Styrene copolymer, resin composition, metal foil laminate substrate, and methods for producing the same.

Abstract

The present invention provides materials and resin compositions that offer both low dielectric loss and improved processability. [Solution] This disclosure provides a styrene copolymer that is very uniform and / or has a low dielectric loss tangent (Df), a resin composition containing the styrene copolymer, a prepreg and resin-coated copper foil prepared from the resin composition, a metal foil laminated substrate manufactured from the resin composition, and a method for manufacturing the metal foil laminated substrate. The styrene copolymer contains styrene units and conjugated diene units. The styrene units are present in an amount of 20% to 60% by weight based on the total weight of the styrene copolymer. The styrene copolymer has a blockiness index of more than 55%.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to U.S. Provisional Application No. 63 / 733,185, filed on 12 December 2024, the entirety of which is incorporated herein by reference.

[0002] This disclosure relates to styrene copolymers, resin compositions, metal foil laminated substrates, and methods for producing the same. In particular, the present invention relates to block styrene copolymers, resin compositions containing the same, metal foil laminated substrates produced from the resin compositions, and methods for producing metal foil laminated substrates. [Background technology]

[0003] Fifth-generation (5G) mobile network technology represents the latest generation of mobile communication methods. 5G is characterized by high-speed communication, low latency, and large-scale connectivity. Based on the frequency bands used, 5G can be classified into high-frequency, intermediate-frequency, and low-frequency categories. High-frequency 5G delivers ultra-high data speeds. However, its signal transmission and reception quality are significantly affected by high-frequency propagation loss, conductor loss, and dielectric loss. Therefore, developing metal foil laminate substrates with low dielectric loss is essential to improve signal transmission and reception performance in high-frequency 5G applications.

[0004] Common compositions used to form prepregs in metal foil laminated substrates often suffer from poor processability, limited fluidity, and inadequate fit. Poor fit can lead to uneven dispersion and aggregation. Conversely, inadequate fluidity results in insufficient filling performance, rendering the final product unusable. Furthermore, compositions formulated without any rubber for prepreg formation may exhibit low toughness and brittleness. Moreover, improving the dielectric, thermal, and mechanical properties of copper-clad laminated substrates (CCLs) remains a significant challenge in this field. Therefore, materials and resin compositions that offer both low dielectric loss and improved processability are still needed. [Overview of the project]

[0005] In view of the above issues, the present disclosure provides a styrene copolymer that is very uniform and / or has a low dielectric loss tangent (Df), a resin composition containing the styrene copolymer, a prepreg and a resin-coated copper foil prepared from the resin composition, a metal foil laminated substrate manufactured from the resin composition, and a method for manufacturing the metal foil laminated substrate.

[0006] One embodiment of the present disclosure provides a styrene copolymer comprising styrene units and conjugated diene units. The styrene units are present in an amount of 20% to 60% by weight based on the total weight of the styrene copolymer. The styrene copolymer has a blockiness index of more than 55%.

[0007] One embodiment of the present disclosure provides a resin composition comprising the styrene copolymer described above.

[0008] One embodiment of the present disclosure provides a prepreg manufactured from the above-described resin composition.

[0009] One embodiment of the present disclosure provides a metal foil laminated substrate including the prepreg described above.

[0010] One embodiment of the present disclosure provides a resin-coated copper foil manufactured from the above-described resin composition.

[0011] One embodiment of the present disclosure provides a metal foil laminated substrate including the above-described resin-coated copper foil.

[0012] One embodiment of the present disclosure provides a method for manufacturing a metal foil laminated substrate. The method includes forming a mixture including a hydrocarbon resin and the above-described styrenic copolymer.

[0013] One embodiment of the present disclosure provides a styrenic copolymer including a styrene block and a conjugated diene block. In the styrenic copolymer, the content of the styrene block is in the range of 20% to 60% by weight based on the total weight of the styrenic copolymer, and the styrenic copolymer has a glass transition temperature of -20°C or higher.

[0014] One embodiment of the present disclosure provides a resin composition including the above-described styrenic copolymer.

[0015] One embodiment of the present disclosure provides a prepreg manufactured from the above-described resin composition.

[0016] One embodiment of the present disclosure provides a metal foil laminated substrate including the above-described prepreg.

[0017] One embodiment of the present disclosure provides a resin-coated copper foil manufactured from the above-described resin composition.

[0018] One embodiment of the present disclosure provides a metal foil laminated substrate including the above-described resin-coated copper foil.

[0019] Furthermore, one embodiment of the present disclosure provides a method for manufacturing a metal foil laminated substrate. The method includes forming a mixture including a hydrocarbon resin and the above-described styrenic copolymer.

[0020] The present invention can be more fully understood by reading the following detailed description and examples with reference to the accompanying drawings.

Brief Description of the Drawings

[0021] [Figure 1] SEM image of a prepreg produced from a resin composition containing a styrene copolymer having a blockification index of less than 55%. [Figure 2] SEM image of a prepreg produced from a resin composition containing a styrene copolymer having a blockification index of less than 55%. [Figure 3] SEM image of a prepreg produced from a resin composition containing a styrene copolymer according to an embodiment of the present disclosure. [Figure 4] SEM image of a prepreg produced from a resin composition containing a styrene copolymer having a glass transition temperature of less than -20°C according to an embodiment of the present disclosure.

Modes for Carrying Out the Invention

[0022] The following description is made to represent the general principles of the present disclosure and should not be construed in a limiting sense. The scope of the present disclosure is best determined by reference to the appended claims.

[0023] As used herein, the terms "comprises" and / or "includes" specify the presence of the recited features, integers, steps, operations, members, components, and / or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, operations, members, components, and / or groups thereof. It will be further understood that, unless otherwise specified in the context, the singular form "a" as used herein is intended to include the plural as well.

[0024] Terms such as "First," "Second," etc., are used herein to describe various members, components, regions, layers, and / or parts, but it will be understood that these members, components, regions, layers, and / or parts are not to be limited by these terms. These terms are used to distinguish one member, component, region, layer, or part from another member, component, region, layer, or part, but do not imply any required order of members.

[0025] As used herein, the terms “about,” “approximately,” and “nearly” will be understood to mean a value of a given value or range that varies by 20%, preferably 10%, and preferably 5%, or 3%, or 2%, or 1%, or 0.5%. The values ​​described herein are approximate. That is, “about,” “approximately,” or “nearly” may be implied even without explicit mention. It will be further understood that the values ​​shown herein may include deviations that fall within the above values ​​and the range of deviations acceptable to those skilled in the art. As used herein, the expression “a~b” representing a specific range of values ​​will be understood to mean “≧a and ≦b.”

[0026] As used herein, "C 1-20 The term "alkyl group" refers to a monovalent, linear, branched, or cyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms in its carbon backbone. 1-20 Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, hexyl, decyl, dodecyl, cyclohexyl, cyclooctyl, and cyclododecyl groups.

[0027] The term "C" used in this specification 2-20 The term "alkenyl group" refers to a monovalent, linear, branched, or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms and at least one carbon-carbon double bond in its carbon backbone. 2-20Examples of alkenyl groups include, but are not limited to, ethenyl, propenyl, isobutenyl, sec-butenyl, tert-butenyl, pentenyl, isopentenyl, hexenyl, decenyl, dodecenyl, pentadecenyl, cyclohexenyl, cyclooctenyl, cyclopentenyl, cyclopentadienyl, and cyclopentadecenyl.

[0028] Unless otherwise specified, all terms used herein (including technical and scientific terms) have the same meaning as those commonly understood by those skilled in the art to whom the present invention relates. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the relevant art and the context or background of this disclosure, and it will be further understood that they should not be interpreted in an idealized or overly formal sense unless expressly defined herein. Descriptions of known features and structures that could unnecessarily obscure this disclosure are omitted below.

[0029] One embodiment of the present disclosure provides a styrene copolymer comprising styrene units and conjugated diene units. The styrene units are present in an amount of about 20% to about 60% by weight, based on the total weight of the styrene copolymer. The styrene copolymer has a blockiness index of more than about 55%.

[0030] In some embodiments, the weight ratio of styrene units to conjugated diene units is not particularly limited, but is 20:80 to 60:40. In this disclosure, the weight ratio of styrene units to conjugated diene units is used for proton nuclear magnetic resonance ( 1 It is measured by the 1H-NMR method.

[0031] Styrene copolymers have a blockiness index of over 55%, indicating that the styrene units are not randomly distributed along the polymer chain but are primarily arranged in continuous segments. In some embodiments, the blockiness index may be in the range of over 60%, over 70%, over 75%, over 80%, over 90%, over 95%, or over 55% to over 60%. In some embodiments, the blockiness index of the styrene copolymers of this disclosure may be in the range of over 60% to over 99.5%, over 70% to over 99.5%, over 75% to over 99.5%, over 80% to over 99.5%, over 90% to over 99.5%, or over 95% to over 99.5%. This segmental arrangement results in a favorable combination of mechanical, thermal, and dielectric properties. The styrene-based segments provide rigidity and a high glass transition temperature, while the diene segments maintain sufficient elasticity, toughness, and fluidity. As a result, the copolymer exhibits improved toughness, dimensional stability, and processability while reducing dielectric loss. In some embodiments, this further improves compatibility and adhesion with other resin components, imparts high uniformity to the resin composition, and thereby contributes to the overall performance and reliability of the metal foil laminate substrate.

[0032] Styrene units are present in an amount of about 20% to about 60% by weight, based on the total weight of the styrene copolymer. This means that the total weight of all structural units in the copolymer, including styrene units and other copolymer units, is 100% by weight, and styrene units account for about 20% to about 60% by weight of the total weight. In some embodiments, styrene units are present in an amount of about 40% to about 60% by weight, about 30% to about 50% by weight, or less than about 20% to about 40% by weight. In some embodiments, the styrene units of the disclosure may be present in an amount of about 25% to 55% by weight, about 25% to 45% by weight, about 25% to 35% by weight, about 35% to 55% by weight, or about 45% to 55% by weight. In some embodiments, the styrene units of the disclosure may account for 30%, 40%, or 50% by weight. Within the range defined above, styrene-based units yield a balanced combination of dielectric, thermal, and mechanical properties. Styrene-based units can form styrene blocks. Styrene blocks can function as hard segments, resulting in a higher glass transition temperature (Tg) and contributing to strength, hardness, and high-temperature performance.

[0033] As used herein, the term “conjugated diene unit” refers to a unit within the polymer chain of a styrene copolymer derived from a conjugated diene monomer (compound). Examples of conjugated diene monomers include, but are not limited to, butadiene, isoprene, myrcene, or combinations thereof. As used herein, the term “butadiene” refers to the following structure: [ka] This refers to a compound (or monomer) having the following structure, also known as 1,3-butadiene. The term "isoprene" as used herein refers to the following structure: [ka] This refers to a compound (or monomer) having the following structure, also known as 2-methyl-1,3-butadiene. The term "myrcene" as used herein refers to the following structure: [ka] This refers to a compound (or monomer) having 7-methyl-3-methylideneocta-1,6-diene. In some embodiments, the conjugated diene unit may be selected from the group consisting of butadiene units, isoprene units, myrcene units, or combinations thereof.

[0034] Conjugated diene units may contain vinyl groups. A vinyl group refers to a pendant vinyl portion located in the main polymer backbone formed by the conjugated diene units. In some embodiments, the vinyl content of the conjugated diene units may exceed approximately 70% by weight, based on the total amount of conjugated diene units. A higher vinyl content leads to a higher curing density of the styrene copolymer, thereby improving its heat resistance and dielectric properties.

[0035] In embodiments where the conjugated diene unit is a butadiene unit, the butadiene unit may include a 1,2-bond structure of formula (1) and / or a 1,4-bond structure of formula (2). In these embodiments, the molar ratio of the 1,2-bond structure of formula (1) to the 1,4-bond structure of formula (2) may vary in the range of 90:10 to 10:90. [ka]

[0036] In some embodiments, the butadiene unit may further include the ring structure of formula (3). [ka] In some embodiments, the 1,2-vinyl content of the styrene copolymer (i.e., the amount of 1,2-bonded structures of formula (1)) may be greater than about 70 based on the total amount of butadiene units. In some embodiments, the 1,2-vinyl content of the styrene copolymer may be in the range of about 75% to about 85% by weight. In some embodiments, the ring content of the styrene copolymer (i.e., the amount of ring structures of formula (3)) may be about 14% or less based on the total amount of butadiene units. In some embodiments, the ring content may be in the range of about 10% or less, about 7% or less, about 3% to about 7%, about 3% to about 6%, or about 5% to about 6%, resulting in improved dielectric properties.

[0037] In some embodiments, conjugated diene units may form conjugated diene blocks. These conjugated diene blocks may contain functional groups (such as vinyl groups) and may function as soft segments for curing, contributing to elasticity, toughness, and resilience. In further embodiments, the conjugated diene blocks contain butadiene units. In some embodiments, the 1,2-vinyl content of the conjugated diene block may be greater than about 70% by weight, based on the total amount of butadiene units in the conjugated diene block. In some embodiments, the ring content of the conjugated diene block may be about 14% or less, based on the total amount of butadiene units in the conjugated diene block. In some embodiments, the ring content of the conjugated diene block may be about 10% or less, about 7% or less, in the range of about 3% to about 7%, in the range of about 3% to about 6%, or in the range of about 5% to about 6%, based on the total amount of butadiene units in the conjugated diene block. The molar ratios of the structures in formulas (1) and (2), the vinyl content, and the ring content (amount of the ring structure in formula (3)) are determined by proton nuclear magnetic resonance ( 1 It can be measured by 1H-NMR analysis.

[0038] As used herein, the term "styrene unit" refers to a unit within the polymer chain of a styrene copolymer derived from a styrene monomer (compound). Examples of styrene monomers may include unsubstituted styrene or substituted styrene. As used herein, the term "styrene monomer" refers to the following structure: [ka] This refers to a compound (or monomer) having [a specific characteristic]. Examples of substituted styrenes include, but are not limited to, α-methylstyrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, tert-butylstyrene, vinyltoluene, or combinations thereof. In some embodiments, the styrene-based unit may be selected from the group consisting of styrene units, α-methylstyrene units, p-methylstyrene units, o-methylstyrene units, m-methylstyrene units, tert-butylstyrene units, vinyltoluene units, and combinations thereof.

[0039] In some embodiments, the styrene copolymer may include a conjugated diene block and at least one styrene block, but the number of blocks is not particularly limited. In some embodiments, the styrene copolymer may consist of two or three blocks. In some embodiments, the blockiness index of such a styrene copolymer may be greater than about 55%. In some embodiments, the blockiness index of such a styrene copolymer may be greater than about 80%, and this structure allows for the achievement of an optimal balance of mechanical, thermal, and dielectric properties of the styrene copolymer, and enables the optimization of the uniformity of the prepreg or resin-coated copper foil, thereby improving the toughness, dimensional stability, and processability of the final metal foil laminate substrate.

[0040] In some embodiments, the styrene copolymer may be a diblock copolymer, resulting in excellent electrical performance. In some embodiments, the styrene copolymer may be a styrene-butadiene diblock copolymer (SB), comprising a styrene block and a butadiene block. In these embodiments, the weight ratio of the styrene block to the butadiene block is not particularly limited, but may range from 20:80 to 60:40. In other embodiments, the styrene copolymer may be a styrene-isoprene diblock copolymer (SI), comprising a styrene block and an isoprene block. The weight ratio of the styrene block to the isoprene block is not particularly limited, but may range from 20:80 to 40:60. In some embodiments, the styrene copolymer may be a styrene-butadiene / isoprene diblock copolymer (SB / I), comprising a styrene block and a butadiene / isoprene block. The weight ratio of the styrene block to the butadiene / isoprene block is not particularly limited, but may range from 20:80 to 60:40. In some embodiments, the styrene copolymer may be a styrene-butadiene / myrcene diblock copolymer (SB / M) containing styrene blocks and butadiene / myrcene blocks. The weight ratio of styrene blocks to butadiene / myrcene is not particularly limited, but may range from 20:80 to 60:40. In some embodiments, the styrene copolymer may be a styrene-styrene / butadiene diblock copolymer (SS / B) containing styrene blocks and styrene / butadiene blocks. The weight ratio of styrene blocks to styrene / butadiene is not particularly limited, but may range from 20:80 to 60:40. In some embodiments, the styrene copolymer may be a styrene-butadiene / butadiene diblock copolymer (S / BB) containing styrene blocks and styrene / butadiene blocks. The weight ratio of styrene / butadiene blocks to butadiene blocks is not particularly limited, but may range from 20:80 to 60:40.In some embodiments, the styrene copolymer may be a styrene / butadiene-styrene / butadiene diblock copolymer (S / BS / B) comprising a styrene / butadiene block mainly composed of styrene and a styrene / butadiene block mainly composed of butadiene. The weight ratio of the styrene / butadiene block mainly composed of styrene to the styrene / butadiene block mainly composed of butadiene is not particularly limited, but may be in the range of 20:80 to 60:40.

[0041] In some embodiments, the styrene copolymer may be a triblock copolymer. In some embodiments, the styrene copolymer may be a styrene-butadiene-isoprene block copolymer (SBI) or styrene-isoprene-butadiene block copolymer (SIB), comprising a styrene block, a butadiene block, and an isoprene block. In some embodiments, the styrene copolymer may be a styrene-butadiene-styrene block copolymer (SBS), comprising a styrene block and a butadiene block. In some embodiments, the styrene copolymer may be a butadiene-styrene-butadiene block copolymer (BSB), comprising a styrene block and a butadiene block. In some embodiments, the styrene copolymer may be a styrene-isoprene-styrene block copolymer (SIS), comprising a styrene block and an isoprene block. In these embodiments, the weight ratio of the total styrene blocks to the total butadiene and / or isoprene blocks is not particularly limited, but may range from 20:80 to 60:40. In some embodiments, the styrene copolymer may be a triblock copolymer containing butadiene units, and the ring content of the styrene copolymer may be about 14% or less based on the total amount of butadiene units.

[0042] In some embodiments, the styrene copolymers of the present disclosure may further include randomized regions.

[0043] In some embodiments, the amount of styrene blocks may range from about 20% to about 60% by weight, and the amount of conjugated diene blocks may range from about 40% to about 80% by weight, based on the total weight of the styrene copolymer. In some embodiments, the styrene block content may range from about 30% to about 50% by weight, about 40% to about 60% by weight, or less than about 40% by weight, based on the total weight of the styrene copolymer. In some embodiments, the weight ratio of styrene blocks to conjugated diene blocks is not particularly limited, but is 20:80 to 60:40. In this disclosure, the weight ratio of styrene blocks to conjugated diene blocks is defined as proton nuclear magnetic resonance ( 1 It is measured by the 1H-NMR method.

[0044] In some embodiments, the styrene copolymer may comprise at least one block containing styrene units and conjugated diene units, such as a styrene / butadiene block, a styrene / isoprene block, or a styrene / myrcene block. In some embodiments, the styrene block is a block comprising styrene units and conjugated diene units, with styrene units present in greater than 50% of the total weight of the styrene block. In some embodiments, the conjugated diene block is a block comprising styrene units and conjugated diene units, with conjugated diene units present in greater than 50% of the total weight of the conjugated diene block. In some embodiments, the styrene copolymer may comprise at least one block comprising styrene units and conjugated diene units, and the blockiness index of such a styrene copolymer may be greater than 55%. In some embodiments, the styrene copolymer may contain at least one block comprising styrene units and conjugated diene units, the blockiness index of such a styrene copolymer may be in the range of greater than 55% to 60%, and this structure allows the styrene copolymer to maintain a partial segmental arrangement, resulting in a balance of rigidity and elasticity within the same block. As a result, the styrene copolymer exhibits good toughness, elasticity, and fluidity, thereby improving processability while maintaining satisfactory uniformity and mechanical and dielectric properties.

[0045] In some embodiments, the styrene copolymer is liquid at approximately 25°C, contributing to its fluidity and suitability in the manufacturing process. In some embodiments of this disclosure, the styrene copolymer has a polydispersity index (PDI) in the range of approximately 1.0 to approximately 1.20. In some embodiments, the styrene copolymer may have a weight-average molecular weight of approximately 10,000 g / mol or less, resulting in improved processability during the CCL manufacturing process. Specifically, the styrene copolymer has a weight-average molecular weight of approximately 5,000 g / mol to approximately 6,000 g / mol. In some embodiments, the weight-average molecular weight may be in the range of approximately 5,000 g / mol to approximately 9,500 g / mol, approximately 5,300 g / mol to approximately 9,500 g / mol, approximately 5,300 g / mol to approximately 6,000 g / mol, or approximately 5,300 g / mol to approximately 5,800 g / mol. The molecular weight and polydispersity index mentioned above are measured by gel permeation chromatography (GPC).

[0046] In some embodiments, the styrene copolymer for preparing a low-dielectric resin composition having a dielectric loss tangent (Df) in the range of greater than 0.00170 and less than 0.00180 comprises styrene units and conjugated diene units, wherein the styrene units are present in an amount of 20% to less than 40% by weight based on the total weight of the styrene copolymer, and the styrene copolymer has a blockiness index greater than 55%. In further embodiments, the blockiness index of the styrene copolymer for preparing a low-dielectric resin composition having a dielectric loss tangent (Df) in the range of greater than 0.00170 and less than 0.00180 is 80% or more, optimizing the uniformity of the prepreg or resin-coated copper foil. This improves the toughness, dimensional stability, and processability of the final metal foil laminate substrate. In some embodiments, the styrene copolymer for preparing a low-dielectric resin composition having a dielectric loss tangent (Df) in the range of greater than 0.00170 and less than 0.00180 is a diblock copolymer.

[0047] In some embodiments, a styrene copolymer for preparing a low-dielectric resin composition having a dielectric loss tangent (Df) in the range of 0.00170 or less comprises styrene units and conjugated diene units, wherein the styrene units are present in an amount of 40% to 60% by weight based on the total weight of the styrene copolymer, and the styrene copolymer has a blockiness index greater than 55%. The block structure and blockiness index of the selected styrene copolymer are important for optimizing uniformity. In some embodiments, a styrene copolymer for preparing a low-dielectric resin composition having a dielectric loss tangent (Df) in the range of 0.00170 or less consists of conjugated diene blocks and at least one styrene block, but the number of blocks is not particularly limited. The blockiness index of the styrene copolymer is greater than 80%, improving the uniformity of the prepreg or resin-coated copper foil. In other embodiments, a styrene copolymer for preparing a low-dielectric resin composition having a dielectric loss tangent (Df) in the range of 0.00170 or less comprises at least one block containing styrene units and conjugated diene units, with a blockiness index in the range of greater than 55% to 60%, and improves the uniformity of the prepreg or resin-coated copper foil.

[0048] The styrene copolymers described above exhibit a blocky arrangement of styrene units and conjugated diene units, as reflected by their high blockiness index, and have a specific styrene content. These structural features can result in high uniformity and / or low dielectric loss tangent (Df), which contribute to the consistent material and improved electrical properties of the styrene copolymers. In some embodiments, styrene copolymers can be used to prepare low dielectric resin compositions having a dielectric loss tangent (Df) of less than 0.00200. In some embodiments, styrene copolymers can be used to prepare low dielectric resin compositions having a dielectric loss tangent (Df) of 0.00180 or less. In some embodiments, styrene copolymers can be used to prepare low dielectric resin compositions having a dielectric loss tangent (Df) of 0.00170 or less.

[0049] One embodiment of the present disclosure provides a styrene copolymer comprising a styrene block and a conjugated diene block. A styrene block refers to a block mainly composed of styrene units, and a conjugated diene block refers to a block mainly composed of conjugated diene units. The styrene block can function as a hard segment, resulting in a higher Tg and contributing to strength, hardness, and high-temperature performance, while the conjugated diene block may contain functional groups (such as vinyl groups) and can function as a soft segment for curing, contributing to elasticity, toughness, and resilience. The styrene block content may range from about 20% to about 60% by weight based on the total weight of the styrene copolymer, and the styrene copolymer has structural features that ensure a glass transition temperature of -20°C or higher, excellent dielectric properties, and uniformity within a metal foil laminate substrate. In some embodiments, the glass transition temperature may be in the range of about -18°C or higher, about -17.5°C to about 15°C, about -17.5°C to about 10°C, or about -17.5°C to about 7°C.

[0050] In some embodiments, the styrene copolymer comprises a styrene block and a conjugated diene block, and based on the total weight of the styrene copolymer, the amount of styrene blocks may range from about 20% to about 60% by weight, and the amount of conjugated diene blocks may range from about 40% to about 80% by weight. In some embodiments, the styrene block content may range from about 30% to about 50% by weight, about 40% to about 60% by weight, or less than about 20% to about 40% by weight, based on the total weight of the styrene copolymer. In some embodiments, the weight ratio of styrene blocks to conjugated diene blocks is not particularly limited, but is 20:80 to 60:40. In this disclosure, the weight ratio of styrene blocks to conjugated diene blocks is defined as proton nuclear magnetic resonance ( 1 It is measured by the 1H-NMR method.

[0051] In some embodiments, the styrene copolymer comprises a styrene block and a conjugated diene block, and the conjugated diene block may contain the conjugated diene units described above, but is not limited thereto. In some embodiments, the conjugated diene units may be selected from the group consisting of butadiene units, isoprene units, myrcene units, or combinations thereof. The conjugated diene units may contain vinyl groups. A vinyl group refers to a pendant vinyl portion located in the main polymer backbone formed by the conjugated diene units. In some embodiments, based on the total amount of conjugated diene units, the vinyl content of the conjugated diene units may be more than about 70% by weight. A higher vinyl content results in a higher curing density of the styrene copolymer, thereby improving the heat resistance and dielectric properties of the styrene copolymer.

[0052] In some embodiments, the styrene copolymer comprises a styrene block and a conjugated diene block, and the styrene copolymer comprises conjugated diene units, the conjugated diene units being butadiene units. The butadiene units may each include the 1,2-bonded structure of formula (1) and / or the 1,4-bonded structure of formula (2) described above. In these embodiments, the molar ratio of the 1,2-bonded structure of formula (1) to the 1,4-bonded structure of formula (2) may vary in the range of 90:10 to 10:90. In some embodiments, the butadiene units may further include the ring structure of formula (3) described above.

[0053] In some embodiments, the styrenic copolymer comprises a styrene block and a conjugated diene block, the conjugated diene block contains butadiene units, and the 1,2-vinyl content of the styrenic copolymer can be more than about 70 wt% based on the total amount of butadiene units in the conjugated diene block. In some embodiments, the 1,2-vinyl content of the styrenic copolymer can be in the range of about 75 wt% to about 86 wt% based on the total amount of butadiene units in the conjugated diene block. In some embodiments, the ring content of the styrenic copolymer can be about 14% or less, about 10% or less, or about 7% or less based on the total amount of butadiene units, resulting in improved dielectric properties. The molar ratio, vinyl content, and ring content (the amount of the ring structure of formula (3) in the conjugated diene block) of the structures of formula (1) and formula (2) can be measured by proton nuclear magnetic resonance ( 1 1H-NMR) analysis.

[0054] In some embodiments, the styrenic copolymer comprises a styrene block and a conjugated diene block, and the styrene block can contain the above-mentioned styrenic units, but the present disclosure is not limited thereto. In some embodiments, the styrenic units can be selected from the group consisting of styrene units, α-methylstyrene units, p-methylstyrene units, o-methylstyrene units, m-methylstyrene units, tert-butylstyrene units, vinyltoluene units, and combinations thereof. In some embodiments, the styrenic units are present in an amount of about 20 wt% to about 60 wt% based on the total weight of the styrenic copolymer. This means that the total weight of all structural units in the copolymer, including styrenic units and other copolymerized units, is 100 wt%, and the styrenic units account for about 20 wt% to about 60 wt% of the total weight. In some embodiments, the styrenic units are present in an amount of about 40 wt% to about 60 wt%, about 30 wt% to about 50 wt%, or less than about 20 wt% to about 40 wt%. Within the ranges defined above, the styrenic units provide a balanced combination of dielectric, thermal, and mechanical properties.

[0055] Styrene copolymers containing styrene blocks and conjugated diene blocks may have a blockiness index of about 55% or more. In some embodiments, the blockiness index may be in the range of about 80% or more, about 91% or more, greater than 55% to 60%, or about 55% to about 60%. In some embodiments, the blockiness index may be about 80% or more, while the styrene units are present in an amount of less than 40% by weight based on the total weight of the styrene copolymer. In some embodiments, the blockiness index may be about 80% or more, while the styrene units are present in an amount of about 20% to less than 40% by weight based on the total weight of the styrene copolymer. In some embodiments, the blockiness index may be about 80% or more, while the styrene units are present in an amount of about 40% to less than 60% by weight based on the total weight of the styrene copolymer.

[0056] In some embodiments, the styrene copolymer comprises styrene blocks and conjugated diene blocks, and the styrene copolymer may comprise at least one block comprising styrene units and conjugated diene units, and the blockification index of such a styrene copolymer may be greater than 55%. In some embodiments, the styrene copolymer comprises styrene blocks and conjugated diene blocks, and the styrene copolymer may comprise at least one block comprising styrene units and conjugated diene units, and the blockification index of such a styrene copolymer may be greater than 55% to 60%. Styrene copolymers having the above blockification index can exhibit improved toughness, dimensional stability, and processability while reducing dielectric loss and improving compatibility and adhesion with other resin components, thereby imparting high uniformity to the resin composition, and thereby contributing to the overall performance and reliability of the metal foil laminate substrate.

[0057] In some embodiments, a styrene copolymer comprising a styrene block and a conjugated diene block comprises styrene units and conjugated diene units, and the weight ratio of styrene units to conjugated diene units in the styrene copolymer is not particularly limited, but is 20:80 to 60:40. In this disclosure, the weight ratio of styrene units to conjugated diene units in the styrene copolymer is determined by proton nuclear magnetic resonance ( 1 It is measured by the 1H-NMR method.

[0058] In some embodiments, the styrene copolymer comprising styrene blocks and conjugated diene blocks may consist of two or three blocks. In some embodiments, the styrene copolymer comprising styrene blocks and conjugated diene blocks may be a diblock copolymer, exhibiting excellent molecular arrangement and further optimizing the uniformity of the prepreg or the resin-coated copper foil using the prepreg. In some embodiments, the styrene copolymer comprising styrene blocks and conjugated diene blocks may be selected from the group consisting of styrene-butadiene diblock copolymer (SB), styrene-isoprene diblock copolymer (SI), styrene-butadiene / isoprene diblock copolymer (SB / I), styrene-butadiene / myrcene diblock copolymer (SB / M), styrene-styrene / butadiene diblock copolymer (SS / B), styrene / butadiene-butadiene diblock copolymer (S / BB), and styrene / butadiene-styrene / butadiene diblock copolymer (S / BS / B), which comprises a styrene / butadiene block mainly composed of styrene and a styrene / butadiene block mainly composed of butadiene. In some embodiments, the styrene copolymer comprising styrene blocks and conjugated diene blocks may be styrene-butadiene diblock copolymer (SB), which comprises a styrene block and a butadiene block. In these embodiments, the weight ratio of styrene blocks to butadiene blocks is not particularly limited, but may be in the range of 20:80 to 60:40. In some embodiments, the styrene copolymer comprising a styrene block and a conjugated diene block may be a styrene-butadiene / isoprene diblock copolymer (SB / I) comprising a styrene block and a butadiene / isoprene block. The weight ratio of the styrene block to the butadiene / isoprene block is not particularly limited, but may be in the range of 20:80 to 60:40. In some embodiments, the styrene copolymer comprising a styrene block and a conjugated diene block may be a styrene-butadiene / myrcene diblock copolymer (SB / M) comprising a styrene block and a butadiene / myrcene block.The weight ratio of styrene blocks to butadiene / myrcene is not particularly limited, but may range from 20:80 to 60:40. In some embodiments, the styrene copolymer comprising styrene blocks and conjugated diene blocks may be a styrene-styrene / butadiene diblock copolymer (SS / B) comprising styrene blocks and styrene / butadiene blocks. The weight ratio of styrene blocks to styrene / butadiene is not particularly limited, but may range from 20:80 to 60:40. In some embodiments, the styrene copolymer comprising styrene blocks and conjugated diene blocks may be a styrene / butadiene-styrene / butadiene diblock copolymer (S / BS / B) comprising styrene / butadiene blocks mainly composed of styrene and styrene / butadiene blocks mainly composed of butadiene. The weight ratio of styrene / butadiene blocks mainly composed of styrene to styrene / butadiene blocks mainly composed of butadiene is not particularly limited, but may range from 20:80 to 60:40.

[0059] In some embodiments, the styrene copolymer containing styrene blocks and conjugated diene blocks may be a triblock copolymer. In some embodiments, the styrene copolymer may be selected from the group consisting of styrene-butadiene-isoprene block copolymer (SBI), styrene-isoprene-butadiene block copolymer (SIB), styrene-butadiene-styrene block copolymer (SBS), butadiene-styrene-butadiene block copolymer (BSB), and styrene-isoprene-styrene block copolymer (SIS). In these embodiments, the weight ratio of the total styrene blocks to the total butadiene and / or isoprene blocks is not particularly limited, but may be in the range of 20:80 to 60:40. In some embodiments, the styrene copolymer containing styrene blocks and conjugated diene blocks may be a triblock copolymer containing butadiene units, and the ring content of the styrene copolymer may be about 14% or less based on the total amount of butadiene units.

[0060] In some embodiments, the styrene copolymer, comprising a styrene block and a conjugated diene block, is liquid at about 25°C, contributing to the fluidity of the styrene copolymer in the manufacturing process. In some embodiments of this disclosure, the styrene copolymer, comprising a styrene block and a conjugated diene block, has a polydispersity index (PDI) in the range of about 1.0 to about 1.20, or about 1.0 to about 1.10. In some embodiments, the styrene copolymer, comprising a styrene block and a conjugated diene block, may have a weight-average molecular weight of about 10,000 g / mol or less, resulting in improved processability during the CCL manufacturing process. Specifically, the styrene copolymer has a weight-average molecular weight of about 5,000 g / mol to about 6,000 g / mol. The above molecular weight and polydispersity index are measured by GPC.

[0061] Compared to other materials with similar physical properties, such as styrene random copolymers or styrene copolymers with low Tg, the styrene copolymers of this disclosure may exhibit even better thermal properties, thereby meeting the dielectric and mechanical requirements of CCL and improving thermal stability throughout the CCL manufacturing process.

[0062] In some embodiments, a styrene copolymer for preparing a low-dielectric resin composition having a dielectric loss tangent (Df) in the range of greater than 0.00170 and less than 0.00180 comprises styrene blocks and conjugated diene blocks, the styrene copolymer contains styrene units, the styrene units present in an amount of less than 40% by weight based on the total weight of the styrene copolymer. In further embodiments, the stucco index of the styrene copolymer containing styrene blocks and conjugated diene blocks for preparing a low-dielectric resin composition having a dielectric loss tangent (Df) in the range of greater than 0.00170 and less than 0.00180 is 80% or more, optimizing the uniformity of the prepreg or resin-coated copper foil. This improves the toughness, dimensional stability, and processability of the final metal foil laminate substrate. In some embodiments, the styrene copolymers comprising styrene blocks and conjugated diene blocks for preparing low-dielectric resin compositions having a dielectric loss tangent (Df) in the range of greater than 0.00170 and less than 0.00180 are diblock copolymers.

[0063] In some embodiments, a styrene copolymer for preparing a low-dielectric resin composition having a dielectric loss tangent (Df) in the range of 0.00170 or less comprises styrene blocks and conjugated diene blocks, the styrene copolymer contains styrene units, the styrene units present in an amount of 40% to 60% by weight based on the total weight of the styrene copolymer. The block structure and blockiness index of the selected styrene copolymer are important for optimizing the uniformity of the prepreg or resin-coated copper foil. In some embodiments, a styrene copolymer comprising styrene blocks and conjugated diene blocks for preparing a low-dielectric resin composition having a dielectric loss tangent (Df) in the range of 0.00170 or less has a blockiness index of over 80% and improves the uniformity of the prepreg or resin-coated copper foil. In other embodiments, a styrene copolymer comprising styrene blocks and conjugated diene blocks for preparing a low dielectric resin composition having a dielectric loss tangent (Df) in the range of 0.00170 or less comprises at least one block comprising styrene units and conjugated diene units, has a blockiness index in the range of greater than 55% to 60%, and improves the uniformity of prepregs or resin-coated copper foils.

[0064] The method for producing any one of the styrene copolymers of this disclosure is not particularly limited. For example, the styrene copolymers can be produced by the methods described in Japanese Patent Publication No. 06-192502, Japanese Patent Publication No. 2000-514122 (translation of a PCT application), and Japanese Patent Publication No. 2007-302901, or by similar methods. In some embodiments, any one of the styrene copolymers of this disclosure can be produced by the steps of purifying a styrene monomer and a conjugated diene monomer under an inert atmosphere, introducing the styrene monomer, introducing the conjugated diene monomer, and terminating the reaction, thereby obtaining the styrene copolymer.

[0065] A resin composition comprising at least one of the styrene copolymers described above can be provided. In some embodiments, the styrene copolymer is present in an amount of about 5% to about 20% by weight based on the total weight of the resin composition. In some embodiments, the styrene copolymer is present in an amount of about 9% to about 18% by weight based on the total weight of the resin composition. As described above, the styrene copolymer exhibits excellent compatibility and curing reactivity with other components in the resin composition. In some embodiments, a styrene copolymer having a weight-average molecular weight of 10,000 g / mol or less can function as a cushioning agent under impact. Therefore, a resin composition containing at least one of the styrene copolymers described above can be used to produce a prepreg with extremely low dielectric loss and improved toughness.

[0066] In some embodiments, the resin composition may further contain a hydrocarbon resin. Hydrocarbon resins, composed of carbon and hydrogen atoms, can exhibit low dielectric loss due to the limited number of polar functional groups. In this disclosure, the hydrocarbon resin contains nonpolar aromatic units, which result in good thermal stability during the heating process and excellent oxidation resistance compared to hydrocarbon resins lacking such nonpolar aromatic units. Resin compositions containing hydrocarbon resins may exhibit good electrical and thermal performance after the heating process. In some embodiments, the resin composition may contain about 30% to about 90% by weight of hydrocarbon resin, based on the total weight of the resin composition.

[0067] In some embodiments, the hydrocarbon resin may be an olefin-aromatic vinyl compound-aromatic polyen copolymer. In some embodiments, known or commercially available hydrocarbon resin products may also be used. In certain embodiments, the hydrocarbon resin of the Disclosure may be the polymer described in whole in U.S. Patent Application No. 18 / 128,716, which is incorporated herein by reference. In other embodiments, the hydrocarbon resin may comprise 0 mol% to about 40 mol% of repeating units (A) derived from a crosslinked ring monomer compound, about 15 mol% to about 92 mol% of repeating units (B) derived from a monovinyl aromatic compound, and about 8 mol% to about 80 mol% of repeating units (C) derived from a divinyl aromatic compound.

[0068] As used herein, the term “crosslinked ring monomer compound” refers to a compound having a crosslinked ring structure that can be polymerized with the same compound or different compounds to form polymers. A crosslinked ring structure refers to a structure having at least two carbon rings, where at least two carbon rings share two carbon atoms that are not directly connected. In some embodiments of this disclosure, the crosslinked ring structure in the crosslinked ring monomer compound may consist of 3 to 12 ring atoms and 1 to 2 double bonds. In some embodiments, the crosslinked ring structure may be unsubstituted. In some embodiments, at least one hydrogen atom on the crosslinked ring structure is C 1-20 Alkyl alkyl group, C 2-20 Alkenyl group, and C 1-20 It can be substituted with at least one substituent selected from the group consisting of carboxylate groups having alkyl chain groups. In some embodiments, the crosslinked ring structure may have at least two substituents. The at least two substituents are C 1-20 Alkyl alkyl group, C 2-20 Alkenyl group, and C 1-20The substituents may be any two substituents selected from the group consisting of carboxylate groups having alkyl chain groups. At least two adjacent substituents may combine to form a ring. For example, the crosslinked ring monomer compound may be selected from the group consisting of norbornene (NB), dicyclopentadiene (DCPD), dicycloheptadiene (NBD), 5-acetyl-2-norbornene, methyl 5-norbornene-2-carboxylate, vinylnorbornene, and ethylidene-norbornene, but the disclosure is not limited to these.

[0069] Compared to linear repeating units, repeating units (A) having a crosslinked ring structure have greater rigidity. Therefore, repeating units (A) can increase the glass transition temperature of the resin composition or improve the thermal performance of the resin composition. If the content of repeating units (A) in the hydrocarbon resin is too high, for example, more than 40 mol%, the cost-effectiveness of the hydrocarbon resin decreases. In some embodiments, the hydrocarbon resin of the present disclosure may contain repeating units (A) in amounts of 0 mol% to about 38 mol%, 0 mol% to about 30 mol%, 0 mol% to about 25 mol%, 0 mol% to about 20 mol%, about 20 mol% to about 40 mol%, about 20 mol% to about 38 mol%, about 20 mol% to about 30 mol%, or about 20 mol% to about 25 mol%. In some embodiments, the hydrocarbon resins of the present disclosure may contain about 3 mol%, about 5 mol%, about 7 mol%, about 9 mol%, about 10 mol%, about 20 mol%, about 22 mol%, about 25 mol%, about 30 mol%, about 32 mol%, about 35 mol%, or about 38 mol% repeating units (A).

[0070] As used herein, the term “monovyl aromatic compound” refers to a compound comprising a carbocyclic aromatic structure in which one hydrogen atom on the ring carbon atom of the carbocyclic aromatic structure is substituted by 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 1-20It may be substituted with alkyl groups. In some embodiments, the carbocyclic aromatic structure may contain 6 to 60 or 6 to 20 ring carbon atoms. In some embodiments, the carbocyclic aromatic structure may be unsubstituted. In some embodiments, at least one hydrogen atom on the ring carbon atoms in the carbocyclic aromatic structure is C 1-20 They can be substituted with alkyl groups. Examples of monovinyl aromatic compounds include, but are not limited to, styrene, methylstyrene, ethylstyrene (EVB), and combinations thereof.

[0071] Repeating units (B) can increase the solubility of the hydrocarbon resin in organic solvents such as toluene. In one embodiment, the hydrocarbon resin of the Disclosure contains about 15% mol% to about 92 mol% of repeating units (B). If the content of repeating units (B) in the hydrocarbon resin is too low, for example less than about 15 mol%, the solubility of the hydrocarbon resin in organic solvents will be insufficient. If the content of repeating units (B) in the hydrocarbon resin is too high, for example more than about 92 mol%, other properties of the hydrocarbon resin, such as thermal properties, may deteriorate. In some embodiments, the hydrocarbon resin of the Disclosure may contain about 20 mol% to about 92 mol%, about 20 mol% to about 90 mol%, about 25 mol% to about 85 mol%, about 30 mol% to about 80 mol%, about 35 mol% to about 80 mol%, about 40 mol% to about 80 mol%, or about 45 mol% to about 80 mol% of repeating units (B). In some embodiments, the hydrocarbon resins of the present disclosure may contain about 46 mol%, about 48 mol%, about 50 mol%, about 55 mol%, about 60 mol%, about 67 mol%, about 72 mol%, about 76 mol%, or about 78 mol% repeating units (B).

[0072] As used herein, the term “divinyl aromatic compound” refers to a compound comprising a carbocyclic aromatic structure in which two hydrogen atoms on the ring carbon atoms of the carbocyclic aromatic structure are substituted by vinyl groups. In some embodiments, the vinyl groups may be unsubstituted. In some embodiments, at least one hydrogen atom on the vinyl group is C 1-20It may be substituted with alkyl groups. In some embodiments, the carbocyclic aromatic structure may contain 6 to 60 or 6 to 20 ring carbon atoms. In some embodiments, the carbocyclic aromatic structure may be unsubstituted. In some embodiments, at least one hydrogen atom on the ring carbon atoms in the carbocyclic aromatic structure is C 1-20 They may be substituted with alkyl groups. Examples of divinyl aromatic compounds include, but are not limited to, divinylbenzene (DVB), diisopropenylbenzene, or any combination thereof.

[0073] In some embodiments, the repeating unit (C) may include crosslinked units and non-crosslinked units. In some embodiments, the repeating unit (C) is [ka] This disclosure may include, but is not limited to, crosslinking units represented by . In some embodiments, the repeating unit (C) is [ka] This disclosure may include, but is not limited to, non-crosslinked units represented by . In the above structure, "*" represents a connection site that connects to other groups.

[0074] In some embodiments, the degree of crosslinking of the repeating unit (C) is 0.2 to 0.6. The range of the degree of crosslinking contributes to excellent thermal and electrical properties without causing processability problems. Higher degrees of crosslinking of the hydrocarbon resin result in better thermal performance, thermal stability, and / or electrical performance; however, processability deteriorates when the degree of crosslinking exceeds 0.6. In some embodiments, the degree of crosslinking of the repeating unit (C) may be 0.2 to 0.5. In some embodiments, the degree of crosslinking of the repeating unit (C) may be 0.3, 0.35, 0.4, or 0.45. However, this disclosure is not limited to these. The degree of crosslinking of the repeating unit (C) is calculated by the following formula:

number

[0075] The degree of crosslinking of the repeating unit (C) is as follows: 13 13C-NMR (Nuclear Magnetic Resonance, NMR) and 1 It is measured using 1H-NMR.

[0076] Repeating units (C) can increase the degree of crosslinking of hydrocarbon resins. The higher the degree of crosslinking of a hydrocarbon resin, the better its thermal performance, thermal stability, and / or electrical performance.

[0077] If the content of repeating units (C) in the hydrocarbon resin is too low, for example less than about 8 mol%, the degree of crosslinking of the hydrocarbon resin will be low, and the thermal properties and / or electrical properties of the hydrocarbon resin will be insufficient. If the content of repeating units (C) in the hydrocarbon resin is too high, for example more than about 80 mol%, the processability of the hydrocarbon resin will be poor. In some embodiments, the hydrocarbon resin of the present disclosure may contain about 8 mol% to about 80 mol%, about 8 mol% to about 70 mol%, about 8 mol% to about 60 mol%, about 8 mol% to about 50 mol%, about 8 mol% to about 45 mol%, about 8 mol% to about 40 mol%, or about 8 mol% to about 35 mol% of repeating units (C). In some embodiments, the hydrocarbon resins of the present disclosure may contain about 8 mol%, about 9 mol%, about 10 mol%, about 11 mol%, about 12 mol%, about 16 mol%, about 20 mol%, about 30 mol%, about 32 mol%, about 35 mol%, about 40 mol%, or about 45 mol% of repeating units (C). In some embodiments, the total of repeating units (A) and repeating units (C) is about 8 mol% or more. In some embodiments, the total of repeating units (A) and repeating units (C) is about 13 mol% or more, or even more, about 15 mol% or more. Both repeating units (A) and repeating units (C) as described above affect the thermal properties and thermal stability of the hydrocarbon resin. The inventors have found that when the total of repeating units (A) and repeating units (C) is about 8 mol% or more, a hydrocarbon resin with excellent thermal properties and thermal stability can be provided.

[0078] In some embodiments, reactive double bonds may be present in hydrocarbon resins. As used herein, the term “reactive double bond” refers to a double bond in a repeating unit (A) or repeating unit (C) that is reactive with other compounds or polymers. For example, in some embodiments, the reactive double bond is: [ka] The double bond in the repeating unit (A) represented by, [ka] The repeating unit (C) represented by includes, but is not limited to, a double bond outside the benzene ring.

[0079] In some embodiments, the hydrogen atom content in the reactive double bonds of the hydrocarbon resin is less than 10%. If the hydrogen atom content in the reactive double bonds is too high, for example, more than 10%, the hydrocarbon resin becomes susceptible to oxidation during heating, resulting in insufficient electrical properties. In some embodiments, the hydrogen atom content in the reactive double bonds is greater than 2.2%. In other embodiments, the hydrogen atom content is in the range of 2.2% to 10%, or preferably 2.3% to 6.6%. If the hydrogen atom content is too low (e.g., less than 2.2%), the peel strength of the layer containing the hydrocarbon resin will be insufficient. In some embodiments, the hydrogen atom content in the reactive double bonds may be 2.3% to 10%, 2.3% to 9%, 2.3% to 7%, 2.3% to 6%, or 2.3% to 4%. When the hydrogen atom content in the reactive double bond falls within one of the above ranges, the hydrocarbon resin does not easily oxidize under high-temperature conditions (e.g., above 150°C), and the crosslinking reaction tends to be completed before oxidation occurs. Therefore, the electrical performance of the hydrocarbon resin can be improved.

[0080] In some embodiments, the number-average molecular weight (Mn) of the hydrocarbon resin can range from approximately 2,500 g / mol to approximately 13,000 g / mol, as measured by GPC. If the number-average molecular weight of the hydrocarbon resin is too high, the solubility of the hydrocarbon resin decreases.

[0081] The hydrocarbon resins of the present disclosure having the above characteristics have good thermal performance, thermal stability, and / or good electrical performance. For example, in some embodiments, the hydrocarbon resins of the present disclosure have a glass transition temperature above about 100°C, a dielectric constant (Dk) of less than about 3.4, a dielectric loss tangent (Df) of less than about 0.0030, a small difference in dielectric constant and / or dielectric loss tangent before and after the heating process, and / or a dielectric loss tangent of less than about 0.0020 after the heating process.

[0082] The Dk / Df of hydrocarbon resins is analyzed by a method that includes dissolving approximately 20 g of resin in approximately 20 g of toluene to form a mixture, immersing a glass fiber fabric in the mixture for approximately 16 hours to form a sample, and measuring the Dk / Df of the sample at 28 GHz using network analyzer software (Network analyzer Keysight, P5007A, SCR). The glass transition temperature of hydrocarbon resins is measured by dynamic mechanical analysis (DMA, TA / Q800).

[0083] Furthermore, the hydrocarbon resins of this disclosure also have good solubility and / or processability. Therefore, the hydrocarbon resins of this disclosure can readily dissolve in a solvent and form resin compositions having good thermal performance, thermal stability, good electrical performance, and / or good processability.

[0084] In one embodiment of this disclosure, the weight ratio of the hydrocarbon resin to the styrene copolymer (hydrocarbon resin:styrene copolymer) is 10:1 to 1:1. In some embodiments, the weight ratio of the hydrocarbon resin to the styrene copolymer of this disclosure may be 100:12, 100:14, 100:17, 100:19, 100:21, or 100:23. In some embodiments, the weight ratio of the hydrocarbon resin to the styrene copolymer of this disclosure may be 10:1 to 4:1 or 100:14 to 100:21. In embodiments where the weight ratio of the hydrocarbon resin to the styrene copolymer is within the above range, the resin composition may exhibit excellent dielectric and mechanical properties.

[0085] In some embodiments, the resin composition may further include additives for modifying the performance of the resin composition. In some embodiments, based on 100 parts by weight of the total hydrocarbon resin and styrene copolymer, the resin composition may contain about 0.1 to about 50 parts by weight of additives. The additives may be selected from the group consisting of reaction initiators, flame retardants, inorganic fillers, crosslinking aids, or combinations thereof. In this disclosure, reaction initiators, flame retardants, inorganic fillers, and crosslinking aids are not particularly limited.

[0086] In some embodiments, the reaction initiator may be a peroxide-type compound. Examples of reaction initiators include, but are not limited to, benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexine-3, di-t-butyl peroxide, t-butylcumyl peroxide, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumyl peroxide, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di(trimethylsilyl)peroxide, trimethylsilyltriphenylsilyl peroxide, or combinations thereof.

[0087] In some embodiments, the resin composition may contain about 0.1 to about 10 parts by weight of a reaction initiator, based on 100 parts by weight of the total hydrocarbon resin and styrene copolymer, but the disclosure is not limited thereto.

[0088] Examples of flame retardants include halogenated flame retardants (such as brominated flame retardants), phosphorus-based flame retardants, or other suitable flame retardants, or combinations thereof, but the disclosure is not limited to these. Examples of phosphorus-based flame retardants include phosphate esters (such as condensed phosphate esters and cyclic phosphate esters), phosphazene compounds (such as cyclic phosphazene compounds), phosphinate-based flame retardants (such as aluminum dialkyl phosphinates), melamine-based flame retardants (such as melamine phosphates and melamine polyphosphates), or other suitable flame retardants, or combinations thereof, but the disclosure is not limited to these.

[0089] In some embodiments, the resin composition may contain about 1 to about 20 parts by weight of a phosphorus-based flame retardant, based on 100 parts by weight of the total hydrocarbon resin and styrene copolymer, but is not limited thereto.

[0090] In this disclosure, a styrene copolymer may function as a phase solvent between the hydrocarbon resin and the inorganic filler to prevent phase separation problems, thereby resulting in excellent dielectric properties. Examples of inorganic fillers include, but are not limited to, silica, alumina, talc, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica, aluminum borate, barium sulfate, calcium carbonate, or other suitable materials, or any combination thereof. In some embodiments, the inorganic filler may be post-modified on its surface with vinyl functional groups. In certain embodiments, the amount of vinyl functional groups may range from about 0.1 to about 5 parts by weight, based on 100 parts by weight of the inorganic filler. In some embodiments, the inorganic filler may be silica post-modified with at least one functional group selected from the group consisting of vinyl groups, acrylate groups, methyl acrylate groups, thiol groups, and amino groups.

[0091] In some embodiments, the resin composition may contain about 10 to about 50 parts by weight of inorganic filler, based on 100 parts by weight of the total hydrocarbon resin and styrene copolymer, but the disclosure is not limited thereto. In some embodiments, the resin composition may contain about 20 to about 30 parts by weight of inorganic filler, based on 100 parts by weight of the total hydrocarbon resin and styrene copolymer.

[0092] Crosslinking agents can improve the thermal properties of resin compositions. Examples of crosslinking agents include, but are not limited to, triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), trimethyl isocyanurate (TMAIC), diallyl phthalate, or divinylbenzene (DVB), 1,2,4-trialyl trimellitate, or combinations thereof.

[0093] In some embodiments, the resin composition may contain about 1 to about 50 parts by weight of a crosslinking agent, based on 100 parts by weight of the total hydrocarbon resin and styrene copolymer, but is not limited thereto.

[0094] In some embodiments, the resin composition includes both a crosslinking aid and a reaction initiator, the reaction initiator being a peroxide-type compound. In these embodiments, the crosslinking aid is divinylbenzene, triallyl isocyanurate (TAIC), or a combination thereof, but is not limited to these.

[0095] The method for producing the resin composition is not particularly limited. In some embodiments, the resin composition can be prepared in a batch process by mixing a hydrocarbon resin, a styrene copolymer, and any additives (e.g., a crosslinking aid, a reaction initiator, or an inorganic filler) with an organic solvent. The organic solvent may be, for example, methyl ethyl ketone or toluene, but other suitable solvents may also be used. The mixing process can be carried out by either simultaneous or sequential addition of the components. In some embodiments, the mixing process is carried out using a suitable blender, selected according to the scale of production. In one embodiment, the mixing process is carried out at room temperature and continued until the components are sufficiently dispersed.

[0096] Embodiments of the present disclosure provide prepregs manufactured from any of the resin compositions described above. The method for manufacturing the prepreg is not particularly limited. In some embodiments, the prepreg is made from a mixture of a fibrous base material and one of the resin compositions described above, or from a mixture of a fibrous base material and a resin varnish containing one of the resin compositions described above. In some embodiments, the method for manufacturing the prepreg may include the steps of: providing a resin varnish containing one of the resin compositions described above; impregnating a fibrous base material with the resin varnish to form a mixture; and heating the mixture under desired heating conditions, for example, at about 100°C to about 180°C for about 1 minute to about 15 minutes, removing the solvent, and semi-curing the resin, thereby obtaining a semi-cured prepreg.

[0097] Examples of fibrous base materials include, but are not limited to, glass fiber fabrics, aramid fabrics, polyester fabrics, glass nonwovens, aramid nonwovens, polyester nonwovens, pulp paper, printer paper, other suitable materials, or any combination thereof. In some embodiments, the fibrous base material may be a glass fiber fabric having a dielectric loss tangent (Df) of 0.0030 or less.

[0098] In some embodiments, the resin varnish is prepared by a resin varnish preparation method, which comprises a dissolution step and a dispersion step. In some embodiments, the dissolution step includes dissolving a hydrocarbon resin, a styrene copolymer, and any additive soluble in an organic solvent in an organic solvent until completely dispersed. In some embodiments, the dispersion step includes adding any additive insoluble in an organic solvent (such as an inorganic filler) using a ball mill, bead mill, planetary mixer, roll mill, other suitable device, or a combination thereof, and dispersing until a predetermined dispersion state is reached.

[0099] The prepreg of this disclosure may have a dielectric loss tangent (Df) of less than 0.00200, and can be used to prepare a metal foil laminate having a dielectric loss tangent (Df) of less than 0.00200. In some embodiments, the prepreg of this disclosure may have a dielectric loss tangent (Df) of 0.00180 or less, and can be used to prepare a metal foil laminate having a dielectric loss tangent (Df) of 0.00180 or less. In some embodiments, the prepreg of this disclosure may have a dielectric loss tangent (Df) of 0.00170 or less, and can be used to prepare a metal foil laminate having a dielectric loss tangent (Df) of 0.00170 or less.

[0100] Embodiments of this disclosure provide resin-coated copper foil (RCC) manufactured from any of the resin compositions described above. The method for manufacturing the resin-coated copper foil is not particularly limited. In some embodiments, the resin-coated copper foil can be prepared by coating at least one surface of a metal foil with one of the resin compositions of this disclosure. In some embodiments, the resin-coated copper foil can be manufactured by a method comprising the steps of: providing a resin varnish containing one of the resin compositions described above; coating at least one surface of a metal foil with the resin varnish to form a resin layer; and curing the resin layer under desired heating conditions to obtain the resin-coated copper foil. In some embodiments, a well-known drying step may be performed after the curing step, if necessary. Examples of metal foils include, but are not limited to, copper foil.

[0101] The method for coating at least one surface of a metal foil with a resin composition or resin varnish is not particularly limited. Specifically, the coating method includes introducing the resin composition or resin varnish into a coater device and coating at least one surface of the metal foil with the resin composition or resin varnish to a desired thickness. Examples of coater devices include, but are not limited to, comma coaters, blade coaters, lip coaters, roll coaters, squeeze coaters, reverse coaters, transfer roll coaters, gravure coaters, and spray coaters.

[0102] The resin-coated copper foil of this disclosure comprises the resin composition of this disclosure, which exhibits superior thermal properties, uniformity, and mechanical properties compared to conventional metal foils.

[0103] Embodiments of this disclosure provide a metal foil laminated substrate including the above-described prepreg or resin-coated copper foil. In some embodiments, the metal foil laminated substrate may comprise one or more layers of resin-coated copper foil. In some embodiments, the metal foil laminated substrate may be a single-sided or double-sided metal-clad laminate obtained by laminating one or more layers of resin-coated copper foil. In some embodiments, the metal foil laminated substrate may comprise a prepreg having a structure in which metal foil is laminated on top of the prepreg or a prepreg stack, and the laminated structure is integrally laminated by hot press molding to obtain a single-sided or double-sided metal-clad laminate. In some embodiments, the metal foil laminated substrate may include copper foil.

[0104] The hot press conditions during hot press molding can be appropriately set based on the thickness of the metal foil laminate substrate to be manufactured and the type of resin composition used in the prepreg or resin-coated copper foil. For example, the hot press conditions can be set so that the temperature is approximately 170°C to 220°C, the pressure is approximately 1.0 MPa to 4.0 MPa, and the time is approximately 60 minutes to 180 minutes.

[0105] In some embodiments, the metal foil laminate has a difference in glass transition temperature (ΔTg) between thermal cycles of 4°C or less, as measured by tanδ in dynamic mechanical analysis (DMA). The term "ΔTg" is used as an indicator of uniformity in the metal foil laminate. A low ΔTg value indicates improved compatibility between components in the composition due to less difference in energy requirements for crosslinking reactions between different thermal cycles, imparting a high degree of uniformity to the prepreg and thereby contributing to the overall performance and reliability of the metal foil laminate. In some embodiments, the difference in glass transition temperature (ΔTg) between thermal cycles of the metal foil laminate is less than 4°C. In some embodiments, the difference in glass transition temperature (ΔTg) between thermal cycles of the metal foil laminate is less than 3°C. Furthermore, the metal foil laminate has a relative rate of change (ΔFWHM%) of the full width at half maximum of the tanδ peak between thermal cycles of 4% or less, as measured by dynamic mechanical analysis (DMA). The relative rate of change of the full width at half maximum (ΔFWHM%) also functions as an indicator of uniformity in a metal foil laminated substrate. The lower the value of ΔFWHM%, the higher the uniformity of the metal foil laminated substrate. In some embodiments, the full width at half maximum (FWHM) of the tanδ peak of the styrene copolymer is 4% or less. In some embodiments, the full width at half maximum (FWHM) of the tanδ peak of the styrene copolymer is 2% or less. In some embodiments, the full width at half maximum (FWHM) of the tanδ peak of the styrene copolymer is 1% or less.

[0106] One embodiment of the present disclosure provides a method for manufacturing a metal foil laminate. The method includes forming a mixture comprising a hydrocarbon resin and one of the styrene copolymers described above. [Examples]

[0107] One or more embodiments of the present disclosure are 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.

[0108] [Preparation of styrene copolymers (triblock) S1-S3] Under a high-purity nitrogen atmosphere, approximately 2 kg to 5 kg of cyclohexane / n-hexane mixed solvent, approximately 0.05 kg to 0.25 kg of styrene monomer, tetrahydrofuran, and ether derivatives are added to a 10 L polymerization reactor according to the desired molar ratio. Polymerization is initiated at room temperature by adding approximately 0.1 kg to 0.2 kg of n-butyllithium. After the completion of styrene block polymerization, approximately 0.5 kg to 0.9 kg of conjugated diene monomer (i.e., isoprene and / or butadiene) is introduced, and polymerization is continued at approximately 70°C. After the completion of conjugated diene block polymerization, an additional approximately 0.05 kg to 0.25 kg of styrene monomer is added to form terminal styrene blocks. Polymerization is stopped by adding a termination agent such as methanol or deionized water (DIW). The product is purified to remove residual monomers and impurities to obtain styrene copolymers S1 to S3. The product is characterized using NMR and GPC to verify its molecular structure and properties. The measured molecular structures and properties of styrene copolymers S1 to S3 are listed in Tables 1 to 3 below.

[0109] [Preparation of styrene copolymers (Diblock) S4-S7] Under a high-purity nitrogen atmosphere, approximately 2 kg to 5 kg of cyclohexane / n-hexane mixed solvent, approximately 0.1 kg to 0.5 kg of styrene monomer, tetrahydrofuran, and ether derivatives are added to a 10 L polymerization reactor according to the desired molar ratio. Polymerization is initiated at room temperature by adding approximately 0.1 kg to 0.2 kg of n-butyllithium. After the completion of styrene block polymerization, approximately 0.5 kg to 0.9 kg of conjugated diene monomer (i.e., isoprene and / or butadiene) is introduced, and polymerization is continued at approximately 70°C. Polymerization is stopped by adding a suitable termination agent such as methanol or deionized water (DIW). The product is purified to remove residual monomers and impurities to obtain styrene copolymers S4 to S7. The product is characterized using NMR and GPC, and its molecular structure and properties are verified. The measured molecular structures and properties of styrene copolymers S4 to S7 are listed in Tables 1 to 3 below.

[0110] [Styrene copolymer S0] R100 (product name: Ricon 100), purchased from Cray Valley, was used as the styrene copolymer S0. The type of styrene copolymer S0 is styrene-butadiene random copolymer (SBR). It has a number-average molecular weight (Mn) of 4,500 g / mol, a styrene content of 20 wt%, a glass transition temperature (Tg) of -22°C, and a vinyl content of 70 wt%. The molecular structure and properties of R100 are listed in Tables 1-3 below.

[0111] [Preparation of Styrene Copolymer (Diblock) S8] Under a high-purity nitrogen atmosphere, approximately 550 g of cyclohexane / n-hexane mixed solvent, approximately 18 g of styrene monomer, tetrahydrofuran, and ether derivatives are added to a 1.6 L polymerization reactor according to the desired molar ratio. Polymerization is initiated at approximately 30°C by adding approximately 9.4 g of 15% n-butyllithium. After styrene block polymerization is completed at approximately 30°C, approximately 27 g of styrene monomer and 44 g of butadiene are introduced, and polymerization is continued at approximately 10°C to approximately 30°C. Polymerization is stopped by adding a suitable termination agent such as methanol or deionized water (DIW). The product is purified to remove residual monomers and impurities to obtain styrene copolymer S8.

[0112] [Preparation of Styrene Copolymer (Diblock) S9] Under a high-purity nitrogen atmosphere, approximately 550 g of cyclohexane / n-hexane mixed solvent, approximately 28 g of styrene monomer, approximately 23 g of butadiene, tetrahydrofuran, and ether derivatives are added to a 1.6 L polymerization reactor according to the desired molar ratio. Polymerization is initiated at approximately 14°C by adding approximately 9.7 g of 15% n-butyllithium. After the polymerization of one segment is completed at approximately 14°C to 20°C, approximately 18 g of styrene monomer and approximately 23 g of butadiene are introduced, and polymerization is continued at approximately 13°C to 21°C. Polymerization is stopped by adding a suitable termination agent such as methanol or deionized water (DIW). The product is purified to remove residual monomers and impurities to obtain the styrene copolymer S9.

[0113] [Preparation of styrene copolymer (Diblock) S10] Under a high-purity nitrogen atmosphere, approximately 550 g of cyclohexane / n-hexane mixed solvent, approximately 50 g of styrene monomer, tetrahydrofuran, and an ether derivative are added to a 1.6 L polymerization reactor according to the desired molar ratio. Polymerization is initiated at room temperature by adding approximately 10.4 g of 15% n-butyllithium. After the polymerization of one segment is completed at approximately 25°C to 37°C, approximately 5 g of isoprene and approximately 45 g of butadiene are introduced, and polymerization is continued at approximately 23°C to 36°C. Polymerization is stopped by adding a suitable termination agent such as methanol or deionized water (DIW). The product is purified to remove residual monomers and impurities to obtain the styrene copolymer S10.

[0114] [Preparation of styrene copolymer (Diblock) S11] Under a high-purity nitrogen atmosphere, approximately 600 g of cyclohexane / n-hexane mixed solvent, approximately 50 g of styrene monomer, tetrahydrofuran, and an ether derivative are added to a 1.6 L polymerization reactor according to the desired molar ratio. Polymerization is initiated at approximately 21°C by adding approximately 11 g of n-butyllithium (15 wt%). After the completion of one-segment polymerization at approximately 39°C, approximately 15 g of myrcene and 35 g of butadiene are introduced, and polymerization is continued at approximately 38°C. Polymerization is stopped by adding a suitable termination agent such as methanol or deionized water (DIW). The product is purified to remove residual monomers and impurities to obtain styrene copolymer S11.

[0115] [Measured values ​​of number-average molecular weight (Mn), weight-average molecular weight (Mw), and polydispersity index (PDI) for styrene copolymers S0 to S11] Using polystyrene as a standard, the number-average molecular weight and polydispersity index (PDI) of styrene copolymers S0-S11 were measured. Approximately 5 mL of tetrahydrofuran (THF) was added to approximately 0.01 g of styrene copolymers S0-S11. After filtration through a 0.22 μm filter, the samples were analyzed using an instrument to obtain the weight-average molecular weight (Mw) and polydispersity index of styrene copolymers S1-S11, the number-average molecular weight (Mn) of styrene copolymer S0, and the number-average molecular weight (Mn) and polydispersity index of the hydrocarbon resin. The results are listed in Tables 2 and 4 below.

[0116] [Vinyl content, styrene unit content, and styrene block content of styrene copolymers S0-S11] The vinyl content and styrene unit content of styrene copolymers S0 to S11 are determined by proton nuclear magnetic resonance ( 1 The styrene block content of styrene copolymers S0 to S11 was also measured by 1H-NMR spectroscopy. 1 The measurement was performed by 1H-NMR spectroscopy. The NMR measurement method involves dissolving the styrene copolymers S0-S11 in a suitable solvent such as CDCl3 to obtain a homogeneous solution, and then using a 400 MHz spectrometer to measure proton nuclear magnetic resonance (NMR). 1 The procedure includes the steps of performing 1H NMR analysis and then analyzing the resulting spectrum. The results are listed in Tables 2 and 3 below.

[0117] [Measurement and calculation of the blockiness index of styrene copolymers S0 to S11] Styrene copolymers S0-S11 were dissolved in a suitable solvent such as CDCl3 to obtain a homogeneous solution. High-resolution NMR spectra were obtained using a 400 MHz proton nuclear magnetic resonance (NMR) spectrometer. 1 In the 1H NMR spectrum, the chemical shift region from 6.0 ppm to 6.95 ppm corresponds to aromatic protons in the styrene block segment. The integral value in this region was used to quantify the block content. The blockiness index (BI) for each styrene copolymer (S0 to S11) was measured using the following formula:

number

[0118] [Measurement of glass transition temperature (Tg) of styrene copolymers S0-S11] The glass transition temperatures (Tg) of styrene copolymers S0-S11 were measured using a differential scanning calorimeter (DSC, TA Instruments Discovery 2500) with a sample mass of approximately 3 mg under a nitrogen atmosphere. Before analysis, the thermal history of each sample was excluded by equilibrating at -100°C, heating to 60°C at a rate of 10°C / min, holding at 60°C for 1 minute, cooling again to -100°C at 10°C / min, and holding at -100°C for 1 minute. For the actual measurement, each sample was again equilibrated at -100°C and heated to 60°C at a rate of 10°C / min. The glass transition temperature (Tg) was measured according to ASTM D3418. The results are listed in Table 2 below.

[0119] [Measurement of the ring content (%) of styrene copolymers S0-S11] The ring content in the polybutadiene segments of styrene copolymers S0 to S11 is 1 Quantification was performed using 1H NMR spectra.

[0120] 1 In the 1H NMR spectrum, the chemical shift region between 5.6 ppm and 5.8 ppm corresponds to the vinyl portion of the ring structure within the polybutadiene segment. The integrated intensity of this region was used to quantify the ring content. The weight ratio of the ring structure to the butadiene units in each styrene copolymer (S0-S11) was measured using the following formula:

number

[0121] [Preparation of hydrocarbon resins] A crosslinked ring monomer compound, a monovinyl aromatic compound, a divinyl aromatic compound, and toluene were added to a two-necked flask to form a mixture in the proportions shown in Table 4. Next, the catalysts listed in Table 4 were added to the mixture. The mixture was stirred for approximately 3 hours at the reaction temperature shown in Table 4 to polymerize the crosslinked ring monomer, monovinyl aromatic compound, and divinyl aromatic compound. Ammonium hydroxide (NH4OH) was then added to the flask to stop the polymerization reaction. The resulting polymer solution was precipitated in isopropanol to obtain a white solid, which was filtered and dried under vacuum to obtain a hydrocarbon resin. [Table 4]

[0122] [Additives] Divinylbenzene (DVB) compound (trade name "DVB") purchased from Deltech is used as a crosslinking aid. α,α-bis(t-butylperoxy)diisopropylbenzene compound (trade name "PERBUTYL P") manufactured by NOF is used as a reaction initiator. Silica with post-modified vinyl functional groups on its surface (trade name "CSS-03C10V") purchased from Union Chemical Ind. Co. Ltd is used as an inorganic filler.

[0123] [Preparation of metal foil laminated substrates MC1, MC2, and ME1-ME10] The above materials were mixed in the ratios shown in Table 5 to form resin compositions RC1, RC2, and RE1-RE10. Here, the abbreviation "phr" represents "parts per 100 parts of resin". Next, each resin composition was mixed with approximately 50-60 parts by weight of toluene to prepare resin varnishes VC1, VC2, and VE1-VE10. Pieces of glass fiber fabric (Asahi 2116, 10 GHz, Dk / Df = 3.3 / 0.0030) were immersed in each resin varnish and baked at approximately 160°C-170°C for approximately 5-15 minutes to form prepregs PC1, PC2, and PE1-PE10. For lamination, high-temperature stretched copper foil was placed between two prepregs of the same type (PC1, PC2, or PE1-PE10). Next, the copper foil and prepreg were laminated at approximately 210°C for approximately 1 hour under a pressure of approximately 400 psi to obtain metal foil laminate substrates MC1, MC2, and ME1-ME10, respectively. The components of the resin compositions RC1, RC2, and RE1-RE10 are listed in Tables 5 and 6 below. [Table 5] [Table 6]

[0124] [Property measurement of metal foil laminated substrates MC1, MC2, and ME1-ME10] The glass transition temperatures (Tg) of metal foil laminates MC1, MC2, and ME1-ME10 were measured by dynamic mechanical analysis (DMA, TA / Q800). The glass transition temperatures (Tg) of metal foil laminates MC1, MC2, and ME1-ME10 were obtained from the tanδ peak of the DMA chart.

[0125] Rectangular specimens (10 mm × 6 mm) of metal foil laminated substrates MC1, MC2, and ME1-ME10 were tested in a three-point bending configuration at a frequency of 1 Hz with an amplitude within the linear viscoelastic region. The measurement procedure included isothermal holding at 0°C, heating to 270°C at 3°C / min (first heating), cooling to 0°C at 10°C / min, and reheating to 270°C at 3°C / min (second heating). The maximum value of the tanδ peak during each heating cycle was recorded as the glass transition temperature (Tg), and the difference in Tg values ​​(ΔTg) between thermal cycles was calculated using the following formula.

number

[0126] The full width at half maximum (FWHM) of the tanδ peaks of metal foil laminates MC1, MC2, ME1-ME5, and ME10 was measured by Gaussian fitting using OriginPro 2022b, and the relative rate of change (ΔFWHM%) of the tanδ peaks of metal foil laminates MC1, MC2, ME1-ME5, and ME10 was also calculated using the following formula.

number

[0127] The relative permittivity (Dk), dielectric loss tangent (Df), and RC% of metal foil laminated substrates MC1, MC2, and ME1-ME10 at 10 GHz were measured using network analyzer software (Network analyzer Keysight, P5007A, SCR). The dielectric loss tangent (Df) results are listed in Table 7 below.

number

[0128] In some embodiments, as shown in Table 7, metal foil laminates ME1 to ME10 exhibit lower Df values ​​at 10 GHz than those of metal foil laminates MC1 and MC2. In particular, the Df values ​​of ME1 to ME10 at 10 GHz are all less than 0.00200, and even lower than 0.0018. The Df values ​​of ME1 to ME9 at 10 GHz are 0.0017 or less, and the Df values ​​of ME2 to ME5 and ME8 at 10 GHz are even lower, less than 0.0016. That is, some of the metal foil laminates containing prepregs made from the styrene copolymer-containing resin compositions of this disclosure may have a dielectric loss tangent (Df) of 0.00180 or less, thereby exhibiting low dielectric loss. This demonstrates that the styrene copolymer itself can have a dielectric loss tangent (Df) of 0.00180 or less, and that a resin composition containing the copolymer, and a prepreg or resin-coated copper foil prepared from the resin composition, can also exhibit a dielectric loss tangent (Df) of 0.00180 or less.

[0129] In some embodiments, according to Table 7, metal foil laminates ME1 to ME9 exhibit lower ΔTg than metal foil laminates MC1 and MC2. In particular, the ΔTg values ​​of ME1 to ME9 are all less than 4.0, and all of them are even less than 3.8. The ΔTg values ​​of ME1 and ME4 to ME7 are less than 3.0, and the ΔTg value of ME4 is even lower, less than 1.0. That is, metal foil laminates containing prepregs made from resin compositions containing the styrene copolymer of this disclosure can exhibit high uniformity. This indicates that the styrene copolymer of this disclosure itself can have high uniformity, and that resin compositions containing the copolymer, and prepregs or resin-coated copper foils prepared from these resin compositions, can also exhibit high uniformity.

[0130] In some embodiments, as shown in Table 8, metal foil laminates ME1 to ME5 exhibit lower ΔFWHM% than metal foil laminates MC1 and MC2. In particular, the ΔFWHM% values ​​of ME1 to ME5 are all less than 4.0, and all of them are even less than 2. The ΔFWHM% values ​​of ME2 and ME4 to ME5 are less than 1.0, and the ΔFWHM% values ​​of ME2 and ME4 are even lower, less than 0.5. That is, metal foil laminates containing prepregs manufactured from the styrene copolymer-containing resin compositions of this disclosure can exhibit high uniformity.

[0131] Prepregs PC1, PC2, PE2, and PE10 were placed in a mold, and liquid epoxy resin was poured over them. The resin completely filled the pores and irregularities on the surface of the prepregs PC1, PC2, PE2, and PE10. The resin was then allowed to cure at room temperature, which typically took several hours. After complete curing, the samples were polished to a smooth surface using a series of sandpaper or grinding wheels, from coarse to fine. Polishing reduced micro-damage and scratches on the surface. A thin conductive coating of gold, carbon, or platinum was applied to the samples by vacuum deposition or sputter coating. The samples were then fixed to an SEM sample holder using conductive adhesive or carbon tape to ensure stability and good conductivity. SEM observation was performed using a JEOL JSM-IT200 instrument. Figures 1-4 are SEM images of prepregs PC1, PC2, PE2, and PE10. Specifically, Figure 1 is an SEM image of prepreg PC1 manufactured from resin composition RC1 containing styrene copolymer S0, Figure 2 is an SEM image of prepreg PC2 manufactured from resin composition RC2 containing styrene copolymer S1, Figure 3 is an SEM image of prepreg PE2 manufactured from resin composition RE2 containing styrene copolymer S5, and Figure 4 is an SEM image of prepreg PE10 manufactured from resin composition RE10 containing styrene copolymer S2.

[0132] As shown in Figure 3, the prepreg PE2 showed little aggregation and exhibited high uniformity, which corresponds to the ΔTg and ΔFWHM% results of the metal foil laminated substrate ME2. This indicates that the styrene copolymer itself can have high uniformity, and that the resin composition containing the copolymer, as well as the prepreg or resin-coated copper foil prepared from the resin composition, can also exhibit high uniformity.

[0133] While this disclosure has been described by example and in terms of preferred embodiments, it should be understood that this disclosure is not limited to the embodiments disclosed. In contrast, the present invention is intended to encompass a variety of modifications and similar arrangements. Accordingly, the appended claims should be consistent with the broadest interpretation to encompass all such modifications and similar arrangements.

Claims

1. Styrene units and, Conjugated diene units, A styrene copolymer containing, The styrene-based units are present in an amount of 20% to 60% by weight, based on the total weight of the styrene-based copolymer, and the styrene-based copolymer has a blockiness index of more than 55%.

2. The styrene copolymer according to claim 1, wherein the styrene copolymer is in a liquid state at 25°C.

3. The styrene copolymer according to claim 1, wherein the styrene copolymer has a weight-average molecular weight of 10,000 g / mol or less.

4. The styrene copolymer according to claim 1, wherein the styrene copolymer comprises two or three blocks.

5. The styrene copolymer according to claim 1, wherein the vinyl content of the conjugated diene units is more than 70% by weight, based on the total amount of the conjugated diene units.

6. The styrene copolymer according to claim 1, wherein the polydispersity index of the styrene copolymer is 1.0 to 1.

20.

7. The styrene copolymer according to claim 1, wherein the conjugated diene unit is selected from the group consisting of butadiene units, isoprene units, myrcene units, or combinations thereof.

8. The styrene copolymer according to claim 7, wherein the conjugated diene units include butadiene units, the butadiene units include a ring structure, and the ring content of the styrene copolymer is 14% or less based on the total amount of butadiene units.

9. The styrene copolymer according to claim 1, wherein the styrene-based unit is selected from the group consisting of styrene units, α-methylstyrene units, p-methylstyrene units, o-methylstyrene units, m-methylstyrene units, tert-butylstyrene units, vinyltoluene units, or combinations thereof.

10. The styrene copolymer according to claim 1, wherein the styrene units are present in an amount of less than 40% by weight, based on the total weight of the styrene copolymer.

11. The styrene copolymer according to claim 10, wherein the block-forming index of the styrene copolymer is 80% or more.

12. The styrene copolymer according to claim 11, wherein the styrene copolymer is a diblock copolymer.

13. The styrene copolymer according to claim 1, wherein the styrene units are present in an amount of 40% to 60% by weight, based on the total weight of the styrene copolymer.

14. The styrene copolymer according to claim 13, wherein the styrene copolymer is composed of a conjugated diene block and at least one styrene block, and the blockification index of the styrene copolymer is greater than 80%.

15. The styrene copolymer according to claim 13, wherein the styrene copolymer comprises at least one block containing styrene units and conjugated diene units, and the blockiness index of the styrene copolymer is in the range of more than 55% to 60%.

16. Styrene block and Conjugated diene block and A styrene copolymer containing, The styrene block content is in the range of 20% to 60% by weight based on the total weight of the styrene copolymer, and the styrene copolymer is a styrene copolymer having a glass transition temperature of -20°C or higher.

17. The styrene copolymer according to claim 16, wherein the styrene copolymer has a weight-average molecular weight of 10,000 g / mol or less.

18. The styrene copolymer according to claim 16, wherein the styrene copolymer comprises two or three blocks.

19. The styrene copolymer according to claim 16, wherein the conjugated diene block comprises a conjugated diene unit selected from the group consisting of butadiene units, isoprene units, myrcene units, or combinations thereof.

20. The styrene copolymer according to claim 19, wherein the conjugated diene block contains butadiene units, the butadiene units contain a ring structure, and the ring content of the styrene copolymer is 14% or less based on the total amount of butadiene units.

21. The styrene copolymer according to claim 19, wherein the vinyl content of the conjugated diene units is more than 70% by weight, based on the total amount of the conjugated diene units.

22. The styrene copolymer according to claim 16, wherein the styrene block comprises a styrene-based unit selected from the group consisting of styrene units, α-methylstyrene units, p-methylstyrene units, o-methylstyrene units, m-methylstyrene units, tert-butylstyrene units, vinyltoluene units, and combinations thereof.

23. The styrene copolymer according to claim 16, wherein the styrene copolymer contains styrene units, and the styrene units are present in an amount of less than 40% by weight based on the total weight of the styrene copolymer.

24. The styrene copolymer according to claim 23, wherein the block-forming index of the styrene copolymer is 80% or more.

25. The styrene copolymer according to claim 24, wherein the styrene copolymer is a diblock copolymer.

26. The styrene copolymer according to claim 16, wherein the styrene copolymer contains styrene units, and the styrene units are present in an amount of 40% to 60% by weight based on the total weight of the styrene copolymer.

27. The styrene copolymer according to claim 26, wherein the block-forming index of the styrene copolymer is greater than 80%.

28. The styrene copolymer according to claim 26, wherein the styrene copolymer comprises at least one block containing styrene units and conjugated diene units, and the blockiness index of the styrene copolymer is in the range of more than 55% to 60%.

29. A resin composition comprising the styrene copolymer described in claim 1.

30. The resin composition according to claim 29, further comprising a hydrocarbon resin, wherein the weight ratio of the hydrocarbon resin to the styrene copolymer is 10:1 to 1:

1.

31. A prepreg manufactured from the resin composition described in claim 29.

32. A metal foil laminated substrate comprising the prepreg described in claim 31.

33. The metal foil laminated substrate according to claim 32, wherein the metal foil laminated substrate has a difference in glass transition temperature (ΔTg) between thermal cycles of 4°C or less.

34. The metal foil laminated substrate according to claim 32, wherein the metal foil laminated substrate has a relative rate of change (ΔFWHM%) of the full width at half maximum of the tanδ peak between thermal cycles of 4% or less.

35. A resin-coated copper foil manufactured from the resin composition described in claim 29.

36. A metal foil laminate substrate comprising the resin-coated copper foil described in claim 35.

37. A resin composition comprising the styrene copolymer described in claim 16.

38. A prepreg manufactured from the resin composition described in claim 37.

39. A metal foil laminated substrate comprising the prepreg described in claim 38.

40. A resin-coated copper foil manufactured from the resin composition described in claim 37.

41. A metal foil laminate substrate comprising the resin-coated copper foil described in claim 40.

42. A method for producing a metal foil laminate, comprising forming a mixture containing a hydrocarbon resin and the styrene copolymer described in claim 1.

43. A method for manufacturing a metal foil laminate, comprising forming a mixture containing a hydrocarbon resin and the styrene copolymer described in claim 16.

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