Polyolefin composition

Abstract

The present invention relates to a polyolefin composition comprising one or more olefin-based polymers and polyethylene, wherein the crystal distribution width of the high crystal portion and the medium crystal portion is maintained at 22°C or more, thereby minimizing the creep phenomenon, and thus, when used to manufacture a composition for a sealing film or a sealing film, the deformation of the film can be minimized even with long-term use.

Description

Technical Field

[0001] Cross-reference to related applications

[0002] This application claims the benefit of Korean Patent Application No. 10-2023-0189949, filed on December 22, 2023, with the Korean Intellectual Property Office, the contents of which are incorporated herein by reference.

[0003] This invention relates to a polyolefin composition. Background Technology

[0004] Recently, due to global environmental issues and the consumption of fossil fuels, interest in renewable and clean energy is increasing. In particular, photovoltaic devices that utilize light, such as photovoltaic cells, light-emitting diodes (LEDs), or organic light-emitting diodes (OLEDs), are gaining attention as pollution-free energy devices. Specifically, photovoltaic cells, such as solar cells, are being rapidly adopted in residential and industrial applications.

[0005] A photovoltaic cell is a device that converts light into electrical energy. Because photovoltaic cells usually need to be exposed to the external environment for a long time in order to easily absorb light, they are made into units using various encapsulation processes to protect the internal components. These units are usually called photovoltaic modules.

[0006] In conventional solar cell modules, two sealing sheets are formed between the surface-side glass substrate and the rear protective film, which serves as a back-side protector, to enclose the solar cell. Such solar cell modules are manufactured by sequentially laminating the glass substrate, sealing sheets, solar cell, sealing sheets, and rear protective film, followed by a process of heating / pressurizing to completely melt the sealing sheets while simultaneously pressurizing and degassing in the vertical direction to ensure sufficient polymer mobility.

[0007] Perovskite materials have attracted much attention as light-absorbing materials for solar cells. However, they have poor thermal stability and are greatly affected by external environmental factors such as temperature and humidity. Therefore, they undergo phase transitions at high temperatures or their photoelectric conversion efficiency deteriorates rapidly when humidity is high.

[0008] Therefore, a polyolefin composition for preparing a sealing film has been developed, which can maintain creep properties and adhesive strength while adhering to heat-sensitive compounds such as perovskite using low-temperature lamination. Summary of the Invention

[0009] Technical issues

[0010] One aspect of the present invention provides a polyolefin composition that exhibits excellent creep properties by maintaining a wide crystallinity distribution and a crystal distribution width of high-crystal and medium-crystal portions above 22°C.

[0011] Technical solution

[0012] 1. According to one aspect of the invention, a polyolefin composition is provided comprising one or more olefin polymers and polyethylene, and satisfying the following conditions (1) to (3): (1) Density is above 0.855 g / cc and below 0.895 g / cc. (2) The melt flow index (MI, 190℃, 2.16kg load) is above 0.3dg / min and below 40.0dg / min. (3) When measured by differential scanning calorimetry (DSC-SSA) with continuous self-nucleation and annealing, a) T(90)-T(75)>21.5℃, b) T(95)-T(90)<18℃, c) T(98)-T(95)<10℃, Among them, when the temperature-heat capacity curves measured by differential scanning calorimetry continuous self-nucleation and annealing (DSC-SSA) are graded, T(98), T(95), T(90) and T(75) are the temperatures at which the heat capacity reaches 98%, 95%, 90% and 75%, respectively.

[0013] 2. The present invention provides a polyolefin composition according to 1, wherein the polyolefin composition satisfies the following condition (4): (4) Melt Flow Rate Ratio (MFRR, MI) 10 / MI 2.16 The value is between 7.5 and 9.5.

[0014] 3. The present invention provides a polyolefin composition according to 1 or 2, wherein the polyolefin composition satisfies the following condition (5): (5) The weight-average molecular weight is above 10,000 g / mol and below 500,000 g / mol.

[0015] 4. The present invention provides a polyolefin composition according to any one of 1 to 3, wherein the polyolefin composition satisfies the following condition (6): (6) The molecular weight distribution is above 1.5 and below 3.0.

[0016] 5. The present invention provides a polyolefin composition according to any one of 1 to 4, wherein T (95) is above 100°C and below 110°C.

[0017] 6. The present invention provides a polyolefin composition according to any one of 1 to 5, wherein T (90) is 85.9°C or higher.

[0018] 7. The present invention provides a polyolefin composition according to any one of 1 to 6, wherein the polyethylene is present in an amount of 1 part by weight or more and 5 parts by weight or less relative to 100 parts by weight of the olefin polymer.

[0019] 8. The present invention provides a polyolefin composition according to any one of 1 to 7, wherein the one or more olefin polymers comprise a first olefin polymer and a second olefin polymer, and

[0020] The weight ratio of the first olefin polymer to the second olefin polymer is greater than 1:0.1 and less than 1.

[0021] 9. The present invention provides a polyolefin composition according to any one of 1 to 8, wherein the olefin polymer is a copolymer of ethylene and α-olefin comonomer.

[0022] 10. The present invention provides a polyolefin composition according to claim 9, wherein the α-olefin comonomer is an α-olefin comonomer with 3 to 12 carbon atoms.

[0023] 11. The present invention provides a polyolefin composition according to 9 or 10, wherein the α-olefin comonomer comprises at least one selected from polypropylene, 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-eicosene, norbornene, norbornediene, ethylidene norbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, α-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.

[0024] Beneficial effects

[0025] The polyolefin composition of the present invention has a wide crystallinity distribution, and the crystal distribution width of the high-crystal and medium-crystal portions is maintained above 22°C, so that the sealing film prepared thereby has excellent adhesive strength and light transmittance while minimizing creep, thus ensuring stability. Attached Figure Description

[0026] Figure 1 This is a graph showing the measurement results of continuous self-nucleation and annealing (SSA) using differential scanning calorimetry for the polyolefin compositions of Example 1 and Comparative Example 1 in this invention. Detailed Implementation

[0027] The invention will be described in more detail below to aid in understanding it.

[0028] It should be understood that, based on the principle that inventors can appropriately define the meaning of words or terms to best interpret the invention, the words or terms used in this disclosure and claims should not be interpreted as having the meaning defined in a common dictionary, but should be interpreted as having a meaning consistent with their meaning in the technical concept of the invention.

[0029] As used in this specification, the term "polymer" refers to a polymer compound prepared by polymerization of the same or different types of monomers. The general term "polymer" includes the terms "homopolymer," "copolymer," "terpolymer," and "interpolymer." The term "interpolymer" refers to a polymer prepared by polymerization of two or more different types of monomers. The general term "interpolymer" includes the term "copolymer" (which is generally used to refer to a polymer prepared from two different types of monomers) and the term "terpolymer" (which is generally used to refer to a polymer prepared from three different types of monomers). Ternary copolymers include polymers prepared by polymerization of four or more types of monomers.

[0030] [Polyolefin Composition]

[0031] The present invention relates to a polyolefin composition comprising one or more olefin polymers and polyethylene and satisfying the following conditions (1) to (3).

[0032] The polyolefin composition has a density of (1) 0.855 g / cc or more and 0.895 g / cc or less. Density may refer to the density measured according to ASTM D-792. Specifically, the composition for use in sealing films may have a density of 0.855 g / cc or more, 0.860 g / cc or more, 0.865 g / cc or more, 0.870 g / cc or more, and may also have a density of 0.895 g / cc or less, 0.890 g / cc or less, 0.885 g / cc or less.

[0033] In this invention, a catalyst composition comprising a transition metal compound having a specific structure is used, and a large amount of comonomer can be introduced. As a result, the polyolefin composition according to one embodiment of the invention can have the low density described above, and therefore can exhibit excellent light transmittance and low-temperature adhesion properties. More specifically, the polyolefin composition can have a density of 0.855 g / cc or more and 0.895 g / cc or less. In this case, by controlling the density within the above-mentioned density range, the effect of maintaining physical properties such as adhesive strength and light transmittance, as well as improving creep phenomena, is more significant.

[0034] Furthermore, the polyolefin composition has a melt index (MI, 190°C, 2.16 kg load conditions) of (2) 0.3 dg / min or more and 40.0 dg / min or less. Specifically, the melt index of the polyolefin composition may be 0.3 dg / min or more, 0.5 dg / min or more, 1.0 dg / min or more, 1.5 dg / min or more, 2.0 dg / min or more, and may further be 40.0 dg / min or less, 35.0 dg / min or less, 30.0 dg / min or less, 25.0 dg / min or less, 20.0 dg / min or less, 15.0 dg / min or less, 10.0 dg / min or less, 9.0 dg / min or less, 8.0 dg / min or less, 7.0 dg / min or less, 6.0 dg / min or less, 5.0 dg / min or less, 4.5 dg / min or less, or 4.0 dg / min or less. Melt flow index can be controlled by adjusting the amount of comonomer in the catalyst used in the polymerization of olefin polymers, and it affects the mechanical properties, impact strength, and molding properties of olefin polymers.

[0035] Furthermore, when the melt flow index is within this range, melt flowability suitable for forming a sealing film for solar cells can be achieved.

[0036] In addition, the polyolefin composition satisfies: (3) when measured by differential scanning calorimetry continuous self-nucleation and annealing (DSC-SSA), a) T(90)-T(75) > 21.5 °C, b) T(95)-T(90) < 18 °C, and c) T(98)-T(95) < 10 °C. Specifically, T(90)-T(75) can be above 22 °C, above 22.5 °C, or above 23 °C, T(95)-T(90) can be below 17.9 °C, below 17.8 °C, below 17.7 °C, below 17.6 °C, or below 17.5 °C, and T(98)-T(95) can be below 9.9 °C, below 9.8 °C, below 9.7 °C, below 9.6 °C, or below 9.5 °C. In this case, when the temperature-heat capacity curves measured by differential scanning calorimetry continuous self-nucleation and annealing (DSC-SSA) are graded, T(98), T(95), T(90) and T(75) are the temperatures at which the heat capacity reaches 98%, 95%, 90% and 75%, respectively.

[0037] The crystal distribution of the polyolefin composition of the present invention can be seen through T(90)-T(75), T(95)-T(90), and T(98)-T(95). The distribution degree of high crystals, medium crystals, and low crystals can be seen through T(90)-T(75), T(95)-T(90), and the distribution of high crystals in the high crystal region can be seen through T(98)-T(95). When T(90)-T(75), T(95)-T(90), and T(98)-T(95) meet the ranges, it means that high crystals, medium crystals, and low crystals are uniformly distributed in the polyolefin composition of the present invention, and since each crystal does not exist alone but is distributed together in some regions, they are firmly held together and can maintain the cohesiveness and adhesion of the polyolefin composition. Conversely, when T(90)-T(75), T(95)-T(90), or T(98)-T(95) deviates too much or too little from the range, high-crystal, medium-crystal, and low-crystal exist separately, causing the crystal distribution to be separated and not adhered, or the interval between them is too narrow to behave like a single crystal. Therefore, the crystal melts or breaks immediately, and creep may occur more frequently.

[0038] Polyolefin compositions can be prepared, for example, in a reactor at a specific temperature using two types of catalysts with different activities, copolymerization properties, and additionally by adding polyethylene responsible for high crystallinity, such that a wide region in which high, medium, and low crystallinity are distributed together is present, while having a crystallinity distribution that achieves each property. Thus, the polyolefin compositions of the present invention do not have a separate distribution of low, medium, and high crystallinity, but rather a distribution of crystals such that even small amounts are distributed together like bridges to have interconnected regions, so as to firmly hold each other together to achieve not only excellent cohesion and adhesion, but also minimized creep.

[0039] The T (95) of the polyolefin composition can be above 100°C and below 110°C. Specifically, it can be above 101°C, above 102°C, above 103°C, and can also be below 109°C, below 108°C, below 107°C, below 106°C, below 105°C, and below 104°C. When T (95) meets this range, a region is formed that is distributed together with intermediate crystals and can be connected with intermediate crystals, so that creep can be minimized.

[0040] Furthermore, the T(90) of the polyolefin composition can be 85.9°C or higher. Specifically, it can be 86°C or higher, 86.1°C or higher, 86.2°C or higher, and can also be 100°C or lower, 95°C or lower, or 90°C or lower. When T(90) meets this range, a region is formed that is distributed together with the medium crystals and can be connected with the medium crystals, so that creep can be minimized.

[0041] Furthermore, the polyolefin compositions of the present invention can satisfy the following conditions (4) to (6).

[0042] The polyolefin composition may have a melt flow rate ratio (MFRR, MI) of (4) 7.5 or more and 9.5 or less. 10 / MI 2.16 The melt flow rate ratio can be obtained by dividing the melt index measured at 190°C and 10 kg load by the melt index measured at 190°C and 2.16 kg load. Specifically, the melt flow rate ratio can be 7.5 or higher, 7.6 or higher, 7.7 or higher, 7.8 or higher, 7.9 or higher, and can also be 9.5 or lower, 9.4 or lower, 9.3 or lower, 9.2 or lower, 9.1 or lower.

[0043] When the polyolefin composition meets the melt flow rate ratio within this range, the adhesive properties of the composition of the present invention for sealing films containing the polyolefin composition and the films manufactured using the composition can be improved.

[0044] The polyolefin composition may have a weight-average molecular weight (Mw) of 10,000 g / mol or more and 500,000 g / mol or less, specifically 15,000 g / mol or more, 20,000 g / mol or more, 25,000 g / mol or more, and may also be 450,000 g / mol or less, 400,000 g / mol or less, 350,000 g / mol or less, 300,000 g / mol or less, 250,000 g / mol or less, 200,000 g / mol or less.

[0045] The molecular weight distribution of the polyolefin composition (6) can be 1.5 or more and 3.0 or less. The molecular weight distribution is the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) (Mw / Mn). Specifically, the molecular weight distribution of the polyolefin composition can be 1.6 or more, 1.7 or more, 1.8 or more, 1.9 or more, 2.0 or more, and can also be 2.9 or less, 2.8 or less, 2.7 or less, 2.6 or less, 2.5 or less, 2.4 or less, 2.3 or less.

[0046] Since the weight-average molecular weight and molecular weight distribution of the polyolefin composition of the present invention meet the specified range, the adhesiveness, optical properties and mechanical properties of the composition of the present invention for sealing films containing the polyolefin composition and the films manufactured using the composition can be improved.

[0047] In the polyolefin composition of the present invention, polyethylene may be included in an amount of 1 part by weight or more and 5 parts by weight or less relative to 100 parts by weight of the olefin polymer. Specifically, polyethylene may be included in an amount of 1 part by weight or more, 1.5 parts by weight or more, 1.7 parts by weight or more, 1.9 parts by weight or more, or 2 parts by weight or more relative to 100 parts by weight of the olefin polymer, and may also be included in an amount of 5 parts by weight or less, 4.5 parts by weight or less, 4 parts by weight or less, 3.5 parts by weight or less, 3 parts by weight or less, or 2.5 parts by weight or less.

[0048] Including polyethylene within this range improves creep resistance and adhesion; however, optical properties may deteriorate when polyethylene is included in amounts exceeding 5 parts by weight.

[0049] According to ASTM D1505, polyethylene can have a strength of 0.90 g / cm³. 3 Above and 0.95g / cm 3 The following density. Specifically, the density of polyethylene can be 0.91 g / cm³. 3 Above or 0.92g / cm 3 The above, and also 0.94 g / cm³ 3 Below or 0.93g / cm 3 the following.

[0050] Additionally, according to ASTM D1238 (190°C, 2.16 kg load conditions), polyethylene can have a melt index of 0.5 g / 10 min or higher and 2.5 g / 10 min or lower. Specifically, the melt index of polyethylene can be 0.6 g / 10 min, 0.7 g / 10 min, 0.8 g / 10 min, 0.9 g / 10 min, or higher than 1 g / 10 min, and can also be lower than 2.4 g / 10 min, lower than 2.3 g / 10 min, lower than 2.2 g / 10 min, or lower than 2.1 g / 10 min.

[0051] By using polyethylene with these properties, it can be thoroughly mixed with the olefin polymers of the present invention, and the effect of improving the creep properties of the composition of the present invention for sealing films and the films made using the composition can be obtained.

[0052] By blending and using polyethylene with the aforementioned physical properties with olefin polymers, the optical and adhesive properties of olefin polymers with low and medium crystallinity can be maintained, while resistance to creep can be improved by using polyethylene with high crystallinity.

[0053] In the polyolefin composition of the present invention, one or more olefin polymers may include a first olefin polymer and a second olefin polymer. In this case, the weight ratio of the first olefin polymer and the second olefin polymer may be 1:0.1 or more and 1 or less. Specifically, the weight ratio of the first olefin polymer and the second olefin polymer may be 1:0.1 or more, 0.2 or more, 0.3 or more, 0.4 or more, and may also be 1 or less, 0.9 or less, 0.8 or less, or 0.7 or less.

[0054] When the first olefin polymer and the second olefin polymer meet this range, they can maintain transmittance while exhibiting a significant improvement in creep. When the first olefin polymer and the second olefin polymer are used in a ratio less than or greater than this range, defects in the solar module may occur due to creep, or the efficiency of the solar module may decrease due to low transmittance characteristics.

[0055] Olefin polymers can be copolymers of ethylene and α-olefin comonomers. Specifically, α-olefin comonomers can be α-olefin comonomers with 3 to 12 carbon atoms. For example, an α-olefin comonomer can be at least one selected from 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-eicosene, norbornene, norbornediene, ethylidene norbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, α-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.

[0056] When the olefin polymer is a copolymer of ethylene and α-olefin, the amount of α-olefin relative to the total weight of the copolymer can be less than 90% by weight, more specifically less than 70% by weight, even more specifically 5% to 60% by weight, or even more specifically 20% to 50% by weight.

[0057] According to one embodiment of the invention, olefin polymers can be prepared in a single reactor via continuous solution polymerization in the presence of a metallocene catalyst composition comprising one or more transition metal compounds. Therefore, the olefin polymers according to one embodiment of the invention do not form blocks in the polymer formed by linear linkages of two or more repeating units from any monomers constituting the polymer. That is, the olefin polymers according to the invention do not include block copolymers and can be selected from random copolymers, alternating copolymers, and graft copolymers; more specifically, they can be random copolymers.

[0058] Specifically, the olefin copolymers of the present invention can be obtained by a preparation method including the step of polymerizing olefin monomers in the presence of a catalyst composition for olefin polymerization, wherein the catalyst composition comprises a transition metal compound of Formula 1 (first transition metal compound) and a transition metal compound of Formula 2 (second transition metal compound) in an equivalent ratio of 1:0.1 or more and 5 or less. The equivalent ratio of the transition metal compounds of Formula 1 and Formula 2 can specifically be 1:0.1 or more, 0.2 or more, 0.3 or more, 0.4 or more, and can also be 5 or less, 4.5 or less, 4 or less, 3.5 or less, 3 or less, and 2.5 or less. By using both the transition metal compound of Formula 1 and the transition metal compound of Formula 2 within the above ranges, olefin copolymers with a crystallinity distribution that allows for excellent adhesion and optical properties while minimizing creep can be obtained.

[0059] However, in the preparation of the olefin polymer according to one embodiment of the present invention, the structural range of the first and second transition metal compounds is not limited to the specific disclosed forms, and should be understood to include all modifications, equivalents and substitutions within the concept and scope of the present invention.

[0060] [Formula 1]

[0061] In Equation 1, R1 may be the same or different from each other, and each independently is hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group, a silyl group, an alkylaryl group, an arylalkyl group, or a metalloid group of a group IV metal substituted with a hydrocarbon group, wherein two R1 may be linked together to form a ring by a pinalkyl group comprising an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; R2 may be the same or different from each other, and each is independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; aryl; alkoxy; aryloxy; amide, and two or more R2 may be linked together to form an aliphatic ring or an aromatic ring; R3 may be the same as or different from each other and are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; or an aliphatic or aromatic ring containing nitrogen, aryl-substituted or unsubstituted, and when there are multiple substituents, two or more of the substituents may be linked together to form an aliphatic or aromatic ring. M1 is a group 4 transition metal; Q1 and Q2 are each independently halogens; alkyl groups having 1 to 20 carbon atoms; alkenyl groups; aryl groups; alkylaryl groups; arylalkyl groups; alkylamide groups having 1 to 20 carbon atoms; arylamide groups; or subalkyl groups having 1 to 20 carbon atoms.

[0062] [Equation 2]

[0063] In Equation 2, R4 may be the same or different from each other, and each independently is hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group, a silyl group, an alkylaryl group, an arylalkyl group, or a metalloid group of a group IV metal substituted with a hydrocarbon group, wherein two R4 may be linked together to form a ring by a pinalkyl group comprising an alkyl group having 1 to 20 carbon atoms or an alkylidene group having 6 to 20 carbon atoms; R5 may be the same or different from each other and are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; aryl; alkoxy; aryloxy; amide, wherein R5 may be linked to each other to form an aliphatic ring or an aromatic ring; R6 may be the same or different from each other and are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; or contain nitrogen, an aliphatic ring or an aromatic ring substituted or unsubstituted with aryl, and when there are multiple substituents, two or more of the substituents may be linked together to form an aliphatic ring or an aromatic ring. M2 is a group 4 transition metal; Q3 and Q4 are each independently halogens; alkyl groups having 1 to 20 carbon atoms; alkenyl groups; aryl groups; alkylaryl groups; arylalkyl groups; alkylamide groups having 1 to 20 carbon atoms; arylamide groups; or subalkyl groups having 1 to 20 carbon atoms.

[0064] Meanwhile, in the preparation of the olefin polymer according to one embodiment of the present invention, the catalyst composition may further include a co-catalyst to activate the transition metal compound of formula 1 or formula 2.

[0065] The cocatalyst can be a borate compound in the form of, for example, a trisubstituted ammonium salt, a dialkylammonium salt, or a trisubstituted phosphonium salt. More specifically, borate compounds in the form of trialkylammonium salts, such as dimethylphenylammonium tetra(pentafluorophenyl)borate, trimethylammonium tetraphenylborate, methyl dioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, methyltetradecylcyclooctadecylammonium tetraphenylborate, N,N-dimethylphenylammonium tetraphenylborate, N,N-diethylphenylammonium tetraphenylborate, N,N-dimethyl(2,4,6-trimethylphenylammonium tetraphenylborate, trimethylammonium tetra(pentafluorophenyl)borate, methyl dioctadecylammonium tetra(pentafluorophenyl)borate, methyl dioctadecylammonium tetra(pentafluorophenyl)borate, triethylammonium tetra(pentafluorophenyl)borate, and tripropylammonium tetra(pentafluorophenyl)borate. Tri(n-butyl)ammonium tetra(pentafluorophenyl)borate, tri(sec-butyl)ammonium tetra(pentafluorophenyl)borate, N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, N,N-diethylphenylammonium tetra(pentafluorophenyl)borate, N,N-dimethyl(2,4,6-trimethylphenylammonium tetra(pentafluorophenyl)borate, trimethylammonium tetra(2,3,4,6-tetrafluorophenyl)borate, triethylammonium tetra(2,3,4,6-tetrafluorophenyl)borate, tetra(2, Tripropylammonium tetra(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammonium tetra(2,3,4,6-tetrafluorophenyl)borate, dimethyl(tert-butyl)ammonium tetra(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylphenylammonium tetra(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylphenylammonium tetra(2,3,4,6-tetrafluorophenyl)borate, or N,N-dimethyl-(2,3,4,6-tetrafluorophenyl)borate ,4,6-trimethylphenylamine); borate compounds in the form of dialkylammonium salts, such as bis(octadecyl)ammonium tetra(pentafluorophenyl)borate, bis(tetradecyl)ammonium tetra(pentafluorophenyl)borate or dicyclohexylammonium tetra(pentafluorophenyl)borate; or borate compounds in the form of trisubstituted phosphonium salts, such as triphenylphosphonium tetra(pentafluorophenyl)borate, methylbis(octadecyl)phosphonium tetra(pentafluorophenyl)borate or tri(2,6-dimethylphenyl)phosphonium tetra(pentafluorophenyl)borate.

[0066] The co-catalyst can be used in an appropriate amount to ensure sufficient activation of the transition metal compound of Formula 1 or the transition metal compound of Formula 2. For example, the co-catalyst can be used in a molar ratio of 1 to 5 relative to the total number of moles of the transition metal compound of Formula 1 and the transition metal compound of Formula 2. Specifically, the molar ratio can be 1.2 or more, 1.4 or more, 1.6 or more, 1.8 or more, 2 or more, and can also be 4.8 or less, 4.6 or less, 4.4 or less, 4.2 or less, and 4 or less.

[0067] By using a co-catalyst within this range, the molecular weight distribution of the final ethylene / α-olefin copolymer can be more uniform, and the polymerization activity can be improved.

[0068] Furthermore, in the preparation of the olefin polymer according to one embodiment of the present invention, the catalyst composition may further comprise a scavenging compound for removing moisture from the reactor during the polymerization reaction. Specific examples of scavenging compounds include triisobutylaluminum, trialkylaluminum, dialkylaluminum halide, alkyl dihalide, dialkylaluminum hydride, or alkylaluminum sesquihalides.

[0069] The scavenger compound can be continuously introduced into the reactor, and those skilled in the art can appropriately adjust and introduce the content of the scavenger compound according to the reaction conditions or the type of catalyst. For example, relative to the total flow rate of hexane solvent, ethylene, and α-olefins introduced during the polymerization reaction, the scavenger compound can be introduced in an amount of 10 ppm or more and 1000 ppm or less, more specifically, in amounts of 50 ppm or more, 100 ppm or more, 150 ppm or more, 200 ppm or more, 250 ppm or more, and 300 ppm or more, and also in amounts of 900 ppm or less, 800 ppm or less, 700 ppm or less, 600 ppm or less, 500 ppm or less, and 400 ppm or less.

[0070] [Composition for sealing films]

[0071] Furthermore, the present invention relates to a composition for a sealing film comprising the above-described polyolefin composition.

[0072] The composition for use in sealing films may further comprise at least one selected from crosslinking agents, crosslinking aids, silane coupling agents, light stabilizers, UV absorbers, and heat stabilizers.

[0073] Crosslinking agents can be used as initiators to initiate reactions in which unsaturated silane compounds are grafted onto compositions used for sealing films. Grafting of silane compounds can improve the glass adhesion properties of the final products, such as films or sealing sheets.

[0074] The crosslinking agent may be, for example, one or two or more selected from organic peroxides, hydroperoxides and azo compounds.

[0075] The crosslinking agent is included in an amount of 0.01 to 1 part by weight, for example, 0.05 to 0.55 parts by weight, 0.1 to 0.5 parts by weight, or 0.15 to 0.45 parts by weight, relative to 100 parts by weight of the composition for the sealing film. When the crosslinking agent is included in an amount less than 0.01 parts by weight, the effect of improving glass adhesion may not be significant; when the crosslinking agent is included in an amount greater than 1 part by weight, the molding properties of the final product, such as the sealing sheet, may be reduced, which may lead to process limitation problems and may affect the physical properties of the sealant.

[0076] The silane coupling agent may be at least one selected from, for example, vinyltrimethoxysilane (VTMS), 3-aminopropyltriethoxysilane (APS), N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloyloxypropyltrimethoxysilane (MEMO).

[0077] The silane coupling agent can be included in an amount of 0.1 to 4 parts by weight, more specifically 0.5 to 3 parts by weight, relative to 100 parts by weight of the composition for the sealing film. When used in an amount less than 0.1 parts by weight, adhesion to the glass is poor during the manufacture of the solar module, making it easy for moisture to penetrate, which may compromise the long-term performance of the module. When used in an amount of 4 parts by weight or more, the melt index increases and the molecular weight decreases due to the disruption of the polymer structure, which is undesirable.

[0078] In addition, as needed, the composition for the sealing film may additionally contain one or more additives selected from light stabilizers, UV absorbers and heat stabilizers.

[0079] Depending on the application of the composition, the light stabilizer can prevent photo-oxidation by capturing the photothermally induced active substances in the resin. There are no particular limitations on the type of light stabilizer that can be used; for example, known compounds such as hindered amine compounds or hindered piperidine compounds can be used.

[0080] Depending on the application of the composition, the UV absorber can prevent the photothermal activation of active substances in the resin composition by absorbing ultraviolet rays from sunlight and converting them into harmless intramolecular heat energy. There are no particular limitations on the specific type of UV absorber that can be used; for example, a mixture of one or more types of inorganic UV absorbers selected from benzophenones, benzotriazoles, acrylonitrile, metal complexes, hindered amines, ultrafine titanium dioxide, or ultrafine zinc oxide can be used.

[0081] In addition, examples of heat stabilizers that can be used include phosphorus heat stabilizers such as tris(2,4-di-tert-butylphenyl) phosphite, bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl]ethyl phosphite, tetra(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4'-dimethyl diphosphonate and bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite; lactone heat stabilizers such as the reaction product of 8-hydroxy-5,7-di-tert-butyl-furan-2-one with o-xylene; and one or more of these.

[0082] There are no particular restrictions on the content of light stabilizers, UV absorbers, and / or heat stabilizers. That is, the content of additives can be appropriately selected taking into account the purpose of the resin composition, the shape or density of the additives, etc., and the total solids content relative to 100 parts by weight of the composition for sealing film can be appropriately adjusted in the range of 0.01 parts by weight to 5 parts by weight.

[0083] In addition, depending on the purpose of applying the resin components, the composition for the sealing film may appropriately contain various additives known in the relevant art in addition to the components mentioned above.

[0084] Furthermore, the composition for sealing films can be molded into various molded products by methods such as injection molding or extrusion. Specifically, it can be used as a sealant for sealing elements in various optoelectronic devices such as solar cells, and can also be used as an industrial material applied to, for example, a heated lamination process.

[0085] [Sealing film]

[0086] In addition, the present invention relates to a sealing film formed using the above-described composition for sealing films.

[0087] The sealing film of the present invention can be manufactured by molding the aforementioned composition for sealing films into a film or sheet shape. There are no particular limitations on the molding method; for example, the sealing film can be manufactured by forming a sheet or film using common processes such as T-die processes or extrusion. For example, the manufacturing of the sealing film can be carried out as an in-situ process using an apparatus in which the preparation of a modified resin composition using the composition for sealing films is combined with the process of forming a film or sheet.

[0088] Taking into account the support efficiency and breakage probability of components in optoelectronic devices, the weight reduction of the device, or the processing performance, the thickness of the sealing film can be adjusted from about 10 μm to 2,000 μm or from about 100 μm to 1,250 μm, and can be changed according to specific applications.

[0089] [Solar Cell Module]

[0090] Furthermore, the present invention provides a solar cell module including the sealing film. In the present invention, the solar cell module can have a configuration in which the gaps between the cells of solar cells arranged in series or parallel are filled with the sealing film of the present invention, the glass surface is located on the side exposed to sunlight, and the back is protected by a backplate. Various types and shapes of solar cell modules including sealing films manufactured in related technical fields can be applied to the present invention.

[0091] Tempered glass can be used on the glass surface to protect solar cells from external impacts and prevent damage, and low-iron tempered glass with low iron content can be used to prevent sunlight reflection and increase sunlight transmittance.

[0092] A backsheet is a weather-resistant film that protects the back of a solar cell module from external influences, and includes, for example, fluorinated resin sheets, metal plates or foils such as aluminum, cyclic olefin resin sheets, polycarbonate resin sheets, poly(meth)acrylic resin sheets, polyamide resin sheets, polyester resin sheets, and composite sheets laminated with weather-resistant films and barrier films.

[0093] In addition to including the sealing film described above, the solar cell module of the present invention can also be manufactured without limitation according to methods known in the art.

[0094] The solar cell module of the present invention is manufactured using a sealing film with minimal creep, so it hardly undergoes deformation even when used for a long time and in extreme environments (e.g., it maintains durability even at temperatures of 85°C and humidity of 85%), and has excellent durability because delamination is minimized and problems such as reduced output can be greatly suppressed.

[0095] Example

[0096] The invention will be described in more detail below with reference to embodiments. However, the embodiments are intended to illustrate the invention, and the scope of the invention is not limited thereto.

[0097] [Preparation of transition metal compound catalysts]

[0098] Preparation Example 1: Preparation of Transition Metal Compound 1

[0099] (1) Preparation of 8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline

[0100] (i) Preparation of lithium carbamate

[0101] 1,2,3,4-Tetrahydroquinoline (13.08 g, 98.24 mmol) and diethyl ether (150 mL) were placed in a Schlenk flask. The Schlenk flask was immersed in a -78°C cryogenic bath obtained using dry ice and acetone and stirred for 30 minutes. Then, n-butyllithium (39.3 mL, 2.5 M, 98.24 mmol) was injected using a syringe under a nitrogen atmosphere, forming a pale yellow slurry. After stirring the flask for 2 hours, the temperature of the flask was raised to room temperature while removing the generated butane gas. The flask was immersed in the -78°C cryogenic bath again to lower the temperature, and then CO2 gas was added. Upon the addition of carbon dioxide gas, the slurry disappeared, forming a clear solution. The flask was connected to a bubbler to remove the carbon dioxide gas and the temperature was raised to room temperature. Subsequently, excess CO2 gas and solvent were removed under vacuum. After transferring the flask to a drying oven, pentane was added, and the mixture was stirred vigorously and filtered to obtain a white solid compound, lithium carbamate. A white solid compound coordinates with diethyl ether. In this case, the yield is 100%.

[0102] 1 ¹H NMR (C6D6, C5D5N): δ 1.90 (t, J = 7.2 Hz, 6H, ether), 1.50 (br s, 2H, quinoline-CH₂), 2.34 (br s, 2H, quinoline-CH₂), 3.25 (q, J = 7.2 Hz, 4H, ether), 3.87 (br, s, 2H, quinoline-CH₂), 6.76 (br d, J = 5.6 Hz, 1H, quinoline-CH) ppm

[0103] 13 C NMR(C6D6): δ 24.24, 28.54, 45.37, 65.95, 121.17, 125.34, 125.57,142.04, 163.09(C=O) ppm

[0104] (ii) Preparation of 8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline

[0105] The lithium carbamate compound prepared in step (i) (8.47 g, 42.60 mmol) was placed in a Schlenk flask. Then, tetrahydrofuran (4.6 g, 63.9 mmol) and 45 mL of diethyl ether were added sequentially. The Schlenk flask was immersed in a -20°C cryogenic bath obtained using acetone and a small amount of dry ice and stirred for 30 minutes, followed by the addition of t-BuLi (25.1 mL, 1.7 M, 42.60 mmol). Under these conditions, the reaction mixture turned red. The mixture was stirred for 6 hours while maintaining the temperature at -20°C. A solution of CeCl3·2LiCl (129 mL, 0.33 M, 42.60 mmol) dissolved in tetrahydrofuran and tetramethylcyclopentanone (5.89 g, 42.60 mmol) were mixed in a syringe and injected into the flask under a nitrogen atmosphere. The temperature of the flask was slowly raised to room temperature, and after 1 hour, the cryogenic bath was removed and the temperature was maintained at room temperature. Next, water (15 mL) was added to the flask, followed by ethyl acetate, and the mixture was filtered to obtain a filtrate. The filtrate was transferred to a separatory funnel, and hydrochloric acid (2 N, 80 mL) was added, followed by shaking for 12 minutes. Then, saturated sodium bicarbonate aqueous solution (160 mL) was added to neutralize the solution, and the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer to remove water, the product was filtered, the filtrate was collected, and the solvent was removed. The filtrate thus obtained was purified by column chromatography using hexane and ethyl acetate (v / v, 10:1) as solvents to obtain a yellow oil. The yield was 40%.

[0106] 1 ¹H NMR (C6D6): δ 1.00 (br d, 3H, Cp-CH3), 1.63 - 1.73 (m, 2H, quinoline-CH2), 1.80 (s, 3H, Cp-CH3), 1.81 (s, 3H, Cp-CH3), 1.85 (s, 3H, Cp-CH3), 2.64 (t, J = 6.0 Hz, 2H, quinoline-CH2), 2.84 - 2.90 (br, 2H, quinoline-CH2), 3.06 (br s, 1H, Cp-H), 3.76 (br s, 1H, NH), 6.77 (t, J = 7.2 Hz, 1H, quinoline-CH), 6.92 (d, J = 2.4 Hz, 1H, Quinoline-CH), 6.94 (d, J = 2.4 Hz, 1H, quinoline-CH) ppm

[0107] (2) [(1,2,3,4-tetrahydroquinoline-8-yl)tetramethylcyclopentadienyl-η] 5 Preparation of [κ-N]dimethyltitanium

[0108] (i) [(1,2,3,4-tetrahydroquinoline-8-yl)tetramethylcyclopentadienyl-η] 5 Preparation of [κ-N] dilithium compounds

[0109] In a drying oven, 8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline (8.07 g, 32.0 mmol) prepared in step (1) and 140 mL of diethyl ether were placed in a round-bottom flask, and the temperature was lowered to -30 °C. Then, n-butyllithium (17.7 g, 2.5 M, 64.0 mmol) was slowly added with stirring. The reaction was carried out for 6 hours while the temperature was raised to room temperature. Afterward, the solid was obtained by filtration after washing several times with diethyl ether. The remaining solvent was removed by applying vacuum to obtain a yellow solid dilithium compound (9.83 g). The yield was 95%.

[0110] 1 ¹H NMR (C6D6, C5D5N): δ 2.38 (br s, 2H, quinoline-CH₂), 2.53 (br s, 12H, Cp-CH₃), 3.48 (br s, 2H, quinoline-CH₂), 4.19 (br s, 2H, quinoline-CH₂), 6.77 (t, J = 6.8Hz, 2H, quinoline-CH), 7.28 (br s, 1H, quinoline-CH), 7.75 (br s, 1H, quinoline-CH) ppm

[0111] (ii) (1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl-η 5 Preparation of [κ-N]dimethyltitanium

[0112] In a drying oven, TiCl4·DME (4.41 g, 15.76 mmol) and diethyl ether (150 mL) were placed in a round-bottom flask, and MeLi (21.7 mL, 31.52 mmol, 1.4 M) was slowly added while stirring at -30 °C. After stirring for 15 minutes, the [(1,2,3,4-tetrahydroquinoline-8-yl)tetramethylcyclopentadienyl-η-O ... 5 A [κ-N] dilithium compound (5.30 g, 15.76 mmol) was added to a flask. The temperature was raised to room temperature and stirred for 3 hours. After the reaction was complete, the solvent was removed by applying vacuum, and the result was dissolved in pentane and filtered to obtain the filtrate. The pentane was removed by vacuum to give a dark brown compound (3.70 g). The yield was 71.3%.

[0113] 1 ¹H NMR (C6D6): δ 0.59 (s, 6H, Ti-CH3), 1.66 (s, 6H, Cp-CH3), 1.69 (br t, J = 6.4 Hz, 2H, quinoline-CH2), 2.05 (s, 6H, Cp-CH3), 2.47 (t, J = 6.0 Hz, 2H, quinoline-CH2), 4.53 (m, 2H, quinoline-CH2), 6.84 (t, J = 7.2 Hz, 1H, quinoline-CH), 6.93 (d, J = 7.6 Hz, quinoline-CH), 7.01 (d, J = 6.8 Hz, quinoline-CH) ppm

[0114] 13 C NMR(C6D6): δ 12.12, 23.08, 27.30, 48.84, 51.01, 119.70, 119.96,120.95, 126.99, 128.73, 131.67, 136.21 ppm

[0115] Preparation Example 2: Preparation of Transition Metal Compound 2

[0116] (1) Preparation of 2-methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)dihydroindole

[0117] Except that 2-methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)dihydroindole was used instead of 1,2,3,4-tetrahydroquinoline in Preparation Example 1 (1), the same method as Preparation Example 1 (1) was used. The yield was 19%.

[0118] 1 ¹H NMR (C6D6): δ 6.97 (d, J=7.2Hz, 1H, CH), δ 6.78 (d, J=8Hz, 1H, CH), δ 6.67 (t, J=7.4Hz, 1H, CH), δ 3.94 (m, 1H, quinoline-CH), δ 3.51 (br s, 1H, NH), δ 3.24–3.08 (m, 2H, quinoline-CH₂, Cp-CH), δ 2.65 (m, 1H, quinoline-CH) 2), δ 1.89(s, 3H, Cp-CH3), δ 1.84(s, 3H, Cp-CH3), δ 1.82(s, 3H, Cp-CH3), δ 1.13(d, J=6Hz, 3H, quinoline-CH3), δ 0.93(3H, Cp-CH3) ppm.

[0119] (2) [(2-methylindoline-7-yl)tetramethylcyclopentadienyl-η] 5 Preparation of [κ-N]dimethyltitanium

[0120] (i) Except that 2-methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-dihydroindole (2.25 g, 8.88 mmol) was used instead of 8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline, a dilithium salt compound coordinated with 0.58 equivalents of diethyl ether (4 g of the compound) (1.37 g, 50%) was obtained by the same method as in (2)(i) of Preparation Example 1.

[0121] 1 H NMR (pyridine-d8): δ 7.22(br s, 1H, CH), δ 7.18(d, J=6Hz, 1H, CH), δ6.32(t, 1H, CH), δ 4.61(brs, 1H, CH), δ 3.54(m, 1H, CH), δ 3.00(m, 1H, CH), δ2.35-2.12(m,13H, CH, Cp-CH3), δ 1.39(d,indoline-CH3) ppm.

[0122] (ii) The titanium compound was prepared using the dilithium salt compound (4 g of the compound) (1.37 g, 4.44 mmol) prepared in (i) above by the same method as in (2) (ii) of Preparation Example 1.

[0123] 1 H NMR(C6D6): δ 7.01-6.96(m, 2H, CH), δ 6.82(t, J=7.4 Hz, 1H, CH), δ

[0124] 4.96(m, 1H, CH), δ 2.88(m, 1H, CH), δ 2.40(m, 1H, CH), δ 2.02(s, 3H,Cp-CH3), δ 2.01(s, 3H, Cp-CH3), δ 1.70(s, 3H, Cp-CH3), δ 1.69(s, 3H, Cp-CH3), δ 1.65(d, J=6.4Hz, 3H, indoline-CH3), δ 0.71(d, J=10Hz, 6H, TiMe2-CH3) ppm.

[0125] [Preparation of ethylene / α-olefin copolymers]

[0126] Preparation Example 3

[0127] Hexane solvent and butene were charged into a 1.5L continuous process reactor at a weight ratio of 13:1 (kg / h), and the temperature at the top of the reactor was preheated to 160°C. Triisobutylaluminum compound (350 ppm relative to the total flow rate of hexane solvent + butene + ethylene), a mixture of transition metal compounds obtained by mixing transition metal compound 1 obtained in Preparation Example 1 and transition metal compound 2 obtained in Preparation Example 2 at a molar ratio of 4:6, and dimethylphenylammonium tetra(pentafluorophenyl)borate cocatalyst were simultaneously added to the reactor at a molar ratio of 1:3 (μmol / min) for catalyst and cocatalyst. Ethylene (0.87 kg / h) was then injected into the reactor, and a copolymerization reaction was carried out by maintaining the temperature at 160°C for at least 30 minutes continuously at a pressure of 89 bar to obtain a copolymer. The copolymer was dried in a vacuum furnace for at least 12 hours, and then its physical properties were measured.

[0128] Preparation Examples 4 and 5

[0129] The copolymerization reaction was carried out using two transition metal catalysts in the same manner as in Preparation Example 3, and the ratio of the two transition metals in the catalyst was changed to carry out the copolymerization reaction as shown in Table 1 below, thereby obtaining a copolymer.

[0130] [Table 1]

[0131] [Preparation of Polyolefin Compositions]

[0132] Example 1

[0133] Polyethylene (produced by LG Chem, product name BF315) was added to the ethylene / α-olefin copolymer prepared in Preparation Example 3 above at an amount of 2 parts by weight relative to 100 parts by weight of the ethylene / α-olefin copolymer, blended, and then extruded using a twin-screw extruder (70-210°C, 200 rpm). Finally, the sample was granulated using a granulator to prepare a polyolefin composition.

[0134] Example 2

[0135] Except that the ethylene / α-olefin copolymer of Preparation Example 4 was used as the ethylene / α-olefin copolymer, the polyolefin composition was prepared in the same manner as in Example 1.

[0136] Example 3

[0137] Except that the ethylene / α-olefin copolymer of Preparation Example 5 was used as the ethylene / α-olefin copolymer, the polyolefin composition was prepared in the same manner as in Example 1.

[0138] Example 4

[0139] The polyolefin composition was prepared in the same manner as in Example 1, except that 60% by weight and 40% by weight of LC565 and LC385 (LG Chem's product names) were used as ethylene / α-olefin copolymers, respectively.

[0140] Example 5

[0141] The polyolefin composition was prepared in the same manner as in Example 1, except that 70% by weight and 30% by weight of LC565 and LC385 (LG Chem's product names) were used as ethylene / α-olefin copolymers, and 2.5 parts by weight of polyethylene were added relative to 100 parts by weight of ethylene / α-olefin copolymer.

[0142] Comparative Example 1

[0143] The ethylene / α-olefin copolymer prepared as described above in Preparation Example 3 was used.

[0144] Comparative Example 2

[0145] 40% by weight and 60% by weight of LC565 and LC385 (LG Chem's product names) were blended separately as ethylene / α-olefin copolymers, then extruded using a twin-screw extruder (70-210°C, 200 rpm), and finally granulated using a granulator to prepare polyolefin compositions.

[0146] Comparative Example 3

[0147] Except that 60% by weight and 40% by weight of LG Chem's product LC565 and ethylene-butene copolymer (MI: 3.6 dg / min, density: 0.885 g / cc, Tg: -44 °C, Tm: 71 °C) were used as ethylene / α-olefin copolymers, respectively, the polyolefin composition was prepared in the same manner as in Comparative Example 2.

[0148] Comparative Example 4

[0149] The polyolefin composition was prepared in the same manner as in Example 1, except that 60% by weight and 40% by weight of LG Chem's product LC565 and ethylene-butene copolymer (MI: 3.6 dg / min, density: 0.885 g / cc, Tg: -44 °C, Tm: 71 °C) were used as ethylene / α-olefin copolymers, respectively.

[0150] Comparative Example 5

[0151] The polyolefin composition was prepared in the same manner as in Example 1, except that 60% by weight and 40% by weight of LG Chem's LC565 and ethylene-butene copolymer (MI: 3.6 dg / min, density: 0.885 g / cc, Tg: -44 °C, Tm: 71 °C) were used as ethylene / α-olefin copolymers, and LG Chem's BF415 was used as polyethylene.

[0152] The composition ratios used in the manufacture of the embodiments and comparative examples are shown in Table 2 below.

[0153] [Table 2]

[0154] Experimental Example 1

[0155] The physical properties of the polyolefin compositions of Examples 1 to 5 and Comparative Examples 1 to 5 were evaluated according to the following methods and are shown in Tables 3 and 4 below.

[0156] 1) Polymer density

[0157] Measured according to ASTM D-792.

[0158] 2) Melt Flow Index (MI)

[0159] Measurements were taken using ASTM D-1238 (Condition E, 190°C, 2.16 kg load).

[0160] 3) Melt Flow Ratio (MFR)

[0161] The melt flow index is calculated as the ratio of the melt flow index measured according to ASTM D-1238 (Condition E, 190°C, 10 kg load) to the melt flow index measured according to ASTM D-1238 (Condition E, 190°C, 2.16 kg load) (MI). 10 / MI 2.16 ).

[0162] 4) Weight-average molecular weight (Mw, g / mol) and molecular weight distribution (MWD)

[0163] Number-average molecular weight (Mn) and weight-average molecular weight (Mw) were measured using gel permeation chromatography (GPC), and the molecular weight distribution was calculated by dividing the weight-average molecular weight by the number-average molecular weight.

[0164] Column: PL Olexis

[0165] Solvent: Trichlorobenzene (TCB)

[0166] Flow rate: 1.0 ml / min

[0167] Sample concentration: 1.0 mg / ml

[0168] Injection volume: 200 μl

[0169] Column temperature: 160℃

[0170] Detector: Agilent high-temperature RI detector

[0171] Standard: Polystyrene (calibrated via cubic function)

[0172] 5) T(98), T(95), T(90) and T(75)

[0173] The above values ​​were obtained using a continuous self-nucleation / annealing (SSA) measurement method using a differential scanning calorimeter (DSC: Differential Scanning Calorimeter 250) manufactured by TA Instruments.

[0174] Specifically, in the first cycle, the temperature is raised to 150°C, held at that temperature for 1 minute, and then cooled to -100°C. In the second cycle, the temperature is raised to 120°C, held at that temperature for 30 minutes, and then cooled to -100°C. In the third cycle, the temperature is raised to 110°C, held at that temperature for 30 minutes, and then cooled to -100°C. This process of raising the temperature in 10°C intervals and cooling to -100°C is repeated up to -60°C to ensure crystallization at each temperature interval.

[0175] In the final cycle, the heat capacity is determined while the temperature is raised to 150°C.

[0176] The temperature-heat capacity curves obtained in this way are integrated over each region to classify the heat capacity of each region relative to the total heat capacity. In this case, the temperature of 98% of the total melt is defined as T(98), the temperature of 95% of the melt is defined as T(95), the temperature of 90% of the melt is defined as T(90), and the temperature of 75% of the melt is defined as T(75).

[0177] [Table 3]

[0178] [Table 4]

[0179] At the same time, Figure 1 The graph shows the measurement results of Example 1 and Comparative Example 1 using differential scanning calorimetry (DSC) for continuous self-nucleation and annealing (SSA). (Refer to...) Figure 1 As shown in Table 2 above, unlike the comparative example, the embodiment has T(90)-T(75) greater than 22°C, T(95)-T(90) less than 18°C ​​and T(98)-T(95) less than 10°C, so that high crystal, medium crystal and low crystal are evenly distributed, and it can be confirmed that each crystal is distributed together in some areas and acts as a connecting bridge between the individual crystals.

[0180] Experimental Example 2

[0181] The creep properties of the polyolefin compositions of Examples 1 to 5 and Comparative Examples 1 to 5 were evaluated according to the methods described below, and are shown in Table 5 below.

[0182] For each polyolefin composition of Examples 1 to 5 and Comparative Examples 1 to 5, a composition for sealing film was prepared as follows.

[0183] Add 500g of the polyolefin composition to a planetary mixer preheated to 40°C, and, relative to 100 parts by weight of the composition for sealing film, use an extruder to add 1.72 parts by weight of a silane coupling agent (vinyltrimethoxysilane (VTMS):γ-aminopropyltriethoxysilane = 9:1 weight ratio) and 0.09 parts by weight of an organic peroxide (2,5-dimethyl-2,5-di(tert-butylperoxy)hexane; C) as an initiator. 16 H 34 A mixture of O4 (ACros Co.) liquids is extruded to obtain a composition for use in sealing films. The extruder is a twin-screw extruder and is used at 70-210°C and 200 rpm.

[0184] The composition for sealing film prepared above is blended with a polyolefin composition at a weight ratio of 1:2, and then injected into an extruder with a T-shaped die discharge section to manufacture a film.

[0185] Cut the membrane manufactured as described above into 9cm pieces. The membrane was 9 cm thick and two membranes were stacked together to prepare the membrane.

[0186] Prepare two 10cm 12cm glass plates (low-iron tempered glass), each with a 2cm edge, so that they overlap by 10cm. 10cm, and place the above-prepared overlapping film between them, and then laminate at 110°C for 15 minutes.

[0187] Creep characteristics were confirmed by fixing only one side vertically in an oven and measuring the glass slippage (cm) at 105°C for 2 weeks.

[0188] [Table 5]

[0189] As shown in Table 5 above, the polyolefin compositions of Examples 1 to 5 showed almost no creep.

[0190] Meanwhile, in Comparative Example 1, unmixed polyethylene and T(98)-T(95) values ​​greater than 10°C resulted in a wide distribution of high crystallinity within the high crystallinity region without specific peaks. Therefore, creep occurred compared to Example 1. In Comparative Example 2, the region where high and medium crystallinity were distributed together was relatively narrow, and the high crystallinity was widely distributed without specific peaks, resulting in poor bonding between crystals and confirming that creep occurred more frequently.

[0191] In Comparative Example 3, an ethylene-butene copolymer with a narrow crystal distribution was used instead of a polyethylene with high crystallinity. As a result, the high crystallinity was widely distributed without specific peaks, and thus creep occurred more frequently than in the examples.

[0192] In Comparative Examples 4 and 5, an ethylene-butene copolymer with a narrow crystal distribution was used, and a high-crystal polyethylene was also mixed and used. However, since there was no point connecting the high-crystal and medium-crystal distributions, creep was confirmed to occur significantly and frequently.

Claims

1. A polyolefin composition comprising one or more olefin polymers and polyethylene, and satisfying the following conditions (1) to (3): (1) Density is above 0.855 g / cc and below 0.895 g / cc. (2) The melt flow index (MI, 190℃, 2.16kg load) is above 0.3dg / min and below 40.0dg / min, and (3) When measured by differential scanning calorimetry (DSC-SSA) with continuous self-nucleation and annealing, a) T(90)-T(75)>21.5℃, b) T(95)-T(90)<18℃, c) T(98)-T(95)<10℃, in, When the temperature-heat capacity curves measured by differential scanning calorimetry (DSC-SSA) are graded, T(98), T(95), T(90) and T(75) are the temperatures at which the heat capacity reaches 98%, 95%, 90% and 75%, respectively.

2. The polyolefin composition according to claim 1, wherein, The polyolefin composition satisfies the following condition (4): (4) Melt Flow Rate Ratio (MFRR, MI) 10 / MI 2.16 The value is between 7.5 and 9.

5.

3. The polyolefin composition according to claim 1, wherein, The polyolefin composition satisfies the following condition (5): (6) The weight-average molecular weight is above 10,000 g / mol and below 500,000 g / mol.

4. The polyolefin composition according to claim 1, wherein, The polyolefin composition satisfies the following condition (6): (6) The molecular weight distribution is above 1.5 and below 3.

0.

5. The polyolefin composition according to claim 1, wherein, T(95) is above 100℃ and below 110℃.

6. The polyolefin composition according to claim 1, wherein, T(90) is above 85.9℃.

7. The polyolefin composition according to claim 1, wherein, The polyethylene is present in an amount of 1 part by weight or more and 5 parts by weight or less, relative to 100 parts by weight of the olefin polymer.

8. The polyolefin composition according to claim 1, wherein, The one or more olefin polymers include a first olefin polymer and a second olefin polymer, and The weight ratio of the first olefin polymer to the second olefin polymer is greater than 1:0.1 and less than 1.

9. The polyolefin composition according to claim 1, wherein, The olefin polymer is a copolymer of ethylene and α-olefin comonomer.

10. The polyolefin composition according to claim 9, wherein, The α-olefin comonomer is an α-olefin comonomer with 3 to 12 carbon atoms.

11. The polyolefin composition according to claim 10, wherein, The α-olefin comonomer includes at least one selected from 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-eicosene, norbornene, norbornediene, ethylidene norbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, α-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.

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