Polymer composite, use thereof, low dielectric resin composition, prepreg, and metal foil laminated board

Abstract

To provide a polymer composite for preparing a low dielectric resin composition having a dielectric loss tangent (Df) that is less than or equal to 0.00200.SOLUTION: A polymer composite includes a first styrene-based copolymer having a weight average molecular weight that is lower than 20,000 g / mol and a second styrene-based copolymer having a weight average molecular weight that is higher than 20,000 g / mol, wherein the weight ratio of the first styrene-based copolymer to the second styrene-based copolymer is from 5 / 95 to 95 / 5.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] Cross - reference to Related Applications This application claims the benefit of U.S. Provisional Patent Application No. 63 / 589,732, filed on October 12, 2023, which is hereby incorporated herein by reference in its entirety.

[0002] The present invention relates to polymer composites, their uses, low - dielectric resin compositions, prepregs, and metal - foil laminates. Specifically, the present invention relates to polymer composites containing two styrene - based copolymers, their uses, low - dielectric resin compositions, prepregs, and metal - foil laminates.

Background Art

[0003] The fifth - generation (abbreviated as 5G) mobile network technology is the latest generation of mobile communication technology. The 5G mobile network technology has the characteristics of high - speed transmission, wide - range connection, and low latency. The 5G mobile communication technology can be divided into three types: high - frequency 5G, mid - frequency 5G, and low - frequency 5G according to the frequency bands used. High - frequency 5G can achieve ultra - high - speed connection speeds.

[0004] However, in high - frequency 5G, during the process of signal transmission and reception, the quality of signal transmission and reception can be affected by high - frequency path loss, conductor loss, and dielectric loss. Therefore, it is necessary to develop a copper - clad laminate (CCL) material with low dielectric loss to reduce the dielectric loss during the process of signal transmission and reception in high - frequency 5G and improve the quality of signal transmission and reception.

[0005] The purpose of reducing dielectric loss can be achieved by lowering the dielectric properties (dielectric constant (Dk) and / or dielectric tangent (Df)) of the metal - foil substrate material. In addition to the need for dielectric properties, general compositions also face difficulties in terms of processability and fluidity. This low fluidity makes the filling performance insufficient and renders the product unusable. Therefore, materials and their resin compositions with lower dielectric loss and better processing performance are still in demand.

Summary of the Invention

Problems to be Solved by the Invention

[0006] In view of the above problems, the present disclosure provides a polymer composite used to produce a low-dielectric resin composition having a low dielectric tangent (Df), a low-dielectric resin composition containing the same, a prepreg manufactured from the low-dielectric resin composition, and a metal foil laminate containing the prepreg.

Means for Solving the Problems

[0007] Embodiments of the present disclosure provide a polymer composite used to produce a low-dielectric resin composition having a dielectric tangent (Df) of 0.00200 or less. The polymer composite includes a first styrenic copolymer having a weight average molecular weight of less than 20,000 g / mol and a second styrenic copolymer having a weight average molecular weight of greater than 20,000 g / mol, and the weight ratio of the first styrenic copolymer to the second styrenic copolymer is from 5 / 95 to 95 / 5.

[0008] Embodiments of the present disclosure provide a polymer composite used to produce a low-dielectric resin composition having a dielectric tangent (Df) of 0.00200 or less. The polymer composite includes a first styrenic copolymer that is liquid at 25°C and a second styrenic copolymer that is solid at 25°C, and the weight ratio of the first styrenic copolymer to the second styrenic copolymer is from 5 / 95 to 95 / 5.

[0009] Embodiments of the present disclosure provide a method of using a polymer composite, the method including the step of making a mixture containing a hydrocarbon resin used to produce a metal foil laminate having a dielectric tangent (Df) of 0.00200 or less using the polymer composite. The polymer composite includes a first styrenic copolymer having a weight average molecular weight of less than 20,000 g / mol and a second styrenic copolymer having a weight average molecular weight of greater than 20,000 g / mol, and the weight ratio of the first styrenic copolymer to the second styrenic copolymer is from 5 / 95 to 95 / 5.

[0010] Embodiments of the present disclosure provide a low dielectric resin composition. The low dielectric resin composition includes a first styrenic copolymer having a weight average molecular weight of less than 20,000 g / mol and a second styrenic copolymer having a weight average molecular weight of greater than 20,000 g / mol. The weight ratio of the first styrenic copolymer to the second styrenic copolymer is from 5 / 95 to 95 / 5, and the low dielectric resin composition has a dissipation factor (Df) of 0.00200 or less.

[0011] Embodiments of the present disclosure provide a low dielectric resin composition. The low dielectric resin composition includes a first styrenic copolymer that is liquid at 25°C and a second styrenic copolymer that is solid at 25°C. The weight ratio of the first styrenic copolymer to the second styrenic copolymer is from 5 / 95 to 95 / 5, and the low dielectric resin composition has a dissipation factor (Df) of 0.00200 or less.

[0012] Embodiments of the present disclosure provide a low dielectric resin composition. The low dielectric resin composition includes a hydrocarbon resin, a first styrenic copolymer having a weight average molecular weight of less than 20,000 g / mol, and a second styrenic copolymer having a weight average molecular weight of greater than 20,000 g / mol.

[0013] Embodiments of the present disclosure provide a low dielectric resin composition. The low dielectric resin composition includes a hydrocarbon resin, a first styrenic copolymer that is liquid at 25°C, and a second styrenic copolymer that is solid at 25°C.

[0014] Embodiments of the present disclosure provide a prepreg manufactured from a low dielectric resin composition including a polymer composite. The polymer composite includes a first styrenic copolymer having a weight average molecular weight of less than 20,000 g / mol and a second styrenic copolymer having a weight average molecular weight of greater than 20,000 g / mol. The weight ratio of the first styrenic copolymer to the second styrenic copolymer is from 5 / 95 to 95 / 5.

[0015] Embodiments of the present disclosure provide a prepreg manufactured from a low dielectric resin composition containing a polymer composite. The polymer composite includes a first styrenic copolymer that is liquid at 25°C and a second styrenic copolymer that is solid at 25°C, and the weight ratio of the first styrenic copolymer to the second styrenic copolymer is from 5 / 95 to 95 / 5.

[0016] Embodiments of the present disclosure provide a prepreg manufactured from a low dielectric resin composition. The low dielectric resin composition includes a hydrocarbon resin, a first styrenic copolymer having a weight average molecular weight of less than 20,000 g / mol, and a second styrenic copolymer having a weight average molecular weight of greater than 20,000 g / mol.

[0017] Embodiments of the present disclosure provide a prepreg manufactured from a low dielectric resin composition. The low dielectric resin composition includes a hydrocarbon resin, a first styrenic copolymer that is liquid at 25°C, and a second styrenic copolymer that is solid at 25°C.

[0018] Embodiments of the present disclosure provide a metal foil laminate. The metal foil laminate includes a prepreg manufactured from a low dielectric resin composition containing a polymer composite. The polymer composite includes a first styrenic copolymer having a weight average molecular weight of less than 20,000 g / mol and a second styrenic copolymer having a weight average molecular weight of greater than 20,000 g / mol, and the weight ratio of the first styrenic copolymer to the second styrenic copolymer is from 5 / 95 to 95 / 5.

[0019] Embodiments of the present disclosure provide a metal foil laminate. The metal foil laminate includes a prepreg manufactured from a low dielectric resin composition containing a polymer composite. The polymer composite includes a first styrenic copolymer that is liquid at 25°C and a second styrenic copolymer that is solid at 25°C, and the weight ratio of the first styrenic copolymer to the second styrenic copolymer is from 5 / 95 to 95 / 5.

[0020] Embodiments of the present disclosure provide a metal foil laminate. The metal foil laminate includes a prepreg manufactured from a low dielectric resin composition. The low dielectric resin composition includes a hydrocarbon resin, a first styrene copolymer having a weight average molecular weight of less than 20,000 g / mol, and a second styrene copolymer having a weight average molecular weight of greater than 20,000 g / mol.

[0021] Embodiments of the present disclosure provide a metal foil laminate. The metal foil laminate includes a prepreg manufactured from a low dielectric resin composition. The low dielectric resin composition includes a hydrocarbon resin, a first styrene copolymer that is liquid at 25°C, and a second styrene copolymer that is solid at 25°C.

Brief Description of the Drawings

[0022] The present invention can be more fully understood by reading the following detailed description and examples with reference to the accompanying drawings.

Figure 1

Modes for Carrying Out the Invention

[0023] As used herein, the terms “comprise” and / or “include” are intended to indicate the presence of the recited features, integers, steps, operations, components, elements, and / or groups thereof, and do not preclude the presence or addition of one or more other features, integers, steps, operations, components, elements, and / or groups thereof. It should be further understood that, unless otherwise specified in the context, the singular forms “a,” “an,” and “the” as used in the specification are intended to include the plural forms as well.

[0024] The terms "first", "second", etc. may be used herein to describe various components, elements, regions, layers, and / or positions, but it should be understood that these components, elements, regions, layers, and / or positions should not be limited by these terms. These terms are used to distinguish one component, element, region, layer, or position from another, but do not imply an order of the necessary elements.

[0025] As used herein, it should be understood that the terms "about", "approximately", "substantially" generally indicate a given numerical value or a value within a range that varies within 20%, preferably within 10%, preferably within 5%, or within 3%, or within 2%, or within 1%, or within 0.5%. The given numerical values herein are approximate values, that is, even if "about", "approximately" or "substantially" is not explicitly stated, the meaning of "about", "approximately" or "substantially" may be included. Further, it should be further understood that the numerical values shown herein include not only the aforementioned numerical values, but also deviation values within the range of deviations acceptable to those of ordinary skill in the art. It should be understood that the expression "a~b" or "a to b" used herein to indicate a specific range of numerical values is defined as "≧a and ≦b".

[0026] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms as defined in commonly used dictionaries should be interpreted to have a meaning consistent with the relevant technology, context or background of this disclosure, and should not be interpreted in an idealized or overly formal sense unless explicitly defined herein. Hereinafter, descriptions of known functions and structures that may unnecessarily obscure this disclosure are omitted.

[0027] The term "C" used herein1-20 "Alkyl group" refers to a monovalent group of a linear, branched, or cyclic aliphatic hydrocarbon having 1 to 20 carbon atoms in the carbon main chain. As used herein, the term "C 1-4 alkyl group" refers to a monovalent group of a linear, branched, or cyclic aliphatic hydrocarbon having 1 to 4 carbon atoms in the carbon main chain. C 1-20 Examples of C alkyl groups include, but are not limited to, methyl group, ethyl group, propyl group, iso-butyl group, sec-butyl group, tert-butyl group, pentyl group, iso-amyl group, hexyl group, decyl group, dodecyl group, cyclohexyl group, cyclooctyl group, and cyclododecyl group. C 1-4 Examples of C alkyl groups include, but are not limited to, methyl group, ethyl group, and propyl group.

[0028] As used herein, the term "C 2-20 alkenyl group" refers to a monovalent group of a linear, branched, or cyclic aliphatic hydrocarbon having 2 to 20 carbon atoms and at least one carbon-carbon double bond in the carbon main chain. C 2-20 Examples of alkenyl groups include, but are not limited to, ethenyl group, propenyl group, isobutenyl group, sec-butenyl group, tert-butenyl group, pentenyl group, isopentenyl group, hexenyl group, decenyl group, dodecenyl group, pentadecenyl group, cyclohexenyl group, cyclooctenyl group, cyclopentenyl group, cyclopentadienyl group, and cyclopentadecenyl group.

[0029] As used herein, the term "C 1-20 "Carboxylate group having an alkyl chain group" refers to a group having the following structure.

[0030]

Chemical formula

[0031] Among these, "*" represents the connection position to another group, and R 1 represents a C 1-20 alkyl group, and R2 is a single bond or C 1-20 represents an alkyl group, and R 1 and R 2 The total number of carbon atoms in the carbon main chain of the alkyl groups of is 1 to 20.

[0032] Embodiments of the present disclosure provide a polymer composite used to produce a low dielectric resin composition having a dielectric tangent (Df) of 0.00200 or less. The polymer composite includes a first styrenic copolymer and a second styrenic copolymer different from the first styrenic copolymer, and the weight ratio of the first styrenic copolymer to the second styrenic copolymer is from 5 / 95 to 95 / 5. In some embodiments, the weight ratio of the first styrenic copolymer to the second styrenic copolymer can be in the range of 10 / 90 to 90 / 10, 20 / 80 to 80 / 20, or 25 / 75 to 80 / 20. In some embodiments, the weight ratio of the first styrenic copolymer to the second styrenic copolymer can be 5 / 95, 10 / 90, 15 / 85, 20 / 80, 25 / 75, 30 / 70, 35 / 65, 40 / 60, 45 / 55, 50 / 50, 55 / 45, 60 / 40, 65 / 35, 70 / 30, 75 / 25, 80 / 20, 85 / 15, 90 / 10, or 95 / 5, but the present disclosure is not limited thereto.

[0033] In some embodiments, the weight average molecular weight of the first styrenic copolymer is less than 20,000 g / mol, and the weight average molecular weight of the second styrenic copolymer is greater than 20,000 g / mol, but the present disclosure is not limited thereto. In some embodiments, the first styrenic copolymer is a liquid at 25°C and the second styrenic copolymer is a solid at 25°C.

[0034] In embodiments where the weight average molecular weight of the first styrenic copolymer is less than 20,000 g / mol and the weight average molecular weight of the second styrenic copolymer is greater than 20,000 g / mol, the molecular weight of the first styrenic copolymer is measured by gel permeation chromatography (GPC). In some embodiments, the weight average molecular weight of the first styrenic copolymer may be less than 10,000 g / mol, whereby the processability and fluidity in the copper-clad laminate (CCL) manufacturing process are improved. In some embodiments, the weight average molecular weight of the first styrenic copolymer can be in the range of 5,000 g / mol or more and less than 10,000 g / mol. In some embodiments, the weight average molecular weight of the first styrenic copolymer can be in the range of from 5,000 g / mol to 9,000 g / mol, from 5,000 g / mol to 8,000 g / mol, from 5,000 g / mol to 7,000 g / mol, or from 5,000 g / mol to 6,000 g / mol. In some embodiments, the weight average molecular weight of the first styrenic copolymer can be in the range of from 5,000 g / mol to 8,000 g / mol.

[0035] In embodiments where the first styrenic copolymer is liquid at 25 °C and the second styrenic copolymer is solid at 25 °C, the weight average molecular weight of the first styrenic copolymer may be less than 20,000 g / mol. In some embodiments, the weight average molecular weight of the first styrenic copolymer may be less than 10,000 g / mol, whereby the processability and fluidity in the copper-clad laminate (CCL) manufacturing process are improved. In some embodiments, the weight average molecular weight of the first styrenic copolymer can be in the range of 5,000 g / mol or more and less than 10,000 g / mol. In some embodiments, the weight average molecular weight of the first styrenic copolymer can be in the range of from 5,000 g / mol to 9,000 g / mol, from 5,000 g / mol to 8,000 g / mol, from 5,000 g / mol to 7,000 g / mol, or from 5,000 g / mol to 6,000 g / mol. In some embodiments, the weight average molecular weight of the first styrenic copolymer can be in the range of from 5,000 g / mol to 8,000 g / mol.

[0036] In some embodiments of the present disclosure, the polydispersity index (PDI) of the first styrenic copolymer is in the range of 1.0 to 1.1, and the polydispersity index (PDI) is measured by gel permeation chromatography (GPC).

[0037] The first styrenic copolymer may have a styrene block (as a hard segment) and a soft segment. The hard segment provides a higher Tg and contributes to the strength, hardness, and high-temperature performance of the first styrenic copolymer. The soft segment has several functional groups (such as vinyl groups) used for curing and contributes to the elasticity, toughness, and resilience of the first styrenic copolymer. In some embodiments, with the total weight of the first styrenic copolymer being 100 wt%, the first styrenic copolymer may contain 10 - 90 wt% of the hard segment and 90 - 10 wt% of the soft segment. Examples of the soft segment are butadiene blocks and isoprene blocks, but the present disclosure is not limited thereto.

[0038] In an embodiment where the first styrenic copolymer contains a butadiene block and a styrene block as soft segments, the weight ratio of the styrene block to the butadiene block may be from 10:90 to 90:10. In some embodiments, the weight ratio of the styrene block to the butadiene block may be from 10:90 to 80:20, from 10:90 to 70:30, from 10:90 to 60:40, or from 10:90 to 50:50, but the present disclosure is not limited thereto. In some embodiments, the weight ratio of the styrene block to the butadiene block is from 10:90 to 50:50. In the present disclosure, the above-mentioned weight ratio of the styrene block to the butadiene block is measured by proton nuclear magnetic resonance ( 1 1H-NMR) method.

[0039] The butadiene block may contain only the 1,2-bond structure represented by formula (1), or may contain the 1,2-bond structure represented by formula (1) and the 1,4-bond structure represented by formula (2).

[0040]

Chemical formula

[0041] In some embodiments, in the butadiene block, the molar ratio of the 1,2-bond structure represented by formula (1) to the 1,4-bond structure represented by formula (2) may be from 50:50 to 100:0. In embodiments where the molar ratio of the 1,2-bond structure represented by formula (1) to the 1,4-bond structure represented by formula (2) of the first styrenic copolymer is within the above range, the first styrenic copolymer has a high cure density. Therefore, the thermal properties of the first styrenic copolymer can be improved. In some embodiments, in the butadiene block, the molar ratio of the 1,2-bond structure represented by formula (1) to the 1,4-bond structure represented by formula (2) may be from 3:1 to 99:1. In some embodiments, in the butadiene block, the molar ratio of the 1,2-bond structure represented by formula (1) to the 1,4-bond structure represented by formula (2) may be from 3:1 to 7:1, thereby providing excellent thermal performance. In some embodiments, the first styrenic copolymer is a styrene-butadiene-styrene triblock copolymer (SBS), and in the butadiene block, the molar ratio of the 1,2-bond structure represented by formula (1) to the 1,4-bond structure represented by formula (2) may be from 5:1 to 7:1. In the present disclosure, the molar ratio of formula (1) to formula (2) is measured by proton nuclear magnetic resonance ( 1 1H-NMR) method.

[0042] The first styrenic copolymer may be a styrene block copolymer or a styrene random copolymer. In some embodiments, the first styrenic copolymer is a styrene block copolymer having less than 50 wt% of random copolymer repeating units, with the total weight of the first styrene block copolymer being 100 wt%, thereby providing excellent electrical performance. In some embodiments, the first styrenic copolymer may be a styrene block copolymer selected from the group consisting of styrene-butadiene block copolymer (SB), styrene-butadiene-styrene triblock copolymer (SBS), and butadiene-styrene-butadiene triblock copolymer (BSB), or any combination thereof, although the present disclosure is not limited thereto. In some embodiments, the first styrenic copolymer may be a styrene-butadiene-styrene triblock copolymer (SBS) or a styrene-butadiene diblock copolymer (SB). In some embodiments, the first styrenic copolymer may be a styrene-butadiene-styrene triblock copolymer (SBS). In some embodiments, the first styrenic copolymer may be a styrene-butadiene-styrene triblock copolymer (SBS) that is liquid at 25°C.

[0043] In some embodiments, in the embodiment where the first styrenic copolymer is a styrene-butadiene-styrene triblock copolymer (SBS), the molar ratio of the 1,2-bond structure represented by formula (1) to the 1,4-bond structure represented by formula (2) in the butadiene block of the styrene-butadiene-styrene triblock copolymer (SBS) may be from 3:1 to 7:1.

[0044] In some embodiments, the first styrenic copolymer can be prepared using the methods described in JP-A-1994-192502, JP-A-2000-514122, or JP-A-2007-302901, but the present disclosure is not limited thereto. In some embodiments, the first styrenic copolymer can be prepared by a method for preparing the first styrenic copolymer. The method for preparing the first styrenic copolymer may include introducing a first styrene monomer and reacting the first styrene monomer to form a first styrene block, introducing a butadiene monomer and reacting the butadiene monomer to form a butadiene block bonded to the first styrene block, and optionally introducing a second styrene monomer and reacting the second styrene monomer to form a second styrene block connected to the butadiene block. In some embodiments, the method for preparing the first styrenic copolymer may further include a step of purifying the first styrene monomer, the second styrene monomer, and the butadiene monomer under an inert atmosphere before the introduction. In some embodiments, the method for preparing the first styrenic copolymer may further include a termination step after obtaining the first styrenic copolymer having a desired weight average molecular weight.

[0045] The above-described first styrenic copolymer has high fluidity. Therefore, the processability of the polymer composite containing the same can be improved. In addition, the short molecular chains of the first styrenic copolymer can act as a buffer during impact, so that the toughening effect of the product made from the polymer composite containing the same is increased.

[0046] In embodiments where the weight average molecular weight of the first styrenic copolymer is less than 20,000 g / mol and the weight average molecular weight of the second styrenic copolymer is greater than 20,000 g / mol, the molecular weight of the second styrenic copolymer is measured by gel permeation chromatography (GPC). In some embodiments, the weight average molecular weight of the second styrenic copolymer can be in the range greater than 20,000 g / mol and less than 80,000 g / mol. In some embodiments, the weight average molecular weight of the second styrenic copolymer can be in the range from 40,000 g / mol to 78,000 g / mol, from 40,000 g / mol to 60,000 g / mol, from 40,000 g / mol to 70,000 g / mol, or from 40,000 g / mol to 50,000 g / mol. In some embodiments, the weight average molecular weight of the second styrenic copolymer can be in the range from 40,000 g / mol to 60,000 g / mol.

[0047] In embodiments where the first styrenic copolymer is a liquid at 25°C and the second styrenic copolymer is a solid at 25°C, the weight average molecular weight of the second styrenic copolymer may be greater than 20,000 g / mol. In some embodiments, the weight average molecular weight of the second styrenic copolymer can be in the range greater than 20,000 g / mol and less than 80,000 g / mol. In some embodiments, the weight average molecular weight of the second styrenic copolymer can be in the range from 40,000 g / mol to 78,000 g / mol, from 40,000 g / mol to 70,000 g / mol, from 40,000 g / mol to 60,000 g / mol, or from 40,000 g / mol to 50,000 g / mol. In some embodiments, the weight average molecular weight of the second styrenic copolymer can be in the range from 40,000 g / mol to 60,000 g / mol.

[0048] The second styrenic copolymer may have a styrene block (as a hard segment) and a soft segment. The hard segment provides a higher Tg and contributes to the strength, hardness, and high-temperature performance of the second styrenic copolymer. The soft segment has several functional groups (such as vinyl groups) used for curing and contributes to the elasticity, toughness, and resilience of the second styrenic copolymer. In some embodiments, with the total weight of the second styrenic copolymer being 100 wt%, the second styrenic copolymer may contain 10 - 90 wt% of the hard segment and 90 - 10 wt% of the soft segment. An example of the soft segment is a butadiene block or an isoprene block, but the present disclosure is not limited thereto.

[0049] In an embodiment where the second styrenic copolymer contains a butadiene block as the soft segment and a styrene block as the hard segment, the weight ratio of the styrene block to the butadiene block may be from 10:90 to 90:10. In some embodiments, the weight ratio of the styrene block to the butadiene block may be from 10:90 to 80:20, from 10:90 to 70:30, from 10:90 to 60:40, from 20:80 to 80:20, from 30:70 to 80:20, or from 40:60 to 80:20, but the present disclosure is not limited thereto. In some embodiments, the weight ratio of the styrene block to the butadiene block is from 10:90 to 50:50. In the present disclosure, the above-described weight ratio of the styrene block to the butadiene block is measured by proton nuclear magnetic resonance ( 1 1H-NMR) method.

[0050] In an embodiment where the second styrenic copolymer contains a butadiene block as the soft segment, the butadiene block may contain only the 1,2-bond structure represented by the above formula (1) or may contain the 1,2-bond structure represented by the above formula (1) and the 1,4-bond structure represented by the above formula (2).

[0051] In some embodiments, in the butadiene block, the molar ratio of the 1,2-bond structure represented by formula (1) to the 1,4-bond structure represented by formula (2) may be from 50:50 to 100:0. In embodiments where the molar ratio of the 1,2-bond structure represented by formula (1) to the 1,4-bond structure represented by formula (2) in the second styrenic copolymer is within the above range, the second styrenic copolymer has a high cure density. Thus, the thermal properties of the second styrenic copolymer can be improved. In some embodiments, in the butadiene block, the molar ratio of the 1,2-bond structure represented by formula (1) to the 1,4-bond structure represented by formula (2) may be from 80:20 to 99:1. In some embodiments, in the butadiene block, the molar ratio of the 1,2-bond structure represented by formula (1) to the 1,4-bond structure represented by formula (2) may be from 5:1 to 7:1. In the present disclosure, the molar ratio of formula (1) to formula (2) is measured by proton nuclear magnetic resonance ( 1 1H-NMR) method.

[0052] The second styrenic copolymer may be a styrene block copolymer or a styrene random copolymer. In some embodiments, the second styrenic copolymer is a styrene block copolymer having less than 50 wt% of random copolymer repeating units, with the total weight of the second styrene block copolymer being 100 wt%. In some embodiments, the second styrenic copolymer may be a styrene block copolymer selected from the group consisting of styrene-butadiene block copolymer (SB), styrene-butadiene-styrene triblock copolymer (SBS), and butadiene-styrene-butadiene triblock copolymer (BSB), or any combination thereof, but the present disclosure is not limited thereto. In some embodiments, the second styrenic copolymer may be a styrene-butadiene-styrene triblock copolymer (SBS) having a weight average molecular weight of less than 80,000 g / mol. In some embodiments, the second styrenic copolymer may be a styrene-butadiene-styrene triblock copolymer (SBS) that is solid at 25°C.

[0053] In some embodiments, the second styrenic copolymer may have a viscosity in the range of 54.4 Pa·s or more and less than 521.4 Pa·s. In some embodiments, the viscosity of the second styrenic copolymer may be in the range of 114.8 Pa·s to 327.4 Pa·s, thereby providing excellent mechanical properties. The viscosity is measured with a rheometer and shall follow the method described below. A sample with a concentration of 35 wt% is prepared in methyl ethyl ketone (MEK), and the shear rate parameter is set at 50 s -1 at 25 °C.

[0054] In some embodiments, the second styrenic copolymer can be prepared using a method substantially similar to the method for preparing the first styrenic copolymer, and thus will not be repeated here.

[0055] The second styrenic copolymer has high molecular entanglements. The second styrenic copolymer may have desirable thermal and physical properties. Thus, the thermal and physical properties of the polymer composite containing this can be improved.

[0056] The polymer composite of the present disclosure including the above-described first styrenic copolymer and second styrenic copolymer can provide a low dielectric resin composition with a low dielectric tangent (Df) by blending a hydrocarbon resin. In some embodiments, the weight ratio of the first styrenic copolymer to the second styrenic copolymer can be in the range of 5 / 95 to 95 / 5, 10 / 90 to 90 / 10, 20 / 80 to 80 / 20, or 25 / 75 to 80 / 20. In some embodiments, the weight ratio of the first styrenic copolymer to the second styrenic copolymer can be 5 / 95, 10 / 90, 15 / 85, 20 / 80, 25 / 75, 30 / 70, 35 / 65, 40 / 60, 45 / 55, 50 / 50, 55 / 45, 60 / 40, 65 / 35, 70 / 30, 75 / 25, 80 / 20, 85 / 15, 90 / 10, or 95 / 5, but the present disclosure is not limited thereto. In some embodiments, the polymer composite of the present disclosure can also improve the thermal properties and / or mechanical properties of the low dielectric resin composition containing the hydrocarbon resin while preventing embrittlement during the use of the hydrocarbon resin. Thus, in some embodiments, the low dielectric resin composition and the hydrocarbon resin containing the polymer composite of the present disclosure can have good thermal properties and / or mechanical properties (high peel strength).

[0057] The polymer composite of the present disclosure can be used to manufacture a metal foil laminate having a dielectric tangent (Df) of 0.00200 or less. Specifically, the polymer composite of the present disclosure can provide a low dielectric tangent (Df) low dielectric resin composition that can be used to manufacture a metal foil laminate by blending a hydrocarbon resin. In some embodiments, the metal foil laminate includes a glass fiber cloth having a dielectric tangent (Df) of 0.0030 or less.

[0058] Embodiments of the present disclosure provide a low dielectric resin composition. In some embodiments, the low dielectric resin composition may include the polymer composite and the poly(arylene ether) compound described above. In some embodiments, the low dielectric resin composition does not include a poly(arylene ether) compound. In the present disclosure, the poly(arylene ether) compound may be a polymer containing a plurality of units represented by the following formula (3).

[0059] [Chemical formula]

[0060] Among these, in each structural unit, each R 3 is independently hydrogen or a C 1-4 alkyl group, and "*" represents the connection position for connecting to other groups.

[0061] The low dielectric resin composition of the present disclosure includes a hydrocarbon resin, a first styrenic copolymer, and a second styrenic copolymer. In some embodiments, the weight average molecular weight of the first styrenic copolymer is less than 20,000 g / mol, and the weight average molecular weight of the second styrenic copolymer is greater than 20,000 g / mol, but the present disclosure is not limited thereto. In some embodiments, the first styrenic copolymer is liquid at 25°C, and the second styrenic copolymer is solid at 25°C. In some embodiments, the hydrocarbon resin, the first styrenic copolymer, and the second styrenic copolymer can be separated from each other by a general purification method.

[0062] In some embodiments, the low dielectric resin composition contains more than 53 wt% of a hydrocarbon resin, based on the total weight of the low dielectric resin composition. In some embodiments, the low dielectric resin composition contains more than 57 wt% of a hydrocarbon resin, based on the total weight of the low dielectric resin composition. In some embodiments, the low dielectric resin composition contains more than 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 60 wt%, 61 wt% or 62 wt% of a hydrocarbon resin, based on the total weight of the low dielectric resin composition.

[0063] In some embodiments, based on 100 parts by weight of the hydrocarbon resin, the low dielectric resin composition may contain from 1 to 50 parts by weight of a first styrenic copolymer and from 1 to 50 parts by weight of a second styrenic copolymer. In some embodiments, based on 100 parts by weight of the hydrocarbon resin, the low dielectric resin composition may contain more than 1 part by weight and less than 50 parts by weight of a first styrenic copolymer, and more than 1 part by weight and less than 50 parts by weight of a second styrenic copolymer. In some embodiments, based on 100 parts by weight of the hydrocarbon resin, the low dielectric resin composition may contain from 4 to 40 parts by weight of a first styrenic copolymer and from 2 to 20 parts by weight of a second styrenic copolymer. In some embodiments, based on 100 parts by weight of the hydrocarbon resin, the low dielectric resin composition may contain from 4 to 20 parts by weight of a first styrenic copolymer and from 2 to 17 parts by weight of a second styrenic copolymer.

[0064] The weight ratio of the total of the first styrenic copolymer and the second styrenic copolymer of the hydrocarbon resin is in the range greater than 100 / 50 and less than or equal to 100 / 10. The weight ratio of the total of the first styrenic copolymer and the second styrenic copolymer of the hydrocarbon resin is in the range greater than 100 / 35 and less than or equal to 100 / 10. In embodiments where the weight ratio of the total of the first styrenic copolymer and the second styrenic copolymer of the hydrocarbon resin is within the above range, the low dielectric resin composition exhibits mechanical strength (peel strength). In some embodiments, the weight ratio of the total of the first styrenic copolymer and the second styrenic copolymer of the hydrocarbon resin may be from 100 / 45 to 100 / 10, from 100 / 40 to 100 / 15, from 100 / 35 to 100 / 20, or from 100 / 34 to 100 / 20. In some embodiments, the weight ratio of the total of the first styrenic copolymer and the second styrenic copolymer of the hydrocarbon resin may be 100 / 21.

[0065] The weight ratio of the first styrenic copolymer and the second styrenic copolymer can be in the range from 5 / 95 to 95 / 5, from 10 / 90 to 90 / 10, from 20 / 80 to 80 / 20, or from 25 / 75 to 80 / 20. In some embodiments, the weight ratio of the first styrenic copolymer and the second styrenic copolymer may be 5 / 95, 10 / 90, 15 / 85, 20 / 80, 25 / 75, 30 / 70, 35 / 65, 40 / 60, 45 / 55, 50 / 50, 55 / 45, 60 / 40, 65 / 35, 70 / 30, 75 / 25, 80 / 20, 85 / 15, 90 / 10, or 95 / 5, but the present disclosure is not limited thereto.

[0066] Since the first styrenic copolymer and the second styrenic copolymer contained in the low dielectric resin composition are substantially the same as the first styrenic copolymer and the second styrenic copolymer contained in the polymer composite described above, they will not be repeated here.

[0067] The hydrocarbon resin contained in the low dielectric resin composition may contain a repeating unit (A) derived from a bridged ring monomer compound, a repeating unit (B) derived from a monovinyl aromatic compound, and a repeating unit (C) derived from a divinyl aromatic compound. In some embodiments, taking all the units in the hydrocarbon resin as 100 mol%, the hydrocarbon resin may contain 0 to 40 mol% of the repeating unit (A) derived from the bridged ring monomer compound, 15 to 92 mol% of the repeating unit (B) derived from the monovinyl aromatic compound, and 8 to 80 mol% of the repeating unit (C) derived from the divinyl aromatic compound.

[0068] As used herein, the term "bridged ring monomer compound" refers to a compound having a bridged ring structure and capable of forming a polymer by polymerization with the same or different compounds. The bridged ring structure refers to a structure having at least two carbon rings and sharing two carbon atoms that are not directly connected. In some embodiments, the bridged ring structure in the bridged ring monomer compound may contain 3 to 12 ring atoms and 1 to 2 double bonds. In some embodiments, the bridged ring structure may be unsubstituted. In some embodiments, at least one hydrogen atom in the bridged ring structure is substituted with at least one substituent selected from the group consisting of a C 1-20 alkyl group, a C 2-20 alkenyl group, and a carboxylate group having a C 1-20 alkyl chain group. In some embodiments, the bridged ring structure may have at least two substituents. The at least two substituents are a C 1-20 alkyl group, a C 2-20 alkenyl group, and a C 1-20Any two substituents may be selected from the group consisting of carboxylate groups having an alkyl chain group. Among at least two substituents, adjacent substituents may together form a ring. Examples of the bridged-ring monomer compound include, but are not limited to, norbornene (NB), dicyclopentadiene (DCPD), dicycloheptadiene (NBD), 5-acetyl-2-norbornene, methyl 5-norbornene-2-carboxylate, vinyl norbornene, ethylidene-norbornene, or combinations thereof.

[0069]

Chemical formula

[0070] The repeating unit (A) derived from the bridged-ring monomer compound contains a bridged-ring structure derived from the bridged-ring monomer compound. Thus, the repeating unit (A) may contain a bridged-ring structure having 3 to 12 ring atoms and 0 to 1 double bond. In some embodiments, the repeating unit (A) may have the following structure, but the present disclosure is not limited thereto.

[0071]

Chemical formula

[0072] In the above structure, “*” represents a linking position for linking with other groups. Compared with the linear repeating unit, the repeating unit (A) having a bridged ring structure has higher rigidity. Therefore, the glass transition of the hydrocarbon resin can be increased, or the thermal performance of the hydrocarbon resin can be improved. If the content of the repeating unit (A) in the hydrocarbon resin is too high, for example, exceeding 40 mol%, the cost-effectiveness of the hydrocarbon resin will decrease. In some embodiments, the hydrocarbon resin of the present disclosure may contain the repeating unit (A) in an amount of 0 to 38 mol%, 0 to 30 mol%, 0 to 25 mol%, 0 to 20 mol%, 20 to 40 mol%, 20 to 38 mol%, 20 to 30 mol%, or 20 to 25 mol%. In some embodiments, the hydrocarbon resin of the present disclosure may contain the repeating unit (A) in an amount of 3 mol%, 5 mol%, 7 mol%, 9 mol%, 10 mol%, 20 mol%, 22 mol%, 25 mol%, 30 mol%, 32 mol%, 35 mol%, or 38 mol%.

[0073] As used herein, the term “monovinyl aromatic compound” refers to a compound containing a carbocyclic aromatic structure, wherein one hydrogen at the ring carbon atom of the carbocyclic aromatic structure is substituted with a vinyl group. In some embodiments, the vinyl group may be unsubstituted. In some embodiments, at least one hydrogen atom in the vinyl group may be substituted with a C 1-20 alkyl group. 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 at the ring carbon atom in the carbocyclic aromatic structure may be substituted with a C 1-20 alkyl group. Examples of monovinyl aromatic compounds include, but are not limited to, styrene, methylstyrene, ethylstyrene (EVB), or any combination thereof.

[0074] The repeating unit (B) derived from a monovinyl aromatic compound contains a carbocyclic aromatic structure derived from the monovinyl aromatic compound. For example, in some embodiments, the repeating unit (B) may have the following structure, but the present disclosure is not limited thereto.

[0075]

Chemical formula

[0076] In the above structure, "*" represents the linking position to be linked to another group.

[0077] The repeating unit (B) can increase the solubility of the hydrocarbon resin in a solvent such as toluene. If the content of the repeating unit (B) in the hydrocarbon resin is too low, for example less than 15 mol%, the solubility of the hydrocarbon resin in the solvent will be low. If the content of the repeating unit (B) in the hydrocarbon resin is too high, for example more than 92 mol%, other properties of the hydrocarbon resin such as thermal properties may deteriorate. In some embodiments, the hydrocarbon resin of the present disclosure may contain 15 to 92 mol% of the repeating unit (B). In some embodiments, the hydrocarbon resin polymer of the present disclosure may contain 20 to 92 mol%, 20 to 90 mol%, 25 to 85 mol%, 30 to 80 mol%, 35 to 80 mol%, 40 to 80 mol%, or 45 to 80 mol% of the repeating unit (B). In some embodiments, the hydrocarbon resin polymer of the present disclosure may contain 46 mol%, 48 mol%, 50 mol%, 55 mol%, 60 mol%, 67 mol%, 72 mol%, 76 mol%, or 78 mol% of the repeating unit (B).

[0078] As used herein, the term "divinyl aromatic compound" refers to a compound containing a carbocyclic aromatic structure, and two hydrogens or ring carbon atoms on the ring carbon atoms of the carbocyclic aromatic structure are substituted with vinyl groups. In some embodiments, the vinyl group may be unsubstituted. In some embodiments, at least one hydrogen atom in the vinyl group is C 1-20It may be substituted with an alkyl group. 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 at the ring carbon atoms in the carbocyclic aromatic structure is C 1-20 It may be substituted with an alkyl group. Examples of the divinyl aromatic compound include, but are not limited to, divinylbenzene (DVB), diisopropenylbenzene, or any combination thereof.

[0079] The repeating unit (C) derived from the divinyl aromatic compound contains a carbocyclic aromatic structure derived from the divinyl aromatic compound. In some embodiments, the repeating unit (C) may contain a crosslinked unit and a non-crosslinked unit. In some embodiments, the repeating unit (C) may contain a crosslinked unit shown below, but the present disclosure is not limited thereto.

[0080] [Chemical formula]

[0081] In some embodiments, the repeating unit (C) may contain a non-crosslinked unit shown below, but the present disclosure is not limited thereto.

[0082] [Chemical formula]

[0083] In the above structure, "*" represents the connection position to be connected to other groups.

[0084] 3 The degree of crosslinking of the repeating unit (C) is measured by using 13C-NMR (nuclear magnetic resonance, NMR) and 1-H-NMR and using a sample prepared in CDCl [Formula]

[0085] In some embodiments, the crosslinking degree of the repeating unit (C) is 0.2 to 0.6. The crosslinking degree in this range contributes to excellent thermal and electrical properties and does not cause processability problems. The higher the crosslinking degree of the hydrocarbon resin, the better the thermal performance, thermal stability and / or electrical performance of the hydrocarbon resin composition. However, when the crosslinking degree exceeds 0.6, its processability will deteriorate. In some embodiments, the crosslinking degree of the repeating unit (C) may be 0.2 to 0.5. In some embodiments, the crosslinking degree of the repeating unit (C) may be 0.3, 0.35, 0.4, or 0.45, but the present disclosure is not limited thereto.

[0086] The repeating unit (C) can increase the crosslinking degree of the hydrocarbon resin. The higher the crosslinking degree of the hydrocarbon resin, the better the thermal performance, thermal stability and / or electrical performance of the hydrocarbon resin. If the content of the repeating unit (C) in the hydrocarbon resin is too low, for example, less than 8 mol%, the crosslinking degree of the hydrocarbon resin will be low, and the thermal performance and / or electrical performance of the hydrocarbon resin will be poor. If the content of the repeating unit (C) in the hydrocarbon resin is too high, for example, more than 80 mol%, the processability of the hydrocarbon resin will decrease. In some embodiments, the hydrocarbon resin of the present disclosure may contain 8-80 mol%, 8-70 mol%, 8-60 mol%, 8-50 mol%, 8-45 mol%, 8-40 mol%, or 8-35 mol% of the repeating unit (C). In some embodiments, the hydrocarbon resin of the present disclosure may contain 8 mol%, 9 mol%, 10 mol%, 11 mol%, 12 mol%, 16 mol%, 20 mol%, 30 mol%, 32 mol%, 35 mol%, 40 mol%, or 45 mol% of the repeating unit (C). In some embodiments, the total of the repeating unit (A) and the repeating unit (C) is 8 mol% or more. In some embodiments, the total of the repeating unit (A) and the repeating unit (C) is 13 mol% or more, or, by extension, 15 mol% or more. As described above, both the repeating unit (A) and the repeating unit (C) affect the thermal properties and thermal stability of the hydrocarbon resin. The inventors have found that when the total of the repeating unit (A) and the repeating unit (C) is 8 mol% or more, the hydrocarbon resin has excellent thermal properties and thermal stability is provided.

[0087] In some embodiments, reactive double bonds may be included in the hydrocarbon resin. As used herein, the term "reactive double bond" refers to a double bond in the repeating unit (A) or the repeating unit (C) that can react with other compounds or polymers. For example, in some embodiments, reactive double bonds include double bonds in the repeating unit (A) shown below and double bonds in the repeating unit (C) shown below that are not in the benzene ring, but the present disclosure is not limited thereto.

[0088]

Chem.

[0089] In some embodiments, the content of hydrogen atoms in the reactive double bonds in the hydrocarbon resin is less than 10%. If the content of hydrogen atoms in the reactive double bonds in the hydrocarbon resin is too high, for example, more than 10%, the hydrocarbon resin is likely to be oxidized during the heating process, and as a result, the electrical properties of the hydrocarbon resin will deteriorate. In some embodiments, the content of hydrogen atoms in the reactive double bonds in the hydrocarbon resin is more than 2.2%. In some embodiments, the content of hydrogen atoms in the reactive double bonds in the hydrocarbon resin ranges from more than 2.2% and less than 10%. In some embodiments, the content of hydrogen atoms in the reactive double bonds in the hydrocarbon resin ranges from 2.3% or more and less than 6.6%. If the content of hydrogen atoms in the reactive double bonds in the hydrocarbon resin is too low, for example, less than 2.2%, the peel strength of the layer containing the hydrocarbon resin will become excessively small. In some embodiments, the content of hydrogen atoms in the reactive double bonds in the hydrocarbon resin may be 2.3% - 10%, 2.3% - 10%, 2.3% - 9%, 2.3% - 7%, 2.3% - 6%, or 2.3 - 4%. When the content of hydrogen atoms in the reactive double bonds in the hydrocarbon resin is within the above range, it is less likely to be oxidized in a high-temperature environment (for example, exceeding 150°C), and tends to complete the cross-linking reaction before being oxidized. Therefore, the electrical performance of the hydrocarbon resin can be improved. In some embodiments, the number average molecular weight (Mn) of the hydrocarbon resin may be 2,500 - 13,000 g / mol, as measured by gel permeation chromatography (GPC). If the number average molecular weight of the hydrocarbon resin is too high, the solubility of the hydrocarbon resin will decrease.

[0090] The hydrocarbon resin of the present disclosure having the above characteristics has good thermal performance, thermal stability, and / or good electrical performance. For example, in some embodiments, the hydrocarbon resin of the present disclosure has a glass transition temperature higher than 100 °C, a dielectric constant (Dk) of less than about 3.4, a dielectric tangent (Df) of less than about 0.0030, a small difference in dielectric constant and / or dielectric tangent before and after the heating process, and / or a dielectric tangent after the heating process of less than about 0.0020. The Dk / Df of the hydrocarbon resin is analyzed by a method including the steps of dissolving 20 g of the resin in 20 g of toluene to form a mixture, immersing a glass fiber cloth in the mixture for 16 hours to form a sample, and measuring the Dk / Df of the sample at 28 GHz by network analyzer software (network analyzer Keysight, P5007A, SCR). The glass transition temperature of the hydrocarbon resin is measured by dynamic mechanical analysis (DMA, TA / Q800). Furthermore, the hydrocarbon resin of the present disclosure also has good solubility and / or processability. Therefore, the hydrocarbon resin of the present disclosure can easily dissolve in a solvent and form a resin composition having good thermal performance, thermal stability, good electrical performance, and / or good processability.

[0091] In some embodiments, the low dielectric resin composition may further include an additive for modifying the performance of the low dielectric resin composition. In some embodiments, with the total of the hydrocarbon resin, the first styrene copolymer, and the second styrene copolymer being 100 parts by weight, the low dielectric resin composition may contain 1 to 50 parts by weight of the additive. The additive may be selected from the group consisting of initiators, flame retardants, inorganic fillers, and crosslinking aids, or any combination thereof. In the present disclosure, the initiator, flame retardant, inorganic filler, and crosslinking aid are not particularly limited.

[0092] Examples of 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)hexyne-3, di-t-butyl peroxide, t-butyl cumene peroxide, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumyl peroxide, di-t-butyl peroxydiisophthalate, t-butyl peroxybenzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di(trimethylsilyl) peroxide, trimethylsilyl triphenylsilyl peroxide, or any combination thereof. In some embodiments, the initiator is a peroxide-type compound. In some embodiments, based on a total of 100 parts by weight of the hydrocarbon resin, the first styrenic copolymer, and the second styrenic copolymer, the low dielectric resin composition may contain 1 to 10 parts by weight of the initiator, but the present disclosure is not limited thereto.

[0093] Examples of flame retardants include, but are not limited to, halogen-based flame retardants (e.g., bromine-based flame retardants), phosphorus-based flame retardants, or other suitable retardants, or any combination thereof. Examples of phosphorus-containing flame retardants include phosphate esters (e.g., condensed phosphate esters and cyclic phosphate esters), phosphazene compounds (e.g., cyclic phosphazene compounds), phosphinate-based flame retardants (e.g., aluminum dialkylphosphinate), melamine-based flame retardants (e.g., melamine phosphate and melamine polyphosphate), or other suitable retardants, or any combination thereof. In some embodiments, based on a total of 100 parts by weight of the hydrocarbon resin, the first styrenic copolymer, and the second styrenic copolymer, the low dielectric resin composition may contain 1 to 20 parts by weight of the phosphorus-containing flame retardant, but the present disclosure is not limited thereto.

[0094] In some embodiments of the present disclosure, examples of inorganic fillers may include silica, alumina, talc, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica, aluminum borate, barium sulfate, calcium carbonate, or other suitable materials, or any combination thereof, but the present disclosure is not limited thereto. In some embodiments, the inorganic filler is silica. In some embodiments, based on a total of 100 parts by weight of the hydrocarbon resin, the first styrenic copolymer, and the second styrenic copolymer, the low dielectric resin composition may contain 10 to 50 parts by weight of the inorganic filler, but the present disclosure is not limited thereto.

[0095] The crosslinking aid can enhance the thermal properties of the low dielectric resin composition. Examples of crosslinking aids include triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), trimethallyl isocyanurate (TMAIC), diallyl phthalate, or divinylbenzene, 1,2,4-triallyl trimellitate, or any combination thereof, but the present disclosure is not limited thereto. In some embodiments, the low dielectric resin composition contains a crosslinking aid and an initiator, and the initiator is a peroxide-type compound. In some embodiments, the crosslinking aid is divinylbenzene, triallyl isocyanurate (TAIC), or a combination thereof, but the present disclosure is not limited thereto. In some embodiments, the crosslinking aid is divinylbenzene. In some embodiments, based on a total of 100 parts by weight of the hydrocarbon resin, the first styrenic copolymer, and the second styrenic copolymer, the low dielectric resin composition may contain 1 to 50 parts by weight of the crosslinking agent, but the present disclosure is not limited thereto.

[0096] The method for manufacturing the low dielectric resin composition in the present disclosure is not particularly limited. In some embodiments, the low dielectric resin composition is prepared by mixing a hydrocarbon resin, a first styrenic copolymer, a second styrenic copolymer, and optionally added additives in an organic solvent in a batch manner. In some embodiments, the organic solvent may include methyl ethyl ketone, toluene, or a combination thereof, but the present disclosure is not limited thereto.

[0097] The mixing process can be carried out simultaneously or sequentially, but the present disclosure is not limited thereto. In some embodiments, the mixing process is carried out using a suitable mixer selected according to the amount of the low dielectric resin composition to be prepared, but the present disclosure is not limited thereto. In some embodiments, the mixing process is carried out at room temperature and is completed when the hydrocarbon resin, the first styrenic copolymer, the second styrenic copolymer, and the optionally added additives are completely dispersed.

[0098] The low dielectric resin composition of the present disclosure has a dissipation factor (Df) of 0.00200 or less. The low dielectric resin composition of the present disclosure can be used to manufacture a metal foil laminate having a dissipation factor (Df) of 0.00200 or less.

[0099] Embodiments of the present disclosure provide a prepreg manufactured from the low dielectric resin composition described above. That is, embodiments of the present disclosure provide a prepreg manufactured from a low dielectric resin composition including the above-described hydrocarbon resin and a polymer composite including a first styrenic copolymer and a second styrenic copolymer. In some embodiments, the weight ratio of the first styrenic copolymer to the second styrenic copolymer is from 5 / 95 to 95 / 5. In some embodiments, the weight average molecular weight of the first styrenic copolymer is less than 20,000 g / mol, and the weight average molecular weight of the second styrenic copolymer is greater than 20,000 g / mol, but the present disclosure is not limited thereto. In some embodiments, the first styrenic copolymer is liquid at 25°C and the second styrenic copolymer is solid at 25°C.

[0100] The method for producing the prepreg is not particularly limited. In some embodiments, the prepreg is made from a mixture of a fiber substrate and the above low-dielectric resin composition, or a resin varnish containing the above low-dielectric resin composition. In some embodiments, the prepreg is produced by a prepreg production method. The prepreg production method includes a step of preparing a resin varnish containing a low-dielectric resin composition, a step of making a mixture by immersing a fiber substrate in the resin varnish, and a step of heating the mixture to 100 to 180 °C to remove the solvent and obtain a semi-cured prepreg.

[0101] In some embodiments, the resin varnish is prepared by a resin varnish preparation method. The resin varnish preparation method includes a dissolution step and a dispersion step. In some embodiments, the dissolution step includes dissolving a hydrocarbon resin, a first styrene copolymer, a second styrene copolymer, and an additive optionally added to be soluble in an organic solvent until they are completely dispersed. In some embodiments, the dispersion step includes adding and dispersing an additive (for example, an inorganic filler) that is insoluble in the organic solvent using a ball mill, a bead mill, a planetary mixer, a roll mill, or other suitable device, or any combination thereof, until a predetermined dispersion state is achieved.

[0102] Examples of the fiber substrate include glass fiber cloth, aramid cloth, polyester cloth, glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, pulp paper, printer paper, or other suitable materials, or any combination thereof, but the present disclosure is not limited thereto. In some embodiments, the fiber substrate is a glass fiber cloth having a dissipation factor (Df) of 0.0030 or less.

[0103] The prepreg of the present disclosure has a dissipation factor (Df) of 0.00200 or less and can be used to produce a metal foil laminate having a dissipation factor (Df) of 0.00200 or less.

[0104] Embodiments of the present disclosure provide a metal foil laminate including the above prepreg. In some embodiments, a metal foil laminate having a dissipation factor (Df) of 0.0020 or less is manufactured by making a mixture containing a hydrocarbon resin using the above-described polymer composite. In some embodiments, the metal foil laminate has a structure in which the metal foil is laminated on the upper surfaces of both the prepreg and the prepreg laminate, and the laminated structure is integrally laminated by hot press molding to obtain a double-sided metal-clad or single-sided metal-clad laminate. In some embodiments, the hot press conditions for complete curing can be appropriately set according to the thickness of the metal foil laminate to be made, the type of hydrocarbon resin composition used for the prepreg, and the like. For example, the hot press conditions can be set such that the temperature is 170 to 220°C, the pressure is 1.0 to 4.0 MPa, and the time is 60 to 180 minutes.

[0105] FIG. 1 is a schematic view of a metal foil laminate 10 according to an embodiment of the present disclosure. As shown, the metal foil laminate 10 includes a base 101, a polymer layer 103 disposed on the base 101, and an adhesive layer 105 disposed between the base 101 and the polymer layer 103. The adhesive layer 105 connects the substrate 101 and the polymer layer 103. The polymer layer 103 may include the above-described prepreg. The metal foil laminate including the above-described prepreg may have a dissipation factor (Df) of 0.00200 or less. In some embodiments, the metal foil laminate including the above-described prepreg may have excellent thermal properties, thermal stability, mechanical properties (high peel strength), and / or reliability.

[0106] In some embodiments, the base 101 may include a metal layer. In some embodiments, the base 101 may include a copper foil. In some embodiments, the adhesive layer 105 may include any material capable of connecting the substrate 101 and the polymer layer 103. In some embodiments, the adhesive layer 105 may include a silane-based adhesive.

[0107] One or more embodiments of the present disclosure will be described in detail with reference to the following examples. However, these examples are merely used to illustrate the embodiments of the present disclosure and are not intended to limit the scope of the embodiments of the present disclosure.

[0108] [Preparation of Hydrocarbon Resins HC1-5]

[0109] A bridged-ring monomer compound, a monovinyl aromatic compound, and a divinyl aromatic compound, and toluene were added to a two-necked flask to form a mixture in the ratios shown in Table 1 below. The catalyst shown in Table 1 was added to the mixture. The mixture was stirred at the reaction temperature shown in Table 1 below for 3 hours to polymerize the bridged-ring monomer compound, the monovinyl aromatic compound, and the divinyl aromatic compound. Ammonium hydroxide (NH 4 OH) was added to the two-necked flask to terminate the polymerization reaction. The polymer solution obtained by the polymerization reaction was dropped into isopropanol to obtain a white solid. The white solid was filtered and dried under vacuum to obtain hydrocarbon resins HC1-5.

[0110] [Measurement of Hydrogen Atom Content in Reactive Double Bonds]

[0111] Hydrocarbon resins HC1-5 were dissolved in deuterated chloroform (CDCl 3 ). The hydrogen atom content in the reactive double bonds of hydrocarbon resins HC1-5 was measured by NMR (JEOL, JNM-ECZ400S / L1), respectively. Specifically, the hydrogen atom content in the reactive double bonds was calculated by dividing the total integral value of the number of hydrogen atoms in the reactive double bonds by the total integral value of all hydrogen atoms of hydrocarbon resins HC1-5.

[0112] [Measurement of Number Average Molecular Weight (Mn) and Polymer Dispersity Index (PDI)]

[0113] Using polystyrene as a reference material, the number-average molecular weight and the polymer dispersity index (PDI) of hydrocarbon resins HC1-5 were measured by gel permeation chromatography (GPC) (Waters APC, column: Waters Acquity XT 900).

[0114] 5 mL of tetrahydrofuran (THF) was added to 0.01 g of each of hydrocarbon resins HC1-5 to obtain samples of hydrocarbon resins HC1-5. After filtering the samples of hydrocarbon resins HC1-5 through a 0.22 μm filter, they were analyzed by an instrument to obtain the number-average molecular weight (Mn) and the polymer dispersity index (PDI) of hydrocarbon resins HC1-5. The results of the measured properties of hydrocarbon resins HC1-5 are shown in Table 1 below.

[0115] [Table 1]

[0116] [Preparation of Examples E1-E13 and Comparative Examples C1 and C2]

[0117] Materials

[0118] Hydrocarbon resin: the above hydrocarbon resins HC1-5

[0119] First styrenic copolymer

[0120] Ricon-100: a styrene-butadiene random copolymer (SBR) manufactured by Cray Valley. The number-average molecular weight of Ricon-100 is 4,500 Da, the viscosity is 40,000 cps at 45 °C, the styrene content is 17-27 wt%, the 1,2-vinyl content is 70 wt%, Tg is -22 °C, and the specific gravity is 0.92 g / cm at 25 °C 3 .

[0121] SBS-L: The weight-average molecular weight of styrene-butadiene-styrene triblock copolymer (SBS) is 6,000 Da, and the PDI is 1.04. The molar ratio of the 1,2-bond structure to the 1,4-bond structure in the butadiene block of SBS-L is from 5:1 to 7:1, and the weight ratio of the styrene block to the butadiene block is from 10:90 to 50:50.

[0122] The second styrenic copolymer

[0123] SBS-1: The weight-average molecular weight of styrene-butadiene-styrene triblock copolymer (SBS) is 80,000 Da, and the viscosity is 521.4 Pa·s. The molar ratio of the 1,2-bond structure to the 1,4-bond structure in the butadiene block of SBS-1 is from 5:1 to 7:1, and the weight ratio of the styrene block to the butadiene block is 50:50.

[0124] SBS-2: The weight-average molecular weight of styrene-butadiene-styrene triblock copolymer (SBS) is 40,000 Da, and the viscosity is 114.8 Pa·s. The molar ratio of the 1,2-bond structure to the 1,4-bond structure in the butadiene block of SBS-2 is from 5:1 to 7:1, and the weight ratio of the styrene block to the butadiene block is 50:50.

[0125] Crosslinking aid: A divinylbenzene compound manufactured by Deltech, trade name "DVB".

[0126] Initiator: An α,α-bis(t-butylperoxy) diisopropylbenzene compound manufactured by NOF, trade name "PERBUTYLP".

[0127] Additive - Inorganic filler: A silica filler manufactured by Admatch, trade name "SS-10".

[0128] Preparation of metal foil laminates of Examples E1 to E13 and Comparative Examples C1 and C2 and measurement of Dk / Df

[0129] The above materials were mixed with 50 to 60 parts by weight of toluene at the ratios shown in Tables 2 to 7 below to prepare the resin varnishes of Examples E1 to E13 and Comparative Examples C1 and C2. The abbreviation "phr" means "parts per 100 parts of resin". Two glass fiber cloths (Asahi 2116, Dk / Df = 3.3 / 0.0030 @ 10 GHz) were immersed in the resin varnishes of Examples E1 to E13 and Comparative Examples C1 and C2, and baked at 160 to 170 °C for 5 to 15 minutes to form two layers of polymer layers for Examples E1 to E13 and Comparative Examples C1 and C2, respectively. Subsequently, high temperature elongation copper foils were respectively disposed between the two layers of polymer layers of Examples E1 to E13 and Comparative Examples C1 and C2. The high temperature elongation copper foils and the two layers of polymer layers of Examples E1 to E13 and Comparative Examples C1 and C2 were laminated at a pressure of 400 psi and a temperature of 210 °C for 1 hour to obtain the metal foil laminates of Examples E1 to E13 and Comparative Examples C1 and C2, respectively.

[0130] The Dk / Df of the metal foil laminates of Examples E1 to E13 and Comparative Examples C1 and C2 was measured at 10 GHz using network analyzer software (Keysight, P5007A, SCR). The results are shown in Tables 2 to 7 below.

[0131] [Table 2]

[0132] [Table 3]

[0133] [Table 4]

[0134] [Table 5]

[0135] [Table 6]

[0136] [Table 7]

[0137] [Peel Strength Test] Four glass fiber cloths (Asahi 2116, Dk / Df = 3.3 / 0.0030 @ 10 GHz) were immersed in the resin varnishes of Examples E7 to E13 and Comparative Examples C1 and C2, baked at 160 °C for 10 minutes, and four polymer layers of Examples E7 to E13 and Comparative Examples C1 and C2 were formed respectively. These four polymer layers were laminated with a copper foil layer. The copper foil layer was disposed between the four polymer layers. The copper foil layer and the polymer layer were pressure-bonded to form the laminated structures of Examples E7 to E13 and Comparative Examples C1 and C2 respectively.

[0138] The peel strength of the laminated structures of Examples E7 to E13 and Comparative Examples C1 and C2 was measured with a tensile testing machine (SHIMADZU AG-Xplus, test conditions: test speed 50.8 mm / min, test length: 20 mm). The results are shown in Table 8 below.

[0139] [Measurement of Glass Transition Temperature (Tg)]

[0140] Two glass fiber cloths (Asahi 2116, Dk / Df = 3.3 / 0.0030 @ 10 GHz) were immersed in the resin varnishes of Examples E7 to E13 and Comparative Examples C1 and C2, baked at 160 - 170 °C for 5 - 15 minutes, and two polymer layers of Examples E7 to E13 and Comparative Examples C1 and C2 were formed respectively. These two polymer layers were laminated with a copper foil layer. The copper foil layer was disposed between the two polymer layers. The copper foil layer and the polymer layer were pressure-bonded to form the laminate plates of Examples E7 to E13 and Comparative Examples C1 and C2 respectively.

[0141] The glass transition temperatures (Tg) of the laminates of Examples E7 to E13 and Comparative Examples C1 and C2 were measured using dynamic mechanical analysis (DMA, TA / Q800) at a test frequency of 1 Hz under test conditions of heating from 25°C to 270°C at a heating rate of 3°C / min. The glass transition temperature (Tg) was obtained from the tan delta peak in the DMA chart. The results are shown in Table 8 below.

[0142]

Table 8

[0143] From the above results, it can be seen that in Comparative Example C1, no measurable results were obtained due to problems with impregnation processability during prepreg production.

[0144] As can be seen from Tables 2 to 7, after baking at 160°C, the dielectric tangent (Df) of the metal foil laminates of Examples E1 to E13 is lower than that of Comparative Example C2, and the dielectric tangent (Df) of the metal foil laminates of Examples E1 to E13 is all 0.0020 or less. That is, by including a prepreg manufactured from a resin varnish containing the polymer composite of the present disclosure, the dielectric tangent (Df) of the metal foil laminate becomes lower. The resin varnish containing the polymer composite of the present disclosure (i.e., the low dielectric resin composition of the present disclosure) exhibits excellent dielectric and / or thermal properties.

[0145] As can be seen from Table 8, the lower the H / S ratio of the resin varnish (i.e., the low dielectric resin composition of the present disclosure), the lower the peel strength. Specifically, in the laminate structure of Example E10, the H / S ratio of the resin varnish is lower (100 / 50), and the peel strength is lower (1.61 lbf / in). Furthermore, as can be seen from Table 8, the peel strength (2.0 lbf / in) of the laminate structure of Example E11 is lower than that of the laminate structure of Example E8. This indicates that a resin varnish containing a second styrene copolymer having a weight average molecular weight of less than 80,000 Da and a viscosity of less than 521.4 Pa·s has better peel strength. Therefore, preferably, in some embodiments, the H / S ratio of the low dielectric resin composition is greater than 100 / 50 and preferably greater than 100 / 35 to 100 / 10. In some embodiments, the weight average molecular weight of the second styrene copolymer is preferably less than 80,000 g / mol and preferably in the range of 40,000 to 60,000. In some embodiments, the viscosity of the second styrene copolymer is preferably less than 521.4 Pa·s and preferably in the range of 114.8 Pa·s to 327.4 Pa·s. Therefore, in addition to excellent thermal stability and electrical performance, a metal foil laminate including a prepreg manufactured from the low dielectric resin composition of the present disclosure can also have high peel strength and good reliability.

[0146] From the various tests described above, it can be seen that the low-dielectric resin composition of the present disclosure, or the low-dielectric resin composition containing the polymer composite of the present disclosure, has good electrical performance. The metal foil laminate or prepreg produced from the low-dielectric resin composition of the present disclosure, or the low-dielectric resin composition containing the polymer composite of the present disclosure, will have good electrical performance. In some embodiments, the low-dielectric resin composition of the present disclosure, or the low-dielectric resin composition containing the polymer composite of the present disclosure, has good processability. The low-dielectric resin composition of the present disclosure, or the low-dielectric resin composition containing the polymer composite of the present disclosure, still maintains good electrical properties after the heating process and / or the hot press process and is cost-effective. In some embodiments, the metal foil laminate or prepreg produced from the low-dielectric resin composition of the present disclosure, or the low-dielectric resin composition containing the polymer composite of the present disclosure, has good thermal properties and / or mechanical properties.

[0147] Although the present invention has been described in terms of examples and preferred embodiments, it should be understood that the present invention is not limited to the disclosed embodiments. Rather, it is intended to cover various modifications and similar configurations (as will be apparent to those skilled in the art). Therefore, the scope of the appended claims should be given the broadest interpretation so as to include all such modifications and similar configurations.

Explanation of Reference Numerals

[0148] 10… Metal foil laminate 101… Substrate 103… Polymer layer 105… Adhesive layer

Claims

1. A polymer composite used to prepare a low dielectric resin composition, comprising: a first styrenic copolymer having a weight average molecular weight of less than 20,000 g / mol; a second styrenic copolymer having a weight average molecular weight greater than 20,000 g / mol; wherein a weight ratio of the first styrene-based copolymer to the second styrene-based copolymer is from 5 / 95 to 95 / 5, and the low dielectric resin composition has a dielectric loss tangent (Df) of 0.00200 or less.

2. A polymer composite used to prepare a low dielectric resin composition, comprising: a first styrenic copolymer that is liquid at 25° C.; a second styrenic copolymer that is solid at 25° C.; and Including, A polymer composite, wherein a weight ratio of the first styrene-based copolymer to the second styrene-based copolymer is from 5 / 95 to 95 / 5, and the low dielectric resin composition has a dielectric loss tangent (Df) of 0.00200 or less.

3. 3. The polymer composite of claim 2, wherein the first styrenic copolymer has a weight average molecular weight less than 10,000 g / mol.

4. 3. The polymer composite of claim 2, wherein the first styrenic copolymer is a styrenic block copolymer.

5. 3. The polymer composite of claim 2, wherein the first styrenic copolymer is a styrene-butadiene-styrene triblock copolymer (SBS), and the styrene-butadiene-styrene triblock copolymer (SBS) has a molar ratio of 1,2-bond structures to 1,4-bond structures in the butadiene block of the SBS is from 3:1 to 7:

1.

6. 3. The polymer composite of claim 2, wherein the second styrenic copolymer is a styrene-butadiene-styrene triblock copolymer (SBS) having a weight average molecular weight of less than 80,000 g / mol.

7. 7. The polymer composite of claim 6, wherein the second styrenic copolymer has a weight average molecular weight of 40,000 to 60,000.

8. 3. The polymer composite of claim 2, wherein the viscosity of the second styrenic copolymer is in the range of 114.8 Pa·s to 327.4 Pa·s.

9. 3. The polymer composite of claim 2, wherein a weight ratio of said first styrenic copolymer to said second styrenic copolymer is from 25 / 75 to 80 / 20.

10. 1. A method of using a polymer composite, comprising: using the polymer composite to form a mixture including a hydrocarbon resin for use in producing a metal foil laminate; The polymer conjugate, a first styrenic copolymer having a weight average molecular weight of less than 20,000 g / mol; a second styrenic copolymer having a weight average molecular weight greater than 20,000 g / mol; wherein a weight ratio of the first styrenic copolymer to the second styrenic copolymer is from 5 / 95 to 95 / 5, and the metal foil laminate has a dissipation factor (Df) of 0.00200 or less.

11. A low dielectric resin composition, A hydrocarbon resin; a first styrenic copolymer having a weight average molecular weight of less than 20,000 g / mol; a second styrenic copolymer having a weight average molecular weight greater than 20,000 g / mol; A low dielectric resin composition comprising:

12. A low dielectric resin composition, A hydrocarbon resin; a first styrenic copolymer that is liquid at 25° C.; a second styrenic copolymer that is solid at 25° C.; and A low dielectric resin composition comprising:

13. The hydrocarbon resin is 0 to 40 mol % of a repeating unit (A) derived from a bridged ring monomer compound, 15 to 92 mol % of repeating units (B) derived from a monovinyl aromatic compound, and Repeating units (C) derived from a divinyl aromatic compound are contained in an amount of 8 to 80 mol%. The low dielectric resin composition according to claim 12 .

14. The low dielectric resin composition according to claim 12, wherein the content of hydrogen atoms in the reactive double bonds of the hydrocarbon resin is in the range of 2.3% or more and less than 6.6%.

15. 13. The low dielectric resin composition according to claim 12, wherein the low dielectric resin composition comprises more than 53 wt% of the hydrocarbon resin, based on a total weight of the low dielectric resin composition.

16. 13. The low dielectric resin composition according to claim 12, wherein a weight ratio of the hydrocarbon resin to the sum of the first styrene-based copolymer and the second styrene-based copolymer is in the range of more than 100 / 50 and not more than 100 / 10.

17. 13. The low dielectric resin composition according to claim 12, further comprising an additive, the additive being selected from the group consisting of an initiator, a flame retardant, an inorganic filler, and a crosslinking aid, or any combination thereof.

18. A prepreg produced from a low dielectric resin composition comprising the polymer composite according to claim 2.

19. A step of preparing a resin varnish containing a low dielectric resin composition including the polymer composite according to claim 2; forming a mixture by immersing a fiber substrate in the resin varnish; heating the mixture to 100 to 180° C. to obtain the prepreg in a semi-cured state; 20. The prepreg of claim 18 made using a method comprising:

20. The prepreg according to claim 19, wherein the fiber base material is a glass fiber cloth having a dielectric loss tangent (Df) of 0.0030 or less.

21. A metal foil laminate comprising the prepreg of claim 18.

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