA / Q800). The test frequency was 1 Hz. The glass transition temperature (Tg) of cured resin bodies 1 to 20 was obtained from the tan delta peak in the DMA plot. The measurement results are shown in Table 13 below.

[0182] [Measurement of the Percent of Thermal Expansion (PTE)]

[0183] Using a thermomechanical analyzer (Model: Q400, Manufacturer: TA), substrate samples 1 through 20 were analyzed according to the following steps.

[0184] Cycles 1 through 4 were performed sequentially, with Cycle 3 serving as the baseline. Dimensions were recorded at different temperatures (50°C and 260°C), and the percentage of dimensional change was calculated. Cycle 1: Under an N2 atmosphere, equilibrium was reached at 25°C and held for 1 minute, then heated from 25°C to 270°C at 20°C / min. Cycle 2: Cooled from 270°C to 25°C at 20°C / min and held for 1 minute, then equilibrium at 25°C. Cycle 3: Heated from 25°C to 270°C at 10°C / min. Cycle 4: Cooled from 270°C to 25°C at 20°C / min. The measurement results are shown in Table 13 below.

[0185] [Table 13]

[0186] [Measurement of electrical performance]

[0187] Using network analyzer software (Network Analyzer Keysight P5007A, SCR), the dielectric constant / loss coefficient (Dk / Df) and RC% of substrate samples 1 to 20 were measured at 28 GHz. The measurement results are shown in Table 14 below.

[0188] [Measurement of resin flow]

[0189] After forming substrate samples 1 to 20, the resin flow length was measured by measuring the edges of the resin layers on substrate samples 1 to 20 using a length measuring tool (e.g., a ruler). Specifically, the sample substrates contained a copper foil layer and a resin layer containing resin solutions 1 to 20, with some of the resin solutions 1 to 20 overflowing during the heat-press curing stage (i.e., protruding from the glass fiber cloth). The resin flow length was defined as the average length of the resin solutions 1 to 20 that protruded from the edges of the glass fiber cloth. A resin flow length of 0.5 cm or less was evaluated as excellent, a resin flow length longer than 0.5 cm but 2.0 cm or less was evaluated as good, and a resin flow length longer than 2.0 cm was evaluated as poor. The measurement results are shown in Table 14 below.

[0190] [Table 14]

[0191] [Peel Strength Test]

[0192] The peel strength of substrate samples 1 through 20, each measuring 12.7 mm x 20 mm, was measured using a SHIMADZU AG-Xplus at a peeling speed of 50.8 mm / min. The measurement results are shown in Table 15 below.

[0193] [Table 15]

[0194] As can be seen from Tables 2, 11, and 14, hydrocarbon polymers have better solubility and resin flow performance when they contain structural units derived from aromatic compounds with a dielectric constant of less than 4. In other words, hydrocarbon polymers have better processability when they contain structural units derived from aromatic compounds with a dielectric constant of less than 4.

[0195] As can be seen from Tables 3-1 to 3-6 and Table 11, hydrocarbon polymers with lower weight-average molecular weights (e.g., <10,000 g / mol) (hydrocarbon polymer 12) exhibit excellent solubility, hydrocarbon polymers with the next lowest weight-average molecular weights (e.g., 10,000 to 100,000 g / mol) have good solubility, and hydrocarbon polymers with higher weight-average molecular weights (e.g., >100,000 g / mol) have poor solubility. As can be seen from Tables 7 to 3-10 and Table 14, in terms of film formation properties, hydrocarbon polymers with weight-average molecular weights within a certain range (e.g., >10,000 g / mol) may exhibit better resin flow performance.

[0196] As can be seen from Tables 7 to 11, hydrocarbon resin polymers with higher Fp values ​​have excellent or good solubility, while hydrocarbon resin polymers with lower Fp values ​​have poor solubility.

[0197] As can be seen from Tables 7 to 10 and Table 13, hydrocarbon polymers with higher Rh exhibit better thermal performance and / or thermal stability (e.g., Tg and coefficient of thermal expansion). Hydrocarbon polymers with lower Rh exhibit inferior thermal performance and / or thermal stability (e.g., Tg and coefficient of thermal expansion).

[0198] As can be seen from Tables 7 to 10 and Table 14, hydrocarbon polymers with Ed within a specific range (e.g., 0.02 to 0.3) exhibit better electrical performance (Df@28GHz). On the other hand, hydrocarbon polymers with Ed outside this range exhibit inferior electrical performance.

[0199] As can be seen from Tables 7 to 10 and Table 15, hydrocarbon polymers with a PL (Particle Level) within a specific range (e.g., 200 to 10,000) exhibit better peel strength. On the other hand, hydrocarbon polymers with a PL outside this range exhibit inferior peel strength.

[0200] It is clear that, in addition to good electrical and thermal performance, the hydrocarbon resin polymers of this disclosure may also possess good processability. Resin compositions comprising the hydrocarbon resin polymers of this disclosure can form cured resin bodies having good peel strength. Resin products comprising such cured resin bodies may possess good electrical and thermal performance and / or reliability.

[0201] The above description outlines some features of embodiments so that those skilled in the art may better understand aspects of the disclosure. Those skilled in the art will understand that the disclosure can be readily used as a basis for designing or modifying other processes and structures to achieve the same objectives and / or advantages as the embodiments introduced herein. Those skilled in the art will also understand that such equivalent configurations will not deviate from the spirit and scope of the disclosure, and that various changes, substitutions, and modifications can be made herein without departing from the spirit and scope of the disclosure.

Claims

1. A structural unit (A) represented by the following formula (I) or formula (II), Structural units (B) derived from monovinyl aromatic compounds, Structural units (C) derived from divinyl aromatic compounds, A hydrocarbon resin polymer containing [a specific component]. 【Chemistry 1-1】 (In equations (I) and (II), R1 is C 1-4 Alkyl or C 1-4 (This is an alkoxy group, where n is an integer selected from 0 to 3, and * represents a linking site to another group or unit.)

2. The hydrocarbon resin polymer according to claim 1, wherein the content of the structural unit (A) is 0.01 to 10 mol%, with the total amount of all units in the hydrocarbon resin polymer being 100 mol%.

3. The hydrocarbon resin polymer according to claim 2, wherein the content of the structural unit (A) is 0.1 to 5 mol%.

4. The hydrocarbon resin polymer according to claim 1, wherein formulas (I) and (II) are derived from aromatic compounds having a dielectric constant of less than 4.

5. In equations (I) and (II), R1 is C 1-4 A hydrocarbon resin polymer according to claim 1, wherein the alkyl group is an alkyl group.

6. The hydrocarbon resin polymer according to claim 1, wherein the content of structural unit (B) is 15 to 95 mol%, with the total amount of all units in the hydrocarbon resin polymer being 100 mol%.

7. The hydrocarbon resin polymer according to claim 1, wherein the content of the structural unit (C) is 1 to 80 mol%, with the total amount of all units in the hydrocarbon resin polymer being 100 mol%.

8. The aforementioned hydrocarbon resin polymer It further includes a structural unit (D) which is a first structural unit (D1) or a second structural unit (D2), The first structural unit (D1) is derived from a cyclic olefin compound or a non-alkenyl-substituted aromatic compound. The second structural unit (D2) is derived from a linear olefin compound or a branched olefin compound, The aforementioned non-alkenyl-substituted aromatic compound refers to an aromatic compound having a substituent other than an alkenyl group. The hydrocarbon resin polymer according to claim 1.

9. The hydrocarbon resin polymer according to claim 8, comprising the second structural unit (D2).

10. The hydrocarbon resin polymer according to claim 8, wherein the content of the second structural unit (D2) is 0.1 to 80 mol%, with the total amount of all units in the hydrocarbon resin polymer being 100 mol%.

11. The hydrocarbon resin polymer according to claim 8, wherein the content of the structural unit (D) is 0.1 to 80 mol%, with the total amount of all units in the hydrocarbon resin polymer being 100 mol%.

12. The hydrocarbon resin polymer according to claim 8, wherein the total amount of all units in the hydrocarbon resin polymer is 100 mol%, and the total content of structural unit (C) and structural unit (D) is 5 mol% or more.

13. The structural unit (C) includes a crosslinkable structural unit (C1) and a crosslinked structural unit (C2), 【number】 (In the formula, R2, R3, R4, and R5 are each independently hydrogen or C) 1-20 These are alkyl groups, where Ar1 and Ar2 are phenylene groups, and * represents a linking site to another group or unit. Assuming the total amount of all units in the hydrocarbon resin polymer is 100 mol%, the Rh of the hydrocarbon resin polymer is 0.5 to 15. However, Rh is calculated using the following formula: [Math 1-1] In the formula, H, C1, and D1 are numerical values ​​expressed as H%, C1%, and D1%, respectively, and the percentage values ​​are used directly in the calculation without being converted to decimals. H% is the hydrogen atom content in the reactive double bond of the hydrocarbon resin polymer. C1% is the content of the crosslinkable structural unit (C1) when the total amount of all units in the hydrocarbon resin polymer is set to 100 mol%, D1% is the content of the first structural unit (D1) when the total amount of all units in the hydrocarbon resin polymer is set to 100 mol%. The hydrocarbon resin polymer according to claim 8.

14. The hydrocarbon resin polymer according to claim 13, wherein the Rh of the hydrocarbon resin polymer is 3 to 10.

15. The hydrocarbon resin polymers are as follows (I) to (IV): (I) Rh / Fp is between 5 and 250. (II) Rh / Ed is between 5 and 250, (III) PL / Rh is between 80 and 1,750, (IV) PL / Ed is between 700 and 250,000 Satisfying at least one of the following conditions, However, Rh = 0.9 * H + 0.1 * (C1 + D1), Fp = 1 / PDI, Ed=0.9*Fp+0.1*Ms, PL=Mn*PDI*H / 100, Ms=(A+B+3*D2) / 1000, And, Mn is the number-average molecular weight (Mn) of the hydrocarbon resin polymer. PDI is the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn), A, B, H, C1, D1, and D2 are numerical values ​​expressed as A%, B%, H%, C1%, D1%, and D2%, respectively, and are used directly in calculations without converting the percentage values ​​to decimals. H% is the hydrogen atom content in the reactive double bond of the hydrocarbon resin polymer. C1% is the content of the crosslinkable structural unit (C1) when the total amount of all units in the hydrocarbon resin polymer is set to 100 mol%, D1% is the content of the first structural unit (D1) when the total amount of all units in the hydrocarbon resin polymer is set to 100 mol%, A% is the content of the structural unit (A) when the total amount of all units in the hydrocarbon resin polymer is taken as 100 mol%, B% is the content of the structural unit (B) when the total amount of all units in the hydrocarbon resin polymer is set to 100 mol%, D2% is the content of the second structural unit (D2) when the total amount of all units in the hydrocarbon resin polymer is set to 100 mol%. The hydrocarbon resin polymer according to claim 13.

16. The hydrocarbon resin polymer according to claim 15, wherein the Rh / Ed of the hydrocarbon resin polymer is 10 to 200.

17. The hydrocarbon resin polymer according to claim 15, wherein the PL / Rh of the hydrocarbon resin polymer is 290 to 1,300.

18. The hydrocarbon resin polymer according to claim 15, wherein the PL / Ed of the hydrocarbon resin polymer is 6,000 to 140,000.

19. The hydrocarbon resin polymer according to claim 15, wherein the Rh / Fp of the hydrocarbon resin polymer is 10 to 200.

20. The Ed of the hydrocarbon resin polymer is 0.02 to 0.

3. However, Ed is calculated using the following formula: [Math 2-1] In the formula, Fp is calculated by the following formula: [Math 3-1] Ms is calculated using the following formula: [Math 4-1] PDI is the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn). A, B, and D2 are numerical values ​​expressed as A%, B%, and D2%, respectively, and are used directly in calculations without converting the percentage values ​​to decimals. A% is the content of the structural unit (A) when the total amount of all units in the hydrocarbon resin polymer is taken as 100 mol%, B% is the content of the structural unit (B) when the total amount of all units in the hydrocarbon resin polymer is set to 100 mol%, D2% is the content of the second structural unit (D2) when the total amount of all units in the hydrocarbon resin polymer is set to 100 mol%. The hydrocarbon resin polymer according to claim 8.

21. The hydrocarbon resin polymer according to claim 20, wherein the Ed of the hydrocarbon resin polymer is 0.03 to 0.

2.

22. The structural unit (C) includes a crosslinkable structural unit (C1) and a crosslinked structural unit (C2), 【Chemistry 3-1】 (In the formula, R2, R3, R4, and R5 are each independently hydrogen or C 1-20 (These are alkyl groups, where Ar1 and Ar2 are phenylene groups, and * represents a linking site to another group or unit.) The hydrocarbon resin polymer according to claim 1, wherein the total amount of all units in the hydrocarbon resin polymer is 100 mol%, and the content of the crosslinkable structural unit (C1) is 1 to 30 mol%.

23. The hydrocarbon resin polymer according to claim 1, wherein the hydrogen atom content in the reactive double bond of the hydrocarbon resin polymer is less than 10%.

24. The hydrocarbon resin polymer according to claim 23, wherein the hydrogen atom content in the reactive double bond of the hydrocarbon resin polymer is 3% to 7%.

25. The hydrocarbon resin polymer according to claim 1, wherein the weight-average molecular weight (Mw) of the hydrocarbon resin polymer is 10,000 to 150,000 g / mol.

26. The Fp of the hydrocarbon resin polymer is 0.02 to 1.

0. However, Fp is calculated using the following formula: [Math 5-1] In the formula, PDI is the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) of the hydrocarbon resin polymer. The hydrocarbon resin polymer according to claim 1.

27. The hydrocarbon resin polymer according to claim 26, wherein the Fp of the hydrocarbon resin polymer is 0.1 to 1.

0.

28. The PL of the hydrocarbon resin polymer is 200 to 10,000. However, PL is calculated using the following formula: [Math 6-1] In the formula, Mn is the number-average molecular weight (Mn) of the hydrocarbon resin polymer. PDI is the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn), H is a numerical value expressed as H%, and the percentage value is used directly in calculations without being converted to a decimal. H% is the content of the hydrogen atoms in the reactive double bond of the hydrocarbon resin polymer. The hydrocarbon resin polymer according to claim 1.

29. The hydrocarbon resin polymer according to claim 28, wherein the PL of the hydrocarbon resin polymer is 400 to 10,000.

30. A method for producing a hydrocarbon resin polymer according to claim 1, This includes a polymerization process to form a hydrocarbon resin polymer from a mixture. The aforementioned mixture Monovinyl aromatic compounds and Divinyl aromatic compounds and The compound represented by the following formula (III), A method for producing hydrocarbon resin polymers, including [the specified element]. 【Chemistry 4-1】 (In equation (III), R1 is C 1-4 Alkyl or C 1-4 (It is an alkoxy group, and n is an integer selected from 0 to 3.)

31. A resin composition comprising the hydrocarbon resin polymer described in claim 1.

32. A curable composite material comprising the hydrocarbon resin polymer described in claim 1.

33. A cured resin body formed from the hydrocarbon resin polymer described in claim 1.

34. A resin product comprising the cured resin body described in claim 33.

Images