JP2021195553A - Propylene-based polymer composition and molded article - Google Patents

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

The present invention relates to a propylene-based polymer composition having a biomass degree of 8.4 to 49% and a molded product thereof. Specifically, the present invention is a propylene-based polymer that provides a molded product having excellent rigidity and not cracking even if it contains biomass polyethylene. Regarding the composition. In the present invention, "breaking" means that a force is applied to divide it into several parts. In addition, "not cracked" means any of the following.
(1) No cracks (crevices, cracks) are formed, and it is not divided into several parts.
(2) There are cracks (crevices, cracks), but they are not divided into several parts.

Propylene-based resins have excellent rigidity, heat resistance, moldability, transparency, and chemical resistance, and are used in various industrial materials, automobile-related parts, various containers for medical and cosmetic products, daily necessities, films, and fibers. Widely used for various purposes.
On the other hand, in recent years, environmental pollution of plastics has become a problem, and how to deal with it has become an issue. One of the measures is to use a plant-derived plastic (biomass plastic) that is carbon-neutral. Although plant-derived polypropylene has been studied, it has not been put on the market at present, 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 polypropylene and biomass polyethylene and melt-kneading them is inferior in miscibility, it is a problem that the molded product obtained from the mixture is cracked. Therefore, there is a demand for a polypropylene composition having excellent miscibility even if it contains biomass polyethylene.

Japanese Unexamined Patent Publication No. 2019-34519 Japanese Unexamined Patent Publication No. 2016-27171

An object of the present invention is to provide a molded product having excellent rigidity and not cracking even if it contains biomass polyethylene in the context of the prior art, and a propylene-based polymer composition having a biomass degree of 8.4 to 49% and molding thereof. It is to provide goods.

The present inventor has made diligent studies, and by using a specific propylene-based polymer mixture, a molded product having excellent rigidity and not cracking even if it contains biomass polyethylene is obtained, and the biomass degree is 8.4 to 49%. We have found a propylene-based polymer composition and a molded product thereof, and have completed the present invention.
That is, the present invention provides a propylene-based polymer composition having the following biomass degree of 8.4 to 49% and a molded product thereof.

[1] 51 to 90 parts by weight of a propylene-based (co) polymer (a) satisfying the following conditions (Hi) to (Hv) and biomass polyethylene (b) 10 to satisfying the following conditions (Li). A propylene-based polymer composition containing 49 parts by weight in a total amount of 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-based copolymer composed of propylene and an α-olefin having a content of less than 1% by weight.
(H-ii) The melt flow rate (hereinafter, abbreviated as MFR) based on JIS K7210 (230 ° C., 2.16 kg load) is in the range of 0.5 to 100 g / 10 minutes.
(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 with respect to 100 parts by weight of the propylene-based polymer composition according to [1].
[3] A molded product obtained by using the propylene-based polymer composition according to [1] or [2].

The molded product produced by using the propylene-based polymer composition having a biomass degree of 8.4 to 49% of the present invention contributes to the reduction of environmental load, and is excellent in rigidity even if it contains biomass polyethylene and does not crack. Is useful for giving. In particular, injection molded products are very useful.

FIG. 1 is a diagram of a crack test in the MD and TD directions carried out by making a cut in an injection test piece having a size of 120 mm × 120 mm × 2 mm.

The propylene-based polymer composition of the present invention comprises 51 to 90 parts by weight of the propylene-based (co) polymer (a) satisfying the following conditions (Hi) to (Hv) and the following conditions (L-i). A propylene-based polymer composition containing 10 to 49 parts by weight of the filled biomass polyethylene (b) and having a biomass degree of 8.4 to 49%, which contributes to reduction of environmental load and deteriorates performance. It is characterized by not doing so.
(Hi) A metallocene-based propylene homopolymer or a metallocene-based propylene-based copolymer composed of propylene and an α-olefin having a 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 minutes.
(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.
Hereinafter, the propylene-based polymer composition and the molded product of the present invention will be described in detail.

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

(I) α-olefin of propylene-based (co) polymer (a) The propylene-based (co) polymer (a) used in the propylene-based polymer composition of the present invention is preferably a metallocene-based propylene homopolymer. It is a metallocene-based propylene-based copolymer composed of propylene and α-olefin having a content of less than 1% by weight, or a mixture thereof.
As the propylene-based (co) polymer (a), a homopolymer is desirable from the viewpoint of rigidity, and a random copolymer composed of propylene and α-olefin is desirable from the viewpoint of transparency. Examples of the α-olefin used for the copolymerization include α-olefins having 2 to 20 carbon atoms excluding propylene, and examples thereof include ethylene, 1-butene, 1-hexene, and 1-octene. One type or two or more types of α-olefins copolymerized with propylene may be used. Of these, ethylene and 1-butene are preferable. Ethylene is more preferred. Further, these propylene-based polymers may be used by mixing two or more kinds. Further, it is preferable that the content of α-olefin is less than 1% by weight from the viewpoint of rigidity.

Specific examples of the propylene-based copolymer include a propylene-ethylene copolymer, a propylene-1-butene copolymer, a propylene-1-hexene copolymer, a propylene-1-octene copolymer, and a propylene-ethylene. Binary or any combination of any small amounts of comonomer, such as -1-butene copolymer, propylene-ethylene-1-hexene copolymer, propylene-1-butene-1-octene copolymer, etc. A ternary copolymer can be exemplified.

The α-olefin content used in the propylene-based (co) polymer (a) is preferably less than 1% by weight, more preferably less than 0.8% by weight, still more preferably less than 0.5% by weight. When the content of α-olefin is less than 1% by weight, the rigidity is improved and there is no possibility of deformation when the containers are stacked.
Here, each content of propylene and α-olefin is a value measured by ^{the 13 C-NMR method under the following conditions.}
Equipment: JEOL-GSX270 manufactured by JEOL Ltd.
Concentration: 300 mg / 2 mL
Solvent: Orthodichlorobenzene

(Ii) Melt flow rate (MFR) of propylene-based (co) polymer (a)
The propylene-based (co) polymer (a) used in the present invention has a melt flow rate (MFR) in the range of 0.5 to 100 g / 10 minutes according to JIS K7210 (230 ° C., 2.16 kg load). It is preferably 5 to 60 g / 10 minutes, more preferably 10 to 40 g / 10 minutes. When the melt flow rate (MFR) is 0.5 g / 10 minutes or more, the molding processability is improved and a satisfactory product can be obtained. Further, when it is 100 g / 10 minutes or less, the mechanical strength is improved.
The melt flow rate (MFR) is determined by adjusting the temperature and pressure, which are the polymerization conditions of the propylene-based (co) polymer (a), and by controlling the amount of hydrogenation in the method of adding a chain transfer agent such as hydrogen at the time of polymerization. , Can be easily adjusted.

(Iii) Three-dimensional regularity of the propylene-based (co) polymer (a) When the propylene-based (co) polymer (a) used in the present invention is a propylene homopolymer, the isotactic pentad fraction is 0. It is preferably .90 or more, more preferably 0.94 to 0.98. When the isotactic pentad fraction is 0.90 or more, the rigidity can be satisfied.
Here, the isotactic pentad fraction is a value measured by the proton decoupling method using ^{13 C-NMR.}

(Iv) Catalyst of propylene-based (co) polymer (a) The propylene-based (co) polymer (a) used in the present invention is a polymer produced by using a metallocene catalyst as a polymerization catalyst. By using a metallocene catalyst, it becomes difficult to crack when the biomass polyethylene (b) is contained.

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

As the metallocene catalyst, a supported type is preferable.
A particularly preferable example of the supported metallocene catalyst is an ion-exchangeable layered silicate in which the carrier also functions as a co-catalyst. Specifically, it is obtained by combining the component [A] and the component [B] described below and the component [C] added as needed.

-Component [A] Metallocene complex A transition metal compound of Group 4 to 6 of the Periodic Table having at least one conjugated five-membered ring ligand.
-Component [B] Auxiliary catalyst Ion-exchangeable layered silicate
-Component [C] Organoaluminium compound

-Component [A] metallocene complex As the above-mentioned component [A], specifically, a compound represented by the following formula [I] can be used.
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 binding group that bridges two conjugated five-membered ring ligands.
M represents a transition metal of Group 4 to 6 of the periodic table, and titanium, zirconium, and hafnium are preferable.
X and Y are independently hydrogen, halogen, hydrocarbon groups having 1 to 20 carbon atoms, oxygen-containing hydrocarbon groups having 1 to 20 carbon atoms, nitrogen-containing hydrocarbon groups having 1 to 20 carbon atoms, and 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 is shown.

R ¹ and R ² are independently each of 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, and phosphorus. Indicates a hydrocarbon group contained, a hydrocarbon group containing nitrogen, or a hydrocarbon group containing boron. Further, two ^{R 1} or two ^{R 2} adjacent may form a _C 4 _{-C 10} ring bonded respectively. In particular, it is preferable to form a 6-membered ring and a 7-membered ring to form an indene ring and 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 binding group Q that bridges between the two conjugated five-membered ring ligands include an alkylene group, an alkylidene group, a silylene group, and a germanylene group. These may be hydrogen atoms substituted with an alkyl group, a halogen or the like. In particular, a silylene group is preferable.

Specific 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) Ethylene bis (2-methylindenyl) 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) 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-azurenyl)] zirconium dichloride
(17) Dimethylsilylenebis [1- (2-methyl-4- (4-chlorophenyl) -4H-azurenyl)] zirconium dichloride
(18) Dimethylsilylenebis [1- (2-ethyl-4- (4-chlorophenyl) -4H-azurenyl)] zirconium dichloride
(19) Dimethylsilylenebis [1- (2-ethyl-4-naphthyl-4H-azurenyl)] zirconium dichloride

(20) Diphenylcilylenebis [1- (2-methyl-4- (4-chlorophenyl) -4H-azurenyl)] 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-azurenyl)] zirconium dichloride
(24) Dimethylgelmilenebis (Indenyl) Zirconium Dichloride
(25) Dimethylgelmilene (cyclopentadienyl) (fluorenyl) zirconium dichloride Further, the same compounds as described above are preferably mentioned for other group 4, 5 and 6 transition metal compounds such as titanium compounds and hafnium compounds. These compounds may be used in combination with respect to the catalyst component and the catalyst of the present invention.

-Component [B] co-catalyst (ion-exchangeable layered silicate)
The ion-exchangeable layered silicate is not limited to a naturally produced one, and may be an artificial synthetic product. A clay compound can be used as an ion-exchangeable layered silicate, and specific examples of the clay compound are as follows, for example, described in "Clay Minerals" by Haruo Shiramizu, Asakura Shoten (1995). Examples include layered silicates.
(A) Kaolinites such as Dickite, Nacrite, Kaolinite, Anokisite, Metahaloysite, Halloysite, etc., and serpentine tribes such as Chrysotile, Rizaldite, Antigolite, etc., whose main constituent layers are 1: 1 type structures.
(B) Montmorillonite, Zauconite, Bidelite, Nontronite, Saponite, Hectorite, Smectite such as Stevensite, Vermiculite such as Vermiculite, Mica, Illite, Sericite, whose main constituent layers are 2: 1 type structure. Mica tribe such as sea green stone, attaparjite, sepiolite, parigolskite, bentonite, pyrophyllite, talc, chlorite group

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

The activity can be improved by chemically treating these silicates 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-exchangeable layered silicate particles, exchanges interlayer cations, and elutes some or all of the cations such as Al, Fe, and Mg in the crystal structure. can.
Examples of the acid used in the acid treatment include hydrochloric acid, nitric acid, sulfuric acid and the like, but an inorganic acid is preferable, and sulfuric acid is particularly preferable.
The acid treatment conditions are not particularly limited, but are preferably conditions 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. You may. After acid treatment, washing is usually performed. Cleaning is an operation of separating and removing the acid contained in the treatment system from the ion-exchangeable layered silicate.

As the salts used in the salt treatment, it is preferable to select and use those containing specific cations. As for the types of cations, monovalent to tetravalent metal cations are preferable, and Li, Ni, Zn, and Hf cations are particularly preferable.
Specific examples of salts include the following.
Cations of Li include 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 can be mentioned.
Examples of cations with Ni include NiCO ₃ , Ni (NO ₃ ) ₂ , NiC ₂ O ₄ , Ni (ClO ₄ ) ₂ , NiSO ₄ , NiCl ₂ , and NiBr ₂ .
The cations of Zn are Zn (OOCH ₃ ) ₂ , Zn (CH ₃ COCHCOCH ₃ ) ₂ , ZnCO ₃ , Zn (NO ₃ ) ₂ , Zn (ClO ₄ ) ₂ , Zn ₃ (PO ₄ ) ₂ , and so on. Examples thereof include ZnSO ₄ , ZnF ₂ , ZnCl ₂ , ZnBr ₂ , and ZnI ₂ .
As those cations of _{Hf, Hf (OOCCH 3) 4} , Hf (CO 3) 2, Hf (NO 3) 4, Hf (SO 4) 2, HfOCl 2, HfF 4, HfCl 4, HfBr 4, HfI ₄ mag can be mentioned.

After the chemical treatment, drying is performed, but in general, the drying temperature can be 100 to 800 ° C., and high temperature conditions that cause structural failure (depending on the heating time, for example, 800 ° C. or higher) Not preferred. Since the characteristics change depending on the drying temperature even if the structure is not destroyed, it is preferable to change the drying temperature according to 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. The drying method is not particularly limited and can be carried out by various methods.

-Organoaluminium compound of component [C] The organoaluminum compound of component [C] is a component arbitrarily used as needed, and the compound represented by the following formula [II] is most suitable.
(AlR ⁴ _p X _3-p ) _q ... [II]
Wherein [II], ^{R 4} represents a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, hydrogen, an alkoxy group, an amino group. p is an integer of 1 to 3 and q is an integer of 1 to 2.
The R ^4, alkyl groups are preferred, and X is that it alkoxy group having 1 to 8 carbon atoms in the case of alkoxy groups, in the case of the amino group is preferably an amino group having 1 to 8 carbon atoms.
Of these, trialkylaluminum with p = 3, q = 1 and dialkylaluminum hydride with p = 2, q = 1 are preferable. More preferred are trialkylaluminum R ⁴ is 1 to 8 carbon atoms.

The organoaluminum compound can be used alone, in combination of two or more, or in combination. Further, the organoaluminum compound can be added and used not only at the time of catalyst preparation but also at the time of prepolymerization or main polymerization.

(V) Method for producing propylene-based (co) polymer (a) As a method for producing the propylene-based (co) polymer (a), a slurry polymerization method using an inert solvent or a solution in the presence of the above catalyst. Examples thereof include a polymerization method, a vapor phase polymerization method using substantially no solvent, and a bulk polymerization method using a polymerization monomer as a solvent.
For example, in the case of the 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 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 atm (0.10 to 6.08 MPa), and the molecular weight of the obtained propylene-based (co) polymer (a) is adjusted with hydrogen or another known molecular weight adjusting agent. be able to. The polymerization is carried out by a continuous reaction or a batch reaction, and the conditions may be the conditions usually used. Further, the polymerization reaction may be carried out in one stage or in multiple stages.
It is desirable to perform a prepolymerization treatment before the main polymerization is performed. As the monomer used for the prepolymerization, 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 can be used. ..
This prepolymerization is preferably carried out under mild conditions in an inert solvent, with 0.01 to 1,000 g, preferably 0.1 per 1 g of the solid catalyst (total of component [A] and component [B]). It is desirable to produce a polymer of up to 100 g.

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 increase the amount of polymer produced per solid catalyst (when the solid catalyst is prepolymerized, the polymer produced by the prepolymerization is not included) as much as possible. In order to increase the amount of polymer produced, it is desirable to set both the polymerization temperature and the polymerization pressure 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 the bulk polymerization method, it is preferable that the polymerization temperature is 60 to 80 ° C. and the polymerization pressure is selected from about 2.5 to 4 MPa in correlation with the temperature. On the other hand, in the case of the vapor phase polymerization method, the polymerization temperature is preferably 70 to 90 ° C. and is preferably selected from about 1.5 to 4 MPa.
Further, it is possible to increase the polymer production amount per solid catalyst by increasing the residence time of the solid catalyst, but if it is too long, the productivity will be affected. The 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.
Further, hydrogen may be present in the polymerization system as a molecular weight adjusting agent. Further, the polymerization may be carried out in multiple steps by changing the polymerization temperature, the concentration of the molecular weight adjusting agent and the like.

In the present invention, the propylene-based (co) polymer (a) obtained after completion of polymerization is used with an inert saturated hydrocarbon solvent such as propane, butane, pentane, hexane, and heptane, a liquid α-olefin, or the like. More preferably, cleaning is carried out using an inert hydrocarbon solvent having 3 or 4 carbon atoms or a liquid α-olefin.
The cleaning method is not particularly limited, and known methods such as decantation of the supernatant liquid after the contact treatment in the stirring tank, countercurrent cleaning, and separation from the cleaning liquid by a cyclone can be used.
Further, a deactivating agent may be added before or at the same time as washing. The deactivating agent is not particularly limited, and alcohols such as water, methanol, ethanol and isopropanol, ketones such as acetone and methyl ethyl ketone, or mixtures thereof can be used.

(Vi) Melting peak temperature (Tm)
The melting peak temperature (Tm) of the propylene-based (co) polymer (a) used in the present invention is in the range of 135 to 165 ° C., and when the melting peak temperature (Tm) is 135 ° C. or higher, rigidity and moldability Is good, and when the temperature is 165 ° C. or lower, the impact resistance is good. It is preferably 138 to 160 ° C, more preferably 140 to 155 ° C.
For specific measurement of the melting peak temperature (Tm), take a sample amount of 5 mg using a differential scanning calorimeter (DSC), hold it at 200 ° C for 5 minutes, and then crystallize it to 40 ° C at a temperature decrease rate of 10 ° C / min. The peak position of the curve drawn when the mixture is further melted at a heating rate of 10 ° C./min is defined as the melting peak temperature Tm (° C.).
(Vii) Molecular weight distribution (Mw / Mn) and weight average molecular weight (Mw) of the propylene-based (co) polymer (a).
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] obtained by gel permeation chromatography (GPC) measurement of the propylene-based (co) polymer (a) used in the present invention is 1.5 to 4. It is in the range of 0.0.
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.
When the lower limit of the molecular weight distribution is 1.5 or more, the production efficiency is improved because the range of conditions for producing and purifying the propylene-based (co) polymer (a) is widened, which is preferable. In addition, when the upper limit is 4.0 or less, it indicates that the lengths of the molecular chains are very uniform, and unreacted monomers, dimers, low molecular weight compounds, and amorphous compounds, which are considered to cause the generation of volatile components, are considered. It is preferable because the content of relatively low molecular weight components such as quality components and oligomers is reduced.

The weight average molecular weight (Mw) of the propylene-based (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 becomes easy. On the other hand, when the weight average molecular weight Mw is 100,000 or more, the low crystal component is reduced, mold contamination, bleed-out, solvent elution and the like are suppressed, and the impact resistance of the molded product is improved, which is practical.

_{(Viii) Average elution temperature (T 50} ) and elution dispersion degree (σ) of the propylene-based (co) polymer (a)
_{The average elution temperature (T 50} ) of the propylene-based (co) polymer (a) used in the present invention is preferably 90 to 105 ° C., and the elution dispersion degree (σ) is preferably 9 ° C. or lower.
Here, the average elution temperature is a value based on the elution curve of the polymer by the temperature rise elution fractionation method using o-dichlorobenzene as a solvent, and represents the temperature when the integrated mass of the eluted polymer is 50% by mass. .. The elution dispersion is assumed when the elution amount by the temperature rise elution fractionation method follows a normal probability distribution with respect to the elution temperature, and the mass integrated elution amount I (t) is defined by the following mathematical formula (1). Is the value of σ.

・・・数式（１）
溶出分散度は具体的には、σ＝Ｔ_５０−Ｔ_１５．９である。なお、Ｔ_１５．９は積算質量が１５．９質量％となるときの温度を示す。
平均溶出温度が９０〜１０５℃であることにより、プロピレン系（共）重合体（ａ）の分子量及び融点を成形のために適切なものとすることができ、寸法精度を向上させることができる。平均溶出温度が９０℃以上のときにはプロピレン系（共）重合体（ａ）の分子量及び融点が低くなり過ぎることはなく、成形品の寸法精度が良好となり、１０５℃以下のときにはプロピレン系樹脂の分子量及び融点が高くなり過ぎることはなく好ましい。
また、溶出分散度（σ）が９℃以下であることにより、温度上昇に伴う成分の溶出を抑えることができるとともに、寸法精度を高めることができる。溶出分散度（σ）はより好ましくは７℃以下、更に好ましくは６℃以下である。
このようなプロピレン系（共）重合体（ａ）としては、市販のものを用いることができ、例えば、日本ポリプロ（株）製の商品名：ウィンテック（ＷＩＮＴＥＣ）などを挙げることができる。

・ ・ ・ Formula (1)
Specifically, the dissolution dispersion degree is σ = T ₅₀ −T _15.9 . Note that T _15.9 indicates the temperature when the integrated mass is 15.9 mass%.
When the average elution temperature is 90 to 105 ° C., the molecular weight and melting point of the propylene-based (co) polymer (a) can be made appropriate for molding, and the dimensional accuracy can be improved. When the average elution temperature is 90 ° C. or higher, the molecular weight and melting point of the propylene-based (co) polymer (a) do not become too low, and the dimensional accuracy of the molded product becomes good. When the average elution temperature is 105 ° C. or lower, the molecular weight of the propylene-based resin is good. And the melting point does not become too high, which is preferable.
Further, when the elution dispersion degree (σ) is 9 ° C. or lower, the elution of components due to an increase in temperature can be suppressed and the dimensional accuracy can be improved. The elution dispersion degree (σ) is more preferably 7 ° C. or lower, still more preferably 6 ° C. or lower.
As such a propylene-based (co) polymer (a), a commercially available one can be used, and examples thereof include trade name: WINTEC manufactured by Japan Polypropylene Corporation.

(Vx) Volatile component content The volatile component content of the propylene-based (co) polymer (a) used in the present invention is 50% by weight ppm or less, and when it is 50% by weight or less, the cleanliness is good. , When the biomass polyethylene (b) is contained, it becomes difficult to crack. It is preferably 30% by weight or less, and more preferably 20% by weight or less.
The method for measuring the volatile component content (the amount of oligomer having 30 or less carbon atoms) generated from the propylene-based (co) polymer (a) is measured by dynamic headspace (DHS) -GC / MS. The volatile component content is the ratio of the volatile component content to the propylene-based (co) polymer (a) (unit: ppm by weight). The specific measurement method is shown below.

(A) Outline of measurement and evaluation The powder sample of the propylene-based (co) polymer (a) is heated to 100 ° C., and the volatile components generated there are collected at −150 ° C., and then gas chromatograph (GC) / mass. Separation, detection and identification of each volatile component with a spectrometer (MS). For the calibration curve, an aliphatic linear hydrocarbon having 2 carbon atoms from 10 to 32 carbon atoms was prepared as a standard mixed solution having a concentration of 1000 μg / ml in an n-heptane solvent, and the measurement was performed under the same conditions as the sample to obtain a gas chromatogram /. It is measured and created by mass spectrometry. The quantification is calculated using the standard value of n-icosane.

(B) Equipment and measurement method
(A) Heat expulsion (dynamic headspace) device:
Approximately 50 mg of a powder sample of the propylene-based (co) polymer (a) is precisely weighed, filled in a heated eviction tube (TDS tube manufactured by GERSTEL), and approximately 10 mg of quartz wool (manufactured by GL Sciences) is provided at both ends thereof. Cat. No. 3001-12404) is packed. After charging the above TDS tube into a heating and extracting device (TDS-A manufactured by GERSTEL) at 40 ° C., the inside of the tube is replaced with helium, the temperature is raised to 100 ° C. at a rate of 60 ° C./min, and 30 ° C. is 30 ° C. Heat for minutes. During this heating period, the GC inlet (CIS4 manufactured by GRESTEL) filled with TENAX is cooled to −150 ° C. to collect volatile components generated from the sample. The collected components are vaporized and introduced into the GC column by rapidly heating the collected portion to 320 ° C.
(B) Gas chromatograph (GC):
Agilent HP6890
Column: DB-5ms
Column temperature rise conditions: 40 ° C x 5 min to 10 ° C / min to 300 ° C x 15 min
(C) Mass spectrometer (MS):
Agilent Mass Sensitive Detector 5973N
The electron impact (EI) method is used for ionization of the measurement component.

(2) Biomass polyethylene (b)
The plant-derived ethylene, which is the raw material monomer of the biomass polyethylene (b) used in the present invention, is dehydrated in the molecule by heating ethanol produced by fermenting a plant raw material such as sugar cane by allowing microorganisms to act in the presence of a catalyst. It can be obtained by carrying out a reaction.
Biomass polyethylene (b) is a polymer obtained by polymerizing a monomer containing plant-derived ethylene as a main component. The raw material monomer of the biomass polyethylene (b) does not have to contain 100% of plant-derived ethylene. This is because the environmental load can be reduced by using plant-derived ethylene as a part of the monomer.
As the biomass polyethylene (b), a homopolymer obtained by homopolymerizing plant-derived ethylene or a copolymer obtained by copolymerizing plant-derived ethylene with an α-olefin can also be used. The number of carbon atoms of the α-olefin is not particularly limited, but 1-butene, 1-hexene or 1-octene is preferable. Further, petroleum-derived ethylene may be contained.

(I) Polyethylene of biomass polyethylene (b) Examples of polyethylene used as the biomass polyethylene (b) include medium density polyethylene (MDPE), low density polyethylene (LDPE) and linear low density polyethylene (LLDPE). Can be done. These polyethylenes can be used alone or in a blend of two or more.
The density of the medium-density polyethylene is preferably 0.925 to 0.940 g / cm ³ , and in this range, the rigidity is improved and it is preferable.
Among the above polyethylenes, it is preferable to use at least one of low-density polyethylene and linear low-density polyethylene. As a result, the transparency improving effect becomes sufficient.
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 . When the density is 0.910 g / cm ³ or more, the rigidity is improved and preferable, and when the density is 0.920 g / cm ³ or less, the transparency improving effect is sufficient and preferable.
As the density of the linear low density polyethylene, preferably 0.895~0.925g / cm ^3, more preferably 0.900~0.917g / cm ^3. When the density is 0.895 g / cm ³ or more, the rigidity is improved and preferable, and when the density is 0.925 g / cm ³ or less, the transparency improving effect is sufficient and preferable.

The ratio of plant-derived carbon to the total carbon content in the biomass polyethylene (b) is called the bio-frequency and can be determined by measuring the concentration of ^{14 C contained in the biomass polyethylene (b).} That is, while the atmosphere contains ^{14 C} a percentage, the carbon of the petroleum-derived resin since it does not contain ^{14 C,} to measure the concentration of ^{14 C} contained in the biomass polyethylene (b) By doing so, the biofrequency can be obtained. Specifically, when all the carbon in the biomass polyethylene (b) is derived from petroleum, the bio frequency is 0%, and when all the carbon in the biomass polyethylene (b) is derived from plants, the bio frequency is 100%. It becomes. As a test method for measuring the concentration of ^{14 C, ASTM D6866 can be mentioned.}
As the biomass polyethylene (b), those having a melt flow rate in the range of 0.21 to 72 g / 10 minutes according to ASTM D1238 (190 ° C., 2.16 kg load) are preferably used.

The weight ratio 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, the effect of reducing the environmental load can be expected, and when it is 49 parts by weight or less, sufficient rigidity of the product can be obtained. (Here, the 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.)
Examples of such biomass polyethylene (b) include "Green PE" (trade name manufactured by Braskem).

(3) Biomass degree The biomass degree (%) in the present invention is a numerical value calculated by the following formula.
Biomass degree (%) = [{A × (B ÷ 100)} / C] × 100 ・ ・ ・ Formula (1)
A: Weight of biomass polyethylene (b) B: Bio frequency (%) of biopolyethylene used
C: Weight of propylene-based polymer composition The biofrequency (%) of biomass polyethylene (b) can be measured and calculated by ASTM D6866.

(4) Nucleating Agent The propylene-based polymer composition of the present invention can preferably contain 0.01 to 0.6 parts by weight of a nucleating agent with respect to 100 parts by weight of the propylene-based polymer composition. ..
A variety of common known nucleating agents can be used, such as sterically damaging amide compounds, organic dicarboxylic acid metal salts, organic monocarboxylic acid metal salts, sorbitols or derivatives thereof, nonitols or derivatives thereof, diterpenes. Examples thereof include metal salts of acids and polymer nucleating agents.
Among them, it is particularly preferable to contain a nucleating agent represented by the following formula (1) in terms of exhibiting transparency.

・・・（１）
（式中、ｎは、０〜２の整数であり、Ｒ^１〜Ｒ^５は、それぞれ独立して、同一又は異なって、水素、ハロゲン、炭素数１〜２０のアルキル、炭素数２〜２０のアルケニル、炭素数１〜２０のアルコキシ、炭素数１〜２０のアルコキシカルボニル又はフェニルであり、Ｒ^６は、炭素数１〜２０のアルキルである。）
式（１）で表される造核剤のうち、市販品として入手できる代表的なものは、ミラッドＮＸ８０００Ｊ（ミリケン・アンド・カンパニー社製）などが挙げられる。その化学構造式は、下記式（１−１）のとおりである。この造核剤の分子量は４８４である。この物質は、熱的・化学的にきわめて安定であるため、成形温度においてもほとんど熱分解しないという非常に優れた特徴がある。分解物が成形品の表面にブリードアウトして外観を悪化させるという問題が生じないため、非常に好ましい。

... (1)
(In the formula, n is an integer of 0 to 2, and R ^{1 to} R ⁵ are independently the same or different, hydrogen, halogen, alkyl having 1 to 20 carbon atoms, and 2 to 20 carbon atoms. alkenyl, alkoxy having 1 to 20 carbon atoms or an alkoxycarbonyl or phenyl having 1 to 20 carbon atoms, ^{R 6} is alkyl having 1 to 20 carbon atoms.)
Among the nucleating agents represented by the formula (1), a typical one that can be obtained as a commercially available product is Mirad NX8000J (manufactured by Milliken & Company). The chemical structural formula is as shown in the following formula (1-1). The molecular weight of this nucleating agent is 484. Since this substance is extremely stable thermally and chemically, it has a very excellent feature that it hardly thermally decomposes even at a molding temperature. It is highly preferable because it does not cause the problem that the decomposed product bleeds out to the surface of the molded product and deteriorates the appearance.

・・・（１−１）

... (1-1)

The content of the nucleating agent represented by the formula (1) contained in the propylene-based polymer composition of the present invention is preferably 0.1 to 0. With respect to 100 parts by weight of the propylene-based polymer composition. It is in the range of 6 parts by weight, more preferably 0.2 to 0.4 parts by weight, and further preferably 0.3 to 0.4 parts by weight. When the content of the nucleating agent represented by the formula (1) is 0.1 parts by weight or more, rigidity and transparency can be expected, and when it is 0.6 parts by weight or less, bleeding to the surface of the molded product is expected. It is advantageous in terms of cost-effectiveness (cost performance) and elution in terms of rigidity and transparency.

(5) Other Additives In the propylene-based polymer composition of the present invention, in addition to the above-mentioned components, various antioxidants used as stabilizers of the propylene-based polymer, ultraviolet absorbers, and light stabilizers are used. Additives such as agents and neutralizers can be added.
Specifically, as the antioxidant, 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 phosphorus antioxidants, 2,6-di-t-butyl-p-cresol, tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocin namemate)] methane, 1,3,5-trimethyl-2,4 Penyl antioxidants such as 6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, di- Thio-based antioxidants such as stearyl-β, β'-thio-di-propionate, di-myristyl-β, β'-thio-di-propionate, di-lauryl-β, β'-thio-di-propionate, etc. Can be mentioned.

Examples of the ultraviolet absorber include 2-hydroxy-4-n-octoxybenzophenone, 2- (2'-hydroxy-3', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2). Examples thereof include an ultraviolet absorber such as'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole.

Examples of the light stabilizer 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-succinate (4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl) ) Ethanol condensate, poly {[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4 diyl] [(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- Bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate and other photostabilizers can be mentioned. can.

Further, an amine-based antioxidant represented by the following formula (2) and the following formula (3), which has good NOx gas discoloration resistance, 5,7-di-t-butyl-3- (3,4-di-). Examples thereof include a lactone-based antioxidant such as methyl-phenyl) -3H-benzofuran-2-one, and a vitamin E-based antioxidant such as the following formula (4).

・・・（２）

... (2)

・・・（３）

... (3)

・・・（４）

... (4)

The neutralizing agent is a metal fatty acid salt such as calcium stearate, zinc stearate, magnesium stearate, hydrotalcite (trade name: DHT-4A, represented by the following formula (5) manufactured by Kyowa Chemical Industry Co., Ltd.). Magnesium-aluminum composite hydroxide salt), Mizukarak (trade name, 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 (CO ₃ ) _{x / 2}・ mH ₂ O… (5)
[In the formula, x is 0 <x ≦ 0.5, and m is a number 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 3 or less. ]

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

Polymers other than the propylene-based (co) polymer (a) and the biopolyethylene (b), polyethylene, ethylene-propylene, as long as the properties such as the properties and functions of the propylene-based polymer composition of the present invention are not impaired. One, two, three, such as copolymers, ethylene-propylene-diene copolymers, ethylene-1-butene copolymers, ethylene-vinyl acetate copolymers, ethylene-acrylate copolymers, acrylate polymers. 1 to 30 parts by weight of the original copolymer can be arbitrarily added to 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, EPDM. Furthermore, general-purpose inorganic fillers such as talc, calcium carbonate, silica, alumina, gypsum, and mica can be used in combination.

(6) Flexural Modulus of Propylene 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, and the product has a flexural modulus of 800 MPa or more. The rigidity required to maintain the characteristics and shape is obtained, and when it is 1500 MPa or less, the impact resistance becomes good. It is more preferably 1000 to 1500 MPa, further preferably 1100 to 1450 MPa, and particularly preferably 1200 to 1400 MPa.

(7) Charpy impact strength of the propylene-based polymer composition The Charpy impact strength of the propylene-based polymer composition used in the present invention is preferably in ^{the range of 3.0 kJ / m 2} or more, and the Charpy impact strength is 3. When it is 0 kJ / m ² or more, damage during transportation of the molded product is suppressed. It is more preferably 3.5 kJ / m ² or more, and further preferably 4.0 kJ / m ² or more.

(8) Haze of propylene-based polymer composition The haze of the propylene-based polymer composition used in the present invention at a product wall thickness of 2 mmt is preferably in the range of 50% or less, and the haze is 50% or less. The visibility of the object is improved, and the design is further improved. It is more preferably 45% or less, still more preferably 35% or less.

[2] Method for producing propylene-based polymer composition The propylene-based polymer composition of the present invention comprises a propylene-based (co) polymer (a) and biomass polyethylene (b), and if necessary, other additives. Each predetermined amount of the above is put into a Henshell mixer (trade name), a super mixer, a ribbon blender, etc. and mixed, and then 190 to 260 with a normal single-screw extruder, twin-screw extruder, Banbury mixer, plastic bender, roll, etc. It can be obtained by melt-kneading in a temperature range of ° C.

[3] Molded product obtained by using a propylene-based polymer composition In order to produce a molded product using the propylene-based polymer composition of the present invention, a propylene-based polymer composition is desired by an injection molding method or the like. Mold into a shaped product.
The use of the molded product is not particularly limited, but it can be widely used for various applications such as various industrial materials, automobile-related parts, various containers for medical and cosmetic products, daily necessities, films and fibers.

Hereinafter, the present invention will be described in detail 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-based (co) polymer (a) and the propylene-based polymer composition were measured according to the following method.
<1. Measurement method>

(1) Melt flow rate (MFR):
Measured according to JIS K7210 (230 ° C., 2.16 kg load).

(2) Calculation of ethylene content of propylene-based (co) polymer (a)
¹³ The ethylene content in the random copolymer was measured by infrared spectroscopy using the characteristic absorption band ^{of 733 cm -1} using the ethylene-propylene random copolymer whose composition was verified by C-NMR as a reference material. The pellet was press-molded into a film having a thickness of about 500 μm.

(3) Measurement of molecular weight and molecular weight distribution:
The molecular weight distribution Mw / Mn of the propylene-based (co) polymer (a) was calculated by measuring the weight average molecular weight Mw and the number average molecular weight Mn by a gel permeation chromatography (GPC) method. The measurement conditions are as follows.
Equipment: GPC manufactured by WATERS (ALC / GPC 150C)
Detector: FOXBORO MIRAN 1A IR detector (measurement wavelength: 3.42 μm)
Column: Showa Denko Corporation AD806M / S (3 series)
Mobile phase solvent: ο-dichlorobenzene Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection amount: 0.2 ml

(4) Melting peak temperature (melting point) (Tm, unit: ° C):
Using a differential scanning calorimeter (DSC), take a sample volume of 5.0 mg, raise the temperature to 200 ° C, erase the heat history, hold at 200 ° C for 5 minutes, and then lower the temperature at 10 ° C / min. The temperature at the top of the heat absorption peak was defined as the melting peak temperature (melting point) (Tm) when the temperature was lowered to 40 ° C. to crystallize, and the temperature was measured again at a heating rate of 10 ° C./min for melting.

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

(A) Outline of measurement and evaluation The powder sample of the propylene-based (co) polymer (a) is heated to 100 ° C., and the volatile components generated there are collected at −150 ° C., and then gas chromatograph (GC) / mass. Separation, detection and identification of each volatile component were performed with a spectrometer (MS). For the calibration curve, an aliphatic linear hydrocarbon having 2 carbon atoms from 10 to 32 carbon atoms was prepared as a standard mixed solution having a concentration of 1000 μg / ml in an n-heptane solvent, and the measurement was performed under the same conditions as the sample to obtain a gas chromatogram /. It was measured and prepared by mass spectrometry. The quantification was calculated using the standard value of n-icosane.

(B) Equipment and measurement method (a) Heating eviction (dynamic headspace) equipment:
Approximately 50 mg of a powder sample of the propylene-based (co) polymer (a) is precisely weighed, filled in a heated eviction tube (TDS tube manufactured by GRESTEL), and approximately 10 mg of quartz wool (manufactured by GL Sciences) is provided at both ends thereof. Cat. No. 3001-12404) was packed. After charging the above TDS tube into a heating and extracting device (TDS-A manufactured by GERSTEL) at 40 ° C., the inside of the tube is replaced with helium, the temperature is raised to 100 ° C. at a rate of 60 ° C./min, and 30 ° C. is 30 ° C. Heated for minutes. During this heating period, the GC inlet (CIS4 manufactured by GRESTEL) filled with TENAX was cooled to −150 ° C. to collect volatile components generated from the sample. The collected components were vaporized by rapidly heating the collected portion to 320 ° C. and introduced into the GC column.
(B) Gas chromatograph (GC):
Agilent HP6890
Column: DB-5ms
Column temperature rise conditions: 40 ° C x 5 min to 10 ° C / min to 300 ° C x 15 min
(C) Mass spectrometer (MS):
Agilent Mass Sensitive Detector 5973N
The electron impact (EI) method was used for ionization of the measured components.

(6) Bending elastic modulus Measured according to JIS K7171.

(7) Charpy impact strength The Charpy impact strength at 23 ° C. was measured according to JIS K7111.
(8) Haze value Measured according to JIS K7136 using a sheet piece having a thickness of 2 mm.

(9) Crack test in MD and TD directions A 120 mm × 120 mm × 2 mm test piece is injection molded (molding temperature: 200 ° C., mold temperature: 40 ° C.), and the width is 1. Each cut with a length of about 3 cm was made so as to be 5 cm, and the portion was bent by hand to evaluate the crack according to the following criteria.
⊚: Even if it is bent 90 degrees or more, no cracks (crevices, cracks) are formed and it is not divided into several parts. (Doesn't break)
◯: Even if it is bent 90 degrees or more, cracks (crevices, cracks) are formed, but it is not divided into several parts. (Doesn't break)
X: When bent 90 degrees or more, it is divided into several parts. (Break)

<2. Resins, additives>
2-1. Production of Propylene-based (Co) Polymer (a) (1) Production Example 1
(I) Preparation of catalyst The following operations were carried out using a solvent and a monomer deoxidized and dehydrated under an inert gas.
(Ii) Chemical treatment of ion-exchangeable layered silicate Acid treatment: Add 1130 g of distilled water and 750 g of 96% sulfuric acid to a zeparable flask, keep the internal temperature at 90 ° C., and granulate smectite having an average particle size of 25 μm (ii). 300 g of Benclay SL manufactured by Mizusawa Chemical Co., Ltd. was added and reacted for 5 hours.
Washing: The mixture was cooled to room temperature in 1 hour and washed with distilled water to pH = 3.69. The cleaning ratio at this time was 1 / 10,000 or less (volume ratio). When the solid at this stage was partially dried and the elution rate by acid treatment was determined, it was 33.5% by weight.
Salt treatment: 211 g of lithium sulfate monohydrate was dissolved in 521 g of distilled water, 100 g (dry weight) of the solid obtained by the above acid treatment was added, and the mixture was stirred at room temperature for 120 minutes. The slurry was filtered, 3000 g of distilled water was added to the obtained solid, and the mixture was stirred at room temperature for 5 minutes. Further, this slurry was filtered. 2500 g of distilled water was added to the obtained solid, and the mixture was stirred for 5 minutes and then filtered again. This operation was repeated four more times. The obtained solid was pre-dried at 130 ° C. under a nitrogen stream for 2 days, coarse particles of 53 μm or more were removed, and further dried under reduced pressure at 200 ° C. for 2 hours to obtain a chemically treated smectite.
(Iii) Activation treatment of silicate Introducing 200 g of the above chemically treated smectite into a glass reactor with a stirring blade having an internal volume of 3 L, 750 ml of normal heptane, and a heptane solution of trinormal octyl aluminum (500 mmol). Was added, and the mixture was stirred at room temperature. After 1 hour, the slurry was washed with normal heptane (residual liquid ratio less than 1%) (heptane / weight ratio of solid component) to adjust the slurry to 2000 mL.

(IV) Preparation of Prepolymerization Catalyst Next, (r) -dimethylsilylenebis [2-methyl-4- (4-chlorophenyl) -4H-azurenyl] zirconium dichloride 3 mmol of toluene slurry 870 mL and triisobutylaluminum (15 mmol) The reaction mixture in which 42.6 mL of the heptane solution was previously reacted at room temperature for 1 hour was 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 stirring autoclave having an internal volume of 10 L sufficiently replaced with nitrogen, and the temperature was maintained at 40 ° C. The previously prepared montmorillonite / complex slurry was introduced therein. When the temperature was stable at 40 ° C., propylene was supplied at a rate of 100 g / hour and the temperature was maintained. After 4 hours, the supply of propylene was stopped and maintained for another 2 hours. About 3 L of the supernatant was removed from the recovered prepolymerized catalyst slurry, 170 mL of a heptane solution of triisobutylaluminum (30 mmol) was added, the mixture was stirred for 10 minutes, and then heat-treated under reduced pressure at 40 ° C. By this operation, a prepolymerization catalyst containing 2.30 g of polypropylene per 1 g of the catalyst was obtained.

(V) Production of propylene-based polymer Liquid phase polymer tank with internal volume 270 L stirrer, deactivation tank with internal volume 400 L, slurry circulation pump, circulation line hydraulic classifier, concentrator, countercurrent pump and cleaning liquid receiving tank Propylene-ethylene co-weight by a process incorporating a deactivation cleaning system consisting of a deactivation cleaning system, a high-pressure degassing system consisting of a double-tube heat exchanger and a fluidized flash tank, and an aftertreatment system including a low-pressure degassing tank and a dryer. Continuous production of coalescing was carried out.
The prepolymerization catalyst produced above was added to liquid paraffin (trade name "Whitelex 335" manufactured by Tonen Co., Ltd.) at a concentration of 15% by weight (ratio of 15 parts by weight of prepolymerization catalyst and 85 parts by weight of liquid paraffin to a total of 100 parts by weight). And introduced into a liquid phase polymerization tank at 0.35 g / hr as a catalyst component. Further, liquid propylene was continuously supplied at 40 kg / hr, ethylene at 0.4 kg / hr, hydrogen at 0.25 g / hr, and triisobutylaluminum at 18 g / hr to this polymerization tank, and the temperature in the tank was raised to 70 ° C. It was retained and polymerized. The mixed slurry of the polymer and the liquid propylene was withdrawn from the liquid phase polymerization tank as a polymer into a deactivated washing tank at 12.0 kg / hr. At this time, the average residence time of the catalyst in the polymerization tank was 1.3 hours. Ethanol was supplied to the deactivating washing tank at 21.0 g / hr as a deactivating agent. Further, 40 kg / hr of liquid propylene was supplied, and the temperature inside the tank was maintained at 50 ° C. by heating with a jacket. The polymer was extracted from the lower part of the classifier into a high-pressure degassing tank, passed through a low-pressure degassing tank, and dried in a dryer. The temperature inside the dryer was adjusted to 80 ° C. and the residence time was 1 hour, and dry nitrogen at room temperature was flowed in the direction of the powder flow at a flow rate of ^{12 m 3 / hr.} The dried polymer was removed from the hopper.
On the other hand, the liquid propylene separated from the polymer through the classifier and the concentrator was taken out to the washing liquid receiving tank at 40 kg / hr. The yield of the obtained polymer per 1 g of the solid catalyst was 34.3 kg, ethylene content = 0.8% by weight, MFR = 31 g / 10 minutes, molecular weight distribution (Mw / Mn) = 2.4, Tm = 142 ° C. , Volatile component content = 5 wt ppm.

(Vi) For 100 parts by weight of the powder of the granulated propylene-ethylene copolymer, tetrakis [methylene-3- (3', 5'-di-t-butyl-4'-), which is a phenyl antioxidant. Hydroxyphenyl) Propionate] Ethylene (trade name: IRGANOX1010, manufactured by BASF Japan Co., Ltd.) 0.03 part by weight is blended and mixed at room temperature for 3 minutes using a high-speed stirring mixer (trade name: Henshell mixer). After that, the mixture was melt-kneaded in a nitrogen atmosphere with a twin-screw extruder to obtain pellets of a propylene-ethylene copolymer. For the twin-screw extruder, KZW-25 manufactured by Technobel Co., Ltd. is used, the screw rotation speed is 400 RPM, and the kneading temperature is set to 80, 160, 210, 230 (hereinafter, the same temperature up to the die outlet) ° C from the bottom of the hopper. did.

(2) Production 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 JP2012-149160A.
(Ii) Synthesis of complex 2 (Synthesis example 2: Preparation of component [A-2] (complex 2))
As the component [A-2] (complex 2), rac-dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium is available from JP-A-11-240909. It was synthesized according to the method described in Example 7 of the publication.

(Iii) Preparation of catalyst (iii-1) Chemical treatment of layered silicate To a 1 L three-necked flask equipped with a stirring blade and a reflux device, 645.1 g of distilled water and 82.6 g of 98% sulfuric acid were added, and the temperature was 95 ° C. The temperature was raised to. Commercially available montmorillonite (trade name manufactured by Mizusawa Industrial Chemicals, Inc., Benclay KK, Al = 9.78% by weight, Si = 31.79% by weight, Mg = 3.18% by weight, Al / Si (atomic ratio)). = 0.320, average particle size 14 μm) 100 g was added and 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 reacted at 40 ° C. for 1 hour. After 1 hour, the reaction slurry was filtered and washed 3 times with 1 L of distilled water to obtain a cake-like solid again.
When the recovered cake was dried, 80 g of chemically treated montmorillonite was obtained. The chemical composition of this chemically treated montmorillonite is Al = 7.68% by weight, Si = 36.05% by weight, Mg = 2.13% by weight, Al / Si (atomic ratio) = 0.222, Li = 0.53. It was% by weight.

To (iii-2) reactor Preparation inner volume 1 m ³ of propylene polymerization catalyst, putting chemically treated montmorillonite 150kg obtained as described above (iii-1), and the slurry was added hexane 2832L, thereto 74.4 kg (375 mol) of triisobutylaluminum was added over 85 minutes and stirred for 60 minutes. After that, it was washed with hexane by decantation until the washing rate was 1/32, and the total volume (slurry amount) was set to 900 L.
The slurry solution containing the chemically treated montmorillonite was kept at 50 ° C., and 0.65 kg of triisobutylaluminum (3.28 kg, 4.257 kg as a hexane solution having a concentration of 15.3 wt%) was added thereto.
After stirring for 5 minutes, add 0.657 kg (0.81 mol) of rac-dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium and 96 L of toluene. , Continued stirring for 60 minutes.
Then, 9.758 kg (26.61 mol) of trinormal octyl aluminum was added and stirred for 6 minutes, and then 0.064 kg of triisobutylaluminum (0.064 kg) of toluene was added to 240 L of toluene in a separately prepared solution, that is, a container with another stirring device. Rac-dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-) was added to a toluene solution having a concentration of 0.648% by weight (9.88 kg, 0.32 mol). (4-i-propylphenyl) indenyl}] The prepared solution was added by adding 1.768 kg (1.89 mol) of hafnium, 100 L of toluene was added, and stirring was continued for another 20 minutes.
After that, 2387 L of hexane was added to bring the internal temperature of the reactor to 40 ° C., and then 328.1 kg of propylene was fed over 240 minutes to perform prepolymerization while maintaining 40 ° C.
Then, the propylene feed was stopped and 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 settled. The supernatant was removed so that the solution volume became 1500 L, 12.7 kg of triisobutylaluminum was added, 3974 L of hexane was added again, and the mixture was stirred and then settled, and the supernatant was removed until the solution volume reached 1500 L.
To this, 8.9 kg of triisobutylaluminum (42.9 kg of a hexane solution having a concentration of 20.8% by weight) and 205 L of hexane were added.
Then, the reaction mixture was transferred to a dryer and dried at 40 ° C. for 9 hours to obtain 465 kg of a prepolymerization catalyst (prepolymerization catalyst 1). The prepolymerization ratio (value obtained by dividing the amount of prepolymer by the amount of solid catalyst) was 2.10.

(Iv) Production of propylene-based polymer In ^{a stirring high-pressure reaction vessel (L / D = 1.2) with an internal volume of 100 m 3} , liquefied propylene is 20 T / hr, triisobutylaluminum is 80 kg / hr, and hydrogen is 0.180 kg. / Hr, prepolymerized catalyst 1 is continuously introduced at a flow rate of 0.87 kg / hr (by weight excluding prepolymerized polymer), the temperature is maintained at 70 ± 0.1 ° C., and the polymer slurry in the polymerization reactor is maintained. Continuous polymerization was carried out so that the concentration was maintained at 40% by weight. The production amount of the propylene homopolymer (powder) was 8.0 T / hr.
The obtained propylene homopolymer (powder) was thoroughly dried and then analyzed using the powder. Ethylene content = 0% by weight, MFR = 33 g / 10 minutes, molecular weight distribution (Mw / Mn) = 3.2. , Tm = 154 ° C., volatile component content = 5 wt ppm.
Further, the powder was granulated under the following granulation conditions to obtain pellets of a propylene homopolymer.

(V) For 100 parts by weight of the powder of the granulated propylene homopolymer, tetrakis [methylene-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl), which is a phenol-based antioxidant, is used. ) Propionate] Methylene (trade name: IRGANOX1010, manufactured by BASF Japan Co., Ltd.) 0.125 parts by weight, tris (2,4-di-t-butylphenyl) phosphite (product), which is a phosphite-based antioxidant. Name: IRGAFOS 168, manufactured by BASF Japan Co., Ltd. 0.125 parts by weight is blended, mixed using a high-speed stirring type mixer (trade name: Henshell mixer) at room temperature for 3 minutes, and then used in a twin-screw extruder. Melt-kneading was carried out under a nitrogen atmosphere to obtain pellets of a propylene homopolymer. For the twin-screw extruder, KZW-25 manufactured by Technobel Co., Ltd. is used, the screw rotation speed is 400 RPM, and the kneading temperature is set to 80, 160, 210, 230 (hereinafter, the same temperature up to the die outlet) ° C from the bottom of the hopper. did.

2-2. Production of propylene-based (co) polymer other than propylene-based (co) polymer (a) (1) Production example 3
(I) a solid catalyst prepared stirring blade, a thermometer, jacket reactor 100 liters equipped with a cooling coil, _Mg (OEt) 2: g of 30 mol, then the Ti _{(OBu) 4,} the charged Mg ( It was charged so that Ti (OBu) _{4 /} Mg = 0.60 (mr. (Mole ratio)) with respect to magnesium in OEt) _2. Further, 19.2 kg of toluene (TOR) was charged, and the temperature was raised while stirring. After reacting at 139 ° C. for 3 hours, the temperature was lowered to 130 ° C., and _{the toluene solution of MeSi (OPh) 3} was added to the magnesium in Mg (OEt) ₂ previously charged with MeSi (OPh) ₃ / Mg. It was added so as to be = 0.67 (m.r.). The amount of toluene used here was 7.8 kg. After completion of the addition, the reaction was carried out at 130 ° C. for 2 hours, then the temperature was lowered to room temperature, and Si (OEt) ₄ was added. The addition amount of Si _{(OEt) 4,} to the magnesium in the charged Mg _{(OEt) 2 previously} was Si (OEt) 4 /Mg=0.056(m.r.) And so as.

Next, toluene was added to the obtained reaction mixture so that the magnesium concentration was 0.58 (mol / L-TOR). Further, diethyl phthalate (DEP) was added to the magnesium in Mg (OEt) ₂ previously charged so that DEP / Mg = 0.10 (mr.). The obtained reaction mixture was cooled to 10 ° C. with continued stirring, and TiCl ₄ was added dropwise over 2 hours to obtain a homogeneous solution. Incidentally, TiCl _4, relative to the magnesium of the charged Mg _{(OEt) 2 previously} was set to TiCl 4 /Mg=4.0(m.r.). After TiCl ₄ addition was complete, the temperature was raised to 15 ℃ with stirring 0.5 ° C. / min, and held at the same temperature for 1 hour. Then, the temperature was raised again to 50 ° C. at 0.5 ° C./min, and the temperature was maintained at the same temperature for 1 hour. Further, the temperature was raised to 118 ° C. at 1 ° C./min, and the treatment was performed at the same temperature for 1 hour. After the treatment was completed, stirring was stopped, the supernatant was removed, and the mixture was washed with toluene so that the residual liquid ratio = 1/73 (toluene / volume ratio of solid component) to obtain a slurry of solid components.

_{Next, toluene and TiCl 4} were added to the slurry obtained here at room temperature. The TiCl _{4 was set to TiCl 4} / Mg (OEt) ₂ = 5.0 (m.r.) with respect to the magnesium in Mg (OEt) _{2 charged earlier.} Further, toluene, TiCl ₄ concentration was adjusted to 2.0 (mol / L-TOL) . The temperature of this slurry was raised while stirring, and the reaction was carried out at 118 ° C. for 1 hour. After completion of the reaction, stirring was stopped, the supernatant was removed, and the mixture was washed with toluene so that the residual liquid ratio = 1/150 (toluene / volume ratio of solid component) to obtain a slurry of solid components.

(Ii) Preparation of solid catalyst component (A) Of the solid component obtained in (i), 400 g was transferred to another reactor having a stirring blade, a thermometer, and a cooling jacket, and normal hexane was added. The solid component was diluted to a concentration of 5.0 (g / l). While stirring the obtained slurry, trimethylvinylsilane, TEA and TBMDES were added at 15 ° C. 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 with respect to 1 g of the solid component in the solid catalyst component (A), respectively. After the addition was completed, the mixture was kept at 15 ° C. for 1 hour with continuous stirring, further heated to 30 ° C., and stirred at the same temperature for 2 hours. Next, the temperature was lowered to 15 ° C. again, and while maintaining the same temperature, 4.8 kg of propylene gas was fed to the gas phase portion of the reactor at a constant speed for 8 hours to perform prepolymerization. After the feed was completed, stirring was stopped to remove the supernatant, and then washing was performed with normal hexane to obtain a slurry of the solid catalyst component (A). The residual liquid ratio was 1/12 (normal hexane / volume ratio of solid catalyst component (A)). The obtained solid catalyst component (A) contained 12.0 g of a propylene polymer per 1 g of the solid catalyst component (A).

(Iii) Production of propylene-ethylene copolymer By a process in which a degassing system consisting of a double-tube heat exchanger and a fluidized flash tank is incorporated in the wake of a liquid-phase polymerization tank with an ^{internal volume of 0.4 m 3 and a stirrer.} , A propylene-ethylene copolymer was continuously produced. Liquefied propylene, ethylene, hydrogen, TEA, and TBEDMS were continuously fed into the liquid phase polymerization tank. TBEDMS indicates t-butylethyldimethoxysilane, and t-butyl indicates a tertiary butyl group. The feed amounts of liquefied propylene, TEA, and TBEDMS are 163 kg / hr, 8.86 g / hr, and 1.37 g / hr, respectively. Hydrogen has a gas phase concentration of 6.15 mol%, and ethylene has a vapor phase. Was fed so that the concentration of the above was 0.74 mol%. Further, the solid catalyst component (A) obtained in (ii) above was fed as a solid component contained in (A) so as to be 0.13 g / hr. Further, the liquid phase polymerization tank was cooled so that the polymerization temperature became 70 ° C. The slurry polymerized in this liquid phase polymerization tank was heated by a double tube heat exchanger and extracted into a fluidized flash tank. The extraction rate of the slurry was adjusted to be about 24 kg / hr as the propylene-ethylene copolymer particles contained in the slurry. The average residence time of the propylene-ethylene copolymer particles in the liquid phase polymerization tank was 1.4 hours. Analysis of the extracted propylene-ethylene copolymer revealed that the MFR was 25.0 g / 10 minutes, the ethylene content was 0.7% by weight, the molecular weight distribution (Mw / Mn) was 5.6, and the Tm was 156 ° C. The volatile component content was 130 wt ppm.

(Iv) Tetrakiss [methylene-3- (3', 5'-di-t-butyl-4'-), which is a phenyl-based antioxidant, based on 100 parts by weight of the granulated propylene-ethylene copolymer powder. Hydroxyphenyl) propionate] methane (trade name: IRGANOX1010, manufactured by BASF Japan Ltd.) 0.03 part by weight, tris (2,4-di-t-butylphenyl) phosphite, which is a phosphite-based antioxidant. (Product name: IRGAFOS 168, manufactured by BASF Japan, Ltd.) 0.03 parts by weight, calcium stearate "CAST" as a neutralizing agent, 0.05 parts by weight, manufactured by NOF CORPORATION, and a high-speed stirring mixer. After mixing for 3 minutes at room temperature using a (trade name: Henshell mixer), melt-kneading was carried out in a nitrogen atmosphere with a twin-screw extruder to obtain pellets of a propylene-ethylene copolymer. For the twin-screw extruder, KZW-25 manufactured by Technobel Co., Ltd. is used, the screw rotation speed is 400 RPM, and the kneading temperature is set to 80, 160, 210, 230 (hereinafter, the same temperature up to the die outlet) ° C from the bottom of the hopper. did.

2-3. Propylene-based (co) polymer (a)
(PP-1) Propylene-based resin obtained by polymerizing in Production Example 1 (PP-2) Propylene-based resin obtained by polymerizing in Production Example 2 2-4. A propylene-based resin obtained by polymerizing in Production Example 3 of a propylene-based (co) polymer (PP-3) other than the propylene-based (co) polymer (a).

2-5. Biomass polyethylene (b)
Low density polyethylene (LDPE)
(PE-1) Product name "Green PE SPB608" manufactured by Braskem.
Density: 0.915 g / cm ³ , ASTM D1238 (190 ° C, 2.16 kg load) compliant melt flow rate 30 g / 10 min, bio frequency: 95%. (Each characteristic shows the manufacturer's catalog value.)
Linear low density polyethylene (LLDPE)
(PE-2) Product name "Green PE SLL118" manufactured by Braskem
Density: 0.916 g / cm ³ , ASTM D1238 (190 ° C, 2.16 kg load) compliant melt flow rate 1 g / 10 min, bio frequency: 87%. (Each characteristic shows the manufacturer's catalog value.)
2-6. Biomass polyethylene other than biomass polyethylene (b) High-density polyethylene (HDPE)
(PE-3) Product name "Green PE SGM9450F" manufactured by Braskem.
Density: 0.952 g / cm ³ , ASTM D1238 (190 ° C, 5 kg load) compliant melt flow rate 0.33 g / 10 min, bio frequency: 96%. (Each characteristic shows the manufacturer's catalog value.)

2-6. Other Additives (A-1) Hindered Phenolic Antioxidant "IR1010" Tetrakis [methylene-3- (3', 5'-di-t-butyl-4'-hydroxylphenyl) propionate] Methane. Product name "IRGANOX1010" manufactured by BASF Japan Ltd.
(A-2) Phosphorus-based antioxidant "IF168" Tris (2,4-di-t-butylphenyl) phosphite. Product name "IRGAFOS 168" manufactured by BASF Japan Ltd.
(B-1) Neutralizer "CAST" Calcium stearate. Made by NOF CORPORATION.
(N-1) Nucleating agent "NX8000J" 1,2,3-trideoxy-4,6: 5,7-bis-[(4-prolphenyl) methylene] -nonitol. Product name "Mirad NX8000J" manufactured by Milliken & Company.

<3. Examples 1-7, Comparative Examples 1-9>
Each polymer (pellet) and additive were prepared in the blending ratio (part by weight) shown in Table 1, dry-blended with a super mixer, and then used with a TEM-35B twin-screw extruder manufactured by Toshiba Machine Co., Ltd. It was melt-kneaded at a die outlet temperature of 220 ° C. under a nitrogen atmosphere and pelletized. Physical characteristics were measured using the obtained pellets. The evaluation results are shown in Table 1.

As is clear from Table 1, Examples 1 to 7 contain a specified amount of the propylene-based (co) polymer (a) and the biomass polyethylene (b) according to the present invention, and are materials that can reduce the environmental load. It can be seen that it has excellent rigidity and does not crack. Example 1 contains a specified amount of LDPE as the biomass polyethylene (b), and it can be seen that it is also excellent in transparency. In Example 2, the content of biomass polyethylene (b) LDPE was increased in the composition of Example 1, but it can be seen that the degree of biomass is increased while increasing the impact strength, which is excellent in terms of environmental load. In Example 3, the content of biomass polyethylene (b) LDPE is reduced in the composition of Example 1, but it can be seen that the rigidity and transparency are further excellent as compared with Example 1. In Example 4, LLDPE was used as the biomass polyethylene (b), and although the content ratio was the same as that in Example 1, both the rigidity and the impact strength were further improved from those in Example 1. Examples 5 and 6 use a propylene homopolymer as the propylene-based (co) polymer (a), but are derived from the propylene homopolymer by containing LDPE or LLDPE as the biomass polyethylene (b). It can be confirmed that the effect of the present invention is obtained without cracking due to high impact strength while having high rigidity. Example 7 does not contain a nucleating agent in the composition of Example 1, but has lower rigidity and transparency than Example 1 containing a nucleating agent, but the rigidity required for use as a product. It can be seen that it has.
On the other hand, Comparative Examples 1 and 2 have sufficient crack resistance but have a low content of biomass polyethylene (b) LDPE and do not have a sufficient biomass degree. Comparative Examples 3 and 4 contain a specified amount of high-density polyethylene HDPE as biomass polyethylene other than biomass polyethylene (b), but they are very hard and are immediately divided into several parts when bent by a crack test in the TD direction. That is, it breaks. In Comparative Examples 5 to 8, PP-3 is used as the propylene-based (co) polymer other than the propylene-based (co) polymer (a), but the content of volatile components is high and the cleanliness is inferior. It can be seen that Comparative Example 5 has a low degree of biomass, and Comparative Examples 6 and 8 are inferior to Examples 1 and 4, respectively, in the crack test in the TD direction. It can be seen that Comparative Example 9 uses only biomass polyethylene (b) LDPE, which is excellent in crack resistance but extremely low in rigidity, and cannot exhibit sufficient rigidity by itself.

The propylene-based polymer composition of the present invention is useful because it can be used to reduce the environmental load with a biomass degree of 8.4 to 49%, which gives a molded product having excellent rigidity and not cracking even if it contains biomass polyethylene.

Claims (3)

51 to 90 parts by weight of the propylene-based (co) polymer (a) satisfying the following conditions (Hi) to (Hv) and 10 to 49 parts by weight of the biomass polyethylene (b) satisfying the following conditions (Li). A propylene-based polymer composition having a total content of 100 parts by weight and a biomass content of 8.4 to 49%.
(Hi) A metallocene-based propylene homopolymer or a metallocene-based propylene-based copolymer composed of propylene and an α-olefin having a 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 minutes.
(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. A propylene-based polymer composition containing 0.01 to 0.6 parts by weight of a nucleating agent with respect to 100 parts by weight of the propylene-based polymer composition according to claim 1. A molded product obtained by using the propylene-based polymer composition according to claim 1 or 2.

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