Title of Invention: Adhesive composition containing ethylene/alpha-olefin copolymer
Technical field
[One]
Mutual citation with related applications
[2]
This application claims the benefit of priority based on the Korean patent applications 2018-0052046 and 2018-0052043 filed on May 4, 2018, and all contents disclosed in the literature of the corresponding Korean patent applications are incorporated as part of this specification.
[3]
[4]
Technical field
[5]
The present invention relates to an adhesive composition comprising an ethylene/alpha-olefin copolymer and an article comprising the same.
Background
[6]
The olefin polymerization catalyst system can be classified into a Ziegler Natta and a metallocene catalyst system, and these two highly active catalyst systems have been developed according to their respective characteristics. Ziegler Natta catalysts have been widely applied to conventional commercial processes since their invention in the 1950s, but since they are multi-site catalysts with multiple active points, they are characterized by a wide molecular weight distribution of polymers and comonomers. There is a problem in that there is a limit to securing desired physical properties because the composition distribution of is not uniform.
[7]
On the other hand, the metallocene catalyst is composed of a combination of a main catalyst composed of a transition metal compound and a cocatalyst composed of an organometallic compound composed mainly of aluminum. Such a catalyst is a homogeneous complex catalyst and is a single site catalyst. A polymer having a narrow molecular weight distribution and a uniform composition distribution of a comonomer is obtained according to the single active point characteristics, and the stereoregularity of the polymer, copolymerization characteristics, molecular weight, and It has properties that can change crystallinity and the like.
[8]
U.S. Patent No. 5,914,289 describes a method of controlling the molecular weight and molecular weight distribution of a polymer using a metallocene catalyst supported on each carrier, but it takes a lot of time and the amount of solvent used to prepare the supported catalyst. In addition, there was a hassle of having to support each of the metallocene catalysts used on the carrier.
[9]
Korean Patent Application No. 10-2003-0012308 discloses a method of controlling the molecular weight distribution by supporting a double-nuclear metallocene catalyst and a single-nuclear metallocene catalyst on a carrier together with an activator to change the combination of catalysts in the reactor and polymerization Is being disclosed. However, this method has a limitation in realizing the characteristics of each catalyst at the same time, and also has a disadvantage in that the metallocene catalyst portion is released from the carrier component of the completed catalyst, causing fouling in the reactor.
[10]
On the other hand, linear low-density polyethylene is a resin prepared by copolymerizing ethylene and alpha olefin at low pressure using a polymerization catalyst, and thus has a narrow molecular weight distribution, short chain branches of a certain length, and no long chain branches. Linear low-density polyethylene film has high breaking strength and elongation as well as the properties of general polyethylene, and has excellent tear strength and drop impact strength, so its use in stretch films and overlap films, which are difficult to apply to existing low-density polyethylene or high-density polyethylene, is increasing Are doing.
[11]
However, linear low-density polyethylene using 1-butene or 1-hexene as a comonomer is mostly manufactured in a single gas phase reactor or a single loop slurry reactor, and has higher productivity compared to the process using 1-octene comonomer, but these products are also used. Due to the limitations of catalyst technology and process technology, physical properties are significantly inferior to when using 1-octene comonomer, and the molecular weight distribution is narrow, resulting in poor processability.
[12]
U.S. Patent No. 4,935,474 reports on a method for preparing polyethylene having a broad molecular weight distribution by using two or more metallocene compounds. U.S. Patent No. 6,828,394 reports on a method for producing polyethylene having good processability and particularly suitable for films by mixing those having good comonomer binding properties and those not having good comonomer binding properties. In addition, U.S. Patent No. 6,841,631 and U.S. Patent No. 6,894,128 disclose a metallocene catalyst in which at least two kinds of metal compounds are used to prepare polyethylene having a bimodal or polymorphic molecular weight distribution, so that it can be used in films, blow molding, pipes, etc. It is reported that it is applicable. However, these products have improved processability, but the dispersion state of each molecular weight within the unit particles is not uniform, so even under relatively good extrusion conditions, the extrusion appearance is rough and physical properties are not stable.
[13]
Against this background, there is a constant demand for manufacturing better products with a balance between physical properties and processability.
Detailed description of the invention
Technical challenge
[14]
Accordingly, the present invention is to solve the problems of the prior art, and has a narrow molecular weight distribution, low density and ultra-low molecular weight characteristics. It is intended to provide an adhesive composition showing excellent physical properties and adhesive properties by including.
Means of solving the task
[15]
In order to solve the above problems, according to an embodiment of the present invention, an ethylene/alpha-olefin copolymer; And a tackifier; and the ethylene/alpha-olefin copolymer satisfies the conditions of the following i) to iv) to provide an adhesive composition:
[16]
i) density: 0.85 to 0.89 g/cc,
[17]
ii) molecular weight distribution (MWD): 1.5 to 3.0,
[18]
iii) Viscosity: 6,000cP to 40,000cP when measured at 180°C,
[19]
iv) Crystalization Index (CI) according to Formula 1 below: 15 to 25
[20]
[Equation 1]
[21]

[22]
In Equation 1, A is the Full Width at Half Maximum (FWHM) of the peak that appears when measuring the crystallization temperature, and B is the Melt Index (MI) as ASTM D-1238 (Condition E, 190°C, 2.16 Kg). It is a value measured in terms of load), and is a value in case of the unit'dg/min'
Effects of the Invention
[23]
The adhesive composition according to the present invention includes an ethylene/alpha-olefin copolymer having a low density, ultra-low molecular weight, a narrow molecular weight distribution and uniform crystallinity, and thus has excellent heat resistance as well as excellent low temperature adhesiveness. Therefore, the adhesive composition of the present invention exhibits excellent adhesive properties.
Best mode for carrying out the invention
[24]
The terms used in the present specification are only used to describe exemplary embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present specification, terms such as "comprise", "include", or "have" are intended to designate the existence of implemented features, steps, components, or a combination thereof, and one or more other features or steps, It is to be understood that the possibility of the presence or addition of components, or combinations thereof, is not excluded in advance.
[25]
The present invention will be described in detail below and exemplifying specific embodiments, which can be made various changes and have various forms. However, this is not intended to limit the present invention to a specific form disclosed, it is to be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.
[26]
[27]
1. Adhesive composition
[28]
One embodiment of the present invention, ethylene/alpha-olefin copolymer; And a tackifier; wherein the ethylene/alpha-olefin copolymer provides an adhesive composition satisfying the conditions of i) to iv) below:
[29]
i) density: 0.85 to 0.89 g/cc,
[30]
ii) molecular weight distribution (MWD): 1.5 to 3.0,
[31]
iii) Viscosity: 4,000cP to 50,000cP when measured at 180°C,
[32]
iv) Crystalization Index (CI) according to Formula 1 below: 15 to 25
[33]
[Equation 1]
[34]

[35]
In Equation 1 above,
[36]
A is the Full Width at Half Maximum (FWHM) of the peak that appears when measuring the crystallization temperature,
[37]
B is a melt index (MI) measured by ASTM D-1238 (condition E, 190°C, 2.16 Kg load), and is a value in the case of the unit'dg/min'.
[38]
[39]
The adhesive composition of the present invention is characterized by having excellent processability and adhesive properties by including an ethylene/alpha-olefin copolymer having a low density, ultra-low molecular weight, narrow molecular weight distribution and uniform crystallinity.
[40]
In the following, the ethylene/alpha-olefin copolymer and a method for producing the same are first described in detail.
[41]
(1) Ethylene/alpha-olefin copolymer
[42]
The ethylene/alpha-olefin copolymer of the present invention satisfies the following conditions i) to iv):
[43]
i) density: 0.85 to 0.89 g/cc,
[44]
ii) molecular weight distribution (MWD): 1.5 to 3.0,
[45]
iii) Viscosity: 4,000cP to 50,000cP when measured at 180°C,
[46]
iv) Crystalization Index (CI) according to Formula 1 below: 15 to 25
[47]
[Equation 1]
[48]

[49]
In Equation 1, A is the Full Width at Half Maximum (FWHM) of the peak that appears when measuring the crystallization temperature, and B is the Melt Index (MI) as ASTM D-1238 (Condition E, 190°C, 2.16 Kg). It is a value measured in terms of load), and is a value in case of the unit'dg/min'
[50]
[51]
Crosslinking between copolymers is caused by vinyl and vinylidene containing double bonds.The ethylene/alpha-olefin copolymer is an alpha-olefin comonomer by introducing an optimized amount of hydrogen together with a catalyst to be described later during polymerization. The incorporation of is uniform, so that the crystallization index satisfies the above range, which can be said to have uniform crystallinity due to the low content of the low-crystalline and high-crystalline copolymer. In general, shear fluidization properties can be measured by measuring complex viscosity according to frequency.These copolymers can have excellent processability because the complex viscosity is kept low at a specific temperature and angular frequency range. have.
[52]
[53]
Specifically, the ethylene/alpha-olefin copolymer of the present invention further has a density of 0.85 g/cc to 0.89 g/cc as measured according to ASTM D-792 under conditions that satisfy the physical property requirements as described above. Specifically, the density may be 0.855 g/cc or more, or 0.86 g/cc or more, or 0.865 g/cc or more, and 0.89 g/cc or less, or 0.885 g/cc or less, or 0.880 g/cc or less.
[54]
In general, the density of olefin-based polymers is affected by the type and content of monomers used in polymerization, and the degree of polymerization, and in the case of copolymers, the influence is large by the content of comonomers. The olefin copolymer can be prepared, and the amount of comonomer that can be introduced into the copolymer can depend on the copolymerization of the catalyst, that is, the properties of the catalyst.
[55]
In the present invention, a large amount of comonomer can be introduced by using a catalyst composition containing a transition metal compound having a specific structure. As a result, the ethylene/alpha-olefin copolymer of the present invention may have a low density as described above, and as a result, may exhibit excellent processability. More specifically, the ethylene/alpha-olefin copolymer may preferably have a density of 0.860 g/cc to 0.885 g/cc, more preferably 0.865 g/cc to 0.880 g/cc, and in this case, according to density control The effect of maintaining mechanical properties and improving impact strength is more remarkable.
[56]
[57]
The ethylene/alpha-olefin copolymer of the present invention has a viscosity measured at 180° C. of 50,000 cP or less under conditions satisfying the low density characteristics as described above. More specifically, the viscosity of the ethylene/alpha-olefin copolymer may be 40,000 cP or less, 37,000 cP or less, or 35,000 cP or less, and may be 4,000 cP or more, or 6,000 cP or more, or 7,000 cP or more, or 8,500 cP or more.
[58]
Further, the ethylene/alpha-olefin copolymer of the present invention has a molecular weight distribution (MWD) of 1.5 to 3.0. Specifically, the molecular weight distribution may be 2.5 or less, more specifically, 1.7 or more, or 1.8 or more, or 1.9 or more, 2.3 or less, or 2.1 or less, or 2.0 or less.
[59]
In general, when two or more kinds of monomers are polymerized, the molecular weight distribution (MWD) increases, and as a result, impact strength and mechanical properties decrease, and a blocking phenomenon occurs. On the other hand, in the present invention, when the optimum amount of hydrogen is added during the polymerization reaction, the molecular weight and molecular weight distribution of the ethylene/alpha-olefin copolymer to be produced is reduced, and as a result, impact strength and mechanical properties are improved.
[60]
On the other hand, in the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are molecular weights in terms of polystyrene analyzed by gel permeation chromatography (GPC), and the molecular weight distribution is from the ratio of Mw/Mn. Can be calculated.
[61]
The ethylene/alpha-olefin copolymer of the present invention may be an ultra-low molecular weight polymer having a weight average molecular weight (Mw) of 15,000 to 45,000 g/mol. More specifically, the weight average molecular weight may be 17,000 g/mol or more, or 19,000 g/mol or more, and 40,000 g/mol or less, or 37,000 g/mol or less, or 35,000 g/mol or less.
[62]
In addition, the ethylene/alpha-olefin copolymer of the present invention may have a number average molecular weight (Mn) of 5,000 to 35,000. More specifically, the number average molecular weight may be 7,000 or more, or 8,000 or more, or 9,000 or more, and may be 30,000 or less, or 25,000 or less.
[63]
When the weight average molecular weight satisfies the above range, it is associated with the viscosity of the adhesive composition including the same, and remarkable improvement in processability can be expected. 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 together with the type of catalyst used in the polymerization process, and in addition to the above conditions, excellent mechanical properties It can exhibit improved processability while maintaining.
[64]
[65]
In addition, the ethylene/alpha-olefin copolymer of the present invention has a crystallization index of 15 to 25 according to Formula 1 below, and specifically, 16 or more, or 17.5 or more, or It may be 18.5 or more, and may be 24 or less, or 23 or less, or 22 or less, or 21 or less.
[66]
In Equation 1, A is the Full Width at Half Maximum (FWHM) of the peak that appears when measuring the crystallization temperature, and B is the Melt Index (MI) as ASTM D-1238 (Condition E, 190°C, 2.16 Kg). It is a value measured by load), and is the value in case of the unit'dg/10min'.
[67]
The peak half width (FWHM) is a value derived from a crystallinity distribution graph drawn as dW/dT values ​​according to temperature measured in a bivariate distribution by cross-fractionation chromatography (CFC), The ethylene/alpha-olefin copolymer may have a value of 30 or less or 23 or less depending on the weight average molecular weight or the melt index, and this peak half width (FWHM) is the melting index and the crystallization index derived by Equation 1 If the relationship is made to satisfy the range, it can be evidence that the crystallinity distribution in the ethylene/alpha-olefin copolymer is fairly uniform, and through this, it can be evaluated as excellent in physical properties and processability, especially processability.
[68]
Specifically, like the ethylene/alpha-olefin copolymer of the present invention, when the above conditions are satisfied, there is little change in the complex viscosity within a specific range of temperature and shear rate during processing, thus exhibiting very excellent processability. I can. Accordingly, the adhesive composition of the present invention including the ethylene-alpha olefin copolymer may also have excellent adhesion and processability.
[69]
[70]
In addition, the ethylene/alpha-olefin copolymer may have a ReХRc value of 1 or less. At this time, Re=kee/kec, Rc=kcc/kce, kee represents the growth reaction rate constant when ethylene is added to the growth chain whose terminal active point is an ethylene monomer, and kec represents the growth chain whose terminal active point is an ethylene monomer. Represents the growth reaction rate when alpha olefin comonomer is added to, kcc represents the growth reaction rate when alpha olefin comonomer is added to the growth chain where the terminal active point is alpha olefin comonomer, and kce is the terminal active point alpha It represents the growth reaction rate constant when ethylene monomer is added to the growth chain, which is an olefin comonomer.
[71]
Growth reaction rate constants such as kee, kec, kcc and kce can be obtained by measuring the arrangement of monomers using C13 NMR, through which Re and Rc can be calculated. If the calculated product of Re and Rc (ReХRc) is 1.0 or less, more specifically 0.95 or less, the possibility that the ethylene/alpha-olefin copolymer is formed as an alternating copolymer is high, and the product of Re and Rc When the value (ReХRc) exceeds 1.0, there is a high possibility that the ethylene-alphaolefin copolymer is formed as a block copolymer. The term "alternating copolymer" refers to a form in which two monomer components (eg, A, B) constituting a copolymer are alternately polymerized (eg -ABABABAB-), and the term "block copolymer" refers to a copolymer In the coalescence, one monomer component (A) is continuously polymerized to form a block, and then another monomer component (B) is then polymerized to form a block (eg -AAAABBBB-).
[72]
Therefore, the ethylene-alphaolefin copolymer of the present invention has a product of Re and Rc (ReХRc) of 1.0 or less, more specifically 0.95 or less, whereby the alpha-olefin comonomer is continuously polymerized, and evenly in the polymer main chain. It may be a distributed alternating copolymer. As such, since the alpha-olefin comonomer is evenly distributed in the polymer backbone, it exhibits excellent structural stability.Therefore, there is little change in the complex viscosity within a specific range of temperature and shear rate during processing, so it has excellent processability. Can represent. Accordingly, the adhesive composition of the present invention including the ethylene-alpha olefin copolymer may also have excellent adhesion and processability.
[73]
[74]
In addition, the melting index (MI) may be 200 dg/min to 1,300 dg/min, specifically, the melting index may be 400 dg/min or more, 500 dg/min or more, and 1,200 dg/min or less, 1,000 dg/min or less. I can.
[75]
Conventionally, in order to apply an ethylene/alpha-olefin copolymer to a hot melt adhesive composition, there have been attempts to implement an ultra-low molecular weight, but if the melt index of the copolymer is largely controlled for this purpose, the crystallinity distribution is widened, resulting in poor processability. There was a problem that physical properties were deteriorated.
[76]
However, the ethylene/alpha-olefin copolymer of the present invention uses a transition metal compound of a specific structure as a catalyst composition according to the production method described below and a method of introducing hydrogen during polymerization is applied, so that a high crystallinity and low crystallinity copolymer Since the content of is low, the complex viscosity at the same temperature is low, and the crystallinity is uniform even when the melt index is controlled high, and accordingly, the physical properties and processability, especially the processability due to the decrease in the complex viscosity may be significantly improved compared to the prior art. .
[77]
In addition, the ethylene/alpha-olefin copolymer of the present invention may have a total number of unsaturated functional groups of 0.8 or less per 1000 carbon atoms in the copolymer. More specifically, the number of unsaturated functional groups is 0.6 or less, or 0.5 or less, or 0.45 or less, or 0.42 or less, or 0.41 or less, 0.1 or more, or 0.20 or less per 1000 carbon atoms constituting the copolymer. It may be more than or more than 0.3. The total number of unsaturated functional groups in the copolymer is possible by controlling the polymerization temperature and the amount of hydrogen input during manufacture.The ethylene/alpha-olefin copolymer according to the present invention has a small number of unsaturated functional groups as described above, so that it is stored for a long time at high temperature (heat aging). When discoloration, molecular weight and viscosity change rate is small, it can exhibit excellent long-term physical properties.
[78]
In the present invention, the number of unsaturated functional groups in the copolymer can be calculated from the results of NMR analysis. Specifically, after dissolving the copolymer in a chloroform-d (w/TMS) solution, an Agilent 500MHz NMR device was used to measure the acquisition time of 2 seconds at room temperature and a pulse angle of 45° 16 times, and the TMS peak at 1 H NMR. Is corrected to 0 ppm, the CH 3 related peak (triplet) of 1-octene at 0.88 ppm , and the CH 2 related peak (broad singlet) of ethylene at 1.26 ppm, respectively, and the CH 3 peak integral value is set to 3. The content is calculated by correction, and the number of double bonds can be calculated based on the integral value of double bonds in the 4.5-6.0 ppm region.
[79]
[80]
In addition, the ethylene/alpha-olefin copolymer of the present invention may have a crystallization temperature (Tc) of 45°C or higher. More specifically, the crystallization temperature may be 50°C or higher, or 51°C or higher, and 60°C or lower, or 58°C or lower, or 56°C or lower. This high crystallization temperature is due to the uniform distribution of the comonomer in the ethylene/alpha-olefin copolymer, and by having the above temperature range, excellent structural stability may be exhibited.
[81]
In addition, the ethylene/alpha-olefin copolymer of the present invention may have a melting temperature (Tm) of 60 to 80°C. More specifically, the melting temperature may be 65°C or higher, or 69°C or higher, or 70°C or higher, and 75°C or lower, or 74.5°C or lower, or 74°C or lower. By having a melting temperature in such a temperature range, excellent thermal stability can be exhibited.
[82]
In the present invention, the crystallization temperature and melting temperature of the ethylene/alpha-olefin copolymer can be measured using a Differential Scanning Calorimeter (DSC). Specifically, the copolymer is heated to 150° C., maintained for 5 minutes, and then lowered to 20° C., and the temperature is increased again. At this time, the rate of rise and fall of temperature are each adjusted to 10℃/min, and the result measured in the second temperature rising section is the melting temperature, and the result measured in the section appearing while decreasing the temperature is the crystallization temperature.
[83]
[84]
In addition, in the ethylene/alpha-olefin copolymer of the present invention, the alpha-olefin monomer as a comonomer may be an olefin monomer having 4 to 20 carbon atoms. Specific examples include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetra Decene, 1-hexadecene, 1-eicosene, and the like, and one of them alone or a mixture of two or more may be used.
[85]
Among these, the alpha-olefin monomer may be 1-butene, 1-hexene or 1-octene, and most preferably 1-octene, when considering the remarkable improvement effect when applied to an adhesive composition.
[86]
In addition, in the ethylene/alpha-olefin copolymer, the content of alpha-olefin, which is the comonomer, may be appropriately selected within a range that satisfies the above-described physical property requirements, and specifically, more than 0 and not more than 99 mol%, or It may be 10 to 50 mol%.
[87]
[88]
The ethylene/alpha-olefin copolymer of the present invention may satisfy the following conditions i) to viii).
[89]
i) density: 0.85 to 0.89 g/cc,
[90]
ii) molecular weight distribution (MWD): 1.5 to 3.0,
[91]
iii) Viscosity: 4,000cP to 50,000cP when measured at 180°C,
[92]
iv) Total number of unsaturated functional groups per 1,000 carbon atoms: 0.8 or less,
[93]
v) Number average molecular weight (Mn): 9,000 to 25,000,
[94]
vi) Melt Index (MI) at 190°C, 2.16 kg load according to ASTM D1238: 200 to 1,300 dg/min,
[95]
vii) Crystalization Index (CI) according to Formula 1 below: 15 to 25,
[96]
[Equation 1]
[97]

[98]
In Equation 1, A is the Full Width at Half Maximum (FWHM) of the peak that appears when measuring the crystallization temperature, and B is the Melt Index (MI) as ASTM D-1238 (Condition E, 190°C, 2.16 Kg). Load), and is the value in the case of the unit'dg/min',
[99]
viii) ReХRc ≤ 1.0
[100]
At this time, Re=kee/kec, Rc=kcc/kce,
[101]
kee represents the growth reaction rate constant when ethylene is added to the growth chain whose terminal active point is an ethylene monomer, and kec represents the growth reaction rate when alpha olefin comonomer is added to the growth chain whose terminal active point is an ethylene monomer, kcc represents the growth reaction rate when an alpha olefin comonomer is added to the growth chain where the terminal active point is an alpha olefin comonomer, and kce represents the growth reaction when an ethylene monomer is added to the growth chain where the terminal active point is an alpha olefin comonomer. Represents the rate constant.
[102]
The above-described copolymer may realize the same effects as described above, and the number of total unsaturated functional groups is small, and effects such as long-term stability can be improved.
[103]
[104]
(2) Method for producing ethylene/alpha-olefin copolymer
[105]
The ethylene/alpha-olefin copolymer having the above physical properties is ethylene and alpha-olefin-based monomers by introducing hydrogen at 45 to 100 cc/min in the presence of a catalyst composition containing a transition metal compound of Formula 1 below. It can be prepared by a manufacturing method comprising the step of polymerizing:
[106]
[Formula 1]
[107]

[108]
In Formula 1,
[109]
R 1 is hydrogen; Alkyl of 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryl of 6 to 20 carbon atoms; Arylalkoxy having 7 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms,
[110]
R 2a to R 2e are each independently hydrogen; halogen; Alkyl of 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Or aryl having 6 to 20 carbon atoms,
[111]
R 3 is hydrogen; halogen; Alkyl of 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl of 6 to 20 carbon atoms; Alkylaryl having 6 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkyl amido having 1 to 20 carbon atoms; Or aryl amido having 6 to 20 carbon atoms; Phenyl substituted with one or more selected from the group consisting of halogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, and aryl having 6 to 20 carbon atoms ego,
[112]
R 4 to R 9 are each independently hydrogen; Silyl; Alkyl of 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl of 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl of 7 to 20 carbon atoms; Or a metalloid radical of a Group 14 metal substituted with a hydrocarbyl having 1 to 20 carbon atoms; Two or more adjacent to each other among the R 6 to R 9 may be connected to each other to form a ring,
[113]
Q is Si or C,
[114]
M is a Group 4 transition metal,
[115]
X 1 and X 2 are each independently hydrogen; halogen; Alkyl of 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl of 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkylamino of 1 to 20 carbon atoms; Or arylamino having 6 to 20 carbon atoms.
[116]
[117]
In the case of polymerizing ethylene and alpha-olefin-based comonomers with hydrogen by including a transition metal compound having the structure of Formula 1 in the catalyst composition as described above, an ethylene/alpha-olefin copolymer having a low density and an ultra-low molecular weight as described above As described above, the ethylene/alpha-olefin copolymer has a crystallization index of more than 15 and less than 25, so that the content of the copolymer of high crystal and low crystal can be greatly reduced, and thus complex Processability can be greatly improved by reducing the viscosity, and physical properties can also be maintained at a level equal to or higher than the conventional one. Therefore, in the case of an adhesive composition comprising the same, both heat resistance and low temperature adhesiveness may be excellent.
[118]
[119]
The substituents in Formula 1 will be described in more detail as follows.
[120]
R 1 is hydrogen; Alkyl of 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryl of 6 to 20 carbon atoms; Arylalkoxy having 7 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or it may be an arylalkyl having 7 to 20 carbon atoms.
[121]
Specifically, R 1 is hydrogen; Alkyl of 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Alkoxy having 1 to 12 carbon atoms; Aryl of 6 to 12 carbon atoms; Arylalkoxy having 7 to 13 carbon atoms; Alkylaryl having 7 to 13 carbon atoms; Or it may be an arylalkyl having 7 to 13 carbon atoms.
[122]
More specifically, R 1 may be hydrogen or alkyl having 1 to 12 carbon atoms.
[123]
[124]
R 2a to R 2e are each independently hydrogen; halogen; Alkyl of 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Alkenyl having 2 to 12 carbon atoms; Alkoxy having 1 to 12 carbon atoms; Or phenyl.
[125]
Specifically, R 2a to R 2e are each independently hydrogen; halogen; Alkyl of 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Alkenyl having 2 to 12 carbon atoms; Alkoxy having 1 to 12 carbon atoms; Or phenyl.
[126]
More specifically, R 2a to R 2e are each independently hydrogen; Alkyl of 1 to 12 carbon atoms; Or it may be alkoxy having 1 to 12 carbon atoms.
[127]
[128]
R 3 is hydrogen; halogen; Alkyl of 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Alkenyl having 2 to 12 carbon atoms; Aryl of 6 to 20 carbon atoms; Alkylaryl having 7 to 13 carbon atoms; Arylalkyl of 7 to 13 carbon atoms; Alternatively, it may be a phenyl substituted with one or more selected from the group consisting of halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkoxy and phenyl having 1 to 12 carbon atoms.
[129]
Specifically, R 3 is hydrogen; halogen; Alkyl of 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Alkenyl having 2 to 12 carbon atoms; Alkylaryl having 7 to 13 carbon atoms; Arylalkyl of 7 to 13 carbon atoms; Phenyl; Or halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, and phenyl substituted with one or more selected from the group consisting of phenyl,
[130]
More specifically, R 3 is hydrogen; Alkyl of 1 to 12 carbon atoms; Or phenyl.
[131]
[132]
Each of R 4 to R 9 is independently hydrogen; Alkyl of 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Aryl of 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or it may be an arylalkyl having 7 to 20 carbon atoms.
[133]
Specifically, the R 4 to R 9 are each independently hydrogen; Alkyl of 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Aryl of 6 to 12 carbon atoms; Alkylaryl having 7 to 13 carbon atoms; Or it may be an arylalkyl having 7 to 13 carbon atoms.
[134]
Specifically, R 4 and R 5 are each independently hydrogen; Or it may be a C1-C12 alkyl.
[135]
Two or more adjacent to each other among the R 6 to R 9 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 12 carbon atoms, or aryl having 6 to 12 carbon atoms.
[136]
In addition, two or more adjacent to each other among the R 6 to R 9 may be connected to each other to form an aliphatic ring having 5 to 12 carbon atoms or an aromatic ring having 6 to 12 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or aryl having 6 to 12 carbon atoms.
[137]
More specifically, R 6 to R 9 may each independently be hydrogen or methyl.
[138]
[139]
In addition, Q may be Si, and M may be Ti.
[140]
X 1 and X 2 are each independently hydrogen; halogen; Alkyl of 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Alkenyl having 2 to 12 carbon atoms; Aryl of 6 to 12 carbon atoms; Alkylaryl having 7 to 13 carbon atoms; Arylalkyl of 7 to 13 carbon atoms; Alkylamino having 1 to 13 carbon atoms; Or it may be arylamino having 6 to 12 carbon atoms.
[141]
Specifically, X 1 and X 2 are each independently hydrogen; halogen; An alkyl group having 1 to 12 carbon atoms; Or it may be an alkenyl having 2 to 12 carbon atoms.
[142]
More specifically, X 1 and X 2 may each independently be hydrogen or alkyl having 1 to 12 carbon atoms.
[143]
[144]
In the transition metal compound of Formula 1, cyclopentadiene in which benzothiophene is fused by a cyclic bond, and an amido group (NR 1 ) are stably crosslinked by Q (Si or C), and a Group 4 transition metal This coordinated structure is formed. When applied to olefin polymerization by using the catalyst composition, it is possible to produce a polyolefin having characteristics such as high activity, high molecular weight, and high copolymerizability even at a high polymerization temperature.
[145]
Furthermore, the transition metal compound of Formula 1 has a structure in which a substituted or unsubstituted phenyl group is bonded to Q when an amido group (NR 1 ) is crosslinked by Q(Si, C), so that it is more stably crosslinked. It can be, and can have excellent electronic stability when coordinated with a transition metal.
[146]
In the case of a transition metal compound having such a structure, since the copolymerization is excellent due to the phenyl group, a low-density copolymer can be prepared with a small amount of comonomer compared to a catalyst that does not have the same core structure as the transition metal compound of Formula 1. At the same time, it is possible to describe the advantage of being able to stably introduce hydrogen as well as high-temperature polymerization due to excellent molecular weight level.
[147]
That is, in the present invention, the above-described transition metal compound is used, but by introducing hydrogen in an optimized amount during the polymerization reaction, an ethylene/alpha-olefin copolymer having a narrow molecular weight distribution and a uniform comonomer distribution with an ultra-low molecular weight is provided. In addition, due to the electronic/structural stability of the transition metal compound, the incorporation of hydrogen is advantageous, and a homogeneous termination reaction by hydrogen occurs in the polymerization reaction to prepare an ultra-low molecular weight copolymer having a narrow molecular weight distribution. You can expect a good effect.
[148]
[149]
More specifically, specific examples of the compound of Formula 1 may include a compound represented by one of the following structural formulas, but the present invention is not limited thereto.
[150]
[Formula 1-1] [Formula 1-2] [Formula 1-3]
[151]

[152]
[Formula 1-4] [Formula 1-5] [Formula 1-6]
[153]

[154]
[Formula 1-7] [Formula 1-8]
[155]

[156]
[Formula 1-9] [Formula 1-10]
[157]

[158]
[159]
Meanwhile, in the preparation of the ethylene/alpha-olefin copolymer of the present invention, the catalyst composition may further include a cocatalyst to activate the transition metal compound of Formula 1.
[160]
The cocatalyst is an organometallic compound containing a Group 13 metal, and specifically, may include at least one of a compound of the following formula 2, a compound of the following formula 3, and a compound of the following formula 4.
[161]
[Formula 2]
[162]
R 41 -[Al(R 42 )-O] n -R 43
[163]
In Formula 2,
[164]
R 41 , R 42 and R 43 are each independently hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms and a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen,
[165]
n is an integer of 2 or more,
[166]
[Chemical Formula 3]
[167]
D(R 44 ) 3
[168]
In Formula 3, D is aluminum or boron,
[169]
R 44 is each independently a halogen, a C 1 to C 20 hydrocarbyl group, and a halogen substituted C 1 to C 20 hydrocarbyl any one of,
[170]
[Formula 4]
[171]
[LH] + [Z (A) 4 ] - or [L] + [Z (A) 4 ] -
[172]
In Chemical Formula 4,
[173]
L is a neutral or cationic Lewis base, H is a hydrogen atom,
[174]
Z is a Group 13 element, and A is each independently a hydrocarbyl group having 1 to 20 carbon atoms; A hydrocarbyloxy group having 1 to 20 carbon atoms; And at least one hydrogen atom of these substituents is any one of a substituent substituted with at least one of halogen, a C1-C20 hydrocarbyloxy group, and a C1-C20 hydrocarbylsilyl group.
[175]
[176]
More specifically, the compound of Formula 2 may be an alkylaluminoxane-based compound in which a repeating unit is bonded in a linear, circular or network type, and specific examples include methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane or tert-butylaluminoxane, etc. are mentioned.
[177]
In addition, specific examples of the compound of Formula 3 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclo Pentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide , Trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron or tributyl boron, and the like, and may be particularly selected from trimethyl aluminum, triethyl aluminum or triisobutyl aluminum.
[178]
Further, examples of the compound of Formula 4 include a trisubstituted ammonium salt, a dialkyl ammonium salt, or a trisubstituted phosphonium salt type borate-based compound. More specific examples include trimetalammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, methyltetradecyclo Octadecylammonium tetraphenylborate, N,N-dimethylaninium tetraphenylborate, N,N-diethylaninium tetraphenylborate, N,N-dimethyl(2,4,6-trimethylaninium)tetraphenylborate, Trimethylammonium tetrakis(pentafluorophenyl)borate, methylditetradecylammonium tetrakis(pentaphenyl)borate, methyldioctadecylammonium tetrakis(pentafluorophenyl)borate, triethylammonium, tetrakis(pentafluoro Phenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (secondary-butyl) ammonium tetrakis (pentafluorophenyl) ) Borate, N,N-dimethylaninium tetrakis (pentafluorophenyl) borate, N,N-diethylaninium tetrakis (pentafluorophenyl) borate, N,N-dimethyl (2,4,6- Trimethylaninium) tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluoro) Rophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tri(n-butyl) ammonium tetrakis (2,3,4,6-, tetrafluorophenyl) Borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N,N-dimethylaninium tetrakis (2,3,4, 6-tetrafluorophenyl) borate, N,N-diethylaninium tetrakis (2,3,4,6-tetrafluorophenyl) borate or N,N-dimethyl-(2,4,6-trimethylanil) Borate compounds in the form of trisubstituted ammonium salts such as nium) tetrakis-(2,3,4,6-tetrafluorophenyl)borate; Dialkyl ammonium salt form such as dioctadecyl ammonium tetrakis (pentafluorophenyl) borate, ditetradecyl ammonium tetrakis (pentafluorophenyl) borate or dicyclohexyl ammonium tetrakis (pentafluorophenyl) borate compound; Or triphenylphosphonium tetrakis(pentafluorophenyl)borate, methyldioctadecylphosphonium tetrakis(pentafluorophenyl)borate or tri(2,6-, dimethylphenyl)phosphonium tetrakis(pentafluorophenyl) ) Borate compounds in the form of a trisubstituted phosphonium salt such as borate.
[179]
By using such a cocatalyst, the molecular weight distribution of the finally produced ethylene/alpha-olefin copolymer becomes more uniform, and polymerization activity may be improved.
[180]
The cocatalyst may be used in an appropriate amount so that the activation of the transition metal compound of Formula 1 is sufficiently performed.
[181]
[182]
In addition, the catalyst composition may include the transition metal compound of Formula 1 supported on a carrier.
[183]
When the transition metal compound of Formula 1 is supported on a carrier, the weight ratio of the transition metal compound to the carrier may be 1:10 to 1:1,000, more specifically 1:10 to 1:500. When the carrier and the transition metal compound are included in the weight ratio within the above range, the optimum shape may be exhibited. In addition, when the cocatalyst is supported on the carrier together, the weight ratio of the cocatalyst to the carrier may be 1:1 to 1:100, more specifically 1:1 to 1:50. When the cocatalyst and the carrier are included in the weight ratio, it is possible to improve the catalytic activity and optimize the microstructure of the polymer to be produced.
[184]
Meanwhile, silica, alumina, magnesia, or a mixture thereof may be used as the carrier, or by drying these materials at a high temperature to remove moisture from the surface, It can also be used. In addition, the high-temperature dried carriers may further include oxides, carbonates, sulfates, or nitrate components such as Na 2 O, K 2 CO 3 , BaSO 4 and Mg(NO 3 ) 2 .
[185]
The drying temperature of the carrier is preferably 200 to 800°C, more preferably 300 to 600°C, and most preferably 300 to 400°C. When the drying temperature of the carrier is less than 200°C, there is too much moisture so that the moisture on the surface and the cocatalyst react, and when it exceeds 800°C, the pores on the surface of the carrier are combined and the surface area decreases. It is not preferable because it disappears and only siloxane groups remain, and the reaction site with the cocatalyst decreases.
[186]
In addition, the amount of hydroxy groups on the surface of the carrier is preferably 0.1 to 10 mmol/g, and more preferably 0.5 to 5 mmol/g. The amount of hydroxy groups on the surface of the carrier can be controlled by a method and conditions for preparing the carrier or drying conditions such as temperature, time, vacuum or spray drying.
[187]
[188]
Meanwhile, the polymerization reaction of the ethylene/alpha-olefin copolymer may be carried out by continuously adding hydrogen in the presence of the above-described catalyst composition and continuously polymerizing ethylene and alpha-olefin-based monomers.
[189]
At this time, the hydrogen gas serves to suppress the rapid reaction of the transition metal compound at the initial stage of polymerization and terminate the polymerization reaction. Accordingly, by controlling the use and amount of hydrogen gas, an ethylene/alpha-olefin copolymer having a narrow molecular weight distribution with an ultra-low molecular weight can be effectively prepared.
[190]
The hydrogen gas may be added at 45 to 100 cc/min, more specifically 50 to 95 cc/min. When introduced under the above conditions, the produced ethylene/alpha-olefin polymer can implement the physical properties in the present invention. If the content of hydrogen gas is less than 45 cc/min, the polymerization reaction is not uniformly terminated, making it difficult to prepare an ethylene/alpha-olefin copolymer having desired properties, and it may exceed 100 cc/min. In this case, the termination reaction occurs too quickly, and there is a concern that an ethylene/alpha-olefin copolymer having an excessively low molecular weight may be produced.
[191]
[192]
In addition, the polymerization reaction may be carried out at 80 to 200°C, but the number of unsaturated functional groups in the ethylene/alpha-olefin copolymer can be more easily controlled by controlling the polymerization temperature together with the amount of hydrogen added. Accordingly, in detail, the polymerization reaction may be 100 to 150°C, more specifically 100 to 140°C.
[193]
[194]
In addition, during the polymerization reaction, an organic aluminum compound for removing moisture in the reactor is further added, so that the polymerization reaction may proceed in the presence of the organic aluminum compound. Specific examples of such an organoaluminum compound include trialkyl aluminum, dialkyl aluminum halide, alkyl aluminum dihalide, aluminum dialkyl hydride, or alkyl aluminum sesqui halide, and more specific examples thereof include Al(C 2 H 5 ) 3 , Al(C 2 H 5 ) 2 H, Al(C 3 H 7 ) 3 , Al(C 3 H 7 ) 2 H, Al(iC 4 H 9 ) 2 H, Al(C 8 H 17 ) 3 , Al(C 12 H 25 ) 3 , Al(C 2 H 5 )(C 12 H 25 ) 2 , Al(iC 4 H 9 )(C 12 H 25 ) 2 , Al(iC 4 H 9 ) 2 H , Al(iC 4 H 9 ) 3 , (C 2 H 5 ) 2 AlCl, (iC 3H 9 ) 2 AlCl or (C 2 H 5 ) 3 A l2 Cl 3 , and the like. These organoaluminum compounds may be continuously introduced into the reactor, and may be added in a ratio of about 0.1 to 10 moles per 1 kg of the reaction medium introduced into the reactor for proper moisture removal.
[195]
In addition, the polymerization pressure may be about 1 to about 100 Kgf/cm 2 , preferably about 1 to about 50 Kgf/cm 2 , more preferably about 5 to about 30 Kgf/cm 2 .
[196]
In addition, when a transition metal compound is used in the form supported on a carrier, the transition metal compound is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, such as pentane, hexane, heptane, nonane, decane, and isomers thereof, and toluene, benzene. It may be dissolved or diluted in an aromatic hydrocarbon solvent such as, dichloromethane, or a hydrocarbon solvent substituted with a chlorine atom such as chlorobenzene. The solvent used here is preferably used after removing a small amount of water or air acting as a catalyst poison by treatment with a small amount of alkyl aluminum, and it is possible to further use a cocatalyst.
[197]
The ethylene/alpha-olefin copolymer prepared by the above-described manufacturing method has an ultra-low molecular weight and a narrow molecular weight distribution, and at the same time, a crystallinity index exceeds 15 and less than 25 to satisfy conditions for excellent crystallinity Meets. Accordingly, it is possible to maintain a low viscosity even at high temperatures, and therefore, an adhesive composition including the same can implement excellent processability and adhesive properties.
[198]
[199]
(3) Additional components of adhesive composition
[200]
The adhesive composition of the present invention may further include a tackifier in addition to the ethylene/alpha-olefin copolymer.
[201]
The tackifier may be an aliphatic hydrocarbon resin, such as a modified C5 hydrocarbon resin (C5/C9 resin), a styrenated tefrene resin, a fully or partially hydrogenated C9 hydrocarbon resin, a hydrogenated cycloaliphatic hydrocarbon resin, a hydrogenated It may be one selected from aromatic modified cycloaliphatic hydrocarbon resins and mixtures thereof.
[202]
The tackifier is not particularly limited, but may be included in 5 parts by weight to 70 parts by weight based on 100 parts by weight of the adhesive composition, and specifically 20 parts by weight to 70 parts by weight. If the tackifier is included in an amount of less than 5 parts by weight, the viscosity of the adhesive composition may increase and thus processability may decrease. If it is included in an amount exceeding 70 parts by weight, heat resistance may decrease.
[203]
In the case of the ethylene/alpha-olefin copolymer, 10 parts by weight to 50 parts by weight may be included based on 100 parts by weight of the adhesive composition, and specifically 15 parts by weight to 30 parts by weight may be included. When the above numerical range is satisfied, excellent adhesive properties can be maintained.
[204]
[205]
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 plasticized oil. Specifically, it may be a low molecular weight polymer such as an olefin oligomer, a liquid polybutene, a polyisoprene copolymer, a liquid styrene-isoprene copolymer or a liquid hydrogenated styrene-conjugated diene copolymer, a vegetable oil and a derivative thereof, or a microcrystalline wax. have.
[206]
The 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, based on 100 parts by weight of the adhesive composition. If the plasticizer is included in an amount of less than 10 parts by weight, the contact degree of the adhesive composition may be increased and processability may be deteriorated.
[207]
[208]
In addition, the adhesive composition may further include an antioxidant to improve heat resistance and color improvement.
[209]
At this time, the antioxidant is not particularly limited, and a commonly known one in the art may be used, and 0.01 to 5 parts by weight, or 0.01 to 1 part by weight, or 0.05 parts by weight based on 100 parts by weight of the adhesive composition It may be included in an amount of 0.75 parts by weight.
[210]
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, crosslinkers, surfactants, solvents, and combinations thereof.
[211]
The fillers are 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 up to 80% by weight of the total composition.
[212]
[213]
One embodiment of the present invention provides an article including a substrate coated with the adhesive composition. The article may be selected from tapes, labels, transfer papers, boxes, cardboards, trays, medical devices, bandages and hygiene products, but is not limited thereto.
Mode for carrying out the invention
[214]
Example
[215]
Hereinafter, preferred embodiments are presented to aid in understanding the present invention. However, the following examples are only provided to more easily understand the present invention, thereby not limiting the content of the present invention.
[216]
[217]
[Synthesis Example: Preparation of transition metal compound]
[218]
Step 1: Preparation of Ligand Compound (1a-1)
[219]
In a 250 mL Schlenk flask, 1, 2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene 10 g (1.0 eq, 49.925 mmol) and THF 100 mL were added, and n-BuLi 22 mL (1.1 eq, 54.918 mmol, 2.5 M in hexane) was added dropwise at -30°C, followed by stirring at room temperature for 3 hours. The stirred Li-complex THF solution was cannulated at -78°C in a Schlenk flask containing 8.1 mL (1.0 eq, 49.925 mmol) of dichloro(methyl)(phenyl)silane and 70 mL of THF, and then stirred at room temperature overnight. After stirring, vacuum drying, and then extracted with 100 mL of hexane.
[220]
T-BuNH in 100 mL of the extracted chloro-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-(methyl)(phenyl)silane hexane solution 2 42 mL (8 eq, 399.4 mmol) was added at room temperature, followed by stirring at room temperature overnight. After stirring, vacuum drying, and then extracted with 150 mL of hexane. After drying the solvent, 13.36 g (68%, dr = 1:1) of a yellow solid was obtained.
[221]
(1a-1)
[222]

[223]
1H NMR (CDCl3, 500 MHz): δ 7.93 (t, 2H), 7.79 (d,1H), 7.71 (d,1H), 7.60 (d, 2H), 7.48 (d, 2H), 7.40-7.10 (m , 10H, aromatic), 3.62(s, 1H), 3.60(s, 1H), 2.28(s, 6H), 2.09(s, 3H), 1.76(s, 3H), 1.12(s, 18H), 0.23( s, 3H), 0.13(s, 3H)
[224]
[225]
Step 2: Preparation of transition metal compound (1a)
[226]
In a 100 mL Schlenk flask, 4.93 g (12.575 mmol, 1.0 eq) of the ligand compound of Formula 2-4 and 50 mL (0.2M) of toluene were added, and 10.3 mL (25.779 mmol, 2.05 eq, 2.5M in hexane) of n-BuLi was added. Was added dropwise at -30°C, followed by stirring at room temperature overnight. After stirring, MeMgBr 12.6 mL (37.725 mmol, 3.0 eq, 3.0 M in diethyl ether) was added dropwise, and then TiCl 4 13.2 mL (13.204 mmol, 1.05 eq, 1.0 M in toluene) was sequentially added and stirred at room temperature overnight. . After stirring, vacuum drying, extraction with 150 mL of hexane, removal of the solvent to 50 mL, and 4 mL of DME (37.725 mmol, 3.0eq) were added dropwise, followed by stirring at room temperature overnight. After vacuum drying again, it was extracted with 150 mL of hexane. After drying the solvent, 2.23 g (38%, dr = 1:0.5) of a brown solid was obtained.
[227]
(1a)
[228]

[229]
1 H NMR (CDCl 3 , 500 MHz): δ 7.98 (d, 1H), 7.94 (d, 1H), 7.71 (t, 6H), 7.50 ~ 7.30 (10H), 2.66 (s, 3H), 2.61 (s , 3H), 2.15(s, 3H), 1.62(s, 9H), 1.56(s, 9H), 1.53(s, 3H), 0.93(s, 3H), 0.31(s, 3H), 0.58(s, 3H), 0.51(s, 3H), -0.26(s, 3H), -0.39(s, 3H)
[230]
[231]
[Production of ethylene/alpha-olefin copolymer]
[232]
Manufacturing Example 1
[233]
After the 1.5L autoclave continuous process reactor was filled with hexane solvent (5.0 kg/h) and 1-octene (1.20 kg/h), the temperature at the top of the reactor was preheated to 150°C. Triisobutylaluminum compound (0.5 mmol/min), transition metal compound (1a) (0.40 μmol/min) prepared in Synthesis Example above as a catalyst, dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst (2.40 μmol) /min) was simultaneously introduced into the reactor. Then, ethylene (0.87 kg/h) and hydrogen gas (85 cc/min) were introduced into the autoclave reactor and maintained at a pressure of 89 bar and a polymerization temperature of 123.9° C. for 60 minutes or more, and the copolymerization reaction was continuously performed to obtain a copolymer Prepared.
[234]
Next, the remaining ethylene gas was removed, and the resulting copolymer-containing solution was dried in a vacuum oven for 12 hours or longer, and then the physical properties of the obtained copolymer were measured.
[235]
[236]
Preparation Examples 2 to 11 and Comparative Preparation Examples 1 and 5 to 12
[237]
A polymer was prepared in the same manner as in Preparation Example 1, except that reactants were added in the amounts shown in Table 1 below.
[238]
[239]
Comparative Preparation Example 2
[240]
As an ethylene/alpha-olefin copolymer, the product name GA1950 (2017, The Dow Chemical Company) was applied.
[241]
[242]
Comparative Preparation Example 3
[243]
As an ethylene/alpha-olefin copolymer, the product name GA1950 (2016, The Dow Chemical Company) was applied.
[244]
[245]
Comparative Preparation Example 4
[246]
As an ethylene/alpha-olefin copolymer, the product name GA1900 (The Dow Chemical Company) was applied.
[247]
[Table 1]
Catalyst input amount (μmol/min) Cocatalyst input amount (μmol/min) 1-C8 input (kg/h) TiBAl(mmol/min) Polymerization temperature(℃) H 2 input amount (cc/min)
Manufacturing Example 1 0.4 2.4 1.2 0.5 123.9 85
Manufacturing Example 2 0.4 2.4 1.05 0.5 125 69
Manufacturing Example 3 0.3 0.9 1.6 0.5 124.1 95
Manufacturing Example 4 0.2 0.6 1.1 0.05 125 85
Manufacturing Example 5 0.35 1.05 0.93 0.03 140 55
Manufacturing Example 6 0.4 1.2 1.0 0.05 125 75
Manufacturing Example 7 0.4 1.2 1.0 0.05 125 50
Manufacturing Example 8 0.4 1.2 1.0 0.05 125 80
Manufacturing Example 9 0.4 1.2 1.0 0.05 125 95
Manufacturing Example 10 0.35 1.05 1.15 0.05 145 50
Manufacturing Example 11 0.35 1.05 1.15 0.05 145 55
Comparative Preparation Example 1 0.2 3.9 1.8 0.5 160 0
Comparative Preparation Example 5 0.65 1.95 2.20 0.05 150 0
Comparative Production Example 6 0.26 0.78 1.2 0.05 125 35
Comparative Preparation Example 7 0.4 1.2 1.0 0.05 125 130
Comparative Production Example 8 0.7 2.1 2.0 0.05 150 0
Comparative Preparation Example 9 0.4 1.2 1.0 0.05 125 0
Comparative Preparation Example 10 0.4 1.2 1.0 0.05 125 10
Comparative Production Example 11 0.4 1.2 1.0 0.05 125 15
Comparative Production Example 12 0.65 1.95 2.2 0.05 160 0
[248]
* In Comparative Preparation Examples 5, 6 and 12, [Me 2 Si(Me 4 C 5 )NtBu]Ti(CH 3 ) 2 was used as a catalyst.
[249]
[250]
The physical properties of the ethylene/alpha-olefin copolymers of Preparation Example and Comparative Preparation Example were measured by the following method, and are shown in Tables 2 and 3.
[251]
1) Density (Density, g/cm 3 ): It was measured according to ASTM D-792.
[252]
2) Viscosity (cP) : It was measured according to the following method using a Brookfield RVDV3T viscometer. Specifically, a sample is placed in a 13ml sample chamber, heated to 180°C using a Brookfield Thermosel, and when the sample is completely dissolved, lower the viscometer device to fix the spindle in the sample chamber, and the spindle (SC-29 hot-melt spindle ) Was fixed at 20 rpm, read for more than 20 minutes or until the value stabilized, and the final value was recorded.
[253]
3) Melt Index (MI, dg/min) : The melt index (MI) of the polymer was measured by ASTM D-1238 (Condition E, 190°C, 2.16 Kg load).
[254]
4) Weight average molecular weight (g/mol) and molecular weight distribution (MWD) : The number average molecular weight (Mn) and the weight average molecular weight (Mw) were determined under the following conditions by gel permeation chromatography (GPC: PL GPC220). Each was measured, and the weight average molecular weight was divided by the number average molecular weight to calculate the molecular weight distribution.
[255]
-Column: PL Olexis
[256]
-Solvent: Trichlorobenzene (TCB)
[257]
-Flow rate: 1.0 ml/min
[258]
-Sample concentration: 1.0 mg/ml
[259]
-Injection volume: 200 µl
[260]
-Column temperature: 160℃
[261]
-Detector: Agilent High Temperature RI detector
[262]
-Standard: Polystyrene (corrected by 3rd order function)
[263]
5) Full Width at Half Maximum (FWHM) of the crystallization peak : PolymerChar's CFC was used as the measuring equipment. First, the solution of the copolymer using o-dichlorobenzene as a solvent was completely dissolved in an oven in a CFC analyzer at 130° C. for 60 minutes, poured into a TREF column adjusted to 135° C., cooled to 95° C., and stabilized for 45 minutes. Then, the temperature of the TREF column was lowered to -20°C at a rate of 0.5°C/min, and then maintained at -20°C for 10 minutes. Then, the elution amount (mass %) was measured using an infrared spectrophotometer. Subsequently, raising the temperature of the TREF column to a preset temperature at a rate of 20 °C/mi and maintaining the temperature at the temperature reached for a preset time (i.e., about 27 minutes), the temperature of the TREF is 130 °C It was repeated until this time, and the amount (mass %) of the eluted fraction was determined during each temperature range. In addition, the molecular weight (Mw) was measured in the same manner as the GPC measurement principle, except that the fraction eluted at each temperature was sent to a GPC column and o-dichlorobenzene was used as a solvent. The FWHM value was calculated after fitting the elution amount graph (dW/dT vs T) according to the temperature obtained through CFC in the form of a Gaussian curve on the program (Origin).
[264]
6) Crystalization Index (CI) : It was calculated through Equation 1 below using the measured melting index and FWHM.
[265]
[Equation 1]
[266]

[267]
In Equation 1, A is the Full Width at Half Maximum (FWHM) of the peak that appears when measuring the crystallization temperature, and B is the Melt Index (MI) as ASTM D-1238 (Condition E, 190°C, 2.16 Kg). It is a value measured in terms of load), and is a value in case of the unit'dg/min'
[268]
7) Melting temperature (Tm, ℃) : The melting temperature of the polymer was measured using a Differential Scanning Calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument). Specifically, the polymer was heated to 150° C. and maintained for 5 minutes, and the temperature was lowered to -100° C. and then the temperature was increased again. At this time, the rate of rise and fall of the temperature were adjusted to 10°C/min, respectively. The melting temperature was taken as the maximum point of the endothermic peak measured in the section where the second temperature rises.
[269]
8) Crystallization temperature (Tc, ℃) : It was carried out in the same manner as the melting temperature measurement using DSC, and the maximum point of the exothermic peak from the curve that appears while decreasing the temperature was taken as the crystallization temperature.
[270]
9) Measurement of monomer reactivity ratio (Re, Rc) : The ethylene-alphaolefin copolymer prepared in Preparation Examples 4 and 6-11 and Comparative Preparation Examples 6 and 12 was used as a solvent (1,1,2,2-tetrachloroethane). After dissolving in -d2 (TCE-d2), about 0.4 ml was put into a tube having a diameter of 5 mm and a length of 18 cm, and the tube was placed in a 13C NMR spectrometer, and the frequency was 150 MHz, the temperature was 100° C., and d1 (relaxation delay). time) The values ​​of kee, kec, kcc and kce were measured under the conditions of 3s, and Scans 4k, and the monomer reactivity ratios were calculated by substituting them into the following equations 2 and 3, and are shown in Table 3.
[271]
[Equation 2]
[272]
Re (reactivity ratio of ethylene monomer)=kee/kec
[273]
[Equation 3]
[274]
Rc (reactivity ratio of alpha olefin comonomer) = kcc/kce
[275]
(In Equations 2 and 3, kee represents the growth reaction rate constant when ethylene is added to the growth chain whose terminal active point is an ethylene monomer, and kec represents the alpha olefin comonomer added to the growth chain whose terminal active point is an ethylene monomer. Represents the growth reaction rate at the time, kcc represents the growth reaction rate when an alpha olefin comonomer is added to the growth chain where the terminal active point is an alpha olefin comonomer, and kce represents the growth reaction rate when the terminal active point is an alpha olefin comonomer. It represents the growth rate constant when the monomer is added.)
[276]
[Table 2]
density Viscosity Melt index FWHM CI Mw(g/mol) MWD Tc/Tm(℃
(g/cc) (cP) (dg/min)
Manufacturing Example 1 0.877 15950 544 21.71 18.81 22,900 1.94 53.8/70.3
Manufacturing Example 2 0.876 14850 591 22.97 20.51 23,000 1.98 52.1/68.9
Manufacturing Example 3 0.871 7300 1149 28.52 20.19 19,000 1.98 49.1/65.0
Manufacturing Example 4 0.875 17000 500 21.38 19.54 24,500 1.96 52.2/68.3
Manufacturing Example 5 0.875 16500 528 20.67 16.73 23,000 2.01 52.3/68.5
Manufacturing Example 6 0.875 16850 509 21.62 19.85 24,400 1.96 52.0/68.1
Manufacturing Example 7 0.873 35000 250 18.21 24.15 34,900 1.98 50.6/66.5
Manufacturing Example 8 0.876 13500 698 23.59 18.81 22,400 1.98 52.3/68.9
Manufacturing Example 9 0.877 8500 989 27.23 20.41 19,500 1.77 53.2/69.7
Manufacturing Example 10 0.876 13500 698 24.14 20.15 22,300 2.00 52.2/68.8
Manufacturing Example 11 0.876 8800 966 27.79 22.22 19,700 1.99 52.5/69.1
Comparative Production Example 1 0.875 15800 550 24.67 27.3 23,700 2.29 51.8/67.9
Comparative Production Example 2 0.875 15600 558 26.22 32.3 24,000 1.96 52.3/68.7
Comparative Production Example 3 0.875 15700 554 25.68 30.57 24,100 1.98 52.4/68.7
Comparative Production Example 4 0.871 7800 1099 32.64 31.64 20,000 1.98 49.3/65.1
Comparative Production Example 5 0.875 15800 550 26.31 33.11 23,000 2.24 51.8/67.8
Comparative Production Example 6 0.876 13900 676 26.89 28.76 22,800 1.94 56.1/73.2
Comparative Production Example 7 0.879 3500 1265 33.65 30.12 14,600 1.97 61.3/77.8
Comparative Production Example 8 0.872 >50000 - - - 46,800 2.14 40.6/58.7
Comparative Production Example 9 0.874 >50000 - - - 75,400 2.08 42.1/59.6
Comparative Production Example 10 0.874 >50000 - - - 57,700 2.09 41.7/59.4
Comparative Production Example 11 0.873 >50000 - - - 48,700 2.08 41.3/58.7
Comparative Production Example 12 0.875 15800 550 26.51 33.87 26,700 2.24 51.9/67.8
[277]
In the case of Comparative Preparation Examples 8 to 11 having too high viscosity, the crystallization index was not measured.
[278]
[279]
[Table 3]
Monomer reactivity ratio
Re Rc ReXRc
Manufacturing Example 4 8.53 0.11 0.94
Manufacturing Example 6 9.30 0.10 0.93
Manufacturing Example 7 7.31 0.13 0.95
Manufacturing Example 8 6.71 0.14 0.94
Manufacturing Example 9 8.09 0.11 0.89
Manufacturing Example 10 8.82 0.11 0.97
Manufacturing Example 11 7.83 0.12 0.94
Comparative Production Example 6 1.29 1.56 1.50
Comparative Production Example 12 8.11 0.25 2.03
[280]
[281]
[Preparation of adhesive composition]
[282]
Example 1
[283]
39.5% by weight of the copolymer of Preparation Example 5 as an ethylene/alpha-olefin copolymer, 40% by weight of SUKOREZ® SU-110S (Kolon Industries, Inc.) as a tackifier, 20% by weight of SASOLWAX H1 (SASOL) as a plasticizer and oxidation An adhesive composition comprising 0.5% by weight of Irganox1010 (BASF) as an inhibitor was prepared.
[284]
[285]
Examples 2 to 8 and Comparative Examples 1 to 8
[286]
An adhesive composition was prepared in the same manner as in Example 1, except that the types and contents of the ethylene/alpha-olefin copolymer, the tackifier, the plasticizer, and the antioxidant were changed as described in Table 4 below.
[287]
[Table 4]
Ethylene/alphaolefin copolymer Tackifier Plasticizer Antioxidant
Manufacturing example Comparative Production Example SU-100S H-100W SasolH1 IR1010
4 5 6 8 5 6 7 12
Example 1 39.5 40 20 0.5
Example 2 39.5 40 20 0.5
Example 3 39.5 40 20 0.5
Example 4 39.5 40 20 0.5
Example 5 39.5 40 20 0.5
Example 6 39.5 40 20 0.5
Example 7 39.5 40 20 0.5
Example 8 39.5 40 20 0.5
Comparative Example 1 39.5 40 20 0.5
Comparative Example 2 39.5 40 20 0.5
Comparative Example 3 39.5 40 20 0.5
Comparative Example 4 39.5 40 20 0.5
Comparative Example 5 39.5 40 20 0.5
Comparative Example 6 39.5 40 20 0.5
Comparative Example 7 39.5 40 20 0.5
Comparative Example 8 39.5 40 20 0.5
[288]
*Eastotac H-100W (Eastman Chemical Company)
[289]
Experimental example
[290]
The physical properties of the adhesive compositions of Examples and Comparative Examples were measured by the following method, and are shown in Table 5.
[291]
1) Heat resistance (℃) : To evaluate heat resistance, a PAFT (Peel Adhesion Failure Temperature) specimen was prepared in the following manner.
[292]
After dissolving the adhesive composition prepared on the HMA coater, it was coated with 75 um on the silicone release-treated PET film and cut into a thickness of 75 um, a width of 25 mm, and a length of 250 mm. Two kraft papers were cut with a basis weight of 160 g/m 2 and a width of 125 mm and a length of 210 mm. HMA in the form of a film was placed horizontally between kraft papers, and cut into 8 samples at 2.5 mm intervals in the width direction. The temperature of the top plate of the hot plate was set to 180°C, and the specimen was placed on it, and then pressed with a 1 kg weight in the center of the specimen for 5 seconds. The prepared specimens were left at room temperature for at least 6 to 24 hours so that the HMA was completely set.
[293]
100 g of the PAFT specimen was suspended and the temperature was raised at a rate of 5° C./10 min to measure the temperature upon drop.
[294]
[295]
2) Low-temperature adhesion (%) : A specimen for low-temperature adhesion evaluation was prepared in the same manner as in the preparation of the PAFT specimen, except that the thickness on the PET film was coated with 100 um.
[296]
Prepare 7 or more specimens per temperature and leave for 6 to 24 hours at -40℃ and -30℃, and then visually check the degree of fiber tear of HMA based on the grid scale in a low-temperature chamber, and the residual rate of kraft paper Is reported as a percentage.
[297]
[298]
3) Heat discoloration resistance (YI) : It was measured according to the following method using a Jeio-Tech forced circulation drying oven (OF-22). Specifically, 100 g of the adhesive composition prepared after cutting to within 2.5 mm X 2.5 mm is weighed. The weighed test piece was put in a 250 ml heat-resistant beaker and heated in a vacuum oven at 140° C. over three or four times for 10 to 20 minutes to remove remaining air bubbles. After sealing the inlet of the beaker with aluminum foil, the temperature of the hot product oven is set to 180° C. and heated continuously for 72 hours. Thereafter, a test piece was prepared with a thickness of 2 mm and the YI value was measured. YI was used as a value obtained by measuring at least different subdivisions of the test piece.
[299]
[Table 5]
　　 Heat resistance (℃)　 Low temperature adhesion (%) Heat discoloration (YI)
-40℃ -30℃
Example 1 57 92 88 61
Example 2 58 88 90 60
Example 3 58 77 80 59
Example 4 60 75 78 60
Example 5 58 92 88 61
Example 6 59 88 90 60
Example 7 59 77 80 60
Example 8 58 75 78 59
Comparative Example 1 54 82 76 64
Comparative Example 2 56 76 78 65
Comparative Example 3 55 68 74 63
Comparative Example 4 56 63 70 63
Comparative Example 5 44 53 58 70
Comparative Example 6 45 54 59 69
Comparative Example 7 56 82 76 64
Comparative Example 8 56 68 75 63
[300]
Referring to Table 5, it can be seen that the adhesive composition according to the present invention is excellent in both heat resistance and low temperature adhesiveness. The heat resistance test is a measurement of a limit temperature at which adhesive strength is maintained under a specific condition, which is an indirect adhesive strength index, and if this value is high, the adhesive strength can be maintained even at high temperatures, so it can be used even in a high temperature environment. In addition, the low-temperature adhesion test is a measurement of adhesion durability at low temperature, and is an important adhesion index in terms of the properties of a polyolefin-based hot melt adhesive composition used as a beverage or food packaging material.
[301]
Specifically, it can be seen that the adhesive composition of the present invention is more excellent in heat resistance since the peeling phenomenon occurs at a higher temperature when compared with the comparative example using the same tackifier.
[302]
In addition, from the fact that the residual ratio (%) of kraft paper is maintained at a much superior level compared to the comparative example in the fiber tear test performed at low temperatures of -40°C and -30°C, respectively, the adhesive composition of the present invention In the case of, it can be confirmed that excellent adhesion is maintained even at very low temperatures.
[303]
[304]
As described above, it can be seen that the adhesive composition of the present invention contains an ethylene/alpha-olefin copolymer having a crystallinity index of 15 to 25 and greatly improved crystallinity, thereby having excellent heat resistance and excellent low-temperature adhesion.
Claims
[Claim 1]
Ethylene/alpha-olefin copolymer; And a tackifier; wherein the ethylene/alpha-olefin copolymer satisfies the conditions of i) to iv) below: i) density: 0.85 to 0.89 g/cc, ii) molecular weight distribution ( MWD): 1.5 to 3.0, iii) Viscosity: 6,000 cP to 40,000 cP when measured at a temperature of 180° C., iv) Crystalization Index (CI) according to Equation 1 below: 15 to 25 [Equation 1] In Equation 1 , A is the full width at half maximum (FWHM) that appears when measuring the crystallization temperature, and B is the melt index (MI), measured by ASTM D-1238 (condition E, 190℃, 2.16 Kg load). It is one number, and it is a number in the case of the unit'dg/min'.
[Claim 2]
The adhesive composition of claim 1, wherein the ethylene/alpha-olefin copolymer has a crystallization index of 16 to 23.
[Claim 3]
The adhesive composition of claim 1, wherein the ethylene/alpha-olefin copolymer further satisfies the condition of v): v) ReХRc ≤ 1.0 At this time, Re=kee/kec, Rc=kcc/kce, and kee is the terminal Represents the growth reaction rate constant when ethylene is added to the growth chain whose active point is an ethylene monomer, kec represents the growth reaction rate when alpha olefin comonomer is added to the growth chain whose terminal active point is an ethylene monomer, and kcc is the terminal Represents the growth reaction rate when an alpha olefin comonomer is added to the growth chain where the active point is an alpha olefin comonomer, and kce represents the growth reaction rate constant when an ethylene monomer is added to the growth chain where the terminal active point is an alpha olefin comonomer. Show.
[Claim 4]
The adhesive composition of claim 1, wherein the ethylene/alpha-olefin copolymer has a ReХRc value of 0.95 or less.
[Claim 5]
The adhesive composition of claim 1, wherein the ethylene/alpha-olefin copolymer has a weight average molecular weight of 17,000 to 40,000 g/mol.
[Claim 6]
The adhesive composition of claim 1, wherein the ethylene/alpha-olefin copolymer has a viscosity of 8,500 to 35,000 cP as measured at 180°C.
[Claim 7]
The adhesive composition of claim 1, wherein the ethylene/alpha-olefin copolymer has a density of 0.860 to 0.885 g/cc.
[Claim 8]
The method of claim 1, wherein the alpha-olefin is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, The adhesive composition comprising at least one selected from the group consisting of 1-dodecene, 1-tetradecene, 1-hexadecene and 1-eicosene.
[Claim 9]
The adhesive composition of claim 1, wherein the alpha-olefin is contained in an amount of more than 0 and 99 mol% or less based on the total weight of the copolymer.
[Claim 10]
The adhesive composition of claim 1, further satisfying the following conditions vi) to viii): vi) Total number of unsaturated functional groups per 1,000 carbon atoms: 0.8 or less, vii) Number average molecular weight (Mn): 9,000 to 25,000, viii ) Melt Index (MI) at 190° C., 2.16 kg load according to ASTM D1238: 200 to 1,300 dg/min.
[Claim 11]
The method of claim 1, wherein the tackifier is a modified C5 hydrocarbon resin, a styrenated tefrene resin, a fully or partially hydrogenated C9 hydrocarbon resin, a hydrogenated cycloaliphatic hydrocarbon resin, a hydrogenated aromatic modified cycloaliphatic hydrocarbon resin, and these Adhesive composition that is one or more selected from the group consisting of mixtures.
[Claim 12]
An article comprising a substrate coated with an adhesive composition according to claim 1.