1-butene·ethylene copolymer, 1-butene-based polymer composition comprising the 1-butene·ethylene copolymer and a propylene-based polymer, 1-butene-based polymer composition comprising the 1-butene·ethylene copolymer, a propylene-based polymer and an ethylene-based polymer, and use thereof

Abstract

The present invention relates to a 1-butene-ethylene copolymer (A) satisfying the following requirements (Al) to (A5). (Al) The content of structural unit (i) derived from 1-butene is in the range of 70 to 99.9 mol%, and the content of structural unit (ii) derived from ethylene is in the range of 0.1 to 30 mol% [wherein the total of structural unit (i) and structural unit (ii) is 100 mol%]. (A2) The crystallization rate is 0.1 to 10.0 min-1. (A3) The intrinsic viscosity [η] in decalin solvent at 135°C is in the range of 0.7 to 2.0 dl / g. (A4) The melt flow rate (MFR) measured in accordance with ASTM D1238 under the conditions of 190°C, 2.16 kg load is in the range of 1 to 100 g / 10 minutes. (A5) In the heat measurement using a differential scanning calorimeter (DSC), no melting peak is observed at the second temperature rise. 13 (A3) The intrinsic viscosity [η] in decalin solvent at 135°C is in the range of 0.7 to 2.0 dl / g. (A4) The melt flow rate (MFR) measured in accordance with ASTM D1238 under the conditions of 190°C, 2.16 kg load is in the range of 1 to 100 g / 10 minutes. (A5) In the heat measurement using a differential scanning calorimeter (DSC), no melting peak is observed at the second temperature rise.

Description

TECHNICAL FIELD

[0001] The present application relates to a 1-butene·ethylene copolymer having a specific composition and having specific properties, a 1-butene-based polymer composition containing the 1-butene·ethylene copolymer and a propylene-based polymer, a 1-butene-based polymer composition containing the 1-butene·ethylene copolymer, a propylene-based polymer, and an ethylene-based polymer, and a use thereof. BACKGROUND

[0002] The 1-butene-based polymer is excellent in creep properties at high temperatures, wear resistance, flexibility, compatibility with polypropylene, and the like, and is thus used for modification of water heating pipes, sheet materials such as skin materials, polypropylene resins, hot-melt adhesives, and the like.

[0003] In Patent Literature 1, as a 1-butene-based polymer which is excellent in balance of flowability, tensile elastic modulus and elongation, secondary processability, a resin modifier formed of a high flowability 1-butene-based polymer having an intrinsic viscosity [η] in the range of 0.01 to 0.5 dl / g measured at 135°C in tetrahydronaphthalene solvent, a melting point in the range of 0 to 100°C measured using a differential scanning calorimeter (DSC), and a stereoregularity index {(mmmm) / (mmrr+rmmr)} of 30 or less, and a hot-melt adhesive containing the 1-butene-based polymer are proposed.

[0004] Further, in Patent Literature 2, a hot-melt adhesive containing a 1-butene copolymer having high melt flowability is proposed, the 1-butene copolymer containing 2 to 6% by weight of a derived unit of ethylene and having a melt flow rate (MFR) of 200 to 1500 when measured in accordance with ISO 1133 (190°C, 2.16 kg).

[0005] However, a 1-butene-based polymer in which the stereoregularity of the 1-butene-based polymer is reduced, or a 1-butene copolymer obtained by copolymerizing 1-butene with an α-olefin has a problem in that the strength and heat resistance are reduced.

[0006] PRIOR ART DOCUMENTS

[0007] PATENT LITERATURE

[0008] Patent Literature 1: International Publication No. 03 / 070788 Pamphlet

[0009] Patent Literature 2: Japanese Patent Application Laid-Open No. 2017-504667 SUMMARY

[0010] PROBLEMS TO BE SOLVED BY THE INVENTION

[0011] The present invention aims to develop a 1-butene·ethylene copolymer which has a slow crystallization rate and is low in crystallinity, while having a balance of excellent strength and flowability.

[0012] Means for solving the problem

[0013] The present invention relates to a 1-butene·ethylene copolymer (A) which satisfies the following requirements (Al) to (A5).

[0014] (A1) The content of a structural unit (i) derived from 1-butene is in the range of 70 to 99.9 mol%, and the content of a structural unit (ii) derived from ethylene is in the range of 0.1 to 30 mol% [wherein the total of the structural unit (i) and the structural unit (ii) is 100 mol%].

[0015] (A2) The isotactic pentad fraction (mmmm) calculated by 13 C-NMR is in the range of 80 to 99.9%.

[0016] (A3) The intrinsic viscosity [η] in decalin solvent at 135°C is in the range of 0.7 to 2.0 dl / g.

[0017] (A4) The melt flow rate (MFR) measured in accordance with ASTM D1238 under the conditions of 190°C, 2.16 kg load is in the range of 1 to 100 g / 10 minutes.

[0018] (A5) Using a differential scanning calorimeter (DSC), the temperature is raised from -70°C to 200°C at a rate of 20°C / minute (first temperature rise), after keeping at 200°C for 10 minutes, the temperature is lowered to -70°C at a rate of 20°C / minute (first temperature fall), after keeping at -70°C for 1 minute, the temperature is again raised from -70°C to 200°C at a rate of 20°C / minute (second temperature rise), and no melting peak is observed when the second temperature rise is performed.

[0019] Further, the present invention relates to a 1-butene-based polymer composition which contains the 1-butene·ethylene copolymer (A) satisfying the following requirements (Al) to (A5) and a propylene-based polymer (B) satisfying the following requirements (Bl) and (B2).

[0020] (A1) When the total of a structural unit (i) derived from 1-butene and a structural unit (ii) derived from ethylene is 100 mol%, the content of the aforementioned structural unit (i) is in the range of 70 to 99.9 mol%, and the content of the aforementioned structural unit (ii) is in the range of 0.1 to 30 mol%.

[0021] (A2) The isotactic pentad fraction (mmmm) calculated by 13The isotactic pentad fraction (mmmm) calculated from C-NMR is in the range of 80 to 99.9%.

[0022] (A3) Intrinsic viscosity [η] in decahydronaphthalene solvent at 135°C is in the range of 0.7 to 2.0 dl / g.

[0023] (A4) Melt flow rate (MFR) measured according to ASTM D1238 at 190°C under a load of 2.16 kg is in the range of 1 to 100 g / 10 minutes.

[0024] (A5) Using a differential scanning calorimeter (DSC), temperature is raised from -70°C to 200°C at a rate of 20°C / minute (first temperature rise), after keeping at 200°C for 10 minutes, temperature is lowered to -70°C at a rate of 20°C / minute (first temperature fall), after keeping at -70°C for 1 minute, temperature is raised again from -70°C to 200°C at a rate of 20°C / minute (second temperature rise), and no melting peak is observed during the second temperature rise.

[0025] (B1) Melting point measured by a differential scanning calorimeter is in the range of 100 to 170°C.

[0026] (B2) Isotactic pentad fraction is in the range of 90 to 99.9%.

[0027] Further, the present application relates to a 1-butene-based polymer composition which is a composition containing a 1-butene-ethylene copolymer (A) and a propylene-based polymer (B), and satisfies the following requirement (X4).

[0028] (X4) Shore D hardness measured according to ASTM D2240 is in the range of 20 to 80.

[0029] Effects of the Invention

[0030] The 1-butene-ethylene copolymer (A) of the present application has a slow crystallization rate and is low in crystallinity, and is excellent in balance of strength and moldability, and is good in softness, and thus can be suitably used for, for example, a modifier for nonwoven fabric, a hot melt adhesive.

[0031] Further, the 1-butene-ethylene copolymer (A) is good in compatibility with the propylene-based polymer (B), and thus the 1-butene-based polymer composition of the present application containing the propylene-based polymer (B) can provide a butene-based polymer composition which can form a molded body excellent in softness and in resistance to whitening upon stretching. Further, it shows excellent heat resistance, and is good in transparency, and can be suitably used for a hot melt adhesive, a packaging material. DETAILED DESCRIPTION

[0032] 1-butene·ethylene copolymer (A)

[0033] The 1-butene·ethylene copolymer (A) of the present application and the 1-butene·ethylene copolymer (A) as one of the components of the 1-butene-based polymer composition of the present application is a 1-butene·ethylene copolymer (A) satisfying the following requirements (Al) to (A5).

[0034] (A1) The content of the structural unit (i) derived from 1-butene is in the range of 70 to 99.9 mol%, and the content of the structural unit (ii) derived from ethylene is in the range of 0.1 to 30 mol% [wherein the total of the structural unit (i) and the structural unit (ii) is 100 mol%].

[0035] The lower limit value of the amount of the structural unit derived from 1-butene of the 1-butene·ethylene copolymer (A) of the present application is 70 mol%. The lower limit value of the amount of the structural unit is preferably 75 mol%, more preferably 80 mol%, and particularly preferably 85 mol%.

[0036] On the other hand, the upper limit value of the amount of the structural unit derived from 1-butene is 99.9 mol%, preferably 98 mol%, more preferably 96 mol%, further preferably 95 mol%, and particularly preferably 90.5 mol%.

[0037] The upper limit value of the amount of the structural unit (ii) derived from ethylene of the 1-butene·ethylene copolymer (A) of the present application is 30 mol%. The upper limit value of the amount of the structural unit is preferably 25 mol%, more preferably 20 mol%, and particularly preferably 15 mol%.

[0038] On the other hand, the lower limit value of the amount of the structural unit (ii) derived from ethylene is 0.1 mol%, preferably 2 mol%, more preferably 4 mol%, further preferably 5 mol%, and particularly preferably 9.5 mol%.

[0039] For the 1-butene-ethylene copolymer (A) of the present invention, good compatibility with the propylene polymer (B) described later can be obtained by keeping the amount of the ethylene-derived structural unit (ii) within the above-mentioned range. If the amount of the ethylene-derived structural unit is below the upper limit, the mechanical strength is excellent, for example, the adhesive strength is excellent when used as a hot melt adhesive, which is preferred from this perspective. When used as a packaging material, the durability of the film is improved, which is also preferred. In addition, if the amount of the structural unit is above the lower limit, the crystallization rate becomes appropriate. For example, when used as a modifier for nonwoven fabrics, the molding conditions for stable spinning are widened, and the formability is improved, which is also preferred. When used as a hot melt adhesive, the long open time characteristic of the present invention can be fully utilized, which is also preferred. When used as a packaging material, the resistance to whitening during stretching is excellent when combined with the propylene polymer, which is also preferred.

[0040] The content (mol%) of each structural unit constituting the aforementioned 1-butene-ethylene copolymer (A) is determined by... 13 The determination is performed using C-NMR. It should be noted that details regarding the determination method are described in the examples below.

[0041] (A2) Through 13 The isotactic five-unit composition percentage (mmmm) calculated by C-NMR is in the range of 80-99.9%.

[0042] For the 1-butene-ethylene copolymer (A) of the present invention, the lower limit of the isotactic five-unit component ratio (mmmm) is preferably 85%, more preferably 90%. Furthermore, the upper limit of the aforementioned isotactic five-unit component ratio (mmmm) is preferably 99.5%, more preferably 99.0%. By keeping the isotactic five-unit component ratio (mmmm) within the above range, appropriate mechanical strength and flexibility can be designed even when controlling compatibility with the propylene copolymer (B) described later by copolymerizing ethylene.

[0043] It should be noted that the details of the method for determining the isotactic five-unit component ratio (mmmm) are as described in the examples described later.

[0044] (A3) The intrinsic viscosity [η] in decahydronaphthalene solvent at 135℃ is in the range of 0.7~2.0 dl / g.

[0045] For the 1-butene-ethylene copolymer (A) of the present application, the intrinsic viscosity [η] is more preferably 0.8 to 1.9 dl / g, further preferably 0.9 to 1.85 dl / g, and particularly preferably 1.0 to 1.8 dl / g. The 1-butene-ethylene copolymer (A) having the intrinsic viscosity [η] within the aforementioned range is excellent in balance between flowability and mechanical strength.

[0046] For example, the 1-butene-ethylene copolymer (A) is excellent in workability of an adhesive such as a hot-melt adhesive, and is suitable for high-speed coating. In addition, a molded article having excellent mechanical properties can be easily obtained, and easiness of molding and durability of a packaging material can be simultaneously achieved, and thus is preferred.

[0047] (A4) The melt flow rate (MFR) measured in accordance with ASTM D1238 at 190°C under a load of 2.16 kg is in the range of 1 to 100 g / 10 minutes, preferably 2 to 90 g / 10 minutes, more preferably 3 to 85 g / 10 minutes, and further preferably 3.2 to 80 g / 10 minutes.

[0048] If the MFR is within the aforementioned range, the flowability is good, and in addition, the mechanical properties of the obtained molded article are good. For example, the 1-butene-ethylene copolymer (A) is excellent in workability of an adhesive such as a hot-melt adhesive, and is suitable for high-speed coating. In the case of use as a hot-melt adhesive, high flowability is required, and thus it is particularly preferred to be in the range of 18 to 80 g / 10 minutes. In addition, a molded article having excellent mechanical properties can be easily obtained. In the case of a molded article for a packaging material or the like, the balance between flowability and mechanical properties suitable for a molding machine is considered, and it is particularly preferred to be 15 g / 10 minutes or less.

[0049] If the MFR is above the lower limit value, flowability is obtained, and the 1-butene-ethylene copolymer (A) is excellent in workability of an adhesive such as a hot-melt adhesive, and is suitable for high-speed coating. If the MFR is below the upper limit value, the 1-butene-ethylene copolymer (A) has excellent mechanical properties, and an adhesive containing the 1-butene-ethylene copolymer (A) is preferred from the viewpoints of adhesive strength, oil resistance, and creep resistance, and in the case of use as a packaging material, durability is excellent, and thus is preferred.

[0050] (A5) In heat measurement using a differential scanning calorimeter (DSC), no melting peak is observed at the second temperature rise.

[0051] In the calorimetry measurement using a differential scanning calorimeter (DSC) in this invention, approximately 6-10 mg of sample is accurately weighed, sealed in an aluminum dish, and heated from -70°C to 200°C at a heating rate of 20°C / min (first heating). The DSC curve is measured. After holding at 200°C for 10 minutes, the sample is cooled to -70°C at a cooling rate of 20°C / min (first cooling). The DSC curve is measured again. After holding at -70°C for 1 minute, the sample is heated again from -70°C to 200°C at a heating rate of 20°C / min (second heating). The DSC curve is measured again.

[0052] In this specification, the melting peak is determined using the measurement method described above. The melting point refers to the temperature at the apex of the melting peak. "Unobservable melting peak" means that no crystalline melting peak with a melting enthalpy greater than 1 J / g is observed. It should be noted that if two or more melting peaks are observed, the lowest temperature among the apex temperatures of these peaks is the melting point.

[0053] For the 1-butene-ethylene copolymer (A) of the present invention, in addition to the above-mentioned requirements (A1) to (A5), the melting point (Tm) measured during the first heating of the differential scanning calorimeter (DSC) is preferably 70°C or less, more preferably 65°C or less.

[0054] For the 1-butene-ethylene copolymer (A) of the present invention, in addition to the above-mentioned requirements (A1) to (A5), the enthalpy of fusion measured during the first heating of the differential scanning calorimeter (DSC) is preferably 1 to 60 J / g, more preferably 2 to 50 J / g. The enthalpy of fusion serves as an indicator of crystallinity. If the enthalpy of fusion is below the upper limit, the crystallinity is low, the softness is excellent, and the flexibility and deformation following properties as a hot melt adhesive are improved. If the enthalpy of fusion is above the lower limit, the mechanical properties are excellent, and the adhesive strength as a hot melt adhesive is improved. If the enthalpy of fusion is within the aforementioned range, the balance between softness and low tackiness is excellent.

[0055] The observation of a melting peak during the first heating, and the absence of a melting peak during the second heating even when crystallization is observed, indicates that the crystallization rate of the 1-butene-ethylene copolymer (A) is extremely slow. Therefore, when using the 1-butene-ethylene copolymer (A) as a modifier for nonwoven fabrics, the molding conditions for stable spinning of the nonwoven fabric are broadened, and the moldability is improved, making it preferred. Furthermore, when used as an adhesive, it exhibits excellent bond strength after curing and can increase the open time during coating.

[0056] For the 1-butene-ethylene copolymer (A) of the present invention, in addition to the above-mentioned requirements (A1) to (A5), the weight average molecular weight (Mw) of (A6) is preferably 100,000 to 400,000.

[0057] In the case of requiring flowability, more preferably 100,000 to 400,000, further preferably 100,000 to 390,000, particularly preferably 100,000 to 380,000. If the weight average molecular weight is within the aforementioned range, the handling property of the adhesive such as hot-melt adhesive containing the 1-butene-ethylene copolymer (A) is good, and is suitable for high-speed coating. In the case of requiring mechanical strength, more preferably 110,000 to 380,000, further preferably 120,000 to 380,000, particularly preferably 132,000 to 380,000. If the weight average molecular weight is within the aforementioned range, a molded body having excellent mechanical properties can be easily obtained. In the case of using as a hot-melt adhesive, the adhesive strength is improved.

[0058] Further, the molecular weight distribution (Mw / Mn) is preferably 1.5 to 3.0, more preferably 1.6 to 2.8. Mw / Mn is a value measured by GPC method, and is a value converted to polystyrene. In the case of the 1-butene-ethylene copolymer (A) in which Mw / Mn is within the aforementioned range, the low-molecular-weight component that decreases the mechanical strength is small, and the high-molecular-weight component that deteriorates the flowability is also small, and thus is preferable.

[0059] For the 1-butene-ethylene copolymer (A) of the present application, in addition to the aforementioned requirements (A1) to (A5), it is preferable that the maximum value of the Shore A hardness (in accordance with ASTM D2244) is 70 to 99, or the maximum value of the Shore D hardness (in accordance with ASTM D2244) is 20 to 70. The more preferable range of the Shore A hardness is 75 to 98, and the further preferable range is 81 to 99. The more preferable range of the Shore D hardness is 25 to 65. The Shore A hardness or the Shore D hardness becomes an index of the crystallinity. If the Shore A hardness or the Shore D hardness is lower than the upper limit value, the crystallinity is low, and a molded body having excellent softness and whitening resistance during stretching can be easily obtained. In the case of using as a hot-melt adhesive, the flexibility and the deformation followability are improved. If the Shore A hardness or the Shore D hardness is higher than the lower limit value, a molded body having excellent mechanical properties can be easily obtained. In the case of using as a hot-melt adhesive, the adhesive strength is improved.

[0060] <Method for producing 1-butene-ethylene copolymer (A)>

[0061] As a method for obtaining the 1-butene-ethylene copolymer (A) according to the present application, a known polymerization method such as a gas phase method, a bulk method, or a slurry method can be exemplified, in which monomers are polymerized in the presence of a catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. Among them, from the viewpoint of not only a narrow molecular weight distribution and a narrow composition distribution of the polymer, excellent balanceability of mechanical strength and softness of a molded article, but also good compatibility in the case of being combined with the propylene-based polymer (B) to be described later, and further, a delay in crystallization rate in a hot melt adhesive, it is preferable to use a metallocene catalyst capable of uniformly controlling the reaction, and it is particularly preferable to use a metallocene compound represented by the following general formula (1) or (2) for polymerization.

[0062] [Chemical Formula 1]

[0063]

[0064] [Chemical Formula 2]

[0065]

[0066] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 are each independently selected from hydrogen, a hydrocarbon group, and a silicon-containing hydrocarbon group.

[0067] As the hydrocarbon group, a C1-20 alkyl group, a C7-20 arylalkyl group, a C6-20 aryl group, or a C7-20 alkylaryl group is preferable, and one or more ring structures can be included. As specific examples thereof, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a 2-methylpropyl group, a 1,1-dimethylpropyl group, a 2,2-dimethylpropyl group, a 1,1-diethylpropyl group, a 1-ethyl-1-methylpropyl group, a 1,1,2,2-tetramethylpropyl group, a sec-butyl group, a t-butyl group, and the like can be exemplified.

[0068] As the silicon-containing hydrocarbon group, a C1-4 silyl group and a C3-20 alkyl group or a C6-20 aryl group are preferable, and as specific examples thereof, a trimethylsilyl group, a t-butyldimethylsilyl group, a triphenylsilyl group, and the like can be exemplified.

[0069] Note that R 2Preferably, the substituent is a hydrocarbon group with a large stereochemical volume, a silicon-containing hydrocarbon group, i.e., a secondary or tertiary substituent, and more preferably a substituent with 4 or more carbon atoms. Specific examples of hydrocarbon groups include isopropyl, 1,1-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, and 1,1-dimethylbutyl. Tert-butyl is particularly preferred. Silicon-containing hydrocarbon groups can be exemplified by compounds in which some or all of the carbon atoms are replaced by silicon.

[0070] R on the fluorene ring 5 To R 12 Adjacent substituents can bond with each other to form a ring. Examples of such substituted fluorene groups include benzo[a]fluorene and dibenzo[a]fluorene. Additionally, the R group on the fluorene ring... 5 To R 12 From a synthetic ease perspective, the substituents are preferably left-right symmetrical, i.e., R. 5 =R 12 R 6 =R 11 R 7 =R 10 R 8 =R 9 More preferably, it is an unsubstituted fluorene, a 3,6-disubstituted fluorene, a 2,7-disubstituted fluorene, or a 2,3,6,7-tetrasubstituted fluorene. Here, positions 3, 6, 2, and 7 on the fluorene ring each correspond to R. 7 R 10 R 6 R 11 R of the above general formula (1) 3 and R 4 The group is selected from hydrogen and hydrocarbon groups, which may be the same or different. As a specific example of a preferred hydrocarbon group, the same hydrocarbon group as described above can be given. Y is carbon or silicon. In the case of general formula (1), R... 13 and R 14 It bonds to Y and serves as a crosslinking portion, constituting a substituted methylene or substituted methylenesilyl group. Preferred specific examples include, for instance, methylene, dimethylmethylene, diisopropylmethylene, methyl tert-butylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, or dimethylmethylenesilyl, diisopropylmethylenesilyl, etc. More preferably, Y is carbon.

[0071] R of general formula (1) or (2) 2 When it is tert-butyl, R 1 Preferably methyl or ethyl, more preferably methyl. In this case, R of general formula (1) 3 R 4 It is methyl or phenyl, preferably methyl. Additionally, R 3 R 4R1and R2are preferably the same as each other. Furthermore, when R1and R2in the aforementioned general formula (1) are each a tertiary butyl group, R3is preferably a methyl group. 2 R3is a methyl group, R4is preferably a hydrogen atom. 1 R3is a methyl group, R4is preferably a hydrogen atom. 5 R3is a methyl group, R4is preferably a hydrogen atom. 12 R3may be a hydrogen atom.

[0072] R1and R2are preferably the same as each other. Furthermore, when R1and R2in the aforementioned general formula (1) are each a tertiary butyl group, R3is preferably a methyl group. 2 R3is a methyl group, R4is preferably a hydrogen atom. 1 R3is a methyl group, R4is preferably a hydrogen atom. 5 R3is a methyl group, R4is preferably a hydrogen atom. 7 R3is a methyl group, R4is preferably a hydrogen atom. 8 R3is a methyl group, R4is preferably a hydrogen atom. 9 R3is a methyl group, R4is preferably a hydrogen atom. 10 R3is a methyl group, R4is preferably a hydrogen atom. 12 R3is a methyl group, R4is preferably a hydrogen atom. 6 R3is a methyl group, R4is preferably a hydrogen atom. 11 R3is a methyl group, R4is preferably a hydrogen atom.

[0073] In the case of general formula (2), Y is bonded to a divalent hydrocarbon group A having 2 to 20 carbon atoms which can include an unsaturated bond and / or an aromatic ring, and forms a cycloalkylidene group or a cyclosilylidene group, etc. As preferred specific examples, for example, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, etc. can be given.

[0074] M in general formulae (1) and (2) is a metal selected from Group 4 of the periodic table, and as M, titanium, zirconium, hafnium can be given. Q can be selected from halogen, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone pair of electrons, in the same or different combinations. As specific examples of halogen, fluorine, chlorine, bromine, iodine can be given, and as specific examples of a hydrocarbon group, the same hydrocarbon groups as mentioned above can be given. As specific examples of an anionic ligand, alkoxy groups such as methoxy, t-butoxy, phenoxy, carboxylate groups such as acetate, benzoate, sulfonate groups such as methanesulfonate, toluenesulfonate, etc. can be given. As specific examples of a neutral ligand capable of coordinating with a lone pair of electrons, organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, etc., or ethers such as tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane, etc. can be given. Among them, Q can be the same or different combinations, but at least one is preferably halogen or an alkyl group.

[0075] Component (C) is composed of at least one compound selected from an organoaluminum oxy compound (C-1), a compound (C-2) which forms an ion pair with the aforementioned metallocene compound (A), and an organoaluminum compound (C-3). Furthermore, as needed, it is composed of a particulate support (D).

[0076] As the organoaluminum oxy compound (C-1) which can be used, an aluminoxane conventionally known can be used directly.

[0077] As the compound (C-2) (hereinafter, sometimes referred to as "ionic compound" simply) which forms an ion pair with the metallocene compound (A), a Lewis acid, an ionic compound, a borane compound, a carborane compound, and the like described in Japanese Patent Application Laid-Open No. 61-501950, Japanese Patent Application Laid-Open No. 2004-51676, and the like can be given. In addition, a heteropoly compound and a homopoly compound can also be given.

[0078] Specifically, triphenylboron, tri (o-tolyl) boron, tri (p-tolyl) boron, tri (3, 5-dimethylphenyl) boron, trimethylboron, triisobutylboron, tri (4-fluorophenyl) boron, tri (3, 5-difluorophenyl) boron, tri (4-fluoromethylphenyl) boron, tri (pentafluorophenyl) boron, and the like having a fluorine-containing aryl group, and the like having a halogen-containing aryl group, and trifluoroboron can be given.

[0079] As the organoaluminum compound (C-3) which forms a polymerization catalyst for olefins, an organoaluminum compound represented by the following general formula (3), and the like can be given.

[0080] an organoaluminum compound represented by the following general formula (3),

[0081] (In the formula, Raand Rbmay be the same as or different from each other, and represent a hydrocarbon group having a carbon atom number of 1 to 15, preferably 1 to 4, Q represents a halogen atom, m is a number of 0 < m < 3, p is a number of 0 ≤ p < 3, q is a number of 0 ≤ q < 3, and m + p + q = 3.) As specific examples of such a compound, trimethylaluminum, triethylaluminum, tri-n-butylaluminum, diisopropylaluminum hydride, diisobutylaluminum hydride, and the like dialkylaluminum hydride, isobutylaluminum methoxide, isobutylaluminum ethoxide, and the like alkylaluminum alkoxide can be given.

[0082] As the organoaluminum compound (C-3), tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-octylaluminum, and the like, tri-branched alkylaluminum such as triisobutylaluminum, and the like are preferred, and trimethylaluminum and triisobutylaluminum are particularly preferred.

[0083] In the present application, the polymerization of the 1-butene-ethylene copolymer (A) can be performed in any method among a liquid phase polymerization method such as solution polymerization, suspension polymerization, and the like, or a gas phase polymerization method. In the liquid phase polymerization method, a non-active hydrocarbon solvent can be used, and specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, and the like; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, and the like; aromatic hydrocarbons such as benzene, toluene, xylene, and the like, or a mixture thereof, and the like can be given. In addition, bulk polymerization in which an olefin such as 1-butene itself is used as a solvent can also be performed.

[0084] When the polymerization is performed, the component (A) is generally 10 to 1000 ppm, preferably 20 to 500 ppm, and more preferably 30 to 300 ppm, in terms of the atom number of the metal of Group 4 of the periodic table, per 1 liter of the reaction volume. -8~10 -2 mole, preferably 10 -7 ~10 -3 Such an amount is used. The component (C-1) is used in a molar ratio [(C-1) / M] of the component (C-1) to the transition metal atom (M) in the component (A) of usually 0.01 to 5000, preferably 0.05 to 2000. The component (C-2) is used in a molar ratio [(C-2) / M] of the component (C-2) to the transition metal atom (M) in the component (A) of usually 1 to 10, preferably 1 to 5. The component (C-3) is used in a molar ratio [(C-3) / M] of the component (C-3) to the transition metal atom (M) in the component (A) of usually 10 to 5000, preferably 20 to 2000.

[0085] The polymerization temperature is in the range of usually -50 to 200°C, preferably 0 to 100°C, more preferably 20 to 100°C. If the polymerization temperature is too low, there is a tendency to be industrially disadvantageous in terms of the polymerization activity per unit catalyst, heat recovery efficiency, and the like.

[0086] The polymerization pressure is under the conditions of 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 methods. In addition, the polymerization can also be carried out in 2 steps or more with different reaction conditions.

[0087] For the purpose of controlling the molecular weight and the polymerization activity of the 1-butene-ethylene copolymer (A) produced at the time of polymerization, hydrogen can be added, and an amount of about 0.001 to 100 NL per 1 kg of the 1-butene-ethylene copolymer (A) is appropriate.

[0088] <Propylene-based polymer (B)>

[0089] The propylene-based polymer (B) which is one of the components of the 1-butene-based polymer composition of the present application is a propylene-based polymer (B) satisfying the following requirements (Bl) and (B2).

[0090] (B1) The melting point measured by a differential scanning calorimeter is in the range of 100 to 170°C, preferably 130 to 170°C.

[0091] The 1-butene-based polymer composition containing the propylene-based polymer (B) having a melting point satisfying the above range exhibits excellent heat resistance, and has a good transparency with a crystallization rate which is moderately slow.

[0092] (B2) The isotactic pentad fraction (mmmm) is in the range of 80 to 99.9%, preferably 85 to 99.9%, further preferably 90 to 99.9%.

[0093] The 1-butene-based polymer composition containing the propylene-based polymer (B) having the isotactic pentad fraction (mmmm) satisfying the above range has a moderately slow crystallization rate, which is preferable from the viewpoint of the open time as a hot melt adhesive.

[0094] For the propylene-based polymer (B) according to the present application, in addition to the above requirements (Bl) and (B2), it is preferable to have the following requirement (B3).

[0095] (B3) The crystallization temperature is in the range of 40°C to 120°C, preferably 60 to 120°C, further preferably 80 to 120°C.

[0096] If the crystallization temperature of the propylene-based polymer (B) according to the present application is below the upper limit value, the crystallinity of the 1-butene copolymer composition does not become excessively high, and has an appropriate crystallization rate, and thus, in the case of use as a hot melt adhesive, it is possible to have a long open time as an object of the present application, and thus is preferable. In addition, if the crystallization temperature of the propylene-based polymer (B) is above the lower limit value, the crystallinity does not become excessively low, and is preferable from the viewpoint of mechanical strength and heat resistance.

[0097] Regarding the crystallization temperature of the propylene-based polymer (B) according to the present application, the peak observed in the first cooling process in a differential scanning calorimeter is taken as the crystallization temperature.

[0098] For the propylene-based polymer (B) according to the present application, in addition to the above requirements (Bl) to (B3), the melt flow rate (MFR) measured under the conditions of a temperature of 230°C and a load of 2.16 kg is preferably in the range of 0.1 to 150 g / 10 minutes. It is more preferable to be in the range of 1 to 100 g / 10 minutes, further preferable to be in the range of 2 to 100 g / 10 minutes, and particularly preferable to be in the range of 3 to 50 g / 10 minutes.

[0099] If the MFR is above the lower limit value, it has flowability, and the compatibility with other polymers containing the above 1-butene-ethylene copolymer (A) becomes good. The handling property of the adhesive such as a hot melt adhesive containing the propylene-based polymer (B) is good, and is suitable for high-speed coating. If the MFR is below the upper limit value, the mechanical properties of the propylene-based polymer (B) are excellent, and the mechanical strength, impact resistance of a molded body containing the propylene-based polymer (B) are excellent, and thus, for example, in the case of use as an adhesive, it is preferable from the viewpoint of the adhesive strength, heat resistance, and creep resistance.

[0100] The propylene-based polymer (B) according to the present application can be exemplified by a propylene homopolymer, or a copolymer of propylene and at least one α-olefin having 2 to 20 carbon atoms other than propylene. Here, as the α-olefin having 2 to 20 carbon atoms other than propylene, ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and the like can be exemplified, and ethylene or an α-olefin having 4 to 10 carbon atoms is preferred.

[0101] The copolymer of propylene and these α-olefins can be a random copolymer, or a block copolymer. In the copolymer of the α-olefin and propylene, a structural unit derived from these α-olefins can be contained in a proportion of 35 mol% or less, preferably 30 mol% or less.

[0102] The method for producing the propylene-based polymer (B) according to the present application is not particularly limited, and a known method using a known catalyst such as a Ziegler-Natta catalyst, a metallocene-based catalyst, and the like can be exemplified.

[0103] <Ethylene-based polymer (C)>

[0104] The 1-butene-based polymer composition according to the present application can further contain an ethylene-based polymer (C). The ethylene-based polymer (C) contains 60 to 100 mol% of a structural unit derived from ethylene. As a specific example of the ethylene-based polymer (C) according to the present application, a high-pressure low-density polyethylene (C1), an ethylene-α-olefin copolymer (C2), and the like can be exemplified.

[0105] By using the ethylene-based polymer (C), the resulting 1-butene-based polymer composition can easily obtain a molded body in which the impact resistance and the transparency are both excellent.

[0106] ≪High-pressure low-density polyethylene (C1)≫

[0107] As the high-pressure low-density polyethylene (C1), a known high-pressure low-density polyethylene can be used without limitation. The so-called high-pressure low-density polyethylene is generally a polyethylene obtained by subjecting ethylene to radical polymerization under high temperature and high pressure, and as a method for producing the same, there is no particular limitation, and for example, a radical polymerization method in which radical polymerization is performed under conditions of 500 to 2000 atm and 150 to 300°C, and the like can be exemplified, and as a polymerization initiator, for example, an organic peroxide can be exemplified.

[0108] The density of the high-pressure low-density polyethylene (C1) measured in accordance with ASTM D1505 is preferably in the range of 900 to 925 kg / m 3 , and more preferably 910 to 925 kg / m 3 .

[0109] The melt flow rate (MFR) of the high-pressure low-density polyethylene (C1) measured in accordance with ASTM D1238 at 190°C under a load of 2.16 kg is preferably 0.1 g / 10 min or more, more preferably 0.5 g / 10 min or more, particularly preferably 1.0 g / 10 min or more, preferably 50 g / 10 min or less, more preferably 30 g / 10 min or less, particularly preferably 20 g / 10 min or less.

[0110] < Ethylene · α-olefin copolymer (C2) >

[0111] The ethylene · α-olefin copolymer (C2) contains at least structural units derived from ethylene and structural units derived from an α-olefin having 3 to 20 carbon atoms.

[0112] The content of the structural units derived from ethylene in the ethylene · α-olefin copolymer (C2) is 60 to 99 mol%, preferably 65 to 99 mol%, more preferably 70 to 99 mol%, particularly preferably 80 to 99 mol%.

[0113] The ethylene · α-olefin copolymer (C2) is characterized by having less long-chain branched structure than the high-pressure low-density polyethylene (C1) and is often referred to as linear low-density polyethylene (LLDPE).

[0114] The content of the structural units derived from an α-olefin having 3 to 20 carbon atoms in the ethylene · α-olefin copolymer (C2) is 1 to 40 mol%, preferably 1 to 35 mol%, more preferably 1 to 30 mol%, particularly preferably 1 to 20 mol%.

[0115] The contents are amounts relative to 100 mol% of the total of the structural units derived from ethylene and the structural units derived from an α-olefin having 3 to 20 carbon atoms.

[0116] If the content of the structural units is within the aforementioned range, a molded body that is excellent in impact resistance and balance of softness can be easily obtained.

[0117] As the aforementioned α-olefin having 3 to 20 carbon atoms, for example, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-nonadecene, and 1-eicosene can be given. Among them, an α-olefin having 3 to 10 carbon atoms is preferred, an α-olefin having 3 to 8 carbon atoms is more preferred, propylene, 1-butene, and 1-octene are further preferred, and propylene is particularly preferred.

[0118] The aforementioned α-olefin having 3 to 20 carbon atoms can be used singly or two or more kinds thereof can be used.

[0119] In the ethylene-α-olefin copolymer (C2), one or two or more kinds of structural units derived from other polymerizable monomers can be contained in addition to the aforementioned structural units, within a range not impairing the object of the present application.

[0120] As such other polymerizable monomers, for example, there can be mentioned styrene, vinylcyclopentene, vinylcyclohexane, vinyl norbornane and the like vinyl compounds; vinyl acetate and the like vinyl esters; maleic anhydride and the like unsaturated organic acids or derivatives thereof; dicyclopentadiene, cyclohexadiene, 5-ethylidene-2-norbornene and the like non-conjugated polyenes.

[0121] As specific examples of the ethylene-α-olefin copolymer (C2), there can be mentioned ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-propylene-1-butene copolymer, ethylene-propylene-ethylidene norbornene copolymer, ethylene-1-butene-1-octene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer. Among them, for example, ethylene-propylene copolymer, ethylene-1-butene copolymer are preferred.

[0122] The density of the ethylene-α-olefin copolymer (C2) is preferably 840 kg / m 3 More preferably, the density is 850 kg / m 3 Particularly preferably, the density is 855 kg / m 3 Preferably, the density is 940 kg / m 3 More preferably, the density is 899 kg / m 3 Further preferably, the density is 890 kg / m 3 Particularly preferably, the density is 885 kg / m 3 Further.

[0123] If the density is within the aforementioned range, a molded body excellent in balance of impact resistance, rigidity and transparency can be easily obtained.

[0124] The density can be measured by a density gradient tube method.

[0125] The MFR (measured in accordance with ASTM D1238 at 190°C under a load of 2.16 kg) of the ethylene-α-olefin copolymer (C2) is preferably 0.01 g / 10 minutes or more, more preferably 0.1 g / 10 minutes or more, preferably 40 g / 10 minutes or less, more preferably 20 g / 10 minutes or less, particularly preferably 10 g / 10 minutes or less.

[0126] If the MFR is within the aforementioned range, a molded body that is excellent in impact resistance, rigidity, and balance of transparency can be easily obtained.

[0127] For the ethylene · α-olefin copolymer (C2), the ratio (MFR 10 / MFR2) of the MFR 10 / MFR2) of the MFR

[0128] If the MFR 10 / MFR2 is within the aforementioned range, a molded body that is excellent in transparency and balance of impact resistance can be easily obtained.

[0129] The ethylene · α-olefin copolymer (C2) can be produced by a conventionally known method using a vanadium-based catalyst, a titanium-based catalyst, or a metallocene-based catalyst, or the like. It is preferable to produce using a metallocene-based catalyst, whereby a copolymer having a narrow molecular weight distribution and composition distribution can be obtained, which is more preferable in terms of mechanical properties, transparency, and impact resistance.

[0130] <1-Butene-based Polymer Composition>

[0131] The 1-butene-based polymer composition of the present application is a composition containing the aforementioned 1-butene · ethylene copolymer (A), the aforementioned propylene-based polymer (B), and further, as necessary, the aforementioned ethylene-based polymer (C). As the 1-butene-based polymer composition, a composition containing the 1-butene · ethylene copolymer (A) and the propylene-based polymer (B); a composition containing the 1-butene · ethylene copolymer (A), the propylene-based polymer (B), and the high-pressure low-density polyethylene (C1); a composition containing the 1-butene · ethylene copolymer (A), the propylene-based polymer (B), and the ethylene · α-olefin copolymer (C2); and a composition containing the 1-butene · ethylene copolymer (A), the propylene-based polymer (B), the high-pressure low-density polyethylene (C1), and the ethylene · α-olefin copolymer (C2) can be exemplified.

[0132] The 1-butene-based polymer composition of the present application is preferably a 1-butene-based polymer composition satisfying the following requirement (X4). It is further preferable to satisfy one or more of the following requirements (X1), (X2), and (X3) as well.

[0133] [Requirement (X1)]

[0134] As a preferable mode of the present application, the following is included:

[0135] (X1-1) A 1-butene-ethylene copolymer (A) comprising 63-99% by mass and a propylene polymer (B) comprising 1-37% by mass [wherein the total content of 1-butene-ethylene copolymer (A) and propylene polymer (B) is defined as 100% by mass].

[0136] (X1-2) A 1-butene-ethylene copolymer (A) comprising 1-62% by mass and a propylene polymer (B) comprising 38-99% by mass [wherein the total content of 1-butene-ethylene copolymer (A) and propylene polymer (B) is set at 100% by mass].

[0137] (X1-3) A 1-butene-ethylene copolymer composition comprising 1 to 50% by mass of 1-butene-ethylene copolymer (A), 30 to 98% by mass of propylene polymer (B), and 1 to 20% by mass of ethylene polymer (C) [wherein the total of 1-butene-ethylene copolymer (A), propylene polymer (B), and ethylene polymer (C) is set at 100% by mass].

[0138] [Requirements (X1-1)]

[0139] Preferably, the content of 1-butene-ethylene copolymer (A) is in the range of 63 to 99% by mass, and the content of propylene polymer (B) is in the range of 1 to 37% by mass [wherein, the total of 1-butene-ethylene copolymer (A) and propylene polymer (B) is set to 100% by mass]. More preferably, the content of 1-butene-ethylene copolymer (A) is in the range of 63 to 97% by mass, and the content of propylene polymer (B) is in the range of 3 to 37% by mass. Even more preferably, the content of 1-butene-ethylene copolymer (A) is in the range of 65 to 95% by mass, and the content of propylene polymer (B) is in the range of 5 to 35% by mass. Particularly preferably, the content of 1-butene-ethylene copolymer (A) is in the range of 71 to 95% by mass, and the content of propylene polymer (B) is in the range of 5 to 29% by mass.

[0140] For 1-butene-ethylene copolymer (A) and propylene polymer (B) included within the above-mentioned range, the 1-butene-ethylene copolymer (A) and propylene polymer (B) exhibit good compatibility, heat resistance, and promote crystallization. By using 1-butene-ethylene copolymer (A) as the main component, the characteristic of 1-butene-ethylene copolymer (A) of slow crystallization is retained, and crystallization is promoted by using propylene polymer (B), thereby improving the granulation properties and facilitating processing into granules.

[0141] For example, in the hot melt adhesive, the content of the 1-butene-ethylene copolymer (A) in the 1-butene-based polymer composition (X) is above the lower limit value, the softness is excellent, the flexibility and surface followability of the adhesive are excellent, and in addition, the open time is long. In the case of being below the upper limit value, the mechanical strength and heat resistance of the composition are excellent, and the adhesive strength and the creep resistance at high temperatures of the obtained adhesive are improved.

[0142] In addition, for example, the 1-butene-based polymer composition (X) can be handled in the form of a pellet, which also contributes to the modification agent that can be used for various molded bodies in a general molding machine. When used as a modifier, the content of the 1-butene-ethylene copolymer (A) in the 1-butene-based polymer composition (X) is above the lower limit value, the modification effects such as softness and whitening resistance at the time of stretching are excellent. In the case of being below the upper limit value, the pelletization becomes easy, and in addition, the mechanical strength and heat resistance of the composition are improved.

[0143] [Condition (X1-2)]

[0144] The content of the 1-butene-ethylene copolymer (A) is preferably in the range of 1 to 62% by mass, and the content of the propylene-based polymer (B) is preferably in the range of 38 to 99% by mass (where the total of the 1-butene-ethylene copolymer (A) and the propylene-based polymer (B) is 100% by mass); further more preferably, the content of the 1-butene-ethylene copolymer (A) is in the range of 3 to 60% by mass, and the content of the propylene-based polymer (B) is in the range of 40 to 97% by mass; further preferably, the content of the 1-butene-ethylene copolymer (A) is in the range of 5 to 55% by mass, and the content of the propylene-based polymer (B) is in the range of 45 to 95% by mass; particularly preferably, the content of the 1-butene-ethylene copolymer (A) is in the range of 5 to 50% by mass, and the content of the propylene-based polymer (B) is in the range of 50 to 95% by mass.

[0145] In addition, if the content of the 1-butene-ethylene copolymer (A) in the 1-butene-based polymer composition (X) in the molded body is in the aforementioned range, a molded body that is moderately soft, has excellent impact resistance, transparency, and whitening resistance at the time of stretching can be easily obtained while the characteristics of the propylene-based polymer (B) such as mechanical strength (bending resistance, breaking point strength, and the like), heat resistance, and the like are exerted due to the 1-butene-ethylene copolymer (A).

[0146] [Condition (X1-3)]

[0147] In the case of the 1-butene-based polymer composition having the three components of the 1-butene-ethylene copolymer (A), the propylene-based polymer (B), and the ethylene-based polymer (C),

[0148] Further more preferably, the content of the 1-butene-ethylene copolymer (A) is in the range of 5 to 40 mass%, the content of the propylene-based polymer (B) is in the range of 42 to 92 mass%, and the content of the ethylene-based polymer (C) is in the range of 3 to 18 mass%;

[0149] Further more preferably, the content of the 1-butene-ethylene copolymer (A) is in the range of 5 to 40 mass%, the content of the propylene-based polymer (B) is in the range of 42 to 92 mass%, and the content of the ethylene-based polymer (C) is in the range of 3 to 18 mass%;

[0150] Further more preferably, the content of the 1-butene-ethylene copolymer (A) is in the range of 5 to 40 mass%, the content of the propylene-based polymer (B) is in the range of 42 to 92 mass%, and the content of the ethylene-based polymer (C) is in the range of 3 to 18 mass%;

[0151] Further, if the content of the 1-butene-ethylene copolymer (A) in the 1-butene-based polymer composition (X) in the molded body is in the aforementioned range, a molded body which is moderately soft, excellent in impact resistance and whitening resistance at the time of stretching, can be easily obtained due to the 1-butene-ethylene copolymer (A) and the ethylene-based polymer (C), while the mechanical strength (bending resistance, breaking point strength, etc.), heat resistance, etc. of the propylene-based polymer (B) are exerted. In particular, the ethylene-based polymer (C) has a lower glass transition temperature than the propylene-based polymer (B), and can improve the impact resistance at low temperatures, and in addition, contributes to the improvement of moldability.

[0152] [Condition (X2)]

[0153] Using a differential scanning calorimeter (DSC), the temperature was raised from -70°C to 200°C at a rate of 20°C / minute (first temperature rise), after keeping at 200°C for 10 minutes, the temperature was further lowered to -70°C at a rate of 20°C / minute (first temperature lowering), after keeping at -70°C for 1 minute, the temperature was again raised from -70°C to 200°C at a rate of 20°C / minute (second temperature rise), in the above measurement, the peak on the high temperature side (crystallization temperature) generated at the time of the first temperature lowering was in the range of 40°C or higher and lower than 110°C, the 1st peak (melting peak) generated at the time of the second temperature rise was 20°C or higher and lower than 100°C, and the 2nd peak (melting peak) was in the range of 100°C to 170°C.

[0154] For the 1-butene polymer composition of the present invention, in the DSC curve measured by the second heating of the differential scanning calorimeter (DSC) described above, it is preferable that the melting peak has at least a first peak and a second peak.

[0155] Here, the first peak refers to the peak in the DSC curve that falls below 100°C. The upper limit of the first peak is preferably below 100°C, more preferably below 80°C, and even more preferably below 70°C. On the other hand, the lower limit of the first peak is preferably above 20°C, more preferably above 25°C, and even more preferably above 30°C.

[0156] The first peak is a melting peak originating from the 1-butene-ethylene copolymer (A). More than two of the first peaks can exist. That is, more than two melting peaks can exist in the temperature range below 100°C.

[0157] The second peak refers to a peak located in the range of 100°C or higher. The upper limit of the second peak is preferably 170°C or lower, more preferably 168°C or lower, and even more preferably 165°C or lower. On the other hand, the lower limit of the second peak is preferably 100°C or higher, more preferably 105°C or higher, and even more preferably 110°C or higher.

[0158] The second peak is a melting peak originating from the propylene-based polymer (B). More than two second peaks can exist; that is, more than two melting peaks can exist in the temperature range above 100°C.

[0159] In the 1-butene polymer composition of the present invention, although the reason why the melting peak derived from the 1-butene polymer, which was not observed in the 1-butene-ethylene copolymer (A) of the present invention, is observed in the 1-butene polymer composition of the present invention, is not necessarily clear, it is believed that by properly controlling the ethylene-derived structural units of the 1-butene-ethylene copolymer (A), it has good compatibility with the propylene polymer (B) contained in the ethylene-1-butene polymer composition, and the crystallization of the 1-butene-ethylene copolymer (A) is promoted by containing a small amount of propylene polymer (B).

[0160] [Requirements (X3)]

[0161] The Shore A hardness, as measured according to ASTM D2240, is preferably in the range of 65 to 99, more preferably 70 to 99, even more preferably 71 to 98, and more preferably 72 to 97.

[0162] [Requirement (X4)]

[0163] The preferred Shore D hardness, as determined by ASTM D2240, is 20-80.

[0164] If the upper limit value or less for the Shore A hardness or the Shore D hardness, crystallinity is low, softness is excellent, and flexibility, deformation followability as a hot melt adhesive are improved. If the lower limit value or more for the melting enthalpy, mechanical properties are excellent. In the case of use as a hot melt adhesive, the adhesive strength is improved.

[0165] Especially in the case where softness is required, the Shore D hardness is preferably from 20 to 70, and more preferably from 20 to 43.

[0166] In addition, in the case where excellent mechanical properties are required, the Shore D hardness is preferably from 44 to 80, and more preferably from 44 to 70.

[0167] The melt flow rate (MFR) of the 1-butene-based polymer composition of the present application, measured in accordance with ASTM D1238 at 190°C under a load of 2.16 kg, is not particularly limited, and for example, is preferably in the range of from 0.1 to 100 g / 10 minutes.

[0168] If the MFR is the lower limit value or more, flowability is obtained, the handling properties of a hot melt adhesive containing the 1-butene-based polymer composition of the present application are good, and high-speed coating is possible. If the MFR is the upper limit value or less, the mechanical strength of the 1-butene-based polymer composition of the present application is excellent, and the granulation properties are good. Since the mechanical strength is excellent, the adhesive strength as a hot melt adhesive is improved, and the durability as a packaging material is improved. If the MFR is the lower limit value or more, the flowability of the 1-butene-based polymer composition of the present application is excellent, the coating properties as a hot melt adhesive are good, and the molding of various molded bodies also becomes easy.

[0169] Especially in the case where flowability is required, the MFR is preferably from 12 to 100 g / 10 minutes, and more preferably from 12 to 50 g / 10 minutes.

[0170] In addition, in the case where excellent mechanical strength is required, the MFR is preferably 1 g / 10 minutes or more and less than 12 g / 10 minutes.

[0171] For the 1-butene-based polymer composition of the present application, the melting enthalpy ΔHfus in the 2nd peak, measured at the 2nd heating in a differential scanning calorimeter (DSC), is in the range of from 5 to 100 J / g, preferably from 5 to 90 J / g, more preferably from 5 to 85 J / g, and further preferably in the range of from 5 to 80 J / g.

[0172] The melting enthalpy becomes an index of crystallinity. If the melting enthalpy is below the upper limit value, a molded body having low crystallinity and excellent softness can be easily obtained. In the case of use as a hot melt adhesive, flexibility and deformation followability are improved. If the melting enthalpy is above the lower limit value, a molded body having excellent mechanical properties and heat resistance can be easily obtained. In the case of use as a hot melt adhesive, adhesive strength and creep resistance at high temperatures are improved.

[0173] In the hot melt adhesive, the haze of the 1-butene-based polymer composition of the present application measured according to JIS K 7136 is 50% or less, preferably 45% or less. If the haze of the 1-butene-based polymer composition is within the above range, it has good transparency and is suitable as an adhesive or a packaging material used in applications where designability is required.

[0174] In the 1-butene-based polymer composition of the present application, at least one additive selected from the group consisting of a flowability modifier, a crystal nucleating agent, an antioxidant, a heat-resistant stabilizer, a weather-resistant stabilizer such as an ultraviolet absorber and a light stabilizer, a hydrochloric acid absorber, a pigment, a dye, an antibacterial agent, a mold-proof agent, an antistatic agent, a lubricant, a slip agent, an anti-blocking agent, a haze-preventing agent, a foaming agent, a foaming aid, a plasticizer such as a mineral oil, and a filler can be added as needed without impairing the object of the present application.

[0175] [Method for producing 1-butene-based polymer composition]

[0176] The method for producing the 1-butene-based polymer composition of the present application is not particularly limited, and for example, the 1-butene-ethylene copolymer (A) of the present application and the propylene-based polymer (B), and the ethylene-based polymer (C) as needed, and other optional components as needed can be mixed in the above-mentioned mixing ratio by a method using, for example, a Henschel mixer, a V-type mixer, a belt mixer, a drum mixer, a kneader extruder, or the like, or, after mixing or without mixing, melt-kneading using a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, or the like, whereby adjustment is performed. Furthermore, granulation, pulverization, or the like can be performed as needed.

[0177] At the time of mixing and kneading thereof, each component to be mixed can be added at once or can be added in stages.

[0178] The method for melt-kneading is not particularly limited, and melt-kneading can be performed using a generally commercially available melt-kneading device such as an extruder. For example, the temperature of the portion in which kneading is performed in the melt-kneading device is generally 120 to 250°C, and is preferably 120 to 230°C. The kneading time is generally 0.5 to 30 minutes, and is particularly preferably 0.5 to 5 minutes.

[0179] [Formed body]

[0180] The various molded bodies formed from the 1-butene-ethylene copolymer (A), the 1-butene-based polymer composition containing the 1-butene-ethylene copolymer (A) and the propylene-based polymer (B), or the 1-butene-based polymer composition containing the 1-butene-ethylene copolymer (A), the propylene-based polymer (B) and the ethylene-based polymer (C) of the present application can be widely used for the purposes of the polyolefins known heretofore. The molded bodies are obtained by known thermoforming methods such as extrusion molding, injection molding, blow molding, blow forming, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calender molding, foam molding, etc.

[0181] [Use]

[0182] The 1-butene-ethylene copolymer (A), the 1-butene-based polymer composition containing the 1-butene-ethylene copolymer (A) and the propylene-based polymer (B), or the 1-butene-based polymer composition containing the 1-butene-ethylene copolymer (A), the propylene-based polymer (B) and the ethylene-based polymer (C) of the present application are suitable for use in pellets, hot-melt adhesives which can be used for automobile parts such as interior and exterior decorative parts of automobiles. In addition, the molded bodies containing the 1-butene-based polymer composition can also be used for films, sheets, packaging materials using them, nonwoven fabrics, interior and exterior decorative parts of automobiles, and the like.

[0183] [Preparation of hot-melt adhesive and use thereof]

[0184] The hot-melt adhesive of the present application can be obtained, for example, by the following methods: for the contained components, a method in which the components are sequentially melt-mixed in a melt dissolving tank such as a heating-type melt stirring tank, preferably under vacuum, under a nitrogen stream, by rotation of stirring blades; a method in which melt-mixing is performed by applying shear under heating using the double rotating blades of a kneader; a method in which melt-mixing is performed using the screw of an extruder of single screw or twin screw; and the like. The temperature is adjusted in the range of usually 120 to 230°C, preferably 150 to 200°C. The thus produced bundle- or pellet-like samples can be used for various purposes.

[0185] In the case of the hot-melt adhesive, the adherend can be attached before curing of the adhesive, or the temporarily cured hot-melt adhesive can be heated again to activate it, and then the adherend can be attached. As the shape of such a temporarily cured hot-melt adhesive itself, for example, sheet-like, film-like, nonwoven fabric-like, small piece-like, rod-like shapes can be mentioned.

[0186] The content of the 1-butene-ethylene copolymer (A) in the hot melt adhesive of the present application is usually 1 to 90 mass%, preferably 3 to 50 mass%, and more preferably 5 to 40 mass%, relative to the total amount of the adhesive. If the content is within the aforementioned range, it is preferable from the viewpoint of the balance between the adhesive force and the coatability of the hot melt adhesive.

[0187] The hot melt adhesive of the present application can contain, as needed, an amorphous polyalphaolefin (hereinafter referred to as APAO).

[0188] The melt viscosity of the APAO is preferably 500 to 200,000 mPa-s / 190°C, and more preferably 1,000 to 50,000 mPa-s / 190°C. That is, if the melt viscosity is less than 500 mPa-s / 190°C, sufficient cohesion cannot be obtained, and the adhesive strength of the adhesive decreases, on the other hand, if it is more than 200,000 mPa-s / 190°C, the workability decreases when the hot melt adhesive is applied.

[0189] As the composition of such an APAO, there are various compositions, and, for example, there are random polypropylene, homopolymers or copolymers such as random poly-1-butene, or copolymers or terpolymers of propylene, ethylene, 1-butene, etc., propylene homopolymers, propylene-butene copolymers, propylene-ethylene copolymers, etc.

[0190] The 1-butene-ethylene copolymer (A) of the present application contains a large amount of 1-butene as a structural unit, and has excellent compatibility with propylene-based polymers, and thus has excellent compatibility with APAO using propylene and 1-butene, and can be suitably used.

[0191] As specific examples of the APAO, REXtac LLC. product RT2730 (melt viscosity at 190°C: 4,000 mPa-s), VESTOPLAST 704 (product name, manufactured by Evonik, melt viscosity (190°C): 3,500 mPa-s), etc. can be given.

[0192] The APAO can be used alone or in combination of two or more.

[0193] The content of the APAO in the hot melt adhesive of the present application is usually 1 to 99 mass%, preferably 10 to 90 mass%, and more preferably 20 to 80 mass%, relative to the total amount of the adhesive, in the case where the APAO is used. If the content is within the aforementioned range, it is preferable from the viewpoint of the balance between the adhesive force and the coatability of the hot melt adhesive.

[0194] The hot melt adhesive of the present application can contain, as needed, a tackifier.

[0195] As the tackifier, for example, at least one resin selected from the group consisting of natural rosin, modified rosin, polyterpene-based resin, synthetic petroleum resin, coumarone-based resin, phenol-based resin, xylene-based resin, styrene-based resin, low molecular weight styrene-based resin, and isoprene-based resin can be given. Among them, rosin-based resin, polyterpene-based resin, synthetic petroleum resin are preferable, and further more preferably a tackifier having an aliphatic and / or alicyclic structure.

[0196] Here, as particularly preferable substances among the petroleum resins having an aliphatic and / or alicyclic structure, among the rosin-based resins, partially and completely hydrogenated rosin and their derivatives can be given, among the polyterpene-based resins, homopolymers or copolymers of cyclic terpenes can be given, and among the synthetic petroleum resins, aliphatic petroleum resins, alicyclic petroleum resins, aliphatic- alicyclic copolymer resins, hydrogenated products of copolymers of petroleum naphtha decomposition oil and various terpenes can be given.

[0197] As the tackifier, a tackifier having a softening point in the range of 25 to 160°C is preferable. If the softening point is 25°C or higher, bleeding to the surface can be prevented, and if the softening point is 160°C or lower, the viscosity at the time of melting does not become excessively high, and the processability is good. Specifically, the trade names "ARKON P-70", "ARKON P-90", "ARKON P-100", "ARKON P-115", "ARKON P-125", "ARKON P-140" (all of which are manufactured by Arakawa Chemical Industries, Ltd.) can be suitably used.

[0198] The tackifier can be used singly with one kind, or two or more kinds can be used in combination.

[0199] In the hot melt adhesive of the present application, the content of the tackifier, in the case where the tackifier is used, is generally 1 to 70 mass%, preferably 5 to 50 mass%, and more preferably 10 to 40 mass%, relative to the total amount of the adhesive. If the content is in the aforementioned range, flowability and adhesion can be imparted without reducing the adhesive strength, and thus is preferable.

[0200] The hot melt adhesive of the present application can contain a wax as needed.

[0201] As the wax, for example, Fischer-Tropsch wax, synthetic waxes such as polyethylene wax, polypropylene wax, petroleum waxes such as paraffin wax, microcrystalline wax, natural waxes such as wood wax, carnauba wax, and beeswax can be given. The 1-butene-ethylene copolymer (A) of the present application has excellent compatibility with polypropylene, and thus polypropylene wax is particularly preferable.

[0202] The B-type viscosity of the wax (at 190°C) is preferably 10 to 8000 mPa-s, more preferably 100 to 5000 mPa-s. If the B-type viscosity is within the foregoing range, it is preferable from the viewpoints of cohesiveness and kneading processability.

[0203] The melting point of the wax, as determined by DSC, is preferably 80 to 150°C, more preferably 90 to 140°C. If the melting point is within the foregoing range, it is preferable from the viewpoints of softness and kneading processability when using the adhesive.

[0204] As commercially available products of the wax, for example, the trade name "Mitsui Hi-WAX 420P", the trade name "Mitsui Hi-WAX NL100", the trade name "Mitsui Hi-WAX NP015" (all of which are manufactured by Mitsui Chemicals, Inc.) can be given.

[0205] The wax can be used alone as one kind, or two or more kinds can be used in combination.

[0206] In the hot melt adhesive of the present application, the content of the wax, in the case where the wax is used, is generally 1 to 60 mass%, preferably 1 to 50 mass%, more preferably 1 to 40 mass%, relative to the total amount of the adhesive. If the content is within the foregoing range, it is preferable because flowability and heat resistance can be imparted without reducing the adhesive strength.

[0207] In the hot melt adhesive of the present application, at least one additive selected from the group consisting of flowability modifiers, nucleating agents, antioxidants, heat-resistant stabilizers, ultraviolet absorbers, light stabilizers, pigments, dyes, antibacterial agents, antifungal agents, antistatic agents, foaming agents, foaming aids, plasticizers such as mineral oil, and fillers, which have been known in the past, can be added as needed, within a range that does not impair the object of the present application.

[0208] Regarding the application of the hot melt adhesive, there is no particular limitation as long as the object of the present application can be achieved, and commercially available hot melt applicators can be widely used. As the types of the hot melt applicators, slot coater application, roll coater application, spiral application capable of spiral application, Omega application capable of wave application, control seam application, slot spray application capable of surface application, curtain spray application, dot application capable of dot application, droplet application capable of line application, and the like can be given. As a particularly preferable application target of the hot melt adhesive, the adhesion of corrugated paper to corrugated paper can be given.

[0209] As a method of using the hot melt adhesive of the present application as a hot melt adhesive, there are the following bonding methods: using a screw-type extruder having a die portion called a T-die method, a blow method, a calender method, a spinning method, the obtained hot melt adhesive is formed into a sheet, a film or a nonwoven fabric, is fixed to the middle of the adherends to be laminated and bonded, and is heated and bonded, or the adhesive which has been formed into a sheet is heated and melted on one adherend, and the other adherend is directly pressure-bonded while being cooled. In addition, there are the following methods: using the above-mentioned screw-type extruder to melt the hot melt adhesive of the present application, and directly inserting the adhesive between the adherends to be laminated without performing the above-mentioned forming process, and performing heat bonding; in the case where one adherend is a thermoplastic plastic, directly bonding by co-extrusion, or directly applying to one adherend, and performing heat bonding again.

[0210] The hot melt adhesive of the present application can be suitably used for, for example, the bonding of substrates formed of a polyolefin resin or the like to each other, the bonding of the aforementioned substrates to a metal material (for example: a metal plate, a metal foil, a metal mesh) or another raw material (for example: a nonwoven fabric, a fabric, a cloth, a paper such as a corrugated paper, glass), the bonding of the aforementioned metal material or the aforementioned another raw material to each other. Among them, it can be particularly suitably used for the bonding of a corrugated paper to another adherend, or the bonding of a corrugated paper to a corrugated paper.

[0211] As the aforementioned substrate formed of a polyolefin resin or the like, for example, there can be mentioned a resin sheet of a single layer or a laminate of a polyolefin resin (for example: polyethylene, polypropylene), a polyester resin, a polycarbonate resin, a polyarylate resin, an acrylic resin, a polyphenylene sulfide resin, a polystyrene resin, a vinyl resin, a vinyl chloride resin, a polyimide resin, an epoxy resin or the like.

[0212] [Membrane]

[0213] The membrane containing the 1-butene·ethylene copolymer (A) of the present application or the 1-butene-based polymer composition using the same can be either a stretched membrane or an unstretched membrane, but is preferably an unstretched membrane.

[0214] The aforementioned unstretched film is not particularly limited as long as it is an unstretched film, and the shape, size (thickness), and the like are appropriately selected according to the intended use. In addition, the unstretched film can be a single layer or a multilayer. In the case of a multilayer, at least one layer thereof can be a film containing the 1-butene-ethylene copolymer (A) or the aforementioned composition of the present application. Examples of the film include a film obtained by co-extrusion using a known multilayer film forming method such as a T-die film forming method, a blown film forming method, and the like, and a film obtained by further laminating a layer containing the 1-butene-ethylene copolymer (A) or the aforementioned composition of the present application on a previously formed substrate. The substrate is not particularly limited, and is sometimes a metal such as an aluminum plate, a steel plate, a stainless steel plate, and the like, and sometimes a thermoplastic resin. Note that, in the case of a multilayer of the aforementioned unstretched film, all of the layers are unstretched.

[0215] The thickness of the aforementioned unstretched film (total thickness in the case of a multilayer) is preferably 5 μm or greater, more preferably 10 μm or greater, and is preferably 150 μm or less, more preferably 100 μm or less.

[0216] Note that, in the present specification, a film and a sheet are not particularly distinguished, but generally, a film refers to a film-like body having a thickness of less than 250 μm, and a sheet refers to a thin plate-like body having a thickness of 250 μm or greater.

[0217] As a specific use of the aforementioned unstretched film, for example, a packaging film for packaging food, liquid, pharmaceutical products, and the like, and a packaging material obtained therefrom can be given.

[0218] <Sheet>

[0219] The aforementioned sheet is not particularly limited, and the shape, size (thickness), and the like are appropriately selected according to the intended use. In addition, the sheet can be a single layer or a multilayer. In the case of a multilayer, at least one layer thereof can be a sheet containing the copolymer (A) or the aforementioned composition of the present application.

[0220] The thickness of the aforementioned sheet (total thickness in the case of a multilayer) is preferably 250 to 2000 μm, and more preferably 250 to 1500 μm.

[0221] As a specific use of the aforementioned sheet, for example, a packaging sheet for packaging food, liquid, pharmaceutical products, and the like, and a container (for example, a tray, a cup obtained by heat forming a sheet, and a container obtained by bending a sheet) formed from the sheet can be given.

[0222] Examples

[0223] Hereinafter, the present application will be described more specifically based on examples, but the present application is not limited at all by these examples.

[0224] The following shows the various polymers used in the examples and comparative examples.

[0225] [1-Butene-ethylene copolymer (A)]

[0226] 1-Butene-ethylene copolymers (A-1) to (A-8) obtained from the manufacturing examples described later were used.

[0227] In addition, as a comparative example, a 1-butene-ethylene copolymer (A'-10) with the properties shown in Table 1 was used.

[0228] [Propylene polymer (B)]

[0229] (B-1); Random polypropylene (manufactured by Prime Polymer Co., Ltd., trade name Prime Polypro F327, MFR (230℃, 2.16kg load): 7g / 10min, melting point: 140℃, mmmm: 95.3%)

[0230] (B-2); Propylene homopolymer (manufactured by Prime Polymer Co., Ltd., trade name Prime Polypro F107A, MFR (230℃, 2.16kg load): 7g / 10min, melting point: 160℃, mmmm fraction: 96%)

[0231] [Vinyl polymers (C)]

[0232] (C1-1); Low-density polyethylene (manufactured by DOW-MITSUI POLYCHEMICALS CO., LTD., trade name MIRASON 11P, MFR (190℃, 2.16kg load) 7.2g / 10min, density: 0.917g / cm³) 3 )

[0233] (C2-1); Ethylene-propylene copolymer (MFR (190℃, 2.16kg load): 0.6g / 10min, density: 0.869g / cm³) 3 )

[0234] [Other ingredients]

[0235] (PER-1); Propylene-ethylene copolymer (manufactured by Exxon Mobil Corporation, trade name Vistamaxx 3980FL, ethylene content 9 mol%, MFR (230℃, 2.16 kg load): 9 g / 10 min)

[0236] (PER-2); propylene-ethylene copolymer (manufactured by Exxon Mobil Corporation, trade name Vistamaxx 3000, ethylene content 11 mol%, MFR (230°C, 2.16 kg load): 7 g / 10 min)

[0237] [Manufacture Example of 1-butene-ethylene copolymer (A)]

[0238] [Manufacture Example 1]

[0239] To one supply port of a continuous polymerizer with a volume of 300 liters, n-hexane was supplied at a rate of 14.2 L / h, and from the other supply ports, isopropylidene (3-tert-butyl-5-methylcyclopentadienyl-fluorenyl) zirconium dichloride (main catalyst 1) and a mixed hexane solution of modified methylaluminoxane and triisobutylaluminum (zirconium conversion concentration of main catalyst 1: 0.5 mmol / liter, aluminum conversion concentration of modified methylaluminoxane: 4 mmol / liter, aluminum conversion concentration of triisobutylaluminum: 100 mmol / liter) (total hexane: 10 L / h) were continuously supplied at a rate of 0.22 L / h. At the same time, 1-butene was continuously supplied at a rate of 23.5 kg / h, ethylene was continuously supplied at a rate of 0.39 kg / h, and hydrogen was continuously supplied at a rate of 4 NL / h from another supply port of the polymerizer, and continuous solution polymerization was performed under conditions of a polymerization temperature of 60°C, a polymerization pressure of 0.8 MPaG, and a residence time of 1.5 hours, to obtain 1-butene-ethylene copolymer (A-1).

[0240] [Manufacture Examples 2 to 8]

[0241] The supply amounts of 1-butene, ethylene, and hydrogen, and the polymerization pressure were adjusted as shown in Table 1, and otherwise, the same operations as in the manufacture method of Example 1 above were performed to manufacture 1-butene-ethylene copolymers (A-2) to (A-8).

[0242] The physical properties of the 1-butene-ethylene copolymers (A) and 1-butene-based polymer compositions obtained in the manufacture examples and comparative examples were measured by the following methods.

[0243] The results are shown in Table 1.

[0244] [Table 1]

[0245] Table 1

[0246]

[0247] [1-Butene and ethylene contents in 1-butene-ethylene copolymer (A)]

[0248] The quantification of 1-butene and ethylene content was performed using a Bruker BioSpin AVANCE cryo-500 NMR spectrometer as follows. The solvent was a mixture of o-dichlorobenzene and deuterated benzene (volume ratio: 80 / 20), the sample concentration was 20 mg / 0.6 mL, the measurement temperature was 120 °C, and the observation angle was [missing information]. 13 C (125 MHz), the sequence was a single-pulse proton broadband decoupled sequence with a pulse width of 4.7 μs (45° pulse), a repetition time of 5.5 seconds, and a cumulative count of 128. Regarding the chemical shift reference value, the carbon signal of the methylene group in the butene side chain was 27.50 ppm. Using the obtained... 13 C-NMR spectroscopy was used to quantify the composition of 1-butene (C4 content; mol%) and ethylene (C2 content; mol%).

[0249] [MFR of 1-butene-ethylene copolymer (A)]

[0250] According to ASTM D1238, the MFR was determined under the conditions of 190°C and 2.16 kg load.

[0251] [Determination of the proportions (mmmm) of isotactic five-unit components]

[0252] For the pentadisotacticity (mmmm) of the pentad group of 1-butene-ethylene copolymer (A), with a chemical shift of 27.5 ppm for the peak at the peak apex of the pentad group represented by mmmm, the peak area S at 27.5 ppm and the total area S' of the peaks appearing in the range of 27.3 ppm to 26.3 ppm are calculated using the following formula. (Detection limit: set to 0.01%)

[0253] (mmmm)=S / (S+S')×100(%)

[0254] Here, the main peaks appearing in the range of 27.3 ppm to 26.3 ppm are those attributed to mmmr (27.3 ppm), mmrr and rmmr (27.2 ppm), and mrrm (26.3 ppm).

[0255] [Intrinsic viscosity [η] (dl / g)]

[0256] For the 1-butene·ethylene copolymer (A), it is a value measured using a Ubbelohde viscometer in decalin solvent at 135°C. About 20 mg of the polymerized powder, and a pellet or a block of resin is dissolved in 15 mL of decalin, and the specific viscosity ηsp is measured in an oil bath that has been heated to 135°C. After dilution by adding 5 mL of decalin solvent to the decalin solution, the specific viscosity ηsp is measured in the same manner. This dilution operation is further repeated twice, and the value of ηsp / C when the concentration (C) is extrapolated to zero is calculated as the intrinsic viscosity [η].

[0257] [η] = lim (ηsp / C) (C→0)

[0258] [Weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn)]

[0259] As the GPC device, a Waters Corporation's gel permeation chromatograph Alliance GPC-2000 type was used to measure the Mw and Mn in terms of polystyrene under the following conditions, and Mw / Mn was calculated.

[0260] Separation column: 2 of TSKgel GNH6-HT manufactured by Tosoh Corporation, and 2 of TSKgel GNH6-HTL manufactured by Tosoh Corporation (both of which have a column size of 7.5 mm in diameter and 300 mm in length)

[0261] Column temperature: 140°C

[0262] Mobile phase: o-dichlorobenzene (manufactured by FUJIFILM Wako Pure Chemical Corporation) containing 0.025% by weight of BHT (manufactured by Takeda Pharmaceutical Co., Ltd.) as an antioxidant

[0263] Mobile speed: 1.0 mL / minute

[0264] Sample concentration: 15 mg / 10 mL

[0265] Sample injection amount: 400 μL

[0266] Detector: differential refractometer

[0267] Standard polystyrene: In the case where the molecular weight is Mw < 1000, and Mw > 4 x 10 6 , manufactured by Tosoh Corporation was used. In the case where the molecular weight is 1000 ≤ Mw ≤ 4 x 10 6 , manufactured by Pressure Chemical Co. was used.

[0268] [Melting point and melting enthalpy]

[0269] The melting point and the melting enthalpy ΔHfus (1st, 2nd) were measured by the above-described measuring method.

[0270] Note that the melting point of the 1-butene-based polymer composition derived from the 1-butene-ethylene copolymer (A) measured in the first temperature rise in the heat measurement using a differential scanning calorimeter (DSC) was set as "melting point (1st)_C4", and the melting enthalpy was set as "melting enthalpy (1st)_C4". The melting point of the 1-butene-ethylene copolymer (A) measured in the second temperature rise was set as "melting point (2nd)_C4", and the melting enthalpy was set as "melting enthalpy (2nd)_C4". The melting point of the propylene-based polymer (B) measured in the second temperature rise was set as "melting point (2nd)_PP", and the melting enthalpy was set as "melting enthalpy (2nd)_PP".

[0271] [Crystallization temperature and crystallization enthalpy]

[0272] In addition, the crystallization temperature of the propylene-based polymer (B) measured in the first temperature decrease in the heat measurement using a differential scanning calorimeter (DSC) was set as "crystallization temperature_PP", and the crystallization enthalpy was set as "crystallization enthalpy_PP".

[0273] [Press molding conditions]

[0274] For the press-molded sheet prepared under the following conditions, the resulting product (hereinafter, test piece for mechanical properties) was used for the test, after being stored at room temperature for 10 days or more in Manufacturing Examples 1 to 4, Manufacturing Examples 7 to 8, and Comparative Example 1, and after being stored at room temperature for 15 days or more in Manufacturing Examples 5 and 6.

[0275] Press machine: manufactured by KANSAI ROLL Co., Ltd. (model: PEWE-70 / 50 35)

[0276] After-heat time: 4 min

[0277] After-heat and press temperature: 120°C

[0278] Pressure: 10 MPa

[0279] Pressing time: 3 min

[0280] Cooling rate: 40°C / min (using another press machine set at 20°C, press under the conditions of 10 MPa for 4 min, and cool to room temperature)

[0281] [Half-crystallization time (sec)]

[0282] The half crystallization time of the 1-butene-ethylene copolymer (A) was measured using a differential scanning calorimeter (DSC) with a DSC8500 apparatus manufactured by Perkin-Elmer. The sample was annealed at 200°C for 10 minutes, and then cooled to a predetermined temperature (30°C) at a rate of 500°C / min, and the half crystallization time was measured.

[0283] [mechanical properties (at room temperature)]

[0284] The yield stress, breaking point strength (TS), breaking point elongation (between chucks, EL), and Young's modulus (YM) were measured in accordance with JIS K 6251 for the test pieces used for the aforementioned mechanical properties (measurement temperature: 23°C, tensile speed = 200 mm / min, maximum strain = 800%). In addition, in the case where the sample did not break at a strain of 800%, the stress at that time was taken as TS.

[0285] [Shore A hardness (instantaneous value) and Shore D hardness]

[0286] For the 1-butene-ethylene copolymer (A) and the 1-butene-based polymer composition (X), an oil pressure type hot press molding machine was used, and after heating for 4 minutes, molding was performed under a pressure of 10 MPa for 3 minutes, and then cooling was performed at 20°C under a pressure of 10 MPa for 4 minutes, whereby a 2 mm thick sheet (test piece) was produced.

[0287] Manufacturing Examples 1 to 4, Manufacturing Examples 7 to 8, and Comparative Example 1 were stored at room temperature for 10 days or more after molding, and Manufacturing Examples 5 to 6 were stored at room temperature for 15 days or more, and then the Shore A and Shore D were measured.

[0288] The Shore A hardness was measured using a type A tester, and the scale was read immediately after the pressure needle contacted the test piece. (In accordance with ASTM D2240).

[0289] The Shore D hardness was measured using a type D tester, and the scale of the maximum value was read after the pressure needle contacted the test piece. (In accordance with ASTM D2240).

[0290] Note that, in the press molding, a release PET film (100 μm thick, manufactured by Toray, trade name Lumirror) was used as a release film.

[0291] [ haze (transparency)]

[0292] The haze was measured using a 2 mm thick sheet obtained by press molding, using a digital haze meter "NDH-20D" manufactured by Nippon Denshoku Industries Co., Ltd., in accordance with JIS K 7136.

[0293] [Example 1]

[0294] The 1-butene-ethylene copolymer (A-1) obtained in Manufacturing Example 1 was press-molded using the method described above, and the physical properties of the resulting molded body were measured using the method described above.

[0295] The results are shown in Table 2.

[0296] [Examples 2-15, Comparative Example 1]

[0297] Using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.), the polymer was mixed for 5 minutes at 200°C and 40 rpm in the proportions (mass%) listed in Table 2 to obtain a 1-butene-based polymer composition. The obtained composition was then press-molded using the method described above, and the physical properties of the resulting molded articles were determined using the method described above.

[0298] The results are shown in Table 2.

[0299] [Table 2]

[0300] Table 2

[0301]

[0302] The following shows the ingredients used in Examples 16, 17 and Comparative Example 2.

[0303] [Adhesive]

[0304] Alicyclic saturated hydrocarbon resin: manufactured by Arakawa Chemical Industry Co., Ltd., trade name ARKON P-115

[0305] [Basic Polymer (Z)]

[0306] Base polymer (Z1): Trade name RT2730 manufactured by REXtac LLC. (melt viscosity at 190°C is 4,000 mPa·s)

[0307] [Antioxidants]

[0308] Phenolic antioxidant: Ciba Specialty Chemicals Corporation, trade name Irganox 1010

[0309] The evaluation of the hot melt adhesive compositions used in Examples 16, 17 and Comparative Example 2 was carried out by the following methods.

[0310] [Experimental film preparation method]

[0311] Using a hot melt adhesive gun (TR-60LCD) manufactured by REKA Klebetechnik Co., the hot melt adhesive composition was charged into a tank and melted at 180°C for 10 minutes or more.

[0312] 〔Adhesive strength〕

[0313] The obtained hot melt adhesive composition was applied to a 400-μm-thick polypropylene sheet in bead form, and the polypropylene sheets were adhered after standing for a prescribed period of time (1 minute / 10 minutes) at room temperature, and a load of 400 g was applied for 1 day, whereby the polypropylene sheets were adhered to each other. Then, the adhered sheets were cut into 15-mm-wide long strips to produce test pieces. The test pieces were subjected to T-type peel test at a measurement temperature of 23°C, and the adhesive strength was measured (tensile speed: 50 mm / min).

[0314] 〔Adhesive area〕

[0315] The area of the portion where the adhesive of the test piece produced by the above-described method was in close contact with the polypropylene sheet was taken as the adhesive area.

[0316] 〔Open time〕

[0317] The open time was evaluated using the adhesive area and the retention rate of the adhesive strength for the test pieces whose adhesive strength was measured as described above. Note that the retention rate was calculated based on Equation (1) using the adhesive area and the adhesive strength of the test pieces adhered after 1 minute and 10 minutes after application.

[0318] a: Adhesive area (adhesive strength) of the test piece adhered after 1 minute after application

[0319] b: Adhesive area (adhesive strength) of the test piece adhered after 10 minutes after application

[0320] (Equation 1): Retention rate = b / a x 100 [%]

[0321] 〔B-type viscosity (180°C)〕

[0322] The B-type viscosity at 180°C was measured using a B-type viscometer (DVII+PRO RV) manufactured by Brookfield Co.

[0323] 〔Softening temperature (ring and ball method)〕

[0324] For the adhesive composition, the hot melt adhesive composition was melted using an iron plate heated to 230°C, and then, a disc-shaped pressure sheet was produced by cooling and pressing for 5 minutes.

[0325] The softening temperature was measured by the ring and ball method using a softening temperature measuring device (ASP-MG type) manufactured by MEITECH Co.

[0326] [Examples 16, 17, Comparative Example 2]

[0327] In a separable flask with a volume of 500 mL, the respective resins were sequentially added to the system in the proportions described in Table 3, while confirming that each resin had completely melted, using an anchor-type stirring blade, under a nitrogen atmosphere, at a heating temperature of 200°C, a kneading time of 40 minutes (the stage at which the APAO was added to the system was taken as the start of kneading), and a stirring speed in the system of 10 to 200 rpm, and the system was stirred under these conditions, thereby obtaining a hot-melt adhesive composition.

[0328] The hot-melt adhesive composition obtained was evaluated by the methods described above.

[0329] The results are shown in Table 3.

[0330] [Table 3]

[0331] Table 3

[0332]

[0333] The hot-melt adhesive composition obtained was evaluated by the methods described above.

[0334] The results are shown in Table 2.

[0335] [Examples 18 to 27 and Comparative Examples 3 to 4]

[0336] For the polymers described in Table 4, a Labo Plastomill (manufactured by Toyo Precision Machinery and Instrument Co., Ltd.) was used, and the polymers were kneaded for 5 minutes at 200°C and 40 rpm at the proportions (mass %) described in Table 4, thereby obtaining a 1-butene-based polymer composition. The composition obtained was subjected to press molding by the methods described above, and the physical properties of the molded body obtained were measured by the methods described above.

[0337] [Whitening Resistance Test]

[0338] A sheet having a thickness of 500 μm was produced using the obtained composition by heating for 5 minutes using an oil pressure type heat press molding machine set to 190°C, followed by molding under pressure of 10 MPa for 2 minutes, and then cooling under pressure of 10 MPa at 20°C for 4 minutes. A No. 2 dumbbell shape prescribed in JIS K 6251 was produced from the sheet, and the color phase (L value (before elongation)) before elongation and the color phase (L value (after elongation)) when elongated by 15 mm at a stretching speed of 50 mm / min were measured using a spectrophotometer (KONICA MINOLTA, INC. manufactured, CM-3700d), and the color phase change (ΔL) was calculated based on the following formula. In addition, the color phase change (ΔL) was similarly calculated using a sheet that had been heat treated at 85°C for 5 days. The smaller the ΔL value, the better the whitening resistance. The results are shown in Table 4.

[0339] ΔL = L value (after elongation) - L value (before elongation)

[0340] [Table 4]

[0341] Table 4

[0342]

[0343] [Examples 28 to 35]

[0344] A 1-butene-based polymer composition was obtained by the same procedure as in Example 18, using the raw materials in the proportions (parts by weight) described in Table 5, except that the raw materials were kneaded using a Labo Plastomill (manufactured by Toyo Precision Machinery & Instrument Co., Ltd.) at 200°C and 40 rpm for 5 minutes.

[0345] The obtained composition was pressure-molded by the method described above, and the physical properties of the obtained molded body were measured by the method described above, by the same procedure as in Example 18.

[0346] The results are shown in Table 5-1 and Table 5-2.

[0347] [Comparative Examples 5 to 6]

[0348] A propylene-based polymer composition was obtained by the same procedure as in Example 18, using the raw materials in the proportions (parts by weight) described in Table 5, except that the raw materials were kneaded using a Labo Plastomill (manufactured by Toyo Precision Machinery & Instrument Co., Ltd.) at 200°C and 40 rpm for 5 minutes.

[0349] The obtained composition was pressure-molded by the method described above, and the physical properties of the obtained molded body were measured by the method described above, by the same procedure as in Example 18.

[0350] The results are shown in Table 5-1 and Table 5-2.

[0351] <Melting point and melting enthalpy>

[0352] The melting point Tm (2nd) and the melting enthalpy ΔHfus (2nd) were measured by the measurement method described above.

[0353] Note that the strongest melting peak in the temperature range of 70°C to 170°C in the melting peak measured in the second temperature rise was taken as the melting point Tm (2nd), and the area of the melting peak in the aforementioned temperature range was taken as the melting enthalpy ΔH (2nd).

[0354] <Crystallization temperature and crystallization enthalpy>

[0355] The crystallization temperature Tc and the crystallization enthalpy ΔHc were measured by the measurement method described above. Note that the strongest crystallization peak in the temperature range of 50°C to 100°C in the crystallization peak measured in the first temperature decrease in the heat measurement using a differential scanning calorimeter (DSC) was taken as the crystallization temperature Tc, and the area of the crystallization peak in the aforementioned temperature range was taken as the crystallization enthalpy ΔHc.

[0356] <Yield point elongation>

[0357] The yield point elongation was measured in accordance with JIS K 6251 for the aforementioned test piece for mechanical properties (measurement temperature: 23°C, tensile speed = 50 mm / min).

[0358]

[0359]

[0360] [Examples 36 to 38 and Comparative Examples 7 to 8]

[0361] The 1-butene-based polymer compositions (X-2), (X-14) obtained in Examples 3, 15 were used, and the raw materials described in Table 6 were kneaded in the proportions (parts by weight) of Table 6 using an extruder (CIM-40mm) to produce a 100-μm-thick single-layer unstretched film by extruding the obtained pellets at 230°C using a cast film molding machine. The obtained single-layer unstretched film was evaluated as follows.

[0362] The results are shown in Table 6.

[0363] <Heat seal (HS) strength (before heat treatment)>

[0364] ​A test body was produced by sequentially stacking a Teflon (registered trademark) sheet having a thickness of 50 μm, the obtained single-layer unstretched film 2 pieces, and a Teflon (registered trademark) sheet having a thickness of 50 μm.

[0365] The heat-seal tester (TESTER SANGYO CO,. LTD., TB-701B) was set so that the heat-seal bar had a width of 15 mm and a length of 300 mm, the temperature on the lower side of the heat-seal bar was set to 70°C, and the temperature on the upper side of the heat-seal bar was set to 190°C. The aforementioned test body was sandwiched by the heat-seal bar, and heat-sealed for 1.0 seconds at a pressure of 0.2 MPa. Then, the two Teflon sheets were removed, and thus a laminated film was obtained. The laminated film was left to stand at 23°C for 1 day. A slit having a width of 15 mm was cut in the laminated film so as to include the heat-sealed portion, and the portion not heat-sealed was sandwiched by a tensile tester (INTESCO Co., Ltd., IM-20ST). The maximum load when the heat-sealed portion was peeled in the direction of 180° at a speed of 300 mm / minute was measured. This measurement was performed 5 times, and the average of the maximum loads was taken as the heat-seal strength.

[0366]

Claims

1. 1-Butene-ethylene copolymer (A) that satisfies the following requirements (A1) to (A5) and (A8): (A1) The content of structural unit (i) derived from 1-butene is in the range of 70 to 99.9 mol%, and the content of structural unit (ii) derived from ethylene is in the range of 0.1 to 30 mol%, wherein, Set the total of structural unit (i) and structural unit (ii) to 100 mol% %. (A2) Through 13 The isotactic five-unit component percentage (mmmm) calculated by C-NMR is in the range of 80-99.9%; (A3) The intrinsic viscosity [η] in decahydronaphthalene solvent at 135℃ is in the range of 0.7~2.0 dl / g; (A4) Melt flow rate (MFR) measured in accordance with ASTM D1238 at 190°C and 2.16 kg load, in the range of 1 to 100 g / 10 min; (A5) Using a differential scanning calorimeter (DSC), the temperature was increased from -70°C to 200°C at a heating rate of 20°C / min as the first heating. After holding at 200°C for 10 minutes, the temperature was decreased to -70°C at a cooling rate of 20°C / min as the first cooling. After holding at -70°C for 1 minute, the temperature was increased from -70°C to 200°C at a heating rate of 20°C / min as the second heating. No melting peak was observed during the second heating. (A8) The Shore D hardness, as determined by ASTM D2240, is in the range of 25 to 65.

2. The 1-butene-ethylene copolymer (A) as described in claim 1, wherein it satisfies any one or more of the following requirements (A6) to (A7); (A6) Weight-average molecular weight (Mw) is 100,000~400,000; (A7) The Shore A hardness, as determined by ASTM D2240, is in the range of 81 to 99. 3.1-Butene-based polymer composition comprising a 1-butene-ethylene copolymer (A) satisfying the following requirements (A1) to (A5) and (A8) and a propylene-based polymer (B) satisfying the following requirements (B1) and (B2). (A1) The content of structural unit (i) derived from 1-butene is in the range of 70 to 99.9 mol%, and the content of structural unit (ii) derived from ethylene is in the range of 0.1 to 30 mol%, wherein, Set the total of structural unit (i) and structural unit (ii) to 100 mol% %. (A2) Through 13 The isotactic five-unit component percentage (mmmm) calculated by C-NMR is in the range of 80-99.9%; (A3) The intrinsic viscosity [η] in decahydronaphthalene solvent at 135℃ is in the range of 0.7~2.0 dl / g; (A4) Melt flow rate (MFR) measured in accordance with ASTM D1238 at 190°C and 2.16 kg load, in the range of 1 to 100 g / 10 min; (A5) Using a differential scanning calorimeter (DSC), the temperature was increased from -70°C to 200°C at a heating rate of 20°C / min as the first heating. After holding at 200°C for 10 minutes, the temperature was decreased to -70°C at a cooling rate of 20°C / min as the first cooling. After holding at -70°C for 1 minute, the temperature was increased from -70°C to 200°C at a heating rate of 20°C / min as the second heating. No melting peak was observed during the second heating. (A8) The Shore D hardness, as determined by ASTM D2240, is in the range of 25 to 65; (B1) The melting point determined using a differential scanning calorimeter is in the range of 100~170℃; (B2) The percentage of isotactic five-unit components is in the range of 90-99.9%.

4. The 1-butene polymer composition according to claim 3, wherein it satisfies the following requirement (X4). (X4) The Shore D hardness, as determined by ASTM D2240, is in the range of 20 to 80.

5. The 1-butene-based polymer composition according to claim 4, wherein, The Shore D hardness of the 1-butene polymer composition, as determined according to ASTM D2240, is in the range of 20 to 43.

6. The 1-butene-based polymer composition of claim 4, wherein, The Shore D hardness of the 1-butene polymer composition, as determined according to ASTM D2240, is in the range of 44 to 80.

7. The 1-butene-based polymer composition according to any one of claims 3 to 6, wherein the following requirement (X2) is satisfied: (X2) Using a differential scanning calorimeter (DSC), the temperature was increased from -70°C to 200°C at a heating rate of 20°C / min as the first heating. After holding at 200°C for 10 minutes, the temperature was decreased to -70°C at a cooling rate of 20°C / min as the first cooling. After holding at -70°C for 1 minute, the temperature was increased from -70°C to 200°C again at a heating rate of 20°C / min as the second heating. The first peak, which is the melting peak, generated during the second heating was above 20°C and below 100°C, and the second peak, which is the melting peak, was in the range of 100°C to 170°C.

8. The 1-butene polymer composition according to any one of claims 3 to 6, wherein it satisfies the following requirement (X1-1): The content of (X1-1)1-butene-ethylene copolymer (A) is in the range of 63-99% by mass, and the content of propylene polymer (B) is in the range of 1-37% by mass, wherein, The total mass of 1-butene-ethylene copolymer (A) and propylene polymer (B) is set to 100.

9. The 1-butene polymer composition according to any one of claims 3 to 6, wherein it satisfies the following requirements (X1-2): The content of (X1-2)1-butene-ethylene copolymer (A) is in the range of 62-1% by mass, and the content of propylene polymer (B) is in the range of 38-99% by mass, wherein, The total mass of 1-butene-ethylene copolymer (A) and propylene polymer (B) is set to 100.

10. The 1-butene-based polymer composition according to any one of claims 3, 4 or 6, comprising an ethylene-based polymer (C).

11. The 1-butene-based polymer composition of claim 10, wherein, The ethylene polymers (C) include one or more selected from the group consisting of high-pressure low-density polyethylene (C1) and ethylene-α-olefin copolymers (C2).

12. The 1-butene-based polymer composition of claim 10, wherein the following requirements (X1-3) are satisfied: The content of (X1-3)1-butene-ethylene copolymer (A) is 1~50% by mass. The content of propylene polymer (B) is 30-98% by mass. The content of ethylene polymers (C) is 1-20% by mass. in, The total mass of 1-butene-ethylene copolymer (A), propylene polymer (B), and ethylene polymer (C) is set to 100.

13. The 1-butene-based polymer composition according to any one of claims 3 to 6, wherein, The melting enthalpy ΔHfus of the 1-butene polymer composition derived from the propylene polymer (B), as determined by differential scanning calorimetry (DSC) during the second heating, is 5~100 J / g.

14. The 1-butene-based polymer composition according to any one of claims 3 to 6, wherein, The haze of the 1-butene polymer composition, as determined according to JIS K 7136, is less than 50%.

15. The 1-butene-based polymer composition according to any one of claims 3 to 6, wherein, The Shore D hardness of the 1-butene polymer composition, as determined according to ASTM D2240, is in the range of 40 to 80.

16. Granules containing the 1-butene-ethylene copolymer (A) according to claim 1 or 2, or granules containing the 1-butene polymer composition according to any one of claims 3 to 15.

17. A hot melt adhesive comprising the 1-butene-ethylene copolymer (A) according to claim 1 or 2, or the 1-butene polymer composition according to any one of claims 3 to 15.

18. An automotive component selected from interior trim components and exterior trim components, said automotive component comprising the hot melt adhesive of claim 17.

19. A membrane comprising the 1-butene-ethylene copolymer (A) according to claim 1 or 2, or the 1-butene polymer composition according to any one of claims 3 to 15.

20. A nonwoven fabric comprising the 1-butene-ethylene copolymer (A) as described in claim 1 or 2, or the 1-butene polymer composition as described in any one of claims 3 to 15.

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