JP2003246900A - Propylene based composition, its production process, polypropylene-based composition and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polypropylene-based composition for obtaining various molded articles excellent in moldability, molding shrinkage, rigidity, flexibility, impact resistance, particularly impact resistance at low temperature, transparency, gloss, and resistance to whitening, with excellent balance among these characteristics, and various molded articles having those characteristics. <P>SOLUTION: The polypropylene based composition is based on a propylene composition characterized by comprising a propylene homopolymer and a propylene/ethylene copolymer, with the copolymer having an intrinsic viscosity ([η]RC) of 1.7-2.8 dL/g, the ratio of the intrinsic viscosity of the copolymer to that of the homopolymer, ([η]RC/[η]PP), being 0.7 to 1.2, and the product of the weight ratio (WPP/WRC) of the homopolymer to the copolymer and the intrinsic viscosity ratio thereof, (WPP/WRC)×([η]RC/[η]PP), being 1.0 to 3.0. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene-based composition, and more specifically, a composition comprising a propylene homopolymer and a propylene-ethylene copolymer, a method for producing the same, and a polypropylene-based composition containing this composition as a main component. Compositions and molded articles of these compositions,
In particular, it relates to injection molded products, extruded sheets, films and hollow molded products.

[0002]

Background of the Invention Polypropylene resins are relatively inexpensive and
Due to its excellent properties, various molded products are available today.
For example, it is used in a wide variety of fields such as sheets, containers, caps (plugs) and the like, and injection molded products having a hinge structure thereof, hollow molded products such as films and air ducts. The film is also widely used as a packaging material for foods, textiles and the like by utilizing its mechanical, optical and thermal characteristics.

Then, in accordance with the properties required for each molding application, a composition comprising a propylene homopolymer, a copolymer of propylene and an α-olefin, particularly an enalene, and a propylene pomopolymer and a propylene-α-olefin copolymer. Polypropylene-based compositions whose main components are used.

In general, propylene homopolymer has high rigidity and excellent heat resistance, but lacks flexibility and is inferior in impact resistance, particularly impact resistance at low temperature, and tear strength when formed into a film. There is. The propylene-α-olefin copolymer is excellent in transparency and flexibility, but is inferior in heat resistance and impact resistance at low temperature. Further, conventionally known compositions are excellent in heat resistance and impact resistance at low temperature,
It is widely used in various industrial fields such as automobiles and home appliances, but it is more transparent than homopolymer.
The gloss is inferior and the molding shrinkage is large like the homopolymer, while the tear strength and flexibility are inferior to the copolymer. In any case, the phenomenon of whitening due to impact or bending is observed, and the whitening resistance is insufficient.

Methods for improving these insufficient properties include a method of changing the properties of a polymer, a copolymer or a composition and a method of using an additive.

[0006] For example, as a general method, a method of improving the molding shrinkage of a composition by filling an inorganic substance such as talc is adopted, but in order to improve the molding shrinkage, a large amount of talc or the like is used. Since it is necessary to add an inorganic substance, the weight of the molded product increases greatly and the appearance remarkably deteriorates. on the other hand,
Although the method of reducing the ethylene content of the copolymer in the composition to improve transparency and gloss is also adopted, the reduction of the ethylene content in the copolymer contributes to the improvement of gloss, but at the same time impact resistance at low temperature and rigidity Is generally low.

Japanese Unexamined Patent Publication (Kokai) No. 60-28411 discloses a high-rigidity ethylene, in which an ethylene-propylene copolymer is divided into three stages and the ethylene content of each is changed to perform sequential copolymerization.
Disclosed is a method for producing a propylene copolymer, that is, a propylene-based composition. The composition obtained by this method is
In addition to having high rigidity, it also has excellent whitening resistance, impact resistance, heat resistance, etc., but there are points that should be improved such as transparency, gloss, appearance of the molded product, molding shrinkage at the time of molding. Have

Japanese Patent Publication No. 7-30145 discloses a crystalline polypropylene part and an ethylene-propylene random copolymer block, the content of the crystalline polypropylene component is 55 to 95% by weight, and the intrinsic viscosity ratio ([η ] _EP /
Disclosed is a propylene block copolymer, that is, a propylene-based composition, in which [η] _PP ) is 0.5 to 2.0 and the glass transition temperature of the ethylene-propylene random copolymer block is -30 ° C or lower. This composition has an ethylene-propylene copolymer component content and an intrinsic viscosity ratio of the propylene homopolymer and the copolymer component in substantially the same range,
It has excellent mechanical properties such as impact resistance and rigidity, but has the point that the transparency, gloss and appearance of the molded product, especially the whitening property of the molded product and the molding shrinkage ratio during molding, should be improved. ing.

Japanese Unexamined Patent Publication (Kokai) No. 6-93061 discloses an ethylene-propylene copolymer part in which a polymer mainly containing propylene is polymerized in an amount of 60 to 80% by weight based on the total polymerization amount, and then an ethylene content is 20 to 50% by weight. A block copolymer obtained by polymerizing ethylene, wherein the ethylene-propylene copolymer has an intrinsic viscosity ([η] _B ) of 2.0 dl / g or more and an intrinsic viscosity ratio of both components.
Proposed is a polypropylene block copolymer obtained by melt-kneading a block copolymer having a ([η] _B / [η] _A ) of 1.8 or less. This composition also has an ethylene-propylene copolymer component content and an intrinsic viscosity ratio of the propylene homopolymer and the copolymer component in substantially the same range, and has excellent low temperature impact resistance, blocking resistance, and appearance. , Mechanical properties such as rigidity, and molding shrinkage during molding should be improved.

Japanese Unexamined Patent Publication (Kokai) No. 6-328640 proposes a multilayer film in which a layer of polypropylene resin is laminated on both surfaces of a linear low-density polyethylene layer and tear strength is greatly improved. In this multilayer film, the compatibility between the low-density polyethylene and the polypropylene resin to be laminated is not so good, so that fish eyes are likely to occur when remelted and reused as a film.

JP-A-52-126450 discloses a three-component blend of ethylene-α-olefin copolymer rubber, polypropylene or high density polyethylene, and paraffin oil or naphthenic oil. This formulation is excellent in flexibility, but has low heat resistance.

Japanese Unexamined Patent Publication (Kokai) No. 4-228232 proposes a resinous tubular body in which a rigid portion formed of a hard polyolefin resin and a flexible portion formed of a thermoplastic elastomer are connected. This tubular body lacks the joint strength between the rigid portion and the flexible portion.

[0013]

DISCLOSURE OF THE INVENTION The present invention is directed to impact resistance of various molded products, particularly impact resistance at low temperature, rigidity, tear strength,
A propylene-based composition suitable as a base resin for a polypropylene-based composition having various properties such as heat resistance, transparency, gloss, and whitening resistance, and a molding shrinkage ratio during molding thereof, and an excellent balance between them. And a method for manufacturing the same.

It is another object of the present invention to provide a polypropylene composition containing the above propylene composition as a base resin.

A further object of the present invention is to provide various molded articles using the polypropylene composition and a method for producing them.

[0016]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that in the presence of a stereoregular catalyst using a titanium-containing solid catalyst component having a large particle size,
A propylene-based composition consisting of propylene homopolymer and propylene-ethylene copolymer obtained by continuously vapor-phase polymerizing propylene alone and then a mixture of propylene and ethylene has an intrinsic viscosity of propylene-ethylene copolymer, When the intrinsic viscosity ratio and the product of this intrinsic viscosity ratio and the weight ratio of both components are within a certain range,
The inventors have found that they have excellent impact resistance, especially impact resistance at low temperature, rigidity, transparency, gloss, whitening resistance, mold shrinkage ratio during molding, and the balance between them, and completed the present invention. .

The present invention relates to propylene homopolymer (PP)
And propylene-ethylene copolymer (RC)
The intrinsic viscosity of propylene-ethylene copolymer (RC)
([η]_{R C}) Is 1.7 to 2.8 dl / g; propylene homopolymer
-(PP) and propylene-ethylene copolymer (RC)
Intrinsic viscosity ratio ([η]_RC/ [Η]_PP) Is 0.7-1.2; and professional
Pyrene homopolymer (PP) and propylene-ethylene copo
Weight ratio of rimer (RC) (W_PP/ W_RC) And their intrinsic viscosity
Ratio ([η]_RC/ [Η]_PP) And ((η]_RC/ [Η]_PP) × (W_PP/
W_RC) Is in the range of 1.0 to 3.0;
It is a propylene-based composition (A).

Another invention is that the average particle size is 25 to 300 μm.
Titanium-containing solid catalyst component (a) of the general formula AlR ¹ mX
_3-m (wherein R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, and m is a positive number of 3 ≧ m> 1.5) (b); and the general formula R ² _X R ³ _Y Si (OR ⁴ ) _Z (wherein R ² and R ⁴ represent a hydrocarbon group, R ³ represents a hydrocarbon group or a hydrocarbon group containing a hetero atom, X, Y and Z are 0 ≦ X ≦ 2, 1 ≦ Y ≦
3, 1 ≦ Z ≦ 3, and X + Y + Z = 4) in the presence of a stereoregular catalyst in which an organic silicon compound (c); Polymerization step of producing 78 to 60% by weight of propylene homopolymer (PP); then propylene-ethylene copolymer in which ethylene and propylene are copolymerized, and the ethylene unit content in the polymer is 25 to 55% by weight. A second polymerization step in which (RC) is produced in an amount of 22 to 40% by weight based on the total weight; is the method for producing the propylene-based composition (A).

Another invention is the above-mentioned propylene composition (A).
Is a polypropylene-based composition (C) containing, as a main component, an additive that is optionally added.

Still another invention is a molded product (D) using the polypropylene composition, particularly an injection molded product, a sheet,
Films and hollow moldings.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION In the propylene composition (A) of the present invention, the propylene homopolymer (PP) has an isotactic pentad fraction (P) of 0.95 or more,
Preferred is polypropylene having a high crystallinity of 0.955 or more, that is, stereoregularity. Isotactic pentad fraction (P) of propylene homopolymer (PP)
Influences mechanical properties such as rigidity and heat resistance of the molded product (D), and the larger the value, the higher rigidity and heat resistance.

On the other hand, propylene-ethylene copolymer
(RC) is an ethylene-propylene random copolymer containing 25 to 55% by weight, preferably 30 to 55% by weight, of ethylene polymerized units, based on the weight of the propylene-ethylene copolymer (RC).

The ethylene polymerized units in the propylene-ethylene copolymer (RC) affect the rigidity, flexibility and impact resistance of the molded product (D), especially impact resistance and whitening resistance at low temperature. And the impact resistance is improved,
If it is too large, the dispersibility of the propylene-ethylene copolymer (RC) in the propylene homopolymer (PP) is affected, and the transparency, gloss, and whitening property of the molded product (D) are reduced.

Further, propylene-ethylene copolymer
(RC) is the intrinsic viscosity measured in 135 ° C tetralin
([η] _RC ) is in the range of 1.7 to 2.8 dl / g and the intrinsic viscosity ratio ([η] _PP ) between the propylene homopolymer (PP) and the intrinsic viscosity ([η] _PP ) measured under the same conditions ( [η] _RC / [η] _PP ) is 0.
It is in the range of 7 to 1.2, preferably 0.8 to 1.2.

Since the intrinsic viscosity ([η] _RC ) of propylene-ethylene copolymer (RC) cannot be directly measured, the intrinsic viscosity ([η] _PP ) of propylene homopolymer (PP) which can be directly measured.
And the intrinsic viscosity of the whole propylene composition (A) ([η]
_WHOLE ), and propylene-ethylene copolymer (R
It is determined from the weight% (W _RC ) of C) by the following formula.

[0026]

[Equation 1] [η] _RC = [[η] _WHOLE − (1-W _RC / 100) [η]
_PP ] / (W _RC / 100) Intrinsic viscosity of propylene-ethylene copolymer (RC)
([η] _RC ) is the molding cycle property of the polypropylene-based composition (C), the film-forming property when the film is manufactured, and the molded product.
(D) affects mechanical properties such as rigidity and heat resistance, and the intrinsic viscosity ratio ([η] _RC / [η] _PP ) of propylene-ethylene copolymer (RC) and propylene homopolymer ( _PP ) is propylene- It affects the dispersibility of the ethylene copolymer (RC) in the propylene homopolymer (PP). As the intrinsic viscosity ([η] _RC ) of the propylene-ethylene copolymer (RC) is larger, the mechanical properties of the molded product (D) are improved, but the molding cycle property of the polypropylene composition (C) is decreased and the propylene homopolymer is reduced. If the intrinsic viscosity ratio ([η] _RC / [η] _PP ) to the polymer (PP) is too large or too small, the molded product (D) will lack impact resistance and whitening resistance at low temperatures. . If it is too small, the flexibility of the molded product (D) is insufficient, and if it is too large, the effect of improving the molding shrinkage of the polypropylene composition (C) and the transparency of the molded product (D) decreases, The desired characteristics cannot be achieved.

Propylene-ethylene copolymer (RC)
Contains 80% by weight or more, preferably 85% by weight, of a 20 ° C. xylene-soluble component based on the weight of the propylene-ethylene copolymer (RC). Propylene-ethylene copolymer (RC) 20 ° C xylene soluble component weight% (CXS _RC ).
Propylene homopolymer (PP)
20% xylene solubles by weight (CXS _PP ) and 20% xylene solubles by weight (CXS) of the entire composition (A).
_WHOLE ), and propylene-ethylene copolymer (R
It is determined from the weight% (W _RC ) of C) by the following formula.

[0028]

[Formula 2] CXS _RC = [CXS _WHOLE- (1-W _RC / 100)
CXS _PP ] / (W _RC / 100) In the propylene composition (A) of the present invention, propylene homopolymer (PP) and propylene-ethylene copolymer
(RC) the weight ratio of (W _PP / W _RC), as a product of the intrinsic viscosity ratio of both components mentioned above _{([η] RC / [η} ] PP), ([η] RC /
[η] _PP ) × (W _PP / W _RC ) is in the range of 1.0 to 3.0.

The product of the weight ratio of both components and the intrinsic viscosity ratio is an index showing the molding shrinkage of the polypropylene composition (C). When the value becomes smaller, the molding shrinkage and molded products
Although the tear strength and weld strength of (D) are improved, the heat resistance and rigidity of the molded product (D) are greatly reduced, and when it is large, the whitening property is decreased and the desired molding shrinkage ratio and tear strength are increased. Strength and weld strength cannot be improved.

The specific composition of the propylene composition (A) is 22 to 40% by weight, preferably 25 to 4% by weight of the propylene-ethylene copolymer (RC) based on the weight of the composition (A).
It is 0% by weight.

The propylene composition (A) has a Q value of
It has a narrow dispersible molecular weight distribution of (Mw / Mn) of 5 or less, more preferably 4.5 or less. When the width of the molecular weight distribution becomes large, the gloss and weld strength of the molded product (D) decrease.

The propylene-based composition (A) of the present invention satisfies the above-mentioned various characteristics, so that the molding shrinkage rate at the time of molding, the film-forming property, and the transparency, gloss, rigidity, flexibility of the molded product, Polypropylene-based composition (C) for producing a molded article having excellent impact resistance, particularly impact resistance at low temperature, mechanical properties such as tear strength, weld strength and the balance between them (C)
It is preferably used as a base resin of.

The propylene composition (A) of the present invention may be produced by any method as long as the above-mentioned various properties are satisfied.
For example, separately produced propylene homopolymer (P
P) and propylene-ethylene copolymer (RC) can be mixed and produced using a mixing device, but can be suitably produced by employing the production method of the present invention.

The process for producing the propylene-based composition (A) of the present invention is a stereoregular catalyst comprising a titanium-containing solid catalyst component (a) having a large particle size, an organoaluminum compound (b) and an organosilicon compound (c). In the presence of the above, a propylene homopolymer is produced in the first step in the gas phase (first polymerization step), and then a propylene-ethylene copolymer is produced in the second step (second polymerization step).

In the production method of the present invention, the titanium-containing solid catalyst component (a) is obtained by supporting a titanium compound on an inorganic carrier such as a magnesium compound, a silica compound or alumina, or an organic carrier such as polystyrene, or on such a carrier. Any known one can be used as long as it is reacted with an electron-donating compound such as an ether or an ester, if necessary.

For example, a titanium-containing solid catalyst component obtained by spraying an alcohol solution of a magnesium compound to partially dry the solid component and then treating the dried solid component with titanium halide and an electron donating compound (Japanese Patent Laid-Open No. 3-119).
No. 003), a magnesium compound is dissolved in tetrahydrofuran / alcohol / electron donor, and TiCl ₄
A titanium-containing solid catalyst component obtained by treating a magnesium simple substance, which is deposited alone or in combination with an electron donor, with a titanium halide and an electron-donating compound (JP-A-4-1036).
No. 04) and the like.

As the titanium-containing solid catalyst component (a), one having an average particle size of 25 to 300 μm, preferably 30 to 150 μm is used. The average particle size of the titanium-containing catalyst component is 25
When the particle size is less than μm, the fluidity of the powder of the propylene composition (A) produced is remarkably impaired, and the inside of the polymerization system is contaminated due to the adhesion to the vessel wall of the polymerization vessel or the stirring blade, and the powder discharged from the polymerization vessel. It becomes difficult to carry out the stable operation because it becomes difficult to carry the product.

The titanium-containing catalyst component (a) preferably has a homogeneity in normal distribution of 2.0 or less. When the homogeneity exceeds 2, the powder fluidity of the propylene composition (A) is deteriorated, and stable operation in which the first polymerization step and the second polymerization step are continuous becomes difficult.

As the organoaluminum compound (b), R ¹ _m X _3-m (wherein R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, and m is 3 ≧ m). An organoaluminum compound represented by a positive number> 1.5) can be used.

Specifically, trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri-n-butyl aluminum, tri-i-butyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum sesquichloride, and di- Examples include -n-propylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum iodide, ethoxydiethylaluminum, and the like, and triethylaluminum is preferably used.

These organoaluminum compounds can be used alone or as a mixture of two or more.

As the organosilicon compound (c), a compound represented by the general formula R² _X
R³ _YSi (OR_Four)_Z(R in the formula²And R ^FourIs a hydrocarbon group, R³
Represents a hydrocarbon group or a hydrocarbon group containing a hetero atom.
Where X, Y and Z are 0 ≦ X ≦ 2, 1 ≦ Y ≦ 3, 1 ≦ Z
≦ 3, and X + Y + Z = 4)
Elementary compounds are used.

Specifically, methyltrimethoxysilane,
Ethyltrimethoxysilane, n-propyltrimethoxysilane, phenylmethyldimethoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane,
Phenyltriethoxysilane, methylethyldimethoxysilane, methylphenyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, diphenyldimethoxysilane, trimethylmethoxysilane, cyclohexyl Methyldimethoxysilane, trimethylethoxysilane and the like can be mentioned, and preferably diisobutyldimethoxysilane, diisopropyldimethoxysilane, di-t-butyldimethoxysilane, cyclohexylmethyldimethoxysilane and diphenyldimethoxysilane are used.

These organosilicon compounds may be used alone or as a mixture of two or more.

In the method for producing the propylene-based composition (A) of the present invention, prior to the homopolymerization of propylene in the first polymerization step, the titanium-containing solid catalyst component (a), the organoaluminum compound (b ') and the necessary amount are used. Depending on the organosilicon compound
In the presence of (c '), it is preferable to pre-activate the α-olefin by pre-reacting it and use it. In the pre-activation treatment of the titanium-containing solid catalyst component (a), the amount of the organoaluminum compound (b ') used is not particularly limited, but it is usually 1 mol of titanium atom in the titanium-containing solid catalyst component. 0.1 to 40 mol, preferably 0.3 to 20 mol, and the α-olefin is 0.1 to 100 per gram of titanium-containing solid catalyst component at 10 to 80 ° C. for 10 minutes to 48 hours. Grams, preferably 0.5 to 50 grams are reacted.

In the preliminary activation treatment, the organosilane compound (c ') may be used in advance in an amount of 0.01 to 10 mol, preferably 0.05 to 5 mol, based on 1 mol of the organoaluminum compound.

Examples of the organoaluminum (b ') used for the above pre-activation treatment include the above-exemplified organoaluminum (b) used for the main polymerization. this
As the organoaluminum compound (b ') (B'), the same kind as the organoaluminum compound (b) used in the main polymerization or a different kind can be used, but triethylaluminum is preferably used.

Examples of the organosilicon compound (c ') used for the preliminary activation treatment as required include the same kind as the above-exemplified organosilicon compound (c). As the organosilicon compound (c ′), the same kind as the organosilicon compound (c) used in the main polymerization or a different kind can be used. Preferably, diisobutyldimethoxysilane, diisopropyldimethoxysilane, di-t-butyldimethoxysilane, cyclohexylmethyldimethoxysilane and diphenyldimethoxysilane are used.

The olefins used for pre-activating the titanium-containing solid catalyst component (a) are ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 4-methyl-1-pentene, 3-methyl-1-pentene and the like. These olefins may contain not only one but also one kind or a mixture of two or more kinds of other olefins. In addition, a molecular weight regulator such as hydrogen may be used in combination during the polymerization to regulate the molecular weight of the polymer.

The inert solvent used for the preliminary activation treatment of the titanium-containing solid catalyst component (a) is hexane, heptane,
It is an inert solvent that does not significantly affect the polymerization reaction such as liquid saturated hydrocarbons such as octane, decane, dodecane and liquid paraffin, and silicone oil having a structure of dimethylpolysiloxane. These inert solvents may be either a single solvent or a mixture of two or more solvents.

When using these inert solvents, it is preferable to use them after removing impurities such as water and sulfur compounds which adversely affect the polymerization.

In the method for producing the propylene-based composition (A) of the present invention, propylene is polymerized in the gas phase in the presence of the pre-activated titanium-containing solid catalyst component (a) to produce a propylene homopolymer. The first polymerization step of forming (PP) and the second polymerization step of copolymerizing ethylene and propylene to form a propylene-ethylene copolymer (RC) are continuously performed. The first polymerization step is not limited to gas phase polymerization, and slurry polymerization or bulk polymerization may be adopted, but since the second polymerization step following it is preferably gas phase polymerization, the first polymerization step is also gas phase polymerization. It is preferable to employ phase polymerization. When slurry polymerization or bulk polymerization is adopted as the second polymerization step, the propylene-ethylene copolymer (RC) elutes in the solution, making it difficult to continue stable operation.

The polymerization conditions of the propylene homopolymer (PP) differ depending on the polymerization mode, but in the case of the gas phase polymerization method, the titanium-containing solid catalyst component (a) pre-activated while mixing and stirring a certain amount of powder, In the presence of a stereoregular catalyst composed of the organoaluminum component (b) and the organosilicon compound (c), the polymerization temperature is 20 to 120 ° C., preferably 40 to 100.
C., polymerization pressure atmospheric pressure to 9.9 MPa, preferably 0.59
Propylene is supplied and polymerized under the conditions of up to 5.0 MPa to form a propylene homopolymer (A). The usage rate of the organoaluminum compound (b) and the titanium-containing solid catalyst component (a) is Al / Ti = 1 to 500 (molar ratio), preferably 10
~ 300. In this case, the titanium-containing solid catalyst component
The number of moles of (a) is substantially the solid catalyst component containing titanium (a)
It refers to the number of Ti gram atoms in the medium.

The use ratio of the organosilicon compound (c) and the organoaluminum component (b) is b / c = 1 to 10 (molar ratio), preferably 1.5 to 8.

If the molar ratio of b / c is too large, the crystallinity of the propylene homopolymer (PP) is lowered and the rigidity of the molded product (D) becomes insufficient. On the other hand, when the b / c molar ratio is too small, the polymerization activity is remarkably reduced and the productivity is lowered.

To control the molecular weight of the propylene homopolymer (PP), it is possible to use a molecular weight regulator such as hydrogen during the polymerization, so that the intrinsic viscosity of the propylene homopolymer (PP) satisfies the requirements of the present invention. Be implemented. After polymerizing propylene homopolymer (PP), part of the produced powder was extracted and the intrinsic viscosity ([η] _PP ) and melt flow rate
(MFR _PP ), the amount of xylene-soluble components at 20 ° C. and the isotactic fraction (P), and the polymerization yield per unit weight of the catalyst.

Following the propylene homopolymerization in the first polymerization step, the polymerization temperature is 20 to 120 ° C., preferably 40 to 1
00 ° C., polymerization pressure atmospheric pressure to 9.9 MPa, preferably 0.1.
A second polymerization step of copolymerizing a mixed monomer of ethylene and propylene to form a propylene-ethylene copolymer (RC) is performed under the conditions of 59 to 5.0 MPa. The ethylene unit content in the propylene-ethylene copolymer (RC) is controlled so that the ethylene unit content in the propylene-ethylene copolymer (RC) is 25 to 5 by controlling the gas molar ratio of the ethylene monomer and the propylene monomer in the comonomer gas.
Adjust to 5% by weight.

On the other hand, the weight of the propylene-ethylene copolymer (RC) relative to the weight of the propylene homopolymer (PP) can be adjusted by controlling the polymerization time and using a polymerization activity modifier such as carbon monoxide or hydrogen sulfide as a catalyst. -Adjust the weight of ethylene copolymer (RC) to 22-40% by weight. Furthermore, propylene-ethylene copolymer (R
The molecular weight of C) is propylene-ethylene copolymer (RC)
The intrinsic viscosity of (1) is adjusted by adding a molecular weight modifier such as hydrogen during the propylene-ethylene copolymer polymerization so as to satisfy the requirements of the propylene composition (A). Further, hydrogen is supplied so that the Q value (Mw / Mn) of the propylene-based composition (A) satisfies the requirements of the propylene-based composition (A).

As the polymerization system, any of a batch system, an anti-continuous system and a continuous system can be adopted, but industrially the continuous system is preferred.

After the completion of the second polymerization step, the monomer can be removed from the polymerization system to obtain a particulate polymer. The obtained polymer is _{subjected to measurement} of intrinsic viscosity ([η] _WHOLEE ), amount of xylene-soluble component at 20 ° C., Q value (M _w / M _n ), ethylene content, and polymerization yield per unit weight of catalyst.

The polypropylene composition (C) of the present invention comprises
A composition in which the propylene-based composition (A) is used as a base resin, and desired additive components corresponding to the required characteristics of the molded product and the molding method are blended.

The polypropylene composition (C) of the present invention is
Usually, as additives, various additives generally used in polyolefin compositions, for example, antioxidants such as phenol-based, thioether-based and phosphorus-based antioxidants; dispersants or neutralizing agents such as higher fatty acids such as calcium stearate. Salts (metal soaps), etc .; Light stabilizers; Heavy metal deactivators (copper damage inhibitors); Clarifying agents; β-crystal nucleating agents; Lubricants such as steric acid amide; Antistatic agents such as glycerin monostearate Fatty acid esters, etc .; cloud proofing agents; anti-drop agents; flame retardants; flame retardant aids; pigments; halogen scavengers; organic and inorganic antibacterial agents; inorganic fillers and antiblocking agents such as talc, mica, clay, Wollastonite, zeolite, kaolin, bentonite, perlite, diatomaceous earth, asbestos, calcium carbonate,
Magnesium carbonate, aluminum hydroxide, magnesium hydroxide, hydrotalcite, basic aluminum lithium hydroxy carbonate carbonate hydrate, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide, calcium oxide, zinc oxide, barium sulfate, sulfuric acid Magnesium, calcium silicate, aluminum silicate,
Glass fibers, potassium titanate, carbon fibers, carbon black, graphite and metal fibers, etc., coupling agents such as silane-based, titanate-based, boron-based, aluminate-based, zircoaluminate-based, and the like, and surface-treated with them. Inorganic fillers or organic fillers such as wood flour, pulp, waste paper, synthetic fibers and natural fibers are usually contained within a range not impairing the object of the invention.

Generally, the polypropylene composition (C) is blended with a phenolic antioxidant and / or a phosphorus antioxidant and calcium stearate as a neutralizing agent (dispersing agent).

The polypropylene-based composition (C) obtained by blending the above-mentioned polyolefin of the present invention with a general additive is the polypropylene-based composition for injection molding (Ci), the polypropylene-based composition for sheet molding (Cs) and It can be suitably used as a polypropylene composition (Cf) for film formation.

The polypropylene composition (C
In (i), 100 parts by weight of the propylene-based composition (A) is mixed with 0.0001 to 1 part by weight, preferably 0.001 to 0.8 part by weight of an α-crystal nucleating agent, and injection molding is performed. The rigidity of the product can be increased and the impact resistance at low temperature can be further improved.

Examples of the α crystal nucleating agent include inorganic compounds such as talc, alum, silica, titanium oxide, calcium oxide, magnesium oxide, carbon black, and clay minerals; malonic acid, succinic acid, adipic acid, maleic acid, azelaic acid. , Sebacic acid, dodecanedioic acid, citric acid, butanetricarboxylic acid, butanetetracarboxylic acid, naphthenic acid, cyclopentanecarboxylic acid, 1-methylcyclopentanecarboxylic acid, 2-methylcyclopentanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid Acid, 1-methylcyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid, 3,5-dimethylcyclohexanecarboxylic acid, 4-butylcyclohexanecarboxylic acid, 4-octylcyclohexanecarboxylic acid, cyclohexanecarboxylic acid, 4 Aliphatic monocarboxylic acids such as cyclohexane-1,2-dicarboxylic acid, benzoic acid, toluic acid, xylyl acid, ethylbenzoic acid, 4-t-butylbenzoic acid, salicylic acid, phthalic acid, trimellitic acid and pyromellitic acid Excluding carboxylic acids; lithium, sodium, potassium, magnesium, calcium, strontium, barium, zinc of the non-aliphatic monocarboxylic acids
Normal or basic salts such as aluminum; 1, 2, 3
4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1
-3-benzylidene-2,4-p-ethylbenzylidene sorbitol, 1-3-p-methylbenzylidene-2
4-benzylidene sorbitol, 1.3-p-ethylbenzylidene-2,4-benzylidene sorbitol, 1
3-p-methylbenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol, 1
・ 3,2,4-bis (p-methylbenzylidene) sorbitol, 1,3,2,4-bis (p-ethylbenzylidene)
Sorbitol, 1,3,2,4-bis (pn-propylbenzylidene) sorbitol, 1,3,2,4-bis (p
-I-Propylbenzylidene) sorbitol, 1,3,2
-4-bis (pn-butylbenzylidene) sorbitol, 1,3,2,4-bis (ps-butylbenzylidene) sorbitol, 1,3,2,4-bis (pt-butylbenzylidene) Sorbitol, 1,3- (2 ', 4'-dimethylbenzylidene) -2,4-benzylidene sorbitol, 1,3-benzylidene-2,4- (2', 4'-dimethylbenzylidene) sorbitol, 1,3, 2,4-bis (2 ', 4'-dimethylbenzylidene) sorbitol, 1
・ 3,2,4-bis (3 ', 4'-dimethylbenzylidene) sorbitol, 1,3,2,4-bis (p-methoxybenzylidene) sorbitol, 1,3,2,4-bis (p-ethoxy) Benzylidene) sorbitol, 1.3-benzylidene-2,4-p-chlorobenzylidene sorbitol, 1
-3-p-chlorobenzylidene-2,4-benzylidene sorbitol, 1-3-p-chlorobenzylidene-2
4-p-methylbenzylidene sorbitol, 1.3-p
-Chlorobenzylidene-2,4-p-ethylbenzylidene sorbitol, 1.3-p-Methylbenzylidene-2
* 4-p- chlorobenzylidene sorbitol, 1.3-
Dibenzylidene sorbitol compounds such as p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol, and 1,3,2,4-bis (p-chlorobenzylidene) sorbitol; lithium-bis (4-t-butylphenyl) ) Phosphate, sodium-bis (4-t
-Butylphenyl) phosphate, lithium-bis (4
-Cumylphenyl) phosphate, sodium-bis
(4-cumylphenyl) phosphate, potassium-bis
(4-t-butylphenyl) phosphate, calcium-mono (4-t-butylphenyl) phosphate, calcium-bis (4-t-butylphenyl) phosphate, magnesium-mono (4-t-butylphenyl) Phosphate, magnesium-bis (4-t-butylphenyl) phosphate, zinc-mono (4-t-butylphenyl) phosphate, zinc-bis (4-t-butylphenyl) phosphate, aluminum dihydroxy- (4 -T-butylphenyl) phosphate, aluminum hydroxy-bis (4-t-butylphenyl) phosphate, aluminum-tris (4-t-butylphenyl) phosphate, sodium-2,2'-methylene-
Bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-
2,2'-methylene-bis (4-cumyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, lithium- 2,2'-ethylidene-bis (4,6-di-
t-butylphenyl) phosphate, lithium-2,
2'-methylene-bis (4-cumyl-6-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4-i-propyl-6-t-butylphenyl)
Phosphate, lithium-2,2'-methylene-bis
(4-Methyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-ethyl-)
6-t-Butylphenyl) phosphate, sodium-2,2'-butylidene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-butylidene-bis (4,6-di-) t-Butylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis
(4,6-Di-methylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis (4,6-di-t-butylphenyl) phosphate, sodium-
2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, sodium ( 4,4'-Dimethyl-6,6'-
Di-t-butyl-2,2'-biphenyl) phosphate, sodium-2,2'-ethylidene-bis (4-s-)
Butyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-) Di-ethylphenyl) phosphate, potassium-2,2'-ethylidene-bis (4,6-di-
t-Butylphenyl) phosphate, calcium-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2 '
-Methylene-bis (4,6-di-t-butylphenyl) phosphate], zinc-bis [2,2'-methylene-bis]
(4,6-di-t-butylphenyl) phosphate], aluminum-tris [2,2'-methylene-bis (4,6-)
Di-t-butylphenyl) phosphate], calcium-bis [2,2'-methylene-bis (4-methyl-6-t-)
Butylphenyl) phosphate], calcium-bis
[2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], calcium-bis [2,2'-
Thiobis (4-methyl-6-t-butylphenyl) phosphate], calcium-bis [2,2'-thiobis (4-
Ethyl-6-t-butylphenyl) phosphate], calcium-bis [2,2'-thiobis (4,6-di-t-butylphenyl) phosphate], magnesium-bis
[2,2′-thiobis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2′-thiobis
(4-t-octylphenyl) phosphate], barium-bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], calcium-bis
[(4,4'-Dimethyl-6,6'-di-t-butyl-2,2 '
-Biphenyl) phosphate], magnesium-bis
[2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate Fate], aluminum-tris [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], aluminum dihydroxy-2,2′-methylene-bis (4,6-di-t) -Butylphenyl) phosphate, aluminum dihydroxy-2,2'-methylene-bis (4-cumyl-6-t-butylphenyl) phosphate, aluminum hydrodoxy-bis [2,2'-methylene-bis (4 , 6-Di-t-butylphenyl) phosphate], aluminum hydrodoxy-bis [2,2′-methylene-bis (4-cumyl-6-t-butylphenyl) phosphate], titanium dihydroxy-bis [ , 2'-methylene - bis (4,6-di -t- butyl phenyl) phosphate], tin dihydroxy - bis [2,2'-methylene -
Bis (4,6-di-t-butylphenyl) phosphate], zirconiumoxy-bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate],
Aluminum dihydroxy-2,2'-methylene-bis
(4-Methyl-6-t-butylphenyl) phosphate, aluminum hydroxy-bis [2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate], aluminum dihydroxy-2,2 Such as'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, aluminum hydroxy-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate] Aryl phosphate-based compounds; Among the aryl phosphate-based compounds, cyclic polyvalent metal aryl phosphate-based compounds and acetic acid, lactic acid, propionic acid, acrylic acid, octylic acid, isooctylic acid, nonanoic acid, decanoic acid, lauric acid, Myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, 12-hydroxystear Of fatty acid group monocarboxylic acids such as acid, ricinoleic acid, behenic acid, erucic acid, montanic acid, melissic acid, stearoyl lactic acid, β-N-laurylaminopropionic acid, β-N-methyl-N-lauroylaminopropionic acid Mixtures of fatty acid monocarboxylic acid alkali metal salts such as lithium, sodium or potassium salts, or basic aluminum lithium hydroxycarbonate hydrate; poly-3-methyl-1-butene, poly-3-methyl-1-pentene, Poly-3-ethyl-1-pentene, poly-4-methyl-
1-pentene, poly 4-methyl-1-hexene, poly 4,4-dimethyl-1-pentene, poly 4, 4-dimethyl-1-hexene, poly 4-ethyl-1-hexene, poly 3-ethyl-1 -Hexene, polyallylnaphthalene,
Polyallyl norbornane, atactic polystyrene, syndiotactic polystyrene, polydimethylstyrene, polyvinylnaphthalene, polyallylbenzene, polyallyltoluene, polyvinylcyclopentane,
Examples thereof include polymer compounds such as polyvinyl cyclohexane, polyvinyl cyclopeptane, polyvinyl trimethylsilane, and polyallyl trimethylsilane.

Among them, talc, aluminum hydroxy-bis (4-t-butylbenzoate), 1 ·
3,2.4-Dibenzylidene sorbitol, 1,3,2-
4-bis (p-methylbenzylidene) sorbitol, 1 ·
3,2,4-bis (p-ethylbenzylidene) sorbitol, 1,3,2,4-bis (2 ', 4'-dimethylbenzylidene) sorbitol, 1,3,2,4-bis (3', 4) '-
Dimethylbenzylidene) sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-bis (p-chlorobenzylidene) sorbitol, sodium-bis (4-t-butyl) Phenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, calcium-2,2'-methylene-bis (4,6-)
Di-t-butylphenyl) phosphate, aluminum-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, aluminum dihydroxy-
2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate or aluminum hydroxy-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate A mixture of a cyclic polyvalent metal arylphosphate compound such as a phosphate and a fatty acid monocarboxylic acid alkali metal salt, poly-3-methyl-1-butene, polyvinylcyclohexane or polyallyltrimethylsilane is preferable.

These α-crystal nucleating agents may be used alone or in combination of two or more kinds.

The polypropylene composition of the present invention (C
A radical generator and / or a crystalline propylene homopolymer (PHP) may be further added to i) to further improve the whitening of the injection molded product.

Crystalline Propylene Homopolymer Incorporated
(PHP) has a density of 0.91 to 0.89 g / cm ³ and a propylene composition (A) and a crystalline propylene homopolymer (P).
HP) melt flow rate ratio (MFR _WHOLE / MFR
A propylene homopolymer having a _Ph ) of 0.5-2, preferably 0.8-1.2.

In this composition, a propylene-based composition
MFR of (A) and crystalline propylene homopolymer (Ph)
The ratio affects the whitening property of the molded product, and if it is too large or too small, the whitening property is insufficient.

The compounding amount of the crystalline propylene homopolymer (PHP) is 10 to 95% by weight based on the resin, and the content of the propylene composition (A) depends on the balance between rigidity and impact resistance of the molded product. It is in the range of 5 to 90% by weight based on the resin.

That is, in this composition, since the propylene-based composition (A) acts as a whitening agent for preventing whitening of a molded product, this composition has a bent portion such as a hinge or a stopper (cap) of a container. It is suitable for molding products.

On the other hand, the radical generator makes the compound highly fluid and remarkably improves the moldability.

As the radical generator, the decomposition temperature is preferably not too low in order to obtain a uniform composition, and the temperature for obtaining a half-life of 10 hours is 70 ° C. or higher, preferably 1
It is more than 00 ° C. For example, benzoyl peroxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl peroxyisopropyl carbonate, 2,5-di-methyl-2,5-di- (t-benzoyl peroxy) hexane, 2 , 5-di-methyl-2,
5-di- (t-benzoylperoxy) hexyne-3, t
-Butyl-di-peradipate, t-butylperoxy-3,5,5-trimethylhexanoate, methyl-ethyl ketone peroxide, cyclohexanone peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,5-di-methyl-2,5-di- (t-butylperoxy) hexane, 2,5-di-methyl-2,5
-Di- (t-butylperoxy) hexyne-3,1,3-
Bis- (t-butylperoxyisopropyl) benzene,
t-Butyl cumyl peroxide, 1,1-bis- (t
-Butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis- (t-butylperoxy) cyclohexane, 2,2-bis- (t-butylperoxybutane), p-menthane hydroper Oxide, di-isopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, p-cymen hydroperoxide, 1,1,
Organic peroxides such as 3,3-tetra-methylbutyl hydroperoxide and 2,5-di-methyl-2,5-di- (hydroperoxy) hexane are mentioned. Particularly, 2,5-di-methyl-2,5-di- (t-butylperoxy) hexane, 2,5-di-methyl-2,5-di- (t-
Butylperoxy) hexyne-3 and 1,3-bis-
(t-Butylperoxyisopropyl) benzene is preferred. These radical generators can be used alone, and
It is also possible to use two or more species together. The polypropylene-based composition (C) obtained by blending the above-mentioned polyolefin of the present invention with a general additive can also be used as a polypropylene-based composition (Cb) for molding a hollow molded product.

This polypropylene composition (Cb) contains
By adding 5 to 20 parts by weight of a plasticizing component to 100 parts by weight of the propylene composition (A), flexibility can be imparted to the molded product.

As the plasticizing component (Ps), a density of 0.910 to 0.93, which is generally called low density polyethylene, is generally used.
0 g / cm ³ , crystal melting point (Tm) 100 to 115 ° C, melt flow rate (MFR: 190 ° C; 21.18N) 0.1 to 5
g / 10 min, preferably 0.1-1 g / 10 min of ethylene homopolymers and ethylene-α-olefin copolymers, and density of 0.92-0.935 g / cm ³ , crystalline melting point (Tm) 90-108 ° C., melt flow Rate (MFR:
190 ° C .: 21.18 N) 0.1-5 g / 10 min, preferably 0.1-1 g / 10 min ethylene-vinyl acetate copolymer.

Since the compounding of the plasticizing component imparts flexibility to the molded product, this polypropylene composition (Cb) is suitable for molding hollow molded products and films having a bellows structure.

Each of the polypropylene-based compositions of the present invention described above is prepared by mixing the propylene-based composition (A) and each optional additive component with a high-speed mixing device such as a Henschel mixer.
(Trade name), a ribbon blender, a tumbler mixer, and the like, and mixed using a single-screw extruder, a twin-screw extruder, a kneader, or the like at 150 to 300 ° C., preferably 200 to 250
It is melt-kneaded at ℃ and pelletized, and used for molding various molded products.

The molded product of the present invention is a molded product molded by various molding methods using the above polypropylene-based compositions.

The molded article of the first aspect is an injection molded article. More specifically, it is a molded product obtained by injection molding pellets of the above polypropylene-based composition, such as a sheet-shaped molded product, a container, a container stopper (cap), and a hinged molded product.

Any of the above-mentioned polypropylene compositions may be used as the injection molding polypropylene composition, but the injection molding polypropylene composition (Ci) is preferably used.

A composition containing an α-crystal nucleating agent, a radical generator, and / or a crystalline propylene homopolymer, etc. is used depending on the molded article to be molded and the characteristics required for it.

By using these polypropylene-based compositions (Ci), the bent part (hinge structure part, etc.) has whitening resistance, transparency, luster, rigidity, impact resistance, especially impact resistance at low temperature, during molding. It is possible to manufacture an injection-molded article having excellent molding shrinkage and the balance thereof.

The molded article of the second aspect of the present invention is a sheet, and from the viewpoint of printability and flexibility of the sheet, the sheet has a Young's modulus in the longitudinal direction at 23 ° C. of 200 to 450 MP.
a, preferably 300 to 400 MPa, and a tensile yield point strength in the longitudinal direction at 50 ° C. of 15 MPa or more, preferably 17 MPa or more.

The sheet of the present invention can be produced by any known sheet forming method, but extrusion or calendering is preferable because of its good productivity. Specifically, extruder, T-die, polishing roll
(Cooling roll), guide roll, take-up roll, trimming cutter, masking, fixed length cutting cutter, stacker, etc.
Die method, Banbury mixer, mixing roll, warming roll, extruder, calender roll,
Sheets are formed by a device (calender forming machine) having steps such as a cooling roll, a trimming cutter, masking, a constant length cutting cutter, and a winding machine.

More preferably, the polypropylene composition (C), preferably the same polypropylene composition (Cs) as mentioned in the above injection molding, is subjected to a resin temperature treatment by the method for producing a sheet of the present invention, that is, the T-die method. 180-30
It is extruded at 0 ° C., the cooling roll temperature is set to 5 to 80 ° C., the difference from the resin temperature is set to 120 ° C. or more, and the sheet speed is molded at 0.1 to 100 m / min.

When the resin temperature is in the range of 180 to 300 ° C., the polypropylene composition (Cs) is sufficiently melted and is not thermally deteriorated, so that the melt tension of the sheet is maintained and good moldability is obtained. It is possible to obtain a sheet which is obtained and has an excellent appearance without the surface of the sheet becoming shark skin.

If the temperature of the chill roll is 5 ° C. or higher, no spotted pattern is generated on the surface of the sheet due to no condensation on the chill roll, and if it is 80 ° C. or lower, the sheet can be cooled sufficiently and roll-shaped. A linear pattern does not occur when the sheet is unwound, and a sheet with a good appearance can be obtained.

Since the sheet has weak molecular orientation, and the difference between the heat shrinkage ratios in the longitudinal direction and the transverse direction is small, the following formula is used between the resin temperature and the chill roll temperature.

[0091]

## EQU3 ## By maintaining the relationship represented by the resin temperature-cooling roll temperature ≧ 120, a sheet having excellent moldability can be obtained.

If the forming speed of the sheet is 0.1 m / min or more, a sheet having a uniform thickness and a low defect rate can be obtained at a sufficient production rate, while if it is 100 m / min or less, the sheet is sufficiently cooled. Since it is possible to prevent the occurrence of a linear pattern when unrolling the roll-shaped sheet, a sheet having a good appearance can be obtained.

The molded article of the third aspect of the present invention is a polypropylene composition (Cf), preferably a propylene composition (A) containing a general polyolefin additive (Cf). ) Is a film formed using. This film includes unstretched, uniaxially stretched and biaxially stretched films.

The unstretched film is produced by the T-die method or the inflation method used for the production of ordinary polyolefin films, and the uniaxially stretched film or the biaxially stretched film is obtained by the tenter method of the unstretched film obtained by the above method. It can be produced by uniaxial stretching or sequential biaxial stretching method or simultaneous biaxial stretching method by tubular method.

These films are polypropylene-based compositions containing the propylene-based composition of the present invention as a base resin.
By using (C), it is excellent in impact resistance at low temperature, heat resistance and tear strength.

Another embodiment of the film of the present invention is a laminated film in which a functional polymer layer is laminated on one side or both sides of the above film.

The laminated film of the present invention is not particularly limited as long as it is a film made of the above-mentioned polypropylene composition (C) and a polymer layer capable of imparting a specific function, but at least a heat-sealable layer is formed. Have.

The heat sealable layer has a density of 0.89 to
Propylene homopolymer with 0.91 g / cm ³ , crystalline melting point 165-160 ° C. and / or density 0.89-0.91 g / cm
^3. A propylene-α-olefin copolymer having a crystal melting point of 159 to 110 ° C. is preferably used.

The melt flow rate (230 ° C .; 21.18 N) of the polymer used in these heat-sealable layers is
From the viewpoint of the moldability during film forming and the appearance of the obtained film, 0.1 to 50 g / 10 minutes, preferably 1 to 20 g /
10 minutes. Examples of the α-olefin copolymerized with propylene include ethylene, butene-1, pentene-1 and the like.

As the propylene-α-olefin copolymer, an ethylene-propylene copolymer having an ethylene component content of 0.2 to 10% by weight, an ethylene component content of 0.2 to 10% by weight, and a butene-1 component content of 0. .4-5
The ethylene-propylene-butene-1-copolymer and the like in weight% can be exemplified.

The crystalline melting point of the propylene homopolymer is 165 to 160 ° C. in that a multilayer film excellent in surface gloss, surface hardness and rigidity can be obtained.

The crystalline melting point of the propylene-α-olefin copolymer is 159 ° C. to 110 ° C., preferably 14 ° C., from the viewpoint that a laminated film having excellent heat sealability can be obtained.
It is 0 to 110 ° C.

These propylene homopolymer and propylene-α-olefin copolymer are composed of a complex containing at least magnesium, titanium and halogen, an organometallic compound of a metal of Groups 1 to 3 of the Periodic Table, and an electron donor. Propylene can be produced by a known publicly known polymerization method using the catalyst formed, or a method of copolymerizing propylene and an α-olefin.

The multilayer film of the present invention is an unstretched, uniaxially stretched or biaxially stretched multilayer film having a layer using the polypropylene composition and the functional polymer layer.

The layer structure of the multi-layer film is a functional polymer layer / polypropylene type composition layer, two layers of two types,
Examples thereof include functional polymer layer / polypropylene-based composition layer / functional polymer layer: two kinds of three layers or three kinds of three layers. Among them, a laminated film composed of a propylene homopolymer layer / a polypropylene composition layer / a propylene-α-olefin copolymer layer is preferable in terms of heat resistance and heat sealability of the obtained laminated film.

Although the thickness of the laminated film is not particularly limited, it is preferably 10 to 100 μ, more preferably 15 to 70 μ from the viewpoint of film moldability. The thickness of each layer of the laminated film is not particularly limited, but in terms of impact resistance at low temperature, heat resistance, and tear strength, the ratio of the thickness of the propylene-based composition layer to the total thickness of the film is 30 to 90%, preferably 50 to 90%.

Examples of the method for producing a laminated film include a multilayer extrusion molding method, a dry lamination method, an extrusion lamination method, and the like, and examples of the multilayer extrusion molding method include a T-die method or an inflation method usually used for producing a polyolefin film. . Examples of the stretching method include a sequential biaxial stretching method using a tenter method and a simultaneous biaxial stretching method using a tubular method.

When the laminated film is produced by the publicly known method described above, the melt flow rate (MFR) of the polypropylene-based composition and the functional polymer constituting each layer is not particularly limited, but the moldability of the film and the product film In terms of appearance, the ratio of MFR between the polypropylene composition and the functional polymer is 0.1 to 10, preferably 0.5 to 2.

The laminated film of the present invention can also be produced by laminating a transparent base film such as BOPP film, PET film, nylon film or Eval film via an adhesive by a method such as dry lamination. is there.

The film and laminated film of the present invention are
Further, surface treatment such as corona discharge treatment, flame treatment, plasma treatment and the like by a method usually employed in the industry for the purpose of imparting printability, laminating suitability and metal vapor deposition characteristics is further possible.

The molded product of the fourth aspect of the present invention is a hollow molded product of the above-mentioned polypropylene composition (C), particularly the composition (Cb) in which a plasticizing component is added to the propylene composition. This hollow molded article preferably has a bellows structure.

The hollow molded article of the present invention can be easily manufactured by a blow molding method in which pellets of the polypropylene composition (C) are supplied to an extruder of a blow molding machine and extruded into a hollow cylindrical shape. In addition, the mold of the molding machine has an uneven surface.
By using a mold having (bellows surface), it is possible to easily manufacture a hollow molded article having a bellows structure.

Another embodiment of the hollow molded product of the present invention is a composite in which a hollow molded product part having a bellows structure and a hollow molded product part made of a polyolefin composition (PO) having excellent rigidity and impact resistance are connected. It is a hollow molded product.

The polyolefin-based composition (PO) used for the hollow molded article portion connected to this bellows structure is an ethylene-propylene copolymer 1-20 containing 25 to 55% by weight of ethylene polymerized units, preferably 35 to 55% by weight. Inorganic fillers, such as talc, calcium carbonate, calcium silicate, etc., added for the purpose of imparting rigidity to a composition consisting of 10% by weight, preferably 10-20% by weight and 99-80% by weight of propylene homopolymer, according to the invention. The composition is compounded within a range that does not impair the purpose of. The compounding ratio of the inorganic filler is preferably 20% by weight or less based on the weight of the composition.

This hollow molded product is composed of a set of mold clamping devices,
An accumulator-type blow molding machine equipped with one ram cylinder and at least two extruders was used, and the polypropylene composition (C) of the present invention was used in one extruder and the polyolefin composition (PO) was used in another extruder. ) Is supplied, and the composition melted from one extruder is first stored in the ram cylinder, and then the composition melted from the other extruder is stored in the ram cylinder.

Next, the melted polypropylene composition (C)
The parison is manufactured by extruding the parison from the ram cylinder while setting it so that it is introduced into the mold part having an uneven surface (bellows surface), and blowing pressurized air with a pressure of 0.5 to 1 MPa into the parison. be able to.

[0117]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. A. Synthesis of Propylene-based Composition (A) 1) Measurement of Various Physical Properties In the synthetic process of the propylene-based composition, various physical properties of an intermediate product and a final product were measured by the following methods. The synthesis conditions and measurement results are shown in Tables 1 and 2. a) Average particle size (μm) of titanium-containing solid catalyst component (a): Calculated from particle size distribution measured using Mastersizer (manufactured by MALVERN). b) Homogeneity of titanium-containing solid catalyst component (a): The particle size under 60% sieve obtained from the particle size distribution measured using Mastersizer (manufactured by MALVERN) is divided by the particle size under 10% sieve. Calculated. c) Polymer yield per unit weight of catalyst: Mg in sample
Measured by inductively coupled plasma emission spectrometry (IPC method). d) Isotactic pentad fraction P in polypropylene molecular chain P: according to macromolecules 8687 (1975), ¹³ C
-Measured using NMR. e) Ethylene unit content (% by weight): Measured by infrared absorption spectroscopy. f) Intrinsic viscosity (dl / g): Measured in a tetralin (tetrachloronaphthalene) solvent under a temperature condition of 135 ° C. using an automatic viscosity measuring device (AVS2 type, manufactured by Mitsui Toatsu Co., Ltd.). g) Melt flow rate (g / 10 minutes): JIS K 67
Measured according to 60. h) Average molecular weight Q value (Mn / Mw): A sample dissolved in orthodichlorobenzene at 135 ° C. was analyzed by GPC (Gel Per
mination Chromatograph, 150C type, manufactured by Waters,
Used column; measured using TSK GEL GMH6-HT). i) 20 ° C xylene soluble component amount (% by weight): ISO / DI
Measured in accordance with S1873-1. j) Powder fluidity: The compressibility of powder is calculated by the following formula.

[Equation 4] Compressibility = (solid apparent density-loose apparent density)
× 100 / solid apparent density The higher the compression degree, the poorer the powder fluidity.

2) Preparation of titanium-containing solid catalyst component (a) a) Titanium-containing solid catalyst component: a-1 Nitrogen-substituted SUS autoclave, anhydrous MgCl 2
95.3 g of ₂ and 352 ml of dry EtOH were added, and the mixture was heated to 105 ° C. with stirring to dissolve it. After stirring for 1 hour, this solution was heated to 105 ° C under pressurized nitrogen (1.1MPa).
Into a two-fluid spray nozzle in a). The flow rate of nitrogen gas was 381 / min. Liquid nitrogen was introduced into the spray tower for cooling, and the tower internal temperature was maintained at -15 ° C.
The product was collected in cooled hexane introduced at the bottom of the column to obtain 256 g. From the analysis result of the product, the composition of this carrier was the same MgCl ₂ .6EtOH as the starting solution. For use as a carrier, 205 g of a spherical carrier having a particle size of 45 to 212 μm was sieved and obtained. The obtained carrier was dried by aeration at room temperature for 181 hours using nitrogen at a flow rate of 31 / min to obtain a dry carrier having a composition of MgCl ₂ .1.7 EtOH.

Dry carrier 20 in a glass flask.
g, 160 ml of titanium tetrachloride and 240 ml of purified 1,2-dichloroethane were mixed and heated to 100 ° C. with stirring. Then add 6.8 ml of diisobutyl phthalate and add another 100
After heating at ℃ for 2 hours, the liquid phase part was removed by decantation. Again, 160 ml of titanium tetrachloride, purified 1,2-
320 ml of dichloroethane was added, and the mixture was heated and kept at 100 ° C. for 1 hour. The liquid phase was removed by decantation, washed with purified hexane, and dried to obtain a titanium-containing solid catalyst component: a-1. Obtained titanium-containing solid catalyst component:
The average particle size of a-1 is 115 μm, and its analytical value is
Mg; 19.5% by weight, Ti; 1.6% by weight, Cl; 5
The content was 9.0% by weight, diisobutyl phthalate; 4.5% by weight.

B) Titanium-containing solid catalyst component: a-2 Nitrogen-substituted SUS autoclave, refined kerosene 1,
050 ml, 15 g anhydrous MgCl ₂ , 36.3 g dry ethanol
And surfactants (brand name Emazol 320, Kao Atlas
After adding 4.5 g (manufactured by KK), the temperature of this mixture was raised with stirring at 800 rpm and kept at 120 ° C. for 30 minutes. Refining kerosene 1, cooled to -10 ° C, using a Teflon ^(R) tube having an inner diameter of 5 mm while stirring the molten mixture at high speed.
Transferred to a 3000 ml stirred flask filled with 500 ml. After filtering the product, it was thoroughly washed with hexane to obtain a carrier.

At room temperature, 15 g of the carrier is treated with 300 m of titanium tetrachloride.
After suspending in l, 2.6 ml of diisobutyl phthalate was added and the solution of the mixture was warmed to 120 ° C. 120 ° C
After stirring and mixing at the temperature of 2 hours, the solid was filtered and resuspended in 300 ml of titanium tetrachloride. 1 suspension solution
After stirring and mixing at 30 ° C. for 2 hours, the solid substance was filtered and thoroughly washed with purified hexane to give a titanium-containing solid catalyst component:
a-2 was obtained. Obtained titanium-containing solid catalyst component: a-
The average particle size of 2 is 72 μm, and the analysis value is Mg;
21.1% by weight, Ti; 2.4% by weight, Cl; 64.15
% By weight, diisobutyl phthalate; 5.3% by weight.

C) Titanium-containing solid catalyst component: a-3. A mixture of 300 g of magnesium ethoxide, 550 ml of 2-ethylhexanol and 600 ml of toluene was added to 0.1 g.
The mixture was stirred at 93 ° C. for 3 hours in a carbon dioxide atmosphere of 20 MPa. 800 ml toluene and 800 n-decane
ml was added to obtain a magnesium carbonate solution. Toluene 80
0 ml, chlorobenzene 60 ml, tetraethoxysilane 1
8 ml, titanium tetrachloride 17 ml and Isopar G (isoparaffinic hydrocarbon having an average carbon number of 10, boiling point 156 to 17)
While stirring 200 ml (6 ° C.) at 30 ° C. for 5 minutes, 100 ml of the magnesium carbonate solution prepared above was added.

After stirring for another 5 minutes, 44 ml of tetrahydrofuran was added, and the mixture was stirred at 60 ° C. for 1 hour. After the stirring was stopped and the supernatant was removed, the resulting solid was mixed with toluene 10
200 ml of chlorobenzene was added to the solid obtained by washing with 0 ml.
And 200 ml of titanium tetrachloride were added, and the mixture was stirred at 135 ° C for 1 hour. After stirring was stopped and the supernatant was removed, 500 ml of chlorobenzene, 200 ml of titanium tetrachloride and 4.2 ml of di-n-butyl phthalate were added, and the mixture was stirred at 135 ° C. for 1.5 hours. After removing the supernatant, 1,200 ml of toluene,
Titanium-containing solid catalyst component for comparison: a-3 by washing the solid sequentially with 1,600 ml of Isopar G and 800 ml of hexane
Was collected. Obtained titanium-containing solid catalyst component: a-3
Has an average particle size of 18.5 μm and its analysis value is Mg;
17.0 wt%, Ti; 2.3 wt%, Cl; 55.0 wt%, di-n-butyl phthalate; 7.5 wt%.

3) Pre-activation treatment of titanium-containing solid catalyst component (a) After replacing the stainless steel reactor with an inclined blade with an internal volume of 15 liters with nitrogen gas, the kinematic viscosity at 40 ° C. was 7.3 centistokes. A saturated hydrocarbon solvent (CRYSTOL-52,
Esso Oil Co., Ltd.) 8.3 liters, triethylaluminum 525 mmol, diisopropyldimethoxysilane 80 m
After adding 700 g of the titanium-containing solid catalyst component prepared in the above paragraph at room temperature, the mixture was heated to 40 ° C. and propylene was reacted at a partial pressure of 0.15 MPa for 7 hours to carry out a preliminary activation treatment. As a result of the analysis, 3.0 g of propylene was reacted with 1 g of the titanium-containing solid catalyst component.

4) Synthesis of Propylene Homopolymer (PP): First Polymerization Step In the flow sheet shown in FIG. 3 attached, a horizontal polymerization vessel having stirring blades; 1 (L / D = 6, internal volume 100 liters)
0.5 g of titanium-containing solid catalyst component pre-activated.
/ Hr, triethylaluminum as the organoaluminum compound (b) and diisopropyldimethoxysilane as the organosilicon compound (c) Al /
It was continuously supplied so as to have a Si molar ratio. Reaction temperature 7
Propylene was continuously fed so as to maintain the conditions of 0 ° C., reaction pressure of 2.5 MPa, and stirring speed of 40 rpm, and further hydrogen gas was circulated to regulate the molecular weight of the produced propylene homopolymer. The intrinsic viscosity of the produced propylene homopolymer was controlled by controlling the hydrogen concentration in the gas phase of the reactor. The heat of reaction was removed by the heat of vaporization of the raw material propylene supplied from the pipe;

Unreacted gas discharged from the polymerization reactor is piped;
It was cooled and condensed outside the reactor system through 4 and was refluxed to the polymerization vessel; Polymerizer: The propylene homopolymer obtained in 1 is a polymerizer in the second polymerization step, which is continuously withdrawn from the polymerizer 1 through a pipe 5 so that the retained level of the polymer is 50% by volume of the reaction volume; Supplied to 10. At this time, a part of the propylene homopolymer was intermittently withdrawn from the pipe; 5, and the isotactic pentad fraction (P), 20
The sample was used to measure the amount of xylene-soluble component, intrinsic viscosity ([η] _PP ) and polymer yield per unit weight of catalyst.

5) Propylene-ethylene copolymer (R
Synthesis of C): Second polymerization step Horizontal polymerization vessel having stirring blades; 10 (L / D = 6, internal volume 100 liters) were continuously charged with propylene homopolymer and ethylene-propylene mixed gas from the first polymerization step. It was supplied, and ethylene and propylene were copolymerized.
The reaction conditions are stirring speed 40 rpm, temperature 60 ° C., pressure 2.1M.
The gas composition of Pa and the gas phase was adjusted such that the ethylene / propylene molar ratio and the hydrogen / ethylene molar ratio were as shown in Tables 1 and 2. Carbon monoxide was supplied as a polymerization activity inhibitor to control the polymerization amount of the produced propylene-ethylene copolymer, and hydrogen gas was supplied from a pipe; 7 to adjust the molecular weight of the produced propylene-ethylene copolymer. The reaction heat was removed by the heat of vaporization of the raw material liquid propylene supplied from the pipe;

The unreacted gas discharged from the polymerization vessel was cooled and condensed outside the reactor system through a pipe; 8 and was refluxed in the copolymerization step. The propylene-based composition (A) produced in the copolymerization step was withdrawn from the polymerization vessel; 10 with piping; 9 so that the retained level of the polymer was 50% by volume of the reaction volume. The production rate of the propylene-based composition (A) is 8 to 12 kg.
/ Hr.

The monomer was removed from the extracted propylene-based composition (A), and a part of the composition had an intrinsic viscosity ([η] _WHOLE ) and a Q value (M
w / Mn), the amount of xylene soluble components at 20 ° C., and infrared in the propylene-ethylene copolymer were measured, and the polymerization ratio of the propylene-ethylene copolymer was measured. Further, the fluidity of the powder of the propylene composition (A) was evaluated.

Type of titanium-containing solid catalyst component (a) used, Al / Si molar ratio and hydrogen / propylene molar ratio in the first polymerization step, ethylene / ethylene in the second polymerization step /
Inventive Samples A-1 to A-14 and Comparative Sample cA-1 by changing the propylene molar ratio and the hydrogen / ethylene molar ratio.
cA-14 was obtained.

The reaction conditions and the measurement results of various physical properties are shown in Table 1.
Table 2 shows the production conditions and characteristics of the propylene-based composition of the present invention, and Table 2 shows the production conditions and characteristics of the propylene-based comparative composition.

[0132]

[Table 1]

[0133]

[Table 2]

[0134]

[Table 3]

[0135]

[Table 4]

B. Polypropylene-based composition for injection molding
(Ci) and injection-molded article 1) Polypropylene-based composition A high-speed agitating mixer was added to each powder of the propylene-based composition A-1 to 6 of the present invention and the comparative composition cA-1 to 7 by adding various additive components. (Henschel mixer), mix at room temperature for 5-10 minutes, and screw the mixture with a screw diameter of 40 mm.
The pelletizer was prepared by granulating at a cylinder setting temperature of 230 ° C.

In Tables 3 and 4, the polypropylene compositions Ci-1 to 12 and Ci-13 to 18 for injection molding of the present invention are shown.
Table 5 and Table 6 show the addition components of the comparative compositions cCi-1 to 7 and cCi-13 and the addition amounts thereof. The added components used and the abbreviations in the table are shown below.

Propylene homopolymer PHP1: Titanium-containing solid catalyst component: a-1 was used, A
1 / Si molar ratio 2, hydrogen / propylene molar ratio 0.03,
Melt flow rate MFR obtained by homopolymerizing propylene under the conditions of polymerization pressure of 2.5 MPa and polymerization temperature of 70 ° C.
A crystalline propylene homopolymer with _PHP 1 and a melting point of 163 ° C. PHP2: Titanium-containing solid catalyst component: a-1, using A
1 / Si molar ratio 2, hydrogen / propylene molar ratio 0.01,
Melt flow rate MFR obtained by homopolymerizing propylene under the conditions of polymerization pressure of 2.5 MPa and polymerization temperature of 70 ° C.
Crystalline propylene homopolymer with _PHP 1.9 and melting point 164 ° C. PHP3: Titanium-containing solid catalyst component: a-1, using A
1 / Si molar ratio 2, hydrogen / propylene molar ratio 0.05
5. Melt flow rate MF obtained by homopolymerizing propylene under the conditions of polymerization pressure of 2.5 MPa and polymerization temperature of 70 ° C.
Crystalline propylene homopolymer with R _PHP 6 and melting point 164 ° C. (for comparison).

Antioxidant Ph-1: Phenolic heat stabilizer Ph-2: Tetrakis (methylene-3- (3 ', 5'-di-
t-Butyl-4'-hydroxyphenyl) propionate) methane.

Α-crystal nucleating agent α-1: aluminum hydroxy-bis (4-t-butylbenzoate) α-2: 1,3,2,4-bis (p-methylbenzylidene) sorbitol α-3: sodium- 2,2'-methylene-bis (4,6-
Di-t-butylphenyl) phosphate. Radical generator: 1,3-bis (t-butylperoxyisopropyl) benzene Neutralizer: Calcium stearate

[0141]

[Table 5]

[0142]

[Table 6]

[0143]

[Table 7]

[0144]

[Table 8]

2) Injection molding Each pellet prepared above was melted at a molten resin temperature of 2 using an injection molding machine.
The temperature was set to 30 ° C and the mold temperature was set to 50 ° C, and a JIS type test piece and a test piece for measuring various physical properties were prepared. After the test piece was conditioned for 72 hours in a room with a humidity of 50% and a room temperature of 23 ° C., various physical properties were measured by the following methods.

A) Molding shrinkage ratio: The ratio of the length obtained by subtracting the length of the tensile test piece (JIS K 7113 No. 1 tensile test piece) prepared from the entire length of the mold of the molding machine to the length of the mold. 1
Calculated by the formula below that is multiplied by 00.

[Formula 5] Molding shrinkage ratio = (total length of mold-total length of test piece) x 10
0 / Full length of mold b) Flexural modulus (MPa): Measured according to JIS K7203. c) Impact resistance (J / m): Measured at -20 ° C or 23 ° C according to JIS K 7110. d) Izod impact strength (J / m ² ): JIS K 7110
Measured at -30 ° C according to. e) Haze: Measured according to ASTM D1003 using a flat plate-shaped test piece of 25 × 50 × 1 mm. f) Gloss: Measured at an indicated angle of 60 degrees according to the ASTM D 523 specular gloss method. g) Whitening resistance: Using a test piece having a hinge structure, the degree of whitening by bending was visually observed at the hinge portion, and evaluated according to the following three grades. ○: The color of the hinge part is the same as other parts. Δ: The color of the hinge part is slightly whiter than the other parts. X: The color of the hinge part is remarkably white compared to other parts. The measurement results are shown in Tables 3 to 6. In the impact test data in the table, NB means that the test piece did not break under the set conditions.

The relationship between the product of the intrinsic viscosity ratio and the weight ratio of the propylene homopolymer and the propylene-ethylene copolymer of the inventive samples Ci-1 to 6 and the comparative samples cCi-1 to 6 and the molding shrinkage ratio is shown in FIG. The relationship between flexural moduli is shown in FIG.

C. Polypropylene composition for sheet molding
(Cs) and Production of Sheet 1) Polypropylene-based Composition Various additive components were added to each powder of the propylene-based compositions A-1 to A-6 of the present invention and the comparative compositions cA-1, 3, 5 and 7. High-speed stirring mixer (Henschel mixer)
Was mixed at room temperature for 5 to 10 minutes, and the mixture was granulated at a cylinder setting temperature of 230 ° C. using an extruder having a screw diameter of 40 mm to prepare pellets.

The polypropylene composition Cs-1 of the present invention
6 and Comparative Compositions cCs-1 to 4 are shown in Tables 7 and 8, respectively. The added components used and the abbreviations in the table are shown below. Antioxidant P-1: Phosphorus heat stabilizer P-2: Tris (2,4-di-t-butylphenyl) phosphite neutralizer: Same as above.

[0150]

[Table 9]

[0151]

[Table 10]

2) Sheet Molding Each of the above-prepared compositions was treated with a sheet molding machine having a T-die and a polishing roll to obtain a cylinder having a thickness of 5 mm at a cylinder set temperature, a cooling roll temperature and a molding speed shown in Tables 9 and 10. The sheet was molded. The molded sheet was conditioned for 72 hours in a room having a humidity of 50% and a room temperature of 23 ° C., and the following physical properties were measured. The molding conditions and the physical property measurement results are shown in Tables 7 and 8.

A) Tensile Strength at Yield Point (MPa): Measured in accordance with ASTM D 882 after leaving in a constant temperature bath at 50 ° C. for 30 minutes or more. b) Young's modulus (MPa): measured in accordance with ASTM D 882 after being left in a room at 23 ° C. for 48 hours or more. c) Punching impact strength (J): measured according to ASTM D 781. d) Bending whitening property (mmφ): width 10 mm, length 120 m
A sheet of m was used as a punching test piece. Bend while gradually approaching both ends of this test piece, measure the curvature at the time when whitening occurred in the curved portion, calculate the diameter of the circle corresponding to this curvature as bending whitening property, and as an index of whitening property did. e) Printability: Drying temperature of 50 using a gravure printing machine.
Three-color printing was performed at a temperature of 5 ° C. and a printing speed of 5 m / min, and the print misalignment was visually observed. ◯: No printing deviation x: There is obvious printing deviation Tables 7 and 8 show the molding conditions and the results of physical property measurement.

D. Polypropylene composition for film
(Cf) and production of film 1) Polypropylene-based composition Propylene-based composition A-7 to 14, 2, 4 and 5 of the present invention, and propylene-based comparative composition cA8 to 14,
5 and 6 were mixed with each additive component, mixed with a Henschel mixer (trade name), and then melt-kneaded into pellets using a single-screw extruder (caliber 40 mmφ), and polypropylene composition Cf-1 for film 12 and comparative composition cCf-1
~ 9 were prepared. The polypropylene-based composition and the comparative composition are shown in Tables 9 and 10.

The added components used and the abbreviations in the table are shown below.

Antioxidant Ph-2: Tetrakis [methylene (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane P-2: Tris (2,4-di-t-butylphenyl) phos Fight Neutralizer: Calcium Stearate Blocking Agent: Silica Lubricant: Amide Oleate

[0157]

[Table 11]

[0158]

[Table 12]

2) Molding of monolayer film a) Unstretched film Cf-using a monolayer extruder (caliber 65 mmφ) equipped with a T-die
1 to 8 and cCf-1 to 7 were extruded at an extrusion temperature of 230 ° C. and rapidly cooled by an air chamber and a cooling roll having a surface temperature of 30 ° C. to obtain an unstretched film having a thickness of 25 μm. b) Cf-using a single-layer extruder (diameter 40 mmφ) equipped with a biaxially stretched film T-die
9 to 11, cCf8-8 and 9 were extruded at an extrusion temperature of 230 ° C. and cooled and solidified with an air knife and a cooling roll having a surface temperature of 30 ° C. to form an unstretched sheet having a thickness of 2.0 mm. Then, the obtained unstretched sheet was biaxially stretched (5.0 times in the extrusion direction and 8.0 times in the transverse direction) at a stretching temperature of 157 ° C. using a batch-type biaxial stretching machine to obtain a biaxial sheet having a thickness of 50 μm. A stretched film was obtained. c) Cf-using a single layer extruder (diameter 40 mmφ) equipped with a uniaxially stretched film T-die
9 to 11, cCf8-8 and 9 were extruded at an extrusion temperature of 230 ° C. and cooled and solidified with an air knife and a cooling roll having a surface temperature of 60 ° C. to form an unstretched sheet having a thickness of 0.25 mm. Then, the obtained unstretched sheet was uniaxially stretched 5.0 times in the extrusion direction at a stretching temperature of 120 ° C. using a batch type biaxial stretching machine to obtain a uniaxially stretched film having a thickness of 50 μm.

3) Molding of Laminated Film a) Unstretched Film Two kinds of three layers of the polypropylene compositions Cf-2 and 4 of the present invention and the comparative compositions cCf-1 and 6 and the following polyolefin composition or A three-kind three-layer unstretched film is prepared.

Polyolefin-based composition PO-1: 99.49% by weight of a propylene homopolymer having a density of 0.90 g / cm ³ , a crystal melting point of 163 ° C. and a melt rate (MFR) of 7.0 g / 10 min. Methylene (3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] Methane 0.03% by weight, Tris (2,4
-Di-t-butylphenyl) phosphite 0.08% by weight, calcium stearate 0.1% by weight, silica (antiblocking agent) 0.2% by weight and oleic acid amide (lubricant) 0.1% by weight. , Henschel mixer (trade name), and then a single-screw extruder (caliber 40 mm
φ) Melt-kneading and pelletizing the composition.

PO-2: Propylene-ethylene-butene-1 copolymer 99. having a density of 0.90 g / cm ³ , a crystal melting point of 132 ° C. and a melt rate (MFR) of 6.0 g / 10 minutes.
To 49% by weight, tetrakis [methylene (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate]
Methane 0.03% by weight, tris (2,4-di-t-butylphenyl) phosphite 0.08% by weight, calcium stearate 0.1% by weight, silica (antiblocking agent) 0.2% by weight and oleic acid. Amide (lubricant) 0.
A composition in which 1% by weight is blended, mixed with a Henschel mixer (trade name), melt-kneaded with a single-screw extruder (diameter 40 mmφ), and pelletized.

A polypropylene type composition was prepared by using a three-kind three-layer extruder equipped with a multilayer T-die (one uniaxial extruder for the intermediate layer having a diameter of 65 mmφ and two uniaxial extruder for the surface layer having a diameter of 50 mmφ). The composition is fed to a single-screw extruder for an intermediate layer, and the polyolefin composition is fed to a single-screw extruder for a surface layer, and melted at 230 ° C. to perform a two-kind three-layer or a three-kind three-layer multi-layer coextrusion, and an air chamber. And solidified by cooling with a cooling roll having a surface temperature of 30 ° C. to obtain a 2-kind 3-layer or 3-kind 3-layer unstretched film having a thickness of 30 μm (thickness composition ratio = 1: 4: 1). Table 1
1 and Table 12 show the layer structure.

B) Biaxially Stretched Film A three-kind three-layer extruder equipped with a multilayer T-die (one uniaxial extruder for the intermediate layer having a diameter of 65 mmφ and two uniaxial extruder for the surface layer having a diameter of 50 mmφ) was used. Used polypropylene composition Cf-12
Alternatively, cCf-8 was fed to a single-screw extruder for the intermediate layer, and the polyolefin-based composition was fed to a single-screw extruder for the surface layer, and 230
Melted at ℃ 2 and 3 layer multi-layer coextrusion, cooled and solidified with an air knife and a chill roll with a surface temperature of 30 ℃, and have a thickness of 2.0 mm (thickness composition ratio = 1/18/1) 2 kinds 3
A layer unstretched sheet was formed. Then, the obtained Type 2 3-layer unstretched sheet is stretched at a stretching temperature of 1 using a batch type biaxial stretching machine.
Biaxially stretched at 57 ℃ (5.0 times in extrusion direction, 8.0 in transverse direction)
To obtain a biaxially stretched film having a thickness of 50 μm. Table 1
1 and Table 12 show the layer structure.

[0165]

[Table 13]

[0166]

[Table 14]

4) Physical Properties of Film The following physical properties of the above-prepared monolayer film and laminated film were evaluated. a) Transparency (%): According to ASTM D 1003, the haze of the film was measured and used as the standard of transparency. b) Gloss (%): According to ASTM D 523, the gloss of the film is measured at an indicated angle of 20 degrees. c) Tear strength (N / mm): The Elemendorff tear strength of the film is measured according to ASTM D1922. d) Tensile breaking strength (MPa): The tensile breaking strength of the film is measured according to ASTM D882. e) Tensile breaking elongation (MPa): The tensile breaking elongation of the film is measured according to ASTM D882. f) Cold resistance (° C.): The holding temperature of a film, which is obtained by measuring the impact strength of the film according to ASTM D781 after holding the film in a constant temperature bath for 15 minutes. g) Heat resistance (° C.): A sample cut into a strip of 10 × 100 mm from the film is held for 10 minutes in a silicone oil bath set to a predetermined temperature, and then the length in the longitudinal direction is measured to determine the contracted length. Temperature at which the value expressed as a percentage of the initial length exceeds 2%. h) Heat-sealing temperature (° C): Dry laminated with biaxially oriented polypropylene film (20μ) and adhesive,
The laminated film is sealed at a temperature of 130 ° C to 1
After heat-sealing a width of 10 mm at a sealing pressure of 2 MPa and a sealing time of 0.5 seconds at intervals of 5 ° C. in the range of 90 ° C. (total of 8 temperature conditions), each sample was cut into strips of 15 mm width. 90 ° C peeling test of the seal part at temperature
Measured with a tensile tester at a tensile speed of 300 mm / min,
Minimum seal temperature that shows peel strength of 0.5N / 15mm or more. The evaluation results of the single layer film are shown in Tables 9 and 10, and the evaluation results of the laminated film are shown in Tables 11 and 12.

E. Polypropylene-based composition (Cb) for hollow molding and hollow-molded product 1) Polypropylene-based composition Propylene-based compositions A-1, 2 of the present invention and comparative composition cA-3 were blended with various additive components to prepare a Henschel mixer. Is melted and kneaded and extruded by an extruder set at 250 ° C., and pelletized polypropylene composition Cb-1 to 7 and comparative composition cCb-1 to
4 was prepared.

The polypropylene-based composition and the comparative composition are shown in Tables 13 and 14.

The added components used and the abbreviations in the table are shown below.

Plasticizing component LPDE: Low density polyethylene having a melt rate (MFR) of 0.4 g / 10 minutes, a crystal melting point of 110 ° C. and a density of 0.920 g / cm ³ . EVAC: Ethylene vinyl acetate copolymer having a melt rate (MFR) of 0.5 g / 10 minutes, a crystal melting point of 104 ° C., a density of 0.925 g / cm ³ , and a butyl acetate content of 3% by weight. Antioxidants and Neutralizers: As above.

[0172]

[Table 15]

[Table 16]

2) Molding of hollow molded product a) Hollow molded product (single product) Pellet-shaped polypropylene composition Cb prepared above
-1 to 6 or cCb-1 to 3 are supplied to an extruder of a hollow molding machine (SN-50 (Plastic Co.)) to extrude a parison at 200 ° C, and the parison is adjusted to 30 ° C in a mold. A hollow cylindrical product that is blown and has a bellows structure on the side surface.
(60φ × 300 × 1.6 mmt / belt structure 7 pitch in the central portion, pitch interval 10 mm, groove depth 10 mm, average wall thickness of bellows portion 0.9 mmt) were molded. The top and bottom were cut to obtain a hollow molded product. b) Hollow molded product (composite product) Extruding one of the hollow molding machines having two extruders with the polypropylene composition Cb-1, 2 or 7 in the form of pellets or the comparative composition cCb-1, 2 or 4 And one of the following polymer compositions is fed to the other extruder, first the parison is extruded from the extruder at 200 ° C., and then the parison is extruded from the extruder at 200 ° C. to give two compositions. A parison in which objects are connected is made, and this parison is blown in a mold adjusted to 30 ° C. to form a cylindrical hollow molded product having a bellows structure on the side surface (60φ × 300 ×
1.6mmt / 7 pitches of bellows structure in the center, 10m between pitches
m, the groove depth was 10 mm, and the average wall thickness of the bellows portion was 0.9 mmt. At this time, the parison extruded from the extruder was adjusted to come to the bellows. The top and bottom surfaces were cut to obtain a hollow molded product (composite product).

EP-1: 12.7% by weight of ethylene-propylene copolymer having an ethylene content of 59% by weight and 87% of propylene homopolymer having a crystalline melting point of 165 ° C., a flexural modulus of 1,100 MPa, an MFR of 0.65 g / 10 min. 0.05 parts by weight of tris (2,4-di-t-butylphenyl) phosphite and tetrakis [methylene (3,5-di-t) per 100 parts by weight of a propylene-based composition consisting of 3% by weight.
-Butyl-4-hydroxyhydrocinnamate)] 0.15 parts by weight of methane and 0.1 parts by weight of calcium stearate.

EP-2: EP-1 A polymer composition having 100 parts by weight of talc having an average particle size of 1.6 μm and 10 parts by weight of flexural modulus of 2,100 MPa and MFR of 0.72 g / 10 minutes.

The combinations of polypropylene-based composition and polymer composition are shown in Tables 13 and 14.

3) Evaluation of Hollow Molded Product The hollow molded product prepared above was evaluated according to the following characteristics and evaluation criteria.

A) Moldability: A molten parison was extruded at a molding temperature of 200 ° C., a screw diameter of 50φ and a screw rotation speed of 40 rpm (die diameter 21 mm, core diameter 19 mm). The speed at which the parison droops to 12 cm and 50 cm was measured. The difference in the hanging speed (speed up to 50 cm-1
Judgment based on the speed (up to 2 cm). A: Drawdown is small and the speed difference is less than 5% B: Drawdown speed difference is 5 to 20% C: Drawdown speed difference is more than 20%.

B) Flexibility: One end of the hollow molded article was fixed in a room of 23 ± 2 ° C., and the amount of deformation when a load of 1 kg was applied to one side was judged by angle. A: Deformation amount of 30 degrees or more B: Deformation amount of 20 degrees or more and less than 30 degrees C: Deformation amount of 10 degrees or more, less than 20 degrees D: Deformation amount of less than 10 degrees.

C) Impact whitening resistance: The hollow molded product is laid horizontally in an environment of 20 to 25 ° C., and the molded product (the part where the polypropylene composition is used) has a hammer core (19) with a tip radius of 6.35 mm.
0 g), apply a load of 500 g from the height of 50 cm onto the shooting core, and measure the diameter of the whitened surface generated around the shooting core. A: Scratches are found on the shooting core, but no whitening is observed B: Whitening of the shooting center is less than 8 mmφ C: Whitening of the shooting center is 8 to 15 mmφ D: Whitening of the shooting center exceeds 15 mmφ.

D) Heat resistance: Visual observation of deformation and appearance when the molded product is left in an oven at 150 ° C. for 500 hours. A: No deformation or appearance abnormality B: Almost no change in appearance with dimensional change of 2% or less C: Appearance change (deterioration) with dimensional change of 2% or more

E) Weld strength: The weld part of the molded product was compressed (50 mm) and visually observed for whitening and cracks along the extrusion direction of the parison. A: No whitening or crack generation C: Whitening or crack generation.

F) Bonding strength: A test piece was cut out from the joint between the polymer composition and the composition other than the tubular molded article, and the tensile strength was measured, and the value was compared with the value of the following standard product.
Standard product: A test piece cut out from a part made of polypropylene composition from a hollow molded product. A: Strength exceeding 85% of standard product B: 85 to 70% strength of standard product C: Strength less than 70% of standard product.

Tables 13 and 14 show the evaluation results of each physical property.

[0185]

The propylene composition of the present invention is excellent in moldability, molding shrinkage, rigidity, flexibility and impact resistance, particularly impact resistance at low temperature, transparency, gloss and whitening resistance, and It is preferably used as a base resin of a polypropylene composition for obtaining various molded products having an excellent balance among them.

As shown in FIGS. 1 and 2, in the injection-molded article using the polypropylene composition having the propylene composition of the present invention as a base resin, the propylene homopolymer (PP ) And the intrinsic viscosity ratio and the weight ratio of the propylene-ethylene copolymer (RC) ([η] _RC / [η] _PP ) × (W _PP / W _RC ) is 1.0 to
When it is in the range of 3.0, the molding shrinkage is almost 1.
It has a high flexural modulus (rigidity) and, as shown in Tables 3 and 5, has excellent low-temperature impact resistance, transparency, gloss and whitening resistance. Further, in the polypropylene-based compositions Ci-7 to 12 in which the α-crystal nucleating agent was added, the low temperature impact resistance was further improved, and as shown in Tables 4 and 6, the radical generator and / or the highly crystalline propylene were used. Polypropylene composition containing homopolymer Ci-13-
In No. 18, the whitening property is further improved.

Using these polypropylene compositions, various sheet-shaped molded products as well as molded products having complicated structures such as containers and their plugs (caps) and molded products having a hinge structure are injection-molded. Can be manufactured by.

In the sheet using the polypropylene composition containing the propylene composition of the present invention as a base resin, punching impact strength and bending whitening were observed as shown in Tables 7 and 8 depending on the combination with the molding method. It is possible to obtain a sheet having excellent properties and printability, and having a good balance between tensile strength at yield and Young's modulus.

As shown in Tables 9 and 10, the monolayer film formed by using the polypropylene composition containing the propylene composition of the present invention as a base resin is excellent in transparency and heat resistance, tear strength, (EN) An unstretched, biaxially stretched and uniaxially stretched film having excellent balance of mechanical properties such as tensile breaking strength, breaking elongation and low temperature impact resistance.
In addition, the laminated film of the polypropylene composition and the polyolefin composition has excellent heat sealability while maintaining the characteristics of the above single layer film as shown in Tables 11 and 12.

These films are suitable as various packaging films including those for food packaging.

Hollow molded articles molded by using the polypropylene composition containing the propylene composition of the present invention as a base resin, particularly hollow molded articles having a bellows structure, are molded as shown in Table 13 and Table 14. Properties, flexibility, impact whitening resistance, heat resistance, and weld characteristics. In particular, in the polypropylene compositions Cb-2, 3, 5 and 7 to which a plasticizing component is added, the flexibility is further improved. In addition, a composite article bonded with another polymer composition has high bonding strength.

The hollow molded article having the bellows structure and the composite article thereof are suitable as an air duct and the like.

The present invention provides a polypropylene composition used for molding various molded articles and a propylene composition suitable as a base resin therefor, and has a great significance in the art.

[Brief description of drawings]

FIG. 1 Propylene homopolymer (PP) and propylene-
Product of ethylene copolymer (RC) intrinsic viscosity ratio and weight ratio
A curve representing the molding shrinkage ratio with respect to ([η] _RC / [η] _PP ) × (W _PP / W _RC ).

FIG. 2: Propylene homopolymer (PP) and propylene-
Product of ethylene copolymer (RC) intrinsic viscosity ratio and weight ratio
A curve representing the bending elastic modulus with respect to ([η] _RC / [η] _PP ) × (W _PP / W _RC ).

FIG. 3 is a flow sheet of a continuous polymerization apparatus for the propylene-based composition used in the examples.

[Explanation of symbols]

1, 10: Polymerizer 2: Hydrogen piping 3: Raw material propylene piping 4, 8: Unreacted gas pipe 5, 9: Polymer extraction piping 6: Raw material mixed gas piping

   ─────────────────────────────────────────────────── ─── Continued front page    (31) Priority claim number Japanese Patent Application No. 8-174178 (32) Priority date June 13, 1996 (June 13, 1996) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 8-181141 (32) Priority date June 21, 1996 (June 21, 1996) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 8-209030 (32) Priority date July 18, 1996 (July 18, 1996) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 8-209031 (32) Priority date July 18, 1996 (July 18, 1996) (33) Priority claiming country Japan (JP) (72) Inventor Mayumi Wakata             2-17 Tatsumidai East, Ichihara City, Chiba Prefecture (72) Inventor Kazuhiro Kimura             8890 Goi, Ichihara City, Chiba Prefecture (72) Inventor Toshiki Yamamoto             2-17 Tatsumidai East, Ichihara City, Chiba Prefecture (72) Inventor Hirohisa Ishii             28-5, Nishigosho, Ichihara-shi, Chiba (72) Inventor Masataka Sugimoto             3-27-2, Tatsumidai-higashi, Ichihara-shi, Chiba (72) Inventor Kunio Gota             8-14 Wakamiya, Ichihara City, Chiba Prefecture (72) Inventor Yasuhiro Mochizuki             3-4 Takasu, Mihama-ku, Chiba City, Chiba Prefecture (72) Inventor Noriaki Saito             5-23 Kimitsuka, Ichihara-shi, Chiba 1 (72) Inventor Junichiro Yokota             357-1 Fujii, Ichihara City, Chiba Prefecture (72) Inventor Shoji Kono             3-27-2, Tatsumidai-higashi, Ichihara-shi, Chiba (72) Inventor Yasuhiko Nakagawa             3-27-2, Tatsumidai-higashi, Ichihara-shi, Chiba F-term (reference) 4J002 BB121 BB152                 4J026 HA04 HA27 HA35 HA38 HA48                       HB03 HB04 HB20 HB27 HB35                       HB38 HB42 HB45 HB48

Claims (3)

[Claims] 1. A propylene-ethylene copolymer containing from 60 to 78% by weight of a propylene homopolymer, and from 22 to 40% by weight of a propylene-ethylene copolymer containing 25 to 55% by weight of an ethylene polymer unit.
A propylene-based composition comprising a propylene homopolymer having an isotactic pendat fraction (P) of 0.
95 or more; intrinsic viscosity of propylene-ethylene copolymer
([η] _RC ) is in the range of 1.7 to 2.8 dl / g; the intrinsic viscosity ratio ([η] _RC / [η] _PP ) of the propylene homopolymer and the propylene-ethylene copolymer is 0.7 to 1. 2; and the weight ratio of propylene homopolymer and propylene-ethylene copolymer (W _PP / W _RC ), and their intrinsic viscosity ratio ([η] _RC /
The product of [η] _PP ) (W _PP / W _RC ) × ([η] _RC / [η] _PP ) is 1.0
A range of .about.3.0; a propylene composition. 2. The propylene-ethylene copolymer is 2
The propylene-based composition according to claim 1, wherein the xylene-soluble component at 0 ° C is contained in an amount of 80% by weight or more based on the weight of the propylene-ethylene copolymer. 3. The propylene-based composition has a Q value (Mw / Mn)
The propylene-based composition according to claim 1, which has 5 or less.