High-melt flow hydrogenated styrene-based block copolymer

Abstract

This invention provides a high-MFR polymer with balanced elasticity and strength, which is compatible with other polymer systems. [Solution] A bisbroken hydrogenated styrene-based block copolymer (m-HSBC) is provided. The m-HSBC comprises at least one vinyl-aromatic block "S" and at least one rubbery block "R" derived from a hydrogenated diene unit. It is produced by controlled chain scission of an HSBC precursor. The chain scission process forms low molecular weight species and increases the melt flow rate (MFR). The m-HSBC has a GPC main peak molecular weight (M) of 10-200 kg / mol. p ), has a maximum residual unsaturation (RU) of 0.5 meq / g, and a melt flow rate (MFR) of 10 to 2000 g / 10 min at 190°C / 2.16 kg. m-HSBC may be functionalized with anhydrous, epoxy, silane, or (meth)acrylate groups.

Description

[Technical Field]

[0001] This disclosure relates to high-melt-flow hydrogenated styrene-based block copolymers and compositions thereof. [Background technology]

[0002] Hydrogenated styrene block copolymers (HSBCs) are widely used in a variety of applications, such as polymer additives for rubber and in thermoplastic compositions requiring a combination of elasticity, strength, and chemical resistance. However, a continuing challenge is to achieve a high melt flow rate (MFR) at high temperatures (e.g., 150°C) while maintaining rubbery consistency and solid form at the use or storage temperature without the use of plasticizers. High-MFR HSBCs are desirable in solid form for blending with rubbers, such as polyisobutylene (PIB) and polyolefins. Furthermore, high-MFR HSBCs are of interest for use in copper-clad laminates (CCLs) and related electronic applications.

[0003] One approach is to produce low molecular weight HSBCs. However, such materials often fail to achieve the desired high MFR or are in liquid form. The lack of sufficient MFR or the inability to remain in solid form can limit their applicability in processes requiring solid materials. Another alternative is to use high MFR polypropylene (PP), but this material is typically rigid and crystalline and therefore lacks the essential rubber-like properties. Similarly, amorphous poly-α-olefins (APAOs) and low molecular weight rubbers are often liquid or form agglomerated veils, presenting challenges in handling and processing. [Overview of the project] [Problems that the invention aims to solve]

[0004] There is still a need for high-MFR polymers that are compatible with other polymer systems and possess a balanced combination of elasticity and strength. [Means for solving the problem]

[0005] (Summary) In one embodiment, the disclosure relates to a bisbroken styrene-hydrogenated block copolymer (bisbroken HSBC) comprising at least one block "S" composed of vinyl aromatic units and at least one block "R" composed of hydride diene units. The diene units are 1 Bisbroken HSBCs have a hydrogenation level of >50% as measured by 1H NMR. Bisbroken HSBCs have a low Mw broadness index (LMBI) of ≥25%; as measured according to ASTM D5296, the GPC main peak molecular weight (M) is 10-200 kg / mol. p );Measured according to ASTM D5296, the GPC molecular weight (M) of block "S" in the range of 3-20 kg / mol p ); 1 Residual unsaturation (RU) up to 0.5 meq / g, as measured by 1H NMR; tan δ peak temperature from -42 to 20°C, as measured by dynamic viscoelasticity measurements; 1 It is characterized by an aliphatic methyl proton index (AlMPI) of 18-45% determined by 1H NMR, and a melt flow rate (MFR) of 10-2000 g / 10 min, preferably 10-400 g / 10 min, or more preferably 10-250 g / 10 min, measured according to ASTM D1238 at 190°C and a load of 2.16 kg.

[0006] In a second embodiment, bisbroken HSBC has at least one of the following properties: an aromatic proton content of 1-30%; an aromatic block proton index (ArBPI) of 10-50%; and an aliphatic methyl proton index (AlMPI) of 23-40%, and all properties are 1 It is measured by 1H NMR.

[0007] In a third embodiment, the disclosure relates to a sealant composition comprising, essentially, or consisting of, (a) 5 to 40% by weight of bisbroken HSBC; (b) 25 to 90% by weight of polyisobutylene; (c) 0 to 30% by weight of polyolefin; (d) 0 to 60% by weight of filler; and (e) 0 to 15% by weight of additives, based on the total weight of the sealant composition. The polyolefin may be selected from the group consisting of amorphous polyalphaolefin (APAO), polyethylene, polypropylene, polyolefin elastomer, ethylene-α-olefin copolymer, and mixtures thereof.

[0008] In a fourth embodiment, the disclosure also relates to a curable resin composition comprising, essentially, or consisting of, (a) 10 to 90% by weight of bisbroken HSBC; (b) 20 to 90% by weight of resin; (c) 0 to 70% by weight of filler; and (d) 0 to 30% by weight of additives, based on the total weight of the curable resin composition. The resin may be selected from the group consisting of epoxy resins, polyphenylene ether resins, cyanate ester resins, benzoxazine resins, phenolic resins, vinyl ester resins, bismaleimide resins, polyester resins, polyamide resins, ionomer resins, aromatic resins, and combinations thereof. If additives are added, they may be selected from the group consisting of fillers, curing agents, catalysts, flame retardants, coupling agents, processing aids, stabilizers, and mixtures thereof. [Brief explanation of the drawing]

[0009] [Figure 1] This is a schematic diagram of a GPC graph showing the low molecular weight broadness index (LMBI) for an embodiment of the HSBC precursor before bis-breaking. [Figure 2] Figure 1 is a schematic diagram of a GPC graph showing LMBI for bisbroken HSBCs prepared from HSBC precursors. [Modes for carrying out the invention]

[0010] The following terms will be used throughout this specification.

[0011] "Essentially consisting of" means that the claimed composition primarily consists of the specified material and allows for additional components that do not substantially affect the novel properties or functions of the claimed invention, and if additional components exist, they are in an amount of <30%, <20%, or <10%.

[0012] "At least one of A, B, and C" means one or more members selected from the group consisting of A, B, and C. Therefore, it includes A only, B only, C only, A and B, A and C, B and C, and A, B and C.

[0013] Unless the context explicitly indicates otherwise, any list of embodiments that includes "A, B, or C" shall be interpreted as including A only, B only, C only, or any combination of two or more of A, B, and C.

[0014] "Any of A, B, or C" means one member selected from A, B, and C.

[0015] When used, "Any of A, B, and C" means one or more members selected from A, B, and C, and is intended to have the same scope as "at least one of A, B, and C".

[0016] The "vinyl aromatic unit content" or VAC of a block copolymer is expressed as the weight percent of polymerized vinyl aromatic monomers in the block copolymer, such as styrene and para-methylstyrene, by dividing the total molecular weight of all vinyl aromatic units by the total molecular weight of the block copolymer. VAC is determined by proton nuclear magnetic resonance spectroscopy. 1 1H NMR) and 13 This can be determined using 13C NMR. VAC is sometimes used interchangeably with polystyrene content (PSC).

[0017] "Butylene unit content" indicates the content of butylene units ("B") in weight % relative to all diene-based units in a given polymer (e.g., a hydrogenated block copolymer). Butylene units are formed through the polymerization of 1,3-butadiene monomers via 1,2-addition, followed by hydrogenation. 1,3-butadiene monomers can also polymerize via 1,4-addition and upon hydrogenation, become ethylene units ("E"). Both butylene units and ethylene units can be present in the hydrogenated block copolymer, which can also include other units derived from vinyl aromatic units and / or conjugated diene monomers arranged in any order. The butylene unit content is 1 measurable by 1H NMR and 13 13C NMR.

[0018] "Molar mass" or M m refers to the mass of one mole of a particular substance and is expressed in kg / mol.

[0019] "Apparent molecular weight of polystyrene" or Ms refers to the molecular weight (kg / mol) of a polymer or copolymer measured by gel permeation chromatography (GPC) calibrated with a polystyrene standard according to ASTM D5296. The GPC detector can be an ultraviolet detector, a refractive index detector, or a combination thereof. A polymer or copolymer with a given Ms exhibits the same GPC elution time as a polystyrene standard having the same molecular weight. Unless otherwise specified, the molecular weight values described herein refer to the GPC peak molecular weight (Mp) corresponding to the tip of a given polymer peak.

[0020] "GPC main peak molecular weight" refers to the Mp of the peak having the maximum detection intensity among all GPC peaks corresponding to a polymer species. Each block copolymer measured by GPC has several Mp values, but only one GPC main peak molecular weight, and the main peak is selected from polymer peaks having a GPC peak molecular weight exceeding 5 kg / mol.

[0021] "M of block segments" in block copolymers p " refers to the GPC molecular weight corresponding to the polymer chain or chain segment containing the monomer units of that block. For a block copolymer, the M of a given block p This can be determined from gel permeation chromatography (GPC) analysis performed according to ASTM D5296, using calibration with polystyrene standards, by identifying the GPC signals attributable to the monomer units of the block. Such identification can be performed using a detector selective to the monomer units of the block, such as an ultraviolet (UV) detector for vinyl aromatic blocks, optionally combined with a refractive index detector. For example, for a styrene-based block "S", M p This corresponds to the tip of the GPC peak derived from styrene. In the embodiment, the molecular weight of each GPC block was measured before and after the block polymerization considered. p It can be calculated by the difference between them. For example, the molecular weight of block "S" is the same as the M of species SR. p - Block "R" M p That is the case.

[0022] A “block” (e.g., block “R” or block “S”) refers to a polymer segment defined by the dominant chemical units intentionally incorporated into that segment and responsible for its characteristic properties. Therefore, blocks named E / B, EP / MB, E / B / S, or similar contain primarily the enumerated units, but may also include small amounts of other units resulting from polymerization, hydrogenation, catalyst selectivity, monomer feed compositions, or subsequent chemical modifications. Such small amounts of units may include non-hydrogenated units, partially hydrogenated units, isomerized units, or residual vinyl aromatic units, provided that they do not substantially alter the defining characteristics of the block. The use of a block name separated by a slash (“ / ”) alone identifies the dominant unit type present and does not imply a specific sequence, order, or compositional ratio unless explicitly stated.

[0023] The "LMBI," or "Low Mw Broadness Index," represents the relative presence of a wide variety of low molecular weight polymer chains compared to the most representative polymer species visible in a gel permeation chromatography (GPC) trace obtained using a refractive index detector. To determine the LMBI, 1) identify the highest polymer peak (GPC main peak molecular weight Mp) in the GPC chromatogram and draw a vertical line through its maximum height; 2) draw the largest semicircle on the low molecular weight side of the vertical line, with the arc completely below the GPC curve; and 3) measure the height, i.e., the radius, of the semicircle. The LMBI is calculated as the ratio of the circle's radius to the height of the highest peak. Figures 1 and 2 illustrate the LMBI of HSBC precursors and bisbroken HSBC (prepared from HSBC precursors), respectively.

[0024] "Bis-broken styrene-hydrogenated block copolymer" or "bis-broken HSBC" refers to an HSBC that has undergone controlled polymer chain cleavage, meaning the cleavage or rupture of covalent bonds within the polymer backbone, branch chains, pendant groups, or graft polymer chains under conditions that generate free radicals or other reactive species that can alter the molecular weight distribution of the polymer. Bis-broken HSBCs are distinguished from precursor (non-bis-broken) HSBCs by a measurable change in molecular weight distribution, including a low Mw broadness index (LMBI) of ≥25% under the constraints of the ±2% point measurable tolerance determined herein, as well as by corresponding changes in melt-flow behavior, end-chain concentration, and dynamic-mechanical properties associated with controlled chain cleavage. Bis-broken HSBCs may be interchangeably referred to as m-HSBCs or modified HSBCs.

[0025] "HSBC" refers to a hydrogenated styrene-based block copolymer. HSBC is a hydrogenated form of a non-hydrogenated styrene-based block copolymer (USBC). HSBC is selectively hydrogenated in which a substantial proportion (e.g., >50%) of one type of unsaturated bond, an olefinic bond usually originating from conjugated diene units, is hydrogenated, while the majority of the other unsaturated bonds, usually aromatic bonds (e.g., >90%), are dehydrogenated. In this disclosure, the term "HSBC" includes its isolated form of the hydrogenated polymer before bis-breaking (also referred to herein as "HSBC precursor") and corresponds to the polymer product obtained after solvent removal by methods such as steam stripping or drying. The product obtained after solvent removal can be processed to obtain product forms such as pellets, extrudes, or flakes, or it can be further modified to form bis-broken HSBC through controlled polymer chain severance.

[0026] "Hydrogenation level" refers to the saturation level (in %) of double bonds (e.g., olefinic, aromatic, etc.) in a block copolymer. 1 It can be measured by 1H NMR.

[0027] "Residual unsaturation" or "RU" refers to the level of olefinic unsaturation, i.e., carbon-carbon double bonds, of a block copolymer, and is expressed in milliequivalents per gram (meq / g). Here, 1 equivalent is 1 mole of olefinic double bonds. RU is, 1 It can be measured using 1H NMR or ozonolysis titration.

[0028] A "unit" refers to a polymerized structural building block derived from a single monomer, representing a repeating element that forms part of a polymer or copolymer chain. Unlike "monomers," which are individual molecules before polymerization, a "unit" is a transformed version of the monomer after the polymerization process. Polymerized units can be further converted into hydrogenated units or functionalized units.

[0029] "Coupling efficiency" or "CE" refers to the quotient obtained by dividing the weight of coupled polymer molecules by the total weight of coupled and uncoupled polymer molecules, and is expressed as a percentage (%). Using CE, the amount of diblocks, or more broadly, "uncoupled arms," ​​in the total block copolymer can be determined. For example, if the coupling efficiency is 80%, the polymer contains 20 wt% diblocks or uncoupled arms and 80 wt% triblocks and multi-arm species.

[0030] The "polydispersity index" or "PDI" is sometimes called the molecular weight distribution, and refers to the weight-average molecular weight (M w ) Logarithmic mean molecular weight (M n This refers to the ratio of ). PDI is used to show the distribution of polymer chain molecular weight in a given polymer. PDI can be calculated over the entire GPC or over a portion of the GPC, such as a peak between two extreme values ​​of apparent molecular weight.

[0031] "Tangent delta," also known as tan delta, tan D, or tan δ, refers to the ratio between the loss modulus and the elastic modulus. Tan δ is also called the damping rate, loss tangent, or dielectric loss rate, and is commonly used as a measure of damping in viscoelastic systems. The Tan δ value can be measured by DMA (dynamic viscoelasticity measurement).

[0032] "Tan δ peak maximum" or tan δ max refers to the maximum rate of decay of a material, as measured by DMA. In DMA testing, the tan δ of a material is recorded over a range of temperatures, yielding several broad peaks within the measured temperature range. Each of these peaks has a maximum value called the "tan δ peak maximum".

[0033] "Tan δ peak temperature" or T (tan δ max) refers to the temperature at which the maximum tan δ peak is observed, measured at 10 radians / second.

[0034] The "Aromatic Block Proton Index" or ArBPI refers to the proportion of aromatic protons in a block copolymer to the total aromatic protons in the block copolymer, expressed as a percentage. 1 It can be measured by 1H NMR and calculated using equations.

[0035]

number

[0036] "Aromatic proton content" refers to the protons bonded to aromatic carbon atoms within an aromatic ring structure (expressed as a percentage of all protons). 1 In 1H NMR, aromatic protons typically resonate within a chemical shift range of 7.5–6.0 ppm.

[0037] The "Aliphatic Methyl Proton Index" or AlMPI refers to the ratio of aliphatic protons belonging to methyl groups bonded to aliphatic carbons to the total aliphatic protons in a block copolymer, and is expressed as a percentage. AlMPI is, 1 It can be measured by 1H NMR and calculated using equations.

[0038]

number

[0039] The "complex modulus" or G* of a block copolymer is a material property that characterizes the deformation resistance of the polymer under vibrational shear stress and is measured by DMA.

[0040] "Gel content" refers to the percentage of bisbroken HSBCs that remain insoluble after immersion in toluene, and is expressed as a weight percentage (wt%) of the bisbroken HSBCs before immersion. In embodiments, the gel content is <10, or <5, or <1, ​​or >0.01 wt%, which corresponds to >90, or >95, or >99 wt% of bisbroken HSBCs dissolving in toluene.

[0041] The "gel content test" refers to determining the gel content by placing a known weight of bisbroken HSBC (G1) in toluene equal to 20 times the volume of the sample at room temperature (e.g., 25°C) for a period sufficient to reach equilibrium, e.g., about 24 hours. The mixture is then filtered to recover the insoluble fraction, dried to remove the solvent, and weighed to obtain the weight of the insoluble fraction (G2). The gel content is calculated as 100% × (G2 / G1) and reported as weight %.

[0042] This disclosure relates to bis-broken styrene-hydrogenated block copolymers (bis-broken HSBCs) obtained through controlled polymer chain scission of HSBC precursors, and, in some embodiments, functionalized bis-broken HSBCs (fm-HSBCs) derived therefrom. The resulting bis-broken HSBCs exhibit increased MFR and an optimized balance of elasticity and storage stability, thereby efficiently minimizing low-temperature flow. Bis-broken HSBCs are suitable for incorporation into a variety of compositions, such as polyolefins, rubbers, and other polymer systems, to improve processability, rubberiness, or adhesion.

[0043] (Bisbroken Hydrogenated Styrene Block Copolymer): Bisbroken HSBCs are produced by subjecting an HSBC precursor to controlled polymer chain scaling. In embodiments, the HSBC precursor is a linear, radial, or branched block copolymer comprising at least one block "S" composed of vinyl aromatic units and at least one rubbery block "R" (block "R") composed of hydrogenated diene units, wherein block R optionally contains vinyl aromatic units. The HSBC precursor may have any of the following block structures: diblocks, triblocks, tetrablocks, pentablocks, and higher-order block structures, or mixtures thereof. The vinyl aromatic units are derived from polymerized vinyl aromatic monomers, and the hydrogenated diene units are derived from polymerized conjugated diene monomers before hydrogenation.

[0044] During the chain scalding process, covalent bonds within the HSBC precursor are broken, resulting in molecular weight redistribution and the formation of shorter polymer chains, yielding bisbroken HSBCs with an increased melt flow rate.

[0045] In the embodiment, each block "S" of the HSBC precursor has a GPC molecular weight (M) of ≤20, <18, <15, >2, >3, 3-25, 3-18, 5-15, 4-15, 3-15, 4-10, 3-9, or 3-18 kg / mol. p ) has. This means that if the HSBC precursor has multiple "S" blocks, then each "S" block has a GPC molecular weight (M) of 20 kg / mol or less. p ) also means having.

[0046] In the embodiment, the HSBC precursor has a GPC main peak molecular weight (M) of 10-210, 10-200, 20-150, 30-100, 10-140, 10-100, 40-120, or >25, <210, or <200 kg / mol. p ) has.

[0047] In one embodiment, bisbroken HSBC is SR, (SR) n X, SRS, SRSR, RSRSR, (RSR) n X, SRSRS, (SRS) n It is derived from an HSBC precursor having a linear or branched (multi-armed) structure selected from X (where n is an integer between 2 and 30, or between 2 and 20, or between 2 and 10, and X is a residue of the coupling agent) and mixtures thereof.

[0048] In this embodiment, each block "R" is selected from E / B, E / B / S, EP / MB, EP / MB / S, E / B / EP / MB, and combinations thereof.

[0049] In the embodiment, block "R" in the form of E / B contains ethylene ("E") units and butylene ("B") units, corresponding to hydrogenated 1,4-butadiene units and hydrogenated 1,2-butadiene units, respectively. The ethylene ("E") unit content can be <55, <40, <30, or >10% by weight of the total weight of block "R".

[0050] In embodiments, a block "R" in the form of E / B / S contains ethylene ("E") units, butylene ("B") units, and vinyl aromatic units. The ethylene ("E") units may be <55, <40, <30, or >10% by weight of the combined weight of the "E" and "B" units.

[0051] In the embodiment, block "R" in the form of EP / MB contains ethylene-propylene (EP) units and methyl-butylene (MB) units, where each EP unit corresponds to a hydrogenated 1,4-isoprene unit and each MB unit corresponds to a hydrogenated 3,4-isoprene unit and / or a hydrogenated 1,2-isoprene unit. The MB unit content can be >5, >10, >25, >40, or <70% by weight of the total weight of block "R".

[0052] In the embodiment, block "R" in the form of EP / MB / S contains EP units, MB units, and vinyl aromatic units. The MB unit content can be >5, >10, >25, >40, or <70% by weight relative to the total weight of EP units and MB units.

[0053] In the embodiment, block "R" in the form of E / B / EP / MB contains ethylene ("E") units, butylene ("B") units, EP units, and MB units. The ethylene ("E") unit content can be <55, <40, <30, or >10% by weight of the total weight of block "R".

[0054] In embodiments, coupling agents used to prepare multiblock HSBC precursors include difunctional or polyfunctional compounds, such as divinylbenzene, halides of aliphatic or aromatic aliphatic hydrocarbons (e.g., 1,2-dibromoethane, bis(chloromethyl)benzene), silicon tetrachloride, dialkyl or diaryl silicon dichlorides, alkyl or aryl silicon trichlorides, tin tetrachloride, alkyl silicon methoxides, alkyl silicon ethoxides, polyfunctional aldehydes, ketones, esters, anhydrides, epoxides, and mixtures thereof. In embodiments, coupling agents are selected from methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, dimethyl adipate, γ-glycidoxypropyltrimethoxysilane, and mixtures thereof.

[0055] In embodiments, the vinyl aromatic monomer is selected from the group consisting of styrene, para-methylstyrene, para-ethylstyrene, para-n-propylstyrene, para-iso-propylstyrene, para-n-butylstyrene, para-sec-butylstyrene, para-iso-butylstyrene, para-t-butylstyrene, isomers of para-decylstyrene, isomers of para-dodecylstyrene, ortho-substituted styrene, meta-substituted styrene, α-methylstyrene, 1,1-diphenylethylene, and mixtures thereof.

[0056] In embodiments, the conjugated diene monomer is selected from the group consisting of isoprene, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1-phenyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 3-butyl-1,3-octadiene, farnesene, myrcene, piperylene, cyclohexadiene, and mixtures thereof.

[0057] In the embodiment, each block "S" has a hydrogenation level of <30%, or <20%, or <10%, or <5% relative to all aromatic double bonds. In the embodiment, the diene units in each block "R" have a hydrogenation level of >50%, or >55%, or >60%, or >65%, or >90%, or >95%, or >98%, or >99%, or <90%, or 50-98%, or 50-90%, or 55-85%, or 60-80%, or 65-90%, or 50-75%.

[0058] Bisbroken hydride styrene-based block copolymers contain the same type of block constructs as HSBC precursors, including diblock and triblock species, forming new species with reduced molecular weight. Examples of bisbroken HSBC structures include diblock, triblock, and multiblock constructs derived from S-blocks and R-blocks, e.g., SE / B, S-EP / MB, SE / B / EP / MB, SE / B / S, S-EP / MB / S, and (SE / B) n X, (S-EP / MB) n X, (SE / B / EP / MB) n X, (SE / B / S) n X, (S-EP / MB / S) n X, SE / BS, S-EP / MB-S, SE / B / EP / MB-S, SE / B / SS, S-EP / MB / SS, (SE / BS) n X, (S-EP / MB-S) n X, (SE / B / EP / MB-S) n X, (SE / B / SS) n X, (S-EP / MB / SS)n X and their coupling or extended forms, and multiblock arrangements such as SE / BSE / B, S-EP / MB-S-EP / MB, SE / B / EP / MB-SE / B / EP / MB, SE / B / SSE / B / S, S-EP / MB / SS-EP / MB / S, SE / BSE / BS, S-EP / MB-S-EP / MB-S, SE / B / EP / MB-SE / B / EP / MB-S, SE / B / SSE / B / SS, S-EP / MB / SS-EP / MB / SS, E / BSE / BSE / B, EP / MB-S-EP / MB-S-EP / MB, E / B / EP / MB-SE / B / EP / MB-SE / B / EP / MB, E / B / SSE / B / SSE / B / SSE / B / S, EP / MB / SS-EP / MB / SS-EP / MB / S, and (E / BSE / B) n X, (EP / MB-S-EP / MB) n X, (E / B / EP / MB-SE / B / EP / MB) n X, (E / B / SSE / B / S) n X, (EP / MB / SS-EP / MB / S) n Examples include X, its coupled analogues, and mixtures thereof. In these structures, n is an integer between 2 and 30, and X is a residue of the coupling agent.

[0059] In the embodiment, when the bisbroken HSBC contains blocks such as E / B, E / B / EP / MB, or E / B / S, the butylene unit ("B") content is 60-90% by weight.

[0060] In this embodiment, bisbroken HSBC has a RU of 0.001 to 0.3 meq / g, (SE / B) n X, or (SE / B / S) n X, or (S-EP / MB) n It has a structure selected from X.

[0061] In embodiments, the bisbroken HSBC comprises a mixture of diblock and multiblock varieties. The proportion of diblock can be 3-90, or 10-90, or 35-85, or 40-70, or 45-65, or 30-65, or 45-80, or 5-20, or >3, or >30, or <80% by weight. The proportion of multiblock can be 10-80, or 15-65, or 30-60, or 35-55, or 35-70, or >20, or <70% by weight relative to the total weight of the bisbroken HSBC.

[0062] In the embodiment, the bisbroken HSBC has a coupling efficiency (CE) of >10%, >20%, or 10-100%, 20-95%, or 70-95%, or >90%, or 80-98%, or 85-95%.

[0063] In the embodiment, the bisbroken HSBC has a residual unsaturation (RU) of up to 0.5, or 0 to 0.4, or 0 to 0.2, or 0.001 to 0.1, or <0.4, or <0.3, or <0.2, or <0.1, or >0.001 meq / g.

[0064] In embodiments, the bisbroken HSBC has a butylene unit ("B") content of >5, >30, >40, >45, >50, >60, >70, or <95, or 5-95, 30-95, 45-95, 50-90, 60-85, 60-90, or 45-85% by weight of the bisbroken HSBC.

[0065] In this embodiment, the bisbroken HSBC has a total VAC of <70, <60, <55, or >10, or 5-70, 5-60, 10-55, 15-50, 35-55, 15-35, or 18-40% by weight of the bisbroken HSBC.

[0066] In this embodiment, bisbroken HSBC has a GPC main peak molecular weight (M) of 10-210, 10-200, 20-150, 30-100, 10-140, 10-100, 40-120, or >25, <210, or <200 kg / mol. p ) has.

[0067] In the embodiment, after bis-breaking, the GPC molecular weight (M) of at least one block "S" in the bis-broken styrene-hydrogenated block copolymer is p ) is the GPC molecular weight (M) of the corresponding block "S" in the HSBC precursor. p The range remains within ±20% in another embodiment, within ±10% in yet another embodiment, and within ±5% in yet another embodiment, indicating that the chain severance occurs mainly within the non-styrene portion of the polymer. In embodiments, at least one block "S" in the bisbroken HSBC has a GPC molecular weight (M) of <20, or <18, or <15, or >2, or >3, or 3-25, or 3-18, or 5-15, or 4-15, or 3-15, or 4-10, or 3-9, or 3-18 kg / mol. p ) has.

[0068] In embodiments, bisbroken HSBC has an aliphatic methyl proton index (AlMPI) of 18-45%, 20-42%, 23-40%, 18-38%, 20-35%, 30-45%, or >18%, >23%, or <45%.

[0069] In one embodiment, the bisbroken HSBC has an aromatic proton content of 1-30%, 1-20%, 5-25%, 3-15%, or 4-18%.

[0070] In embodiments, the bisbroken HSBC has an aromatic block proton index (ArBPI) of 10-100%, 10-50%, 15-45%, 18-42%, 18-50%, 10-42%, >18%, <45%, or <100%.

[0071] In the embodiment, chain severance during bis-breaking occurs within the rubbery block "R," primarily within butylene units, EP units, or MB units, rather than within the styrene-based segment. Such preferential severance within the rubbery segment facilitates molecular weight reduction while substantially preserving the integrity of the styrene-based block.

[0072] As a result of chain severance within the rubbery segments, bisbroken styrene-hydrogenated block copolymers exhibit a molecular weight redistribution characterized by an increase in the low molecular weight species population and a decrease in the high molecular weight species population. Since the severance is largely statistically performed along the polymer backbone, the resulting molecular weight distribution is broadened to reflect an increase in the low Mw broadness index (LMBI). In embodiments, bisbroken HSBCs have an LMBI of ≥25%, or >30%, or >40%, or >45%, or >50%, or >55%, or >60%, or <90%, or <100%, or 25-90%, or 30-80%, or 30-75%, or 35-65%.

[0073] In the embodiment, bisbroken HSBCs exhibit an increase of at least 5%, at least 10%, at least 15%, or at least 20% in LMBI compared to HSBC precursors.

[0074] In embodiments, chain severance also results in a corresponding increase in the melt flow rate (MFR). Prior to severance, the HSBC precursor may have an MFR of 0.1–200, or 0.5–200, or 1–100, or 2–60, or 5–50, or >2, or <200, or <100 g / 10 min, as measured at 190°C and a load of 2.16 kg according to ASTM D1238. After screw breaking, the MFR of screw-broken HSBC, measured according to ASTM D1238 at 190°C and a load of 2.16 kg, is significantly higher than the MFR of the precursor for MFRs of 10-2000, or 10-1500, or 15-500, or 50-250, or 10-400, or 10-250, or >5, or >10, or >100, or <2000 g / 10 mins.

[0075] In this embodiment, bisbroken HSBC is 10-55 wt% total VAC; 4-15 kg / mol block "S" M p ; GPC main peak M for 40-150 kg / mol p ; and it has an MFR of 15-500g / 10min at 190℃ / 2.16kg.

[0076] (Optional functionalizing agent): In the embodiment, bisbroken HSBC is reacted with at least one functionalizing agent to obtain functionalized bisbroken HSBC. In the embodiment, bisbroken and functionalized HSBC ("fm-HSBC") are obtained by (i) functionalizing bisbroken HSBC, (ii) bisbreaking functionalized HSBC, or (iii) simultaneously bisbreaking and functionalizing an HSBC precursor under melt-reactive or solid-state conditions.

[0077] In embodiments, the functionalizing agent is a compound comprising a styrene-based aromatic group and at least one functional substituent capable of radical grafting or post-grafting. Examples include p-styryltrimethoxysilane, p-styryltriethoxysilane, methacrylate-functionalized styrene, glycidyl-functionalized styrene, amino-functionalized styrene, and mixtures thereof. Non-functionalized styrene monomers (e.g., para-methylstyrene, para-ethylstyrene, α-methylstyrene) are not functionalizing agents within the scope of the present invention unless they are derivatized to contain a reactive functional group.

[0078] In embodiments, the functionalizing agent is an acrylate-type activator, such as a functional (meth)acrylate, which can introduce polar or reactive groups into the polymer backbone. Examples of such activators include methacrylic acid, acrylic acid, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, dimethylaminoethyl methacrylate, methacrylamide, alkyl (meth)acrylamide, and mixtures thereof. Non-functional acrylates (e.g., methyl acrylate, ethyl acrylate, butyl acrylate) can also be used for graft modification, but do not introduce functional groups unless otherwise derivatized. In embodiments, both functional and non-functional acrylates can be included to adjust the polarity, compatibility, or reactivity in the graft.

[0079] Examples of silane-functionalized agents include vinyltrimethoxysilane (VTMOS), vinyltriethoxysilane (VTEOS), vinyltributoxysilane, vinyldimethoxyethoxysilane, vinyldimethoxybutoxysilane, vinyldiethoxybutoxysilane, allyltrimethoxysilane, allyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, diethoxymethylvinylsilane, and mixtures thereof. Silane-functionalized styrene-based activators (e.g., p-styryltrimethoxysilane, p-styryltriethoxysilane) are also suitable due to the reactivity of their aromatic compounds combined with silane.

[0080] Examples of anhydride functionalizers include maleic anhydride, tetrahydrophthalic anhydride, dodecenyl succinic anhydride, itaconic anhydride, methyltetrahydrophthalic anhydride, alkenyl succinic anhydride, octenyl succinic anhydride, chlorendic anhydride, and related anhydrides that can undergo free radical grafting.

[0081] In the embodiment, if a functionalizing agent is used, it is present in an amount of up to 10 phr, or 0.1 to 10, or 0.5 to 8, or 1 to 10, or 0.5 to 5, or 0.1 to 4 phr, relative to 100 phr of HSBC precursor.

[0082] (Properties of Bisbroken HSBC / fm-HSBC by Controlled Bisbrokening): Structural changes introduced by controlled chain severing of HSBC precursors, including molecular weight reduction, increase in low molecular weight species, modification of interblock connections, and alteration of viscoelastic damping behavior, impart unique rheological, mechanical, and adhesive properties to the resulting bisbroken HSBC and optionally functionalized bisbroken HSBC (fm-HSBC). These properties are inherent in the polymer constructs produced by the bisbrokening and optionally functionalization steps described herein. Bisbroken HSBC or fm-HSBC can be supplied in pellet form, thereby allowing for convenient use in standard pellet feeds and melt mixing equipment, and the material behaves as a solid rubbery plasticizer.

[0083] In embodiments, fm-HSBC exhibits improved adhesion to both polar and non-polar substrates, including glass, silicon wafers, ceramics, metals, plastics, fibers, fabrics, wood, leather, masonry, concrete, rock, paper, cardboard, brick, plaster, cement, tiles, mortar, and asphalt, without the need for an adhesive or primer layer.

[0084] In the embodiment, bisbroken HSBC and fm-HSBC each independently have at least one of the following characteristics.

[0085] The tan δ value at 50°C for values ​​between 0.08 and 1, or 0.10 and 0.90, or 0.11 and 0.80, or 0.12 and 0.70, or 0.08 and 0.65, or 0.12 and 0.70, or >0.08, or <1.

[0086] Measured at 10 radians / second, this is the tan delta peak (TanDmax) temperature for the ranges of -42 to 20°C, -38 to 10°C, -35 to 5°C, -34 to 0°C, -42 to 0°C, -34 to -3°C, >-42°C, or <0°C.

[0087] Complex modulus (G*) at 100°C for 10-2000, or 30-1800, or 50-1600, or 100-1500, or 200-1000, or 50-600, or 100-500, or 150-450, or >10, or >20, or >50, or <1000kPa.

[0088] Shore A hardness (10 sec) measured according to ASTM D2240, ranging from 10 to 60, or 15 to 55, or 20 to 50, or 30 to 45, or 25 to 45, or >25, or <50.

[0089] Tensile strength measured according to ASTM D412 of 1 to 20, or 1 to 15, or 1 to 10, or 1 to 8, or 2 to 7, or >1, or <15 MPa.

[0090] Elongation at break measured according to ASTM D412: 200–1000%, or 500–900%, or 550–800%, or 600–750%, or 550–700%, or >600%, or <900%.

[0091] Tear strength of >10, <40, or 10-40, or 15-35, or 10-30, or 15-25 N / mm, as measured according to ASTM D412.

[0092] For samples prepared at 125°C, measurements at 25°C yielded values ​​of >1800, >2000, <4000, 1800-5000, 1900-4000, 2000-3700, 2200-3500, or 2400-3000 N / inch. 2 Shear delamination strength. Shear delamination strength indicates the adhesive strength to glass.

[0093] Samples prepared at 130°C were measured at 25°C and showed >26, or <45, or 26-45, or 28-42, or 30-40 N / inch at 180°C. o Peel strength.

[0094] Melt viscosity at 140°C measured according to ASTM D3835, >150,000, or <300,000, or 150,000 to 300,000, or 160,000 to 250,000, or 165,000 to 200,000 cP (150 to 300 Pa·s).

[0095] Melt viscosity at 190°C measured according to ASTM D3835, >12000, or <40000, or 14000-40000, or 15000-30000, or 16000-25000 cP (12-40 Pa·s).

[0096] Gel content of <10, <5, <1, or >0.01% by weight relative to the total weight of the bisbroken HSBC before immersion in toluene.

[0097] Loss loss tangent (Df) at 10 GHz, measured according to ASTM D2520, with a value of <0.0100, <0.0050, <0.0010, or >0.00001. Df is measured for bisbroken HSBC (or uncured fm-HSBC).

[0098] (Chain Severance Mechanism): Bisbroken HSBCs are produced by subjecting HSBC precursors to controlled polymer chain severance. Chain severance can be induced by exposing HSBC precursors to ultraviolet (UV) rays, gamma rays, electron beams, microwave energy, X-rays, heat, hot air, elemental oxygen, chain severing agents, or a combination thereof (e.g., gamma rays together with a chain severing agent).

[0099] In embodiments, the chain cleavage agent is selected from the group consisting of organic peroxides, hydrogen peroxide, sodium hypochlorite, ozone, potassium permanganate, sodium periodate, periodic acid, peracids (e.g., peracetic acid, performic acid), azobisisobutyronitrile (AIBN) or other azo initiators, Fenton-type redox systems, halogenating agents (e.g., chlorine, N-halosuccinimide), strong acids that promote main chain cleavage (e.g., sulfuric acid, methanesulfonic acid, trifluoroacetic acid, trifluic acid), strong bases that can induce β-cleavage (e.g., potassium tert-butoxide, sodium tert-butoxide, sodium amide, lithium diisopropylamide), photosensitizers (e.g., benzophenone, acetophenone, benzoyl peroxide, anthraquinone, thioxanthone), and mixtures thereof.

[0100] In embodiments, the chain severing agents include dicumyl peroxide (DCP), 1,3-bis(tert-butylperoxyisopropyl)benzene, diacyl peroxide, alkyl perester, percarbonate, dilauroyl peroxide (DLPO), dibenzoyl peroxide (DBPO), tert-butylperoxy-2-ethylhexanoate (TBPEH), tert-butylperoxy-isobutyrate (TBPIB), 1,1-di-(tert-butylperoxy)cyclohexane (DTBPC), and tert-butylperbenzoate. (TBPB), 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (DBPH), 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyn-3 (DYBP), di-tert-butylperoxide (TBP), cumenehydroperoxide (CHP), tert-butylhydroperoxide (TBHP), lauroylperoxide, dipropionylperoxide, p-menthanehydroperoxide, diphenylcyclohexylperoxide, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxide Xonane, t-butylperoxy-maleic acid, OO-(t-butyl)O-isopropyl monoperoxycarbonate, OO-t-butyl O-(2-ethoxyl) monoperoxycarbonate, OO-t-amyl O-(2-ethylhexyl) monoperoxycarbonate, t-butylperoxyacetate, t-amylperoxyacetate, t-amylperoxybenzoate, di-t-butyldiperoxyphthalate, t-butylcumylperoxide, α-α-bis(t-butylperoxy), diisopropylbenzene, di-t-butylperoxy The organic peroxide is selected from oxides, n-butyl-4,4-bis(t-butylperoxy)valerate, 1,1-di(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 1,1-di-(t-amylperoxy)cyclohexane, 2,2-di(t-butyl-peroxy)butane, ethyl-3,3-di(t-butylperoxy)butyrate, 2,2-di(t-amylperoxy)propane, ethyl-3,3-di(t-amylperoxy)butyrate, and mixtures thereof.

[0101] In the embodiment, the chain severing agent is used in an amount of 0.001 to 5, 0.05 to 4, 0.01 to 3, 0.001 to 3, or 0.05 to 3 phr per 100 phr of HSBC precursor.

[0102] (Preparation of Bisbroken / Functionalized Bisbroken HSBCs): In embodiments, bisbroken HSBCs are prepared from HSBC precursors by inducing controlled polymer chain severance. Chain severance can be achieved by exposure to ultraviolet (UV) rays, gamma rays, electron beams, microwave energy, X-rays, heat, hot air, elemental oxygen, and chain-severing agents. Chain-severing agents include free radical initiators, such as organic peroxides, hydroperoxides, peresters, percarbonates, persulfates, azo initiators, and combinations thereof.

[0103] In embodiments, chain severance is performed in the presence of a chain severant in an extruder, such as a single-screw or twin-screw extruder, or other melt-reactive equipment capable of maintaining a controlled thermal and shear environment having a melt-working zone. The maximum extrusion temperature can be 100-400°C, or 130-380°C, or 150-350°C, or 170-340°C, or 170-400°C, or 100-340°C, and the residence time can be 5 seconds-10 minutes, or 5-30 minutes, or 20 seconds-2 minutes.

[0104] In embodiments, bisbroken HSBCs are produced using two or more separate chain-breaking stages ("multi-chop bis-breaking") or more than one bis-breaking pass. In multi-chop bis-breaking, an HSBC precursor or partially bisbroken intermediate is subjected to chain-breaking conditions in a first melting zone, and then subjected to one or more additional chain-breaking events in a downstream zone or second pass using the same or different melting equipment. Each stage may utilize the same or different temperature, shear profile, residence time, chain-breaking agent, or chain-breaking agent concentration. Multi-chop bis-breaking can be performed in multiple passes in a single extruder, a multi-zone extruder with continuous initiator addition, or a cascade extruder. Multi-chop bis-breaking provides a means to adjust the degree and distribution of chain-breaking beyond the degree and distribution of chain-breaking achievable in a single stage.

[0105] In embodiments, the multi-chop process includes introducing a second or different HSBC precursor into a downstream or second bis-breaking step such that the polymer melt in a later step contains a mixture of (i) the bis-broken intermediate from the first step and (ii) the fresh HSBC precursor. This allows for a more suitable molecular weight distribution and the formation of lower molecular weight species, in a manner different from bis-breaking a premixed blend in a single step.

[0106] In embodiments, different chain severants are used in different multi-chop bis-breaking stages. For example, in the first stage, a dialkyl peroxide having a first decomposition temperature can be used, and in the second stage, a perester, hydroperoxide, percarbonate, or azo initiator having a different decomposition temperature or radical generation profile can be used. Using successive initiators provides additional control over chain severance compared to a single-initiator process.

[0107] In the embodiment, the temperatures used in the continuous screw-breaking stage are intentionally different. Subsequent stages can be operated at higher temperatures to promote chain severance, or at lower temperatures to mitigate radical activity while maintaining fusion homogeneity. By adjusting the thermal profile throughout the stages, further control over molecular weight distribution and chain severance uniformity is achieved.

[0108] In some embodiments, the chain severance step is carried out together with the functionalization to produce functionalized bisbroken HSBCs (fm-HSBCs). In such embodiments, the functionalizing agent is added simultaneously with the chain severing agent under melt-reactive or solid-state conditions such that radical-mediated chain severance and graft functionalization occur simultaneously. This one-pot process is particularly suitable for functionalizing agents that undergo free radical grafting, including anhydrides, epoxides, silanes, and functional (meth)acrylates as defined herein. In other embodiments, the functionalizing agent is introduced after the formation of bisbroken HSBCs to separately control molecular weight reduction and graft level.

[0109] In one embodiment, fm-HSBC is prepared by a solid-phase method in which an HSBC precursor, a chain scalder, and a functionalizing agent are combined in a reactor at a temperature between 40°C and the melting or softening temperature of the HSBC precursor, while maintaining conditions sufficient to generate radicals without completely melting the polymer matrix. After the reaction is complete, the fm-HSBC is recovered from the reactor.

[0110] In embodiments, the fm-HSBC contains chemically bonded functional groups in amounts of 0.5 to 25, 0.7 to 10, 1 to 25, 1 to 20, 1 to 15, 5 to 15, 1 to 10, 1 to 5, or >1, >5, >10, >15, or <25% by weight relative to the total weight of the fm-HSBC. The fm-HSBC may further contain unreacted (free) functionalizing agents in amounts of <1% by weight or any partial range thereof relative to the total amount of the functionalizing agent to which the functionalizing agent has been added. Examples of chemically bonded groups include grafted anhydrides, epoxides, silanes, acids, or functional (meth)acrylate moieties introduced through a radical grafting process.

[0111] (End Uses of Bisbroken HSBCs): Optionally functionalized bisbroken HSBCs (fm-HSBCs) can be incorporated into a wide range of end-use products due to their combination of rubbery elasticity, high substrate wettability, and improved melt mobility. Bisbroken polymers act as solid rubbery plasticizers, improving processability, tackiness, cohesive strength, and flowability in melt-processed compositions. In embodiments, bisbroken HSBCs function as flow enhancers or dispersion aids, improving the distribution of fillers, pigments, or other polymer components within a formulation. In embodiments, m-HSBCs and fm-HSBCs, due to their higher melt mobility compared to non-bisbroken precursors, can also be used to modify reactive resins, including epoxy resins, polyester resins, and associated thermoplastic or thermosetting systems.

[0112] Typical end-use applications include a) adhesives and sealants, including glass, metal, ceramic, polymer, and composite substrates; b) electronic coatings and encapsulation materials, including copper-clad laminates (CCL), barrier coatings, and protective layers; c) overmolded articles and impact-modified thermoplastics; d) films, fibers, tapes, and laminates; e) medical, hygiene, and packaging products requiring softness, elasticity, or improved adhesion; f) lubricating gels, greases, and concentrated formulations; and g) photovoltaic and electrical insulating components.

[0113] In embodiments where bisbroken HSBC is provided as a solid at room temperature (e.g., 25°C) in which it is uniformly melted and dispersed, it may be compounded using standard thermoplastic melting methods such as extrusion, compounding, injection molding, or film casting.

[0114] Generally, bisbroken HSBC is added to different (additional) polymers in a formulation, relative to the total weight of the polymer composition, including (a) 1 to 60% (or 5 to 55% by weight) of bisbroken HSBC and / or functionalized bisbroken HSBC (fm-HSBC), (b) 40 to 99% (or 45 to 95% by weight) of at least one polymer selected from the group consisting of polyolefins (e.g., polyethylene, polypropylene, polyisobutylene), rubber (e.g., EPDM, IIR, SBR), polyesters (e.g., PET, PBT), polyamides (e.g., nylon 6, nylon 12), and mixtures thereof, and (c) up to 10% by weight of at least one additive, including stabilizers, antioxidants, fillers, tackifiers, adhesion promoters, or other common modifiers. Other compatible polymers include polystyrene (PS), polyphenylene ether (PPE or PPO), thermoplastic starch-based materials, thermoplastic polyolefins, thermoplastic copolyester elastomers, polyether block amides, thermoplastic vulcanized products, thermoplastic polyurethane (TPU), epoxy resins, polyester resins, bismaleimide resins (BMI), ionomer resins (ION), styrene-based block copolymers (SBCs) other than bisbroken HSBC or fm-HSBC (e.g., USBC, SIS, SBS, SIBS, HSBC, SEBS, SEBSS, SiBS, etc.), and mixtures thereof.

[0115] The performance of polymer compositions containing bisbroken HSBCs depends on the selection and relative amounts of additional polymers, fillers, and additives. However, compositions incorporating bisbroken HSBCs typically exhibit improved melt mobility, improved substrate wettability, and higher adhesive strength compared to similar formulations prepared without bisbroken HSBCs. Such improvements correlate with an increase in LMBI of the bisbroken material, which introduces mobile low Mw segments that facilitate flow, surface wetting, and energy dissipation at the adhesive interface.

[0116] Since the compound governs the absolute melt flow rate and adhesive strength values, the following ranges illustrate polymer compositions in which bisbroken HSBC is used as a performance modifier.

[0117] In embodiments, polymer compositions containing bisbroken HSBC or fm-HSBC exhibit higher melt mobility and improved adhesion compared to similar compositions lacking bisbroken HSBC. The following values ​​are representative and not limiting; they depend on the properties and proportions of the companion polymer, fillers, oils, tackifiers, and additives.

[0118] Melt flow rate (MFR) measured at 130°C / 2.16 kg according to ASTM D1238, with values ​​of 0.1–50, or 0.5–40, or 0.5–20, or >0.50, or >0.55, or <50 g / 10 min.

[0119] Samples prepared at 125°C were measured at 25°C and yielded values ​​of >250, >300, >250, <1000, 250-1000, 300-800, 350-700, 250-700, or 350-1000 N / inch. 2 This is the shear peel strength, which suggests the adhesive strength.

[0120] For samples prepared at 130°C, measurements were taken at 25°C and the values ​​were >55, or >60, or <200, or 50-200, or 55-180, or 60-150, or 65-150, or 70-120, or 65-200, or 55-120 N / inch at 180. o Peel strength.

[0121] (Final Use - PIB-containing compositions for adhesive and sealant applications): In embodiments, bisbroken HSBC (or fm-HSBC) is blended with polyisobutylene (PIB), including solid or semi-solid PIB homopolymers and copolymers. The PIB typically contains at least 60% by weight of isobutylene units and may have an Mw value of >20, or <1000, or 20-1000, or 30-800, or 50-700, or 400-600, or 20-200, or 0.5-20, or 0.5-10 kg / mol. The PIB has a glass transition temperature (T) of -50 to -80°C, or -55 to -75°C, or -60 to -70°C, as measured by DSC. g ), and measured according to ASTM D1505, the range is 0.85-0.98, or 0.87-0.95, or 0.88-0.93 g / cm³. 3 It can have a density of [value missing]. PIB provides tackiness, hydrophobicity, and low-temperature flexibility, while bisbroken HSBC provides cohesive strength, improved melt flow, and enhanced substrate wettability.

[0122] In embodiments, bisbroken HSBC and / or fm-HBSC are intended for use in a PIB-containing sealant composition comprising (a) 5 to 40% by weight of bisbroken HSBC and / or fm-HSBC; (b) 25 to 90% by weight of PIB; (c) 0 to 30% by weight of polyolefin; (d) 0 to 60% by weight of filler; and (e) up to 15% by weight of additives (e.g., stabilizers, desiccants, adhesion promoters). The amounts of (a) to (e) are independently selected within the specified range so that the sum of all components is 100% by weight. The polyolefin may be selected from the group consisting of amorphous polyalphaolefin (APAO), polyethylene, polypropylene, polyolefin elastomer, ethylene-α-olefin copolymer, and mixtures thereof. Examples of fillers include CaCO3, silica, talc, kaolin, zinc oxide, barium sulfate, carbon black, glass spheres, or mixtures thereof. Examples of desiccants include alkoxysilanes, CaO, ZnO, zeolites, or anhydrous sulfates. In embodiments, the sealant composition further comprises a tackifier selected from the group consisting of aliphatic hydrocarbon resins, aromatic hydrocarbon resins, C5-C9 petroleum resins, polyterpene resins, terpene-phenolic resins, rosin-based resins (e.g., gum rosin, wood rosin, tall oil rosin, hydrogenated rosin, disproportionated rosin, rosin esters, hydrogenated rosin esters), coumarone-indene resins, dicyclopentadiene (DCPD) resins, alicyclic hydrocarbon resins; and mixtures thereof.

[0123] A blend of PIB and bisbroken HSBC unexpectedly and significantly increases adhesive strength compared to PIB alone. A sealant composition comprising PIB and bisbroken HSBC and / or fm-HSBC is characterized by having at least one of the following properties before curing (i.e., in the uncured state):

[0124] Storage modulus (G') measured by DMA, where >0.001, >0.002, >0.003, or <0.010, or measured at 100°C at 0.001 to 0.010 MPa.

[0125] Measured by DMA, T is <-20℃, or <-30℃, or <-40℃, or >-50℃, or -20℃ to -50℃. g .

[0126] Storage modulus (G') measured by DMA, where >0.050, >0.055, >0.060, or <0.100, or measured at 50°C at 0.050–0.100 MPa.

[0127] Softening point measured according to ASTM D36: >100°C, >105°C, >110°C, <150°C, or 100-150°C.

[0128] Measure according to ASTM D5M and report to the nearest 0.1 mm, with needle penetration of 5-15, 6-12, or 5-10.

[0129] >45°C, >50°C, <70°C, or shear bond failure temperature (SAFT) between 45 and 70°C.

[0130] In some embodiments, after curing, the (cured) sealant composition exhibits at least one of the following properties:

[0131] MFR >10, <100, 10-100, 12-50, or 10-30 g / 10 mins, measured according to ASTM D1238 at 130°C with a load of 2.16 kg.

[0132] Measured on a glass substrate, >900, or <2000, or 900-2000, or 950-1600, or 1000-15000 N / inch 2 Shear delamination strength at 25°C. Shear delamination strength is measured for glass substrates after thermal conditioning at 125°C for 20 minutes before testing, followed by 24 hours of conditioning.

[0133] A 5% weight loss is measured by thermogravimetric analysis (TGA) at a heating rate of 6°C / min, and is performed at temperatures of at least 350°C, or <420°C, or 350-420°C, or 350-380°C.

[0134] A 10% weight loss is measured by thermogravimetric analysis (TGA) at a heating rate of 6°C / min at temperatures of at least 355°C, <420°C, 355–420°C, or 360–380°C.

[0135] Measured by DMA, T is <-20℃, or <-30℃, or <-40℃, or >-50℃, or -20℃ to -50℃. g .

[0136] Storage modulus (G') measured by DMA, >0.050, >0.055, >0.060, or <0.100, measured at 50°C at 0.050-0.100 MPa.

[0137] Storage modulus (G') measured by DMA, >0.010, >0.011, >0.012, or <0.100, measured at 100°C with a pressure of 0.010 to 0.100 MPa.

[0138] Softening point measured according to ASTM D36: >100°C, >110°C, >115°C, <170°C, or 100-170°C.

[0139] Measure according to ASTM D5M and report to the nearest 0.1 mm, with needle penetration of 5-15, 6-12, or 5-10.

[0140] >45°C, >50°C, <70°C, or shear bond failure temperature (SAFT) between 45 and 70°C.

[0141] (End-use application - Curable resin composition containing bisbroken HSBC for CCL): In embodiments, bisbroken HSBC or fm-HSBC is incorporated into a curable resin composition suitable for use in copper-clad laminates (CCL), printed circuit boards (PCBs), dielectric substrates, and other high-frequency electronic materials.

[0142] In embodiments, the curable resin composition comprises (a) 10 to 90% by weight of bisbroken HSBC and / or fm-HSBC; (b) 20 to 90% by weight of resin; (c) 0 to 70% by weight of filler; and (d) up to 30% by weight of at least one additive. The amounts of (a) to (d) are independently selected within a specified range such that the sum of all components is 100% by weight.

[0143] In embodiments, the resin is selected from the group consisting of epoxy resins, polyphenylene ethers (PPE), cyanate ester resins, benzoxazine resins, phenolic resins, vinyl ester resins, bismaleimide resins, cyclic olefin polymers, polyolefin resins, polyester resins, polyamide resins, ionomer resins, divinylbenzene-based reactive resins, aromatic resins, and combinations thereof.

[0144] Examples of fillers include silica, alumina, aluminum hydroxide, magnesium hydroxide, boron nitride, aluminum nitride, talc, clay, kaolin, mica, wollastonite, calcium carbonate, barium sulfate, glass fibers, glass cloth, glass flakes, ceramic fillers, quartz, and mixtures thereof.

[0145] Examples of additives include curing agents, catalysts, flame retardants, coupling agents, processing aids, stabilizers, and mixtures thereof.

[0146] In embodiments, the curable resin composition is processed using a solvent-based method to promote homogeneous mixing, impregnation, or film formation before curing. The components can be dissolved or dispersed in an organic solvent to form a homogeneous resin solution or varnish. Examples of solvents include toluene, xylene, ethylbenzene, hexane, heptane, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, propyl acetate, butyl acetate, and mixtures thereof. In embodiments, the solvent content is selected to achieve 10-60% by weight or 20-50% by weight of solids for coating, impregnation of reinforcing substrates, or film casting. After application, the solvent is removed by ambient, heating, or evaporation under reduced pressure before curing.

[0147] A curable resin composition can be converted into a curable material (or cured composition) by subjecting the composition to thermosetting conditions suitable for the selected resin system. In embodiments, curing is carried out in a single heating step or through a stepwise curing process, depending on whether the composition is used as a bulk resin, film, coating, or prepreg for CCL production.

[0148] In embodiments utilizing stepwise curing, the composition is first heated at 80–140°C for 1–20 minutes to partially cure (often referred to as step B), producing a non-stick, handleable prepreg. The step B material or uncured composition can then be optionally fully cured by heating under pressure at 150–220°C for 15–150 minutes when applied to a reinforcing substrate such as glass fabric. Post-curing at 180–250°C for 0.5–3 hours can be used to improve thermal stability and dielectric consistency.

[0149] In one embodiment, after curing, the cured resin composition exhibits at least one of the following properties.

[0150] Dielectric constant (Dk) of <3.0, <2.8, <2.6, <2.5, >0.1, or 0.1–3.0 at 10 GHz, according to ASTM D2520.

[0151] According to ASTM D2520, the loss tangent (Df) at 10 GHz is <0.006, or <0.005, or <0.003, or <0.002, or >0.0001, or 0.0001 to 0.006.

[0152] Gel content of >90%, >80%, >70%, >60%, >50%, <99%, or 90-99%.

[0153] Tensile strength of >5, >7, <30, or 5-30 MPa, as measured according to ASTM D412.

[0154] Elongation measured according to ASTM D412: >450, >500, <900, or 450-900 MPa.

[0155] (Analysis method): GPC main peak molecular weight (M p The molecular weight distribution of bisbroken HSBCs is measured by GPC according to ASTM D5296, including the determination of the low Mw broadness index (LMBI). The GPC chromatogram is M p This method determines the retention time, peak position, and peak area used to calculate LMBI based on the presence of low molecular weight species. The GPC method uses log elution time. 10The GPC chromatogram is operated under conditions suitable for polymer molecular weight measurement, including operations in a region that changes linearly with (Mw). The GPC chromatogram is presented as a detector response plotted against elution time or elution volume, where the detector signal is proportional to the concentration of the polymer species eluting from the column. Therefore, the resulting trace reflects the relative amount of polymer eluting at each retention time. Using an appropriate calibration standard, such as a narrow polystyrene standard, the corresponding polystyrene-equivalent molecular weight is assigned to each retention time. The GPC column and operating conditions are selected so that the polymer species elutes within a linear calibration region, and the retention time is proportional to the logarithm of the molecular weight, allowing for accurate determination of the molecular weight distribution.

[0156] Proton nuclear magnetic resonance ( 1 Using 1H NMR spectroscopy, the (i) residual unsaturation (RU) and (ii) aliphatic methyl proton index (AlMPI) of a copolymer can be determined. The RU value corresponds to the amount of remaining olefinic units present in the polymer chain. AlMPI reflects the relative abundance of protons belonging to methyl groups located at the tips of short or long aliphatic branches. Both RU and AlMPI are, 1 This is obtained by using the quantitative integration of each resonance signal appearing in the 1H NMR spectrum and calculating it using the chemical unit molar mass.

[0157] The hydrogenation levels of blocks "R" and "S" are: 1 Using 1H NMR spectroscopy, integrals related to olefinic protons in HSBCs can be determined by comparing them with those present in the corresponding non-hydrogenated styrene-based block copolymers from which HSBCs were derived. The hydrogenation level of block "R" is calculated based on the percentage reduction in the olefinic proton signal intensity related to the diene units after hydrogenation. The hydrogenation level of block "S" is assessed by confirming that the aromatic proton signal intensity remains substantially unchanged compared to the non-hydrogenated styrene-based block copolymer, indicating that hydrogenation occurs primarily in the diene-derived segment.

[0158] The viscoelastic properties of bisbroken HSBCs, including tan δ at a specified temperature, tan δ peak temperature, and, where applicable, complex modulus (G*), can be measured using dynamic viscoelastic measurement (DMA). DMA provides a temperature-dependent viscoelastic profile that can determine the tan δ peak temperature, the tan δ value at a selected frequency, and G* at a given temperature.

[0159] The melt flow rate (MFR) of bisbroken HSBC can be measured under specified temperature and load conditions according to ASTM D1238. The MFR value is used to characterize the melt flow behavior of the polymer at high temperatures. [Examples]

[0160] The following examples are not limiting.

[0161] The following test methods will be used.

[0162] Glass transition temperature (T) of all polymer samples g Unless otherwise specified, the temperature was measured by DMA according to ASTM 4065. Here, the tan δ peak temperature is the T of the polymer. g It is considered that... Temperature sweep experiments were performed in the range of -80 to 200°C, with a heating gradient of 2°C / min and a shear mode of 10 radians / second using a plate / plate tool unless otherwise specified, and the complex modulus (G*), storage modulus (G'), loss modulus (G''), and dielectric loss (tan δ) were obtained as functions of temperature.

[0163] Unless otherwise specified, all reported melt flow rates (MFRs) were measured according to D1238 at a load of 2.16 kg and 190°C.

[0164] The components used in the examples include the following:

[0165] HSBC-1 (precursor) has a structure (SE / B) with 93% CE. nA coupled hydrogenated block copolymer having X, containing 7 wt% diblock. HSBC-1 is the main peak M of the block copolymer at 20 wt% VAC, 67 kg / mol. p , 5kg / mol block "S" M p It has a butylene unit ("B") content of 78% by weight, a RU of 0.1 meq / g, and a diene unit hydrogenation level of >99%.

[0166] HSBC-2 (precursor) has a structure (SE / B / S) with 93% CE. n It is a coupled hydrogenated block copolymer having X, and contains 7 wt% diblock. HSBC-2 is the main peak M of the block copolymer at 34 wt% total VAC, 125 kg / mol. p , block "S" with approximately 7 kg / mol p It has a butylene unit ("B") content of 72% by weight, a RU of 0.04 meq / g, and diene units with a hydrogenation level of >99%.

[0167] HSBC-3 (precursor) has the following structure (pMS-pMS / E / B) n This is a coupled hydrogenated block copolymer having X (n=2, 3, 4 and more). HSBC-3 contains 13 wt% diblock, 87% CE, 50 wt% VAC, and 123 kg / mol of block copolymer with a main peak M p , 11 kg / mol block "pMS" M p It has a butylene unit ("B") content of 76% by weight, a RU of 0.10 meq / g, and diene units with a hydrogenation level of >99%.

[0168] HSBC-4 (precursor) has a structure (SE / B) with 30% CE. n A coupled hydrogenated block copolymer having X, containing 70 wt% diblock. The HSBC-4 precursor is n=2, 30 wt% VAC, 37 kg / mol of the block copolymer, with the main peak M p , 7kg / mol block "S" M p, having a butylene unit (``B'') content of 40 wt%, 0.10 meq / g of RU, and the diene units having a hydrogenation level >99%.

[0169] HSBC-5 (precursor) has a structure (S-E / B) with 95% CE n A coupled hydrogenated block copolymer having X and containing 5 wt% of diblock content. HSBC-5 has 31 wt% of VAC, a main peak M of 57 kg / mol p , an M of the block ``S'' of 6 kg / mol p , having a butylene unit (``B'') content of 40 wt%, and the diene units having a hydrogenation level >99%.

[0170] SBC-6 (precursor) is a continuous non-hydrogenated block copolymer having a structure S-polybutadiene-S. SBC-6 has 38 wt% of VAC, a main peak M of 102 kg / mol p , an M of the block ``S'' of 10 kg / mol p and the diene units having a hydrogenation level of 0%.

[0171] HSBC-7 (precursor) has a structure (S-E / B) with 93% CE n A coupled hydrogenated block copolymer having X and containing 7 wt% of diblock content. HSBC-7 has 13 wt% of VAC, a main peak M of the block copolymer of 171 kg / mol p , an M of the block ``S'' of 6 kg / mol p , having a butylene unit (``B'') content of 80 wt%, and the diene units having a hydrogenation level of 99.97%.

[0172] APAO-1 is an amorphous polyolefin having a melt viscosity of 3000 mPa.s and a softening point of 108 °C measured at 190 °C.

[0173] APAO-2 is a silane-modified amorphous poly-α-olefin from Evonik.

[0174] Peroxide-1 (PO-1): 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane (DBPH).

[0175] Peroxide-2 (PO-2): bis(isobutyryl)peroxide (BIBP).

[0176] Peroxide-3 (PO-3): tert-butyl hydroperoxide (TBHP).

[0177] Peroxide-4 (PO-4): cumene hydroperoxide (CHP).

[0178] Peroxide-5 (PO-5): benzoyl peroxide (BPO).

[0179] Peroxide-6 (PO-6): lauroyl peroxide (LPO).

[0180] MA: maleic anhydride.

[0181] Silane: vinyltrimethoxysilane (VTMOS)

[0182] PIB-1 is a polyisobutylene having a Mw of 500 kg / mol, a DSC T of -64 °C g , and a density of 0.91 g / cm 3 .

[0183] PIB-2 is a polyisobutylene having a Mw of 53 kg / mol, a PDI of 3.2, a DSC T of -64 °C g , and a density of 0.91 g / cm 3 .

[0184] HCR-1 is a hydrogenated aliphatic hydrocarbon resin from Eastman having a softening point of 100 °C and a molecular weight (M z ).

[0185] TAIC: triallyl isocyanurate.

[0186] PPE-1: 160℃ T g and a modified low molecular weight bifunctional oligomer based on a polyphenylene ether having vinyl-terminated groups and a number-average molecular weight of 2300 g / mol.

[0187] (Examples 1-55): 100 parts of HSBC precursor were premixed at 25°C with a suitable amount of peroxide and, if applicable, a functionalizing agent (e.g., silane or maleic anhydride). The premixed contents were then fed into a twin-screw extruder at 25°C, and the extruder temperature (extruder temperature or "ET") was subsequently raised to a temperature in the range of 180-330°C. During melt processing in the extruder, controlled polymer chain severance occurred to produce bisbroken HSBC, and if a functionalizing agent was present, a functionalization reaction proceeded simultaneously to form functionalized bisbroken HSBC (fm-HSBC). Under these conditions, the molecular weight of each styrene-based block "S" in the bisbroken HSBC or fm-HSBC was substantially maintained compared to the corresponding block "S" in the HSBC precursor. The molten bisbroken or fm-HSBC exiting the extruder die was pelletized using an underwater pelletizer. The resulting pellets were then used to prepare specimens for various tests. The amounts of components used in each example and the extruder temperature are listed in Tables 1A to 1F. Unless otherwise specified, all examples were prepared using a single screw-breaking pass. The measured characteristics of the examples are summarized in Tables 2A to 2F and Table 3.

[0188] [Table 1]

[0189] [Table 2]

[0190] [Table 3]

[0191] Table 4

[0192] Table 5

[0193] Table 6

[0194] Table 7

[0195] Table 8

[0196] Table 9

[0197] Table 10

[0198] Table 11

[0199] Table 12

[0200] Table 13

[0201] (Examples 56-62): Preparation of PIB-based sealant compositions. Sealant compositions were prepared using bisbroken HSBC in the amounts described in Table 4 in combination with additional polymer components and additives. The components of each composition were combined and melt-mixed at 200°C for 45 minutes to obtain a homogeneous sealant composition. After melt processing, the sealant composition containing dibutyltin dilaurate as a curing catalyst (0.1 wt%) was cured by immersion in a water bath maintained at 60°C for 7 days. The water-to-sealant sample weight ratio during curing was 7:1. After curing, the cured sealant samples were removed from the water bath and their physical, mechanical, and thermal properties were evaluated. The compositions and corresponding measured properties are summarized in Table 4.

[0202] [Table 14]

[0203] (Examples 63-71): Preparation of CCL compositions. Compositions were prepared using bisbroken HSBC, PPE, and additives in the amounts described in Table 5. In each example, the components were combined using a solvent-based blending method with toluene, resulting in a total solids content of 25-30% by weight. BIBP (0.5% by weight) was added as a curing agent. After solution blending, the solvent was removed. The resulting compositions were then formed into test specimens for dielectric property evaluation using a hot press curing process, which included a step of preheating at 110°C, followed by final curing at 180°C for 2 hours to obtain a cured sample. After curing, the specimens were evaluated for dielectric, thermal, and mechanical properties. The compositions of Examples 63-71 and their corresponding measured properties are summarized in Table 5.

[0204] [Table 15]

Claims

1. At least one block "S" composed of vinyl aromatic units, and １ At least one block "R" consisting of hydrogenated diene units having a hydrogenation level of >50% as measured by 1H NMR. A bisbroken hydrogenated styrene-based block copolymer comprising, Low Mw Broadness Index (LMBI) ≥ 25% The GPC main peak molecular weight (M) for 10–200 kg / mol was measured according to ASTM D5296. ｐ ), The GPC molecular weight (M) of block "S" in the range of 3-20 kg / mol was measured according to ASTM D5296. ｐ ), １ Measured by 1H NMR, the maximum residual unsaturated uric acid (RU) was 0.5 meq / g. Measured by dynamic viscoelasticity, the tan δ peak temperature ranges from -42 to 20°C. １ The aliphatic methyl proton index (AlMPI) of 18–45% is measured by 1H NMR, and The melt flow rate (MFR) was measured according to ASTM D1238 at 190°C and a load of 2.16 kg, with a range of 10 to 2000 g / 10 min, preferably 10 to 400 g / 10 min, or more preferably 10 to 250 g / 10 min. A bisbroken hydrogenated styrene-based block copolymer characterized by the following:

2. Aromatic proton content of 1-30%, Aromatic block proton index (ArBPI) of 10-50%, and Aliphatic methyl proton index (AlMPI) of 23-40% (However, all characteristics are １ (Measured by 1H NMR) The bisbroken hydrogenated styrene-based block copolymer according to claim 1, having at least one of the following.

3. The bisbroken hydrogenated styrene-based block copolymer according to claim 1, having a residual unsaturated (RU) of 0 to 0.4 meq / g, or preferably 0 to 0.2 meq / g.

4. S-R, (S-R) ｎ X, S-R-S, S-R-S-R, R-S-R-S-R, (R-S-R) ｎ X, S-R-S-R-S, (S-R-S) ｎ The bis-broken hydrogenated styrene-based block copolymer according to any one of claims 1 to 3, having a general structure selected from X (where n is an integer from 2 to 30 and X is a residue of a coupling agent), and mixtures thereof.

5. １ A bisbroken hydrogenated styrene-based block copolymer according to any one of claims 1 to 3, having a butylene unit ("B") content of >40% by weight as measured by 1H NMR.

6. Block "R" is selected from E / B, E / B / S, EP / MB, EP / MB / S, E / B / EP / MB, and any combination thereof. Each block E / B is composed of ethylene ("E") units and butylene ("B") units. Each block E / B / S is composed of ethylene ("E") units, butylene ("B") units, and vinyl aromatic ("S") units. Each block EP / MB is composed of ethylene-propylene (EP) units and methylene-butylene (MB) units. Each block EP / MB / S is composed of ethylene-propylene (EP) units, methylene-butylene (MB) units, and vinyl aromatic ("S") units. Each block E / B / EP / MB consists of ethylene ("E") units, butylene ("B") units, ethylene-propylene (EP) units, and methylene-butylene (MB) units. A bisbroken styrene-hydrogenated block copolymer according to any one of claims 1 to 3.

7. (S-E / B) ｎ X, (SE / B / S) ｎ X, (pMS-pMS / E / B) ｎ The structure is selected from X (where n is an integer from 2 to 10, and X is a residue of the coupling agent) and combinations thereof. Each block "S" is composed of styrene units. Each block E / B is composed of ethylene ("E") units and butylene ("B") units. Each block E / B / S is composed of ethylene ("E") units, butylene ("B") units, and vinyl aromatic ("S") units. Each block pMS is composed of para-methylstyrene units. Each block pMS / E / B is composed of para-methylstyrene units, ethylene ("E") units, and butylene ("B") units. A bisbroken styrene-hydrogenated block copolymer according to any one of claims 1 to 3.

8. The tan δ value at 50°C was measured by dynamic viscoelasticity measurement, ranging from 0.08 to 1. Dynamic viscoelasticity measurements were taken at 100°C to obtain the complex modulus (G*) from 10 to 2000 kPa, and Gel content of <10% by weight, measured as described herein. A bisbroken hydrogenated styrene-based block copolymer according to any one of claims 1 to 3, having at least one of the above.

9. A bisbroken hydrogenated styrene-based block copolymer according to any one of claims 1 to 3, which is functionalized with at least one functionalizing agent selected from the group consisting of (meth)acrylate, alkoxysilane, anhydride, epoxide, acid, isocyanate, and combinations thereof.

10. The bisbroken hydrogenated styrene-based block copolymer according to claim 9, wherein the functionalizing agent is selected from maleic anhydride, vinyltrimethoxysilane, and combinations thereof.

11. １ A bisbroken hydrogenated styrene-based block copolymer according to any one of claims 1 to 3, having a vinyl aromatic unit content (VAC) of <60% by weight as measured by 1H NMR.

12. A bisbroken hydrogenated styrene-based block copolymer according to any one of claims 1 to 3, having a loss loss tangent (Df) of <0.010 at 10 GHz, as measured for the uncured polymer according to ASTM D2520.

13. A sealant composition, wherein, relative to the total weight of the polymer composition (a) 5 to 40% by weight of the bisbroken hydrogenated styrene-based block copolymer according to any one of claims 1 to 3 (b) 25 to 90% by weight of polyisobutylene, (c) 0 to 30% by weight of polyolefin, selected from the group consisting of amorphous polyalphaolefin (APAO), polyethylene, polypropylene, polyolefin elastomer, ethylene-α-olefin copolymer, and mixtures thereof. (d) 0 to 60% by weight of filler, and (e) 0 to 15% by weight of additives A sealant composition containing the following:

14. According to ASTM D1238, the melt flow rate (MFR) was measured at 130°C and under a load of 2.16 kg, and was >10 g / 10 min. After thermal conditioning at 125°C for 20 minutes, the glass substrate was measured and found to have a N / inch density of 900–2000 N / inch. ２ The shear peel strength at 25°C, and The temperature of 10% weight loss between 355 and 420°C was measured by thermogravimetric analysis (TGA). The sealant composition according to claim 13, having at least one of the following.

15. A curable resin composition, wherein the total weight of the curable resin composition is (a) 10 to 90% by weight of the bisbroken hydrogenated styrene-based block copolymer according to any one of claims 1 to 3 (b) 20 to 90% by weight of a resin, selected from the group consisting of epoxy resins, polyphenylene ether resins, cyanate ester resins, benzoxazine resins, phenolic resins, vinyl ester resins, bismaleimide resins, polyester resins, polyamide resins, ionomer resins, aromatic resins, and combinations thereof, and (c) Additives comprising 0 to 30% by weight, selected from the group consisting of fillers, curing agents, catalysts, flame retardants, coupling agents, processing aids, stabilizers, and mixtures thereof. It contains, and after hardening, <3.0 dielectric constant (Dk), and Loss tangent (Df) < 0.006 at 10 GHz (However, both are measured at 10 GHz according to ASTM D2520.) A curable resin composition having [a certain characteristic].

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