resin composition

Abstract

SOLUTION: A resin composition comprises: a propylene-based polymer (α) having a melt flow rate (MFR) at 230°C under a load of 2.16 kg of 0.1-500 g / 10 min, obtained according to ASTM D1238E; and an olefinic resin (β) containing a graft-type olefinic resin [R1] having a main chain constituted of a copolymer of ethylene and at least one kind of α-olefin selected from 3-20C α-olefins and a side chain constituted of a copolymer of ethylene and at least one kind of cyclic olefin.EFFECT: A resin composition according to the present invention has high impact resistance and high transparency.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition containing a propylene-based polymer and a molded article containing the resin composition. [Background technology]

[0002] Polypropylene resins are used in a variety of fields, including everyday items, kitchen utensils, packaging films, home appliances, machine parts, electrical components, and automotive parts. Propylene-based resin compositions containing various modifiers and additives are used to achieve the required performance. Furthermore, as part of efforts to promote the 3Rs (Reduce, Reuse, Recycle) for creating a recycling-oriented society, various industrial sectors have recently been attempting to reduce weight by producing thin-walled molded products. Progress has been made in improving propylene-based resin compositions so that molded products can maintain sufficient impact resistance even when made lighter or thinner. Furthermore, the development of highly transparent propylene-based resin compositions is desired to meet the demand for applications in decorative materials and sensor materials.

[0003] Generally, flexible olefin resins consisting of ethylene-α-olefin copolymers are blended as modifiers for polypropylene resins. To further improve performance, expectations are high for the application of olefin block polymers, in which crystalline polyethylene segments are chemically bonded to amorphous or low-crystalline ethylene-α-olefin copolymer segments, as modifiers.

[0004] Examples of technologies relating to such olefin block polymers include a technology relating to linear block polymers consisting of polyethylene segments and ethylene-α-olefin copolymer segments obtained using a living polymerization catalyst, as disclosed in Patent Document 1, and a technology relating to the production of polymers with a multi-block structure utilizing a reversible chain transfer reaction between two types of catalysts, as disclosed in Patent Document 2.

[0005] In addition to such linear block polymers, Patent Documents 3 to 8 propose methods for obtaining graft copolymers consisting of heterogeneous segments, each of which is composed of a main chain and a side chain, one of which is a soft segment and the other is a hard segment. These disclosures are generally based on a technique of synthesizing a hard segment such as polyethylene having a vinyl group at its end, and then, following or simultaneously with the synthesis, copolymerizing this hard segment such as polyethylene with ethylene or an α-olefin having 3 or more carbon atoms to introduce it into the soft segment, which is the main chain.

[0006] For example, Patent Documents 3 and 4 disclose methods for obtaining a graft olefin polymer by copolymerizing vinyl-terminated polyethylene produced using a specific metallocene catalyst with ethylene. Although this disclosed technology produces polyethylene having vinyl groups at the terminals, the efficiency of vinyl terminal production is low, resulting in a large amount of polyethylene remaining unincorporated as a side chain. When this graft polymer is blended with a polypropylene resin, the large amount of unreacted polyethylene deteriorates mechanical properties such as impact resistance. Therefore, there is room for improvement in the performance of this graft polymer as a modified resin, and even when this graft polymer is used, a polypropylene resin composition exhibiting desired physical properties has not yet been obtained.

[0007] On the other hand, Patent Documents 5 to 7 disclose techniques for synthesizing vinyl-terminated polyethylene for side chains at high yields by using specific nonmetallocene complex catalysts. The present inventors conducted follow-up experiments using the catalysts for main chain production disclosed in the examples of Patent Documents 5 and 7, and confirmed that although a certain amount of vinyl-terminated polyethylene is copolymerized into the main chain, productivity is low under high-temperature conditions for highly efficient incorporation of vinyl-terminated polyethylene. The amount of side chains introduced into the block polymer obtained in this manner is also limited, so even if this block polymer is used as a polypropylene modifying resin, its modifying performance is insufficient.

[0008] Patent Document 8 discloses a method for introducing side chains with high efficiency using a co-supported catalyst system, but the method is limited to polymers with crystalline main chains, and it is difficult to produce polymers with amorphous or low crystalline regions suitable for modifying propylene-based resins.

[0009] As described above, even if a block polymer or a graft polymer in which different polymers are chemically linked, as disclosed in the prior art, is used as a modifier for a polypropylene resin, a propylene-based resin composition having excellent impact resistance and transparency has not yet been obtained. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-84806 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-237013 [Patent Document 3] Special Publication No. 1996-502303 [Patent Document 4] Special Publication No. 2001-527589 [Patent Document 5] Japanese Patent Application Laid-Open No. 2002-105132 [Patent Document 6] Japanese Patent Application Laid-Open No. 2007-39540 [Patent Document 7] Japanese Patent Application Laid-Open No. 2007-39541 [Patent Document 8] Japanese Patent Application Laid-Open No. 2009-144148 Summary of the Invention [Problem to be solved by the invention]

[0011] An object of the present invention is to provide a propylene-based resin composition having high impact resistance and high transparency. [Means for solving the problem]

[0012] As a result of extensive investigations aimed at solving the above problems, the present inventors have found that the above problems can be solved by blending an olefin resin containing a graft-type olefin polymer having a main chain formed from a copolymer of ethylene and an α-olefin and a side chain formed from a copolymer of ethylene and a cyclic olefin with a propylene-based resin, thereby completing the present invention.

[0013] That is, the present invention relates to the following [1] to [6]. [1] a propylene polymer (α) having a melt flow rate (MFR) of 0.1 to 500 g / 10 min at 230°C under a load of 2.16 kg obtained in accordance with ASTM D1238E; an olefin resin (β) containing a graft-type olefin polymer [R1] having a main chain composed of a copolymer of ethylene and at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms and a side chain composed of a copolymer of ethylene and at least one cyclic olefin; A resin composition comprising: [2] The resin composition according to [1], wherein the copolymer constituting the main chain of the graft type olefin polymer [R1] satisfies the following requirements (i) and (ii): (i) The repeating units derived from ethylene are in the range of 10 to 90 mol %. (ii) The weight average molecular weight, calculated as a styrene equivalent value by gel permeation chromatography (GPC), is in the range of 10,000 to 500,000. [3] The resin composition according to [1] or [2], wherein the copolymer constituting the side chain of the graft type olefin polymer [R1] satisfies the following requirements (iii) and (iv): (iii) The repeating units derived from ethylene are in the range of 50 to 95 mol %. (iv) The weight average molecular weight, calculated as a styrene equivalent value by gel permeation chromatography (GPC), is in the range of 10,000 to 100,000. [4] The resin composition according to any one of [1] to [3], wherein the proportion of the cyclic olefin copolymer contained in the olefin resin (β) is in the range of 5 to 70 mass % (wherein the olefin resin (β) is taken as 100 mass %). [5] The resin composition according to any one of [1] to [4], comprising 1 to 99 parts by mass of the propylene polymer (α) and 1 to 99 parts by mass of the olefin resin (β) (the total of the propylene polymer (α) and the olefin resin (β) is 100 parts by mass). [6] A molded article comprising the resin composition according to any one of [1] to [5]. [Effects of the Invention]

[0014] The resin composition of the present invention has high impact resistance and high transparency. DETAILED DESCRIPTION OF THE INVENTION

[0015] The propylene polymer (α) and the olefin resin (β) contained in the resin composition of the present invention will be described below.

[0016] <Propylene polymer (α)> The propylene polymer (α), which is one of the components contained in the resin composition of the present invention, is a homopolymer of propylene or a copolymer of propylene with at least one selected from ethylene and α-olefins. Specific examples of the α-olefins include 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl-1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene. Among these, α-olefins such as 1-butene, 1-pentene, 1-hexene, and 1-octene can be preferably used.

[0017] The propylene polymer (α) according to the present invention has a melt flow rate (MFR) of 0.1 to 500 g / 10 min, preferably 0.2 to 400 g / 10 min, and more preferably 0.3 to 300 g / 10 min, at 230°C under a load of 2.16 kg, as determined in accordance with ASTM D1238. If the MFR of the propylene polymer is lower than the above range, the dispersibility of the propylene polymer and the olefin resin (β) in the resin composition may deteriorate, resulting in a decrease in mechanical strength. If the MFR of the propylene polymer is higher than the above range, the strength of the propylene polymer itself may decrease, resulting in a decrease in the mechanical strength of the resulting resin composition.

[0018] <Olefin resin (β)> The olefin resin (β), which is one of the components contained in the resin composition of the present invention, contains a graft-type olefin polymer [R1] described below as an essential constituent. The graft olefin polymer [R1] according to the present invention is a graft copolymer having a main chain made of a copolymer of ethylene and at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms (hereinafter sometimes referred to as an "ethylene-α-olefin copolymer") and side chains made of a copolymer of ethylene and at least one cyclic olefin (hereinafter sometimes referred to as a "cyclic olefin copolymer").

[0019] In the present invention, the term "graft (co)polymer" or "graft type polymer" means a polymer having one or more side chains bonded to the main chain.

[0020] The graft type olefin polymer [R1] according to the present invention has a structure in which side chains made of a cyclic olefin copolymer are chemically bonded to a main chain made of an amorphous or low-crystalline ethylene-α-olefin copolymer. Therefore, the olefin resin (β) containing the graft type olefin polymer [R1] has higher compatibility with cyclic olefin resins than ordinary ethylene-α-olefin copolymers.

[0021] The presence of the graft-type olefin polymer [R1] in the olefin resin (β) of the present invention can be confirmed by combining the content ratio of ethylene-α-olefin copolymer / cyclic olefin copolymer in the resulting olefin resin (β) with peak separation by GPC. For example, the reaction rate of the cyclic olefin copolymer can be determined by peak separation from a molecular weight distribution curve measured using GPC, and the formation of the graft-type olefin polymer [R1] can be confirmed from this. Various other analytical methods can also be used to confirm this, and the means are not particularly limited.

[0022] Of the following requirements (I) to (III), the olefin resin (β) preferably satisfies requirement (II), and more preferably satisfies at least one of requirements (I) and (III).

[0023] (I) The intrinsic viscosity [η] measured in decalin at 135°C is in the range of 0.1 to 10.0 dl / g. (II) The olefin resin (β) contains a cyclic olefin copolymer in a proportion of 5 to 70% by mass. (III) The amount of hot xylene insolubles is less than 3% by mass.

[0024] These requirements (I) to (III) will be explained in detail below. [Requirement (I)] The olefin resin (β) according to the present invention preferably has an intrinsic viscosity [η] in the range of 0.1 to 10.0 dL / g, more preferably 0.7 to 4.0 dL / g, and even more preferably 0.8 to 3.0 dL / g, as measured in decalin at 135° C. When the intrinsic viscosity [η] is in the above range, a resin composition containing the olefin resin (β) has good impact resistance, as well as good rigidity and mechanical strength, and also good moldability.

[0025] [Requirement (II)] The proportion of the cyclic olefin copolymer contained in the olefin resin (β) is preferably in the range of 5 to 70 mass%, more preferably 8 to 60 mass%, even more preferably 10 to 55 mass%, and particularly preferably 20 to 55 mass%.

[0026] Here, the cyclic olefin copolymer contained in the olefin resin (β) according to the present invention means both the cyclic olefin copolymer constituting the side chain of the graft type olefin polymer [R1] and the cyclic olefin copolymer not constituting the side chain of the graft type olefin polymer [R1]. For example, when the cyclic olefin copolymer is copolymerized with ethylene and an α-olefin in the polymerization step (B) in the production method of the olefin resin (β) described below, it indicates both the cyclic olefin copolymer incorporated as a side chain of the graft type olefin polymer [R1] and the cyclic olefin copolymer not incorporated into the main chain.

[0027] When the proportion of the cyclic olefin copolymer contained in the olefin resin (β) according to the present invention is within the above range, the compatibility between the cyclic olefin copolymer and the ethylene-α-olefin copolymer contained in the olefin resin (β) is improved, and the resin composition containing the propylene polymer (α) and the olefin resin (β) exhibits better impact resistance.

[0028] If the proportion of the cyclic olefin copolymer is less than 5% by mass, the difference in density between the olefin resin (β) and the propylene polymer (α) is large, and the resulting resin composition may not have excellent transparency.If the proportion of the cyclic olefin copolymer is more than 70% by mass, the relative content of the ethylene-α-olefin copolymer in the olefin resin (β) is low, and the resulting resin composition may not exhibit good physical properties in terms of impact resistance.

[0029] The proportion of the cyclic olefin copolymer contained in the olefin resin (β) can be determined, for example, from the ratio of the mass of the cyclic olefin copolymer used in the polymerization step (B) described below to the mass of the obtained olefin resin (β).

[0030] [Requirement (III)] The olefin resin (β) according to the present invention preferably has a hot xylene insoluble content of less than 3.0% by mass, more preferably less than 2.5% by mass, and even more preferably less than 2.0% by mass.

[0031] The hot xylene insoluble amount is a value calculated by the following method. The sample is heat-pressed (180°C, heating for 5 minutes, cooling for 1 minute) to form a 0.4 mm thick sheet, which is then cut into small pieces. Approximately 100 mg of this is weighed out, wrapped in a 325-mesh screen, and immersed in 30 ml of p-xylene at 140°C for 3 hours in a sealed container. The screen is then removed and dried at 80°C for at least 2 hours until a constant weight is reached. The hot xylene insoluble amount (mass%) is expressed by the following formula: Hot xylene insoluble amount (mass%) = 100 × [(W3 - W2) / (W1 - W2)] W1: total mass of the screen and sample before the test, W2: screen mass, W3: total mass of the screen and sample after the test

[0032] When the olefin resin (β) of the present invention satisfies requirement (III), the olefin resin (β) contains no or only a small amount of hot xylene insoluble matter, as described above, and therefore has excellent appearance and can be more easily dispersed in the propylene polymer (α), resulting in a stronger impact resistance effect in the resulting resin composition. On the other hand, if the hot xylene insoluble matter content is 3% by mass or more, a molded article obtained from the olefin resin (β) or the resin composition may develop a poor appearance called "lumps."

[0033] As shown in the production method described later, by employing a method of obtaining a graft-type olefin polymer directly from the polymerization step, an olefin resin (β) having a hot xylene-insoluble component in the above range can be obtained.

[0034] The main chain of the graft type olefin polymer [R1] according to the present invention is composed of an ethylene-α-olefin copolymer, and is the moiety that provides the properties required of the graft type olefin polymer [R1] as a modifier, such as impact resistance. To ensure such properties, the main chain of the graft type olefin polymer [R1] is composed of repeating units derived from ethylene and repeating units derived from at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms.

[0035] Specific examples of the α-olefin having 3 to 20 carbon atoms copolymerized with ethylene in the ethylene-α-olefin copolymer include propylene, 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, and the like. Examples of the olefins include 1-octene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl-1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene.

[0036] More preferably, it is an α-olefin having 3 to 10 carbon atoms, and even more preferably, it is an α-olefin having 3 to 8 carbon atoms. Specific examples include linear olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 1-decene, and branched olefins such as 4-methyl-1-pentene, 3-methyl-1-pentene, and 3-methyl-1-butene. Among these, propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene are preferred, and 1-butene, 1-pentene, 1-hexene, and 1-octene are more preferred. By using 1-butene, 1-pentene, 1-hexene, or 1-octene as the α-olefin having 3 to 20 carbon atoms to be copolymerized with ethylene, a resin composition with good impact resistance can be obtained.

[0037] The copolymer constituting the main chain of the graft type olefin polymer [R1] according to the present invention preferably satisfies the following requirements (i) and (ii). (i) The repeating units derived from ethylene are in the range of 10 to 90 mol %. (ii) The weight average molecular weight, calculated as a styrene equivalent value by gel permeation chromatography (GPC), is in the range of 10,000 to 500,000.

[0038] These requirements (i) and (ii) will be explained in detail below. [Requirement (i)] The proportion of repeating units derived from ethylene in the copolymer constituting the main chain of the graft olefin polymer [R1] is preferably 10 to 90 mol %, more preferably 50 to 90 mol %, and even more preferably 60 to 90 mol %, based on all repeating units contained in the main chain. The proportion of repeating units derived from α-olefin is preferably 10 to 90 mol %, more preferably 10 to 50 mol %, and even more preferably 10 to 40 mol %, based on all repeating units contained in the main chain.

[0039] When the proportion of repeating units derived from ethylene and α-olefin in the main chain is within the above range, the olefin resin (β) has excellent flexibility and impact resistance, and therefore a resin composition containing the olefin resin (β) has excellent impact resistance. On the other hand, if the repeating units derived from α-olefin are less than 10 mol%, the resulting olefin resin tends to be a resin with poor flexibility, and therefore a resin composition containing the resin may have poor impact resistance.

[0040] The molar ratio of repeating units derived from ethylene and α-olefin in the main chain can be adjusted by controlling the ratio of the concentration of ethylene to the concentration of α-olefin present in the polymerization reaction system in the process of producing the main chain.

[0041] The molar ratio (mol%) of repeating units derived from α-olefins contained in the main chain, i.e., the α-olefin composition in the main chain, can be determined, for example, by determining the α-olefin composition of an ethylene-α-olefin copolymer obtained under conditions that do not contain a terminally unsaturated cyclic olefin copolymer (described below) using a conventional method, or by subtracting the effects of the cyclic olefin copolymer and side chains from the α-olefin composition of the olefin resin (β).

[0042] [Requirement (ii)] The weight-average molecular weight of the ethylene-α-olefin copolymer constituting the main chain of the graft-type olefin polymer [R1] according to the present invention is preferably in the range of 10,000 to 500,000, more preferably in the range of 100,000 to 450,000.

[0043] When the weight-average molecular weight of the ethylene-α-olefin copolymer constituting the main chain of the graft-type olefin polymer [R1] according to the present invention is within the above range, the resin composition containing the olefin resin (β) tends to have a better balance of impact resistance, rigidity, and toughness. On the other hand, when the weight-average molecular weight is less than 10,000, the impact resistance and toughness decrease, and when it is more than 500,000, poor dispersion of the ethylene-α-olefin copolymer in the cyclic olefin resin occurs, making it difficult to obtain the desired balance of physical properties.

[0044] The weight-average molecular weight of the ethylene-α-olefin copolymer constituting the main chain of the graft-type olefin polymer [R1] according to the present invention can be adjusted by controlling the ethylene concentration in the polymerization system in the production process described below. Methods for controlling the ethylene concentration include adjusting the ethylene partial pressure and the polymerization temperature. The weight-average molecular weight of the ethylene-α-olefin copolymer constituting the main chain can also be adjusted by supplying hydrogen to the polymerization system.

[0045] The weight-average molecular weight is a polystyrene-equivalent weight-average molecular weight determined by gel permeation chromatography (GPC). The weight-average molecular weight of the ethylene-α-olefin copolymer constituting the main chain can be determined, for example, by analyzing an ethylene-α-olefin copolymer produced under conditions that do not contain a terminally unsaturated cyclic olefin copolymer (described below), or by analyzing an olefin resin (β) and subtracting the effects of the cyclic olefin copolymer and side chains.

[0046] The side chain of the graft type olefin polymer [R1] according to the present invention is composed of a copolymer of ethylene and a cyclic olefin. The cyclic olefin is a hydrocarbon having a double bond in a ring structure and may have a substituent. Specific examples include monocyclic olefins such as cyclobutene, cyclopentene, and cyclooctene; and compounds having a norbornene ring structure such as norbornene and dicyclopentadiene (hereinafter simply referred to as "norbornene compounds").

[0047] Specific examples of the cyclic olefin include cyclic olefins represented by the following general formula (2).

[0048] [ka] (In formula (2), R 1 ~R 4 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group, and R 1 and R 4 may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond; 1 and R 2 and R may form an alkylidene. 3 and R 4 may form an alkylidene. m is 0 or 1.

[0049] Specific examples of such norbornene compounds include norbornenes in which m = 0, such as 2-norbornene; norbornenes having a halogen atom, such as 5-chloro-2-norbornene and 5-bromo-2-norbornene; norbornenes having an alkyl group, such as 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene and 5-decyl-2-norbornene; norbornenes having an alkenyl group, such as 5-vinyl-2-norbornene and 5-propenyl-2-norbornene; 5-cyclohexyl-2-norbornene and 5-cyclopentyl-2-norbornene; norbornenes having a cycloalkyl group such as 5-cyclopentenyl-2-norbornene and 5-cyclohexenyl-2-norbornene; norbornenes having a cycloalkenyl group such as 5-phenyl-2-norbornene, p-methyl-5-phenyl-2-norbornene, o-methyl-5-phenyl-2-norbornene and m-methyl-5-phenyl-2-norbornene; and norbornenes having a hydrocarbon group substituted with a halogen atom such as 5-chloromethyl-2-norbornene and p-chloro-5-phenyl-2-norbornene.

[0050] m=0 and R 1 and R 4 Examples of compounds in which the above are bonded to each other to form a single or multiple rings include dicyclopentadiene, methyldicyclopentadiene, dihydrodicyclopentadiene (tricyclo[5.2.1.0 2,6 ]dec-8-ene), tetracyclo[9.2.1.0 2,10 .0 3,8 ]tetradeca-3,5,7,12-tetraene (also known as 1,4-methano-1,4,4a,9a-tetrahydro-9H-fluorene), tetracyclo[10.2.1.0 2,11 .0 4,9 ]pentadeca-4,6,8,13-tetraene (also known as 1,4-methano-1,4,4a,9,9a,10-hexahydroanthracene), and the like.

[0051] Also, m=0 and R 1 and R 2 and, or R 3 and R 4 Examples of the alkylidene formed by the above include 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, 5-propylidene-2-norbornene, and 5-isopropylidene-2-norbornene.

[0052] Tetracyclododecenes with m=1 include tetracyclo[6.2.1.13,6.02,7]dodec-4-ene; tetracyclododecenes with halogen atoms such as 9-chlorotetracyclo[6.2.1.13,6.02,7]dodec-4-ene and 9-bromotetracyclo[6.2.1.13,6.02,7]dodec-4-ene; 9-methyltetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-ethyltetracyclo[6.2.1.13,6.02,7]dodec-4-ene, and 9-butyltetracyclo[6.2.1.13,6.02,7]dodec-4-ene. , 9-hexyltetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-decyltetracyclo[6.2.1.13,6.02,7]dodec-4-ene, and other tetracyclododecenes having alkyl groups; 9-vinyltetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-propenyltetracyclo[6.2.1.13,6.02,7]dodec-4-ene, and other tetracyclododecenes having alkenyl groups; 9-cyclohexyltetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-cyclopentyltetracyclo[6.2.1.1 3,6 .0 2,7 ] tetracyclododecenes having cycloalkyl groups such as dodec-4-ene; 9-cyclopentenyltetracyclo[6.2.1.1 3,6 .0 2,7 ]dodec-4-ene, 9-cyclohexenyltetracyclo[6.2.1.1 3,6 .0 2,7 ]dodec-4-ene and other tetracyclododecenes having cycloalkenyl groups; 9-phenyltetracyclo[6.2.1.1 3,6 .02,7 ]dodec-4-ene and other tetracyclododecenes with aromatic hydrocarbon groups; 9-chloromethyltetracyclo[6.2.1.1 3,6 .0 2,7 tetracyclododecenes having a hydrocarbon group substituted with a halogen atom, such as tetracyclododecene-4-ene;

[0053] Also, m=1 and R 1 and R 2 and, or R 3 and R 4 Examples of compounds that form alkylidenes with 9-methylenetetracyclo[6.2.1.1 3,6 .0 2,7 ]dodec-4-ene, 9-ethylidenetetracyclo[6.2.1.1 3,6 .0 2,7 ]dodec-4-ene and the like.

[0054] The cyclic olefins represented by the above formula (2) include 2-norbornene and tetracyclo[6.2.1.1 3,6 .0 2,7 ] dodec-4-ene is preferred.

[0055] The copolymer constituting the side chain of the graft type olefin polymer [R1] according to the present invention preferably satisfies at least one of the following requirements (iii) and (iv). (iii) The repeating units derived from ethylene are in the range of 50 to 95 mol %. (iv) The weight average molecular weight, calculated as a styrene equivalent value by gel permeation chromatography (GPC), is in the range of 10,000 to 100,000.

[0056] These requirements (iii) and (iv) will be explained in detail below. [Requirement (iii)] The proportion of repeating units derived from ethylene contained in the copolymer constituting the side chain is preferably 50 to 95 mol %, more preferably 60 to 90 mol %, based on all repeating units contained in the side chain, and the proportion of repeating units derived from cyclic olefin is preferably 5 to 50 mol %, more preferably 10 to 40 mol %, based on all repeating units contained in the side chain.

[0057] [Requirement (iv)] The weight-average molecular weight of the cyclic olefin copolymer constituting the side chain of the graft-type olefin polymer [R1] according to the present invention is preferably in the range of 10,000 to 100,000. From the viewpoint of improving compatibility with the propylene polymer (α) described below and impact resistance, it is preferably in the range of 10,000 to 70,000.

[0058] On the other hand, if the weight average molecular weight is less than 10,000, the impact resistance decreases due to the brittleness of the cyclic olefin resin, and if it is more than 100,000, poor dispersion of the olefin resin (β) in the propylene polymer (α) may occur, making it difficult to obtain impact resistance.

[0059] The weight-average molecular weight of the cyclic olefin copolymer constituting the side chain of the graft-type olefin polymer [R1] according to the present invention can be adjusted by controlling the ethylene concentration in the polymerization system in the production process described below. Methods for controlling the ethylene concentration include adjusting the ethylene partial pressure and adjusting the polymerization temperature.

[0060] The weight-average molecular weight is a weight-average molecular weight calculated in terms of polystyrene by gel permeation chromatography (GPC). The weight-average molecular weight of the cyclic olefin copolymer constituting the side chain can be determined, for example, by analyzing the polymer obtained in step A of the production method for an olefin resin described below.

[0061] <Method for producing olefin-based resin (β)> The olefin resin (β) according to the present invention is produced, for example, by a production method including the following steps (A) and (B).

[0062] Step (A): A step of polymerizing ethylene and a cyclic olefin in the presence of an olefin polymerization catalyst containing a transition metal compound [A] of Group 4 of the periodic table represented by the following general formula (1) to produce a terminally unsaturated cyclic olefin copolymer.

[0063] Step (B): A step of copolymerizing the terminally unsaturated cyclic olefin copolymer obtained in Step (A) with at least one α-olefin selected from ethylene and olefins having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing a transition metal compound [B] of Group 4 of the periodic table.

[0064] [ka] (In the general formula (1), M represents a transition metal of Group 4 of the periodic table, m represents an integer of 1 to 4, and R 1 and R 6 is a hydrocarbon group having 1 to 30 carbon atoms, and R 2 ~R 5 may be the same or different and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a cyclic unsaturated hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring. When m is 2 or more, R 2 ~R 6 two of the groups represented by the formula (I) may be linked together, n is a number that satisfies the valence of M, X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, the groups may be the same or different from each other, and multiple groups represented by X may be bonded to each other to form a ring.

[0065] Steps (A) and (B) will be explained below in order. [Process (A)] Step (A) is a step for producing a terminally unsaturated cyclic olefin copolymer which is a raw material for the side chains of the graft-type olefin polymer [R1] according to the present invention. This step is a step of polymerizing ethylene and a cyclic olefin in the presence of a transition metal compound [A] of Group 4 of the periodic table, which will be described later, to produce a terminally unsaturated cyclic olefin copolymer. Here, the terminally unsaturated cyclic olefin copolymer produced in step (A) includes a cyclic olefin copolymer having a vinyl group at one end of the polymer chain.

[0066] The terminally unsaturated cyclic olefin copolymer produced in step (A) may contain, in addition to the cyclic olefin copolymer having a vinyl group at one end, a cyclic olefin copolymer having an unsaturated carbon-carbon bond such as a vinylene group or a vinylidene group, or a cyclic olefin copolymer that is unsaturated at both ends. These are contained as they are in the resin (β) obtained through step (B). In addition, these constitute the cyclic olefin copolymer not incorporated into the main chain in resin (β) described above, together with the cyclic olefin copolymer having a vinyl group at one end that did not contribute to the production of the graft polymer in step (B).

[0067] Among the copolymers produced in step (A), the position of the unsaturated carbon-carbon bond in the copolymer having a vinylene group is thought to be near the terminal of the copolymer, and in the present invention, the copolymer produced in step (A) including the copolymer having a vinylene group is referred to as a "terminally unsaturated cyclic olefin copolymer."

[0068] The terminal vinyl ratio (the ratio of the number of vinyl groups to all unsaturated carbon-carbon bonds) of the terminally unsaturated cyclic olefin copolymer is usually 40% or more, preferably 50%, more preferably 60% or more, and even more preferably 70% or more.

[0069] The proportion of terminal vinyl groups in the terminally unsaturated cyclic olefin copolymer per 1000 carbon atoms is usually 0.1 to 20, preferably in the range of 0.4 to 20. If the terminal vinyl ratio (the proportion of vinyl groups to all unsaturated carbon-carbon bonds) and the proportion of terminal vinyl groups per 1000 carbon atoms are low, the amount of the terminally unsaturated cyclic olefin copolymer (specifically, a cyclic olefin copolymer having a vinyl group at one end) introduced into the main chain in the subsequent step (B) will be low, and the amount of graft-type olefin polymer produced will be low, so that the desired effect may not be obtained.

[0070] The terminal vinyl ratio (the ratio of the number of vinyl groups to the total number of unsaturated carbon-carbon bonds) and the ratio of terminal vinyl groups per 1,000 carbon atoms are: 1 It can be calculated by a conventional method using polymer structure analysis by H-NMR measurement.

[0071] [Transition metal compounds [A]] The transition metal compound [A] used in the present invention is a specific compound having a structure represented by the following general formula (1), which functions as an olefin polymerization catalyst and functions more favorably in the presence of the compound (C) described below.

[0072] The olefin polymerization catalyst containing the transition metal compound [A] is characterized by polymerizing mainly ethylene and at least one cyclic olefin selected from the above-mentioned cyclic olefins to produce a terminally unsaturated cyclic olefin copolymer.

[0073] The chemical structural characteristics of the transition metal compound [A] used in the present invention will be described below. The transition metal compound [A] used in the present invention is a transition metal compound represented by the following general formula (1).

[0074] [ka] In the general formula (1), N...M generally indicates coordination, but in the present invention, it may or may not be coordination.

[0075] In the general formula (1), M represents a transition metal atom of Group 4 of the periodic table, specifically titanium, zirconium, hafnium, etc., and preferably zirconium. m represents an integer of 1 to 4, preferably 1 or 2, and particularly preferably 2. R 1 represents a hydrocarbon group having 1 to 30 carbon atoms. Specific examples of the hydrocarbon group include linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, and n-hexyl groups; linear or branched alkenyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as vinyl, allyl, and isopropenyl groups; linear or branched alkynyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as ethynyl and propargyl groups; cyclopropyl, cyclobutyl, and cyclopropyl groups; Examples include cyclic saturated hydrocarbon groups having 3 to 30, preferably 3 to 20, carbon atoms, such as a cyclopentyl group, a cyclohexyl group, and an adamantyl group; cyclic unsaturated hydrocarbon groups having 5 to 30, carbon atoms, such as a cyclopentadienyl group, an indenyl group, and a fluorenyl group; aryl groups having 6 to 30, preferably 6 to 20, carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, and an anthracenyl group; and alkyl-substituted aryl groups, such as a tolyl group, an isopropylphenyl group, a t-butylphenyl group, a dimethylphenyl group, and a di-t-butylphenyl group.

[0076] The hydrocarbon group may have a hydrogen atom substituted with a halogen, and examples thereof include halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as a trifluoromethyl group, a pentafluorophenyl group, a bis(trifluoromethyl)phenyl group, and a chlorophenyl group. The hydrocarbon group may also be substituted with another hydrocarbon group, and examples thereof include aryl-substituted alkyl groups such as a benzyl group and a cumyl group.

[0077] R 2 ~R5 may be the same or different and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring. When m is 2 or more, R 2 ~R 5 Two groups among the groups represented by the formula may be linked together, and examples of the halogen atom include fluorine, chlorine, bromine and iodine.

[0078] Specific examples of the hydrocarbon group include linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, and n-hexyl groups; linear or branched alkenyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as vinyl, allyl, and isopropenyl groups; linear or branched alkynyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as ethynyl and propargyl groups; cyclopropyl, cyclobutyl, and cyclopropyl groups; Examples include cyclic saturated hydrocarbon groups having 3 to 30, preferably 3 to 20, carbon atoms, such as a cyclopentyl group, a cyclohexyl group, and an adamantyl group; cyclic unsaturated hydrocarbon groups having 5 to 30, carbon atoms, such as a cyclopentadienyl group, an indenyl group, and a fluorenyl group; aryl groups having 6 to 30, preferably 6 to 20, carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, and an anthracenyl group; and alkyl-substituted aryl groups, such as a tolyl group, an isopropylphenyl group, a t-butylphenyl group, a dimethylphenyl group, and a di-t-butylphenyl group.

[0079] The hydrocarbon group may have a hydrogen atom substituted with a halogen, and examples thereof include halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as a trifluoromethyl group, a pentafluorophenyl group, and a chlorophenyl group. The hydrocarbon group may also be substituted with another hydrocarbon group, and examples thereof include aryl-substituted alkyl groups such as a benzyl group and a cumyl group.

[0080] Furthermore, the hydrocarbon group may be a heterocyclic compound residue; an oxygen-containing group such as an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, or a carboxylic anhydride group; a nitrogen-containing group such as an amino group, an imino group, an amido group, an imido group, a hydrazino group, a hydrazono group, a nitro group, a nitroso group, a cyano group, an isocyano group, a cyanate ester group, an amidino group, a diazo group, or an amino group in the form of an ammonium salt; a boranediyl group, a boranetriyl group, a diboranyl group, etc. a boron-containing group; a sulfur-containing group such as a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group, a thioether group, a thiocyanate ester group, an isocyanate ester group, a sulfone ester group, a sulfonamide group, a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, or a sulfenyl group; a phosphorus-containing group such as a phosphido group, a phosphoryl group, a thiophosphoryl group, or a phosphato group, a silicon-containing group, a germanium-containing group, or a tin-containing group.

[0081] Among these, particularly preferred are linear or branched alkyl groups having 1 to 30, preferably 1 to 20, carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, and n-hexyl; aryl groups having 6 to 30, preferably 6 to 20, carbon atoms, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, and anthracenyl; and substituted aryl groups in which these aryl groups are substituted with 1 to 5 substituents, such as halogen atoms, alkyl or alkoxy groups having 1 to 30, preferably 1 to 20, carbon atoms, or aryl or aryloxy groups having 6 to 30, preferably 6 to 20, carbon atoms.

[0082] Examples of the oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, and phosphorus-containing group include the same as those exemplified above. Examples of the heterocyclic compound residue include residues of nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine, oxygen-containing compounds such as furan and pyran, and sulfur-containing compounds such as thiophene, as well as groups in which these heterocyclic compound residues are further substituted with a substituent such as an alkyl group or alkoxy group having 1 to 30, preferably 1 to 20, carbon atoms.

[0083] Examples of silicon-containing groups include silyl groups, siloxy groups, hydrocarbon-substituted silyl groups, and hydrocarbon-substituted siloxy groups, specifically methylsilyl groups, dimethylsilyl groups, trimethylsilyl groups, ethylsilyl groups, diethylsilyl groups, triethylsilyl groups, diphenylmethylsilyl groups, triphenylsilyl groups, dimethylphenylsilyl groups, dimethyl-t-butylsilyl groups, and dimethyl(pentafluorophenyl)silyl groups. Among these, methylsilyl groups, dimethylsilyl groups, trimethylsilyl groups, ethylsilyl groups, diethylsilyl groups, triethylsilyl groups, dimethylphenylsilyl groups, and triphenylsilyl groups are preferred. Particularly preferred are trimethylsilyl groups, triethylsilyl groups, triphenylsilyl groups, and dimethylphenylsilyl groups. Specific examples of hydrocarbon-substituted siloxy groups include trimethylsiloxy groups.

[0084] The germanium-containing group and the tin-containing group include those in which the silicon of the above silicon-containing group is substituted with germanium and tin. Next, the R 2 ~R 5 Examples of the alkoxy group are described in more detail below. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group.

[0085] Specific examples of alkylthio groups include methylthio groups, ethylthio groups, etc. Specific examples of aryloxy groups include phenoxy groups, 2,6-dimethylphenoxy groups, 2,4,6-trimethylphenoxy groups, etc. Specific examples of arylthio groups include phenylthio groups, methylphenylthio groups, naphthylthio groups, etc.

[0086] Specific examples of the acyl group include a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, a p-methoxybenzoyl group, etc. Specific examples of the ester group include an acetyloxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, a p-chlorophenoxycarbonyl group, etc.

[0087] Specific examples of thioester groups include acetylthio, benzoylthio, methylthiocarbonyl, and phenylthiocarbonyl groups. Specific examples of amide groups include acetamide, N-methylacetamide, and N-methylbenzamide groups. Specific examples of imide groups include acetimide and benzimide groups. Specific examples of amino groups include dimethylamino, ethylmethylamino, and diphenylamino groups.

[0088] Specific examples of imino groups include methylimino, ethylimino, propylimino, butylimino, and phenylimino groups. Specific examples of sulfone ester groups include methyl sulfonate, ethyl sulfonate, and phenyl sulfonate groups. Specific examples of sulfonamide groups include phenylsulfonamide, N-methylsulfonamide, and N-methyl-p-toluenesulfonamide groups.

[0089] R 6 represents a hydrocarbon group having 1 to 30 carbon atoms. Specific examples of the hydrocarbon group include linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, and n-hexyl groups; linear or branched alkenyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as vinyl, allyl, and isopropenyl groups; linear or branched alkynyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as ethynyl and propargyl groups; cyclopropyl, cyclobutyl, and cyclopropyl groups; Examples include cyclic saturated hydrocarbon groups having 3 to 30, preferably 3 to 20, carbon atoms, such as a cyclopentyl group, a cyclohexyl group, and an adamantyl group; cyclic unsaturated hydrocarbon groups having 5 to 30, carbon atoms, such as a cyclopentadienyl group, an indenyl group, and a fluorenyl group; aryl groups having 6 to 30, preferably 6 to 20, carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, and an anthracenyl group; and alkyl-substituted aryl groups, such as a tolyl group, an isopropylphenyl group, a t-butylphenyl group, a dimethylphenyl group, and a di-t-butylphenyl group.

[0090] The hydrocarbon group may have a hydrogen atom substituted with a halogen, and examples thereof include halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as a trifluoromethyl group, a pentafluorophenyl group, and a chlorophenyl group. The hydrocarbon group may also be substituted with another hydrocarbon group, and examples thereof include aryl-substituted alkyl groups such as a benzyl group and a cumyl group.

[0091] In particular, it is preferably a group selected from aryl groups having 6 to 20 carbon atoms, such as phenylethyl, diphenylmethyl, cumyl, diphenylethyl, and triphenylmethyl groups, and further from cyclic saturated hydrocarbon groups having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Particularly preferred are aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as phenyl, naphthyl, fluorenyl, anthranyl, and phenanthryl, or hydrocarbon-substituted silyl groups, and R 6 When the substituent is the above, the copolymerizability of the cyclic olefin in step (A) is improved.

[0092] R 2 ~R 6 Among these, two or more groups, preferably two or more adjacent groups, may be linked to each other to form an alicyclic ring, an aromatic ring, or a hydrocarbon ring containing a heteroatom such as a nitrogen atom, and these rings may further have a substituent. 2 ~R 6 Two of the groups represented by the formula (I) may be linked together. Furthermore, when m is 2 or more, R 1 Comrade, R 2 Comrade, R 3 Comrade, R 4 Comrade, R 5 Comrade, R 6 They may be the same or different from each other.

[0093] n is a number that satisfies the valence of M, and specifically is an integer of 0 to 5, preferably 1 to 4, and more preferably 1 to 3. X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. When n is 2 or more, X may be the same or different.

[0094] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. The hydrocarbon group may be any of the above-mentioned R 2 ~R 5 Examples of the hydrocarbon group include, but are not limited to, alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and eicosyl; cycloalkyl groups having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl, and adamantyl; alkenyl groups such as vinyl, propenyl, and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, and phenylpropyl; and aryl groups such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl, and phenanthryl. These hydrocarbon groups also include halogenated hydrocarbons, specifically hydrocarbon groups having 1 to 20 carbon atoms in which at least one hydrogen atom has been substituted with a halogen atom.

[0095] Among these, those having 1 to 20 carbon atoms are preferred. The heterocyclic compound residue includes the above-mentioned R 2 ~R 6 Examples include the same as those exemplified above.

[0096] The oxygen-containing group includes the above-mentioned R 2 ~R 5 Specific examples include a hydroxy group; alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; aryloxy groups such as a phenoxy group, a methylphenoxy group, a dimethylphenoxy group, and a naphthoxy group; arylalkoxy groups such as a phenylmethoxy group and a phenylethoxy group; an acetoxy group; and a carbonyl group, but are not limited to these.

[0097] The sulfur-containing group includes the above-mentioned R 2 ~R 6Specific examples include sulfonate groups such as a methyl sulfonate group, a trifluoromethane sulfonate group, a phenyl sulfonate group, a benzyl sulfonate group, a p-toluene sulfonate group, a trimethyl benzene sulfonate group, a triisobutyl benzene sulfonate group, a p-chlorobenzene sulfonate group, and a pentafluorobenzene sulfonate group; sulfinate groups such as a methyl sulfinate group, a phenyl sulfinate group, a benzyl sulfinate group, a p-toluene sulfinate group, a trimethyl benzene sulfinate group, and a pentafluorobenzene sulfinate group; an alkylthio group; and an arylthio group, but are not limited to these.

[0098] Specific examples of the nitrogen-containing group include the above-mentioned R 2 ~R 5 Specific examples include amino groups; alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, and dicyclohexylamino; arylamino groups or alkylarylamino groups such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, and methylphenylamino, but are not limited to these.

[0099] Specific examples of the boron-containing group include BR4 (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.). Specific examples of the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine group, tributylphosphine group, and tricyclohexylphosphine group; triarylphosphine groups such as triphenylphosphine group and tritolylphosphine group; phosphite groups (phosphido groups) such as methylphosphine group, ethylphosphite group, and phenylphosphite group; phosphonic acid groups; and phosphinic acid groups, but are not limited to these.

[0100] Specific examples of the silicon-containing group include the above-mentioned R 2 ~R 5Specific examples include hydrocarbon-substituted silyl groups such as phenylsilyl group, diphenylsilyl group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, methyldiphenylsilyl group, tritolylsilyl group, and trinaphthylsilyl group; hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether group; silicon-substituted alkyl groups such as trimethylsilylmethyl group; and silicon-substituted aryl groups such as trimethylsilylphenyl group.

[0101] Specific examples of the germanium-containing group include the R 2 ~R 5 Specific examples of the tin-containing group include groups in which the silicon of the silicon-containing group is substituted with germanium. 2 ~R 5 More specifically, the silicon-containing group may be substituted with tin instead of silicon.

[0102] Specific examples of halogen-containing groups include, but are not limited to, fluorine-containing groups such as PF6 and BF4, chlorine-containing groups such as ClO4 and SbCl6, and iodine-containing groups such as IO4. Specific examples of aluminum-containing groups include, but are not limited to, AlR4 (wherein R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.).

[0103] When n is 2 or more, the groups represented by X may be the same or different, and the groups represented by X may be bonded to each other to form a ring. The transition metal compounds [A] represented by the above general formula (1) can be used singly or in combination of two or more.

[0104] Such transition metal compounds are preferred in terms of the proportion of terminal vinyl groups and copolymerizability with cyclic olefins. Particularly preferred are compounds represented by the following formula:

[0105] [ka]

[0106] Step (A) can be carried out by solution (dissolution) polymerization, and the polymerization conditions are not particularly limited as long as a solution polymerization process for producing an olefin-based polymer is used, but it is preferable to have a step of obtaining the following polymerization reaction liquid.

[0107] The step of obtaining a polymerization reaction liquid is a step of obtaining a polymerization reaction liquid of a copolymer of ethylene and a cyclic olefin using an aliphatic hydrocarbon or an aromatic hydrocarbon as a polymerization solvent in the presence of the transition metal compound described above.

[0108] Examples of the polymerization solvent for step (A) include aliphatic hydrocarbons and aromatic hydrocarbons. Specific examples include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. These solvents may be used alone or in combination. The polymerization solvent for step (A) may be the same as or different from the polymerization solvent for step (B), which will be described later.

[0109] The polymerization temperature in step (A) is preferably in the range of 15°C to 200°C, more preferably in the range of 20°C to 150°C. The polymerization pressure in step (A) is usually from atmospheric pressure to 10 MPa gauge pressure, preferably from atmospheric pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out by any of batch, semi-continuous, and continuous methods.

[0110] The reaction time in step (A) (average residence time when copolymerization is carried out by a continuous method) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 5 minutes to 3 hours.

[0111] The molecular weight of the resulting terminally unsaturated cyclic olefin copolymer can be adjusted by adding hydrogen to the polymerization system or by changing the polymerization temperature. Furthermore, it can also be adjusted by the amount of the compound [C1] used, which will be described later. Specific examples include triisobutylaluminum, methylaluminoxane, and diethylzinc. When hydrogen is added, the amount is preferably about 0.001 to 100 nL per kg of olefin. To increase the content of terminal vinyl groups, it is preferable to carry out the polymerization under hydrogen-free conditions.

[0112] [Process (B)] Step (B) is a step of copolymerizing the terminally unsaturated cyclic olefin copolymer obtained in step (A) with at least one α-olefin selected from ethylene and olefins having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing a transition metal compound [B] of Group 4 of the periodic table.

[0113] [Periodic Table Group 4 Transition Metal Compounds [B]] The transition metal compound [B] of Group 4 of the periodic table used in the present invention preferably has a structure represented by the following general formula [B0].

[0114] The compound having a structure represented by the following general formula [B0] (hereinafter also referred to as the bridged metallocene compound [B0]) [B0] is a bridged metallocene compound, and functions as an olefin polymerization catalyst for copolymerizing the terminally unsaturated cyclic olefin copolymer produced in step (A), ethylene, and at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms, and functions more preferably when used in combination with the compound [C] described below.

[0115] The chemical structural characteristics of the bridged metallocene compound [B0] used in the present invention will be described below.

[0116] [ka]

[0117] The bridged metallocene compound [B0] has the following structural features [m1] and [m2].

[0118] [m1] Of the two ligands, one is a cyclopentadienyl group which may have a substituent, and the other is a fluorenyl group which has a substituent (hereinafter also referred to as a "substituted fluorenyl group").

[0119] [m2] Two ligands are bonded together by an aryl group-containing covalent bridge (hereinafter also referred to as "bridge") consisting of a carbon atom or silicon atom having an aryl group.

[0120] The cyclopentadienyl group which may have a substituent, the substituted fluorenyl group, the crosslinking portion and other features of the bridged metallocene compound [B0] will be explained below in order. (Optionally substituted cyclopentadienyl group) In formula [B0], R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, a hydrocarbon group, a silicon-containing group, or a heteroatom-containing group other than a silicon-containing group, and R 1 , R 2 , R 3 and R 4 are all hydrogen atoms or R 1 , R 2 , R 3 and R 4 A structure in which at least one of the following is a methyl group is particularly preferred.

[0121] (substituted fluorenyl group) In formula [B0], R 5 , R 8 , R 9 and R12 R each independently represents a hydrogen atom, a hydrocarbon group, a silicon-containing group, or a heteroatom-containing group other than a silicon-containing group, and is preferably a hydrogen atom, a hydrocarbon group, or a silicon-containing group. 6 and R 11 are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, and a heteroatom-containing group other than a silicon-containing group, and are preferably a hydrogen atom, a hydrocarbon group, or a silicon-containing group; R 7 and R 10 are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, and a heteroatom-containing group other than a silicon-containing group, and are preferably a hydrogen atom, a hydrocarbon group, or a silicon-containing group; R 6 and R 7 may be bonded to each other to form a ring, and R 10 and R 11 may be bonded to each other to form a ring; provided that R 6 , R 7 , R 10 and R 11 are not all hydrogen atoms.

[0122] From the viewpoint of polymerization activity, R 6 and R 11 is preferably not a hydrogen atom; 6 , R 7 , R 10 and R 11 It is more preferred that none of R 6 and R 11 are the same group selected from hydrocarbon groups and silicon-containing groups, and R 7 and R 10 It is particularly preferred that R are the same group selected from hydrocarbon groups and silicon-containing groups. 6 and R 7 are bonded to each other to form an alicyclic or aromatic ring, and R 10 and R 11 are also preferably bonded to each other to form an alicyclic or aromatic ring.

[0123] R 5 ~R 12Illustrative and preferred examples of the hydrocarbon group in (f1) include hydrocarbon groups (preferably hydrocarbon groups having 1 to 20 carbon atoms, hereinafter sometimes referred to as "hydrocarbon group (f1)") and silicon-containing groups (preferably silicon-containing groups having 1 to 20 carbon atoms, hereinafter sometimes referred to as "silicon-containing group (f2)"). Other examples of the substituent in the substituted cyclopentadienyl group include heteroatom-containing groups (excluding the silicon-containing group (f2)) such as halogenated hydrocarbon groups, oxygen-containing groups, and nitrogen-containing groups.

[0124] Specific examples of the hydrocarbon group (f1) include linear hydrocarbon groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decanyl, and allyl groups; isopropyl, isobutyl, sec-butyl, t-butyl, amyl, 3-methylpentyl, neopentyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-methyl-1-propylbutyl, 1,1-propylbutyl, and 1,1-dimethyl branched hydrocarbon groups such as 1-methyl-1-isopropyl-2-methylpropyl; cyclic saturated hydrocarbon groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, and adamantyl; cyclic unsaturated hydrocarbon groups such as phenyl, naphthyl, biphenyl, phenanthryl, and anthracenyl, and their nuclear alkyl-substituted derivatives; and saturated hydrocarbon groups in which at least one hydrogen atom has been substituted with an aryl group, such as benzyl and cumyl. 5 ~R 12 The silicon-containing group (f2) in the formula (I) is preferably a silicon-containing group having 1 to 20 carbon atoms, and examples thereof include a group in which a silicon atom is directly covalently bonded to a ring carbon of a cyclopentadienyl group, and specific examples thereof include alkylsilyl groups (e.g., trimethylsilyl group) and arylsilyl groups (e.g., triphenylsilyl group).

[0125] Specific examples of heteroatom-containing groups (excluding silicon-containing groups (f2)) include methoxy groups, ethoxy groups, phenoxy groups, N-methylamino groups, trifluoromethyl groups, tribromomethyl groups, pentafluoroethyl groups, and pentafluorophenyl groups.

[0126] Among the hydrocarbon groups (f1), preferred examples include linear or branched aliphatic hydrocarbon groups having 1 to 20 carbon atoms, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, and n-hexyl groups.

[0127] R 6 and R 7 (R 10 and R 11 ) are bonded to each other to form an alicyclic or aromatic ring, the substituted fluorenyl group preferably includes groups derived from compounds represented by the general formulae [II] to [VI] described later.

[0128] (Bridge part) In formula [B0], R 13 and R 14 each independently represents an aryl group; Y 1 represents a carbon atom or a silicon atom. An important point in the production method of an olefin polymer is that the bridging atom Y 1 and R, which may be the same or different, are aryl groups. 13 and R 14 From the viewpoint of ease of manufacturing, 13 and R 14 are preferably the same as each other.

[0129] Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and groups in which one or more of the aromatic hydrogens (sp2 hydrogens) of these groups are substituted with a substituent. Examples of the substituent include the hydrocarbon group (f1) and the silicon-containing group (f2), as well as a halogen atom and a halogenated hydrocarbon group.

[0130] Specific examples of aryl groups include unsubstituted aryl groups having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms, such as phenyl, naphthyl, anthracenyl, and biphenyl; alkyl-substituted aryl groups such as tolyl, isopropylphenyl, n-butylphenyl, t-butylphenyl, and dimethylphenyl; cycloalkyl-substituted aryl groups such as cyclohexylphenyl; halogenated aryl groups such as chlorophenyl, bromophenyl, dichlorophenyl, and dibromophenyl; and halogenated alkyl-substituted aryl groups such as (trifluoromethyl)phenyl and bis(trifluoromethyl)phenyl. The positions of the substituents are preferably meta and / or para positions. Among these, substituted phenyl groups in which the substituents are located at the meta and / or para positions are more preferred.

[0131] (Other features of the bridged metallocene compound [B0]) In formula [B0], Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or non-conjugated diene having 4 to 10 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair, and j represents an integer of 1 to 4. When j is an integer of 2 or greater, multiple Qs may be the same or different.

[0132] Examples of the hydrocarbon group for Q include linear or branched aliphatic hydrocarbon groups having 1 to 10 carbon atoms and alicyclic hydrocarbon groups having 3 to 10 carbon atoms. Examples of the aliphatic hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, and neopentyl. Examples of the alicyclic hydrocarbon group include cyclohexyl, cyclohexylmethyl, and 1-methyl-1-cyclohexyl.

[0133] Examples of the halogenated hydrocarbon group in Q include groups in which at least one hydrogen atom of the hydrocarbon group in Q has been substituted with a halogen atom. In formula [B0], M 1 represents a zirconium atom or a hafnium atom, and a hafnium atom is preferred in that it can copolymerize a terminally unsaturated cyclic olefin copolymer with high efficiency and control the molecular weight to a high level. Using a catalyst that can copolymerize a terminally unsaturated cyclic olefin copolymer with high efficiency and control the molecular weight to a high level is important for ensuring high productivity. This is because, although it is desirable to carry out the reaction under high-temperature conditions to ensure high productivity, high-temperature conditions tend to result in a decrease in the molecular weight of the product.

[0134] (Examples of preferred bridged metallocene compounds [B0]) Specific examples of the bridged metallocene compound [B0] are shown below. Among the example compounds, octamethyloctahydrodibenzofluorenyl refers to a group derived from a compound having a structure represented by formula [II], octamethyltetrahydrodicyclopentafluorenyl refers to a group derived from a compound having a structure represented by formula [III], dibenzofluorenyl refers to a group derived from a compound having a structure represented by formula [IV], 1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl refers to a group derived from a compound having a structure represented by formula [V], and 1,3,3',6,6',8-hexamethyl-2,7-dihydrodicyclopentafluorenyl refers to a group derived from a compound having a structure represented by formula [VI].

[0135] [ka]

[0136] [ka]

[0137] [ka]

[0138] [ka]

[0139] [ka]

[0140] Examples of the bridged metallocene compound [B0] include: Diphenylmethylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, diphenylmethylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)hafnium dichloride, diphenylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, diphenylmethylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)hafnium dichloride, diphenylmethylene(cyclopentadienyl)(dibenzofluorenyl)hafnium dichloride, diphenylmethylene(cyclopentadienyl)(1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, diphenylmethylene(cyclopentadienyl)(1,3,3' ,6,6',8-Hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, Diphenylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorenyl)hafnium dichloride, Diphenylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride, Diphenylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride diphenylmethylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, diphenylmethylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, diphenylmethylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluorenyl)hafnium dichloride,Di(p-tolyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)hafnium dichloride Di(p-tolyl)methylene(cyclopentadienyl)(dibenzofluorenyl)hafnium dichloride, Di(p-tolyl)methylene(cyclopentadienyl)(1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, Di(p-tolyl)methylene(cyclopentadienyl)(1,3,3',6,6',8-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, Di(p-tolyl)methylene(cyclopentadienyl)(1,3,3',6,6',8-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride )(2,7-diphenyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6-ditert- butylfluorenyl)hafnium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(2,3,6,7-tetramethylfluorenyl)hafnium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluorenyl)hafnium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)hafnium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)hafnium dichloride di(p-chlorophenyl)methylene(cyclopentadienyl)(1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(1,3,3',6,6',8-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluorenyl)hafnium dichloride, Di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)hafnium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride di(m-chlorophenyl)methylene(cyclopentadienyl)(1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)hafnium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)hafnium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl) (1,3,3',6,6',8-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(m-chlorophenyl) ) methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluorenyl)hafnium dichloride, Di(p-bromophenyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, Di(p-bromophenyl)methylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)hafnium dichloride, Di(p-bromophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, Di(p-bromophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride di(p-bromophenyl)methylene(cyclopentadienyl)(1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(p-bromophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)hafnium dichloride, di(p-bromophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)hafnium dichloride, di(p-bromophenyl)methylene(cyclopentadienyl) (1,3,3',6,6',8-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(p-bromophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-bromophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-bromophenyl) ) methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-bromophenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-bromophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluorenyl)hafnium dichloride, Di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, Di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)hafnium dichloride, Di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, Di(m-trifluoromethyl-phenyl)methylene Di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)hafnium dichloride, Di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)hafnium dichloride, Di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, Di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluorenyl)hafnium dichloride, Di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, Di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)hafnium dichloride, Di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, Di(p-trifluoromethyl-phenyl)methylene Di(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)hafnium dichloride, di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)hafnium dichloride, di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluorenyl)hafnium dichloride, Di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, Di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)hafnium dichloride, Di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, Di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodibenzofluorenyl)hafnium dichloride di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)hafnium dichloride, di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(1,3,3',6,6',8-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, Di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, Di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluorenyl)hafnium dichloride, Di(pn-butyl-phenyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, Di(pn-butyl-phenyl)methylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)hafnium dichloride, di(pn-butyl-phenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, di(pn-butyl-phenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)hafnium dichloride, di(pn-butyl-phenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)hafnium Dichloride, di(pn-butyl-phenyl)methylene(cyclopentadienyl)(1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(pn-butyl-phenyl)methylene(cyclopentadienyl)(1,3,3',6,6',8-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(pn-butyl-phenyl)methylene(cyclopentadienyl)(2,7 -diphenyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(pn-butyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(pn-butyl-phenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(pn-butyl-phenyl)methylene(cyclo pentadienyl)(2,7-(dimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(pn-butyl-phenyl)methylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluorenyl)hafnium dichloride, di(p-biphenyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, di(p-biphenyl)methylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-biphenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, di(p-biphenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)hafnium dichloride, di(p-biphenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)hafnium dichloride chloride, di(p-biphenyl)methylene(cyclopentadienyl)(1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(p-biphenyl)methylene(cyclopentadienyl)(1,3,3',6,6',8-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(p-biphenyl)methylene(cyclopentadienyl)(2,7-difluorodiphenyl) di(p-biphenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-biphenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(p-biphenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride di(1-naphthyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, di(p-biphenyl)methylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluorenyl)hafnium dichloride, di(1-naphthyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, di(1-naphthyl)methylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)hafnium dichloride, di(1-naphthyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, di(1-naphthyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)hafnium dichloride, di(1-naphthyl)methylene(cyclopentadienyl) di(1-naphthyl)methylene(cyclopentadienyl)(1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(1-naphthyl)methylene(cyclopentadienyl)(1,3,3',6,6',8-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride di(1-naphthyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(1-naphthyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride, di(1-naphthyl)methylene(cyclopentadienyl)(2,7-(triphenylfluorenyl)hafnium dichloride) (methylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(1-naphthyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(1-naphthyl)methylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluorenyl)hafnium dichloride, Di(2-naphthyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, Di(2-naphthyl)methylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)hafnium dichloride, Di(2-naphthyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, Di(2-naphthyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride di(2-naphthyl)methylene(cyclopentadienyl)(1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(1, 3,3',6,6',8-Hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, Di(2-naphthyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorenyl)hafnium dichloride, Di(2-naphthyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride, Di(2-naphthyl)methylene di(2-naphthyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluorenyl)hafnium dichloride, Di(m-tolyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, di(m-tolyl)methylene(cyclopentadienyl)(2,7-dimethylfluorenyl)hafnium dichloride, di(m-tolyl)methylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)hafnium dichloride, Di(p-isopropylphenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, di(p-isopropylphenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, di(p-isopropylphenyl)methylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, di(p-isopropylphenyl)methylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)hafnium dichloride, Diphenylsilylene(cyclopentadienyl)(2,7-ditert-butylfluorenyl)hafnium dichloride, diphenylsilylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)hafnium dichloride, diphenylsilylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride, diphenylsilylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafnium dichloride tetramethyltetrahydrodicyclopentafluorenyl)hafnium dichloride, diphenylsilylene(cyclopentadienyl)(dibenzofluorenyl)hafnium dichloride, diphenylsilylene(cyclopentadienyl)(1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, diphenylsilylene(cyclopentadienyl)(1,3,3',6,

[0033] Examples of suitable hafnium dichlorides include 6',8-hexamethyl-2,7-dihydrodicyclopentafluorenyl)hafnium dichloride, diphenylsilylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorenyl)hafnium dichloride, diphenylsilylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)hafnium dichloride, diphenylsilylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, diphenylsilylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6-ditert-butylfluorenyl)hafnium dichloride, and diphenylsilylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluorenyl)hafnium dichloride.

[0141] Examples of the bridged metallocene compound [B0] include compounds in which the "dichloride" of the above-exemplified compounds is replaced with "difluoride," "dibromide," "diiodide," "dimethyl," "methylethyl," etc., and compounds in which the "cyclopentadienyl" is replaced with "3-tert-butyl-5-methyl-cyclopentadienyl," "3,5-dimethyl-cyclopentadienyl," "3-tert-butyl-cyclopentadienyl," "3-methyl-cyclopentadienyl," etc.

[0142] The above bridged metallocene compounds can be produced by known methods, and the production method is not particularly limited. Known methods include those described in International Publication Nos. 01 / 27124 and 04 / 029062 by the present applicant.

[0143] In addition to the above-mentioned bridged metallocene compound [B0], examples of the transition metal compound [B] of Group 4 of the periodic table used in the present invention include the transition metal compounds described in paragraphs

[0024] to

[0037] of JP-A No. 2015-500920. The above-mentioned transition metal compounds [B] may be used singly or in combination of two or more.

[0144] Step (B) can be carried out by solution (dissolution) polymerization, and the polymerization conditions are not particularly limited as long as a solution polymerization process for producing an olefin-based polymer is used, but it is preferable to have a step of obtaining the following polymerization reaction liquid.

[0145] The step of obtaining a polymerization reaction liquid is a step of obtaining a polymerization reaction liquid of a copolymer of ethylene, an α-olefin having 3 to 20 carbon atoms, and the terminally unsaturated cyclic olefin copolymer produced in step (A) using an aliphatic hydrocarbon or an aromatic hydrocarbon as a polymerization solvent, in the presence of a transition metal compound [B] of Group 4 of the periodic table, preferably a bridged metallocene compound [B0] which is a metallocene catalyst.

[0146] In step (B), the terminally unsaturated cyclic olefin copolymer produced in step (A) is fed in the form of a solution or a slurry to a reactor in step (B). The feeding method is not particularly limited, and the polymerization liquid obtained in step (A) may be continuously fed to a reactor in step (B), or the polymerization liquid of step (A) may be temporarily stored in a buffer tank and then fed to step (B).

[0147] Examples of the polymerization solvent for step (B) include aliphatic hydrocarbons and aromatic hydrocarbons. Specific examples include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. These solvents can be used alone or in combination of two or more. The polymerization solvent for step (B) may be the same as or different from the polymerization solvent for step (A).

[0148] The polymerization temperature in step (B) is preferably in the range of 50°C to 200°C, more preferably in the range of 80°C to 200°C. Such a temperature is preferred because the terminally unsaturated cyclic olefin copolymer dissolves well at a temperature of 50°C or higher. A higher temperature is preferred in terms of increasing the amount of terminally unsaturated cyclic olefin copolymer introduced. Furthermore, a higher temperature is preferred from the viewpoint of improving productivity.

[0149] The polymerization pressure in step (B) is usually normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous systems.

[0150] The reaction time in step (B) (average residence time when copolymerization is carried out by a continuous method) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 5 minutes to 3 hours.

[0151] The polymer concentration in step (B) during steady operation is 0.5 to 30% by mass, preferably 1 to 25% by mass, and is preferably 1.5 to 20% by mass from the viewpoints of viscosity limitations in polymerization capacity, the load in the post-treatment step (solvent removal), and productivity.

[0152] The molecular weight of the resulting copolymer can be adjusted by adding hydrogen to the polymerization system or by changing the polymerization temperature. Furthermore, it can also be adjusted by the amount of the compound [C1] used, which will be described later. Specific examples include triisobutylaluminum, methylaluminoxane, and diethylzinc. When hydrogen is added, the amount is preferably about 0.001 to 100 nL per kg of olefin.

[0153] [Compound [C]] In the method for producing the olefin resin (β) according to the present invention, it is preferable to use the compound [C] described below together with the transition metal compound [A] and the transition metal compound [B] used as olefin polymerization catalysts in the above-mentioned steps (A) and (B).

[0154] Compound [C] reacts with transition metal compound [A] and transition metal compound [B] to function as an olefin polymerization catalyst, and is specifically selected from [C1] organometallic compounds, [C2] organoaluminum oxy-compounds, and [C3] compounds that react with transition metal compound [A] or transition metal compound [B] to form ion pairs. Compounds [C1] to [C3] will be explained in order below.

[0155] ([C1]organometallic compound) Specific examples of the organometallic compound [C1] used in the present invention include organoaluminum compounds represented by the following general formula (C1-a), complex alkyl compounds of a metal of Group 1 of the periodic table with aluminum represented by the general formula (C1-b), and dialkyl compounds of a metal of Group 2 or Group 12 of the periodic table represented by the general formula (C1-c). Note that the organometallic compound [C1] does not include the organoaluminum oxy compound [C2] described below.

[0156] [Chemical formula] (In the above general formula (C1-a), R a and R b may be the same as or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Y represents a halogen atom, p is a number where 0 < p ≤ 3, q is a number where 0 ≤ q < 3, r is a number where 0 ≤ r < 3, s is a number where 0 ≤ s < 3, and p + q + r + s = 3.)

[0157] [Chemical formula] (In the above general formula (C1-b), M 3 represents Li, Na or K, and R c represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.)

[0158] [Chemical formula] (In the above general formula (C1-c), R d and R e may be the same as or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. M 4 is Mg, Zn or Cd.)

[0159] Examples of the organoaluminum compound represented by the general formula (C1-a) include compounds represented by the following general formulas (C-1a-1) to (C-1a-4).[[ID=​​​​​​​​​​​​​​​ [Chemical formula] (In the formula, R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, and p is preferably a number where 0 < p < 3.)

[0162] [Chemical formula] (In the formula, R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably a number where 2 ≤ p < 3.)

[0163] [Chemical formula] (In the formula, R a and R b may be the same as or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, p is a number where 0 < p ≤ 3, q is a number where 0 ≤ q < 3, s is a number where ≤ s < 3, and p + q + s =.)

[0164] More specifically, the organoaluminum compounds of the general formula (C1-a) include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum; tri-branched alkylaluminums such as triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, and tri-2-ethylhexylaluminum; tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminums such as triphenylaluminum and tritolylaluminum; dialkylaluminum hydrides such as diisobutylaluminum hydride; (i-C4H9) x Al y (C5H 10 ) z (wherein x, y, and z are positive numbers, and z≧2x); alkylaluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide, and isobutylaluminum isopropoxide; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, and dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; R a 2.5 Al(OR b ) 0.5 Partially alkoxylated alkylaluminum having an average composition represented by the formula: a and R bmay be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms; dialkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis(2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), and isobutylaluminum bis(2,6-di-t-butyl-4-methylphenoxide); dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, and diisobutylaluminum chloride; ethylaluminum sesquichloride, butylaluminum partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide; dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride; other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride; and partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide.

[0165] Compounds similar to (C1-a) can also be used in the present invention, such as organoaluminum compounds in which two or more aluminum compounds are bonded via nitrogen atoms, such as (C2H5)2AlN(C2H5)Al(C2H5)2.

[0166] The compound represented by the general formula (C1-b) includes LiAl(C2H5)4, LiAl(C7H 15)4 can be cited as examples. Examples of the compound represented by the general formula (C1-c) include dimethylmagnesium, diethylmagnesium, dibutylmagnesium, butylethylmagnesium, dimethylzinc, diethylzinc, diphenylzinc, di-n-propylzinc, diisopropylzinc, di-n-butylzinc, diisobutylzinc, bis(pentafluorophenyl)zinc, dimethylcadmium, and diethylcadmium.

[0167] In addition, other organometallic compounds [C1] that can be used include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, and butylmagnesium chloride.

[0168] Furthermore, a compound that forms the above-mentioned organoaluminum compound in the polymerization system, such as a combination of an aluminum halide and an alkyllithium, or a combination of an aluminum halide and an alkylmagnesium, can also be used as the organometallic compound [C1]. The organometallic compounds [C1] as described above may be used singly or in combination of two or more.

[0169] ([C2] Organoaluminum oxy compounds) The organoaluminum oxy compound [C2] used in the present invention may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound such as those exemplified in JP-A-2-78687. Specific examples of the organoaluminum oxy compound [C2] include methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane.

[0170] Conventionally known aluminoxanes can be produced, for example, by the following method, and are usually obtained as a solution in a hydrocarbon solvent. (1) A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension of a compound containing adsorbed water or a salt containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, or cerous chloride hydrate, to react the adsorbed water or water of crystallization with the organoaluminum compound.

[0171] (2) A method in which water, ice or water vapor is directly reacted with an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.

[0172] (3) A method in which an organoaluminum compound such as trialkylaluminum is reacted with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene, or toluene.

[0173] The aluminoxane may contain a small amount of an organometallic component. After the solvent or unreacted organoaluminum compound is removed by distillation from the recovered aluminoxane solution, the resulting aluminoxane may be redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

[0174] Specific examples of organoaluminum compounds used in preparing aluminoxane include the same organoaluminum compounds as those exemplified as organoaluminum compounds belonging to the general formula (C1-a) above.

[0175] Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred. The organoaluminum compounds as described above may be used singly or in combination of two or more.

[0176] Examples of solvents that can be used in preparing aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane; petroleum fractions such as gasoline, kerosene, and diesel; and hydrocarbon solvents such as halides, especially chlorides and bromides, of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons. Ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

[0177] The benzene-insoluble organoaluminum oxy-compound used in the present invention preferably has an Al component soluble in benzene at 60°C of typically 10% or less, preferably 5% or less, and particularly preferably 2% or less, calculated as Al atoms. In other words, the compound is preferably insoluble or poorly soluble in benzene.

[0178] The organoaluminum oxy compound [C2] used in the present invention also includes a boron-containing organoaluminum oxy compound represented by the following general formula (III).

[0179] [ka] (In general formula (III), R 17 represents a hydrocarbon group having 1 to 10 carbon atoms, and four R 18 may be the same or different and represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.)

[0180] The boron-containing organoaluminum oxy compound represented by the general formula (III) can be produced by reacting an alkylboronic acid represented by the following general formula (IV) with an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of −80° C. to room temperature for 1 minute to 24 hours.

[0181] [ka] (In general formula (IV), R 19 is R in the general formula (III). 17 )

[0182] Specific examples of alkylboronic acids represented by the general formula (IV) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, and 3,5-bis(trifluoromethyl)phenylboronic acid. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These may be used alone or in combination of two or more.

[0183] Specific examples of organoaluminum compounds to be reacted with such alkylboronic acids include the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the general formula (C1-a) above.

[0184] The organoaluminum compound is preferably a trialkylaluminum or a tricycloalkylaluminum, and more preferably trimethylaluminum, triethylaluminum, or triisobutylaluminum, which may be used singly or in combination of two or more.

[0185] The above-mentioned [C2] organoaluminum oxy compounds may be used singly or in combination of two or more. When a transition metal compound [A], a transition metal compound [B], and an organoaluminum oxy compound [C2] such as methylaluminoxane are used as a cocatalyst component, they exhibit extremely high polymerization activity for olefin compounds.

[0186] ([C3] A compound that reacts with a transition metal compound [A] or a transition metal compound [B] to form an ion pair) Examples of the compound [C3] (hereinafter referred to as "ionizing ionic compound") used in the present invention that reacts with the transition metal compound [A] or the transition metal compound [B] to form an ion pair include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and US Pat. No. 5,321,106. Further examples include heteropoly compounds and isopoly compounds.

[0187] Specifically, the Lewis acid includes a compound represented by BR3 (R is fluorine or a phenyl group which may have a substituent such as fluorine, a methyl group, or a trifluoromethyl group), such as trifluoroboron, triphenylboron, tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron, tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron, and tris(3,5-dimethylphenyl)boron. The ionic compound may, for example, be a compound represented by the following general formula (V).

[0188] [ka] (In general formula (V), R 20 is H + , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, or a ferrocenium cation having a transition metal, and R 21 ~R 24 may be the same or different and are organic groups, preferably aryl groups or substituted aryl groups.

[0189] Specific examples of the carbonium cation include tri-substituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

[0190] Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri(n-butyl)ammonium cation; N,N-dialkylanilinium cations such as N,N-dimethylanilinium cation, N,N-diethylanilinium cation, and N,N-2,4,6-pentamethylanilinium cation; and dialkylammonium cations such as di(isopropyl)ammonium cation and dicyclohexylammonium cation.

[0191] Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation.

[0192] R 15 As the cation, a carbonium cation and an ammonium cation are preferred, and a triphenylcarbonium cation, an N,N-dimethylanilinium cation, and an N,N-diethylanilinium cation are particularly preferred.

[0193] Further, examples of the ionic compound include trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

[0194] Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tri(n-butyl)ammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(m,m-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(p-trifluoromethylphenyl)boron, tri(n-butyl)ammonium tetra(3,5-ditrifluoromethylphenyl)boron, and tri(n-butyl)ammonium tetra(o-tolyl)boron.

[0195] Specific examples of the N,N-dialkylanilinium salt include N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, and N,N,2,4,6-pentamethylanilinium tetra(phenyl)boron.

[0196] Specific examples of the dialkylammonium salt include di(1-propyl)ammonium tetra(pentafluorophenyl)boron and dicyclohexylammonium tetra(phenyl)boron.

[0197] Further examples of the ionic compound include triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, ferrocenium tetra(pentafluorophenyl)borate, triphenylcarbenium pentaphenylcyclopentadienyl complex, N,N-diethylanilinium pentaphenylcyclopentadienyl complex, and boron compounds represented by the following formula (VI) or (VII):

[0198] [ka] (In formula (VI), Et represents an ethyl group.)

[0199] [ka] (In formula (VII), Et represents an ethyl group.)

[0200] Specific examples of borane compounds, which are ionizable ionic compounds (compound [C3]), include decaborane; salts of anions such as bis[tri(n-butyl)ammonium]nonaborate, bis[tri(n-butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium]undecaborate, bis[tri(n-butyl)ammonium]dodecaborate, bis[tri(n-butyl)ammonium]decachlorodecaborate, and bis[tri(n-butyl)ammonium]dodecachlorododecaborate; and salts of metal borane anions such as tri(n-butyl)ammonium bis(dodecahydridedodecaborate)cobaltate(III) and bis[tri(n-butyl)ammonium]bis(dodecahydridedodecaborate)nickelate(III).

[0201] Specific examples of carborane compounds, which are examples of ionizable ionic compounds, include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane, and undecahydride-7,8-dimethyl. 1-methyl-7,8-dicarboxammono-7,8-dicarbaundecaborane, dodecahydride-11-methyl-2,7-dicarboxammono-7,8-dicarbaundecaborane, tri(n-butyl)ammonium 1-carbadecaborate, tri(n-butyl)ammonium 1-carbaundecaborate, tri(n-butyl)ammonium 1-carbadodecaborate, tri(n-butyl)ammonium 1-trimethylsilyl-1-carbadecaborate, tri(n-butyl)ammonium bromo-1-carbadodecaborate, tri(n-butyl)ammonium 6-Carbadecaborate, Tri(n-butyl)ammonium 6-carbadecaborate, Tri(n-butyl)ammonium 7-carbaundecaborate, Tri(n-butyl)ammonium 7,8-dicarbaundecaborate, Tri(n-butyl)ammonium 2,9-dicarbaundecaborate, Tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, Tri(n-butyl)ammonium undecahydride-8-ethyl-7,9-dica Salts of anions such as tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carbaundecaborate; Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)ferrate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)nickelate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)cuprate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)aurate(III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbandecaborate)ferrate salts of metal carborane anions such as salt (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarboxundecaborate)chromate(III), tri(n-butyl)ammonium bis(tribromooctahydride-7,8-dicarboxundecaborate)cobaltate(III), tris[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)chromate(III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)manganate(IV), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)cobaltate(III), and bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)nickelate(IV).

[0202] Heteropoly compounds, which are examples of ionized ionic compounds, are compounds containing an atom selected from silicon, phosphorus, titanium, germanium, arsenic, and tin, and one or more atoms selected from vanadium, niobium, molybdenum, and tungsten.Specific examples include, but are not limited to, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphotungstic acid, germanotungstic acid, tintungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid, phosphomolybdotungstic acid, phosphomolybdoniobic acid, and salts of these acids. Examples of the salts include salts of the acids with metals of Group 1 or 2 of the periodic table, specifically, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc., and organic salts such as triphenylethyl salts.

[0203] Isopoly compounds, which are examples of ionized ionic compounds, are compounds composed of metal ions of one type of atom selected from vanadium, niobium, molybdenum, and tungsten, and can be considered to be molecular ion species of metal oxides. Specific examples include, but are not limited to, vanadic acid, niobic acid, molybdic acid, tungstic acid, and salts of these acids. Examples of the salts include salts of the acids with metals from Group 1 or 2 of the periodic table, such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, and barium, as well as organic salts such as triphenylethyl salts.

[0204] The above-mentioned ionizing ionic compounds (compounds that react with the transition metal compound [A] and the transition metal compound [B] to form an ion pair [C3]) can be used singly or in combination of two or more. The above-mentioned [C3] ionizing ionic compounds may be used singly or in combination of two or more.

[0205] The organometallic compound [C1] is used in an amount such that the molar ratio (C1 / M) of the organometallic compound [C1] to the transition metal atom (M) in the transition metal compound [A] in step (A) and the molar ratio (C1 / M) of the organometallic compound [C1] to the transition metal atom (M) in the transition metal compound [B] in step (B) is usually 0.01 to 100,000, preferably 0.05 to 50,000.

[0206] The organoaluminum oxy compound [C2] is used in an amount such that the molar ratio (C2 / M) of the aluminum atom in the organoaluminum oxy compound [C2] to the transition metal atom (M) in the transition metal compound [A] in step (A) and the molar ratio (C2 / M) of the aluminum atom in the organoaluminum oxy compound [C2] to the transition metal atom (M) in the transition metal compound [B] in step (B) is usually 10 to 500,000, preferably 20 to 100,000.

[0207] The ionizing ionic compound [C3] is used in an amount such that the molar ratio (C3 / M) of the ionizing ionic compound [C3] to the transition metal atom (M) in the transition metal compound [A] in step (A) and the molar ratio (C2 / M) of the ionizing ionic compound [C3] to the transition metal atom (M) (hafnium atom) in the transition metal compound [B] in step (B) are generally 1 to 10, preferably 1 to 5.

[0208] [Process (C)] The method for producing the olefin resin (β) may, in addition to steps (A) and (B), optionally include step (C) of recovering the polymer produced in step (A) or (B), or both steps (A) and (B). This step is a step of separating the organic solvent used in steps (A) and (B) to extract the polymer, and is not particularly limited as long as it is a known step such as solvent concentration, extrusion degassing, pelletizing, or crystallization.

[0209] <Resin composition> The resin composition of the present invention is characterized by containing the propylene polymer (α) and the olefin resin (β). The resin composition of the present invention has excellent impact resistance and transparency due to the inclusion of the propylene polymer (α) and the olefin resin (β). The reason why the transparency is improved by blending the propylene polymer (α) with the olefin resin (β) is unclear, but it is thought that blending the propylene polymer (α) with the olefin resin (β) causes the side chains of the olefin resin (β) to penetrate into the main chain, resulting in the olefin resin (β) becoming salami-like and increasing its density, thereby improving the transparency of the entire composition.

[0210] The olefin resin (β) is well compatible with the propylene polymer (α) at ​​any blend ratio. Therefore, there are no particular limitations on the content ratio of the propylene polymer (α) and the olefin resin (β) in the resin composition of the present invention. However, to improve impact resistance and transparency, the content ratio of the propylene polymer (α) is preferably 50 to 98 parts by mass, more preferably 60 to 95 parts by mass, and even more preferably 65 to 95 parts by mass. The content ratio of the olefin resin (β) is preferably 2 to 50 parts by mass, more preferably 5 to 40 parts by mass, and even more preferably 5 to 35 parts by mass. However, the total parts by mass of the propylene polymer (α) and the olefin resin (β) is 100 parts by mass.

[0211] When the content ratio of the propylene polymer (α) and the olefin resin (β) is within the above range, the resin composition of the present invention has excellent impact resistance and transparency and can be suitably used for producing various molded products.

[0212] Furthermore, the resin composition of the present invention can be blended with other resins, rubbers, inorganic fillers, organic fillers, etc., within the scope of not impairing the object of the present invention, and can also be blended with additives such as weather resistance stabilizers, heat resistance stabilizers, antistatic agents, antislip agents, antiblocking agents, antifogging agents, lubricants, pigments, dyes, plasticizers, antioxidants, hydrochloric acid absorbers, antioxidants, and crystal nucleating agents. In the resin composition of the present invention, the amounts of the other resins, other rubbers, inorganic fillers, additives, etc. added are not particularly limited, so long as they are within the scope of not impairing the object of the present invention.

[0213] The method for preparing the resin composition of the present invention is not particularly limited, and may be a melting method, a solution method, or the like, but from a practical perspective, a melt-kneading method is preferred. As the melt-kneading method, a melt-kneading method generally used for thermoplastic resins can be applied. For example, the powdery or granular components can be uniformly mixed together with additives, etc., as described in the section on additional components, using a Henschel mixer, ribbon blender, V-type blender, or the like, and then kneaded using a single-screw or multi-screw kneading extruder, kneading roll, batch kneader, kneader, Banbury mixer, or the like to prepare the resin composition.

[0214] The melt-kneading temperature of each component (for example, the cylinder temperature in the case of an extruder) is usually 170 to 250° C., preferably 180 to 230° C. Furthermore, the order and method of kneading each component are not particularly limited.

[0215] <Molded body> The molded article according to the present embodiment can be obtained by molding the resin composition of the present invention by a known molding method, such as extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, die molding, powder slush molding, calender molding, or foam molding.

[0216] The use of the obtained molded article is not particularly limited, but it is suitable for use as, for example, an interior or exterior material for an automobile, taking advantage of the high impact resistance and transparency of the resin composition of the present invention. [Example]

[0217] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. 3,6 .0 2,7 ]Dodec-4-ene is abbreviated as "TD." In the following examples and comparative examples, the physical properties were measured or evaluated by the following methods.

[0218] [Molecular weight measurement] The molecular weight and molecular weight distribution of polymer samples were measured using a gel permeation chromatograph (Tosoh Corporation, HLC-8321 GPC / HT model) with two Tosoh Corporation TSKgel GMH6-HT columns and two Tosoh Corporation TSKgel GMH6-HTL columns (both 7.5 mm inner diameter, 300 mm length) connected in series. The mobile phase medium was o-dichlorobenzene supplemented with 0.025% BHT (Wako Pure Chemical Industries) as an antioxidant. Measurements were performed at a sample concentration of 0.15% (W / V), a flow rate of 1.0 mL / min, and 140 °C. Tosoh Corporation standard polystyrenes with molecular weights ranging from 590 to 20,600,000 were used. The resulting chromatograms were analyzed using a calibration curve based on standard polystyrene samples using Waters Empower 3 data processing software, and the number-average molecular weight (Mn), weight-average molecular weight (Mw), and polydispersity (Mw / Mn) were calculated by known methods.

[0219] [Composition of each monomer component] The repeating units derived from each monomer in the copolymer of ethylene and an α-olefin, and the repeating units derived from each monomer in the copolymer of ethylene and a cyclic olefin were determined by analyzing the nuclear magnetic resonance spectrum of the polymer by the following method.

[0220] (Measurement conditions) Equipment: JEOL ECX400P nuclear magnetic resonance spectrometer, Measurement nuclei: 1 H(400MHz); 13 C (125MHz), Measurement mode: Single pulse, Pulse width: 45° (5.25 μsec), Number of points: 32k, Measurement range: 20 ppm (-4 to 16 ppm), Repeat time: 7.0 seconds, Accumulation times: 64 times, Measurement solvent: orthodichlorobenzene-d4, sample concentration: ca. 20 mg / 0.6 mL, Measurement temperature: 120℃, Window function: exponential (BF: 0.12 Hz), Chemical shift reference: orthodichlorobenzene (7.1 ppm).

[0221] The ratio of ethylene to cyclic olefin in the cyclic olefin copolymer obtained in step (A) described in Example 1 below is 125 MHz. 13 The peak intensity (integral value) derived from ethylene and the peak intensity (integral value) derived from cyclic olefins obtained from C-NMR (JEOL ECX400P) were measured and quantified. In addition, the repeating units derived from each monomer of ethylene and α-olefin copolymer of the olefin resin (β) obtained in step (B) have a frequency of 125 MHz. 13 The intensity ratio (integrated value) of the peak derived from ethylene and the peak derived from α-olefins obtained by C-NMR (JEOL ECX400P) was measured and quantified.

[0222] [Measurement of terminal vinyl ratio] The terminal vinyl ratio of terminally unsaturated cyclic olefin copolymers was measured at 400 MHz. 1 The terminal vinyl ratio was determined as the amount of vinyl groups in the total amount of terminal unsaturation from the intensity ratio of peaks derived from unsaturated bonds obtained by H-NMR (JEOL ECX400P).

[0223] [Ratio of cyclic olefin copolymer] The proportion of the cyclic olefin copolymer contained in the olefin resin (β) was calculated from the difference between the amount of the cyclic olefin copolymer charged when the olefin resin was produced by the method described in the Examples below and the amount of the resulting olefin resin (β).

[0224] [Confirmation of grafted olefin polymer [R1]] By peak separation of the chromatogram obtained by gel permeation chromatography, it was confirmed that the cyclic olefin copolymer had been consumed, and that the graft-type olefin polymer [R1] had been produced.

[0225] Melt Flow Rate (MFR) The melt flow rate (MFR) was determined in accordance with ASTM D1238E at 190°C or 230°C under a load of 2.16 kg.

[0226] [Isotactic pentad fraction (mmmm)] The isotactic pentad fraction (mmmm) for propylene polymers was assigned based on Macromolecules 8,687 (1975). 13 It was calculated from the peak intensity ratio of the C-NMR spectrum. 13 C-NMR spectra were measured using a JEOL EX-400 instrument, with TMS as the standard, at a temperature of 130°C, and in o-dichlorobenzene as the solvent.

[0227] [Intrinsic viscosity [η]] The intrinsic viscosity [η] of the copolymer was measured at 135°C in decalin solvent using an Ubbelohde viscometer.

[0228] Approximately 20 mg of copolymer was dissolved in 25 ml of decalin, and the specific viscosity ηsp was measured using an Ubbelohde viscometer in an oil bath at 135°C. This decalin solution was diluted with 5 ml of decalin, and the specific viscosity ηsp was measured in the same manner as above. This dilution procedure was repeated two more times, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was calculated as the limiting viscosity [η] (unit: dL / g) (see Equation 1 below). [η]=lim(ηsp / C) (C→0)...Equation 1

[0229] [Measurement of glass transition temperature Tg] The glass transition temperature Tg was measured by DSC under the following conditions. Using a differential scanning calorimeter (SII RDC220) in a nitrogen atmosphere, approximately 10 mg of sample was heated from 30°C to 200°C at a heating rate of 50°C / min and held at that temperature for 10 minutes. The sample was then cooled to -100°C at a heating rate of 10°C / min, held at that temperature for 5 minutes, and then heated to 200°C at a heating rate of 10°C / min. The glass transition temperature (Tg) was detected during the second heating cycle when the DSC curve bends due to a change in specific heat, resulting in a parallel shift of the baseline. The glass transition temperature (Tg) was determined as the temperature at the intersection of the tangent to the baseline below this bend and the tangent to the point where the slope of the bend is greatest.

[0230] [Tensile test] The tensile test was carried out under the following conditions, and the elastic modulus was determined from this test.

[0231] <Measurement conditions> Test piece: JIS K7162-BA dumbbell 5mm (width) x 2mm (thickness) x 75mm (length) Tensile speed: 500 mm / min Span distance: 58 mm Temperature: 23℃

[0232] [Izod impact test] The Izod impact test was carried out in accordance with ASTM D256 under the following conditions: From this test, the Izod impact strength was determined.

[0233] <Test conditions> Hammer capacity: 3.92J Swing angle: 149.0°C The notch is machined Temperature: -40℃, 23℃

[0234] [Total light transmittance] The total amount of light transmitted through a 1 mm thick press sheet was measured using a digital turbidity meter (Nippon Denshoku Industries Co., Ltd. NDH-2000) and a C light source, and the total light transmittance was calculated using the following formula: Total light transmittance (%) = 100 × (total transmitted light amount) / (incident light amount).

[0235] [Synthesis Example 1] (Production of Propylene Homopolymer Resin (α-1)) (1) Preparation of solid titanium catalyst component 95.2 g of anhydrous magnesium chloride, 442 ml of decane, and 390.6 g of 2-ethylhexyl alcohol were subjected to a heating reaction at 130°C for 2 hours to obtain a homogeneous solution, and then 21.3 g of phthalic anhydride was added to this solution, followed by stirring and mixing at 130°C for an additional 1 hour to dissolve the phthalic anhydride.

[0236] The homogeneous solution thus obtained was cooled to room temperature, and then 75 ml of this homogeneous solution was added dropwise over 1 hour to 200 ml of titanium tetrachloride kept at -20°C. After the dropwise addition was completed, the temperature of this mixture was raised to 110°C over 4 hours, and when it reached 110°C, 5.22 g of diisobutyl phthalate (DIBP) was added, and the mixture was stirred at the same temperature for 2 hours.

[0237] After the 2-hour reaction, the solid was collected by hot filtration, resuspended in 275 ml of titanium tetrachloride, and heated again for 2 hours at 110°C. After the reaction was completed, the solid was collected again by hot filtration and thoroughly washed with decane and hexane at 110°C until no free titanium compounds were detected.

[0238] The detection of free titanium compounds was confirmed using the following method. 10 ml of the washing solution for the solid catalyst component was collected with a syringe and placed in a 100 ml side-arm Schlenk tube that had been previously purged with nitrogen. Next, the hexane was dried using a nitrogen stream, followed by vacuum drying for 30 minutes. 40 ml of ion-exchanged water and 10 ml of (1 + 1) sulfuric acid were added and stirred for 30 minutes. This solution was passed through filter paper and transferred to a 100 ml measuring flask. Next, 1 ml of concentrated H3PO4 as a masking agent for iron(II) ions and 25 ml of 3% H2O as a titanium color-developing reagent were added, and the volume was adjusted to 100 ml with ion-exchanged water. The measuring flask was shaken, and after 20 minutes, the absorbance at 420 nm was measured using a UV meter. The free titanium was removed by washing until no more absorbance was observed.

[0239] The solid titanium catalyst component (A) prepared as described above was stored as a decane slurry, and a portion of this was dried to examine the catalyst composition. The composition of the solid titanium catalyst component (A) thus obtained was 2.3 mass% titanium, 61 mass% chlorine, 19 mass% magnesium, and 12.5 mass% DIBP.

[0240] (2) Preparation of prepolymerization catalyst 100 g of the solid titanium catalyst component (A), 39.3 mL of triethylaluminum, and 100 L of heptane were placed in a 200 L autoclave equipped with a stirrer, the internal temperature was kept at 15 to 20°C, 600 g of propylene was added, and the mixture was reacted with stirring for 60 minutes to obtain a catalyst slurry.

[0241] (3) Main polymerization To a 58 L jacketed tubular polymerization reactor, 43 kg / h of propylene, 177 NL / h of hydrogen, 0.58 g / h of the solid catalyst component (catalyst slurry) prepared in (2), 3.1 ml / h of triethylaluminum, and 3.3 ml / h of dicyclopentyldimethoxysilane were continuously fed, and polymerization was carried out in a liquid-filled state with no gas phase present. The temperature of the tubular polymerization reactor was 70°C, and the pressure was 3.53 MPa / G.

[0242] The resulting slurry was transferred to a 100 L vessel polymerization reactor equipped with a stirrer, where further polymerization was carried out. Propylene was supplied to the polymerization reactor at a rate of 45 kg / h, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 3.2 mol%. Polymerization was carried out at a polymerization temperature of 70°C and a pressure of 3.28 MPa / G.

[0243] The obtained propylene homopolymer resin (α-1) was vacuum dried at 80° C. The physical properties of the propylene homopolymer resin (α-1) were a melt flow rate (MFR) of 30 g / 10 min at 230° C. under a load of 2.16 kg, and an isotactic pentad fraction (mmmm) of 97.8%.

[0244] [Synthesis Example 2] A polymerization example of the olefin resin (β-1) will be described below. Process (A) The compound (i) represented by the following formula (i) used as a catalyst was synthesized by a known method.

[0245] [ka]

[0246] A 2.0 L glass reactor, thoroughly purged with nitrogen, was charged with 1500 mL of toluene and 6.0 mL (0.038 mmol) of TD. The temperature was maintained at 25°C, and while stirring the interior of the polymerization vessel at 600 rpm, ethylene was continuously fed at 198 L / hr to saturate the liquid and gas phases. While ethylene was continuously fed, polymerization was carried out at atmospheric pressure for 4.5 minutes at 25°C with 6.0 mL (6.0 mmol) of a toluene solution of MAO (1.39 mol / L) and 1.0 mL (0.006 mmol) of a toluene solution of the above compound (i) (0.006 mol / L). The polymerization was terminated by the addition of a small amount of isobutanol. The resulting polymerization reaction solution was washed with dilute hydrochloric acid, and the resulting organic layer was poured into a large amount of a methanol / acetone mixture to precipitate a terminally unsaturated cyclic olefin copolymer. The copolymer obtained by filtration was dried under reduced pressure at 130°C for 10 hours to obtain 4.1 g of a terminally unsaturated cyclic olefin copolymer. The resulting terminally unsaturated cyclic olefin copolymer contained 61 mol% repeating units derived from ethylene, 39 mol% repeating units derived from TD, and a weight-average molecular weight of 49,900. This was the side chain composition and molecular weight of the graft-type olefin polymer [R1] contained in the resin (β-1) described below. The resulting terminally unsaturated cyclic olefin copolymer had 0.9 terminal vinyl groups per 1000 carbon atoms, giving a terminal vinyl ratio of 90%.

[0247] Process (B) The compound (ii) represented by the following formula (ii) used as a catalyst was synthesized by a known method.

[0248] [ka]

[0249] Into a glass reactor having an internal volume of 1.0 L that had been thoroughly purged with nitrogen, 3.0 g of the terminally unsaturated cyclic olefin copolymer synthesized above was added and dissolved in 500 ml of xylene. After that, the temperature was raised to 97°C, and while stirring the inside of the polymerization reactor at 600 rpm, ethylene and butene were continuously fed at 99 L / hr and 18.0 L / hr, respectively, to saturate the liquid phase and gas phase. While continuously supplying ethylene and butene, 6.0 mL (6.0 mmol) of a toluene solution (1.0 mol / L) of triisobutylaluminum (also referred to as iBu3Al), 1.5 mL (0.015 mmol) of a toluene solution (0.010 mol / L) of the above compound (ii), and then 6.0 mL (0.060 mmol) of a toluene solution (0.010 mol / L) of triphenylcarbenium tetrakis(pentafluorophenyl)borate (also referred to as Ph3CB(CF5)4) were added, and polymerization was carried out at atmospheric pressure and 97°C for 20 minutes. Gel permeation chromatography confirmed the consumption of the terminally unsaturated cyclic olefin copolymer and the formation of graft-type olefin polymer [R1]. The polymerization was terminated by adding a small amount of isobutanol. The resulting polymerization reaction solution was washed with dilute hydrochloric acid, and the resulting organic layer was separated and poured into a large amount of methanol to precipitate the polymer. The olefin resin obtained by filtration was dried under reduced pressure at 130°C for 10 hours to obtain 12.2 g of resin (β-1). The proportion of cyclic olefin copolymer contained in resin (β-1) was 25 mass%.

[0250] To analyze the structure of the ethylene-butene copolymer that constitutes the main chain of the olefin-based resin (β) produced in step (B) above, the same procedure as step (B) was followed except that no terminally unsaturated cyclic olefin-based copolymer was added, yielding 4.4 g of an ethylene-butene copolymer (resin (γ-1)). The ethylene-butene copolymer had a main chain consisting of 81 mol% ethylene-derived repeating units and a weight-average molecular weight of 402,000. These were the main chain composition and molecular weight of the graft-type olefin-based polymer [R1] contained in resins (β-1) and (β-2), which will be described later.

[0251] [Synthesis Example 3] A polymerization example of the olefin resin (β-2) will be described below. Process (A) The compound (iii) represented by the following formula (iii) used as a catalyst was synthesized by a known method.

[0252] [ka]

[0253] A 2.0 L glass reactor, thoroughly purged with nitrogen, was charged with 1500 mL of toluene and 4.5 mL (0.029 mmol) of TD. The temperature was maintained at 25°C, and while stirring the interior of the polymerization vessel at 600 rpm, ethylene was continuously fed at 99 L / hr to saturate the liquid and gas phases. While ethylene was continuously fed, polymerization was carried out at atmospheric pressure for 4.5 minutes at 25°C with 2.0 mL (2.0 mmol) of a toluene solution of MAO (1.00 mol / L) and 1.0 mL (0.003 mmol) of a toluene solution of the above compound (iii) (0.003 mol / L). The polymerization was terminated by the addition of a small amount of isobutanol. The resulting polymerization reaction solution was washed with dilute hydrochloric acid, and the resulting organic layer was poured into a large amount of a methanol / acetone mixture to precipitate a terminally unsaturated cyclic olefin copolymer. The copolymer obtained by filtration was dried under reduced pressure at 130°C for 10 hours to obtain 2.5 g of a terminally unsaturated cyclic olefin copolymer. The resulting terminally unsaturated cyclic olefin copolymer contained 88 mol% repeating units derived from ethylene, 12 mol% repeating units derived from TD, and a weight-average molecular weight of 70,200. This was the side chain composition and molecular weight of the graft-type olefin polymer [R1] contained in the resin (β-2) described below. The resulting terminally unsaturated cyclic olefin copolymer had 0.74 terminal vinyl groups per 1,000 carbon atoms, giving a terminal vinyl ratio of 90%.

[0254] Process (B) Into a glass reactor having an internal volume of 1.0 L that had been thoroughly purged with nitrogen, 2.7 g of the terminally unsaturated cyclic olefin copolymer synthesized above was added and dissolved in 500 ml of xylene. After that, the temperature was raised to 97°C, and while stirring the inside of the polymerization reactor at 600 rpm, ethylene and butene were continuously fed at 99 L / hr and 18.0 L / hr, respectively, to saturate the liquid phase and gas phase. While continuously supplying ethylene and butene, 6.0 mL (6.0 mmol) of a toluene solution (1.0 mol / L) of triisobutylaluminum (also referred to as iBuAl), 1.5 mL (0.015 mmol) of a toluene solution (0.010 mol / L) of the compound (ii) described above, and then 6.0 mL (0.060 mmol) of a toluene solution (0.010 mol / L) of triphenylcarbenium tetrakis(pentafluorophenyl)borate (also referred to as PhCB(CF)) were added, and polymerization was carried out at atmospheric pressure and 97 °C for 20 minutes. The polymerization was terminated by adding a small amount of isobutanol. The resulting polymerization reaction solution was washed with dilute hydrochloric acid, and the organic layer obtained after separation was poured into a large amount of methanol to precipitate the polymer. The olefin-based resin obtained by filtration was dried under reduced pressure at 130 °C for 10 hours, yielding 12.2 g of resin (β-2). The proportion of the cyclic olefin copolymer contained in the resin (β-2) was 34% by mass.

[0255] [Synthesis Example 4] (Production of olefin resin (γ-2)) To a 100 L stainless steel polymerization vessel equipped with an impeller (agitation speed = 250 rpm, internal temperature = 110°C, polymerization pressure = 1.0 MPa G), dehydrated hexane was continuously fed at a rate of 23 L / hr, compound (2) at 0.0053 mmol / hr, triphenylcarbenium tetrakis(pentafluorophenyl)borate at 0.021 mmol / hr, and triisobutylaluminum at 2.2 mmol / hr. Butene, ethylene, and hydrogen were continuously fed so that the gas composition in the gas-phase polymerization vessel became a butene / ethylene molar ratio of 0.23 and a hydrogen / ethylene molar ratio of 0.017. The resulting polymerization liquid was continuously discharged through an outlet provided on the side wall of the polymerization vessel while adjusting the opening of the liquid level control valve to maintain the volume of the solution in the vessel at 28 L. The resulting polymerization solution was heated to 180°C in a heater, and 80 mL of methanol was added every hour as a catalyst deactivator to terminate the polymerization. The resulting solution was then continuously transferred to a degassing process under reduced pressure and dried to obtain an olefin resin (γ-2) at a production rate of 2.1 kg / hr. Analysis of the resulting resin revealed a glass transition temperature (Tg) of -65.2°C, an intrinsic viscosity (η) of 2.6 dl / g, an MFR of 0.2 g / 10 min at 190°C and a load of 2.16 kg, and an ethylene-1-butene copolymer with a 1-butene content of 19.0 mol%.

[0256] [Synthesis Example 5] A polymerization example of the olefin resin (β-3) will be described below. Process (A) Synthesis was carried out in the same manner as in Synthesis Example 3 (polymerization example of olefin resin (β-2)), except that in step A, the amount of toluene was changed to 500 ml.

[0257] Process (B) The compound (iv) represented by the following formula (iv) used as a catalyst was synthesized by a known method.

[0258] [ka]

[0259] Into a 1.0 L glass reactor whose interior had been thoroughly purged with nitrogen, 2.7 g of the terminally unsaturated cyclic olefin copolymer synthesized above was added and dissolved in 200 ml of xylene. After that, the temperature was raised to 95°C, and while stirring the inside of the polymerization reactor at 600 rpm, ethylene and butene were continuously fed at 120 L / hr and 15.6 L / hr, respectively, to saturate the liquid phase and gas phase. While continuously supplying ethylene and butene, 1.0 mL (1.0 mmol) of a toluene solution (1.0 mol / L) of triisobutylaluminum (also referred to as iBuAl), 2.0 mL (0.005 mmol) of a toluene solution (0.0025 mol / L) of the compound (ii) described above, and then 2.0 mL (0.020 mmol) of a toluene solution (0.010 mol / L) of triphenylcarbenium tetrakis(pentafluorophenyl)borate (also referred to as PhCB(CF)) were added, and polymerization was carried out at atmospheric pressure and 95 °C for 20 minutes. The polymerization was terminated by adding a small amount of isobutanol. The resulting polymerization reaction solution was washed with dilute hydrochloric acid, and the resulting organic layer was poured into a large amount of methanol to precipitate the polymer. The olefin-based resin obtained by filtration was dried under reduced pressure at 130 °C for 10 hours, yielding 11.7 g of resin (β-3). The proportion of the cyclic olefin copolymer contained in the resin (β-3) was 23% by mass.

[0260] [Synthesis Example 6] A polymerization example of the olefin resin (β-4) will be described below. Process (A) A 2.0 L glass reactor, thoroughly purged with nitrogen, was charged with 1500 mL of toluene and 5.4 mL (0.035 mmol) of TD. The temperature was maintained at 25°C, and while stirring the interior of the polymerization vessel at 600 rpm, ethylene was continuously fed at 240 L / h to saturate the liquid and gas phases. While ethylene was continuously fed, 5.4 mL (7.5 mmol) of a toluene solution of MAO (1.39 mol / L) and 2.0 mL (0.006 mmol) of a toluene solution of the above compound (iii) (0.003 mol / L) were added and polymerization was carried out at 25°C for 4.5 minutes under atmospheric pressure. The polymerization was terminated by the addition of a small amount of isobutanol. The resulting polymerization reaction solution was washed with dilute hydrochloric acid, and the resulting organic layer was separated and poured into a large amount of a methanol / acetone mixture to obtain 3.1 g of a terminally unsaturated cyclic olefin copolymer.

[0261] Process (B) Into a 1.0 L glass reactor whose interior volume had been thoroughly purged with nitrogen, 3.0 g of the terminally unsaturated cyclic olefin copolymer synthesized above was added and dissolved in 200 ml of xylene. After that, the temperature was raised to 95°C, and while stirring the inside of the polymerization reactor at 600 rpm, ethylene and butene were continuously fed at 120 L / hr and 15.6 L / hr, respectively, to saturate the liquid phase and gas phase. While continuously supplying ethylene and butene, 1.0 mL (1.0 mmol) of a toluene solution (1.0 mol / L) of triisobutylaluminum (also referred to as iBuAl), 2.0 mL (0.005 mmol) of a toluene solution (0.0025 mol / L) of the above compound (iv), and then 2.0 mL (0.020 mmol) of a toluene solution (0.010 mol / L) of triphenylcarbenium tetrakis(pentafluorophenyl)borate (also referred to as PhCB(CF)) were added, and polymerization was carried out at 95°C for 20 minutes under atmospheric pressure. The polymerization was terminated by adding a small amount of isobutanol. The resulting polymerization reaction solution was washed with dilute hydrochloric acid, and the resulting organic layer was poured into a large amount of methanol to precipitate the polymer. The olefin-based resin obtained by filtration was dried under reduced pressure at 130°C for 10 hours, yielding 10.8 g of resin (β-4). The proportion of the cyclic olefin copolymer contained in the resin (β-4) was 28 mass %.

[0262] [Synthesis Example 7] A polymerization example of the olefin resin (β-5) will be described below. Synthesis was carried out in the same manner as in Synthesis Example 3 (polymerization example of olefin resin (β-2)), except that in step B, the amount of terminally unsaturated cyclic olefin copolymer was changed to 5.4 g.

[0263] [Synthesis Example 8] A polymerization example of the olefin resin (β-6) will be described below. The synthesis was carried out in the same manner as in Synthesis Example 2 (polymerization example of olefin resin (β-1)), except that in step B, the amount of terminally unsaturated cyclic olefin copolymer was changed to 6.0 g.

[0264] [Synthesis Example 9] A polymerization example of the olefin resin (β-7) will be described below. Synthesis was carried out in the same manner as in Synthesis Example 5 (polymerization example of olefin resin (β-3)), except that in step B, the amount of terminally unsaturated cyclic olefin copolymer was changed to 1.35 g. Table 1 shows the physical properties of the olefin resins (β-1) to (β-7) obtained in Synthesis Examples 2 to 9 above. [Table 1]

[0265] [Example 1] (Production of Propylene-Based Resin Composition) As shown in Table 2 for the formulation of Example 1, 80 parts by mass of propylene-based homopolymer resin (α-1), 20 parts by mass of olefin-based resin (β-1), 0.1 parts by mass of heat stabilizer IRGANOX 1010 (Ciba-Geigy Ltd. trademark), and 0.1 parts by mass of heat stabilizer IRGAFOS 168 (Ciba-Geigy Ltd. trademark) were melt-kneaded under the following conditions. Using a hydraulic heat press set at 210°C, the mixture was preheated for 7 minutes, molded under a pressure of 10 MPa for 3 minutes, and then cooled at 20°C under a pressure of 10 MPa for 3 minutes to produce a pressed sheet of a propylene-based resin composition. The physical properties of the resulting pressed sheet were measured using the methods described above. The results are shown in Table 2.

[0266] <Melt-kneading conditions> Mixer: Toyo Seiki Labo Plastomill (two-screw batch melt mixer) Mixing temperature: 210℃ Screw rotation speed: 60 rpm Mixing time: 5 minutes Resin amount: 40g

[0267] [Example 2] Example 2 was carried out in the same manner as Example 1, except that the propylene-based homopolymer resin (α-1) and the olefin-based resin (β-1) were melt-kneaded according to the formulation of Example 2 shown in Table 2.

[0268] [Example 3] Example 3 was carried out in the same manner as Example 1, except that the propylene-based homopolymer resin (α-1) and the olefin-based resin (β-2) were melt-kneaded according to the formulation of Example 3 shown in Table 2.

[0269] [Example 4] The same procedure as in Example 1 was carried out, except that a propylene-based resin (J2021GRP, MFR: 25 g / 10 min) (α-2) manufactured by Prime Polymer Co., Ltd. and an olefin-based resin (β-3) were melt-kneaded according to the formulation of Example 5 shown in Table 2.

[0270] [Example 5] The same procedure as in Example 1 was carried out, except that the propylene-based resin (α-2) and the olefin-based resin (β-4) were melt-kneaded according to the formulation of Example 7 shown in Table 2.

[0271] [Example 6] The same procedure as in Example 1 was carried out, except that the propylene-based resin (α-1) and the olefin-based resin (β-5) were melt-kneaded according to the formulation of Example 9 shown in Table 2.

[0272] [Example 7] The same procedure as in Example 1 was carried out, except that the propylene-based resin (α-1) and the olefin-based resin (β-6) were melt-kneaded according to the formulation of Example 10 shown in Table 2.

[0273] [Example 8] The same procedure as in Example 1 was carried out, except that the propylene-based resin (α-1) and the olefin-based resin (β-4) were melt-kneaded according to the formulation of Example 11 shown in Table 2.

[0274] [Example 9] The same procedure as in Example 1 was carried out, except that the propylene-based resin (α-1) and the olefin-based resin (β-7) were melt-kneaded according to the formulation of Example 12 shown in Table 2.

[0275] [Comparative Example 1] Comparative Example 1 was carried out in the same manner as Example 1, except that the propylene-based homopolymer resin (α-1) and the olefin-based resin (γ-2) were melt-kneaded according to the formulation of Comparative Example 1 shown in Table 2.

[0276] Comparative Example 2 Comparative Example 2 was carried out in the same manner as Example 1, except that a propylene-based homopolymer resin (α-1) was melt-kneaded with a solution blend (γ-3) prepared by solution-blending the cyclic olefin-based copolymer and the olefin-based copolymer synthesized in each step of Synthesis Example 2 by the method described below, according to the formulation of Comparative Example 1 shown in Table 2.

[0277] (Solution Blend (γ-3)) 30 parts by mass of the terminally unsaturated cyclic olefin copolymer described in Step A of Synthesis Example 2 and 70 parts by mass of the resin (γ-1) described in Step B were dissolved in toluene and stirred at 80°C for 1 hour. The solution was then poured into a large amount of methanol to precipitate the resin composition, yielding a solution blend (γ-3).

[0278] Comparative Example 3 This was carried out using a propylene-based resin (α-1).

[0279] Comparative Example 4 This was carried out using a propylene-based resin (α-2). Table 2 shows the physical properties of the resin compositions obtained in the examples and comparative examples.

[0280] [Table 2]

[0281] As can be seen from Table 2, the Izod impact energy values ​​of the propylene-based resin compositions of the Examples were higher than those of the propylene-based resin of Comparative Example 1, higher than those of the resin composition of Comparative Example 2 which contained a blend resin (γ-3) which did not contain the grafted olefin-based polymer [R1], and higher than those of the propylene-based resin (α-1) alone of Comparative Example 3.

[0282] In addition, when comparing the light transmittance between the Examples containing the grafted olefin copolymer [R1] and the olefin-based resin (γ-2), the light transmittance is improved. Furthermore, the light transmittance is significantly reduced in Comparative Example 2, which contains the blended resin (γ-3) that does not contain the grafted olefin-based polymer [R1].

[0283] In addition, even when the propylene-based resin (α-2) was used, the Izod impact energy value was higher than that of the propylene-based resin (α-2) alone in Comparative Example 4. From the above results, it was confirmed that the presence of the grafted olefin copolymer [R1] simultaneously improves the impact resistance and transparency of the propylene-based resin composition.

Claims

1. 50 to 98 parts by mass of a propylene polymer (α) having a melt flow rate (MFR) of 0.1 to 500 g / 10 min at 230°C under a load of 2.16 kg obtained in accordance with ASTM D1238E; 2 to 50 parts by mass of an olefin resin (β) containing a graft-type olefin polymer [R1] having a main chain composed of a copolymer of ethylene and at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms and a side chain composed of a copolymer of ethylene and at least one cyclic olefin (where the total parts by mass of the propylene polymer (α) and the olefin resin (β) is taken as 100 parts by mass), Contains the proportion of repeating units derived from ethylene contained in the main chain of the graft olefin polymer [R1] is 50 to 90 mol % of all repeating units contained in the main chain, The proportion of repeating units derived from ethylene contained in the side chains of the graft type olefin polymer [R1] is 50 to 95 mol % of all repeating units contained in the side chains. Resin composition.

2. 2. The resin composition according to claim 1, wherein the copolymer constituting the main chain of the graft-type olefin polymer [R1] is a copolymer that satisfies the following requirement (ii): (ii) The weight average molecular weight, calculated as a styrene equivalent value by gel permeation chromatography (GPC), is in the range of 10,000 to 500,000.

3. 3. The resin composition according to claim 1, wherein the copolymer constituting the side chain of the graft-type olefin polymer [R1] is a copolymer that satisfies the following requirement (iv): (iv) The weight average molecular weight, calculated as a styrene equivalent value by gel permeation chromatography (GPC), is in the range of 10,000 to 100,000.

4. The resin composition according to any one of claims 1 to 3, wherein the proportion of the cyclic olefin copolymer contained in the olefin resin (β) is in the range of 5 to 70 mass% (wherein the olefin resin (β) is 100 mass%).

5. A molded article comprising the resin composition according to any one of claims 1 to 4.

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