JP2023122573A - Propylene-based polymer composition and molded article - Google Patents

Abstract

To provide a propylene-based polymer composition having a biomass degree of 8.4 to 49%, which gives an unbreakable molded article having excellent rigidity and impact resistance even when containing biomass polyethylene, and a molded article thereof.SOLUTION: There is provided a total 100 pts.wt. of a propylene-based polymer composition which comprises 51 to 95 pts.wt. of a block copolymer (a) of propylene and at least one selected from ethylene and an α-olefin having 4 or more carbon atoms and 5 to 49 pts.wt. of biomass polyethylene (b), wherein the block copolymer (A) satisfies the following conditions (A-i) and (A-ii), the propylene-based polymer composition has a biomass degree of 8.4 to 49%. (A-i) The content of ethylene and an α-olefin having 4 or more carbon atoms is in the range of more than 5 wt.% and 30 wt.% or less. (A-ii) The melt flow rate is in the range of 0.5 to 100 g/10 min, as measured at 230°C under a load of 2.16 kg in accordance with JIS K 7210.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a propylene-based polymer composition having a biomass degree of 8.4 to 49% and a molded product thereof, and more particularly, to a molded product that is excellent in rigidity and impact resistance even if it contains biomass polyethylene, and does not crack. It relates to a propylene-based polymer composition that provides. In the present invention, "cracking" means splitting into several parts when a force is applied. Also, "not crackable" means either of the following when a force is applied.
(1) It does not split into several parts without forming splits (fissures, cracks).
(2) Fissures (fissures, cracks) occur, but do not divide into several parts;

Propylene-based resins are characterized by their excellent rigidity, impact resistance, heat resistance, moldability, transparency, and chemical resistance. It is widely used in various applications such as and textiles.
On the other hand, in recent years, environmental pollution caused by plastics has become a problem, and how to deal with it has become an issue. One of the countermeasures is to use plant-derived plastics (biomass plastics) that are carbon neutral. Plant-derived polypropylene is also being studied, but it is not currently on the market, and studies are being conducted to add biomass polyethylene to polypropylene (see, for example, Patent Documents 1 and 2).

However, since a mixture obtained by mixing and melt-kneading polypropylene and biomass polyethylene has poor miscibility, a molded article obtained from the mixture has a problem of cracking. Therefore, there is a demand for a polypropylene composition that is excellent in miscibility even if it contains biomass polyethylene.

JP 2019-34519 A JP 2016-27171 A

The object of the present invention is to provide a propylene-based polymer having a biomass degree of 8.4 to 49%, which gives a molded article that is excellent in rigidity and impact resistance and does not crack even if it contains biomass polyethylene in the situation of the prior art. An object of the present invention is to provide a composition and a molded article thereof.

The present inventors conducted intensive studies and found that by using a specific propylene-based polymer composition, even if biomass polyethylene is contained, excellent rigidity and impact resistance, giving a molded article that does not break, and having a biomass degree of 8.0. A propylene-based polymer composition having a content of 4 to 49% and a molded article thereof were found, and the present invention was completed.
That is, the present invention provides the following propylene-based polymer composition having a biomass degree of 8.4 to 49% and molded articles thereof.

[1] 51 to 95 parts by weight of a block copolymer (a) of propylene and at least one selected from ethylene and α-olefins having 4 or more carbon atoms, and 5 to 49 parts by weight of biomass polyethylene (b) A total of 100 parts by weight of a propylene-based polymer composition containing
A propylene-based polymer composition, wherein the block copolymer (a) satisfies the following conditions (Ai) and (A-ii), and the biomass degree of the propylene-based polymer composition is 8.4 to 49%. .
(Ai) The content of ethylene and α-olefins having 4 or more carbon atoms is in the range of more than 5% by weight and 30% by weight or less.
(A-ii) According to JIS K7210, the melt flow rate measured at 230° C. and a load of 2.16 kg is in the range of 0.5 to 100 g/10 minutes.
[2] The block copolymer (a) is a random copolymer of propylene and at least one selected from ethylene and an α-olefin having 4 or more carbon atoms, and A random copolymer having an α-olefin content of 5% by weight or less, or a propylene homopolymer (ac-1); and at least one selected from propylene and ethylene and an α-olefin having 4 or more carbon atoms. a random copolymer (ac-2) containing ethylene and an α-olefin having 4 or more carbon atoms in a range of 15 to 85% by weight; and satisfying the following conditions (AC-i) to (AC-iii).
(AC-i) The ratio of (ac-1) and (ac-2) is 40 to 95 parts by weight of (ac-1) and 5 to 60 parts by weight of (ac-2), totaling 100 parts by weight is.
(AC-ii) The melt flow rate of (ac-1) measured at 230° C. and a load of 2.16 kg according to JIS K7210 is in the range of 0.5 to 350 g/10 minutes.
(AC-iii) The melt flow rate of (ac-2) measured at 230° C. and a load of 2.16 kg according to JIS K7210 is in the range of 0.001 to 0.5 g/10 minutes.
[3] The propylene-based polymer composition according to [1] or [2], wherein at least one selected from ethylene and α-olefins having 4 or more carbon atoms is ethylene.
[4] The propylene-based polymer composition according to any one of [1] to [3], wherein the biomass polyethylene (b) is linear low-density polyethylene.
[5] A propylene polymer composition containing 0.01 to 0.6 parts by weight of a nucleating agent per 100 parts by weight of the propylene polymer composition according to any one of [1] to [4]. Combined composition.
[6] A molded article containing the propylene-based polymer composition according to any one of [1] to [5].

Molded articles produced using the propylene-based polymer composition having a biomass degree of 8.4 to 49% of the present invention contribute to the reduction of environmental load, and are excellent in rigidity and impact resistance even if they contain biomass polyethylene. , to give unbreakable moldings. In particular, injection-molded articles of the composition are very useful because they can be applied to various industrial products by taking advantage of their properties.

FIG. 1 is a view of the MD and TD cracking tests performed by cutting a 120 mm×120 mm×2 mm injection test piece. FIG. 2 is a diagram showing an example of the amount of elution and the integrated amount of elution in temperature rising elution fractionation (TREF) measurement of a propylene-ethylene random block copolymer.

The propylene-based polymer composition of the present invention comprises 51 to 95 parts by weight of a block copolymer (a) of propylene and at least one selected from ethylene and α-olefins having 4 or more carbon atoms, and biomass polyethylene ( b) a total of 100 parts by weight containing from 5 to 49 parts by weight of
The block copolymer (a) satisfies the following conditions (Ai) and (A-ii), and the propylene-based polymer composition has a biomass degree of 8.4 to 49%.
(Ai) The content of ethylene and α-olefins having 4 or more carbon atoms is in the range of more than 5% by weight and 30% by weight or less.
(A-ii) According to JIS K7210, the melt flow rate measured at 230° C. and a load of 2.16 kg is in the range of 0.5 to 100 g/10 minutes.
The propylene-based polymer composition contributes to reducing the burden on the environment, is excellent in rigidity and impact resistance, and can provide unbreakable molded articles. The propylene-based polymer composition and the molded article are described in detail below.

<Block copolymer (a) of propylene and at least one selected from ethylene and α-olefin having 4 or more carbon atoms> (hereinafter also referred to as block copolymer (a).)
The block copolymer (a) is a copolymer of propylene and at least one selected from ethylene and α-olefins having 4 or more carbon atoms, and polymerized portions of propylene constitute blocks. By including the block copolymer (a) in the propylene-based polymer composition, it is possible to provide a molded article that is excellent in rigidity and impact resistance and does not crack even if it contains biomass polyethylene.
Examples of α-olefins having 4 or more carbon atoms include α-olefins having 4 to 20 carbon atoms, such as 1-butene, 1-hexene and 1-octene. At least one selected from ethylene and α-olefins having 4 or more carbon atoms to be copolymerized with propylene may be one or two or more. Among these, ethylene and 1-butene are preferred, and ethylene is more preferred. The block copolymer (a) may be used alone or in combination of two or more.

Specific examples of the block copolymer (a) include propylene-ethylene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, propylene - propylene in any combination of comonomers, such as ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, propylene-1-butene-1-octene copolymer, etc. Primary or terpolymers can be exemplified. Among them, propylene-ethylene copolymers, propylene-1-butene copolymers and propylene-ethylene-1-butene copolymers are preferable, from the viewpoint of obtaining molded articles that are excellent in rigidity and impact resistance and do not crack. A propylene-ethylene copolymer is more preferred because it facilitates adjustment of various physical properties.

Block copolymer (a) satisfies the following conditions (Ai).
(Ai) The content of ethylene and α-olefins having 4 or more carbon atoms is in the range of more than 5% by weight and 30% by weight or less.
By setting the content of ethylene and α-olefin having 4 or more carbon atoms to 30% by weight or less, it is possible to improve the rigidity of the obtained molded product, and by making it more than 5% by weight, the durability of the molded product is improved. It becomes possible to improve impact resistance. The content of ethylene and α-olefins having 4 or more carbon atoms is preferably more than 5.5% by weight and 20% by weight or less, more preferably more than 6.0% by weight and 15% by weight or less. More than 5% by weight and not more than 10% by weight is particularly preferred. In addition, the content of ethylene and α-olefins having 4 or more carbon atoms is more than 5% by weight and 20% by weight or less, more than 5.0% by weight and 15% by weight or less, or more than 5.0% by weight and 10% by weight or less. be able to.

Block copolymer (a) satisfies the following condition (A-ii).
(A-ii) According to JIS K7210, the melt flow rate measured at 230° C. and a load of 2.16 kg is in the range of 0.5 to 100 g/10 minutes.
When the melt flow rate of the block copolymer (a) is 0.5 g/10 minutes or more, molding processability is improved, and satisfactory performance as a molded product can be achieved. It can improve the mechanical strength of the product. The block copolymer (a) preferably has a melt flow rate of 5 to 60 g/10 minutes, more preferably 10 to 40 g/10 minutes.

From the viewpoint of the balance between rigidity and impact resistance of the resulting molded article, the block copolymer (a) is a random copolymer of propylene and at least one selected from ethylene and α-olefins having 4 or more carbon atoms. A random copolymer or a propylene homopolymer (ac-1), which is a coalescence and contains ethylene and an α-olefin having 4 or more carbon atoms in an amount of 5% by weight or less, and propylene, ethylene, and carbon atoms A random copolymer with at least one selected from 4 or more α-olefins, wherein the content of ethylene and α-olefins having 4 or more carbon atoms is in the range of 15 to 85% by weight. A multistage polymer comprising (ac-2) is preferred.
Examples of α-olefins having 4 or more carbon atoms include α-olefins having 4 to 20 carbon atoms, such as 1-butene, 1-hexene and 1-octene. At least one selected from ethylene and α-olefins having 4 or more carbon atoms may be one or two or more. Among these, ethylene and 1-butene are preferred, and ethylene is more preferred. (ac-1) and (ac-2) may be used alone or in combination of two or more.

From the viewpoint of the rigidity of the molded article, (ac-1) is preferably a random copolymer or a propylene homopolymer containing ethylene and an α-olefin having 4 or more carbon atoms in an amount of 5% by weight or less. A random copolymer or a propylene homopolymer containing ethylene and an α-olefin having 4 or more carbon atoms in an amount of 1% by weight or less is more preferable, and a propylene homopolymer is particularly preferable.

When (ac-1) is a propylene homopolymer, the isotactic pentad fraction, which is an index of stereoregularity, 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 of the molded product is improved. Here, the isotactic pentad fraction is a value measured by a proton decoupling method using ¹³ C-NMR.

From the viewpoint of improving the impact resistance of the molded article and suppressing cracking, the content of ethylene and an α-olefin having 4 or more carbon atoms in (ac-2) is more preferably 15 to 85% by weight. More preferably 20 to 75% by weight, particularly preferably 35 to 70% by weight.

Specific examples of random copolymers in (ac-1) and (ac-2) include propylene-ethylene copolymers, propylene-1-butene copolymers, propylene-1-hexene copolymers, propylene -1-octene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, propylene-1-butene-1-octene copolymer, etc. Binary or terpolymers in which monomers are arbitrarily combined can be exemplified. Among them, propylene-ethylene copolymer, propylene-1-butene copolymer and propylene-ethylene-1-butene copolymer are preferable, and propylene-ethylene copolymer is more preferable.

When the block copolymer (a) is a multi-stage polymer consisting of (ac-1) and (ac-2), the block copolymer (a) is subjected to the following conditions (AC-i) to (AC-iii ) is preferably satisfied.
(AC-i) The ratio of (ac-1) and (ac-2) is 40 to 95 parts by weight of (ac-1) and 5 to 60 parts by weight of (ac-2), totaling 100 parts by weight is.
(AC-ii) The melt flow rate of (ac-1) measured at 230° C. and a load of 2.16 kg according to JIS K7210 is in the range of 0.5 to 350 g/10 minutes.
(AC-iii) The melt flow rate of (ac-2) measured at 230° C. and a load of 2.16 kg according to JIS K7210 is in the range of 0.001 to 0.5 g/10 minutes.

The ratio of (ac-1) and (ac-2) is preferably 40 to 95 parts by weight of (ac-1) and 5 to 60 parts by weight of (ac-2), for a total of 100 parts by weight; More preferably, (ac-1) is 65 to 95 parts by weight, and (ac-2) is 5 to 35 parts by weight; (ac-1) is 87 to 93 parts by weight, and (ac-2) is 7 13 parts by weight is more preferred, and 90 to 93 parts by weight of (ac-1) and 7 to 10 parts by weight of (ac-2) are particularly preferred. When (ac-2) is 5 parts by weight or more, the impact resistance of the molded article tends to be improved, and when (ac-2) is 60 parts by weight or less, the rigidity of the molded article tends to be improved.

The melt flow rate (MFR) of (ac-1) is preferably 0.5 to 350 g/10 min, more preferably 5 to 150 g/10 min, and further preferably 10 to 100 g/10 min. preferable. When the melt flow rate of (ac-1) is 0.5 g/10 minutes or more, molding processability is improved, and satisfactory performance as a molded product is easily achieved. It is easy to improve the mechanical strength of

The melt flow rate (MFR) of (ac-2) is preferably 0.001 to 0.5 g/10 minutes, more preferably 0.01 to 0.4 g/10 minutes, and 0.01 to It is more preferably 0.3 g/10 minutes, and particularly preferably 0.02 to 0.3 g/10 minutes. When the melt flow rate of (ac-2) is 0.001 g/10 minutes or more, molding processability is improved, and satisfactory performance as a molded product is easily achieved. It is easy to improve the mechanical strength of the molded product.

The melt flow rate (MFR) of (ac-2) is the melt flow rate (MFR) of the block copolymers (a) and (ac-1), and the block copolymer (a) in (ac- It can be calculated using the following formula from the content ratios of 1) and (ac-2).
Log _e [MFR of block copolymer (a)] = [content ratio of (ac-1)] × Log _e [MFR of (ac-1)] + [content ratio of (ac-2)] × Log _e [MFR of (ac-2)]
In this specification, the melt flow rate (MFR) of (ac-2) is calculated from the above formula. is measured at 230° C. and a load of 2.16 kg according to JIS K7210, so the melt flow rate (MFR) of (ac-2) is also defined as measured according to the same standard.

The melt flow rate (MFR) of the block copolymers (a), (ac-1) and (ac-2) can be adjusted by adjusting the polymerization conditions such as temperature and pressure, or by adding a chain transfer agent such as hydrogen during polymerization. Adjustment can be easily made by controlling the amount of hydrogen added in the method.

In the block copolymers (a) and (ac-1), the contents of propylene, ethylene and α-olefins having 4 or more carbon atoms can be measured, for example, by ¹³ C-NMR under the following conditions.
Apparatus: JEOL-GSX270 manufactured by JEOL Ltd.
Concentration: 300 mg/2 mL
Solvent: orthodichlorobenzene In the case of a propylene-ethylene copolymer, the content of propylene and ethylene was determined by infrared spectroscopy using a reference material whose composition was examined by ¹³ C-NMR, as described in the Examples. It can be measured by infrared spectroscopy based on the calibration curve prepared by.

The content of ethylene and α-olefin having 4 or more carbon atoms in the random copolymer (ac-2) is the ethylene and carbon number of the block copolymers (a) and (ac-1) obtained as described above. It can be calculated from the content of 4 or more α-olefins and the content ratio of (ac-1) and (ac-2) in the block copolymer (a).

[Calculation of content of (ac-1) and (ac-2)]
When the block copolymer (a) is a multi-stage polymer consisting of (ac-1) and (ac-2), each content of (ac-1) and (ac-2) is the mass balance at the time of production. (material balance), but in order to specify them more accurately, temperature rising elution fractionation (TREF) can be used for calculation.

Hereinafter, the method for evaluating a propylene-ethylene random copolymer will be described as a representative example, but a random copolymer of propylene and an α-olefin having 4 or more carbon atoms can also be similarly evaluated. Techniques for evaluating the crystallinity distribution of propylene-ethylene random copolymers by TREF are well known to those skilled in the art. For example, the following documents show detailed measurement methods.
G. Glockner, J.; Appl. Polym. Sci. : Appl. Polym. Symp. 45, 1-24 (1990)
L. Wild, Adv. Polym. Sci. ; 98, 1-47 (1990)
J. B. P. Soares, A.; E. Hamielec, Polymer; 36, 8, 1639-1654 (1995)

Since there is a large difference in crystallinity between (ac-1) and (ac-2) in the propylene-ethylene block copolymer (a), it is possible to distinguish both with high accuracy by TREF.

A specific method will be described with reference to FIG. FIG. 2 is a diagram showing an example of the results of the elution amount and the integration of the elution amount in the TREF measurement of a propylene-ethylene random block copolymer. In the TREF elution curve (plot of elution amount against temperature), (ac-1) and (ac-2) show elution peaks at T (β) and T (α), respectively, due to differences in crystallinity, and the difference is sufficiently large that almost separation is possible at the intermediate temperature T(C) (={T(α)+T(β)}/2).

The lower limit of the TREF measurement temperature is -15 ° C. in the apparatus used for this measurement, but if the component (α) has very low crystallinity or is an amorphous component, in this measurement method, the measurement temperature range may not show a peak within (In this case, the concentration of the component (α) dissolved in the solvent is detected at the lower limit of the measurement temperature (that is, −15° C.).)
At this time, T(α) is considered to exist below the lower limit of the measurement temperature, but since its value cannot be measured, in such a case, T(α) is set to −15° C., which is the lower limit of the measurement temperature. defined as Here, if the integrated amount of the component eluted before T(C) is defined as W(α) wt%, and the integrated amount of the component eluted above T(C) is defined as W(β) wt%, then W(α) corresponds almost to the amount of the less crystalline or amorphous component (α), namely (ac-2), and W(β) corresponds to the amount of the relatively highly crystalline component (β), namely (ac- It almost corresponds to the amount of 1). The elution volume curve obtained by TREF and the method of calculating the various temperatures and volumes obtained therefrom are illustrated in FIG.

[Catalyst for block copolymer (a)]
Although the catalyst used for synthesizing the block copolymer (a) is not particularly limited, it is preferable to use a stereoregular catalyst. Stereoregular catalysts include Ziegler catalysts and metallocene catalysts.

Ziegler catalysts include transition metal components such as titanium halide compounds such as titanium trichloride, titanium tetrachloride, and trichloroethoxytitanium, contact products of the titanium halide compounds and magnesium compounds typified by magnesium halides; Two-component catalysts with organometallic components such as aluminum compounds or their halides, hydrides, and alkoxides, and electron-donating compounds containing nitrogen, carbon, phosphorus, sulfur, oxygen, silicon, etc. are added to these components. Ternary catalysts may be mentioned.

A supported metallocene catalyst is preferred.
A particularly preferred example of the supported metallocene catalyst is a metallocene catalyst in which the carrier is an ion-exchange layered silicate that also functions as a cocatalyst. Specifically, such a metallocene catalyst can be obtained by combining component [A], component [B], and component [C], which are added as necessary, as described below.

・Component [A]: Metallocene complex A transition metal compound of groups 4 to 6 of the periodic table having at least one conjugated five-membered ring ligand ・Component [B]: Promoter ion-exchange layered silicate ・Component [C]: organoaluminum compound

• Component [A]: Metallocene Complex As the component [A], specifically, a compound represented by the following formula [I] can be used. Component [A] may be used alone or in combination of two or more.
Q (C ₅ H _4-a R ¹ _a ) (C ₅ H _4-b R ² _b ) MXY [I]
In Formula [I], Q represents a bonding group that bridges two conjugated five-membered ring ligands.
M represents a transition metal of groups 4 to 6 of the periodic table, preferably titanium, zirconium and hafnium.
X and Y are each independently 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 carbon number It represents a phosphorus-containing hydrocarbon group of 1 to 20 or a silicon-containing hydrocarbon group of 1 to 20 carbon atoms.

R ¹ and R ² each independently represents a hydrocarbon group having 1 to 20 carbon atoms, halogen, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an aryloxy group, a silicon-containing hydrocarbon group, phosphorus A hydrocarbon-containing group, a nitrogen-containing hydrocarbon group, or a boron-containing hydrocarbon group is indicated. Two adjacent R ¹ or two adjacent R ² may be combined to form a C ₄ -C ₁₀ ring. In particular, it is preferable to form a 6- or 7-membered ring to form an indene ring or an azulene ring together with the conjugated 5-membered ring.
a and b are integers satisfying 0≤a≤4 and 0≤b≤4.
Examples of the bonding group Q that bridges between two conjugated five-membered ring ligands include an alkylene group, an alkylidene group, a silylene group, a germylene group, and the like. These may have hydrogen atoms substituted with alkyl groups, halogens, or the like. A silylene group is particularly preferred.

As the metallocene complex, specifically, the following compounds can be preferably mentioned.
(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-methylinde Nyl) zirconium dichloride (7) Ethylene 1,2-bis(4-phenylindenyl) zirconium dichloride (8) Ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride

(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) methylphenylsilylene bis[1-( 2-methyl-4,5-benzo(indenyl)]zirconium dichloride (15) dimethylsilylene bis[1-(2-methyl-4,5-benzoindenyl)]zirconium dichloride (16) dimethylsilylene bis[1-( 2-methyl-4H-azulenyl)]zirconium dichloride (17) dimethylsilylene bis[1-(2-methyl-4-(4-chlorophenyl)-4H-azulenyl)]zirconium dichloride (18) dimethylsilylene bis[1-( 2-ethyl-4-(4-chlorophenyl)-4H-azulenyl)]zirconium dichloride (19) dimethylsilylene bis[1-(2-ethyl-4-naphthyl-4H-azulenyl)]zirconium dichloride

(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) dimethylgermylene bis(indenyl) zirconium dichloride (25) dimethylgermylene (cyclopentadienyl) (fluorenyl) zirconium dichloride In addition, other 4th, 5th and 6th compounds such as titanium compounds and hafnium compounds As for the group transition metal compound, the same compounds as those mentioned above are preferably mentioned. These compounds may be used in combination with the catalyst component and catalyst of the present invention.

・Component [B]: co-catalyst (ion-exchange layered silicate)
The ion-exchangeable layered silicate is not limited to a naturally occurring one, and may be an artificially synthesized one. A clay compound can be used as the ion-exchange layered silicate, and specific examples of the clay compound include the following layered compounds described in "Clay Mineralogy" by Haruo Shiramizu, Asakura Shoten (1995). A silicate is mentioned.
(a) Kaolin groups such as dickite, nacrite, kaolinite, anoxite, metahaloysite, halloysite, etc., and serpentinite groups such as chrysotile, lizardite, antigorite, etc. whose main constituent layers are 1:1 type structures (b) Smectite groups such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, and stevensite, vermiculite groups such as vermiculite, mica, illite, sericite, and glauconite, which are mainly composed of 2:1 type structures mica, attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, chlorite group, etc.

The silicate used in the present invention may be a layered silicate in which a mixed layer of (a) and (b) is formed.
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, and particularly preferably montmorillonite. A major component means the component with the largest amount. Component [B] may be used alone or in combination of two or more.

Activity can be improved by chemically treating these silicates with acids, salts, alkalis, oxidizing agents, reducing agents, organic solvents, or the like.
The acid treatment removes impurities on the surface of the ion-exchangeable 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. can.
Acids used in the acid treatment include inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid, with sulfuric acid being particularly preferred.
The conditions for the acid treatment are not particularly limited, but the conditions are preferably such that an aqueous solution of 5 to 50% by weight of acid is reacted at a temperature of 60 to 100° C. for 1 to 24 hours, and the acid concentration is changed during the reaction. may Washing is usually performed after the acid treatment. Washing is an operation for separating and removing the acid contained in the processing system from the ion-exchange layered silicate.

As the salts used in the salt treatment, it is preferable to select and use those containing specific cations. As for the type of cation, monovalent to tetravalent metal cations are preferred, and cations of Li, Ni, Zn and Hf are particularly preferred.
Specific examples of salts include the following.
LiCl, LiBr, Li ₂ SO ₄ , Li ₃ (PO ₄ ), Li(ClO ₄ ), Li ₂ (C ₂ O ₄ ), LiNO ₃ , Li(OOCCH ₃ ), Li ₂ (C ₄ H ₄ O ₄ ) and the like.
Examples of Ni cations include NiCO ₃ , Ni(NO ₃ ) ₂ , NiC ₂ O ₄ , Ni(ClO ₄ ) ₂ , NiSO ₄ , NiCl ₂ , NiBr ₂ and the like.
Examples of Zn as _a cation include Zn( _OOCCH3 ) ₂ , Zn( _CH3COCHCOCH3 ) ₂ , _ZnCO3 , Zn( _NO3 ) ₂ , Zn( _ClO4 ) ₂ , _Zn3 ( _PO4 ) ₂ , ZnSO ₄ , ZnF ₂ , ZnCl ₂ , ZnBr ₂ , ZnI ₂ and the like can be mentioned.
Those having Hf cations include Hf( _OOCCH3 ) ₄ , Hf( _CO3 ) ₂ , Hf( _NO3 ) ₄ , Hf( _SO4 ) ₂ , _HfOCl2 , _HfF4 , _HfCl4 , _HfBr4 , HfI ₄ etc. can be mentioned.

After the chemical treatment, drying is carried out. In general, drying can be performed at a temperature of 100 to 800°C. I don't like it. It is preferable to change the drying temperature depending on the application because the properties change depending on the drying temperature even if the structure is not destroyed. 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. The drying method is not particularly limited, and various methods can be used.

• Component [C]: Organoaluminum compound The organoaluminum compound of component [C] is optionally used as necessary, and the compound represented by the following formula [II] is most suitable.
(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 halogen, hydrogen, an alkoxy group or an amino group. p is an integer of 1-3, q is an integer of 1-2.
R ⁴ is preferably an alkyl group, X is preferably an alkoxy group having 1 to 8 carbon atoms when it is an alkoxy group, and an amino group having 1 to 8 carbon atoms when it is an amino group.
Of these, trialkylaluminums with p=3, q=1 and dialkylaluminum hydrides with p=2, q=1 and X=hydrogen are preferred. More preferably, R ⁴ is a trialkylaluminum having 1 to 8 carbon atoms.

An organoaluminum compound can be used individually or in mixture of multiple types. Moreover, the organoaluminum compound can be added and used not only during catalyst preparation but also during prepolymerization or main polymerization.

[Method for producing block copolymer (a)]
As a method for producing the block copolymer (a), a slurry polymerization method using an inert solvent, a solution polymerization method, a gas phase polymerization method using substantially no solvent, or a solvent is used to polymerize monomers in the presence of the above catalyst. Bulk polymerization method and the like.
For example, in the case of a slurry polymerization method, it can be carried out in an inert hydrocarbon such as n-butane, isobutane, n-pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene or the like, or in a liquid monomer. . 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 obtained block copolymer (a) can be adjusted with hydrogen or other known molecular weight modifiers. . Polymerization may be carried out in a continuous or batch reaction, and the conditions may be those commonly used. Furthermore, the polymerization reaction may be carried out in one step or in multiple steps. When the block copolymer (a) is a multistage polymer, it is preferably a multistage polymer consisting of (ac-1) and (ac-2).
When using a metallocene catalyst, it is desirable to prepolymerize it before the main polymerization. Monomers to be prepolymerized include α-olefins such as ethylene, propylene, 1-butene and 1-hexene, diene compounds such as 1,3-butadiene, and vinyl compounds such as styrene and divinylbenzene. .
This prepolymerization is preferably carried out in an inert solvent under mild conditions, and the solid catalyst (total of component [A] and component [B]) is 0.01 to 1,000 g, preferably 0.1 g per 1 g. It is desirable to work to produce ~100 g of polymer.

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 and cyclohexane, or a liquefied α-olefin. In the present invention, it is desirable to maximize the amount of polymer produced per solid catalyst (when the solid catalyst is prepolymerized, the polymer produced by the prepolymerization is not included). In order to increase the amount of polymer produced, it is desirable to set both the polymerization temperature and the polymerization pressure relatively high.

Usually, 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, it is preferable to select a polymerization temperature of 60 to 80° C. and a polymerization pressure of about 2.5 to 4 MPa in correlation with the temperature. On the other hand, in the case of gas phase polymerization, it is preferable to select a polymerization temperature of 70 to 90° C. and a polymerization pressure of about 1.5 to 4 MPa.
Furthermore, it is possible to increase the amount of polymer produced per solid catalyst by lengthening the residence time of the solid catalyst, but if the residence time is too long, the productivity will be affected. A preferred residence time is 1 to 8 hours, more preferably 1 to 6 hours. It is desirable to set the polymerization conditions so that the amount of polymer produced per 1 g of the solid catalyst including the carrier is 20 kg or more, preferably 25 kg or more, and more preferably 30 kg or more.
In addition, hydrogen may be present as a molecular weight modifier in the polymerization system. Furthermore, the polymerization may be carried out in multiple stages by changing the polymerization temperature, the concentration of the molecular weight modifier, and the like.

In the present invention, after the polymerization is completed, the obtained block copolymer (a) is more preferably treated with an inert saturated hydrocarbon solvent such as propane, butane, pentane, hexane, heptane, liquid α-olefin, or the like. is preferably washed 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, separation from the washing solution by a cyclone, and the like can be used.
Also, a deactivator may be added before or at the same time as washing. The deactivator is not particularly limited, and water, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone and methyl ethyl ketone, and mixtures thereof can be used.
As the block copolymer (a), a commercially available one can be used, and examples thereof include NOVATEC (registered trademark) PP (trade name) manufactured by Japan Polypropylene Corporation.

<Biomass polyethylene (b)>
Plant-derived ethylene, which is a typical raw material monomer of biomass polyethylene (b), is produced by fermenting plant raw materials such as sugarcane with microorganisms, and heating ethanol in the presence of a catalyst to cause an intramolecular dehydration reaction. It can be obtained by doing.
Biomass polyethylene (b) is a polymer obtained by polymerizing a monomer containing plant-derived ethylene as a main component. The raw material monomer for biomass polyethylene (b) may not contain 100% plant-derived ethylene. For example, by using plant-derived ethylene as a part of conventionally known petroleum-derived ethylene monomers, the environmental load can be reduced.
As the biomass polyethylene (b), a homopolymer obtained by homopolymerizing plant-derived ethylene or a copolymer obtained by copolymerizing plant-derived ethylene and α-olefin can be used. Although the number of carbon atoms in the α-olefin is not particularly limited, it is preferably 1-butene, 1-hexene or 1-octene. Furthermore, petroleum-derived ethylene may be included.

Examples of polyethylene used as biomass polyethylene (b) include high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE) and linear low density polyethylene (LLDPE). These polyethylenes can be used singly or in combination of two or more.
The density of the high-density polyethylene is preferably 0.940 to 0.965 g/cm ³ , and this range is preferable because the rigidity of the molded article is improved. The density of the medium-density polyethylene is preferably 0.925 to 0.940 g/cm ³ , and this range is preferable because the rigidity of the molded product is improved.
When low-density polyethylene or linear low-density polyethylene is used, the effects of improving the transparency and impact resistance of molded articles are sufficient.
The density of the low-density polyethylene is preferably 0.910-0.920 g/cm ³ , more preferably 0.913-0.917 g/cm ³ . A density of 0.910 g/cm ³ or more is preferable because the rigidity is improved, and a density of 0.920 g/cm ³ or less is preferable because the effect of improving transparency and impact resistance is sufficient.
The density of the linear low-density polyethylene is preferably 0.895-0.925 g/cm ³ , more preferably 0.900-0.917 g/cm ³ . A density of 0.895 g/cm ³ or more is preferable because the rigidity is improved, and a density of 0.925 g/cm ³ or less is preferable because the effect of improving transparency and impact resistance is sufficient. Linear low density polyethylene is most preferred in terms of providing unbreakable moldings.

The ratio of plant-derived carbon to the total carbon content in biomass polyethylene (b) is called biomass degree, and can be obtained by measuring the concentration of ¹⁴ C contained in biomass polyethylene (b). That is, while the air contains a certain proportion of ¹⁴ C, the carbon of the petroleum-derived resin does not contain ¹⁴ C, so the concentration of ¹⁴ C contained in the biomass polyethylene (b) is measured. The biomass degree can be determined by Specifically, when all the carbon in the biomass polyethylene (b) is petroleum-derived, the biomass degree is 0%, and when all the carbon in the biomass polyethylene (b) is plant-derived, the biomass degree is 100%. becomes. Test methods for measuring the concentration of ¹⁴ C include ASTM D6866.
The biomass polyethylene (b) has a melt flow rate of 0.1 to 72 g/10 minutes according to ASTM D1238 (190° C., 2.16 kg load) from the viewpoint of moldability of the resulting propylene-based polymer composition. A range is preferably used, and a range of 0.21 to 72 g/10 min is more preferred.

Commercially available products of biomass polyethylene (b) include, for example, the “Green PE” series (manufactured by Braskem).

<<Propylene Polymer Composition>>
The propylene-based polymer composition contains 51 to 95 parts by weight of block copolymer (a) and 5 to 49 parts by weight of biomass polyethylene (b), totaling 100 parts by weight. The propylene-based polymer composition preferably contains 51 to 90 parts by weight of the block copolymer (a) and 10 to 49 parts by weight of the biomass polyethylene (b) in a total amount of 100 parts by weight. (a) 55 to 90 parts by weight and biomass polyethylene (b) 10 to 45 parts by weight, more preferably a total of 100 parts by weight, and the propylene-based polymer composition is a block copolymer (a) More preferably, a total of 100 parts by weight containing 60 to 90 parts by weight and 10 to 40 parts by weight of biomass polyethylene (b). When the biomass polyethylene (b) is 5 parts by weight or more, the effect of reducing the environmental load can be expected, and when it is 49 parts by weight or less, the molded article can be sufficiently rigid.

When the biomass polyethylene (b) is high-density polyethylene, the propylene-based polymer composition contains 75 to 95 parts by weight of the block copolymer (a) and 5 to 25 parts by weight of the biomass polyethylene (b). It is preferably 100 parts by weight, more preferably 100 parts by weight in total containing 80 to 90 parts by weight of the block copolymer (a) and 10 to 20 parts by weight of the biomass polyethylene (b).
When the biomass polyethylene (b) is linear low-density polyethylene, the propylene-based polymer composition contains 51 to 80 parts by weight of the block copolymer (a) and 20 to 49 parts by weight of the biomass polyethylene (b). , preferably a total of 100 parts by weight, more preferably a total of 100 parts by weight containing 51 to 70 parts by weight of the block copolymer (a) and 30 to 49 parts by weight of the biomass polyethylene (b) .

The biomass degree of the propylene-based polymer composition is 8.4 to 49%, preferably 8.8 to 45%, more preferably 9.0 to 40%, still more preferably 9.0 to 30%. . When the degree of biomass is 8.4% or more, the effect of reducing the environmental load can be expected, and when it is 49% or less, the rigidity of the molded product is sufficiently obtained.

The biomass degree (%) of the propylene-based polymer composition is a numerical value calculated by the following formula.
Biomass degree (%)=[{A×(B/100)}/C]×100 Expression (1)
A: Weight of biomass polyethylene (b) B: Biomass degree (%) of biomass polyethylene (b)
C: Weight of propylene-based polymer composition The biomass degree (%) of the biomass polyethylene (b) can be measured and calculated according to ASTM D6866.

<Nucleating agent>
From the viewpoint of improving the rigidity of the molded article, the propylene-based polymer composition preferably contains a nucleating agent. Known nucleating agents can be used, for example, sterically hindered amide compounds, organic dicarboxylic acid metal salts, organic monocarboxylic acid metal salts, aromatic carboxylic acid compounds or derivatives thereof, sorbitol compounds or derivatives thereof, Nonitol compounds or derivatives thereof, metal salts of diterpenic acids, polymer nucleating agents, hydrated magnesium silicate, and the like. Among them, aromatic carboxylic acid-based compounds are preferred, and hydroxy-di-P-tert-butyl-aluminum benzoate and hydrous magnesium silicate are more preferred.

The content of the nucleating agent is preferably 0.01 to 0.6 parts by weight, more preferably 0.05 to 0.5 parts by weight, and still more preferably 0 parts by weight with respect to 100 parts by weight of the propylene-based polymer composition. .1 to 0.4 parts by weight, particularly preferably 0.1 to 0.3 parts by weight. The content of the nucleating agent can range from 0.10 to 0.4 parts by weight or from 0.10 to 0.3 parts by weight. When the content of the nucleating agent is 0.01 parts by weight or more, the molded product can be expected to exhibit rigidity. It is advantageous from the point of cost-effectiveness (cost performance) and dissolution.

<Other additives>
In addition to the above components, the propylene-based polymer composition contains additives such as various antioxidants used as stabilizers for propylene-based polymers, ultraviolet absorbers, light stabilizers, and neutralizers. can be compounded.
The content of the antioxidant, ultraviolet absorber and light stabilizer is preferably 0.01 to 1 part by weight, more preferably 0.02 to 0.1 part by weight, per 100 parts by weight of the propylene-based polymer composition. 5 parts by weight, more preferably 0.03 to 0.2 parts by weight.
The content of the neutralizing agent is preferably 0.01 to 0.5 parts by weight, more preferably 0.03 to 0.2 parts by weight, and still more preferably 0 parts by weight with respect to 100 parts by weight of the propylene-based polymer composition. 0.05 to 0.1 parts by weight.

Antioxidants include bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol-di-phosphite, di-stearyl-pentaerythritol-di-phosphite, bis(2,4-di -t-butylphenyl)pentaerythritol-di-phosphite, tris(2,4-di-t-butylphenyl)phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene - di-phosphonite, tetrakis (2,4-di-t-butyl-5-methylphenyl)-4,4'-biphenylene-di-phosphonite and other phosphorous antioxidants, 2,6-di -t-butyl-p-cresol, tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxylphenyl)propionate]methane, 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, tris(3,5 -Di-t-butyl-4-hydroxybenzyl) phenolic antioxidants such as isocyanurate, di-stearyl-β,β'-thio-di-propionate, di-myristyl-β,β'-thio-di- Thio-based antioxidants such as propionate, di-lauryl-β,β'-thio-di-propionate, and the like.

UV absorbers include 2-hydroxy-4-n-octoxybenzophenone, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2 UV absorbers such as '-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole and the like are included.

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-2-(4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl succinate) ) ethanol condensate, poly {[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4diyl][(2,2,6,6- Tetramethyl-4-piperidyl)imino]hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl)imino]}, N,N'-bis(3-aminopropyl)ethylenediamine-2,4- Light stabilizers such as bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-triazine condensates may be mentioned. can.

Furthermore, 5,7-di-t-butyl-3-(3,4-di- Lactone-based antioxidants such as methyl-phenyl)-3H-benzofuran-2-one, vitamin E-based antioxidants such as those represented by the following formula (4), and the like can be used as long as the effects of the present invention are not impaired. It can be mentioned as an additive.

Examples of neutralizing agents include metal fatty acid salts such as calcium stearate, zinc stearate and magnesium stearate; magnesium-aluminum composite hydroxide salt represented by; lithium-aluminum composite hydroxide salt represented by the following formula (6) of Mizucalac (registered trademark) (manufactured by Mizusawa Chemical Industry Co., Ltd.); and the like.
Mg _1-x Al _x (OH) ₂ (CO ₃ ) _x/2 ·mH ₂ O (5)
[In the formula, x is 0<x≤0.5, and m is a positive integer of 3 or less. ]
[Al ₂ Li(OH) ₆ ] _n X·mH ₂ O (6)
[In the formula, X is an inorganic or organic anion, n is the valence of the anion (X), and m is a positive integer of 3 or less. ]

Furthermore, the propylene-based polymer composition can contain various known additives such as antistatic agents, lubricants, dispersants, dyes, pigments, etc., as long as they do not impair the object of the present invention.

Polymers other than block copolymer (a) and biopolyethylene (b), such as polyethylene, ethylene-propylene copolymer, Mono-, binary- and terpolymers such as ethylene-propylene-diene copolymers, ethylene-1-butene copolymers, ethylene-vinyl acetate copolymers, ethylene-acrylate copolymers, acrylate polymers, may contain. The content of the other polymer can be, for example, 1 to 30 parts by weight with respect to 100 parts by weight of the propylene-based polymer composition. Likewise, it is possible to blend elastomers such as natural rubber, butyl rubber, diene rubber, EPR, EPDM. Furthermore, it is also possible to use general-purpose inorganic fillers such as talc, calcium carbonate, silica, alumina, gypsum, and mica.

<<Method for Producing Propylene Polymer Composition>>
The propylene-based polymer composition of the present invention comprises a block copolymer (a), a biomass polyethylene (b), and, if necessary, predetermined amounts of a nucleating agent and other additives. It can be obtained by throwing into a super mixer, ribbon blender, etc. and mixing, and then melt-kneading in a temperature range of 190 to 260 ° C. with a single-screw extruder, twin-screw extruder, Banbury mixer, Prabender, rolls, etc. .

<<Molded article containing propylene-based polymer composition>>
A molded article containing the propylene-based polymer composition of the present invention is obtained by molding the propylene-based polymer composition into a desired shape by a molding method such as injection molding, extrusion molding, hollow molding, vacuum molding, or compression molding. .

The flexural modulus measured according to JIS K7171 is preferably in the range of 700 to 2200 MPa. When the flexural modulus is 700 MPa or more, the releasability from the mold during injection molding is good, and when it is 2200 MPa or less, the impact resistance of the molded product is good. The flexural modulus is more preferably 1000 to 2000 MPa, still more preferably 1100 to 1900 MPa, and particularly preferably 1200 to 1900 MPa.

The Charpy impact strength measured according to JIS K7111 is preferably in the range of 3.0 kJ/m ² or more. When the Charpy impact strength is 3.0 kJ/m ² or more, damage during transportation of the molded product is suppressed. The Charpy impact strength is more preferably 3.5 kJ/m ² or more, still more preferably 4.0 kJ/m ² or more.

A molded article containing a propylene-based polymer composition has excellent characteristics such as being excellent in rigidity and impact resistance and not cracking even when containing biomass polyethylene. The use of the molded article is not particularly limited, but it can be widely used in various applications such as various industrial materials, automobile-related parts, various containers for medical and cosmetic applications, daily necessities, films and fibers.

EXAMPLES The present invention will be described in detail below with reference to Examples, Comparative Examples and Reference Examples, but the present invention is not limited to these Examples.
In the following examples, comparative examples and reference examples, the physical properties of the propylene-ethylene block copolymers (a) and (b) and the propylene-based polymer composition were measured according to the following methods.

<1. Measurement method>
(1) Melt flow rate (MFR):
The melt flow rates (MFR) of the propylene-ethylene block copolymers (a) and (b) and the propylene homopolymers (ac-1) and (ac-1') are 230°C and 230°C in accordance with JIS K7210. Measured with a .16 kg load.

The melt flow rate (MFR) of the propylene-ethylene random copolymer (ac-2) is the melt flow rate (MFR) of the block copolymers (a) and (ac-1), and the block copolymer (a) It was calculated using the following formula from the content ratio of (ac-1) and (ac-2) in.
Log _e [MFR of block copolymer (a)] = [content ratio of (ac-1)] × Log _e [MFR of (ac-1)] + [content ratio of (ac-2)] × Log _e [MFR of (ac-2)]
The melt flow rate (MFR) of the propylene-ethylene random copolymer (ac-2') is similarly the melt flow rate (MFR) of the block copolymers (b) and (ac-1'), and the block copolymer It was calculated using the above formula from the content ratio of (ac-1′) and (ac-2′) in coalescence (b).

(2) Calculation of ethylene content of propylene-ethylene block copolymer (a)
Using an ethylene-propylene random copolymer whose ethylene content was tested by ¹³ C-NMR as a reference material, infrared spectroscopic measurement was performed, and from the peak derived from ethylene appearing around 720 to 730 cm ^-1 , the absorbance - ethylene content A calibration curve for was created. Using the calibration curve thus obtained, the ethylene contents of the propylene-ethylene block copolymers (a) and (b) were calculated. For the infrared spectroscopic measurement, a film having a thickness of about 500 μm was formed by press-molding pellets of each copolymer.

The ethylene content of the propylene-ethylene random copolymer (ac-2) is the ethylene content of the block copolymer (a), and (ac-1) and (ac -2) was calculated from the content ratio. Similarly, the ethylene content of the propylene-ethylene random copolymer (ac-2') is the same as the ethylene content of the block copolymer (b) and (ac-1' in the block copolymer (b). ) and (ac-2′).

(3) Calculation of amount of each component of propylene-ethylene block copolymer (a) and (b) Contents of coalesced (ac-1) and propylene-ethylene random copolymer (ac-2), and propylene homopolymer (ac-1′) and propylene-ethylene in propylene-ethylene block copolymer (b) The content of the random copolymer (ac-2') was calculated. The apparatus and measurement conditions are as follows.

[Device]
(TREF section)
TREF column: 4.3 mmφ×150 mm stainless steel column Column filler: 100 μm surface-deactivated glass beads Heating method: aluminum heat block Cooling method: Peltier element (Peltier element is cooled with water)
Temperature distribution: ±0.5°C
Temperature controller: Chino Co., Ltd. digital program controller KP1000 (valve oven)
Heating method: Air bath oven Measurement temperature: 140°C
Temperature distribution: ±1°C
Valve: 6-way valve 4-way valve

(Sample injection part)
Injection method: loop injection method Injection volume: loop size 0.1ml
Inlet heating method: aluminum heat block Measurement temperature: 140°C

(Detection unit)
Detector: Fixed wavelength infrared detector MIRAN 1A manufactured by FOXBORO
Detection wavelength: 3.42 μm
High-temperature flow cell: Micro flow cell for LC-IR Optical path length 1.5 mm Window shape 2φ×
4mm oblong synthetic sapphire window plate Measurement temperature: 140℃
(pump section)
Liquid transfer pump: SSC-3461 pump manufactured by Senshu Kagaku Co., Ltd.

[Measurement condition]
Solvent: o-dichlorobenzene (containing 0.5 mg/mL BHT)
Sample concentration: 5 mg/mL
Sample injection volume: 0.1 mL
Solvent flow rate: 1 mL/min

(4) Flexural modulus The flexural modulus was measured according to JIS K7171.

(5) Charpy impact strength Charpy impact strength at 23°C was measured according to JIS K7111.

(6) Crack test in MD and TD directions A test piece of 120 mm x 120 mm x 2 mm was produced by injection molding (molding temperature: 200°C, mold temperature: 40°C). As shown in FIG. 1, in parallel to the MD and TD directions of the test piece, two cuts with a length of about 30 mm were made with pruning shears so that the width was 15 mm. Cracks were evaluated according to the following criteria.
◯: When bent at 90 degrees or more, even if a break (tear, crack) or whitening occurs, it does not split into several parts (does not crack).
x: When bent over 90 degrees, it splits into several parts (cracks).

<2. Resin, Additive>
2-1. Production of propylene-ethylene block copolymers (a) and (b) (1) Production Example 1
(i) Production of solid catalyst component (a-1) 20 liters of dehydrated and deoxygenated n-heptane was introduced into a nitrogen-purged vessel with an internal volume of 50 liters and equipped with a stirrer, followed by 10 mol of magnesium chloride and tetrabutoxytitanium. 20 mol and reacted at 95° C. for 2 hours, then the temperature was lowered to 40° C. and 12 liters of methylhydropolysiloxane (viscosity 20 centistokes) was introduced and reacted for an additional 3 hours and then reacted. The liquid was taken out and the solid component formed was washed with n-heptane.
Subsequently, 5 liters of dehydrated and deoxygenated n-heptane was introduced into the vessel using the vessel equipped with a stirrer, and then 3 mol of the solid component synthesized above was introduced in terms of magnesium atom. Next, 5 mol of silicon tetrachloride was mixed with 2.5 liters of n-heptane and introduced at 30° C. over 30 minutes. The resulting solid component was washed with n-heptane.

Furthermore, subsequently, 2.5 liters of dehydrated and deoxygenated n-heptane was introduced into the vessel using the vessel equipped with a stirrer, mixed with 0.3 mol of phthaloyl chloride, and introduced at 90° C. for 30 minutes. and reacted at 95° C. for 1 hour. After completion of the reaction, it was washed with n-heptane. Then, 2 liters of titanium tetrachloride was added at room temperature, and the mixture was heated to 100° C. and reacted for 2 hours. After completion of the reaction, it was washed with n-heptane. Further, 0.6 liter of silicon tetrachloride and 8 liters of n-heptane were introduced, reacted at 90° C. for 1 hour, and thoroughly washed with n-heptane to obtain a solid component. This solid component contained 1.30% by weight of titanium.

Next, 8 liters of n-heptane, 400 g of the solid component obtained above, 0.27 mol of t-butyl-methyl-dimethoxysilane, and 0.27 mol of vinyltrimethylsilane were introduced into the nitrogen-purged vessel equipped with a stirrer. and brought into contact at 30° C. for 1 hour. After cooling to 15° C., 1.5 mol of triethylaluminum diluted in n-heptane was introduced over 30 minutes under 15° C. conditions. 390 g of solid catalyst component (a-1) was obtained by washing with -heptane. The obtained solid catalyst component (a-1) contained 1.22% by weight of titanium.

Further, 6 liters of n-heptane and 1 mol of triisobutylaluminum diluted in n-heptane were introduced over 30 minutes at 15°C, and then propylene was added to about 0.00 while controlling not to exceed 20°C. Prepolymerization was carried out by introducing 4 kg/hour for 1 hour. As a result, a polypropylene-containing solid catalyst component (a-1) in which 0.9 g of propylene was polymerized per 1 g of solid was obtained.

(ii) Production of Propylene-Ethylene Block Copolymer (a) Polymerization was carried out using a continuous reactor comprising two connected fluidized bed reactors each having an internal volume of 230 liters.
First, in the first reactor, the polymerization temperature is 85° C., the propylene partial pressure is 2.16 MPa (absolute pressure), and hydrogen is continuously supplied as a molecular weight modifier so that the molar ratio of hydrogen/propylene is 0.013. At the same time, 5.25 g/hr of triethylaluminum was supplied as the solid catalyst component (a-1) so that the above-described catalyst was supplied so that the polymer polymerization rate was 20 kg/hr. The powder (crystalline propylene polymer) polymerized in the first reactor was continuously extracted so that the amount of powder held in the reactor was 60 kg, and was continuously transferred to the second reactor (previous polymerization step ).

Propylene and ethylene were continuously supplied at a polymerization temperature of 80° C. and a pressure of 1.5 MPa at an ethylene/propylene molar ratio of 1.15. It was continuously supplied so that the molar ratio of hydrogen/propylene was 0.010, and ethyl alcohol was supplied as an active hydrogen compound so that the molar ratio was 3.0 times that of triethylaluminum. The powder polymerized in the second reactor is continuously withdrawn into a vessel so that the amount of powder held in the reactor becomes 40 kg. A polymer was obtained (second stage polymerization step).

The temperature rising elution fractionation (TREF) measurement was performed on the propylene-ethylene block copolymer (a), and a graph showing the amount of elution and the cumulative amount of elution was obtained in the same manner as in FIG. T(α) corresponds to the elution peak temperature of low crystallinity (ac-2), and T(β) corresponds to the elution peak temperature of high crystallinity (ac-1). The T(α) and T(β) elution peaks were well separable.
The integrated amount W(α) of the component eluted by T(C) is the content of (ac-2), and the integrated amount W(β) of the component eluted at T(C) or higher is (ac-1) The content of each component was calculated assuming that it was the content of As a result, the proportions of (ac-1) and (ac-2) in the propylene-ethylene block copolymer (a) were 91.5% by weight and 8.5% by weight, respectively.

The obtained propylene-ethylene block copolymer was designated as PP-1. Table 1 shows the composition and physical properties of PP-1.

(2) Production Example 2
Production of propylene-ethylene block copolymer (b) Polymerization was carried out using the catalyst and polymerization equipment described in Example 1 of JP-A-2015-3981. In the first reactor, polymerization temperature: 75° C., propylene partial pressure: 1.8 MPa (absolute pressure), and hydrogen as a molecular weight modifier is continuously supplied so that the hydrogen/propylene molar ratio is 0.026. At the same time, 5.2 g/hr of triethylaluminum was separately supplied, and the amount of catalyst was supplied so that the production amount was 20 kg/hr. The produced powder was continuously withdrawn at 20 kg/hr so that the amount of powder held in the reactor was 60 kg, and was continuously transferred to the second reactor (first stage polymerization step).

In the second reactor, propylene and ethylene were continuously supplied so that the polymerization temperature was 80° C., the monomer pressure was 1.5 MPa, and the ethylene/propylene molar ratio was 1.1, and the molecular weight was adjusted. Hydrogen as an agent is continuously supplied so that the hydrogen/propylene molar ratio is 0.0020, and ethyl alcohol is supplied to the first reactor so that the molar ratio is 1.6 times that of triethylaluminum. supplied to The powder polymerized in the second reactor was continuously discharged into the vessel at a rate of 22.5 kg/hr so that the amount of powder held in the reactor was 40 kg, and the discharged powder was supplied with nitrogen gas containing moisture. to stop the reaction and obtain a propylene-ethylene block copolymer (post-polymerization step).

The propylene-ethylene block copolymer (b) was subjected to temperature-rising elution fractionation (TREF) measurement, and a graph showing the amount of elution and the cumulative amount of elution was obtained in the same manner as in FIG. T(α) corresponds to the elution peak temperature of low crystallinity (ac-2′), and T(β) corresponds to the elution peak temperature of high crystallinity (ac-1′). . The T(α) and T(β) elution peaks were well separable.
The integrated amount W(α) of the component eluted before T(C) is the content of (ac-2′), and the integrated amount W(β) of the component eluted above T(C) is (ac-1 '), the content of each component was calculated. As a result, the proportions of (ac-1') and (ac-2') in the propylene-ethylene block copolymer (b) were 87.3% by weight and 12.7% by weight, respectively.

The obtained propylene-ethylene block copolymer was designated as PP-2. Table 2 shows the composition and physical properties of PP-2.

2-2. biomass polyethylene (b)
High density polyethylene (HDPE)
PE-1: Trade name “Green PE SGM9450F” manufactured by Braskem
Density: 0.952 g/cm ³ , melt flow rate according to ASTM D1238 (190° C. and 2.16 kg load): 0.12 g/10 minutes, degree of biomass: 96%. (Characteristics other than MFR show manufacturer's catalog values.)
Linear low density polyethylene (LLDPE)
PE-2: Trade name “Green PE SLL118” manufactured by Braskem
Density: 0.916 g/cm ³ , melt flow rate according to ASTM D1238 (190° C. and 2.16 kg load): 1.0 g/10 minutes, degree of biomass: 87%. (All characteristics indicate manufacturer catalog values.)

2-3. Other additives (A-1) Hindered phenolic antioxidant "IR1010"
Tetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxylphenyl)propionate]methane. BASF Japan Ltd., trade name "IRGANOX (registered trademark) 1010".
(A-2) Phosphorus antioxidant "IF168"
Tris(2,4-di-t-butylphenyl)phosphite. BASF Japan Ltd., trade name "IRGAFOS (registered trademark) 168".
(B-1) Neutralizing agent "CAST"
Calcium stearate. Made by NOF Corporation.
(N-1) Nucleating agent "ALPTB"
Aluminum hydroxy-di-P-tert-butyl benzoate. Manufactured by Oxalis Chemicals Co., Ltd., trade name "AL-PTBBA".
(N-2) Nucleating agent "P7"
Hydrous _magnesium silicate ( _Mg3Si4O10 (OH) ₂ ) _. Manufactured by Matsumura Sangyo Co., Ltd., trade name “P7”.

Examples 1 to 4, Comparative Example 1 and Reference Example 1
Each polymer and additive were prepared at the blending ratio (parts by weight) shown in Table 3, and after dry blending with a super mixer, using a TEM-35B twin screw extruder manufactured by Shibaura Kikai Co., Ltd., a die under a nitrogen atmosphere. The mixture was melt-kneaded at an outlet temperature of 220° C. and pelletized. Physical properties were measured using the obtained pellets. Table 3 shows the evaluation results.

As is clear from Table 3, the composition of Example 1 has a high degree of biomass and exhibits good mechanical properties equivalent to those of Reference Example 1, which does not contain biomass polyethylene. Here, the propylene-based polymer compositions of Examples 1 to 4 contain specified amounts of propylene-ethylene block copolymer and biomass polyethylene, are materials that can reduce environmental load, and have excellent impact resistance and rigidity. The results of the cracking test were also good.
Among them, Example 2, which uses linear low-density polyethylene as the biomass polyethylene, maintains rigidity and crack-resistant properties even when the biomass degree is increased to 39.2%, and has much better impact resistance. and is preferred.
On the other hand, in the composition of Comparative Example 1, the content of biomass polyethylene exceeded 49 parts by weight with respect to the total of 100 parts by weight of the propylene-ethylene block copolymer and biomass polyethylene, and cracks occurred in the TD direction cracking test. did.

The propylene-based polymer composition of the present invention provides molded articles that are excellent in rigidity and impact resistance and that do not crack even when containing biomass polyethylene. The composition has a biomass degree of 8.4 to 49% and is useful because it can reduce environmental load.

Claims (6)

51 to 95 parts by weight of a block copolymer (a) of propylene and at least one selected from ethylene and α-olefins having 4 or more carbon atoms, and 5 to 49 parts by weight of biomass polyethylene (b), A total of 100 parts by weight of a propylene-based polymer composition,
The block copolymer (a) satisfies the following conditions (Ai) and (A-ii),
A propylene-based polymer composition having a biomass degree of 8.4 to 49%.
(Ai) The content of ethylene and α-olefins having 4 or more carbon atoms is in the range of more than 5% by weight and 30% by weight or less.
(A-ii) According to JIS K7210, the melt flow rate measured at 230° C. and a load of 2.16 kg is in the range of 0.5 to 100 g/10 minutes. The block copolymer (a) is
A random copolymer of propylene and at least one selected from ethylene and α-olefins having 4 or more carbon atoms, wherein the content of ethylene and α-olefins having 4 or more carbon atoms is 5% by weight or less. a random copolymer or a propylene homopolymer (ac-1), and
A random copolymer of propylene and at least one selected from ethylene and α-olefins having 4 or more carbon atoms, wherein the content of ethylene and α-olefins having 4 or more carbon atoms is 15 to 85% by weight. Range of random copolymers (ac-2)
The propylene-based polymer composition according to claim 1, which is a multi-stage polymer consisting of and satisfies the following conditions (AC-i) to (AC-iii).
(AC-i) The ratio of (ac-1) and (ac-2) is 40 to 95 parts by weight of (ac-1) and 5 to 60 parts by weight of (ac-2), totaling 100 parts by weight is.
(AC-ii) The melt flow rate of (ac-1) measured at 230° C. and a load of 2.16 kg according to JIS K7210 is in the range of 0.5 to 350 g/10 minutes.
(AC-iii) The melt flow rate of (ac-2) measured at 230° C. and a load of 2.16 kg according to JIS K7210 is in the range of 0.001 to 0.5 g/10 minutes. 2. The propylene-based polymer composition according to claim 1, wherein at least one selected from ethylene and α-olefins having 4 or more carbon atoms is ethylene. The propylene-based polymer composition according to claim 1, wherein biomass polyethylene (b) is linear low density polyethylene. A propylene-based polymer composition containing 0.01 to 0.6 parts by weight of a nucleating agent per 100 parts by weight of the propylene-based polymer composition according to claim 1. A molded article comprising the propylene-based polymer composition according to any one of claims 1 to 5.