Ethylene / alpha-olefin copolymer and adhesive composition comprising same

Abstract

The present invention relates to an ethylene / alpha-olefin copolymer exhibiting excellent processability and adhesive properties, and an adhesive composition comprising same.

Description

Ethylene / alpha-olefin copolymer and adhesive composition containing the same

[0001] [Cross-reference with related applications]

[0002] The present application claims the benefit of priority based on Korean patent application 10-2024-0195270 filed December 24, 2024 and Korean patent application 10-2025-0202023 filed December 17, 2025, and all contents disclosed in the documents of said Korean patent applications are incorporated herein as part of the specification.

[0003]

[0004] [Technology Field]

[0005] The present invention relates to an ethylene / alpha-olefin copolymer exhibiting excellent processability and adhesive properties, and an adhesive composition containing the same.

[0006]

[0007] Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed according to their respective characteristics. Since its invention in the 1950s, the Ziegler-Natta catalyst has been widely applied in existing commercial processes. However, because it is a multi-site catalyst with multiple active sites, it is characterized by a wide molecular weight distribution of the polymer and has a problem in that there are limitations in securing desired properties due to the non-uniform compositional distribution of the comonomer.

[0008] Meanwhile, metallocene catalysts consist of a combination of a main catalyst, which is primarily composed of a transition metal compound, and a co-catalyst, which is an organometallic compound primarily composed of aluminum. Such catalysts are homogeneous complex catalysts and single-site catalysts; due to their single-site characteristics, they produce polymers with a narrow molecular weight distribution and a uniform compositional distribution of comonomers. Furthermore, they possess the ability to alter the stereoregularity, copolymerization characteristics, molecular weight, and degree of crystallinity of the polymer by modifying the catalyst's ligand structure and changing the polymerization conditions.

[0009] Meanwhile, linear low-density polyethylene is produced by copolymerizing ethylene and alpha-olefins at low pressure using a polymerization catalyst, and is a resin with a narrow molecular weight distribution, short chain branches of uniform length, and no long chain branches. In addition to the characteristics of general polyethylene, linear low-density polyethylene films have high breaking strength and elongation, as well as excellent tear strength and drop impact strength, so their use is increasing in stretch films and overlap films where it is difficult to apply conventional low-density polyethylene or high-density polyethylene.

[0010] However, when manufacturing linear low-density polyethylene using 1-butene or 1-hexene as a comonomer, productivity is higher compared to the process using 1-octene comonomer, but due to limitations in catalyst technology and process technology, the physical properties of these products are significantly inferior to those using 1-octene comonomer, and there is a problem of poor processability due to a narrow molecular weight distribution.

[0011] In addition, even if processability is improved, there is a problem in that the dispersion state according to molecular weight within the unit particles is not uniform, resulting in a rough extrusion appearance and unstable physical properties even under relatively good extrusion conditions.

[0012] Against this backdrop, there is a constant demand for the manufacture of superior products that strike a balance between physical properties and processability, and in particular, there is an increasing need for polyethylene copolymers with excellent processability.

[0013] [Prior Art Literature]

[0014] [Patent Literature]

[0015] (Patent Document 1) U.S. Registered Patent No. 5,064,802

[0016]

[0017] The objective of the present invention is to provide an ethylene / alpha-olefin copolymer that exhibits excellent processability and adhesive properties by controlling density, viscosity, and melt index, and an adhesive composition using the same.

[0018]

[0019] (1) The present invention provides an ethylene / alpha-olefin copolymer satisfying the following conditions (a) to (c).

[0020] (a) Density: 0.867 g / cc to 0.889 g / cc

[0021] (b) Viscosity: 16,000 to 20,000 cP at 177°C

[0022] (c) Full Width at Half Maximum (FWHM) of the crystallization peak when measuring the crystallization temperature by cross-fractionation chromatography (CFC): 22 to 50.

[0023] (2) The present invention provides an ethylene / alpha-olefin copolymer according to (1), wherein the density is 0.868 g / cc to 0.888 g / cc.

[0024] (3) The present invention provides an ethylene / alpha-olefin copolymer in which, in (1) or (2), the full width at half maximum (FWHM) of the crystallization peak that appears when measuring the crystallization temperature by cross-fractionation chromatography (CFC) is 22.2 to 49.0.

[0025] (4) The present invention provides an ethylene / alpha-olefin copolymer in any one of (1) to (3), wherein the melt index of the ethylene / alpha-olefin copolymer (at 190°C and under a 2.16 kg load) is 400 dg / min to 1,600 dg / min.

[0026] (5) The present invention provides an ethylene / alpha-olefin copolymer in any one of (1) to (4), wherein the number of vinyl functional groups per 1,000 carbons measured by nuclear magnetic spectroscopy is 0.01 to 2.0.

[0027] (6) The present invention provides an ethylene / alpha-olefin copolymer in any one of (1) to (5), wherein the number of vinylidene functional groups per 1,000 carbons measured by nuclear magnetic spectroscopy is 0.01 to 0.9.

[0028] (7) The present invention provides an ethylene / alpha-olefin copolymer in any one of (1) to (6), wherein the number of vinylene functional groups per 1,000 carbons measured by nuclear magnetic spectroscopy is 0.1 to 1.9.

[0029] (8) The present invention provides an ethylene / alpha-olefin copolymer in any one of (1) to (7), wherein the number of trisubstituted vinyl functional groups per 1,000 carbons measured by nuclear magnetic spectroscopy is 0.01 to 0.8.

[0030] (9) The present invention provides an ethylene / alpha-olefin copolymer in any one of (1) to (8), wherein the ethylene / alpha-olefin copolymer has a melting temperature of 50°C to 90°C.

[0031] (10) The present invention provides an ethylene / alpha-olefin copolymer in any one of (1) to (9), wherein the ethylene / alpha-olefin copolymer has a crystallization temperature of 30°C to 70°C.

[0032] (11) The present invention provides an adhesive composition comprising an ethylene / alpha-olefin copolymer according to any one of (1) to (10); and a tackifier.

[0033] (12) The present invention provides an adhesive composition in which, in (11) above, the adhesive agent is one or more selected from the group consisting of modified C5 hydrocarbon resin, styrene-modified terpene resin, fully or partially hydrogenated C9 hydrocarbon resin, hydrogenated cyclic aliphatic hydrocarbon resin and hydrogenated aromatic modified cyclic aliphatic hydrocarbon resin.

[0034] (13) The present invention provides an adhesive composition according to (11) or (12) wherein the adhesive composition has a viscosity of 450 cP to 1,400 cP at 177°C.

[0035]

[0036] The ethylene / alpha-olefin copolymer of the present invention exhibits excellent processability and adhesive properties.

[0037]

[0038] Hereinafter, the present invention will be described in more detail to aid in understanding the invention.

[0039]

[0040] Terms and words used in the description and claims of the present invention shall not be interpreted as being limited to their ordinary or dictionary meanings, and shall be interpreted in a meaning and concept consistent with the technical spirit of the present invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0041]

[0042] Ethylene / alpha-olefin copolymer

[0043] The ethylene / alpha-olefin copolymer of the present invention satisfies the following conditions (a) to (c).

[0044] (a) Density: 0.867 g / cc to 0.889 g / cc

[0045] (b) Viscosity: 16,000 to 20,000 cP at 177°C

[0046] (c) Full Width at Half Maximum (FWHM) of the crystallization peak when measuring the crystallization temperature by cross-fractionation chromatography (CFC): 22 to 50.

[0047]

[0048] The inventors confirmed that the processability and adhesive properties can be uniformly excellent when manufacturing adhesives by controlling the density, viscosity, and half-width of the crystallization peak appearing when measuring the crystallization temperature by cross-fractional chromatography of an ethylene / alpha-olefin copolymer within a specific range, and thus completed the present invention.

[0049]

[0050] The ethylene / alpha-olefin copolymer of the present invention has a density of 0.867 g / cc to 0.889 g / cc as measured according to ASTM D-792. The density may be 0.868 g / cc or higher, 0.869 g / cc or higher, or 0.870 g / cc or higher, and may be 0.888 g / cc or lower, 0.886 g / cc or lower, or 0.885 g / cc or lower, for example, 0.868 to 0.888 g / cc.

[0051] The ethylene / alpha-olefin copolymer has the advantage of excellent processability and adhesion due to having the above density. If the density is less than 0.867 g / cc, the set time increases, which increases the adhesive application time and reduces productivity, and if it exceeds 0.889 g / cc, a problem arises where the melting temperature of the adhesive increases excessively.

[0052]

[0053] The ethylene / alpha-olefin copolymer of the present invention has a viscosity of 16,000 cP to 20,000 cP at 177°C. The ethylene / alpha-olefin copolymer having the above viscosity has the advantage of excellent processability and adhesion. If the viscosity is less than 16,000 cP, the adhesion is inferior, and if it exceeds 20,000 cP, the flowability is low, resulting in poor processability.

[0054]

[0055] The ethylene / alpha-olefin copolymer of the present invention has a Full Width at Half Maximum (FWHM) of the crystallization peak that appears when measuring the crystallization temperature by cross-fractionation chromatography (CFC) of 22 to 50. Specifically, the FWHM may be 22.2 or higher, 22.5 or higher, 22.7 or higher, or 23.0 or higher, and may be 49.0 or lower, 48.0 or lower, 47.0 or lower, 46.0 or lower, or 45.0 or lower, for example, 22.2 to 49.0.

[0056] The ethylene / alpha-olefin copolymer has the advantage of excellent processability and adhesion by having the above half-width. If the above half-width is less than 22, the processability or adhesion is inferior.

[0057]

[0058] In the present invention, the melt index of the ethylene / alpha-olefin copolymer (under conditions of 190°C and a 2.16 kg load) may be 400 dg / min to 1,600 dg / min. Specifically, it may be 420 dg / min or more, 440 dg / min or more, 460 dg / min or more, or 470 dg / min or more, and may be 1,500 dg / min or less, 1,400 dg / min or less, 1,300 dg / min or less, or 1,250 dg / min or less.

[0059] If the above melt index is satisfied, the advantages of excellent processability and adhesion may be exhibited.

[0060]

[0061] In the present invention, the elution temperature (Te) of the ethylene / alpha-olefin copolymer may be 20°C to 35°C. Specifically, it may be 21°C or higher, 22°C or higher, or 23°C or higher, and 34°C or lower, 33°C or lower, 32°C or lower, or 31°C or lower.

[0062] If the above elution temperature is satisfied, the advantages of excellent processability and adhesion may be exhibited.

[0063]

[0064] In the present invention, the melting temperature (Tm) of the ethylene / alpha-olefin copolymer may be 50°C to 90°C. Specifically, it may be 51°C or higher, 52°C or higher, 53°C or higher, 54°C or higher, 55°C or higher, or 56°C or higher, 89°C or lower, 88°C or lower, 87°C or lower, 86°C or lower, 85°C or lower, 84°C or lower, 83°C or lower, 82°C or lower, 81°C or lower, 80°C or lower, 79°C or lower, 78°C or lower, or 77°C or lower.

[0065] In the present invention, the crystallization temperature (Tc) of the ethylene / alpha-olefin copolymer may be 30°C to 70°C. Specifically, it may be 31°C or higher, 32°C or higher, 33°C or higher, 34°C or higher, 35°C or higher, 36°C or higher, or 37°C or higher, 69°C or lower, 68°C or lower, 67°C or lower, 66°C or lower, 65°C or lower, 64°C or lower, 63°C or lower, 62°C or lower, 61°C or lower, 60°C or lower, or 59°C or lower.

[0066] When the above melting temperature and crystallization temperature are met, low-temperature adhesion is excellent and processability is improved.

[0067] The melting temperature and crystallization temperature mentioned above can be measured using a Differential Scanning Calorimeter (DSC). Specifically, the copolymer is heated to 150°C and maintained for 5 minutes, then lowered to 20°C, and then the temperature is increased again. At this time, the rate of increase and decrease in temperature are each controlled to 10°C / min, and the result measured during the second temperature increase is used as the melting temperature, while the result measured during the temperature decrease is used as the crystallization temperature.

[0068]

[0069] In the present invention, the number of vinyl functional groups per 1,000 carbons measured by nuclear magnetic spectroscopy analysis of the ethylene / alpha-olefin copolymer may be 0.01 to 2.0. Specifically, it may be 0.02 or more, 0.03 or more, 1.9 or less, 1.8 or less, 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, or 1.3 or less.

[0070] In addition, the ethylene / alpha-olefin copolymer of the present invention may have 0.01 to 0.9 vinylidene functional groups per 1,000 carbon atoms. Specifically, it may be 0.02 or more, 0.8 or less, 0.7 or less, or 0.6 or less.

[0071] In addition, the ethylene / alpha-olefin copolymer of the present invention may have 0.1 to 1.9 vinylene functional groups per 1,000 carbons as measured by nuclear magnetic spectroscopy. Specifically, it may be 0.11 or more, 0.12 or more, 0.13 or more, or 0.14 or more, 1.8 or less, 1.7 or less, 1.6 or less, or 1.5 or less.

[0072] In addition, the ethylene / alpha-olefin copolymer of the present invention may have 0.01 to 0.8 trisubstituted vinyl functional groups per 1,000 carbon atoms. Specifically, it may be 0.02 or more, 0.03 or more, 0.7 or less, or 0.6 or less.

[0073] In addition, the ethylene / alpha-olefin copolymer of the present invention may have a total number of unsaturated functional groups per 1,000 carbon atoms measured by nuclear magnetic spectroscopy analysis of 0.2 to 5.5. More specifically, it may be 0.21 or more, 0.22 or more, 0.23 or more, 0.24 or more, 0.25 or more, 0.26 or more, or 0.27 or more, 5.0 or less, 4.9 or less, 4.8 or less, 4.7 or less, 4.6 or less, 4.5 or less, 4.4 or less, 4.3 or less, 4.2 or less, 4.1 or less, 4.0 or less, 3.9 or less, 3.8 or less, or 3.7 or less.

[0074] The ethylene / alpha-olefin copolymer according to the present invention has an unsaturated number of functional groups as described above, thereby improving adhesion at low and room temperatures and exhibiting excellent processability, while also showing excellent long-term physical properties.

[0075]

[0076] The vinyl group has the structure R-CH=CH2, the trisubstituted vinyl group has the structure RCH=CR'R", the vinylene has the structure RCH=CHR'(E-form) or Z-RCH=CHR'(Z-form), and the vinylidene has the structure RR'C=CH2. Here, R, R', and R" may each independently be a polymer chain or a branched chain of an alpha-olefin that is a comonomer.

[0077] In the present invention, the content of vinyl, vinylidene, vinylene, and trisubstituted vinyl in the copolymer can be calculated from the results of NMR analysis. Specifically, the copolymer can be dissolved in 1,1,2,2-tetrachloroethane D2 (TCE-d2) solvent and then measured using a Bruker AVANCE III 500 MHz NMR instrument at 393 K. 1 The TCE-d2 peak in the H NMR spectrum is corrected to 6.0 ppm, and the content ratio of the comonomers is calculated using the integrated values ​​in the 1.4 ppm and 0.96 ppm regions. The content of each vinyl group, vinylidene group, vinylene group, and trisubstituted vinyl group observed at 4.7 ppm to 5.6 ppm is calculated (analytical method: AMT-3863). For peak assignment, refer to the literature [Macromolecules 2014, 47, 3282-3790].

[0078]

[0079] In addition, the ethylene / alpha-olefin copolymer of the present invention may have a molecular weight distribution (MWD) of 1.5 to 3.5. Specifically, it may be 1.6 or more, 1.7 or more, 1.8 or more, 1.9 or more, 2.0 or more, 2.1 or more, 2.2 or more, 2.3 or more, or 2.4 or more, 3.4 or less, 3.3 or less, 3.2 or less, 3.1 or less, 3.0 or less, 2.9 or less, or 2.8 or less.

[0080] According to one embodiment of the present invention, the ethylene / alpha-olefin copolymer may have a weight-average molecular weight (Mw) of 16,000 g / mol to 30,000 g / mol. Specifically, it may be 17,000 g / mol or more, 18,000 g / mol or more, 19,000 g / mol or more, 20,000 g / mol or more, 29,000 g / mol or less, or 28,000 g / mol or less.

[0081] When the weight-average molecular weight satisfies the above range, a significant improvement in processability can be expected in conjunction with the viscosity of the adhesive composition containing it. That is, the mechanical properties, impact strength, and viscosity of the ethylene / alpha-olefin copolymer can be controlled by adjusting the amount of catalyst used along with the type of catalyst used in the polymerization process, and in conjunction with the above conditions, improved processability can be exhibited while maintaining excellent mechanical properties.

[0082] Meanwhile, in the present invention, the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) are polystyrene equivalent molecular weights analyzed by gel permeation chromatography (GPC), and the molecular weight distribution can be calculated from the ratio of Mw / Mn.

[0083]

[0084] The ethylene / alpha-olefin copolymer of the present invention is prepared by copolymerizing ethylene with an alpha-olefin monomer, wherein the alpha-olefin, which refers to the portion derived from the alpha-olefin monomer within the copolymer, is a C4 to C20 alpha-olefin, specifically propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicocene, etc., and may be one of these alone or a mixture of two or more.

[0085] Among these, the alpha-olefin may be 1-butene, 1-hexene, or 1-octene, and preferably may be 1-butene, 1-hexene, or a combination thereof.

[0086] In addition, in the above ethylene / alpha-olefin copolymer, the content of alpha-olefin can be appropriately selected within a range that satisfies the above physical property requirements, specifically greater than 0 and less than or equal to 99 mol%, or 10 to 50 mol%.

[0087]

[0088] The ethylene / alpha-olefin copolymer of the present invention can be prepared by thermally decomposing a conventional ethylene / alpha-olefin copolymer at an appropriate temperature and time. Any conventional ethylene / alpha-olefin copolymer that can be easily obtained by a person skilled in the art, regardless of the route, such as a commercially available ethylene / alpha-olefin copolymer or an ethylene / alpha-olefin copolymer produced by a known method, may be used. More specifically, an ethylene / alpha-olefin copolymer having a melt index (MI, under conditions of 190°C and a 2.16 kg load) of 5.0 g / 10 min to 15.0 g / 10 min and a density of 0.850 g / cc to 0.890 g / cc may be used, but is not limited thereto.

[0089] Specifically, the above pyrolysis may be heated at 350°C to 470°C, or at 360°C or higher, 370°C or higher, 380°C or higher, 390°C or higher, or 400°C or higher, 460°C or lower, 450°C or lower, 440°C or lower, 430°C or lower, or 420°C or lower.

[0090] In addition, pyrolysis can be performed for 1 to 7 hours under the above temperature conditions, and specifically, for 1 hour or more, 2 hours or more, 3 hours or more, 6 hours or less, or 5 hours or less.

[0091]

[0092] In addition, the ethylene / alpha-olefin copolymer of the present invention can be manufactured through a manufacturing method of polymerizing ethylene and alpha-olefin monomers while introducing hydrogen under a catalyst composition containing a metallocene compound.

[0093] The above hydrogen input amount may be 100 cc / min to 700 cc / min, 150 cc / min or more, 170 cc / min or more, 200 cc / min or more, 250 cc / min or more, 600 cc / min or less, 500 cc / min or less, 400 cc / min or less, or 380 cc / min or less, but is not limited thereto.

[0094]

[0095] Adhesive composition

[0096] The present invention provides an adhesive composition comprising the ethylene / alpha-olefin copolymer; and a tackifier.

[0097]

[0098] In the present invention, the adhesive composition may have a viscosity of 450 cP to 1,400 cP at 177°C. Specifically, the viscosity may be 460 cP or more, 470 cP or more, 480 cP or more, 490 cP or more, 500 cP or more, 510 cP or more, 520 cP or more, or 530 cP or more, and may be 1,390 cP or less, 1,380 cP or less, 1,370 cP or less, 1,360 cP or less, 1,350 cP or less, 1,340 cP or less, 1,330 cP or less, 1,320 cP or less, or 1,310 cP or less.

[0099]

[0100] The above tackifier may be an aliphatic hydrocarbon resin, for example, a modified C5 hydrocarbon resin (C5 / C9 resin), a styrene-derived terpene resin, a fully or partially hydrogenated C9 hydrocarbon resin, a hydrogenated cyclic aliphatic hydrocarbon resin, a hydrogenated aromatic modified cyclic aliphatic hydrocarbon resin, and a mixture thereof.

[0101] The above tackifier is not particularly limited, but may be included in an amount of 5 to 70 parts by weight per 100 parts by weight of the adhesive composition, specifically in an amount of 20 to 70 parts by weight. If the tack resin is included in an amount less than 5 parts by weight, the viscosity of the adhesive composition may increase and processability may decrease, and if it is included in an amount exceeding 70 parts by weight, heat resistance may decrease.

[0102] The above ethylene / alpha-olefin copolymer may be included in an amount of 10 to 50 parts by weight per 100 parts by weight of the adhesive composition, specifically in an amount of 15 to 30 parts by weight. Excellent adhesive properties can be maintained when the above numerical range is satisfied.

[0103]

[0104] In addition, the adhesive composition may further include a plasticizer. The plasticizer is not particularly limited, but may be, for example, a paraffinic or naphthenic plasticizing oil. Specifically, it may be a low molecular weight polymer such as an olefin oligomer, liquid polybutene, polyisoprene copolymer, liquid styrene-isoprene copolymer, or liquid hydrogenated styrene-conjugated diene copolymer, vegetable oil and derivatives thereof, or microcrystalline wax.

[0105] The above plasticizer is not particularly limited, but may be included in an amount of 10 to 50 parts by weight, specifically 20 to 40 parts by weight, relative to 100 parts by weight of the adhesive composition. If the above plasticizer is included in an amount less than 10 parts by weight, the adhesive strength of the adhesive composition may increase, which may reduce processability, and if it is included in an amount exceeding 50 parts by weight, the adhesive properties may decrease.

[0106]

[0107] In addition, the adhesive composition may further include an antioxidant to improve heat resistance and color.

[0108] At this time, the antioxidant is not particularly limited and may be used if it is commonly known in the art, and may be included in an amount of 0.01 to 5 parts by weight, or 0.01 to 1 part by weight, or 0.05 to 0.75 parts by weight per 100 parts by weight of the adhesive composition.

[0109] In addition, the adhesive composition may further include one or more additives selected from the group consisting of UV stabilizers, colorants or pigments, fillers, flow aids, coupling agents, crosslinking agents, surfactants, solvents, and combinations thereof.

[0110] The above filler may be selected from sand, talc, dolomite, calcium carbonate, clay, silica, mica, wollastonite, feldspar, aluminum silicate, alumina, hydrated alumina, glass beads, glass microspheres, ceramic microspheres, thermoplastic microspheres, barite, wood powder, or a combination thereof, and the filler may be present in an amount of 80 weight percent or less of the total composition.

[0111]

[0112] In the present invention, the adhesive composition may be a hot melt adhesive composition.

[0113] The present invention provides an article comprising a substrate coated with the adhesive composition. The article may be selected from, but is not limited to, tape, label, transfer paper, box, cardboard, tray, medical device, bandage, and sanitary product.

[0114]

[0115] Examples

[0116] The present invention will be explained in more detail below through examples. However, the following examples are intended to illustrate the present invention and do not limit the scope of the present invention.

[0117]

[0118] Preparation Example 1

[0119] (1) Preparation of ligand compounds

[0120] <N-tert-butyl-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-dimethylsilanamine의 합성>

[0121] 4.65 g (15.88 mmol) of chloro(1,2-dimethyl-6,7-dihydro-3H-benzo[b]cyclopenta[d]thiophene-3-yl)dimethylsilane compound was weighed and added to a 100 mL Schrenk flask, after which 80 mL of THF was added. At room temperature, tBuNH2 (4 eq, 6.68 mL) was added, and the reaction was carried out at room temperature for 3 days. After the reaction, the THF was removed, and the mixture was filtered with hexane. After solvent drying, a yellow liquid was obtained in a yield of 4.50 g (86%).

[0122] 1 H-NMR (in CDCl3, 500 MHz): 7.99 (d, 1H), 7.83 (d, 1H), 7.35 (dd, 1H), 7.24 (dd, 1H), 3.49 (s, 1H), 2.37 (s, 3H), 2.17 (s, 3H), 1.27 (s, 9H), 0.19 (s, 3H), -0.17 (s, 3H).

[0123]

[0124] (2) Preparation of transition metal compounds

[0125]

[0126] The above ligand compound (1.06 g, 3.22 mmol / 1.0 eq) and 16.0 mL of MTBE (0.2 M) were placed in a 50 mL Schrenk flask and stirred first. At -40 °C, n-BuLi (2.64 mL, 6.60 mmol / 2.05 eq, 2.5 M in THF) was added, and the reaction was carried out overnight at room temperature. Subsequently, at -40 °C, MeMgBr (2.68 mL, 8.05 mmol / 2.5 eq, 3.0 M in diethyl ether) was slowly added dropwise, followed by the addition of TiCl4 (2.68 mL, 3.22 mmol / 1.0 eq, 1.0 M in toluene), and the reaction was carried out overnight at room temperature. The reaction mixture was then filtered through Celite using hexane. After solvent drying, a brown solid was obtained in a yield of 1.07 g (82%).

[0127] 1 H-NMR (in CDCl3, 500 MHz): 7.99 (d, 1H), 7.68 (d, 1H), 7.40 (dd, 1H), 7.30 (dd, 1H), 3.22 (s, 1H), 2.67 (s, 3H), 2.05 (s, 3H), 1.54 (s, 9H), 0.58 (s, 3H), 0.57 (s, 3H), 0.40 (s, 3H), -0.45 (s, 3H)

[0128]

[0129] Preparation Example 2

[0130] (1) Preparation of ligand compounds

[0131] <N-tert-부틸-1-(1,2-디메틸-3H-벤조[b]시클로펜타[d]티오펜-3-일)-1,1-(메틸)(2-메틸페닐)실란아민의 합성>

[0132] (i) Preparation of chloro-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene-3-yl)-1,1-(methyl)(2-methylphenyl)silane

[0133] 2.0 g (1.0 eq, 9.985 mmol) of 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene and 50 mL of THF were added to a 250 mL Schlenk flask, and 4.2 mL of n-BuLi (1.05 eq, 10.484 mmol, 2.5 M in hexane) was added dropwise at -30°C and stirred overnight at room temperature. The stirred Li-complex THF solution was cannulated at -78°C into a Schlenk flask containing 2.46 g (1.2 eq, 11.982 mmol) of dichloro(O-tolylmethyl)silane and 30 mL of THF, and stirred overnight at room temperature. After stirring, the mixture was vacuum dried and then extracted with 100 mL of hexane.

[0134] (ii) Preparation of N-tert-butyl-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene-3-yl)-1,1-(methyl)(2-methylphenyl)silanamine

[0135] 4.0 g (1.0 eq, 10.0 mmol) of extracted chloro-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene-3-yl)-1,1-(methyl)(2-methylphenyl)silane was stirred in 10 mL of hexane, then 4.2 mL (4.0 eq, 40.0 mmol) of t-BuNH2 was added at room temperature, and the mixture was stirred overnight at room temperature. After stirring, the mixture was vacuum dried and then extracted with 150 mL of hexane. After solvent drying, 4.26 g (99%, dr = 1:0.83) of viscous liquid was obtained.

[0136] 1H-NMR (CDCl3, 500 MHz): δ 7.95(t, 2H), 7.70(d, 1H), 7.52(d, 1H), 7.47-7.44(m, 2H), 7.24-7.02(m, 9H), 6.97(t, 1H), 3.59(s, 1H), 3.58(s, 1H), 2.50(s, 3H), 2.44(s, 3H), 2.25(s, 3H), 2.16(s, 3H), 2.06(s, 3H), 1.56(s, 3H), 1.02(s, 9H), 0.95(s, 9H), -0.03(s, 3H), -0.11(s, 3H)

[0137]

[0138] (2) Preparation of transition metal compounds

[0139]

[0140] The above ligand compound (4.26 g, 10.501 mmol) was added to 53 mL of MTBE (0.2 M) in a 250 mL round-bottom flask and stirred. At -40°C, n-BuLi (8.6 mL, 21.52 mmol, 2.05 eq, 2.5 M in hexane) was added and stirred overnight at room temperature.

[0141] Subsequently, MeMgBr (8.8 mL, 26.25 mmol, 2.5 eq, 3.0 M in diethyl ether) was slowly added dropwise at -40℃, followed by the addition of TiCl4 (10.50 mL, 10.50 mmol) and stirring overnight at room temperature. The reaction mixture was then filtered using hexane. DME (3.3 mL, 31.50 mmol) was added to the filtrate, and the solution was filtered and concentrated using hexane to obtain 3.42 g of a yellow solid (68%, dr=1:0.68).

[0142] 1H NMR (CDCl3, 500 MHz): δ 7.83 (d, 1H), 7.80 (d, 1H), 7.74 (d, 1H), 7.71 (d, 1H), 7.68 (d, 1H), 7.37 (d, 1H), 7.31-6.90 (m, 9H), 6.84(t, 1H), 2.54(s, 3H), 2.47(s, 3H), 2.31(s, 3H), 2.20(s, 3H), 1.65(s, 9H), 1.63(s, 9H), 1.34(s, 3H), 1.00(s, 3H), 0.98(s, 3H), 0.81(s, 3H), 0.79(s, 3H), 0.68(s, 3H), 0.14(s, 3H), -0.03(s, 3H)

[0143]

[0144] Example 1

[0145] 1 kg of ethylene / octene copolymer (LG Chem LC670, MI: 5 g / 10 min, density: 0.871 g / cc) was weighed, placed in a 5 L batch reactor, and under vacuum to remove moisture and oxygen. Once removal was complete, the beaker was filled with argon (Ar) gas to inert it. A mechanical stirrer and impeller were connected to the beaker containing the ethylene / octene copolymer, and it was heated at 400°C for 5 hours while stirring at a speed of 300 rpm to pyrolyze it. After cooling the pyrolyzed copolymer sufficiently under argon (Ar), the beaker was opened to obtain the product.

[0146]

[0147] Example 2

[0148] 1 kg of ethylene / butene copolymer (LG Chem LC575, MI: 5 g / 10 min, density: 0.875 g / cc) was weighed, placed in a 5 L batch reactor, and under vacuum to remove moisture and oxygen. Once removal was complete, the beaker was filled with argon (Ar) gas to make it inert. A mechanical stirrer and impeller were connected to the beaker containing the ethylene / butene copolymer, and it was heated at 400°C for 5 hours while stirring at a speed of 400 rpm to pyrolyze it. After cooling the pyrolyzed copolymer sufficiently under argon (Ar), the beaker was opened to obtain the product.

[0149]

[0150] Example 3

[0151] A 1.5L continuous process reactor was preheated to 150°C while introducing 5.0 kg / h of hexane solvent and 0.7 kg / h of 1-butene. A triisobutylaluminum compound (0.045 mmol / min), a metallocene catalyst (a mixture of the transition metal compounds of Preparation Example 1 and Preparation Example 2 in a 5:5 molar ratio, 0.240 μmol / min), and a dimethylanilinium tetrakis(pentafluorophenyl)borate co-catalyst (2.288 μmol / min) were simultaneously introduced into the reactor. Subsequently, ethylene (0.87 kg / h) and hydrogen gas (280 cc / min) were introduced into the reactor, and the copolymerization reaction was carried out by maintaining the reactor at 150°C for at least 60 minutes under a continuous process at a pressure of 89 bar to obtain an ethylene / butene copolymer. Afterward, the physical properties were measured after drying in a vacuum oven for at least 12 hours.

[0152]

[0153] Example 4

[0154] A 1.5L continuous process reactor was preheated to 150°C while introducing 5.0 kg / h of hexane solvent and 0.85 kg / h of 1-butene. A triisobutylaluminum compound (0.045 mmol / min), a metallocene catalyst (a mixture of the transition metal compounds of Preparation Example 1 and Preparation Example 2 in a 5:5 molar ratio, 0.240 μmol / min), and a dimethylanilinium tetrakis(pentafluorophenyl)borate co-catalyst (2.288 μmol / min) were simultaneously introduced into the reactor. Subsequently, ethylene (0.87 kg / h) and hydrogen gas (250 cc / min) were introduced into the reactor, and the copolymerization reaction was carried out by maintaining the reactor at 150°C for at least 60 minutes under a continuous process at a pressure of 89 bar to obtain an ethylene / butene copolymer. Afterward, the physical properties were measured after drying in a vacuum oven for at least 12 hours.

[0155]

[0156] Example 5

[0157] A 1.5L continuous process reactor was preheated to 150°C while introducing 5.0 kg / h of hexane solvent and 1.2 kg / h of 1-octene. A triisobutylaluminum compound (0.045 mmol / min), a metallocene catalyst (a mixture of the transition metal compounds of Preparation Example 1 and Preparation Example 2 in a 5:5 molar ratio, 0.240 μmol / min), and a dimethylanilinium tetrakis(pentafluorophenyl)borate co-catalyst (2.288 μmol / min) were simultaneously introduced into the reactor. Subsequently, ethylene (0.87 kg / h) and hydrogen gas (280 cc / min) were introduced into the reactor, and the copolymerization reaction was carried out by maintaining the reactor at 150°C for at least 60 minutes under a continuous process at a pressure of 89 bar to obtain an ethylene / octene copolymer. Afterward, the physical properties were measured after drying in a vacuum oven for at least 12 hours.

[0158]

[0159] Comparative Example 1

[0160] 1 kg of ethylene / butene copolymer (LG Chem LC675, MI: 14 g / 10 min, density: 0.877 g / cc) was weighed, placed in a 5 L batch reactor, and under vacuum to remove moisture and oxygen. Once removal was complete, the beaker was filled with argon (Ar) gas to inert it. A mechanical stirrer and impeller were connected to the beaker containing the ethylene / butene copolymer, and it was heated at 380°C for 2 hours while stirring at a speed of 300 rpm to pyrolyze it. After sufficiently cooling the pyrolyzed copolymer under argon (Ar), the beaker was opened to obtain the product.

[0161]

[0162] Comparative Example 2

[0163] 1 kg of ethylene / butene copolymer (LG Chem LC675, MI: 14 g / 10 min, density: 0.877 g / cc) was weighed, placed in a 5 L batch reactor, and under vacuum to remove moisture and oxygen. Once removal was complete, the beaker was filled with argon (Ar) gas to inert it. A mechanical stirrer and impeller were connected to the beaker containing the ethylene / butene copolymer, and it was heated at 430°C for 2 hours while stirring at a speed of 300 rpm to pyrolyze it. After sufficiently cooling the pyrolyzed copolymer under argon (Ar), the beaker was opened to obtain the product.

[0164]

[0165] Comparative Example 3

[0166] A 1.5L continuous process reactor was preheated to 150°C while introducing 5.0 kg / h of hexane solvent and 0.6 kg / h of 1-butene. A triisobutylaluminum compound (0.045 mmol / min), a metallocene catalyst (a mixture of the transition metal compounds of Preparation Example 1 and Preparation Example 2 in a 5:5 molar ratio, 0.240 μmol / min), and a dimethylanilinium tetrakis(pentafluorophenyl)borate co-catalyst (2.288 μmol / min) were simultaneously introduced into the reactor. Subsequently, ethylene (0.87 kg / h) and hydrogen gas (300 cc / min) were introduced into the reactor, and the copolymerization reaction was carried out by maintaining the reactor at 150°C for at least 60 minutes under a continuous process at a pressure of 89 bar to obtain an ethylene / butene copolymer. Afterward, the physical properties were measured after drying in a vacuum oven for at least 12 hours.

[0167]

[0168] Comparative Example 4

[0169] A 1.5L continuous process reactor was preheated to 150°C while introducing 5.0 kg / h of hexane solvent and 0.9 kg / h of 1-butene. A triisobutylaluminum compound (0.045 mmol / min), a metallocene catalyst (a mixture of the transition metal compounds of Preparation Example 1 and Preparation Example 2 in a 5:5 molar ratio, 0.240 μmol / min), and a dimethylanilinium tetrakis(pentafluorophenyl)borate co-catalyst (2.288 μmol / min) were simultaneously introduced into the reactor. Subsequently, ethylene (0.87 kg / h) and hydrogen gas (310 cc / min) were introduced into the reactor, and the copolymerization reaction was carried out by maintaining the reactor at 150°C for at least 60 minutes under a continuous process at a pressure of 89 bar to obtain an ethylene / butene copolymer. Afterward, the physical properties were measured after drying in a vacuum oven for at least 12 hours.

[0170]

[0171] Comparative Example 5

[0172] A 1.5L continuous process reactor was preheated to 150°C while introducing 5.0 kg / h of hexane solvent and 0.8 kg / h of 1-butene. A triisobutylaluminum compound (0.045 mmol / min), a metallocene catalyst (transition metal compound of Preparation Example 1, 0.240 μmol / min), and a dimethylanilinium tetrakis(pentafluorophenyl)borate co-catalyst (2.288 μmol / min) were simultaneously introduced into the reactor. Subsequently, ethylene (0.87 kg / h) and hydrogen gas (330 cc / min) were introduced into the reactor, and the copolymerization reaction was carried out by maintaining the reactor at 150°C for at least 60 minutes under a continuous process at a pressure of 89 bar to obtain an ethylene / butene copolymer. Afterward, the physical properties were measured after drying in a vacuum oven for at least 12 hours.

[0173]

[0174] Comparative Example 6

[0175] A 1.5L continuous process reactor was preheated to 150°C while introducing 5.0 kg / h of hexane solvent and 1.4 kg / h of 1-octene. A triisobutylaluminum compound (0.045 mmol / min), a metallocene catalyst (transition metal compound of Preparation Example 1, 0.240 μmol / min), and a dimethylanilinium tetrakis(pentafluorophenyl)borate co-catalyst (2.288 μmol / min) were simultaneously introduced into the reactor. Subsequently, ethylene (0.87 kg / h) and hydrogen gas (230 cc / min) were introduced into the reactor, and the copolymerization reaction was carried out by maintaining the reactor at 150°C for at least 60 minutes under a continuous process at a pressure of 89 bar to obtain an ethylene / octene copolymer. Afterward, the physical properties were measured after drying in a vacuum oven for at least 12 hours.

[0176]

[0177] Comparative Example 7

[0178] 1 kg of ethylene / butene copolymer (LG Chem LC675, MI: 14 g / 10 min, density: 0.877 g / cc) was weighed, placed in a 5 L batch reactor, and under vacuum to remove moisture and oxygen. Once removal was complete, the beaker was filled with argon (Ar) gas to make it inert. A mechanical stirrer and impeller were connected to the beaker containing the ethylene / butene copolymer, and it was heated at 420°C for 3 hours while stirring at a speed of 300 rpm to pyrolyze it. After sufficiently cooling the pyrolyzed copolymer under argon (Ar), the beaker was opened to obtain the product.

[0179]

[0180] Comparative Example 8

[0181] A 1.5L continuous process reactor was preheated to 150°C while introducing 5.0 kg / h of hexane solvent and 0.7 kg / h of 1-butene. A triisobutylaluminum compound (0.045 mmol / min), a metallocene catalyst (a mixture of the transition metal compounds of Preparation Example 1 and Preparation Example 2 in a 5:5 molar ratio, 0.240 μmol / min), and a dimethylanilinium tetrakis(pentafluorophenyl)borate co-catalyst (2.288 μmol / min) were simultaneously introduced into the reactor. Subsequently, ethylene (0.87 kg / h) and hydrogen gas (380 cc / min) were introduced into the reactor, and the copolymerization reaction was carried out by maintaining the reactor at 150°C for at least 60 minutes under a continuous process at a pressure of 89 bar to obtain an ethylene / butene copolymer. Afterward, the physical properties were measured after drying in a vacuum oven for at least 12 hours.

[0182]

[0183] Comparative Example 9

[0184] 1 kg of ethylene / butene copolymer (LG Chem LC575, MI: 5 g / 10 min, density: 0.875 g / cc) was weighed, placed in a 5 L batch reactor, and under vacuum to remove moisture and oxygen. Once removal was complete, the beaker was filled with argon (Ar) gas to inert it. A mechanical stirrer and impeller were connected to the beaker containing the ethylene / butene copolymer, and it was pyrolyzed by heating at 420°C for 5 hours while stirring at a speed of 420 rpm. After sufficiently cooling the pyrolyzed copolymer under argon (Ar), the beaker was opened to obtain the product.

[0185]

[0186] Experimental Example 1

[0187] The physical properties of each copolymer prepared in the above examples and comparative examples were compared and analyzed. The measurement conditions and methods are as follows.

[0188]

[0189] * Density

[0190] According to ASTM D-792, a sheet with a thickness of 3 mm and a radius of 2 cm was prepared using a 180°C press mold and cooled at 10°C / min and measured on a Mettler balance.

[0191]

[0192] * Viscosity (cP)

[0193] Measurements were taken using a Brookfield RVDV3T viscometer according to the following method. Specifically, a sample was placed in a 13 ml sample chamber and heated to 177°C using a Brookfield Thermosel. Once the sample was completely melted, the viscometer device was lowered and the spindle was fixed in the sample chamber. The rotation speed of the spindle (SC-29 high-temperature melting spindle) was fixed at 10 rpm, and readings were taken for at least 20 minutes or until the value stabilized, and the final value was recorded.

[0194]

[0195] * Melt Index (MI)

[0196] MI according to ASTM D-1238 2.16 (Condition E, 190℃, 2.16 kg load) was measured.

[0197]

[0198] Full Width at Half Maximum (FWHM) of the crystallization peak

[0199] PolymerChar's CFC was used as the measuring instrument. First, a copolymer solution was completely dissolved in an oven inside a CFC analyzer at 130°C for 60 minutes using o-dichlorobenzene as a solvent, then poured into a TREF column adjusted to 135°C, cooled to 95°C, and stabilized there for 45 minutes. Subsequently, the temperature of the TREF column was lowered to -20°C at a rate of 0.5°C / min and maintained at -20°C for 10 minutes. Afterward, the elution amount (mass %) was measured using an infrared spectrophotometer. Next, the temperature of the TREF column was raised at a rate of 20°C / min to a preset temperature and maintained at the reached temperature for a preset time (i.e., approximately 27 minutes), and this process was repeated until the TREF temperature reached 130°C, and the amount of eluted fraction (mass %) was measured during each temperature range. In addition, the fractions eluted at each temperature were sent to a GPC column to measure the molecular weight (Mw) in the same manner as the GPC measurement principle, except that o-dichlorobenzene was used as the solvent. The FWHM value was calculated by fitting the graph of elution amount according to temperature (dW / dT vs T) obtained from CFCs into a Gaussian curve form in the program (Origin).

[0200]

[0201] * Elution temperature (Te)

[0202] The elution temperature was determined as Te, based on the peak of the largest magnitude in the CFC elution curve expressed as the elution amount (dC / dT).

[0203]

[0204] * Molecular weight distribution

[0205] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the produced copolymer were measured under the following gel permeation chromatography (GPC) analysis conditions.

[0206] - Column: Agilent Olexis

[0207] - Solvent: Trichlorobenzene (TCB)

[0208] - Flow rate: 1.0 ml / min

[0209] - Sample concentration: 1.0 mg / ml

[0210] - Injection volume: 200 µl

[0211] - Column temperature: 160℃

[0212] - Detector: Agilent High Temperature RI detector

[0213] - Standard: Polystyrene (corrected by a cubic function)

[0214] - Data processing: Cirrus

[0215] The molecular weight distribution was calculated from the ratio of Mw / Mn.

[0216]

[0217] * Melting temperature, crystallization temperature

[0218] The melting temperature (Tm) and crystallization temperature (Tc) can be obtained using a Differential Scanning Calorimeter (DSC 6000) manufactured by PerkinElmer. Specifically, using DSC, the temperature of the copolymer was increased to 200°C and maintained for 5 minutes under a nitrogen atmosphere, then cooled to 30°C, and the temperature was increased again while observing the DSC curve. At this time, the heating rate and cooling rate were each set to 10°C / min.

[0219] In the measured DSC curve, the melting temperature was determined as the maximum point of the endothermic peak during the second heating increase, and the crystallization temperature was determined as the maximum point of the exothermic peak during cooling.

[0220]

[0221] Referring to Table 1 above, it was confirmed that the ethylene / alpha-olefin copolymers of Examples 1 to 5 according to the present invention have a density of 0.867 g / cc to 0.889 g / cc, a viscosity of 16,000 cP to 20,000 cP at 177°C, and a Full Width at Half Maximum (FWHM) of the crystallization peak appearing when measuring the crystallization temperature by Cross-Fraction Chromatography (CFC) of 22 to 50. Meanwhile, the ethylene / alpha-olefin copolymers of Comparative Examples 1, 2, and 4 to 9 have a viscosity outside the range of 16,000 cP to 20,000 cP, and Comparative Examples 3 and 4 have a density outside the range of 0.867 g / cc to 0.889 g / cc, and Comparative Examples 5 and 6 confirmed that the full width at half maximum of the crystallization peaks exceeded 22 to 50.

[0222]

[0223] * Number of unsaturated functional groups

[0224] In addition, the number of each functional group of vinylene, trisubstituted vinyl, vinyl, and vinylidene per 1,000 carbon atoms in the copolymer was measured through nuclear magnetic spectroscopy analysis according to the following method.

[0225] The copolymer was dissolved in 1,1,2,2-tetrachloroethane D2 (TCE-d2) solvent and measured at 393K using a Bruker AVANCE III 500MHz NMR instrument.

[0226] 1 The TCE-d2 peak in the H NMR spectrum was corrected to 6.0 ppm, and the comonomer content ratio was calculated using the integrated values ​​in the 1.4 ppm and 0.96 ppm regions. The content of vinyl groups, vinylidene groups, vinylene groups, and trisubstituted vinyl groups observed at 4.7 ppm to 5.6 ppm was calculated (analytical method: AMT-3863). Peak assignment was referenced from the literature [Macromolecules 2014, 47, 3282-3790].

[0227]

[0228]

[0229] Experimental Example 2

[0230] 200g of the ethylene / alpha-olefin copolymer of the above-described examples and comparative examples, 200g of Eastman’s Regaltac H100W, 100g of Sasol’s H1, and 2.5g of an antioxidant were placed in a beaker, heated with a heating mantle to melt them, and then thoroughly stirred and mixed with an impeller to prepare an adhesive.

[0231]

[0232] * Viscosity measurement

[0233] Measurements were taken using a Brookfield RVDV3T viscometer according to the following method. Specifically, 8 mL of the obtained adhesive was placed in a sample chamber, heated to 150°C using a Brookfield Thermosel, and once the sample was completely melted, the viscometer device was lowered and the spindle was fixed in the sample chamber. The rotation speed of the spindle (SC-21 high-temperature melt spindle) was fixed at 5 rpm, and readings were taken for at least 20 minutes or until the value stabilized, and the final value was recorded.

[0234] The viscosity was measured using the same method when the heating temperature was set to 177℃. Meanwhile, when the viscosity is less than 450 cp or greater than 1,400 cp, the flowability is too high or too low, resulting in significantly inferior processability and an uneven adhesive surface.

[0235]

[0236] * Fiber Tear Measurement

[0237] The obtained adhesive was used to obtain a film of uniform thickness using a roll coater, transferred onto kraft paper, and adhered. The film was then stored in an oven at -30℃ and 25℃. After storage for a certain period, the film was peeled off, and the ratio of the adhered area was calculated to determine the fiber tear. Fiber tear represents the area where adhesive strength is maintained; a larger area indicates superior adhesive strength.

[0238] The evaluation was conducted according to the criteria below and is shown in Table 3.

[0239] ◎: Fiber Tear Exceeds 75%

[0240] ○: Fiber Tear Exceeds 50%

[0241] △: Fiber Tear Exceeds 25%

[0242] ×: Fiber Tear 25% or less

[0243]

[0244] * Set time measurement

[0245] The adhesive was placed in an oven at 180°C and sufficiently melted, then applied to kraft paper to a uniform thickness. The kraft paper was then quickly attached over it. The time required for the bonded area to exceed 50% was measured while peeling off the kraft paper at 1-second intervals. A shorter set time indicates superior productivity, as it takes less time for the adhesive to solidify and acquire adhesive strength.

[0246] The evaluation was conducted according to the criteria below and is shown in Table 3.

[0247] ◎: Set time less than 5s

[0248] ○: Set time less than 10s

[0249] △: set time less than 15s

[0250] ×: set time 15s or more

[0251]

[0252] Shear Adhesion Breakdown Temperature (SAFT, °C)

[0253] The adhesive was placed in an oven at 180°C to be sufficiently melted, then applied to kraft paper to a uniform thickness, and the kraft paper was rapidly attached over it to prepare test specimens. The shear adhesive failure temperature of each prepared specimen was measured in shear mode using a weight of 500 g according to ASTM D4498. The test was started at room temperature (25°C), the oven temperature was increased at an average rate of 0.5°C / min, and the temperature at which the specimen failed (detach) was recorded. The shear adhesive failure temperature is the temperature at which the adhesive surface separates due to shear load when the adhesive is exposed to high temperatures; a higher temperature indicates superior high-temperature adhesion.

[0254]

[0255] Examples 1 to 5 are ethylene / alpha-olefin copolymers having density, viscosity, and FWHM within the appropriate range of the present invention. They exhibited excellent low-temperature and room-temperature adhesion, and demonstrated excellent productivity due to a short set time. Furthermore, it was confirmed that they had excellent high-temperature adhesion from the elevated shear adhesion failure temperature. Meanwhile, Comparative Example 1 is an adhesive containing an ethylene / alpha-olefin copolymer with very high viscosity. Although it showed excellent adhesion due to its high viscosity, its viscosity exceeded 1,400 cp at 177°C, resulting in very low flowability. This made it difficult to apply the adhesive, leading to poor processability and an uneven adhesive surface. Additionally, it took a long time to solidify, resulting in a long duration of adhesion and poor productivity. On the other hand, Comparative Example 2 had very low viscosity and very high flowability, making it difficult to apply the adhesive and resulting in inferior processability and reduced adhesion.

[0256] In addition, Comparative Examples 3 to 6 had inferior low-temperature adhesive strength and room-temperature adhesive strength, or inferior productivity due to the slow solidification speed of the adhesive, and inferior high-temperature adhesive strength.

[0257] In addition, Comparative Examples 7 to 9 showed a reduced shear adhesive failure temperature compared to the Examples, and from this, it was confirmed that the high-temperature adhesive strength was inferior.

Claims

1. An ethylene / alpha-olefin copolymer satisfying conditions (a) to (c) below: (a) Density: 0.867 g / cc to 0.889 g / cc (b) Viscosity: 16,000 to 20,000 cP at 177°C (c) Full Width at Half Maximum (FWHM) of the crystallization peak when measuring the crystallization temperature by cross-fractionation chromatography (CFC): 22 to 50.

2. In Claim 1, The above ethylene / alpha-olefin copolymer having a density of 0.868 g / cc to 0.888 g / cc.

3. In Claim 1, An ethylene / alpha-olefin copolymer having a Full Width at Half Maximum (FWHM) of the crystallization peak appearing when measuring the crystallization temperature by the above cross-fractionation chromatography (CFC) of 22.2 to 49.

0.

4. In Claim 1, The above ethylene / alpha-olefin copolymer has a melt index (under conditions of 190°C, 2.16 kg load) of 400 dg / min to 1,600 dg / min.

5. In Claim 1, The above ethylene / alpha-olefin copolymer is an ethylene / alpha-olefin copolymer having 0.01 to 2.0 vinyl functional groups per 1,000 carbons as measured by nuclear magnetic spectroscopy.

6. In Claim 1, The above ethylene / alpha-olefin copolymer is an ethylene / alpha-olefin copolymer having 0.01 to 0.9 vinylidene functional groups per 1,000 carbons as measured by nuclear magnetic spectroscopy.

7. In Claim 1, The above ethylene / alpha-olefin copolymer is an ethylene / alpha-olefin copolymer having 0.1 to 1.9 vinylene functional groups per 1,000 carbons as measured by nuclear magnetic spectroscopy.

8. In Claim 1, The above ethylene / alpha-olefin copolymer is an ethylene / alpha-olefin copolymer having 0.01 to 0.8 trisubstituted vinyl functional groups per 1,000 carbons as measured by nuclear magnetic spectroscopy.

9. In Claim 1, The above ethylene / alpha-olefin copolymer is an ethylene / alpha-olefin copolymer having a melting temperature of 50°C to 90°C.

10. In Claim 1, The above ethylene / alpha-olefin copolymer is an ethylene / alpha-olefin copolymer having a crystallization temperature of 30°C to 70°C.

11. An adhesive composition comprising an ethylene / alpha-olefin copolymer according to any one of claims 1 to 10; and a tackifier.

12. In Claim 11, The adhesive composition wherein the above tackifier is one or more selected from the group consisting of modified C5 hydrocarbon resin, styrene-modified terpene resin, fully or partially hydrogenated C9 hydrocarbon resin, hydrogenated cyclic aliphatic hydrocarbon resin, and hydrogenated aromatic modified cyclic aliphatic hydrocarbon resin.

13. In Claim 11, The above adhesive composition is an adhesive composition having a viscosity of 450 cP to 1,400 cP at 177°C.

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