Propylene polymer composition and molded article

Abstract

To provide a propylene-based polymer composition having a biomass degree of 8.4-49% and providing a molded article which contains biomass polyethylene and nonetheless is excellent in rigidity and unbroken, and a molded article.SOLUTION: A propylene-based polymer composition is provided which contains 100 pts.wt. in total, namely: 51-90 pts.wt. of a propylene-based (co) polymer (a) satisfying the conditions of (H-i) to (H-v); and 10-49 pts.wt. of biomass polyethylene (b) satisfying the conditions of (L-i) and has a biomass degree of 8.4-49%. (H-i) a metallocene-based propylene independent polymer or a metallocene- based propylene-α-olefin copolymer having a α-olefin content of less than 1 wt.%; (H-ii) an MFR is 0.5-100 g / 10 minutes; (H-iii) a melting peak temperature Tm is 135-165°C; (H-iv) a molecular weight distribution (a weight average molecular weight / a number average molecular weight) is 1.5-4.0; (H-v) a volatile component content is 50 weight ppm or less; and (L-i) low density polyethylene or linear low density polyethylene.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a propylene-based polymer composition having a biomass content of 8.4 to 49% and a molded article thereof, and more particularly to a propylene-based polymer composition that gives a molded article having excellent rigidity and no cracking even when it contains biomass polyethylene. In the present invention, "crackable" means that it breaks into several parts when a force is applied. Furthermore, "not crackable" means any of the following: (1) It does not split into several parts without splitting (cracks). (2) A fissure (crack) forms, but it does not separate into several parts. [Background technology]

[0002] Propylene-based resins are characterized by their excellent rigidity, heat resistance, moldability, transparency, and chemical resistance, and are therefore widely used in a variety of applications, including various industrial materials, automobile-related parts, various medical and cosmetic containers, daily necessities, films, and fibers. Meanwhile, environmental pollution caused by plastics has become a problem in recent years, and how to address this issue is a challenge. One solution is to use carbon-neutral plant-derived plastics (biomass plastics). Plant-derived polypropylene has also been considered, but is not currently on the market, and the addition of biomass polyethylene to polypropylene is being investigated (see, for example, Patent Documents 1 and 2).

[0003] However, a mixture obtained by mixing polypropylene and biomass polyethylene and then melt-kneading them has poor miscibility, and molded articles obtained from the mixture tend to crack. For this reason, there is a demand for a polypropylene composition that has excellent miscibility even when containing biomass polyethylene. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2019-34519 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-27171 Summary of the Invention [Problem to be solved by the invention]

[0005] In view of the situation of the prior art, an object of the present invention is to provide a propylene-based polymer composition having a biomass content of 8.4 to 49%, which gives molded articles that are excellent in rigidity and do not crack even when containing biomass polyethylene, and a molded article thereof. [Means for solving the problem]

[0006] The present inventors have conducted extensive research and have found a propylene-based polymer composition having a biomass content of 8.4 to 49%, which, when used with a specific propylene-based polymer mixture, gives molded articles that are excellent in rigidity and do not crack even when containing biomass polyethylene, and a molded article thereof, thereby completing the present invention. That is, the present invention provides a propylene-based polymer composition having a biomass degree of 8.4 to 49% as follows, and a molded article thereof.

[0007] [1] A propylene-based polymer composition containing 51 to 90 parts by weight of a propylene-based (co)polymer (a) satisfying the following conditions (Hi) to (Hv) and 10 to 49 parts by weight of a biomass polyethylene (b) satisfying the following condition (Li), the total amount being 100 parts by weight, and having a biomass content of 8.4 to 49%. (Hi) A metallocene-based propylene homopolymer or a metallocene-based propylene copolymer consisting of propylene and an α-olefin content of less than 1% by weight. (H-ii) The melt flow rate (hereinafter sometimes abbreviated as MFR) according to JIS K7210 (230°C, 2.16 kg load) is in the range of 0.5 to 100 g / 10 min. (H-iii) The melting peak temperature (Tm) is in the range of 135 to 165°C. (H-iv) The molecular weight distribution (weight average molecular weight / number average molecular weight) is in the range of 1.5 to 4.0. (Hv) The content of volatile components is 50 ppm by weight or less. (Li) Low density polyethylene or linear low density polyethylene. [2] A propylene-based polymer composition containing 0.01 to 0.6 parts by weight of a nucleating agent based on 100 parts by weight of the propylene-based polymer composition according to [1]. [3] A molded article obtained using the propylene polymer composition according to [1] or [2]. [Effects of the Invention]

[0008] Molded articles produced using the propylene-based polymer composition of the present invention having a biomass content of 8.4 to 49% contribute to reducing environmental impact and are useful because they provide molded articles that are excellent in rigidity and do not crack even when they contain biomass polyethylene. In particular, injection-molded articles are very useful. [Brief explanation of the drawings]

[0009] [Figure 1] Figure 1 shows the cracking test in the MD and TD directions, which is carried out by making cuts in an injection test piece measuring 120 mm x 120 mm x 2 mm. DETAILED DESCRIPTION OF THE INVENTION

[0010] The propylene-based polymer composition of the present invention contains 51 to 90 parts by weight of a propylene-based (co)polymer (a) satisfying the following conditions (Hi) to (Hv) and 10 to 49 parts by weight of a biomass polyethylene (b) satisfying the following condition (Li), totaling 100 parts by weight, and is a propylene-based polymer composition having a biomass degree of 8.4 to 49%, which contributes to reducing environmental load and is characterized by not decreasing performance. (Hi) A metallocene-based propylene homopolymer or a metallocene-based propylene copolymer consisting of propylene and an α-olefin content of less than 1% by weight. (H-ii) The melt flow rate (MFR) according to JIS K7210 (230°C, 2.16 kg load) is in the range of 0.5 to 100 g / 10 min. (H-iii) The melting peak temperature (Tm) is in the range of 135 to 165°C. (H-iv) The molecular weight distribution (weight average molecular weight / number average molecular weight) is in the range of 1.5 to 4.0. (Hv) The content of volatile components is 50 ppm by weight or less. (Li) Low density polyethylene or linear low density polyethylene. The propylene polymer composition and molded article of the present invention will be described in detail below.

[0011] [1] Components constituting the propylene polymer composition (1) Propylene (co)polymer (a)

[0012] (i) α-olefin of propylene (co)polymer (a) The propylene (co)polymer (a) used in the propylene polymer composition of the present invention is preferably a metallocene-based propylene homopolymer, a metallocene-based propylene copolymer comprising propylene and an α-olefin in an amount of less than 1% by weight, or a mixture thereof. The propylene-based (co)polymer (a) is preferably a homopolymer from the viewpoint of rigidity, and is preferably a random copolymer composed of propylene and an α-olefin from the viewpoint of transparency. The α-olefin used for copolymerization includes α-olefins having 2 to 20 carbon atoms excluding propylene, such as ethylene, 1-butene, 1-hexene, and 1-octene. One or more α-olefins may be used as copolymerized with propylene. Among these, ethylene and 1-butene are preferred. Ethylene is more preferred. These propylene-based polymers may be used in combination. From the viewpoint of rigidity, it is preferred that the α-olefin content is less than 1% by weight.

[0013] Specific examples of the propylene copolymer include binary or ternary copolymers in which small amounts of any comonomer are combined, such as propylene-ethylene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, and propylene-1-butene-1-octene copolymer.

[0014] The α-olefin content of the propylene (co)polymer (a) is preferably less than 1 wt%, more preferably less than 0.8 wt%, and even more preferably less than 0.5 wt%. When the α-olefin content is less than 1 wt%, the rigidity is improved and there is no risk of deformation when the containers are stacked. Here, the contents of propylene and α-olefin are determined under the following conditions: 13 This is a value measured by the C-NMR method. Equipment: JEOL-GSX270 manufactured by JEOL Ltd. Concentration: 300mg / 2mL Solvent: orthodichlorobenzene

[0015] (ii) Melt flow rate (MFR) of propylene (co)polymer (a) The propylene (co)polymer (a) used in the present invention has a melt flow rate (MFR) in the range of 0.5 to 100 g / 10 min, preferably 5 to 60 g / 10 min, and more preferably 10 to 40 g / 10 min, according to JIS K7210 (230°C, 2.16 kg load). A melt flow rate (MFR) of 0.5 g / 10 min or more improves molding processability, resulting in a satisfactory product. On the other hand, a MFR of 100 g / 10 min or less improves mechanical strength. The melt flow rate (MFR) can be easily adjusted by adjusting the temperature and pressure, which are the polymerization conditions for the propylene (co)polymer (a), or by controlling the amount of hydrogen added in a method in which a chain transfer agent such as hydrogen is added during polymerization.

[0016] (iii) Stereoregularity of the propylene (co)polymer (a) When the propylene (co)polymer (a) used in the present invention is a propylene homopolymer, the isotactic pentad fraction is preferably 0.90 or more, more preferably 0.94 to 0.98. When the isotactic pentad fraction is 0.90 or more, the rigidity can be satisfactory. Here, the isotactic pentad fraction is 13 This is a value measured by the proton decoupling method using C-NMR.

[0017] (iv) Catalyst for Propylene (Co)polymer (a) The propylene-based (co)polymer (a) used in the present invention is a polymer produced using a metallocene catalyst as a polymerization catalyst. The use of a metallocene catalyst makes the polymer less likely to crack when containing biomass polyethylene (b).

[0018] The metallocene-based propylene homopolymer is a propylene homopolymer obtained by homopolymerizing propylene using a metallocene catalyst. The metallocene-based propylene copolymer is a propylene copolymer obtained by copolymerizing propylene as the main component and ethylene as an α-olefin using a metallocene catalyst.

[0019] The metallocene catalyst is preferably a supported type. A particularly preferred example of the supported metallocene catalyst is an ion-exchanged layered silicate in which the support also functions as a co-catalyst, which is obtained by combining the following components [A], [B], and, if necessary, the component [C].

[0020] Component [A] Metallocene complex Transition metal compounds of groups 4-6 of the periodic table containing at least one conjugated five-membered ring ligand ·Component [B] Promoter Ion-exchange layered silicate Component [C] Organoaluminum compound

[0021] Component [A] Metallocene complex Specifically, the compound represented by the following formula [I] can be used as the component [A]. Q(C5H 4-a R 1 a )(C5H 4-b R 2 b )MXY ···[I] In formula [I], Q represents a linking group that bridges two conjugated five-membered ring ligands. M represents a transition metal of Groups 4 to 6 of the periodic table, and among these, titanium, zirconium and hafnium are preferred. X and Y each independently represent hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms.

[0022] R 1 and R 2 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, a halogen, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an aryloxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, or a boron-containing hydrocarbon group. 1 or two R 2 are bonded to C4~C 10 It may form a ring, and it is particularly preferred that a six-membered ring or a seven-membered ring is formed, and that this, together with the above-mentioned conjugated five-membered ring, forms an indene ring or an azulene ring. a and b are integers satisfying 0≦a≦4 and 0≦b≦4. Examples of the bonding group Q that bridges two conjugated five-membered ring ligands include an alkylene group, an alkylidene group, a silylene group, and a germylene group. These may have hydrogen atoms substituted with alkyl groups, halogens, etc. A silylene group is particularly preferred.

[0023] Specific preferred examples of the metallocene complex include the following compounds: (1) Methylenebis(cyclopentadienyl)zirconium dichloride (2) Methylene(cyclopentadienyl)(3,4-dimethylcyclopentadienyl)zirconium dichloride (3) Isopropylidene(cyclopentadienyl)(3,4-dimethylcyclopentadienyl)zirconium dichloride (4) Ethylene(cyclopentadienyl)(3,5-dimethylpentadienyl)zirconium dichloride (5) Methylenebis(indenyl)zirconium dichloride (6) Ethylenebis(2-methylindenyl)zirconium dichloride (7) Ethylene 1,2-bis(4-phenylindenyl)zirconium dichloride (8) Ethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride

[0024] (9) Dimethylsilylene(cyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dichloride (10) Dimethylsilylenebis(indenyl)zirconium dichloride (11) Dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride (12) Dimethylsilylene(cyclopentadienyl)(fluorenyl)zirconium dichloride (13) Dimethylsilylene(cyclopentadienyl)(octahydrofluorenyl)zirconium dichloride (14) Methylphenylsilylenebis[1-(2-methyl-4,5-benzo(indenyl)]zirconium dichloride (15) Dimethylsilylenebis[1-(2-methyl-4,5-benzoindenyl)]zirconium dichloride (16) Dimethylsilylenebis[1-(2-methyl-4H-azulenyl)]zirconium dichloride (17) Dimethylsilylenebis[1-(2-methyl-4-(4-chlorophenyl)-4H-azulenyl)]zirconium dichloride (18) Dimethylsilylenebis[1-(2-ethyl-4-(4-chlorophenyl)-4H-azulenyl)]zirconium dichloride (19) Dimethylsilylenebis[1-(2-ethyl-4-naphthyl-4H-azulenyl)]zirconium dichloride

[0025] (20) Diphenylsilylenebis[1-(2-methyl-4-(4-chlorophenyl)-4H-azulenyl)]zirconium dichloride (21) Dimethylsilylenebis[1-(2-methyl-4-(phenylindenyl))]zirconium dichloride (22) Dimethylsilylenebis[1-(2-ethyl-4-(phenylindenyl))]zirconium dichloride (23) Dimethylsilylenebis[1-(2-ethyl-4-naphthyl-4H-azulenyl)]zirconium dichloride (24) Dimethylgermylenebis(indenyl)zirconium dichloride (25) Dimethylgermylene(cyclopentadienyl)(fluorenyl)zirconium dichloride In addition, the same compounds as those mentioned above are also preferred as other transition metal compounds of Groups 4, 5 and 6, such as titanium compounds and hafnium compounds. These compounds may be used in combination with the catalyst component and catalyst of the present invention.

[0026] Component [B] Co-catalyst (ion-exchange layered silicate) The ion-exchangeable layered silicate is not limited to a natural product, but may also be an artificially synthesized product. Clay compounds can be used as the ion-exchangeable layered silicate, and specific examples of clay compounds include the following layered silicates described in "Clay Mineralogy" by Haruo Shiramizu, Asakura Shoten (1995): (A) Kaolin group, such as dickite, nacrite, kaolinite, anoxite, metahalloysite, and halloysite, whose main constituent layers are 1:1 type structures; serpentine group, such as chrysotile, lisardite, and antigorite (a) Smectite group such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, etc., vermiculite group such as vermiculite, mica group such as mica, illite, sericite, glauconite, attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, chlorite group, which have a 2:1 type structure as their main constituent layer.

[0027] The silicate used in the present invention may be a layered silicate having a mixed layer of the above (a) and (b). In the present invention, the silicate as the main component is preferably a silicate having a 2:1 type structure, more preferably a smectite group silicate, and particularly preferably montmorillonite.

[0028] The activity of these silicates can be improved by chemically treating them with an acid, a salt, an alkali, an oxidizing agent, a reducing agent, an organic solvent, or the like. The acid treatment removes impurities on the surface of the ion-exchange layered silicate particles, exchanges interlayer cations, and also dissolves some or all of the cations such as Al, Fe, and Mg in the crystal structure. The acid used in the acid treatment includes hydrochloric acid, nitric acid, sulfuric acid, etc., but inorganic acids are preferred, and sulfuric acid is particularly preferred. There are no particular restrictions on the acid treatment conditions, but the preferred conditions are a 5 to 50 wt % aqueous acid solution reacted at a temperature of 60 to 100°C for 1 to 24 hours, with the acid concentration being variable during the reaction. After the acid treatment, washing is usually performed. Washing is an operation for separating and removing the acid contained in the treatment system from the ion-exchanged layered silicate.

[0029] The salts used in the salt treatment are preferably selected to contain specific cations, preferably monovalent to tetravalent metal cations, and more preferably Li, Ni, Zn, or Hf cations. Specific examples of salts include the following: Examples of those with a Li cation include LiCl, LiBr, Li2SO4, Li3(PO4), Li(ClO4), Li2(C2O4), LiNO3, Li(OOCCH3), and Li2(C4H4O4). Examples of those with a Ni cation include NiCO3, Ni(NO3)2, NiC2O4, Ni(ClO4)2, NiSO4, NiCl2, and NiBr2. Examples of compounds with a Zn cation include Zn(OOCH3)2, Zn(CH3COCHCOCH3)2, ZnCO3, Zn(NO3)2, Zn(ClO4)2, Zn3(PO4)2, ZnSO4, ZnF2, ZnCl2, ZnBr2, and ZnI2. Examples of compounds with a cation of Hf include Hf(OOCCH3)4, Hf(CO3)2, Hf(NO3)4, Hf(SO4)2, HfOCl2, HfF4, HfCl4, HfBr4, and HfI4.

[0030] After the chemical treatment, drying is carried out. Generally, drying can be carried out at a temperature of 100 to 800°C, and high temperature conditions that cause structural destruction (for example, 800°C or higher, although this depends on the heating time) are not preferred. Even if the structure is not destroyed, the properties change depending on the drying temperature, so it is preferable to change the drying temperature depending on the application. The drying time is usually 1 minute to 24 hours, preferably 5 minutes to 4 hours, and the atmosphere is dry air, dry nitrogen, dry argon, or under reduced pressure. There are no particular limitations on the drying method, and various methods can be used.

[0031] Component [C] Organoaluminum compound The organoaluminum compound of component [C] is a component that is optionally used as needed, and is most preferably a compound represented by the following formula [II]: (AlR 4 p X 3-p ) q [II] In formula [II], R 4 represents a hydrocarbon group having 1 to 20 carbon atoms, and X represents a halogen, hydrogen, an alkoxy group, or an amino group. p is an integer of 1 to 3, and q is an integer of 1 or 2. R 4 is preferably an alkyl group, and when X is an alkoxy group, it is preferably an alkoxy group having 1 to 8 carbon atoms, and when X is an amino group, it is preferably an amino group having 1 to 8 carbon atoms. Among these, preferred are trialkylaluminums where p=3 and q=1 and dialkylaluminum hydrides where p=2 and q=1. More preferred are R 4 is a trialkylaluminum having 1 to 8 carbon atoms.

[0032] The organoaluminum compounds can be used alone or in combination, and can be added not only during catalyst preparation but also during prepolymerization or main polymerization.

[0033] (v) Production method of propylene (co)polymer (a) Examples of the method for producing the propylene (co)polymer (a) include a slurry polymerization method using an inert solvent in the presence of the catalyst, a solution polymerization method, a gas phase polymerization method using substantially no solvent, and a bulk polymerization method using a polymerizable monomer as a solvent. For example, in the case of a slurry polymerization method, the polymerization can be carried out in an inert hydrocarbon or liquid monomer such as n-butane, isobutane, n-pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, or xylene. The polymerization temperature is usually -80 to 150°C, preferably 40 to 120°C. The polymerization pressure is preferably 1 to 60 atmospheres (0.10 to 6.08 MPa), and the molecular weight of the resulting propylene (co)polymer (a) can be adjusted with hydrogen or other known molecular weight modifiers. The polymerization can be carried out by a continuous or batch reaction, and the conditions may be those usually used. Furthermore, the polymerization reaction may be carried out in one stage or multiple stages. It is desirable to carry out a prepolymerization treatment before carrying out the main polymerization. As the monomer to be subjected to the prepolymerization, an α-olefin such as ethylene, propylene, 1-butene, 1-hexene, etc., a diene compound such as 1,3-butadiene, etc., or a vinyl compound such as styrene, divinylbenzene, etc. can be used. This prepolymerization is preferably carried out in an inert solvent under mild conditions, and is desirably carried out so that 0.01 to 1,000 g, preferably 0.1 to 100 g, of polymer is produced per 1 g of solid catalyst (total of component [A] and component [B]).

[0034] The polymerization reaction is carried out in the presence or absence of a solvent such as an inert hydrocarbon such as butane, pentane, hexane, heptane, toluene, or cyclohexane, or a liquefied α-olefin. In the present invention, it is desirable to maximize the amount of polymer produced per solid catalyst (if the solid catalyst has been prepolymerized, this does not include the polymer produced by the prepolymerization). In order to increase the amount of polymer produced, it is desirable to set both the polymerization temperature and polymerization pressure relatively high.

[0035] Typically, the polymerization temperature is selected from 60 to 90°C, and the polymerization pressure is selected from about 1.5 to 4 MPa. In particular, in the case of bulk polymerization, the polymerization temperature is preferably 60 to 80°C, and the polymerization pressure is preferably selected from about 2.5 to 4 MPa in correlation with the temperature. On the other hand, in the case of gas-phase polymerization, the polymerization temperature is preferably 70 to 90°C, and the polymerization pressure is preferably selected from about 1.5 to 4 MPa. Furthermore, the polymer production amount per solid catalyst can be increased by increasing the residence time of the solid catalyst, but if it is too long, productivity will be affected. The residence time is preferably 1 to 8 hours, more preferably 1 to 6 hours. It is desirable to set the polymerization conditions so that the polymer production amount per 1 g of solid catalyst including the carrier is 20 kg or more, preferably 25 kg or more, more preferably 30 kg or more. Hydrogen may be present in the polymerization system as a molecular weight modifier. Furthermore, the polymerization may be carried out in multiple stages by changing the polymerization temperature, the concentration of the molecular weight modifier, etc.

[0036] In the present invention, after the polymerization is completed, the resulting propylene (co)polymer (a) is preferably washed with an inert saturated hydrocarbon solvent such as propane, butane, pentane, hexane, or heptane, or a liquid α-olefin, more preferably with an inert hydrocarbon solvent having 3 or 4 carbon atoms or a liquid α-olefin. The washing method is not particularly limited, and known methods such as decantation of the supernatant after contact treatment in a stirring tank, countercurrent washing, and separation from the washing liquid using a cyclone can be used. A deactivator may be added before or at the same time as washing. The deactivator is not particularly limited, and examples thereof include water, alcohols such as methanol, ethanol, and isopropanol, ketones such as acetone and methyl ethyl ketone, and mixtures thereof.

[0037] (vi) Melting peak temperature (Tm) The melting peak temperature (Tm) of the propylene (co)polymer (a) used in the present invention is in the range of 135 to 165°C. When the melting peak temperature (Tm) is 135°C or higher, the rigidity and moldability are good, and when it is 165°C or lower, the impact resistance is good. The melting peak temperature (Tm) is preferably 138 to 160°C, more preferably 140 to 155°C. Specifically, the melting peak temperature (Tm) is measured using a differential scanning calorimeter (DSC). A 5 mg sample is taken, held at 200°C for 5 minutes, crystallized at a temperature drop rate of 10°C / min to 40°C, and then melted at a temperature increase rate of 10°C / min. The peak position of the curve drawn when the sample is heated is taken as the melting peak temperature Tm (°C). (vii) Molecular weight distribution (Mw / Mn) and weight average molecular weight (Mw) of propylene (co)polymer (a) The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the propylene (co)polymer (a) used in the present invention, as determined by gel permeation chromatography (GPC), is in the range of 1.5 to 4.0. The lower limit of the molecular weight distribution is preferably 1.8 or more, more preferably 2.0 or more, and the upper limit is preferably 3.5 or less, more preferably 3.0 or less. A lower limit of the molecular weight distribution of 1.5 or more is preferable because it broadens the range of conditions for producing and purifying the propylene (co)polymer (a), thereby improving production efficiency. On the other hand, an upper limit of 4.0 or less indicates that the molecular chain length is very uniform, and is preferable because it reduces the content of relatively low molecular weight components such as unreacted monomers, dimers, low molecular weight compounds, amorphous components, and oligomers, which are thought to cause the generation of volatile components.

[0038] The weight-average molecular weight (Mw) of the propylene (co)polymer (a) used in the present invention is preferably in the range of 100,000 to 600,000. When the weight-average molecular weight Mw is 600,000 or less, molding is easy. On the other hand, when the weight-average molecular weight Mw is 100,000 or more, the amount of low-crystalline components is reduced, mold contamination, bleed-out, solvent elution, etc. are suppressed, and the impact resistance of molded articles is improved, which is practical.

[0039] (viii) Average elution temperature (T 50 ) and dissolution dispersion (σ) The average elution temperature (T 50 ) is preferably 90 to 105°C, and the dissolution dispersion (σ) is preferably 9°C or less. Here, the average elution temperature is a value based on the elution curve of the polymer obtained by temperature rising elution fractionation using o-dichlorobenzene as a solvent, and represents the temperature at which the cumulative mass of the eluted polymer reaches 50% by mass. The elution dispersity is the value of σ when the cumulative mass elution amount I(t) is defined as expressed by the following mathematical formula (1), assuming that the elution amount obtained by temperature rising elution fractionation follows a normal probability distribution with respect to the elution temperature.

[0040]

number

[0041] (vx) Volatile component content The volatile component content of the propylene (co)polymer (a) used in the present invention is 50 ppm by weight or less, and when it is 50 ppm by weight or less, it has good cleanliness and is less likely to crack when containing the biomass polyethylene (b), preferably 30 ppm by weight or less, more preferably 20 ppm by weight or less. The content of volatile components (amount of oligomers with 30 or less carbon atoms) generated from the propylene (co)polymer (a) is measured by dynamic headspace (DHS)-GC / MS. The content of volatile components is the ratio of the content of volatile components to the propylene (co)polymer (a) (unit: ppm by weight). The specific measurement method is shown below.

[0042] (A) Measurement and evaluation overview A powder sample of propylene (co)polymer (a) is heated to 100°C, and the volatile components generated are collected at -150°C. Each volatile component is then separated, detected, and identified using a gas chromatograph (GC) / mass spectrometer (MS). A calibration curve is created by preparing a standard mixed solution of aliphatic linear hydrocarbons, in increments of two carbon numbers from 10 to 32, in n-heptane at a concentration of 1000 μg / ml, and measuring the solution under the same conditions as the sample using gas chromatogram / mass spectrometry. Quantitative calculations are performed using n-eicosane as the standard.

[0043] (B) Apparatus and measurement method (A) Heat removal (dynamic headspace) device: Approximately 50 mg of a powder sample of propylene (co)polymer (a) was weighed and packed into a heated extraction tube (Gerstel TDS tube), and each end of the tube was filled with approximately 10 mg of quartz wool (GL Sciences, Cat. No. 3001-12404). The TDS tube was then placed in a heated extraction apparatus (Gerstel TDS-A) at 40°C. The tube was then purged with helium and heated to 100°C at a rate of 60°C / min. The tube was then heated at 100°C for 30 minutes. During this heating period, a GC injection port (Gerstel CIS4) filled with TENAX was cooled to -150°C to collect volatile components evolved from the sample. The collected components were vaporized by rapidly heating the collection section to 320°C and introduced into the GC column. (a) Gas chromatograph (GC): Agilent HP6890 Column: DB-5ms Column heating conditions: 40°C x 5 min - 10°C / min - 300°C x 15 min (c) Mass spectrometer (MS): Agilent Mass Sensitive Detector 5973N The electron impact (EI) method is used to ionize the components to be measured.

[0044] (2) Biomass polyethylene (b) Plant-derived ethylene, which is the raw material monomer for the biomass polyethylene (b) used in the present invention, can be obtained by fermenting plant materials such as sugarcane with microorganisms to produce ethanol, which is then heated in the presence of a catalyst to cause an intramolecular dehydration reaction. Biomass polyethylene (b) is a polymer obtained by polymerizing a monomer containing plant-derived ethylene as the main component. The raw material monomer for biomass polyethylene (b) does not have to contain 100% plant-derived ethylene. This is because environmental impact can be reduced by using plant-derived ethylene as part of the monomer. The biomass polyethylene (b) may be a homopolymer obtained by homopolymerizing plant-derived ethylene or a copolymer obtained by copolymerizing plant-derived ethylene with an α-olefin. The number of carbon atoms in the α-olefin is not particularly limited, but 1-butene, 1-hexene, or 1-octene is preferred. Furthermore, petroleum-derived ethylene may also be included.

[0045] (i) Biomass polyethylene (b) Polyethylene Examples of polyethylenes that can be used as the biomass polyethylene (b) include medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE). These polyethylenes can be used alone or in combination of two or more. The density of the medium density polyethylene is preferably 0.925 to 0.940 g / cm 3 This range is preferable because it improves rigidity. Among the above polyethylenes, it is preferable to use at least one of low-density polyethylene and linear low-density polyethylene, which will provide a sufficient transparency-improving effect. The density of the low-density polyethylene is preferably 0.910 to 0.920 g / cm 3 and more preferably 0.913 to 0.917 g / cm 3 The density is 0.910 g / cm 3If the density is 0.920 g / cm or more, the rigidity is improved, which is preferable. 3 If it is less than this, the transparency improving effect will be sufficient, which is preferable. The density of the linear low-density polyethylene is preferably 0.895 to 0.925 g / cm 3 and more preferably 0.900 to 0.917 g / cm 3 The density is 0.895g / cm 3 If the density is 0.925 g / cm or more, the rigidity is improved, which is preferable. 3 If it is less than this, the transparency improving effect will be sufficient, which is preferable.

[0046] The ratio of plant-derived carbon to the total carbon in biomass polyethylene (b) is called the bio-content. 14 This can be determined by measuring the concentration of C. In other words, there is a certain percentage of 14 C, while the carbon in petroleum-derived resins contains 14 Since it does not contain C, it is contained in biomass polyethylene (b). 14 The bio content can be calculated by measuring the concentration of C. Specifically, if all the carbon in biomass polyethylene (b) is derived from petroleum, the bio content will be 0%, and if all the carbon in biomass polyethylene (b) is derived from plants, the bio content will be 100%. 14 Test methods for measuring the concentration of C include ASTM D6866. The biomass polyethylene (b) preferably has a melt flow rate in the range of 0.21 to 72 g / 10 min according to ASTM D1238 (190° C., 2.16 kg load).

[0047] The weight proportion of the biomass polyethylene (b) used in the propylene-based polymer composition of the present invention is 10 to 49 parts by weight, preferably 15 to 40 parts by weight. When it is 10 parts by weight or more, an environmental load reduction effect can be expected, and when it is 49 parts by weight or less, sufficient rigidity of the product can be obtained. (Here, a propylene-based polymer composition containing 51 to 90 parts by weight of the propylene-based (co)polymer (a) and 10 to 49 parts by weight of the biomass polyethylene (b) is 100 parts by weight.) An example of such biomass polyethylene (b) is "Green PE" (trade name manufactured by Braskem).

[0048] (3) Biomass ratio The biomass ratio (%) in the present invention is a value calculated by the following formula. Biomass ratio (%) = [{A × (B ÷ 100)} / C] × 100 Formula (1) A: Weight of biomass polyethylene (b) B: Bio content of the bio-polyethylene used (%) C: Weight of propylene polymer composition The bio content (%) of the biomass polyethylene (b) can be measured and calculated according to ASTM D6866.

[0049] (4) Nucleating agent The propylene polymer composition of the present invention may contain preferably 0.01 to 0.6 parts by weight of a nucleating agent based on 100 parts by weight of the propylene polymer composition. Various common known nucleating agents can be used, such as sterically hindered amide compounds, metal salts of organic dicarboxylic acids, metal salts of organic monocarboxylic acids, sorbitol or its derivatives, nonitol or its derivatives, metal salts of diterpenic acids, or polymer nucleating agents. Among these, it is particularly preferable to contain a nucleating agent represented by the following formula (1) in order to achieve transparency.

[0050] [ka] ···(1) (wherein n is an integer of 0 to 2, and R 1 ~R 5 are each independently the same or different and represent hydrogen, halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, alkoxycarbonyl having 1 to 20 carbon atoms, or phenyl; R 6 is alkyl having 1 to 20 carbon atoms. Among the nucleating agents represented by formula (1), a representative commercially available product is Milad NX8000J (manufactured by Milliken & Company). Its chemical structural formula is shown below in formula (1-1). The molecular weight of this nucleating agent is 484. This substance is extremely stable both thermally and chemically, and has the excellent characteristic of hardly decomposing even at molding temperatures. This is highly desirable because it does not cause the problem of decomposition products bleeding out onto the surface of molded products and deteriorating their appearance.

[0051] [ka] (1-1)

[0052] The content of the nucleating agent represented by formula (1) contained in the propylene polymer composition of the present invention is preferably 0.1 to 0.6 parts by weight, more preferably 0.2 to 0.4 parts by weight, and even more preferably 0.3 to 0.4 parts by weight, relative to 100 parts by weight of the propylene polymer composition. When the content of the nucleating agent represented by formula (1) is 0.1 part by weight or more, rigidity and transparency can be expected to be exhibited, while when it is 0.6 part by weight or less, there is less concern about bleeding onto the surface of a molded article, which is advantageous in terms of cost-effectiveness (cost performance) in terms of rigidity and transparency and elution.

[0053] (5) Other additives In addition to the above-mentioned components, the propylene polymer composition of the present invention may contain additives such as various antioxidants used as stabilizers for propylene polymers, ultraviolet absorbers, light stabilizers, and neutralizers. Specifically, examples of the antioxidant include phosphorus-based antioxidants such as bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, di-stearyl-pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, tris(2,4-di-t-butylphenyl)phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene diphosphonite, and tetrakis(2,4-di-t-butyl-5-methylphenyl)-4,4'-biphenylene diphosphonite. antioxidants, phenolic antioxidants such as 2,6-di-t-butyl-p-cresol, tetrakis[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, and tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, and thio antioxidants such as di-stearyl-β,β'-thio-di-propionate, di-myristyl-β,β'-thio-di-propionate, and di-lauryl-β,β'-thio-di-propionate.

[0054] Examples of the ultraviolet absorber include 2-hydroxy-4-n-octoxybenzophenone, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole.

[0055] Light stabilizers include n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, 2,4-di-t-butylphenyl-3',5'-di-t-butyl-4'-hydroxybenzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl succinate-2-(4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl)ethanol condensate, poly{[6-[(1,1,3,3-tetramethylbutyl)acetate] and light stabilizers such as N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-triazine condensate.

[0056] Further examples include amine-based antioxidants represented by the following formula (2) or (3), which have good resistance to NOx gas discoloration, lactone-based antioxidants such as 5,7-di-t-butyl-3-(3,4-dimethyl-phenyl)-3H-benzofuran-2-one, and vitamin E-based antioxidants such as those represented by the following formula (4).

[0057] [ka] ···(2)

[0058] [ka] ···(3)

[0059] [ka] ···(4)

[0060] Examples of neutralizing agents include metal fatty acid salts such as calcium stearate, zinc stearate, and magnesium stearate, hydrotalcite (trade name: DHT-4A, a magnesium aluminum composite hydroxide salt represented by the following formula (5) manufactured by Kyowa Chemical Industry Co., Ltd.), Mizukalac (trade name, a lithium aluminum composite hydroxide salt represented by the following formula (6) manufactured by Mizusawa Chemical Industry Co., Ltd.), and the like. Mg 1-x Al x (OH)2(CO3) x / 2 ·mH2O …(5) [In the formula, x is 0 < x ≦ 0.5, and m is a number of 3 or less.] [Al2Li(OH)6] n X·mH2O …(6) [In the formula, X is an inorganic or organic anion, n is the valence of the anion (X), and m is 3 or less.]

[0061] Furthermore, other known various additives, such as antistatic agents, lubricants, dispersants such as fatty acid metal salts, dyes, pigments, etc., can be blended within the range that does not impair the object of the present invention.

[0062] Within the range that does not impair the properties, functions, and other characteristics of the propylene-based polymer composition of the present invention, other polymers other than the propylene-based (co)polymer (a) and biopolyethylene (b), polyethylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-1-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, acrylate polymer, such monoblock, diblock, and triblock copolymers can be arbitrarily added in amounts of 1 to 30 parts by weight based on 100 parts by weight of the propylene-based polymer composition. Similarly, it is also possible to blend elastomers such as natural rubber, butyl rubber, diene rubber, EPR, and EPDM. Furthermore, it is also possible to use general-purpose inorganic fillers such as talc, calcium carbonate, silica, alumina, gypsum, and mica in combination.

[0063] (6) Flexural modulus of the propylene-based polymer composition The flexural modulus of the propylene polymer composition used in the present invention is preferably in the range of 800 to 1500 MPa. When the flexural modulus is 800 MPa or more, the rigidity required to maintain the product characteristics and shape is obtained, and when it is 1500 MPa or less, the impact resistance is good. It is more preferably 1000 to 1500 MPa, even more preferably 1100 to 1450 MPa, and particularly preferably 1200 to 1400 MPa.

[0064] (7) Charpy impact strength of propylene polymer composition The Charpy impact strength of the propylene polymer composition used in the present invention is preferably 3.0 kJ / m 2 Charpy impact strength is 3.0kJ / m or more. 2 If the viscosity is 3.5 kJ / m or more, damage to the molded product during transportation is suppressed. 2 More preferably, it is 4.0 kJ / m or more. 2 That's all.

[0065] (8) Haze of Propylene Polymer Composition The haze of the propylene polymer composition used in the present invention at a product thickness of 2 mm is preferably 50% or less, and a haze of 50% or less improves the visibility of the contents and improves the design, more preferably 45% or less, and even more preferably 35% or less.

[0066] [2] Method for producing propylene polymer composition The propylene polymer composition of the present invention can be obtained by mixing predetermined amounts of the propylene (co)polymer (a), the biomass polyethylene (b), and, if necessary, other additives in a Henschel mixer (trade name), a super mixer, a ribbon blender, or the like, and then melt-kneading the mixture in a temperature range of 190 to 260°C using a conventional single-screw extruder, a twin-screw extruder, a Banbury mixer, a plavender, a roll, or the like.

[0067] [3] Molded products obtained using propylene polymer compositions To produce a molded article using the propylene polymer composition of the present invention, the propylene polymer composition is molded into a molded article having a desired shape by injection molding or the like. The uses of the molded articles are not particularly limited, but they can be used in a wide variety of applications, such as various industrial materials, automobile-related parts, various containers for medical and cosmetic use, daily necessities, films and fibers. [Example]

[0068] EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples and comparative examples, the physical properties of the propylene (co)polymer (a) and the propylene polymer composition were measured according to the following methods. <1. Measurement method>

[0069] (1) Melt flow rate (MFR): Measurement was performed in accordance with JIS K7210 (230°C, 2.16 kg load).

[0070] (2) Calculation of the ethylene content of propylene (co)polymer (a) 13 The ethylene-propylene random copolymer, the composition of which was verified by C-NMR, was used as the reference material. -1 The ethylene content in the random copolymer was measured by infrared spectroscopy using the characteristic absorption band of the following: The pellets were press-molded into a film of about 500 μm thickness.

[0071] (3) Measurement of molecular weight and molecular weight distribution: The molecular weight distribution Mw / Mn of the propylene (co)polymer (a) was calculated by measuring the weight average molecular weight Mw and the number average molecular weight Mn by gel permeation chromatography (GPC) under the following conditions: Apparatus: WATERS GPC (ALC / GPC 150C) Detector: FOXBORO MIRAN 1A IR detector (measurement wavelength: 3.42 μm) Column: Showa Denko AD806M / S (3 columns in series) Mobile phase solvent: ο-dichlorobenzene Measurement temperature: 140℃ Flow rate: 1.0ml / min Injection amount: 0.2ml

[0072] (4) Melting peak temperature (melting point) (Tm, unit: ° C.): Using a differential scanning calorimeter (DSC), a 5.0 mg sample was taken, the temperature was raised to 200°C to erase the thermal history, and then the sample was held at 200°C for 5 minutes. The temperature was then lowered to 40°C at a rate of 10°C / min to crystallize the sample, and the temperature was then raised again at a rate of 10°C / min to melt the sample. The temperature at the top of the endothermic peak was taken as the melting peak temperature (melting point) (Tm).

[0073] (5) Volatile component content The content of volatile components (amount of oligomers having 30 or less carbon atoms) generated from the propylene (co)polymer (a) was measured by dynamic headspace (DHS)-GC / MS. The content of volatile components is the ratio of the amount of volatile components generated to the propylene polymer (a) (unit: ppm by weight). The measurement method is shown below.

[0074] (A) Measurement and evaluation overview A powder sample of propylene (co)polymer (a) was heated to 100°C, and the volatile components evolved were collected at -150°C. Then, each volatile component was separated, detected, and identified using a gas chromatograph (GC) / mass spectrometer (MS). A calibration curve was created by measuring a standard mixture of aliphatic linear hydrocarbons, in increments of two carbon numbers from 10 to 32, at a concentration of 1000 μg / ml in n-heptane solvent under the same conditions as the sample, using gas chromatogram / mass spectrometry. Quantitative calculations were performed using n-eicosane as the standard.

[0075] (B) Apparatus and measurement method (A) Heat removal (dynamic headspace) device: Approximately 50 mg of a powder sample of propylene-based (co)polymer (a) was weighed and packed into a heated extraction tube (Gerstel TDS tube), and each end of the tube was filled with approximately 10 mg of quartz wool (GL Sciences, Cat. No. 3001-12404). The TDS tube was then placed in a heated extraction apparatus (Gerstel TDS-A) at 40°C. The tube was then purged with helium and heated to 100°C at a rate of 60°C / min. The tube was then heated at 100°C for 30 minutes. During this heating period, a GC injection port (Gerstel CIS4) filled with TENAX was cooled to -150°C to collect volatile components evolved from the sample. The collected components were vaporized by rapidly heating the collection section to 320°C and introduced into the GC column. (a) Gas chromatograph (GC): Agilent HP6890 Column: DB-5ms Column heating conditions: 40°C x 5 min - 10°C / min - 300°C x 15 min (c) Mass spectrometer (MS): Agilent Mass Sensitive Detector 5973N The components to be measured were ionized by electron impact (EI).

[0076] (6) Flexural modulus Measurement was carried out in accordance with JIS K7171.

[0077] (7) Charpy impact strength The Charpy impact strength at 23°C was measured in accordance with JIS K7111. (8) Haze value Measurement was carried out in accordance with JIS K7136 using a 2 mm thick sheet piece.

[0078] (9) Cracking test in MD and TD directions Test pieces measuring 120mm x 120mm x 2mm were injection molded (molding temperature: 200°C, mold temperature: 40°C), and a 3cm long cut was made in each piece with pruning shears to a width of 1.5cm as shown in Figure 1. The cut sections were then bent by hand, and the cracking was evaluated according to the following criteria. ◎: No splits (tears, cracks) or separation into several pieces even when bent more than 90 degrees. (No splits) ○: Even when bent more than 90 degrees, a split (crack) occurs, but it does not separate into several parts (does not split). ×: When bent more than 90 degrees, it separates into several parts (cracks).

[0079] <2. Resins and additives> 2-1. Production of propylene (co)polymer (a) (1) Manufacturing Example 1 (i) Preparation of catalyst The following operations were carried out under an inert gas atmosphere using deoxygenated and dehydrated solvents and monomers. (ii) Chemical treatment of ion-exchanged layered silicates Acid treatment: 1,130 g of distilled water and 750 g of 96% sulfuric acid were added to a separable flask, the internal temperature was kept at 90°C, 300 g of granulated smectite (Benclay SL, manufactured by Mizusawa Chemical Industries, Ltd.) with an average particle size of 25 μm was added, and the mixture was allowed to react for 5 hours. Washing: The solid was cooled to room temperature in 1 hour and washed with distilled water until the pH reached 3.69. The washing ratio was 1 / 10,000 or less (volume ratio). The solid at this stage was partially dried, and the elution rate after acid treatment was determined to be 33.5% by weight. Salt treatment: 211 g of lithium sulfate monohydrate was dissolved in 521 g of distilled water, and 100 g (dry weight) of the solid obtained by the acid treatment was added. The mixture was stirred at room temperature for 120 minutes. The slurry was filtered, and 3000 g of distilled water was added to the resulting solid, followed by stirring at room temperature for 5 minutes. The slurry was then filtered again. 2500 g of distilled water was added to the resulting solid, which was stirred for 5 minutes and then filtered again. This procedure was repeated four more times. The resulting solid was pre-dried at 130°C for two days under a nitrogen stream, after which coarse particles of 53 μm or larger were removed, and the mixture was further dried under reduced pressure at 200°C for two hours to obtain chemically treated smectite. (iii) Silicate activation treatment 200 g of the above chemically treated smectite was placed in a 3 L glass reactor equipped with a stirring blade, and 750 mL of normal heptane and a heptane solution of tri-normal octylaluminum (500 mmol) were added. The mixture was stirred at room temperature. After 1 hour, the mixture was washed with normal heptane (residual liquid rate less than 1%) (weight ratio of heptane to solid component) to adjust the slurry volume to 2000 mL.

[0080] (iV) Preparation of prepolymerized catalyst Next, 870 mL of a toluene slurry containing 3 mmol of (r)-dimethylsilylenebis[2-methyl-4-(4-chlorophenyl)-4H-azulenyl]zirconium dichloride and 42.6 mL of a heptane solution of triisobutylaluminum (15 mmol) were reacted at room temperature for 1 hour. The reaction mixture was then added to the above-mentioned chemically treated smectite slurry and stirred for 1 hour. Subsequently, 2.1 L of normal heptane was introduced into a 10 L stirred autoclave that had been thoroughly purged with nitrogen and maintained at 40°C. The previously prepared montmorillonite / complex slurry was then introduced. Once the temperature stabilized at 40°C, propylene was introduced at a rate of 100 g / h and maintained at that temperature. After 4 hours, the propylene supply was stopped and the mixture was maintained for an additional 2 hours. Approximately 3 L of the supernatant was removed from the recovered prepolymerized catalyst slurry, and 170 mL of a heptane solution of triisobutylaluminum (30 mmol) was added, followed by stirring for 10 minutes and heat treatment under reduced pressure at 40° C. This procedure yielded a prepolymerized catalyst containing 2.30 g of polypropylene per 1 g of catalyst.

[0081] (V) Production of propylene polymers Continuous production of propylene-ethylene copolymer was carried out using a process incorporating a 270 L liquid-phase polymerization tank equipped with a stirrer, a 400 L deactivation tank, a deactivation and washing system consisting of a slurry circulation pump, a circulation line liquid force classifier, a concentrator, a countercurrent pump, and a washing liquid receiving tank, a high-pressure degassing system consisting of a double-pipe heat exchanger and a fluidized flash tank, and a post-treatment system including a low-pressure degassing tank and a dryer. The prepolymerized catalyst prepared above was dispersed in liquid paraffin (Tonen Corporation, trade name "Whitelex 335") at a concentration of 15 wt% (relative to a total of 100 wt. parts of 15 wt. parts prepolymerized catalyst and 85 wt. parts liquid paraffin), and the resulting catalyst component was introduced into a liquid-phase polymerization vessel at a rate of 0.35 g / hr. Liquid propylene, ethylene, hydrogen, and triisobutylaluminum were continuously fed into the polymerization vessel at rates of 40 kg / hr, 0.4 kg / hr, 0.25 g / hr, and 18 g / hr, respectively, while maintaining the temperature inside the vessel at 70°C. Polymerization was carried out by continuously feeding the polymer and liquid propylene into a deactivation washing vessel from the liquid-phase polymerization vessel at a rate of 12.0 kg / hr. The average residence time of the catalyst in the polymerization vessel was 1.3 hours. Ethanol was fed into the deactivation washing vessel as a deactivator at a rate of 21.0 g / hr. Liquid propylene was further supplied at 40 kg / hr, and the temperature inside the tank was maintained at 50°C by heating with a jacket. The polymer was extracted from the bottom of the classifier into a high-pressure degassing tank, then passed through a low-pressure degassing tank, and then dried in a dryer. The temperature inside the dryer was adjusted to 80°C and the residence time to 1 hour. Dry nitrogen at room temperature was then blown in a countercurrent direction to the powder flow for 12 m. 3 The dried polymer was taken out from the hopper. Meanwhile, the liquid propylene separated from the polymer through a classifier and a concentrator was discharged into a washing liquid receiving tank at a rate of 40 kg / hr. The yield of the polymer obtained per gram of solid catalyst was 34.3 kg, the ethylene content was 0.8 wt%, MFR was 31 g / 10 min, the molecular weight distribution (Mw / Mn) was 2.4, Tm was 142°C, and the volatile component content was 5 wt ppm.

[0082] (vi) Granulation 100 parts by weight of propylene-ethylene copolymer powder was blended with 0.03 parts by weight of the phenolic antioxidant tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane (trade name: IRGANOX 1010, manufactured by BASF Japan Ltd.). The mixture was mixed at room temperature for 3 minutes using a high-speed agitator mixer (trade name: Henschel Mixer), and then melt-kneaded in a nitrogen atmosphere using a twin-screw extruder to obtain pellets of propylene-ethylene copolymer. The twin-screw extruder used was a Technovel KZW-25, with a screw rotation speed of 400 RPM and kneading temperatures set at 80, 160, 210, and 230°C from the bottom of the hopper (hereafter, the same temperature was used from the bottom to the die exit).

[0083] (2) Manufacturing Example 2 (i) Synthesis of Complex 1 (Synthesis Example 1: Preparation of Component [A-1] (Complex 1)) As component [A-1] (complex 1), rac-dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)indenyl}]hafnium was synthesized according to the method described in Synthesis Example 1 of JP 2012-149160 A. (ii) Synthesis of Complex 2 (Synthesis Example 2: Preparation of Component [A-2] (Complex 2)) As component [A-2] (complex 2), rac-dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}]hafnium was synthesized according to the method described in Example 7 of JP-A-11-240909.

[0084] (iii) Preparation of catalyst (iii-1) Chemical treatment of layered silicates A 1 L three-neck flask equipped with a stirring blade and reflux device was charged with 645.1 g of distilled water and 82.6 g of 98% sulfuric acid, and the mixture was heated to 95°C. 100 g of commercially available montmorillonite (manufactured by Mizusawa Industrial Chemicals, Ltd. under the trade name Benclay KK, Al = 9.78 wt%, Si = 31.79 wt%, Mg = 3.18 wt%, Al / Si (atomic ratio) = 0.320, average particle size 14 μm) was added, and the mixture was reacted at 95°C for 320 minutes. After 320 minutes, 0.5 L of distilled water was added to stop the reaction, and the mixture was filtered to obtain 255 g of a cake-like solid. 1545 g of distilled water was added to this cake to form a slurry, and the temperature was raised to 40°C. 5.734 g of lithium hydroxide monohydrate was added as a solid, and the reaction was carried out at 40°C for 1 hour. After 1 hour, the reaction slurry was filtered and washed three times with 1 L of distilled water, yielding another cake-like solid. The collected cake was dried to obtain 80 g of chemically treated montmorillonite, whose chemical composition was Al = 7.68 wt%, Si = 36.05 wt%, Mg = 2.13 wt%, Al / Si (atomic ratio) = 0.222, and Li = 0.53 wt%.

[0085] (iii-2) Preparation of propylene polymerization catalyst Internal volume 1m 3 150 kg of chemically treated montmorillonite obtained as in (iii-1) above was placed in a reactor, and 2832 L of hexane was added to form a slurry. 74.4 kg (375 mol) of triisobutylaluminum was added over 85 minutes and stirred for 60 minutes. The mixture was then decanted and washed with hexane until the washing ratio reached 1 / 32, and the total volume (slurry volume) was adjusted to 900 L. The slurry solution containing this chemically treated montmorillonite was kept at 50°C, and 0.65 kg of triisobutylaluminum (3.28 mol, 4.257 kg as a hexane solution with a concentration of 15.3 wt%) was added thereto. After stirring for 5 minutes, 0.657 kg (0.81 mol) of rac-dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}]hafnium and 96 L of toluene were added, and stirring was continued for 60 minutes. Thereafter, 9.758 kg (26.61 mol) of tri-normal octylaluminum was added and stirred for 6 minutes, and then a separately prepared solution was added, that is, a solution prepared by adding 1.768 kg (1.89 mol) of rac-dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)indenyl}]hafnium to 240 L of toluene in another vessel equipped with a stirrer, and 100 L of toluene was added, and stirring was continued for a further 20 minutes. Thereafter, 2387 L of hexane was added, the internal temperature of the reactor was raised to 40°C, and then 328.1 kg of propylene was fed over 240 minutes to carry out prepolymerization while maintaining the temperature at 40°C. Thereafter, the propylene feed was stopped, and the residual polymerization was carried out at 40°C for 80 minutes. After the completion of the residual polymerization, stirring was stopped, and the contents were allowed to settle and settle. The supernatant was removed so that the solution volume was 1500 L, and 12.7 kg of triisobutylaluminum was added, and 3974 L of hexane was added again, and after stirring, the contents were allowed to settle and settle, and the supernatant was removed so that the solution volume was 1500 L. To this solution, 8.9 kg of triisobutylaluminum (42.9 kg of a hexane solution with a concentration of 20.8% by weight) and 205 L of hexane were added. The reaction mixture was then transferred to a dryer and dried at 40°C for 9 hours to obtain 465 kg of a prepolymerized catalyst (prepolymerized catalyst 1). The prepolymerization ratio (the value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 2.10.

[0086] (iv) Production of propylene polymers Internal volume 100m 3Liquefied propylene was continuously introduced into a stirred high-pressure reactor (L / D = 1.2) at flow rates of 20 T / hr, triisobutylaluminum at 80 kg / hr, hydrogen at 0.180 kg / hr, and prepolymerization catalyst 1 at 0.87 kg / hr (weight excluding prepolymerized polymer). The temperature was maintained at 70 ± 0.1°C, and continuous polymerization was carried out so that the polymer slurry concentration in the polymerization reactor was maintained at 40 wt%. The production rate of propylene homopolymer (powder) was 8.0 T / hr. The obtained propylene homopolymer (powder) was thoroughly dried and then analyzed using the powder, and the results were as follows: ethylene content = 0 wt %, MFR = 33 g / 10 min, molecular weight distribution (Mw / Mn) = 3.2, Tm = 154°C, and volatile component content = 5 wt ppm. The powder was granulated under the following granulation conditions to obtain pellets of propylene homopolymer.

[0087] (v) Granulation 100 parts by weight of propylene homopolymer powder was blended with 0.125 parts by weight of tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane (trade name: IRGANOX 1010, manufactured by BASF Japan Ltd.), a phenol-based antioxidant, and 0.125 parts by weight of tris(2,4-di-t-butylphenyl)phosphite (trade name: IRGAFOS 168, manufactured by BASF Japan Ltd.), a phosphite-based antioxidant. The mixture was mixed at room temperature for 3 minutes using a high-speed stirring mixer (trade name: Henschel Mixer), and then melt-kneaded in a twin-screw extruder under a nitrogen atmosphere to obtain pellets of propylene homopolymer. The twin-screw extruder used was a KZW-25 manufactured by Technobel Co., Ltd., with a screw rotation speed of 400 RPM and kneading temperatures set at 80, 160, 210, and 230°C from the bottom of the hopper (the same temperature was maintained from then until the die exit).

[0088] 2-2. Production of propylene-based (co)polymers other than propylene-based (co)polymer (a) (1) Manufacturing Example 3 (i) Preparation of solid catalyst A 100-liter reactor equipped with a stirring blade, thermometer, jacket, and cooling coil was charged with 30 mol of Mg(OEt)2. Ti(OBu)4 was then added so that the molar ratio of Ti(OBu)4 / Mg was 0.60 (mr). 19.2 kg of toluene (TOL) was then added and the temperature was raised with stirring. After reacting at 139°C for 3 hours, the temperature was lowered to 130°C, and a toluene solution of MeSi(OPh)3 was added so that the molar ratio of MeSi(OPh)3 / Mg was 0.67 (mr) relative to the magnesium in the Mg(OEt)2. The amount of toluene used was 7.8 kg. After the addition was completed, the reaction was continued at 130°C for 2 hours. The temperature was then lowered to room temperature, and Si(OEt)4 was added. The amount of Si(OEt)4 added was set to Si(OEt)4 / Mg=0.056(mr) relative to the magnesium in the Mg(OEt)2 previously charged.

[0089] Next, toluene was added to the resulting reaction mixture to adjust the magnesium concentration to 0.58 (mol / L-TOL). Furthermore, diethyl phthalate (DEP) was added so that the DEP / Mg ratio was 0.10 (mr) relative to the magnesium in the Mg(OEt)2 previously charged. The resulting reaction mixture was cooled to 10°C with continued stirring, and TiCl4 was added dropwise over 2 hours to obtain a homogeneous solution. The TiCl4 was added so that the TiCl4 / Mg ratio was 4.0 (mr) relative to the magnesium in the Mg(OEt)2 previously charged. After the TiCl4 addition was completed, the mixture was heated to 15°C at 0.5°C / min with stirring and held at that temperature for 1 hour. The mixture was then heated again to 50°C at 0.5°C / min and held at that temperature for 1 hour. The mixture was then heated to 118°C at 1°C / min and treated at that temperature for 1 hour. After the treatment was completed, stirring was stopped, the supernatant liquid was removed, and the residue was washed with toluene to a residual liquid ratio of 1 / 73 (volume ratio of toluene / solid component) to obtain a slurry of the solid component.

[0090] Next, toluene and TiCl4 were added to the resulting slurry at room temperature. The TiCl4 was adjusted so that the ratio of TiCl4 / Mg(OEt)2 to the magnesium in the Mg(OEt)2 added earlier was 5.0 (mr). The toluene was adjusted so that the TiCl4 concentration was 2.0 (mol / L-TOL). The slurry was heated with stirring and reacted at 118°C for 1 hour. After the reaction was completed, stirring was stopped, the supernatant liquid was removed, and the mixture was washed with toluene to a residual liquid ratio of 1 / 150 (volume ratio of toluene to solid component), yielding a solid component slurry.

[0091] (ii) Preparation of solid catalyst component (A) Of the solid component obtained in (i), 400 g was transferred to another reactor equipped with a stirring blade, thermometer, and cooling jacket, and normal hexane was added to dilute the solid component to a concentration of 5.0 (g / L). Trimethylvinylsilane, TEA, and TBMDES were added to the resulting slurry at 15°C while stirring. TEA represents triethylaluminum, TBMDES represents t-butylmethyldiethoxysilane, and t-butyl represents a tertiary butyl group. The amounts of TEA, trimethylvinylsilane, and TBMDES added were 0.475 g, 0.137 g, and 0.167 g, respectively, per gram of solid component in solid catalyst component (A). After the addition, the mixture was maintained at 15°C for 1 hour while continuing to stir, and then the temperature was raised to 30°C and stirred at the same temperature for 2 hours. Next, the temperature was lowered again to 15°C, and while maintaining the same temperature, 4.8 kg of propylene gas was fed at a constant rate into the gas phase of the reactor over 8 hours to carry out prepolymerization. After the feed was completed, stirring was stopped, the supernatant liquid was removed, and the mixture was washed with normal hexane to obtain a slurry of solid catalyst component (A). The residual liquid ratio was 1 / 12 (volume ratio of normal hexane / solid catalyst component (A)). The obtained solid catalyst component (A) contained 12.0 g of propylene polymer per 1 g of solid catalyst component (A).

[0092] (iii) Production of propylene-ethylene copolymers Internal volume 0.4m 3A continuous production of propylene-ethylene copolymer was carried out using a process incorporating a degassing system consisting of a double-pipe heat exchanger and a fluidized flash tank downstream of a liquid-phase polymerization reactor equipped with an agitator. Liquefied propylene, ethylene, hydrogen, TEA, and TBEDMS were continuously fed into the liquid-phase polymerization reactor. TBEDMS stands for t-butylethyldimethoxysilane, and t-butyl stands for tertiary butyl group. The feed rates of liquefied propylene, TEA, and TBEDMS were 163 kg / hr, 8.86 g / hr, and 1.37 g / hr, respectively. Hydrogen and ethylene were fed to gas phase concentrations of 6.15 mol% and 0.74 mol%, respectively. Furthermore, the solid catalyst component (A) obtained in (ii) above was fed to a rate of 0.13 g / hr as the solid component contained in (A). The liquid-phase polymerization reactor was cooled to maintain the polymerization temperature at 70°C. The slurry polymerized in this liquid-phase polymerization tank was heated in a double-pipe heat exchanger and discharged into a fluidized flash tank. The discharge rate of the slurry was adjusted so that the propylene-ethylene copolymer particles contained in the slurry were approximately 24 kg / hr. The average residence time of the propylene-ethylene copolymer particles in the liquid-phase polymerization tank was 1.4 hours. Analysis of the discharged propylene-ethylene copolymer revealed that the MFR was 25.0 g / 10 min, the ethylene content was 0.7 wt%, the molecular weight distribution (Mw / Mn) was 5.6, the Tm was 156°C, and the volatile component content was 130 wt ppm.

[0093] (iv) Granulation 100 parts by weight of the propylene-ethylene copolymer powder was blended with 0.03 parts by weight of tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane (trade name: IRGANOX 1010, manufactured by BASF Japan Ltd.), a phenol-based antioxidant; 0.03 parts by weight of tris(2,4-di-t-butylphenyl)phosphite (trade name: IRGAFOS 168, manufactured by BASF Japan Ltd.), a phosphite-based antioxidant; and 0.05 parts by weight of calcium stearate "CAST" (manufactured by NOF Corporation), a neutralizing agent. The mixture was mixed at room temperature for 3 minutes using a high-speed agitator mixer (trade name: Henschel Mixer), and then melt-kneaded in a twin-screw extruder under a nitrogen atmosphere to obtain pellets of the propylene-ethylene copolymer. The twin-screw extruder used was a KZW-25 manufactured by Technobel Co., Ltd., with a screw rotation speed of 400 RPM and kneading temperatures set at 80, 160, 210, and 230°C from the bottom of the hopper (the same temperature was maintained from then until the die exit).

[0094] 2-3. Propylene (co)polymer (a) (PP-1) Propylene-based resin obtained by polymerization in Production Example 1 (PP-2) Propylene-based resin obtained by polymerization in Production Example 2 2-4. Propylene-based (co)polymers other than propylene-based (co)polymer (a) (PP-3) Propylene-based resin obtained by polymerization in Production Example 3

[0095] 2-5. Biomass polyethylene (b) Low-density polyethylene (LDPE) (PE-1)Braskem product name "Green PE SPB608" Density: 0.915g / cm 3 The melt flow rate conforming to ASTM D1238 (190°C, 2.16 kg load) is 30 g / 10 min, and the bio content is 95%. (All properties are listed in the manufacturer's catalog.) Linear low-density polyethylene (LLDPE) (PE-2)Braskem product name "Green PE SLL118" Density: 0.916g / cm 3 The melt flow rate conforming to ASTM D1238 (190°C, 2.16 kg load) is 1 g / 10 min, and the bio content is 87%. (All properties are listed in the manufacturer's catalog.) 2-6. Biomass polyethylene other than biomass polyethylene (b) High-density polyethylene (HDPE) (PE-3)Braskem product name "Green PE SGM9450F" Density: 0.952g / cm 3 The melt flow rate conforming to ASTM D1238 (190°C, 5 kg load) is 0.33 g / 10 min, and the bio content is 96%. (All properties are listed in the manufacturer's catalog.)

[0096] 2-6. Other additives (A-1) Hindered phenolic antioxidant "IR1010" tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxylphenyl)propionate]methane. Manufactured by BASF Japan Ltd., trade name "IRGANOX 1010". (A-2) Phosphorus-based antioxidant "IF168" tris(2,4-di-t-butylphenyl) phosphite. Manufactured by BASF Japan Ltd., trade name "IRGAFOS168". (B-1) Neutralizer "CAST" calcium stearate. Manufactured by NOF Corporation. (N-1) Nucleating agent "NX8000J" 1,2,3-trideoxy-4,6:5,7-bis-[(4-propylphenyl)methylene]-nonitol. Manufactured by Milliken & Company, trade name "Milad NX8000J".

[0097] 3. Examples 1 to 7 and Comparative Examples 1 to 9 Each polymer (pellet) and additive were prepared in the blending ratio (parts by weight) shown in Table 1, dry-blended in a super mixer, and then melt-kneaded and pelletized in a nitrogen atmosphere at a die outlet temperature of 220°C using a TEM-35B twin-screw extruder manufactured by Toshiba Machine Co., Ltd. The resulting pellets were used to measure their physical properties. The evaluation results are shown in Table 1.

[0098] Table 1

[0099] As is clear from Table 1, Examples 1 to 7 contain the specified amounts of the propylene-based (co)polymer (a) and biomass polyethylene (b) according to the present invention, and are materials that can reduce environmental impact, have excellent rigidity, and are not prone to cracking. Example 1 contains a specified amount of LDPE as the biomass polyethylene (b), and is also found to be excellent in transparency. Example 2 has the same composition as Example 1, but with an increased content of biomass polyethylene (b) LDPE. This increases the impact strength and biomass content, demonstrating superiority in terms of environmental impact. Example 3 has the same composition as Example 1, but with a reduced content of biomass polyethylene (b) LDPE. This shows that the rigidity and transparency are even superior to those of Example 1. Example 4 uses LLDPE as the biomass polyethylene (b). Although the content is the same as Example 1, both rigidity and impact strength are improved compared to Example 1. In Examples 5 and 6, propylene homopolymer was used as the propylene (co)polymer (a), but by including LDPE or LLDPE as the biomass polyethylene (b), the high rigidity derived from the propylene homopolymer was maintained, and the impact strength was also high, preventing breakage, confirming the effect of the present invention. Example 7 has the same composition as Example 1 but does not include a nucleating agent. Although the rigidity and transparency are lower than in Example 1, which contains a nucleating agent, it is clear that the rigidity required for use as a product is still maintained. On the other hand, Comparative Examples 1 and 2 have sufficient crack resistance, but the content of biomass polyethylene (b) LDPE is low, and they do not have a sufficient biomass content. Comparative Examples 3 and 4 contain a specified amount of high-density polyethylene (HDPE) as a biomass polyethylene other than the biomass polyethylene (b), but are very stiff and immediately separate into several parts when bent in a TD cracking test, i.e., they crack. Comparative Examples 5 to 8 use PP-3 as a propylene-based (co)polymer other than the propylene-based (co)polymer (a), but they contain a high content of volatile components and are inferior in cleanliness. Comparative Example 5 has a low biomass content, and Comparative Examples 6 and 8 are inferior to Examples 1 and 4, respectively, in the TD cracking test and crack easily. Comparative Example 9 uses only biomass polyethylene (b) LDPE, and although it has excellent crack resistance, it has extremely low rigidity and is unable to exhibit sufficient rigidity by itself. [Industrial Applicability]

[0100] The propylene polymer composition of the present invention gives molded articles that are excellent in rigidity and do not crack even when it contains biomass polyethylene, and since the biomass content is 8.4 to 49%, it can be used to reduce the environmental load and is therefore useful.

Claims

1. A propylene-based polymer composition for injection molding contains 51 to 90 parts by weight of a propylene-based (co)polymer (a) satisfying the following conditions (Hi) to (Hv) and 10 to 49 parts by weight of a biomass polyethylene (b) satisfying the following condition (Li), with a total weight of 100 parts by weight, and has a biomass content of 8.4 to 49%. (Hi) A metallocene-based propylene homopolymer or a metallocene-based propylene copolymer comprising propylene and an α-olefin content of less than 1% by weight. (H-ii) The melt flow rate according to JIS K7210 (230°C, 2.16 kg load) is in the range of 0.5 to 100 g / 10 min. (H-iii) The melting peak temperature (Tm) is in the range of 135 to 165°C. (H-iv) The molecular weight distribution (weight average molecular weight / number average molecular weight) is in the range of 1.5 to 4.

0. (Hv) The content of volatile components is 50 ppm by weight or less. (Li) Low density polyethylene or linear low density polyethylene.

2. A propylene polymer composition for injection molding, comprising 0.01 to 0.6 parts by weight of a nucleating agent per 100 parts by weight of the propylene polymer composition according to claim 1.

3. A molded article obtained by using the propylene polymer composition for injection molding according to claim 1 or 2.

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