Polyolefin composition

Abstract

The present invention relates to a polyolefin composition comprising at least one type of olefin-based polymer and polyethylene. The crystal distribution in high-crystalline and medium-crystalline parts is maintained in the range of 22°C or greater to minimize creep such that when used in the manufacture of a encapsulant film composition or an encapsulant film, deformation of the film can be minimized even when used for an extended period of time.

Description

polyolefin composition

[0001] Cross-citation with related applications

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2023-0189949, filed December 22, 2023, the entire contents of which are incorporated herein by reference.

[0003] Technology field

[0004] The present invention relates to a polyolefin composition.

[0005]

[0006] Recently, interest in renewable and clean energy sources has been growing due to global environmental concerns and the depletion of fossil fuels. Among these, optoelectronic devices, such as photovoltaic cells, light-emitting diodes (LEDs), and organic light-emitting diodes (OLEDs), are attracting attention as pollution-free energy sources. In particular, photovoltaic cells, such as solar cells, are rapidly expanding into residential and industrial applications.

[0007] A photovoltaic cell is a device that converts light into electrical energy. Since it must be exposed to the external environment for a long period of time so that it can easily absorb light, it is manufactured in the form of a unit with various packaging methods to protect the internal device. Such a unit is commonly called a photovoltaic module.

[0008] A typical solar cell module consists of two encapsulant sheets sandwiched between a surface-side glass substrate and a back-side protective film, which is a back-side protective member, surrounding the solar cell. Such a solar cell module is manufactured by sequentially laminating a glass substrate, encapsulant sheet, solar cell, encapsulant sheet, and back-side protective film, and then applying pressure and degassing from the top and bottom until the encapsulant sheet is completely melted by heating and pressurization, ensuring sufficient polymer mobility.

[0009] Perovskite materials, which are receiving much attention as light-absorbing materials for solar cells, have poor thermal stability and are greatly affected by external environments such as temperature and humidity. They experience phase transitions at high temperatures and their photoelectric conversion efficiency deteriorates rapidly when humidity is high.

[0010] Accordingly, there is a need to develop a polyolefin composition for manufacturing an encapsulating film that can be attached by low-temperature lamination for compounds vulnerable to high temperatures, such as perovskites, while maintaining creep characteristics and adhesive strength.

[0011]

[0012] The purpose of the present invention is to provide a polyolefin composition having excellent creep properties by having a wide crystallinity distribution and maintaining the crystal distribution width of high-crystallinity and medium-crystallinity portions at 22°C or more.

[0013]

[0014] 1. The present invention provides a polyolefin composition comprising one or more olefin polymers and polyethylene, and satisfying the requirements of (1) to (3) below.

[0015] (1) The density is 0.855 g / cc or more and 0.895 g / cc or less,

[0016] (2) Melt Index (MI, 190 ℃, 2.16 kg load conditions) is 0.3 dg / min or more and 40.0 dg / min or less,

[0017] (3) When measured using Differential Scanning Calorimetry Successive Self-nucleation and Annealing (DSC-SSA),

[0018] a) T(90)-T(75)>21.5℃,

[0019] b) T(95)-T(90)<18℃,

[0020] c) T(98)-T(95)<10℃,

[0021] The above T(98), T(95), T(90) and T(75) are the temperatures at which the heat capacity reaches 98%, 95%, 90% and 75%, respectively, when the temperature-heat capacity curve measured by differential scanning calorimetry-SSA (DSC-SSA) is fractionated.

[0022] 2. The present invention provides a polyolefin composition according to the above 1, wherein the polyolefin composition satisfies the following requirement (4).

[0023] (4) Melt flow rate ratio (MFRR, MI) 10 / MI 2.16 ) is 7.5 or more and 9.5 or less.

[0024] 3. The present invention provides a polyolefin composition according to 1 or 2 above, wherein the polyolefin composition satisfies the following requirement (5).

[0025] (5) The weight average molecular weight is 10,000 g / mol or more and 500,000 g / mol or less.

[0026] 4. The present invention provides a polyolefin composition according to any one of 1 to 3 above, wherein the polyolefin composition satisfies the following requirement (6).

[0027] (6) The molecular weight distribution is 1.5 or more and 3.0 or less.

[0028] 5. The present invention provides a polyolefin composition in which T(95) is 100°C or more and 110°C or less in any one of the above 1 to 4.

[0029] 6. The present invention provides a polyolefin composition in which T(90) is 85.9°C or higher in any one of the above 1 to 5.

[0030] 7. The present invention provides a polyolefin composition in which the polyethylene is included in an amount of 1 part by weight or more and 5 parts by weight or less based on 100 parts by weight of the olefin polymer in any one of 1 to 6 above.

[0031] 8. The present invention is a method according to any one of 1 to 7 above, wherein the at least one olefin polymer comprises a first olefin polymer and a second olefin polymer,

[0032] A polyolefin composition is provided in which the weight ratio of the first olefin polymer and the second olefin polymer is 1:0.1 or more and 1 or less.

[0033] 9. The present invention provides a polyolefin composition according to any one of 1 to 8 above, wherein the olefin polymer is a copolymer of ethylene and an alpha-olefin comonomer.

[0034] 10. The present invention provides a polyolefin composition according to the above 9, wherein the alpha-olefin comonomer is an alpha-olefin comonomer having 3 to 12 carbon atoms.

[0035] 11. The present invention provides a polyolefin composition according to the above 9 or 10, wherein the alpha-olefin comonomer comprises at least one selected from the group consisting of 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, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.

[0036]

[0037] The polyolefin composition of the present invention has a wide crystallinity distribution, and the crystal distribution width of the high-crystallinity and medium-crystallinity portions is maintained at 22°C or higher, so that a sealant film manufactured using the composition has excellent adhesive strength and light transmittance while minimizing creep phenomenon, thereby ensuring stability.

[0038]

[0039] Figure 1 is a graph showing the results of measurement using differential scanning calorimetry (SSA) for the polyolefin compositions of Example 1 and Comparative Example 1 of the present invention.

[0040]

[0041] Hereinafter, the present invention will be described in more detail to help understand the present invention.

[0042] The terms or words used in the description and claims of the present invention should not be interpreted as limited to their usual or dictionary meanings, and should be interpreted as meanings and concepts that conform to the technical idea of ​​the present invention, based on the principle that the inventor can appropriately define the concept of the term to explain his or her own invention in the best way.

[0043] As used herein, the term "polymer" refers to a polymer compound prepared by polymerizing monomers of the same or different types. The generic term "polymer" includes the terms "homopolymer," "copolymer," "terpolymer," as well as "interpolymer." The term "interpolymer" refers to a polymer prepared by polymerizing two or more different types of monomers. The generic term "interpolymer" includes the term "copolymer" (which is commonly used to refer to a polymer prepared from two different monomers) as well as the term "terpolymer" (which is commonly used to refer to a polymer prepared from three different types of monomers). This includes polymers prepared by polymerizing four or more types of monomers.

[0044]

[0045] [Polyolefin composition]

[0046] The present invention relates to a polyolefin composition comprising at least one olefin polymer and polyethylene, and satisfying the following requirements (1) to (3).

[0047] The polyolefin composition has (1) a density of 0.855 g / cc or more and 0.895 g / cc or less. The density may refer to a density measured according to ASTM D-792. Specifically, the density of the composition for the encapsulating film may be 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 be 0.895 g / cc or less, 0.890 g / cc or less, or 0.885 g / cc or less.

[0048] In the present invention, the introduction of a large amount of comonomer is possible by using a catalyst composition comprising a transition metal compound having a specific structure. As a result, a polyolefin composition according to an embodiment of the present invention can have the low density described above, and thus exhibit excellent light transmittance and low-temperature adhesive performance. More specifically, the polyolefin composition can have a density of 0.855 g / cc or more and 0.895 g / cc or less, and in this case, by controlling the density to have a density within the above range, the effect of maintaining physical properties such as adhesive strength and light transmittance and improving creep phenomenon is more remarkable.

[0049] In addition, the polyolefin composition has (2) a melt index (MI, 190°C, 2.16 kg load condition) of 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 also 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. The above melting index can be controlled by controlling the amount of comonomer used in the process of polymerizing an olefin polymer, and affects the mechanical properties, impact strength, and moldability of the olefin polymer.

[0050] In addition, when the melting index is within the above range, it can have melt flowability suitable for forming a solar cell encapsulating film.

[0051] In addition, the polyolefin composition has (3) a) T(90)-T(75)>21.5°C, b) T(95)-T(90)<18°C, and c) T(98)-T(95)<10°C when measured by differential scanning calorimetry successive self-nucleation and annealing (DSC-SSA). Specifically, the T(90)-T(75) may be 22°C or more, 22.5°C or more, or 23°C or more, the T(95)-T(90) may be 17.9°C or less, 17.8°C or less, 17.7°C or less, 17.6°C or less, or 17.5°C or less, and the T(98)-T(95) may be 9.9°C or less, 9.8°C or less, 9.7°C or less, 9.6°C or less, or 9.5°C or less. Here, T(98), T(95), T(90), and T(75) are temperatures at which the heat capacity reaches 98%, 95%, 90%, and 75%, respectively, when the temperature-heat capacity curve measured by differential scanning calorimetry (DSC-SSA) is fractionated.

[0052] The crystal distribution of the polyolefin composition of the present invention can be known through T(90)-T(75), T(95)-T(90), and T(98)-T(95). The degree of distribution of high crystallinity, medium crystallinity, and low crystallinity can be known through T(90)-T(75), T(95)-T(90), and the distribution of high crystallinity within the high crystallinity region can be known through T(98)-T(95). When T(90)-T(75), T(95)-T(90), and T(98)-T(95) satisfy the above range, it means that high crystallinity, medium crystallinity, and low crystallinity are evenly distributed in the polyolefin composition of the present invention, and each crystal does not exist separately, but is distributed together in some sections, so that they firmly hold each other and can maintain the cohesiveness and adhesiveness of the polyolefin composition. On the other hand, if T(90)-T(75), T(95)-T(90), or T(98)-T(95) is too large or too small outside the above range, high crystallinity, medium crystallinity, and low crystallinity may exist separately, resulting in a separation of crystal distribution and failure to adhere, or the intervals between them may be too narrow to act as a single crystal, causing the crystals to melt or break at once, resulting in more creep.

[0053] The above polyolefin composition is manufactured, for example, by using two types of catalysts having different activities, copolymerizabilities, and characteristics at a specific temperature in one reactor, and additionally adding polyethylene responsible for high crystallinity, so that it can have a crystallinity distribution that utilizes the properties of each while having a wide range of sections in which high crystallinity, medium crystallinity, and low crystallinity are distributed together. In this way, the polyolefin composition of the present invention does not have a distribution in which low crystallinity, medium crystallinity, and high crystallinity each exist separately, but the crystals are distributed so that even in small amounts, they are distributed together like a bridge and have sections that are connected to each other, so that they firmly hold each other, so that not only is cohesion and adhesion excellent, but creep can also be minimized.

[0054] The T(95) of the above polyolefin composition may be 100°C or more and 110°C or less. Specifically, it may be 101°C or more, 102°C or more, 103°C or more, and also 109°C or less, 108°C or less, 107°C or less, 106°C or less, 105°C or less, 104°C or less. When T(95) satisfies the above range, a section distributed together with the mesocrystalline material is created and can be connected with the mesocrystalline material, thereby minimizing the creep phenomenon.

[0055] In addition, the T(90) of the polyolefin composition may be 85.9°C or higher. Specifically, it may be 86°C or higher, 86.1°C or higher, 86.2°C or higher, and also 100°C or lower, 95°C or lower, or 90°C or lower. When the T(90) satisfies the above range, a section distributed together with the mesocrystalline material is created, and thus the mesocrystalline material can be connected, thereby minimizing the creep phenomenon.

[0056] In addition, the polyolefin composition of the present invention can satisfy the following requirements (4) to (6).

[0057] The above polyolefin composition has (4) melt flow rate ratio (MFRR, Melt flow rate ratio, MI) 10 / MI 2.16 ) may be 7.5 or more and 9.5 or less. The melt flow index may be obtained by dividing the melt index measured under the conditions of 190°C and 10 kg load by the melt index measured under the conditions of 190°C and 2.16 kg load. Specifically, the melt flow index may be 7.5 or more, 7.6 or more, 7.7 or more, 7.8 or more, 7.9 or more, and may also be 9.5 or less, 9.4 or less, 9.3 or less, 9.2 or less, 9.1 or less.

[0058] Since the polyolefin composition satisfies the melt flow index of the above range, the adhesive properties of the composition for a sealing film of the present invention including the polyolefin composition and the film manufactured using the polyolefin composition can be improved.

[0059] The above polyolefin composition may have (5) 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 further, 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, and 200,000 g / mol or less.

[0060] The above polyolefin composition may have a molecular weight distribution of (6) 1.5 or more and 3.0 or less. The molecular weight distribution is the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn). The molecular weight distribution of the above polyolefin composition may specifically be 1.6 or more, 1.7 or more, 1.8 or more, 1.9 or more, and 2.0 or more, and may 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, and 2.3 or less.

[0061] Since the weight average molecular weight and molecular weight distribution of the polyolefin composition of the present invention satisfy the above ranges, the adhesive and optical properties and mechanical properties of the composition for a sealing film of the present invention including the same and the film manufactured using the same can be improved.

[0062]

[0063] In the polyolefin composition of the present invention, the polyethylene may be included in an amount of 1 part by weight or more and 5 parts by weight or less based on 100 parts by weight of the olefin polymer. Specifically, the 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 based on 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.

[0064] By including the polyethylene in the above range, creep resistance and adhesiveness are improved, and if it is included in an amount exceeding 5 parts by weight, optical properties may deteriorate.

[0065] The above polyethylene has a density of 0.90 g / cm as measured by ASTM D1505. 3 Above, 0.95 g / cm 3 It may be less than or equal to. Specifically, the density of the polyethylene is 0.91 g / cm 3 Above, 0.92 g / cm 3 It may be more than 0.94 g / cm 3 Below, 0.93 g / cm 3 It could be as follows:

[0066] In addition, the polyethylene may have a melting index of 0.5 g / 10 min or more and 2.5 g / 10 min or less, as measured by ASTM D1238 (190°C, 2.16 kg load conditions). Specifically, the melting index of the polyethylene may be 0.6 g / 10 min, 0.7 g / 10 min, 0.8 g / 10 min, 0.9 g / 10 min, 1 g / 10 min or more, and may also be 2.4 g / 10 min or less, 2.3 g / 10 min or less, 2.2 g / 10 min or less, and 2.1 g / 10 min or less.

[0067] By using polyethylene having such properties, it can be well mixed with the olefin polymer of the present invention, and the effect of improving the creep properties of the composition for the sealing film of the present invention and the film manufactured using the same can be obtained.

[0068] By mixing polyethylene having the above properties with an olefin polymer, the optical properties and adhesive properties of the olefin polymer having low and medium crystallinity can be maintained, while using high crystallinity polyethylene together to improve creep resistance.

[0069] In the polyolefin composition of the present invention, the at least one olefin polymer 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.

[0070] When the first olefin polymer and the second olefin polymer satisfy the above range, a significant improvement in creep phenomenon can be exhibited while maintaining light transmittance, and when the first olefin polymer and the second olefin polymer are used in a ratio smaller or larger than the above range, a defect in the solar module may occur due to the occurrence of a creep phenomenon, or a decrease in the efficiency of the solar module may occur due to low light transmittance characteristics.

[0071] The above olefin polymer may be a copolymer of ethylene and an alpha-olefin comonomer. Specifically, the alpha-olefin comonomer may be an alpha-olefin comonomer having 3 to 12 carbon atoms. For example, the alpha-olefin comonomer may be at least one selected from the group consisting of 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, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.

[0072] When the above olefin polymer is a copolymer of ethylene and alpha-olefin, the amount of the alpha-olefin may be 90 wt% or less, more specifically 70 wt% or less, even more specifically 5 wt% to 60 wt%, and even more specifically 20 wt% to 50 wt%, based on the total weight of the copolymer.

[0073] An olefin polymer according to one embodiment of the present invention can be produced through a continuous solution polymerization reaction in the presence of a metallocene catalyst composition comprising one or more transition metal compounds in a single reactor. Accordingly, the olefin polymer according to one embodiment of the present invention does not form a block in which two or more repeating units derived from any one of the monomers constituting the polymer are linearly connected. That is, the olefin polymer according to the present invention does not include a block copolymer, and may be selected from the group consisting of a random copolymer, an alternating copolymer, and a graft copolymer, and more specifically, may be a random copolymer.

[0074] Specifically, the olefin copolymer of the present invention can be obtained by a production method including a step of polymerizing an olefin monomer in the presence of an olefin polymerization catalyst composition comprising a transition metal compound of the following chemical formula 1 (first transition metal compound) and a transition metal compound of the following chemical 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 the above chemical formulas 1 and 2 may specifically be 1:0.1 or more, 0.2 or more, 0.3 or more, or 0.4 or more, and may also be 1:5 or less, 4.5 or less, 4 or less, 3.5 or less, 3 or less, or 2.5 or less. By using the transition metal compound of the chemical formula 1 and the transition metal compound of the chemical formula 2 together in the above ranges, an olefin copolymer having excellent adhesive and optical properties while having a crystallinity distribution that minimizes creep phenomenon can be obtained.

[0075] However, in the production of an olefin polymer according to one embodiment of the present invention, the structural range of the first transition metal compound and the second transition metal compound is not limited to a specific disclosure form, and it should be understood that it includes all modifications, equivalents, and substitutes included in the spirit and technical scope of the present invention.

[0076] [Chemical Formula 1]

[0077]

[0078] In the above chemical formula 1,

[0079] R1 is the same or different from each other, and is independently a metalloid radical of a Group 4 metal substituted with hydrogen, an alkyl having 1 to 20 carbon atoms, an alkenyl having 2 to 20 carbon atoms, an aryl, a silyl, an alkylaryl, an arylalkyl, or a hydrocarbyl, and the two R1 can be connected to each other by an alkylidyne radical including an alkyl having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms to form a ring;

[0080] R2 are the same or different, and each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; aryl; alkoxy; aryloxy; amido radical, and two or more of the R2 can be connected to each other to form an aliphatic ring or an aromatic ring;

[0081] R3 is an aliphatic or aromatic ring containing nitrogen, which is the same or different from each other and is independently substituted or unsubstituted with hydrogen; halogen; alkyl having 1 to 20 carbon atoms; or aryl radical, and when there are multiple substituents, two or more of the substituents may be connected to each other to form an aliphatic or aromatic ring;

[0082] M1 is a group 4 transition metal;

[0083] Q1 and Q2 are each independently halogen; alkyl having 1 to 20 carbon atoms; alkenyl; aryl; alkylaryl; arylalkyl; alkyl amido having 1 to 20 carbon atoms; aryl amido; or alkylidene radical having 1 to 20 carbon atoms;

[0084] [Chemical Formula 2]

[0085]

[0086] In the above chemical formula 2,

[0087] R4 is the same or different from each other, and each independently represents a metalloid group of a Group 4 metal substituted with hydrogen, an alkyl having 1 to 20 carbon atoms, an alkenyl having 2 to 20 carbon atoms, an aryl, a silyl, an alkylaryl, an arylalkyl, or a hydrocarbyl, and the two R4 can be connected to each other by an alkylidyne containing an alkyl having 1 to 20 carbon atoms or an aryl having 6 to 20 carbon atoms to form a ring;

[0088] R5 are the same or different, and each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; aryl; alkoxy; aryloxy; amido, wherein R5 can be connected to each other to form an aliphatic ring or an aromatic ring;

[0089] R6 is the same or different, and each independently represents an aliphatic or aromatic ring containing nitrogen, which is substituted or unsubstituted with hydrogen; halogen; alkyl having 1 to 20 carbon atoms; or aryl, and when there are multiple substituents, two or more of the substituents may be connected to each other to form an aliphatic or aromatic ring;

[0090] M2 is a group 4 transition metal;

[0091] Q3 and Q4 are each independently halogen; alkyl having 1 to 20 carbon atoms; alkenyl; aryl; alkylaryl; arylalkyl; alkyl amido having 1 to 20 carbon atoms; aryl amido; or alkylidene having 1 to 20 carbon atoms.

[0092] Meanwhile, in the production of an olefin polymer according to one embodiment of the present invention, the catalyst composition may further include a cocatalyst to activate the transition metal compound of the chemical formula 1 or 2.

[0093] The above-mentioned cocatalyst may be a borate compound in the form of, for example, a trisubstituted ammonium salt, a dialkyl ammonium salt, or a trisubstituted phosphonium salt, and more specifically, dimethylanilinium tetrakis(pentafluorophenyl)borate, trimethylammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, methyltetradecyclooctadecylammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N-dimethyl(2,4,6-trimethylanilinium)tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl)borate, methylditetradecylammonium tetrakis(pentaphenyl)borate, Methyldioctadecylammonium tetrakis(pentafluorophenyl)borate, triethylammonium, tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethyl(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)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-dimethylanilium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylanilium tetrakis(2,3,4,6-tetrafluorophenyl)borate or N,N-dimethyl-(2,4,6-trimethylanilium)tetrakis-(2,3,4,6-tetrafluorophenyl)borateExamples thereof include borate compounds in the form of trisubstituted ammonium salts such as 6-tetrafluorophenyl)borate; borate compounds in the form of dialkylammonium salts such as dioctadecylammonium tetrakis(pentafluorophenyl)borate, ditetradecylammonium tetrakis(pentafluorophenyl)borate, or dicyclohexylammonium tetrakis(pentafluorophenyl)borate; or borate compounds in the form of trisubstituted phosphonium salts such as triphenylphosphonium tetrakis(pentafluorophenyl)borate, methyldioctadecylphosphonium tetrakis(pentafluorophenyl)borate, or tri(2,6-, dimethylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate.

[0094] The above cocatalyst may be used in an appropriate amount so that the activation of the transition metal compound of the above chemical formula 1 or the transition metal compound of the above chemical formula 2 can sufficiently proceed. For example, the cocatalyst may be used in a molar ratio of 1 to 5 based on the total number of moles of the transition metal compound of the above chemical formula 1 and the transition metal compound of the above chemical formula 2, and specifically, the molar ratio may be 1.2 to 1.4, 1.6 to 1.8, or 2, or more, and further, the molar ratio may be 4.8 to 4.6, 4.4 to 4.2, or 4 to 4.

[0095] By using the cocatalyst within the above range, the molecular weight distribution of the final manufactured ethylene / alpha-olefin copolymer can be made more uniform, and polymerization activity can be improved.

[0096] In addition, in the production of an olefin polymer according to one embodiment of the present invention, the catalyst composition may further include a scavenger compound for removing moisture within the reactor during the polymerization reaction. Specific examples of such scavenger compounds include triisobutylaluminum, trialkylaluminum, dialkyl aluminum halides, alkyl aluminum dihalides, aluminum dialkyl hydrides, or alkyl aluminum sesquihalides.

[0097] The content of the above scavenger compound can be continuously introduced into the reactor, and can be appropriately adjusted and introduced by a person skilled in the art depending on the reaction conditions or the type of catalyst. For example, the scavenger compound can be introduced in an amount of 10 ppm or more and 1000 ppm or less relative to the total flow rate of hexane solvent, ethylene, and alpha-olefin introduced during the polymerization reaction, and more specifically, it can be introduced in an amount of 50 ppm or more, 100 ppm or more, 150 ppm or more, 200 ppm or more, 250 ppm or more, or 300 ppm or more, and also can be introduced in an amount of 900 ppm or less, 800 ppm or less, 700 ppm or less, 600 ppm or less, 500 ppm or less, or 400 ppm or less.

[0098]

[0099] [Composition for packaging film]

[0100] In addition, the present invention relates to a composition for a sealing film comprising the above-described polyolefin composition.

[0101] The composition for the above-mentioned encapsulating film may further include, in addition to the polyolefin composition described above, at least one selected from the group consisting of a crosslinking agent, a crosslinking assistant, a silane coupling agent, a light stabilizer, a UV absorber, and a heat stabilizer.

[0102] The crosslinking agent may act as an initiator to initiate a reaction in which an unsaturated silane compound is grafted onto the composition for the encapsulant film. Grafting of the silane compound may improve the glass adhesion properties of the final product, such as a film or encapsulant sheet.

[0103] The above crosslinking agent may be, for example, one or two or more selected from the group consisting of organic peroxides, hydroperoxides, and azo compounds.

[0104] The crosslinking agent is included in an amount of 0.01 to 1 part by weight, for example, 0.05 to 0.55, 0.1 to 0.5, or 0.15 to 0.45 parts by weight, based on 100 parts by weight of the composition for the encapsulating film. When the crosslinking agent is included in an amount of less than 0.01 part by weight, the effect of improving glass adhesion properties is minimal, and when it is included in an amount of more than 1 part by weight, the formability of the final product, such as the encapsulating sheet, may be reduced, which may cause problems such as limitations in the process and may affect the physical properties of the encapsulating material.

[0105] As the above silane coupling agent, for example, at least one selected from the group consisting of vinyltrimethoxysilane (VTMS), 3-aminopropyltriethoxysilane (APS), N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane (MEMO) can be used.

[0106] The above silane coupling agent may be included in an amount of 0.1 to 4 parts by weight, more specifically 0.5 to 3 parts by weight, based on 100 parts by weight of the composition for the encapsulant film. If used in an amount less than 0.1 parts by weight, adhesion to glass during solar module production becomes poor, leading to easy moisture infiltration, and thus making it difficult to guarantee the long-term performance of the module. If used in an amount greater than 4 parts by weight, the melting index increases and the molecular weight decreases due to destruction of the polymer structure, which is not preferable.

[0107] In addition, the composition for the above-mentioned encapsulating film may additionally include one or more additives selected from a light stabilizer, a UV absorber, a heat stabilizer, etc., as needed.

[0108] The above-mentioned photostabilizer can prevent photooxidation by capturing the active species that initiates photodegradation of the resin, depending on the intended use of the composition. The type of photostabilizer that can be used is not particularly limited, and for example, known compounds such as hindered amine compounds or hindered piperidine compounds can be used.

[0109] The above UV absorber can, depending on the use of the composition, absorb ultraviolet rays from sunlight or the like, convert them into harmless heat energy within the molecule, and prevent the active species that initiates photodegradation in the resin composition from being excited. The specific type of UV absorber that can be used is not particularly limited, and for example, one type or a mixture of two or more types of inorganic UV absorbers such as benzophenone-based, benzotriazole-based, acrylonitrile-based, metal complex-based, hindered amine-based, ultrafine titanium oxide-based, or ultrafine zinc oxide-based can be used.

[0110] In addition, examples of the heat stabilizer include phosphorus-based heat stabilizers such as tris(2,4-di-tert-butylphenyl)phosphite, bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl]ethyl ester phosphorous acid, tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4'-diylbisphosphonate, and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite; lactone-based heat stabilizers such as the reaction product of 8-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene, and one or two or more of the above may be used.

[0111] The content of the above-mentioned light stabilizer, UV absorber, and / or heat stabilizer is not particularly limited. That is, the content of the above-mentioned additives may be appropriately selected in consideration of the intended use of the resin composition, the shape or density of the additives, etc., and may typically be appropriately adjusted within the range of 0.01 to 5 parts by weight relative to 100 parts by weight of the total solid content of the composition for the sealant film.

[0112] In addition, the composition for the above-mentioned encapsulating film may additionally include various additives known in the relevant field, in addition to the above-mentioned components, depending on the application of the resin component.

[0113] In addition, the composition for the encapsulating film can be molded into various molded products by methods such as injection molding or extrusion, and specifically, can be used as an encapsulant for encapsulating elements in various optoelectronic devices, such as solar cells, and can also be used as an industrial material applied to, for example, a temperature-increasing lamination process.

[0114]

[0115] [Bongjijae Film]

[0116] In addition, the present invention relates to a sealing film formed from the composition for the sealing film described above.

[0117] The encapsulating film of the present invention can be manufactured by molding the aforementioned encapsulating film composition into a film or sheet shape. The molding method is not particularly limited, and for example, the encapsulating film can be manufactured by forming it into a sheet or film using a conventional process such as a T-die process or extrusion. For example, the manufacturing of the encapsulating film can be performed in situ using a device in which the manufacturing of a modified resin composition using the encapsulating film composition and the film or sheet manufacturing process are interconnected.

[0118] The thickness of the above-mentioned encapsulating film can be adjusted to about 10 to 2,000 μm, or about 100 to 1,250 μm, taking into consideration the support efficiency and breakage possibility of the element in the optoelectronic device, weight reduction and workability of the device, etc., and can be changed depending on the specific use.

[0119]

[0120] [Solar cell module]

[0121] In addition, the present invention provides a solar cell module comprising the encapsulant film. In the present invention, the solar cell module may have a configuration in which solar cell cells arranged in series or parallel are spaced apart by the encapsulant film of the present invention, a glass surface is arranged on the side that receives sunlight, and the back surface is protected by a back sheet. Various types and shapes of solar cell modules manufactured in the art including the encapsulant film can all be applied to the present invention.

[0122] The above glass surface may be made of tempered glass to protect the solar cell from external impact and prevent breakage, and may be made of low iron tempered glass to prevent reflection of sunlight and increase the transmittance of sunlight.

[0123] The above backsheet is a weather-resistant film that protects the back surface of the solar cell module from the outside, and includes, for example, a fluorine resin sheet, a metal plate or metal foil such as aluminum, a cyclic olefin resin sheet, a polycarbonate resin sheet, a poly(meth)acrylic resin sheet, a polyamide resin sheet, a polyester resin sheet, and a composite sheet in which a weather-resistant film and a barrier film are laminated.

[0124] In addition, the solar cell module of the present invention can be manufactured without limitation according to a method known in the art, except that it includes the aforementioned encapsulant film.

[0125] The solar cell module of the present invention is manufactured using a sealing film with minimized creep phenomenon, and thus hardly undergoes deformation even when used for a long period of time or in an extreme environment (e.g., maintains durability even under conditions of a temperature of 85°C and a humidity of 85%), and has excellent durability by minimizing delamination phenomenon, and can significantly suppress problems such as output reduction.

[0126]

[0127] Example

[0128] Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to illustrate the present invention and are not intended to limit the scope of the present invention solely to these examples.

[0129]

[0130] [Preparation of Transition Metal Compound Catalysts]

[0131] Manufacturing Example 1: Preparation of Transition Metal Compound 1

[0132]

[0133] (1) Preparation of 8-(2,3,4,5-Tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline

[0134] (i) Preparation of lithium carbamate

[0135] 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 cryostat made with dry ice and acetone and stirred for 30 minutes. Next, n-BuLi (39.3 mL, 2.5 M, 98.24 mmol) was added using a syringe under a nitrogen atmosphere, and a pale yellow slurry was formed. The flask was then stirred for 2 hours, and the temperature of the flask was raised to room temperature while removing the butane gas produced. The flask was again immersed in the -78°C cryostat to lower the temperature, and then CO2 gas was introduced. As the carbon dioxide gas was added, the slurry disappeared and a transparent solution was formed. The flask was connected to a bubbler to remove the carbon dioxide gas and the temperature was raised to room temperature. Afterwards, excess CO2 gas and solvent were removed under vacuum. The flask was transferred to a dry box, pentane was added, stirred vigorously, and filtered to obtain lithium carbamate as a white solid compound. This white solid compound is coordinated with diethyl ether. The yield is 100%.

[0136] 1 H NMR(C6D6, C5D5N): δ 1.90 (t, J = 7.2 Hz, 6H, ether), 1.50 (br s, 2H, quin-CH2), 2.34 (br s, 2H, quin-CH2), 3.25 (q, J = 7.2 Hz, 4H, ether), 3.87 (br, s, 2H, quin-CH2), 6.76 (br d, J = 5.6 Hz, 1H, quin-CH) ppm

[0137] 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

[0138] (ii) Preparation of 8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline

[0139]

[0140] The lithium carbamate compound (8.47 g, 42.60 mmol) prepared in the above step (i) was placed in a Schlenk flask. Subsequently, tetrahydrofuran (4.6 g, 63.9 mmol) and 45 mL of diethyl ether were sequentially added. The Schlenk flask was immersed in a -20°C low-temperature bath made with acetone and a small amount of dry ice and stirred for 30 minutes, after which t-BuLi (25.1 mL, 1.7 M, 42.60 mmol) was added. At this time, the color of 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 tetramethylcyclopentinone (5.89 g, 42.60 mmol) were mixed in a syringe and then poured into a flask under a nitrogen atmosphere. The temperature of the flask was slowly raised to room temperature, and after 1 hour, the thermostat was removed and the temperature was maintained at room temperature. Next, water (15 mL) was added to the flask, followed by ethyl acetate and filtering to obtain a filtrate. The filtrate was transferred to a separatory funnel, hydrochloric acid (2 N, 80 mL) was added, and the mixture was shaken for 12 minutes. Then, a saturated aqueous sodium bicarbonate solution (160 mL) was added to neutralize the mixture, and the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer to remove moisture, and the organic layer was filtered. The filtrate was taken and the solvent was removed. The obtained filtrate was purified by column chromatography using hexane and ethyl acetate (v / v, 10:1) as a solvent to obtain a yellow oil. The yield was 40%.

[0141] 1H NMR(C6D6): δ 1.00 (br d, 3H, Cp-CH3), 1.63 - 1.73 (m, 2H, quin-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, quin-CH2), 2.84 - 2.90 (br, 2H, quin-CH2), 3.06 (br s, 1H, Cp-H), 3.76 (br s, 1H, NH), 6.77 (t, J = 7.2 Hz, 1H, quin-CH), 6.92 (d, J = 2.4 Hz, 1H, quin-CH), 6.94 (d, J = 2.4 Hz, 1H, quin-CH) ppm

[0142]

[0143] (2) [(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl-η 5 Preparation of [(1,2,3,4-Tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl-eta5,kapa-N]titanium dimethyl

[0144]

[0145] (i) [(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl-η 5 Preparation of ,κ-N]dilithium compounds

[0146] In a round bottom flask, 8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline (8.07 g, 32.0 mmol) prepared through the above step (1) and 140 mL of diethyl ether were placed, the temperature was lowered to -30°C, and n-BuLi (17.7 g, 2.5 M, 64.0 mmol) was slowly added with stirring. The mixture was allowed to react for 6 hours while the temperature was raised to room temperature. Afterwards, a solid was obtained by filtration while washing several times with diethyl ether. The remaining solvent was removed under vacuum to obtain a dilithium compound (9.83 g) as a yellow solid. The yield was 95%.

[0147] 1 H NMR(C6D6, C5D5N): δ 2.38 (br s, 2H, quin-CH2), 2.53 (br s, 12H, Cp-CH3), 3.48 (br s, 2H, quin-CH2), 4.19 (br s, 2H, quin-CH2), 6.77 (t, J = 6.8 Hz, 2H, quin-CH), 7.28 (br s, 1H, quin-CH), 7.75 (brs, 1H, quin-CH) ppm

[0148]

[0149] (ii) (1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl-η 5 Preparation of ,κ-N]titanium dimethyl

[0150] In a dry box, TiCl4·DME (4.41 g, 15.76 mmol) and diethyl ether (150 mL) were placed in a round 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, [(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl-ηη] prepared in the above step (i) was added. 5,κ-N]dilithium compound (5.30 g, 15.76 mmol) was placed in a flask. The mixture was stirred for 3 hours while warming to room temperature. After the reaction was completed, the solvent was removed by applying a vacuum, dissolved in pentane, and filtered to collect the filtrate. When the pentane was removed by applying a vacuum, a dark brown compound (3.70 g) was obtained. The yield was 71.3%.

[0151] 1 H NMR(C6D6): δ 0.59 (s, 6H, Ti-CH3), 1.66 (s, 6H, Cp-CH3), 1.69 (br t, J = 6.4 Hz, 2H, quin-CH2), 2.05 (s, 6H, Cp-CH3), 2.47 (t, J = 6.0 Hz, 2H, quin-CH2), 4.53 (m, 2H, quin-CH2), 6.84 (t, J = 7.2 Hz, 1H, quin-CH), 6.93 (d, J =7.6 Hz, quin-CH), 7.01 (d, J =6.8 Hz, quin-CH) ppm

[0152] 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

[0153]

[0154] Manufacturing Example 2: Preparation of Transition Metal Compound 2

[0155]

[0156] (1) Preparation of 2-methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)indoline

[0157] 2-Methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)indoline was prepared in the same manner as in (1) of Manufacturing Example 1, except that 2-methyl indoline was used instead of 1,2,3,4-tetrahydroquinoline in (1) of Manufacturing Example 1. The yield was 19%.

[0158] 1 H 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.

[0159]

[0160] (2) Preparation of [(2-Methylindolin-7-yl)tetramethylcyclopentadienyl-eta5,kapa-N]titanium dimethyl

[0161] (i) A dilithium salt compound (compound 4 g) coordinated with 0.58 equivalents of diethyl ether was obtained (1.37 g, 50%) through the same method as (2)(i) of Preparation Example 1, except that 2-methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-indoline (2.25 g, 8.88 mmol) was used instead of 8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline.

[0162] 1 H NMR (Pyridine-d8): δ 7.22 (br s, 1H, CH), δ 7.18 (d, J=6Hz, 1H, CH), δ 6.32 (t, 1H, CH), δ 4.61 (brs, 1H, CH), δ 3.54 (m, 1H, CH), δ 3.00 (m, 1H, CH), δ 2.35-2.12(m,13H, CH, Cp-CH3), δ 1.39(d, indoline-CH3) ppm.

[0163]

[0164] (ii) A titanium compound was prepared using the dilithium salt compound (4 g of compound) (1.37 g, 4.44 mmol) prepared in (i) above, using the same method as (2)(ii) of Manufacturing Example 1.

[0165] 1 H NMR (C6D6): δ 7.01-6.96 (m, 2H, CH), δ 6.82 (t, J=7.4Hz, 1H, CH), δ

[0166] 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.

[0167]

[0168] [Production of ethylene / alpha-olefin copolymers]

[0169] Manufacturing Example 3

[0170] A 1.5 L continuous process reactor was charged with hexane solvent and butene at a weight ratio per unit time of 13:1 in an amount (kg / h), and the temperature at the top of the reactor was preheated to 160°C. A triisobutyl aluminum compound (350 ppm relative to the total flow rate of hexane solvent + butene + ethylene), a mixture of transition metal compounds prepared by mixing the transition metal compound 1 obtained in Preparation Example 1 as a catalyst and the transition metal compound 2 obtained in Preparation Example 2 in a molar ratio of 4:6, and a dimethylanilinium tetrakis(pentafluorophenyl) borate cocatalyst were simultaneously charged into the reactor at a molar ratio per unit time of 1:3 in an amount (μmol / min) of the catalyst and cocatalyst. Next, ethylene (0.87 kg / h) was injected into the reactor, and a copolymerization reaction was performed by maintaining the temperature at 160°C for more than 30 minutes in a continuous process at a pressure of 89 bar to obtain a copolymer. Afterwards, the copolymer was dried in a vacuum oven for more than 12 hours and its physical properties were measured.

[0171]

[0172] Manufacturing Examples 4 and 5

[0173] A copolymerization reaction was carried out using two transition metal catalysts in the same manner as in Manufacturing Example 3, and the ratios of the two transition metals in the catalysts were changed as shown in Table 1 below to carry out the copolymerization reaction, thereby obtaining a copolymer.

[0174]

[0175] Transition metal ratio (molar ratio) in the catalyst Transition metal compound 1 Transition metal compound 2 Preparation example 346 Preparation example 455 Preparation example 564

[0176]

[0177] [Manufacture of polyolefin composition]

[0178] Example 1

[0179] Polyethylene (manufactured by LG Chemical, product name BF315) was added to the ethylene / alpha-olefin copolymer of Manufacturing Example 3 manufactured as described above in an amount of 2 parts by weight based on 100 parts by weight of the ethylene / alpha-olefin copolymer, blended, and then extruded using a twin-screw extruder (70-210°C, 200 rpm), and finally, the sample was pelletized using a pelletizer to manufacture a polyolefin composition.

[0180]

[0181] Example 2

[0182] A polyolefin composition was prepared in the same manner as in Example 1, except that the ethylene / alpha-olefin copolymer of Preparation Example 4 was used as the ethylene / alpha-olefin copolymer.

[0183]

[0184] Example 3

[0185] A polyolefin composition was prepared in the same manner as in Example 1, except that the ethylene / alpha-olefin copolymer of Preparation Example 5 was used as the ethylene / alpha-olefin copolymer.

[0186]

[0187] Example 4

[0188] A polyolefin composition was prepared in the same manner as in Example 1, except that 60 wt% and 40 wt% of LG Chemical's product names LC565 and LC385 were used as ethylene / alpha-olefin copolymers, respectively.

[0189]

[0190] Example 5

[0191] A polyolefin composition was prepared in the same manner as in Example 1, except that 70 wt% and 30 wt% of LG Chemical's product names LC565 and LC385 were used as ethylene / alpha-olefin copolymers, respectively, and 2.5 wt% of polyethylene was added based on 100 wt% of ethylene / alpha-olefin copolymer.

[0192]

[0193] Comparative Example 1

[0194] The ethylene / alpha-olefin copolymer of Manufacturing Example 3 manufactured as described above was used.

[0195]

[0196] Comparative Example 2

[0197] Ethylene / alpha-olefin copolymers, product names LC565 and LC385 of LG Chemical, were blended at 40 wt% and 60 wt%, respectively, and then extruded using a twin-screw extruder (70-210°C, 200 rpm), and finally the sample was pelletized using a pelletizer to manufacture a polyolefin composition.

[0198]

[0199] Comparative Example 3

[0200] A polyolefin composition was prepared in the same manner as in Comparative Example 2, except that 60 wt% and 40 wt% of ethylene / alpha-olefin copolymer (product name LC565 of LG Chemical) and ethylene-butene copolymer (MI: 3.6 dg / min, density: 0.885 g / cc, Tg: -44°C, Tm: 71°C) were used, respectively.

[0201]

[0202] Comparative Example 4

[0203] A polyolefin composition was prepared in the same manner as in Example 1, except that 60 wt% and 40 wt% of ethylene / alpha-olefin copolymer (product name LC565 of LG Chemical) and ethylene-butene copolymer (MI: 3.6 dg / min, density: 0.885 g / cc, Tg: -44°C, Tm: 71°C) were used, respectively.

[0204]

[0205] Comparative Example 5

[0206] A polyolefin composition was prepared in the same manner as in Example 1, except that 60 wt% and 40 wt% of LC565 (product name: LG Chemical) and ethylene-butene copolymer (MI: 3.6 dg / min, density: 0.885 g / cc, Tg: -44°C, Tm: 71°C) from LG Chemical were used as the ethylene / alpha-olefin copolymer, and BF415 (product name: LG Chemical) was used as the polyethylene.

[0207]

[0208] The manufacturing composition ratios of the above examples and comparative examples are shown in Table 2 below.

[0209]

[0210] Ethylene / alpha-olefin copolymerPolyethylene production example (weight %)LC565 (weight %)LC385 (weight %)Ethylene-butene copolymer (weight %)BF315 (phr)BF415 (phr)Example 1 Production example 3 (100)---2-Example 2 Production example 4 (100)---2-Example 3 Production example 5 (100)---2-Example 4-6040-2-Example 5-7030-2.5-Comparative example 1 Production example 3 (100)-----Comparative example 2-4060---Comparative example 3-60-40--Comparative example 4-60-402-Comparative example 5-60-40-2

[0211]

[0212] Experimental Example 1

[0213] The 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.

[0214] 1) Density of polymer

[0215] Measured using ASTM D-792.

[0216] 2) Melt Index (MI)

[0217] Measured according to ASTM D-1238 (condition E, 190℃, 2.16 Kg load).

[0218] 3) Melt flow ratio (MFR)

[0219] The ratio of the melt index measured by ASTM D-1238 (Condition E, 190℃, 10 Kg load) to the melt index measured by ASTM D-1238 (Condition E, 190℃, 2.16 Kg load) (MI) 10 / MI 2.16 ) was calculated.

[0220] 4) Weight average molecular weight (Mw, g / mol) and molecular weight distribution (MWD)

[0221] The 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.

[0222] - Column: PL Olexis

[0223] - Solvent: TCB (Trichlorobenzene)

[0224] - Flow rate: 1.0 ml / min

[0225] - Sample concentration: 1.0 mg / ml

[0226] - Injection volume: 200 ㎕

[0227] - Column temperature: 160℃

[0228] - Detector: Agilent High Temperature RI detector

[0229] - Standard: Polystyrene (corrected with a cubic function)

[0230] 5) T(98), T(95), T(90) and T(75)

[0231] It was obtained using the successive self-nucleation / annealing (SSA) measurement method using a differential scanning calorimeter (DSC: Differential Scanning Calorimeter 250) manufactured by TA instrument.

[0232] Specifically, in the first cycle, the temperature was increased to 150°C, held at that temperature for 1 minute, and then cooled to -100°C. In the second cycle, the temperature was increased to 120°C, held at that temperature for 30 minutes, and then cooled to -100°C. In the third cycle, the temperature was increased to 110°C, held at that temperature for 30 minutes, and then cooled to -100°C. This process of increasing the temperature at 10°C intervals and cooling to -100°C was repeated until -60°C, so that crystallization occurred at each temperature range.

[0233] The heat capacity was determined by increasing the temperature to 150°C in the last cycle.

[0234] The temperature-heat capacity curve thus obtained was integrated for each section to fractionate the heat capacity of each section relative to the total heat capacity. Here, the temperature at which 98% of the total melts was defined as T(98), the temperature at which 95% melts was defined as T(95), the temperature at which 90% melts was defined as T(90), and the temperature at which 75% melts was defined as T(75).

[0235]

[0236] Density (g / cc) MI (dg / min) MFR (dg / min) Mw (g / mol) MWDexample 10.880 3.68.18 144 72.16example 20.880 3.78.08 123 52.15example 30.879 2.59.18 50 142.23example 40.874 3.77.98 415 42.18example 50.873 3.68.78 307 62.2Comparative example 10.877 4.47.679 608 2.12Comparative example 20.879 3.37.68 474 12.14Comparative example 30.874 3.77.88 3160 2.12Comparative example 40.8763.38.3856232.17Comparative example 50.8763.48.3839932.16

[0237]

[0238] T(75)(℃)T(90)(℃)T(95)(℃)T(98)(℃)T(90)-T(75)T(95)-T(90)T(98)-T(95)Example 162.886.0103.4112.423.217.48.9Example 263.286.2103.4112.823.017.29.4Example 363.387.9103.8113.224.615.89.5Example 460.688.0103.3111.927.515.38.6Example 559.187.2103.3111.028.216.17.7Comparative Example 161.483.8100.5113.322.416.712.7Comparative example 264.285.5100.7112.421.315.211.7Comparative example 360.979.693.9110.418.614.316.5Comparative example 463.584.8102.9111.121.218.18.2Comparative example 563.785.8103.8111.622.118.07.8

[0239]

[0240] Meanwhile, the results of measurement using the differential scanning calorimetry (SSA) of Example 1 and Comparative Example 1 are shown in Fig. 1. Referring to Fig. 1, as can also be confirmed in Table 2 above, in the Example, unlike the Comparative Example, T(90)-T(75) is greater than 22°C, T(95)-T(90) is less than 18°C, and T(98)-T(95) is less than 10°C, so that high crystallinity, medium crystallinity, and low crystallinity are evenly distributed, and it can be confirmed that each crystal is distributed together in some sections and acts as a connecting bridge between each crystal.

[0241]

[0242] Experimental Example 2

[0243] The creep properties of the polyolefin compositions of Examples 1 to 5 and Comparative Examples 1 to 5 were evaluated according to the following method, and are shown in Table 5 below.

[0244]

[0245] For each of the polyolefin compositions of Examples 1 to 5 and Comparative Examples 1 to 5, a composition for a sealing film was prepared as follows.

[0246] 500 g of the above polyolefin composition was added to a planetary mixer preheated to 40°C, and 1.72 parts by weight of a silane coupling agent (vinyltrimethoxysilane (VTMS): γ-aminopropyltriethoxysilane = 9:1 weight ratio) based on 100 parts by weight of the composition for a sealing film, and an organic peroxide (2,5-dimethyl-2,5-di(tert-butylperoxy)hexane; C) as an initiator 16 H 34 O4; 0.09 parts by weight of a mixed liquid (ACros) was extruded using an extruder to obtain a composition for a sealing film. The extruder was a twin-screw extruder, and was used at 70 to 210°C and 200 rpm.

[0247] The composition for a sealing film manufactured as described above and the polyolefin composition were blended at a weight ratio of 1:2, and then fed into an extruder having a T-die-shaped discharge portion to manufacture a film.

[0248] The film manufactured as above was cut into 9 cm x 9 cm pieces and prepared by overlapping two sheets.

[0249] Two 10 cm x 12 cm glass plates (low-iron tempered glass) were prepared with a 10 cm x 10 cm overlap with a 2 cm margin between them, and the overlapping film prepared above was placed between them, and lamination was performed at 110°C for 15 minutes.

[0250] Creep properties were determined by fixing only one side vertically in an oven and measuring the extent to which the glass slipped (cm) for two weeks at 105°C.

[0251]

[0252] Creep (cm) Example 10.2 Example 20.4 Example 30.4 Example 40.4 Example 50.5 Comparative Example 10.7 Comparative Example 21.0 Comparative Example 310 Comparative Example 410 Comparative Example 510

[0253]

[0254] As shown in Table 5 above, it was confirmed that the polyolefin compositions of Examples 1 to 5 exhibited almost no creep phenomenon.

[0255] Meanwhile, Comparative Example 1 did not mix polyethylene, and the T(98)-T(95) value was greater than 10℃, so that high crystals were widely spread within the high crystal area without a specific peak, and thus a creep phenomenon occurred compared to Example 1. In Comparative Example 2, the section where high crystals and medium crystals were distributed together was relatively narrow, and relatively, high crystals were widely spread without a specific peak, so it was confirmed that the connection between crystals was not good, and thus a creep phenomenon occurred more frequently.

[0256] In the case of Comparative Example 3, an ethylene-butene copolymer with a narrow crystallinity distribution was used, and high-crystallinity polyethylene was not used. As the high-crystallinity was widely spread without a specific peak, the creep phenomenon occurred more frequently than in the example.

[0257] In Comparative Examples 4 and 5, high-crystal polyethylene was additionally mixed and used along with the use of an ethylene-butene copolymer with a narrow crystal distribution, but it was confirmed that the creep phenomenon occurred significantly because there was no distribution point where the high-crystal and medium-crystal were connected.

Claims

1. A polyolefin composition comprising at least one olefin polymer and polyethylene and satisfying the requirements of (1) to (3) below: (1) The density is 0.855 g / cc or more and 0.895 g / cc or less, (2) The melting index (MI, 190 ℃, 2.16 kg load condition) is 0.3 dg / min or more and 40.0 dg / min or less, (3) When measured using Differential Scanning Calorimetry Successive Self-nucleation and Annealing (DSC-SSA), a) T(90)-T(75)>21.5 ℃, b) T(95)-T(90)<18 ℃, c) T(98)-T(95)<10℃, The above T(98), T(95), T(90), and T(75) are the temperatures at which the heat capacity reaches 98%, 95%, 90%, and 75%, respectively, when the temperature-heat capacity curve measured by differential scanning calorimetry-scanning standard analysis (DSC-SSA) is fractionated.

2. In claim 1, The above polyolefin composition is a polyolefin composition satisfying the following requirements (4): (4) Melt flow rate ratio (MFRR, MI) 10 / MI 2.16 ) is 7.5 or more and 9.5 or less.

3. In claim 1, The above polyolefin composition is a polyolefin composition satisfying the following requirements (5): (6) The weight average molecular weight is 10,000 g / mol or more and 500,000 g / mol or less.

4. In claim 1, The above polyolefin composition is a polyolefin composition satisfying the following requirements (6): (6) The molecular weight distribution is 1.5 or more and 3.0 or less.

5. In claim 1, A polyolefin composition having the above T(95) of 100 ℃ or more and 110 ℃ or less.

6. In claim 1, A polyolefin composition having a T(90) of 85.9 ℃ or higher.

7. In claim 1, A polyolefin composition in which the polyethylene is included in an amount of 1 part by weight or more and 5 parts by weight or less based on 100 parts by weight of the olefin polymer.

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

9. In claim 1, The above olefin polymer is a polyolefin composition which is a copolymer of ethylene and an alpha-olefin comonomer.

10. In claim 9, A polyolefin composition wherein the above alpha-olefin comonomer is an alpha-olefin comonomer having 3 to 12 carbon atoms.

11. In claim 10, A polyolefin composition, wherein the alpha-olefin comonomer comprises at least one selected from the group consisting of 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, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.

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