JP2021175794A - Propylene-based polymer composition and molding - Google Patents

Abstract

To provide a propylene-based polymer composition that provides a molding that is excellent in the toughness and is not cracked even when biomass polyethylene is contained and that has the degree of the biomass of 8.4 to 49%, and the molding.SOLUTION: A propylene-based polymer composition comprises, in total of 100 pts.mass, 26 to 87 pts.mass of propylene-based copolymer (a) satisfying conditions (H-i) to (H-ii), 3 to 25 pts.mass of propylene-based copolymer (b) satisfying the conditions (A-i) to (A-iii) and 10 to 49 pts.mass of the biomass polyethylene (c) and has the degree of biomass of 8.4 to 49%: (H-i) propylene homo-polymer or propylene-based copolymer having α-olefin content smaller than 1 wt.%, (H-ii) MFR is 0.5 to 100 g/10 minutes; (A-i) propylene-α-olefin random copolymer; (A-ii) α-olefin content is 1 wt.% or larger and smaller than 3 wt.%; and (A-iii) MFR is 0.5 to 80 g/10 minutes.SELECTED DRAWING: None

Description

The present invention relates to a propylene-based polymer composition having a biomass content 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 (cracks, cracks), but they are not divided into several parts.

Propylene-based resins are characterized by 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. Plant-derived polypropylene has also been studied, but 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 a 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.

JP-A-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, gives a molded product having excellent rigidity and not cracking even if it contains biomass polyethylene, and has a biomass degree of 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 content of 8.4 to 49% and a molded product thereof.

[1] 26 to 87 parts by weight of the propylene-based (co) polymer (a) satisfying the following conditions (Hi) to (Hiii), and propylene satisfying the following conditions (Ai) to (A-iii). A propylene-based polymer composition containing 3 to 25 parts by weight of the based copolymer (b) and 10 to 49 parts by weight of biomass polyethylene (c) in a total amount of 100 parts by weight and having a biomass degree of 8.4 to 49%. ..
(Hi) A propylene homopolymer or a 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, may be abbreviated as MFR) conforming to JIS K7210 (230 ° C., 2.16 kg load) is in the range of 0.5 to 100 g / 10 minutes.
(Ai) A propylene-α-olefin random copolymer.
(A-ii) The α-olefin content is in the range of 1% by weight or more and less than 3% by weight.
(A-iii) MFR is in the range of 0.5 to 80 g / 10 minutes.
[2] The propylene-based polymer composition according to [1], wherein the propylene-based copolymer (b) satisfies the following conditions (A-iv) to (Av).
(A-iv) A metallocene-based propylene-ethylene random copolymer.
(Av) The melting peak temperature (Tm) is in the range of 126 ° C. or higher and lower than 142 ° C.
[3] 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] or [2].
[4] A molded product obtained by using the propylene-based polymer composition according to any one of [1] to [3].

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 has excellent rigidity even if it contains biomass polyethylene and does not crack. It 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 has 26 to 87 parts by weight of the propylene-based (co) polymer (a) satisfying the following conditions (Hi) to (H-ii), and the following conditions (Ai) to. A total of 100 parts by weight containing 3 to 25 parts by weight of the propylene copolymer (b) satisfying (A-iii) and 10 to 49 parts by weight of the biomass polyethylene (c), and the degree of biomass is 8.4 to 49%. It is a propylene-based polymer composition, which is characterized by contributing to reduction of environmental load and not deteriorating performance.
(Hi) A propylene homopolymer or a 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, may be abbreviated as MFR) conforming to JIS K7210 (230 ° C., 2.16 kg load) is in the range of 0.5 to 100 g / 10 minutes.
(Ai) A propylene-α-olefin random copolymer.
(A-ii) The α-olefin content is in the range of 1% by weight or more and less than 3% by weight.
(A-iii) MFR is in the range of 0.5 to 80 g / 10 minutes.
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 propylene homopolymer or propylene. A propylene-based copolymer composed of an 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 copolymerization include α-olefins having 2 to 20 carbon atoms excluding propylene, and examples thereof include ethylene, 1-butene, 1-hexene, and 1-octene. The α-olefin copolymerized with propylene may be used alone or in combination of two or more. Of these, ethylene and 1-butene are preferable. More preferably, ethylene is preferable. Moreover, you may use these propylene-based polymers in mixture of 2 or more types. 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 a small amount 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 α-olefin content is less than 1% by weight, the rigidity is improved and there is no risk 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 in accordance with 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 not particularly limited as a catalyst to be used, but it is better to use a stereoregular catalyst. preferable. Examples of the stereoregular catalyst include a Ziegler catalyst and a metallocene catalyst.

Examples of the Cheegler catalyst include a transition metal component such as a titanium halide compound such as titanium trichloride, titanium tetrachloride, and trichloroethoxytitanium, a contact substance between the titanium halide compound and a magnesium compound typified by magnesium halide, and alkylaluminum. A two-component catalyst with a compound or an organometallic component such as a halide, a hydride, or an alkoxide thereof, and an electron donating compound containing nitrogen, carbon, phosphorus, sulfur, oxygen, silicon, etc. are added to these components 3 Examples include component-based catalysts.

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 Transition metal compounds of groups 4 to 6 of the periodic table having at least one conjugated five-membered ring ligand.
-Component [B] Cocatalyst 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. Indicates a phosphorus-containing hydrocarbon group of 1 to 20 or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms.

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 containing, 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 gelmilene group. These may be hydrogen atoms substituted with an alkyl group, 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) Ethylenebis (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) Dimethylcilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride
(13) Dimethylcilylene (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 The same compounds as described above are preferably used 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. Clay compounds can be used as ion-exchangeable layered silicates, and specific examples of clay compounds 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, lizardite, and antigolite, whose main constituent layers are 1: 1 type structures.
(B) Montmorillonite, Zauconite, Bidelite, Nontronite, Saponite, Hectorite, Smectite such as Stephensite, Vermiculite such as Vermiculite, Mica, Illite, Serisite, whose main constituent layers are 2: 1 type structure. Mica tribe such as sea green stone, attapargit, sepiolite, parigolskate, 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) formed 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 principal component means the most abundant component.

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 in which 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 a specific cation. As for the type of cation, monovalent to tetravalent metal cations are preferable, and Li, Ni, Zn, and Hf cations are particularly preferable.
Specific examples of salts include the following.
The cations of Li are 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 .
As for the cations of Zn, 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 , 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 _4th grade 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 (for example, 800 ° C. or higher depending on the heating time) Not preferable. 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 that is arbitrarily used as needed, and the compound represented by the following formula [II] is optimal.
^{_{(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 preferred. More preferably trialkylaluminum R ⁴ is 1 to 8 carbon atoms.

The organoaluminum compound can be used alone or 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 that does not substantially use a solvent, and a bulk polymerization method that uses 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 or liquid monomer such as n-butane, isobutane, n-pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene and xylene. .. 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.
When a metallocene catalyst is used, it is desirable to perform a prepolymerization treatment before the main polymerization is carried out. 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 g per 1 g of the solid catalyst (total of component [A] and component [B]). It is desirable to produce up to 100 g of the 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 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 70 to 90 ° C., and it is preferable to select from about 1.5 to 4 MPa.
Further, it is possible to increase the amount of polymer produced 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 modifier. Further, the polymerization temperature, the concentration of the molecular weight adjusting agent and the like may be changed to carry out the polymerization in multiple steps.

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, or heptane, or a liquid α-olefin. 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 after contact treatment in a stirring tank, countercurrent cleaning, and separation from the cleaning liquid by a cyclone can be used.
Further, the deactivator may be added before or at the same time as washing. The deactivator is not particularly limited, and alcohols such as water, methanol, ethanol and isopropanol, ketones such as acetone and methyl ethyl ketone, or a mixture thereof can be used.
As such a propylene-based (co) polymer (a), a commercially available one can be used. For example, trade names manufactured by Japan Polypropylene Corporation: WINTEC, Novatec PP, etc. Can be mentioned.

(Vi) 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 7. .0 is preferred.
The lower limit of the molecular weight distribution is preferably 2.0 or more, more preferably 3.0 or more, and the upper limit is preferably 6.0 or less, more preferably 5.0 or less.
When the lower limit of the molecular weight distribution is at least a certain level, 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 below a certain level, it indicates that the lengths of the molecular chains are very uniform, and unreacted monomers, dimers, low molecular weight compounds, and amorphous components that are considered to cause the generation of volatile components. , Oligo, etc., which are preferable because the content of relatively low molecular weight components 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.

_{(Vii) Average elution temperature (T 50} ) and elution dispersion (σ) of the propylene-based (co) polymer (a)
_{When a metallocene catalyst is used, 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 dissolution dispersity (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 defined as the mass integrated elution amount I (t) expressed by the following mathematical formula (1), assuming that the elution amount by the temperature rise elution fractionation method follows a normal probability distribution with respect to the elution temperature. 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共に、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、さらに好ましくは６℃以下である。
このようなメタロセン触媒を用いるプロピレン系（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 dissolution dispersion degree (σ) is more preferably 7 ° C. or lower, still more preferably 6 ° C. or lower.
As the propylene-based (co) polymer (a) using such a metallocene catalyst, a commercially available one can be used, and examples thereof include trade name: WINTEC manufactured by Japan Polypropylene Corporation. Can be done.

(2) Propylene copolymer (b)
(I) Catalyst of propylene-based copolymer (b) The catalyst of the propylene-based copolymer (b) is not particularly limited, but it is preferable to use a stereoregular catalyst. Examples of the stereoregular catalyst include a Ziegler catalyst and a metallocene catalyst. The Ziegler catalyst and the metallocene catalyst are the same as those listed above, respectively. Preferably, it is preferable to use a metallocene catalyst that is less likely to crack when the biomass polyethylene (c) is contained.

(Ii) α-olefin of propylene-based polymer (b) The α-olefin content of the propylene-based polymer (b) used in the present invention is in the range of 1% by weight or more and less than 3% by weight. It is preferably in the range of 1 to 2.9% by weight, more preferably 1.5 to 2.4% by weight, and when it is 1% by weight or more, the impact resistance is sufficient, and when it is less than 3% by weight, high rigidity is achieved. Can be maintained and the mold releasability during injection molding is improved. Examples of the α-olefin used for copolymerization include α-olefins having 2 to 20 carbon atoms excluding propylene, and examples thereof include ethylene, 1-butene, 1-hexene, and 1-octene. The α-olefin copolymerized with propylene may be used alone or in combination of two or more. Of these, ethylene and 1-butene are preferable. More preferably, ethylene is preferable. Moreover, you may use these propylene-based copolymers in mixture of 2 or more types.
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 triadic combination of arbitrary amounts of comonomers such as -1-butene copolymer, propylene-ethylene-1-hexene copolymer, propylene-1-butene-1-octene copolymer and the like. A former copolymer can be exemplified.
Such a propylene-based copolymer (b) satisfies the condition that it is a metallocene-based propylene-α-olefin random copolymer. The metallocene-based propylene-α-olefin random copolymer is a propylene-α-olefin random copolymer obtained by polymerization using a metallocene catalyst.

Further, the propylene copolymer (b) used in the present invention preferably satisfies the following conditions (A-iv) to (Av).
(A-iv) A metallocene-based propylene-ethylene random copolymer.
(Av) The melting peak temperature (Tm) is in the range of 126 ° C. or higher and lower than 142 ° C.
The metallocene-based propylene-ethylene random copolymer is a propylene-based copolymer (b) obtained by polymerizing propylene as a main component and ethylene as an α-olefin using a metallocene catalyst.

(Iii) MFR of propylene copolymer (b)
The melt flow rate (MFR: 230 ° C., 2.16 kg load) of the propylene copolymer (b) is in the range of 0.5 to 80 g / 10 minutes.
When the melt flow rate (MFR: 230 ° C., 2.16 kg load) of the propylene copolymer (b) used in the present invention is 0.5 g / 10 minutes or more, molding becomes easy, and in 80 g / 10 minutes or less. If there is, the component having a relatively low molecular weight in the propylene-based copolymer (b) is less likely to bleed on the surface of the molded product, and the appearance is improved.
The melt flow rate (MFR) can be easily determined by adjusting the temperature and pressure, which are the polymerization conditions of the propylene copolymer (b), 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 adjusted.

(Iv) Tm of propylene-based copolymer (b)
The melting peak temperature (Tm) of the propylene-based copolymer (b) used in the present invention is 126 ° C. or higher and lower than 142 ° C., preferably 128 to 141 ° C., more preferably 130 to 140 ° C., and melting. When the peak temperature (Tm) is 126 ° C. or higher, the rigidity and moldability are good, and when it is less than 142 ° C., the transparency is good.
The specific method for measuring the melting peak temperature (Tm) is to use a differential scanning calorimeter (DSC), take a sample amount of 5.0 mg, hold it at 200 ° C for 5 minutes, and then lower the temperature to 40 ° C at 10 ° C / min. The peak position of the curve drawn when the product is crystallized in 1 and further melted at a heating rate of 10 ° C./min is defined as the melting peak temperature Tm (° C.).

(V) Content of propylene-based copolymer (b) The propylene-based polymer composition of the present invention has 26 to 87 parts by weight of the propylene-based (co) polymer (a), and the propylene-based copolymer (b) 3 A total of 100 parts by weight containing ~ 25 parts by weight and 10 to 49 parts by weight of the biomass polyethylene (c). The propylene-based copolymer (b) is obtained by adding 3 to 25 parts by weight to 26 to 87 parts by weight of the propylene-based (co) polymer (a) and 10 to 49 parts by weight of the biomass polyethylene (c). be. However, the propylene-based polymer composition containing the propylene-based (co) polymer (a), the propylene-based copolymer (b), and the biomass polyethylene (c) is 100 parts by weight.
When the content of the propylene-based copolymer (b) is 3 parts by weight or more, the impact resistance is improved, and when it is 25 parts by weight or less, the rigidity is improved, which is preferable.

(Vi) Method for producing propylene-based copolymer (b) The method for producing the propylene-based copolymer (b) is not particularly limited, and usually any method for producing the propylene-based copolymer is used. good. The catalyst used for production is not particularly limited, but it is preferable to use a stereoregular catalyst. Examples of the stereoregular catalyst include a Ziegler catalyst and a metallocene catalyst. Preferably, it is preferable to use a metallocene catalyst that is less likely to crack when the biomass polyethylene (c) is contained. The metallocene catalyst is the same as that listed above.
As such a propylene-based copolymer (b), a commercially available product can be used. For example, a product name manufactured by Exxon Mobil Co., Ltd.: Vistamax or a product name manufactured by Japan Polypropylene Corporation: WELNEX. ), WINTEC, Novatec PP, and the like.

(3) Biomass polyethylene (c)
The plant-derived ethylene, which is the raw material monomer of the biomass polyethylene (c) used in the present invention, is dehydrated intramolecularly 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 (c) is a polymer obtained by polymerizing a monomer containing plant-derived ethylene as a main component. The raw material monomer of the biomass polyethylene (c) 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 (c), a homopolymer obtained by homopolymerizing plant-derived ethylene or a copolymer obtained by copolymerizing plant-derived ethylene with α-olefin can also be used. The number of carbon atoms of the α-olefin is not particularly limited, but it is preferably 1-butene, 1-hexene or 1-octene. Further, it may contain petroleum-derived ethylene.

Examples of the polyethylene used as the biomass polyethylene (c) include high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE). These polyethylenes can be used alone or in a blend of two or more.
The density of the high-density polyethylene is preferably 0.940 to 0.965 g / cm ³ , and in this range, the rigidity is improved and it is preferable. 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-mentioned 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 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 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 biomass polyethylene (c) is called biofrequency and can be determined by measuring the concentration of ^{14 C contained in biomass polyethylene (c).} 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 (c) By doing so, the biofrequency can be obtained. Specifically, when all the carbon in the biomass polyethylene (c) is derived from petroleum, the biofrequency is 0%, and when all the carbon in the biomass polyethylene (c) is derived from plants, the biofrequency is 100%. It becomes. As a test method for measuring the concentration of ^{14 C, ASTM D6866 can be mentioned.}
As the biomass polyethylene (c), those having a melt flow rate in the range of 0.21 to 72 g / 10 minutes in accordance with ASTM D1238 (190 ° C., 2.16 kg load) are preferably used.

The weight ratio of the biomass polyethylene (c) used in the propylene-based copolymer 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, a propylene-based weight containing 26 to 87 parts by weight of the propylene-based (co) polymer (a), 3 to 25 parts by weight of the propylene-based copolymer (b), and 10 to 49 parts by weight of the biomass polyethylene (c). The combined composition is 100 parts by weight.)
Examples of such biomass polyethylene (c) include "Green PE" (trade name manufactured by Braskem).

(4) Biomass degree The biomass degree (%) in the present invention is a numerical value calculated by the following mathematical formula.
Biomass degree (%) = [{A × (B ÷ 100)} / C] × 100 ・ ・ ・ Formula (2)
A: Weight of biomass polyethylene (c) B: Bio frequency (%) of biopolyethylene used
C: Weight of propylene-based polymer composition The bio-frequency (%) of biomass polyethylene (c) can be measured and calculated by ASTM D6866.

(5) 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. ..
Various general known nucleating agents can be used, for example, sterically disordered amide compounds, organic dicarboxylic acid metal salts, organic monocarboxylic acid metal salts, sorbitols or derivatives thereof, nonitols or derivatives thereof, diterpenes. Examples 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. It is an alkenyl, an alkoxy having 1 to 20 carbon atoms, an alkoxycarbonyl or phenyl ^{having 1 to 20 carbon atoms, and R 6} is an 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 Millad 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 even more 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 property regarding rigidity and transparency.

(6) 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, the antioxidants include bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, di-stearyl-pentaerythritol-di-phosphofite, and bis (2,6-di-t-butyl-4-methylphenyl). 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-based antioxidants, 2,6-di-t-butyl-p-cresol, tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamete)] methane, 1,3,5-trimethyl-2,4 Phenolic 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', and 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- Photostabilizers such as bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate can be mentioned. can.

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

・・・（２）

... (2)

・・・（３）

... (3)

・・・（４）

... (4)

Examples of the neutralizing agent include metal fatty acid salts such as calcium stearate, zinc stearate, and magnesium stearate, and hydrotalcite (trade name: DHT-4A, represented by the following formula (5) manufactured by Kyowa Chemical Industry Co., Ltd.). Magnesium-aluminum composite hydroxide salt), Mizukarakku (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.

Other than the propylene-based (co) polymer (a), the propylene-based polymer (b), and the biopolyethylene (c), as long as the properties such as properties and functions of the propylene-based polymer composition of the present invention are not impaired. Polymers, polyethylene, ethylene-propylene copolymers, ethylene-propylene-diene copolymers, ethylene-1-butene copolymers, ethylene-vinyl acetate copolymers, ethylene-acrylate copolymers, acrylate polymers. 1 to 30 parts by weight can be arbitrarily added to 100 parts by weight of the propylene-based polymer composition. Similarly, elastomers such as natural rubber, butyl rubber, diene rubber, EPR and EPDM can be blended. Furthermore, general-purpose inorganic fillers such as talc, calcium carbonate, silica, alumina, gypsum, and mica can be used in combination.

(7) 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 1000 to 1500 MPa, and is injected when the flexural modulus is 1000 MPa or more. The mold releasability from the mold at the time of molding becomes good, and the impact resistance becomes good when it is 1500 MPa or less. It is more preferably 1100 to 1450 MPa, still more preferably 1200 to 1400 MPa.

(8) 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 even more preferably 4.0 kJ / m ² or more.

(9) 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 when the HAZE is 50% or less, the visibility of the contents is improved and the design is further improved. Becomes good. 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), a propylene-based copolymer (b), and biomass polyethylene (c). , If necessary, add each predetermined amount of other additives to a Henschel mixer (trade name), super mixer, ribbon blender, etc. and mix them, and then use a normal single-screw extruder, twin-screw extruder, Banbury mixer, etc. It can be obtained by melt-kneading with a plastic bender, a roll or the like in a temperature range of 190 to 260 ° 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 molded product of shape.
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), the propylene-based copolymer (b), and the propylene-based polymer composition were measured according to the following methods. ..
<1. Measurement method>

(1) Melt flow rate (MFR):
The measurement was performed in accordance with JIS K7210 (230 ° C., 2.16 kg load).

(2) Calculation of ethylene content of propylene-based (co) polymer (a) and propylene-based copolymer (b)
¹³ The ethylene content in the random copolymer was measured by infrared spectroscopy using a characteristic absorption band ^{of 733 cm -1} using an 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:
For the molecular weight distribution Mw / Mn of the propylene-based (co) polymer (a) and the propylene-based copolymer (b), the weight average molecular weight Mw and the number average molecular weight Mn were measured by a gel permeation chromatography (GPC) method. Calculated. The measurement conditions are as follows.
Equipment: Waters GPC (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 velocity: 1.0 ml / min
Injection volume: 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 of 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 temperature rising rate of 10 ° C./min to melt.

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

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

(8) 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 notch having 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 some parts. (Doesn't break)
X: When bent 90 degrees or more, it is divided into several parts. (Crack)

<2. Resins, additives>
2-1. Production of propylene-based (co) polymer (a) (1) Production example 1
(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 _{a toluene solution of MeSi (OPh) 3} was added to magnesium in Mg (OEt) ₂ previously charged with MeSi (OPh) ₃ / Mg. It was added so as to be = 0.67 (mr.). The amount of toluene used here was 7.8 kg. After completion of the addition, the mixture was reacted at 130 ° C. for 2 hours, then cooled 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 resulting mixture was cooled to 10 ° C. with continued stirring and TiCl ₄ was added dropwise over 2 hours to give 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 carried out at the same temperature for 1 hour. After completion of the treatment, stirring was stopped, the supernatant was removed, and the mixture was washed with toluene so that the residual liquid ratio = 1/73 (volume ratio of toluene / solid component) to obtain a slurry of solid components.

_{Next, toluene and TiCl 4} were added to the slurry obtained here at room temperature. In addition, TiCl _{4 was adjusted so that TiCl 4} / Mg (OEt) ₂ = 5.0 (mr.) 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 (volume ratio of toluene / 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 set to 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 completion of the addition, the mixture was kept at 15 ° C. for 1 hour with continued 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 represents t-butylethyldimethoxysilane and t-butyl represents 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 polypropylene particles contained in the slurry. The average residence time of the polypropylene particles in the liquid phase polymerization tank was 1.4 hours. Analysis of the extracted polypropylene 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 5.7, and the Tm was 156 ° C.

(2) Manufacturing example 2
(I) Preparation of solid catalyst 20 L of dehydrated and deoxidized n-heptane was introduced into a tank with a stirrer having an internal volume of 50 L sufficiently substituted with nitrogen, and then _{10 mol of magnesium chloride (MgCl 2} ) and tetrabutoxytitanium [Ti] were introduced. (On-C ₄ H ₉ ) ₄ ] was introduced in 20 mol and reacted at 95 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., ^{12 L of methylhydropolysiloxane [kinematic viscosity: 20 centistokes (cSt) = 2 × 10-5} m ² / s] was introduced, and the reaction was carried out for 3 hours. The solid component produced was washed with n-heptane.
Subsequently, using the tank with a stirrer, 5 L of n-heptane purified in the same manner as described above was introduced into the tank, and 3 mol of the solid component synthesized above was introduced in terms of Mg atoms. _{Next, 5 mol of tetrachlorsilane (SiCl 4} ) was mixed with 2.5 L of n-heptane, introduced into a flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After completion of the reaction, the mixture was washed with n-heptane.
Next, 2.5 L of n-heptane was introduced into the tank with a stirrer, 0.3 mol of phthalic acid chloride was mixed, introduced at 70 ° C. for 30 minutes, and reacted at 90 ° C. for 1 hour. After completion of the reaction, the mixture was washed with n-heptane. Subsequently, 2 _{L of tetrachlorotitanium (TiCl 4} ) was introduced and reacted at 110 ° C. for 3 hours. After completion of the reaction, the solid component (b1) for preparing the solid catalyst component (b) was obtained by washing with n-heptane. The titanium content of this solid component (b1) was 2.0% by weight.
Thereafter, nitrogen-purged 8L said agitator with tank n- heptane, the synthetic solid component (b1) introducing 400 g, and 0.6L introducing SiCl ₄ as the component (b2), 2 hours at 90 ° C. It was reacted. _{After completion of the reaction, 0.54 mol of vinyltrimethylsilane [(CH 2} = CH) Si (CH ₃ ) ₃ ] as the component (b3) and _{t-butylmethyldimethoxysilane [(t-C 4} ) as the component (b4) were added. H ₉ ) (CH ₃ ) Si (OCH ₃ ) ₂ ] 0.27 mol and 1.5 mol of triethylaluminum [Al (C ₂ H ₅ ) ₃ ] as component (a5) were sequentially introduced and 2 at 30 ° C. Contacted for hours.
After the contact was completed, the mixture was thoroughly washed with n-heptane to obtain 390 g of a solid catalyst component (b) mainly composed of magnesium chloride. The titanium content of this solid catalyst component (b) was 1.8% by weight.

(Ii) Prepolymerization Using the solid catalyst component (b) obtained above, prepolymerization was carried out by the following procedure. Purified n-heptane was introduced into the above slurry to adjust the concentration of the solid catalyst component (b) to 20 g / L. After cooling the slurry to 10 ° C., and 10g added _Al of _{(C 2} H _{5) 3} of n- heptane diluent as _{Al (C 2} H _{5) 3,} was fed over 4 hours propylene 210g. After the supply of propylene was finished, the reaction was continued for another 30 minutes.
The gas phase was then thoroughly replaced with nitrogen and the reaction product was thoroughly washed with purified n-heptane. The obtained slurry was extracted from the autoclave and vacuum dried to obtain a prepolymerized solid catalyst component (B). The solid catalyst component (B) contained 2.0 g of polypropylene per 1 g of the solid catalyst component (B). As a result of analysis, the portion of the solid catalyst component (B) excluding polypropylene contained 1.0% by weight of Ti and 8.2% by weight of _{(i-C 3} H ₇ ) ₂ Si (OCH ₃ ) _2. It was.

(Iii) Production of propylene homopolymer propylene polymerization was carried out using a fluidized bed reactor having an internal volume of 230 L as a continuous reactor. The reactor continuously mixes propylene and hydrogen so that the polymerization temperature is 85 ° C., the partial pressure of propylene is 1.8 MPa (absolute pressure), hydrogen as a molecular weight modifier is 0.010 in a hydrogen / propylene molar ratio. Supplied. Further, 5.25 g / hour of triethylaluminum and 0.50 g of the prepolymerized solid catalyst component (B) described above were supplied so that the propylene polymerization rate was 20 kg / hour to produce a propylene homopolymer.
The powder polymerized in the reactor was continuously withdrawn into a vessel so that the amount of powder retained in the reactor was 60 kg. A nitrogen gas containing water was supplied to stop the reaction, and a propylene homopolymer was obtained.
The MFR of this propylene homopolymer was 9 g / 10 minutes.

2-2. Propylene-based (co) polymer (a)
(PP-1) Propylene resin obtained by polymerizing in Production Example 1 (PP-2) Propylene resin obtained by polymerizing in Production Example 2 2-3. Propylene-based copolymer (PP-3) other than propylene-based copolymer (b) Product name "WINTEC WMG03" manufactured by Japan Polypropylene Corporation, MFR = 30 g / 10 minutes, ethylene content = 0.9% by weight, Tm = 142 ° C
2-4. Propylene copolymer (b)
(PP-4) Product name "WINTEC WFW4M" manufactured by Japan Polypropylene Corporation, MFR = 7.0 g / 10 minutes, ethylene content = 1.9% by weight, Tm = 135 ° C.
(PP-5) Product name "NOVATEC PP MG03BD" manufactured by Japan Polypropylene Corporation, MFR = 30 g / 10 minutes, ethylene content = 2.4% by weight, Tm = 152 ° C.

2-5. Biomass polyethylene (c)
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.)
High density polyethylene (HDPE)
(PE-3) Product name "Green PE SGM9450F" manufactured by Braskem
Density: 0.952 g / cm ³ , melt flow rate according to ASTM D1238 (190 ° C, 5 kg load) 0.33 g / 10 minutes, 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'-Hydroxyphenyl) 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 "IRGAFOS168" 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 1-10, Comparative Examples 1-9>
Each polymer and additive are prepared in the blending ratio (part by weight) shown in Table 1, dry-blended with a super mixer, and then a die outlet portion under a nitrogen atmosphere using a TEM-35B twin-screw extruder manufactured by Toshiba Machinery Co., Ltd. It was melt-kneaded at a temperature of 220 ° C. 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 10 contain a specified amount of the propylene-based (co) polymer (a), the propylene-based copolymer (b), and the biomass polyethylene (c) according to the present invention. Therefore, it can be seen that it is a material that can reduce the environmental load, has excellent rigidity, and does not crack. In Example 1, a predetermined amount of LDPE was contained as the biomass polyethylene (c), and it can be seen that the transparency is also excellent. In Example 2, the content of biomass polyethylene (c) LDPE was reduced in the composition of Example 1, but it can be seen that it is more excellent in rigidity and transparency than in Example 1. In Examples 3 and 4, LLDPE and HDPE were used as the biomass polyethylene (c), respectively, and in Examples 5 to 7, a propylene homopolymer was used as the propylene-based (co) polymer (a). be. In Examples 8 to 9, the content of the propylene-based copolymer (b) was increased or decreased, and in Example 10, different propylene-based copolymers (b) were used. It can be confirmed that the effect is obtained.
On the other hand, Comparative Examples 1 and 2 have a lower α-olefin content than the propylene-based copolymer (b) or do not contain the propylene-based copolymer (b), and have a slightly higher rigidity than that of Example 1. Although it is excellent, it can be seen that it cracks by a crack test in the TD direction. Comparative Examples 3 and 4 have physical characteristics of a composition containing PP-1 or PP-4 alone, but have a biomass degree of 0%. Comparative Example 5 has insufficient rigidity due to the physical characteristics of the composition containing PE-1 alone. In Comparative Example 6, since the content of the propylene-based copolymer (b) was low, the TD direction was broken, and in Comparative Example 9, the content of the propylene-based copolymer (b) was high, resulting in insufficient rigidity. Become. In Comparative Example 7, the content of biomass polyethylene (c) was low, so the degree of biomass was too low, and in Comparative Example 8, since the propylene copolymer (b) was not used, cracking was performed in the TD direction. I understand.

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

Claims (4)

26 to 87 parts by weight of the propylene-based (co) polymer (a) satisfying the following conditions (H-i) to (H-ii), and the propylene-based copolymer satisfying the following conditions (A-i) to (A-iii). A propylene-based polymer composition having a total of 100 parts by weight containing 3 to 25 parts by weight of the coalesced (b) and 10 to 49 parts by weight of the biomass polyethylene (c) and having a biomass degree of 8.4 to 49%.
(Hi) A propylene homopolymer or a 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, may be abbreviated as MFR) conforming to JIS K7210 (230 ° C., 2.16 kg load) is in the range of 0.5 to 100 g / 10 minutes.
(Ai) A propylene-α-olefin random copolymer.
(A-ii) The α-olefin content is in the range of 1% by weight or more and less than 3% by weight.
(A-iii) MFR is in the range of 0.5 to 80 g / 10 minutes. The propylene-based polymer composition according to claim 1, wherein the propylene-based copolymer (b) satisfies the following conditions (A-iv) to (Av).
(A-iv) A metallocene-based propylene-ethylene random copolymer.
(Av) The melting peak temperature (Tm) is in the range of 126 ° C. or higher and lower than 142 ° C. 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 or 2. A molded product obtained by using the propylene-based polymer composition according to any one of claims 1 to 3.

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