JP2010248363A - Polypropylene-based resin composition and film made of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polypropylene-based resin composition having glossiness suitable for a matte film having appearance of moisture feeling and graceful feeling and excellent in balance between impact resistance and rigidity at a low temperature and blocking resistance. <P>SOLUTION: The polypropylene-based resin composition is obtained by melt kneading a polypropylene-based copolymer including a polymer component (component A) consisting essentially of a structure unit originating from propylene and a polymer component (component B) of propylene, ethylene and a ≥4C α-olefin wherein a content (X) of a structure unit originating from propylene is in the range of 10≤X<50 wt.%, a content (Y) of a structure unit originating from ethylene is in the range of 50<Y≤70 wt.% and a content (Z) of a structure unit originating from a ≥4C α-olefin is in the range of 0<Z≤20 wt.% in the presence of an organic peroxide and has ≥5g/10 min melt flow rate. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a polypropylene resin composition.

Polypropylene is widely used in the field of packaging materials such as food packaging and fiber packaging because it is excellent in rigidity, heat resistance and packaging suitability. In recent years, a matte film having a moist appearance with polypropylene as a main component has been developed, and a matte film having a high-class feeling and excellent in impact resistance has been demanded.

JP-A-4-356532 discloses a film produced using a composition containing 100 parts by weight of a specific crystalline propylene-ethylene block copolymer and 0.001 to 1 part by weight of an organic peroxide. In addition, it is described that the film has a remarkably increased degree of transparency, which is a measure of translucency.

Japanese Patent Application Laid-Open No. 5-448 discloses a specific crystalline propylene-ethylene block copolymer, an organic peroxide having a decomposition temperature of 60 ° C. or more with a half-life of 10 hours, and an ethylene content of 50% or more. Films made from compositions containing polyethylene or copolymers of ethylene with other α-olefins and / or radically polymerizable polar unsaturated compounds have significantly increased the degree of transparency, a measure of translucency. It is described that it is a film.

Japanese Patent Application Laid-Open No. 2003-213068 discloses a propylene polymer having a polymer component (A) of 60 to 80% by weight obtained by polymerizing a monomer component mainly composed of propylene and an ethylene content of 50 to 80% by weight. Propylene-based copolymer (I) having a specific property consisting of 20 to 40% by weight of ethylene copolymer component (B) and 30 to 70% by weight of propylene-based copolymer having a melt flow rate of 5 g / 10 min or more A polypropylene-based resin composition containing 30 to 70% by weight of polymer (II) is described, and a film made of the composition has a moist feeling, a high-grade appearance, and excellent impact strength. Are listed.

JP-A-4-356532 JP-A-5-448 Japanese Patent Laid-Open No. 2003-213068

However, further improvement is desired in the balance between appearance and impact resistance.
An object of the present invention is a polypropylene resin having a gloss suitable for a matte film having a moist and high-quality appearance, and having excellent balance between impact resistance and rigidity at low temperature and blocking resistance It is to provide a composition.

As a result of intensive studies, the present inventors have found that the present invention can solve the above problems, and have completed the present invention.

That is, the present invention has a polymer component (component A) of 50 to 95% by weight whose main component is a structural unit derived from propylene, and the content (X) of the structural unit derived from propylene is 10 ≦ X <50 weight. %, The content of structural units derived from ethylene (Y) is 50 <Y ≦ 70 wt%, and the content of structural units derived from α-olefins having 4 or more carbon atoms (Z) is 0 <Z ≦ 20% by weight (provided that the total of X, Y and Z is 100% by weight), and a structure derived from an α-olefin having 4 or more carbon atoms with respect to the content (X) of a structural unit derived from propylene Polypropylene copolymer containing 5 to 50% by weight of a polymer component (component B) of propylene, ethylene and an α-olefin having 4 or more carbon atoms, having a unit content (Z) weight ratio of 1 or less. In the presence of organic peroxide Obtained by mixing, to a polypropylene resin composition melt flow rate is equal to or is 5 g / 10 minutes or more.

According to the present invention, a polypropylene resin having a gloss suitable for a matte film having a moist and high-quality appearance, excellent balance between impact resistance at low temperature and rigidity, and excellent blocking resistance A composition can be obtained.

The polypropylene resin composition of the present invention comprises a polymer component (component A) whose main component is a structural unit derived from propylene, and a polymer component (component B) of propylene, ethylene and an α-olefin having 4 or more carbon atoms. And a polypropylene-based resin composition obtained by melt-kneading a polypropylene-based copolymer in the presence of an organic peroxide.

Here, the proportion of component A and component B in the polypropylene copolymer is in the range of 50 to 95% by weight of component A and 5 to 50% by weight of component B, preferably 60 to 95% by weight of component A. %, Component B is 5 to 40% by weight, more preferably component A is 60 to 90% by weight, and component B is 10 to 40% by weight. When component B is less than 5% by weight, impact resistance at low temperatures is poor, and when component B exceeds 50% by weight, blocking resistance may be deteriorated.

Component A is a polymer whose main component is a structural unit derived from propylene. From the viewpoint of rigidity, the melting point preferably exceeds 155 ° C, more preferably 160 ° C or higher. Component A may be copolymerized with an α-olefin such as ethylene or 1-butene within a range where the melting point does not become 155 ° C. or less, but is preferably a propylene homopolymer. When an α-olefin such as ethylene or 1-butene is copolymerized, the content of the structural unit derived from the α-olefin in the polymer component (component A) whose main component is the structural unit derived from propylene is 5% by weight or less, preferably 3% by weight or less (the polymer component mainly composed of propylene is 100% by weight). Although there is no restriction | limiting in particular about the intrinsic viscosity of the component A, the range of 1.5-3.0 dL / g is preferable, and the range of 1.5-2.5 dL / g is further more preferable.

The content (Y) of the structural unit derived from ethylene contained in Component B is 50 <Y ≦ 70 wt%, preferably 52 ≦ Y ≦ 70 wt%, more preferably 54 ≦ Y ≦ 70 wt%. % (However, the content of structural units derived from propylene contained in component B (X), the content of structural units derived from ethylene (Y), and the structural units derived from α-olefins having 4 or more carbon atoms) The total content (Z) is 100% by weight). When the content of the structural unit derived from ethylene is 50% by weight or less, or exceeds 70% by weight, impact resistance at low temperatures may be lowered.

The content (Z) of the structural unit derived from the α-olefin contained in Component B is 0 <Z ≦ 20 wt%, preferably 1 ≦ Z ≦ 16 wt%, more preferably 1 ≦ Z ≦ 10% by weight (provided that the content of structural units derived from propylene contained in component B (X), the content of structural units derived from ethylene (Y), and α-olefins having 4 or more carbon atoms) The total content of structural units (Z) is 100% by weight). When the content of the structural unit derived from α-olefin exceeds 0% by weight or 20% by weight, the impact resistance at low temperature may be lowered.

The weight ratio of the content (Z) of the structural unit derived from the α-olefin having 4 or more carbon atoms to the content (X) of the structural unit derived from propylene in the component B is 1 or less. When the weight ratio of the content (Z) of structural units derived from α-olefins having 4 or more carbon atoms to the content (X) of structural units derived from propylene is 1 or less, impact resistance at low temperatures Will improve.

Examples of the α-olefin having 4 or more carbon atoms contained in Component B include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, vinylcyclohexane, vinylnorbornane. 1-butene is preferable. Although there is no restriction | limiting in particular about the intrinsic viscosity of the component B, the range of 2.0-5.0 dL / g is preferable from a viewpoint of fish-eye generation | occurrence | production, and the range of 2.5-4.5 dL / g is further more preferable.

As a method for producing a polypropylene copolymer contained in the polypropylene resin composition of the present invention, after polymerizing a polymer component (component A) whose main component is a structural unit derived from propylene, propylene is continuously produced. And a method of polymerizing a polymer component (component B) of ethylene and an α-olefin having 4 or more carbon atoms, which can be produced by various polymerization methods using a normal stereoregular catalyst. it can.

Examples of the stereoregular catalyst include a catalyst comprising a solid titanium catalyst component, an organometallic compound catalyst component, and an electron donor used as necessary, and a transition of group IVB of the periodic table having a cyclopentadienyl ring. Examples include a catalyst system composed of a metal compound and an alkylaluminoxane, or a compound composed of a group IVB transition metal compound having a cyclopentadienyl ring and a compound which reacts with it to form an ionic complex and an organoaluminum compound. . Among them, a method of producing using a catalyst comprising a solid titanium catalyst component, an organometallic compound catalyst component, and an electron donor used as necessary is preferable.

Examples of the solid titanium catalyst component include a solid catalyst component precursor obtained by reducing a titanium compound with an organic magnesium compound in the presence of a silicon compound, a halogenated compound (for example, titanium tetrachloride), and an electron donor ( For example, a trivalent titanium compound-containing solid catalyst component obtained by contact treatment of an ether compound or a mixture of an ether compound and an ester compound) may be mentioned.

Examples of the organometallic compound catalyst component include an organoaluminum compound having at least one Al-carbon bond in the molecule, and a trialkylaluminum, a mixture of a trialkylaluminum and a dialkylaluminum halide, or an alkylalumoxane is preferable. In particular, triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride, or tetraethyldialumoxane is preferable.

Examples of the electron donor include oxygen-containing compounds, nitrogen-containing compounds, phosphorus-containing compounds, and sulfur-containing compounds, among which oxygen-containing compounds or nitrogen-containing compounds are preferable, oxygen-containing compounds are more preferable, and alkoxysilicones or Ethers are particularly preferred.

Specifically, for example,
(A) In the coexistence of a silicon compound having a Si—O bond, the general formula Ti (OR ₁ ) _n X _4-n (R ₁ is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen electron, and n is 0 <Representing a number of n ≦ 4.) The solid product obtained by reducing the titanium compound represented by the organic magnesium compound is treated with a mixture of an ester compound, an ether compound and titanium tetrachloride. -Valent titanium compound-containing solid catalyst component,
(B) Organoaluminum compound (c) A catalyst system comprising a silicon compound having a Si—OR ₂ bond (R ₂ is a hydrocarbon group having 1 to 20 carbon atoms) can be mentioned.

Further, the molar ratio of Al atom in component (b) / Ti atom in component (a) is 1 to 2000, preferably 5 to 1500, and the molar ratio of Al atom in component (c) / component (b) is It is used so that it may become 0.02-500, preferably 0.05-50.

The polymerization method will be described below. The polymerization format may be either batch type or continuous type. Further, slurry polymerization or solution polymerization using an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, and octane, and bulk polymerization or gas phase polymerization using a liquid olefin as a medium at the polymerization temperature are also possible. Although superposition | polymerization temperature can be implemented over -30-300 degreeC normally, 20-180 degreeC is preferable. Although there is no restriction | limiting in particular regarding the polymerization pressure, Generally the pressure of a normal pressure-10MPa, Preferably about 200kPa-5MPa is employ | adopted by the point that it is industrial and economical. In particular, the second step described later is preferably gas phase polymerization.
During polymerization, a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the polymer.

Examples of the polypropylene copolymer contained in the polypropylene resin composition of the present invention include a method of producing by the following steps using the catalyst and the polymerization method.
Polymerization step 1: Propylene is homopolymerized to produce a polypropylene homopolymer component (component A), or propylene and an olefin selected from the group consisting of ethylene and an α-olefin having 4 to 10 carbon atoms. A step of copolymerization to produce a polymer component (component A) whose main component is a structural unit derived from propylene. Polymerization step 2: Mainly the structural unit derived from the polypropylene homopolymer component or propylene obtained in step 1 above. In the presence of a copolymer component as a component, propylene, ethylene and an α-olefin having 4 or more carbon atoms are copolymerized to form a polymer component (component) of propylene, ethylene and an α-olefin having 4 or more carbon atoms. B) generating step

A time for polymerizing a polymer component (component A) whose main component is a structural unit derived from propylene, and a time for polymerizing a polymer component (component B) of propylene, ethylene and an α-olefin having 4 or more carbon atoms; , The ratio of component A and component B can be changed.
In addition, by polymerizing a polymer component (component B) of propylene, ethylene and an α-olefin having 4 or more carbon atoms, by changing the gas composition in the mixed gas of propylene, ethylene and α-olefin, the component The composition of B can be changed.

Examples of the organic peroxide used in the present invention include conventionally known organic peroxides. For example, an organic peroxide having a decomposition temperature of 120 ° C. or higher at which the half-life is 1 minute is preferable. Examples of the organic peroxide having a decomposition temperature of 120 ° C. or more with a half-life of 1 minute include 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-di-). t-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5 dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) butene, t-butylper Oxybenzoate, n-butyl-4,4-bis (t-beroxy) valerate, di-t-butylberoxyisophthalate, dicumy Peroxide, α-α′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t- Butylperoxydiisopropyl) benzene, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 Etc.
An organic peroxide having a decomposition temperature of 150 ° C. or higher at which the half-life is 1 minute is more preferable.

The addition amount of the organic peroxide is preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the polypropylene copolymer. More preferably, it is 0.01-2 weight part, More preferably, it is 0.01-1 weight part.

The polypropylene resin composition of the present invention comprises a polymer component (component A) whose main component is a structural unit derived from propylene, and a polymer component (component B) of propylene, ethylene and an α-olefin having 4 or more carbon atoms. ) And a polypropylene-based copolymer obtained by melt-kneading in the presence of an organic peroxide.

Said melt-kneading can be performed using a conventionally well-known method and apparatus. For example, a method in which a propylene copolymer, an organic peroxide, and various additives are mixed using a mixing device such as a Henschel mixer, a ribbon blender, a tumble mixer, and then melt kneaded; After obtaining a homogeneous mixture by continuously supplying a propylene-based copolymer, an organic peroxide, and various additives at a certain ratio, the mixture is extruded into a single-screw or twin-screw extruder. And a melt kneading method using a Banbury mixer, a roll-type kneader or the like.

The melt kneading temperature is preferably 180 ° C to 350 ° C. More preferably, it is 180 degreeC-320 degreeC, More preferably, it is 180 degreeC-300 degreeC.

In the polypropylene resin composition of the present invention, a phenolic antioxidant or a phosphorus resin is used for the purpose of suppressing the oxidative deterioration of the resin composition or the film and improving the matting effect and impact resistance when the film is produced. You may contain antioxidant.

Examples of the phenolic antioxidant include 2,6-di-t-butyl-4-methylphenol, tetrakis [methylene-, which is a hindered phenolic antioxidant or a hindered phenolic antioxidant. 3 (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5 · 5] Undecane, 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanate, 1,3,5-to Limethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3 , 5-Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ], Triethylene glycol-N-bis-3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-t-butyl) -4-hydroxyphenyl) propionate], 2,2-thiobis-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ], 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2′-methylene-bis- (4-ethyl-6-tert-butylphenol), 2,2′-methylene -Bis- (4,6-di-t-butylphenol), 2,2'-ethylidene-bis- (4,6-di-t-butylphenol) (cheminox 1129), 2,2'-butylidene-bis- ( 4-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 2-t-butyl-6- (3-t-butyl-2-hydroxy-5- Methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t-amyl-6- (1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate, representative of vitamin E Α-tocopherols and the like.

Examples of the phosphorus antioxidant include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, trilauryl phosphite, and trioctadecyl phosphite. , Distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methyl) Phenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol diphosphite, Tristearyl sorbitol triphospha And tetrakis (2,4-di-t-butylphenyl) -4,4'-diphenylenediphosphonite, 2,2'-methylenebis (4,6-di-t-butylphenyl) -2-ethylhexylphos Phyto, 2,2′-ethylidenebis (4,6-di-t-butylphenyl) fluorophosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, bis (2, 4-di-t-butyl-6-methylphenyl) methyl phosphite, 2- (2,4,6-tri-t-butylphenyl) -5-ethyl-5-butyl-1,3,2-oxaphospho Linnan, 2,2 ′, 2 ″ -nitrilo [triethyl-tris (3,3 ′, 5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl) phosphite, 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4 Hydroxy -5-t-butylphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphepin, and mixtures of at least two or more thereof.

The polypropylene resin composition of the present invention has a melt flow rate of 5.0 g / 10 min or more. In the present invention, the melt flow rate is a value measured according to JIS K7210 at a temperature of 230 ° C. and a load of 2.16 kgf. When the melt flow rate of the polypropylene resin composition is less than 5.0 g / 10 min, the extrusion load during film processing increases, and the productivity of the film may be inferior. From the viewpoint of productivity, it is preferably 6.0 g / 10 min or more. From the viewpoint of fish eyes, the melt flow rate is preferably 15 g / 10 min or less.

As a method for controlling the melt flow rate of the polypropylene resin composition of the present invention, a method for adjusting the intrinsic viscosity of the propylene copolymer; a method for adjusting the temperature, kneading force, etc. during melt kneading of the propylene copolymer A method of adjusting the content of the organic peroxide at the time of melt-kneading the propylene copolymer.

You may add an additive and another resin to the polypropylene resin composition of this invention as needed. Examples of the additive include other antioxidants, ultraviolet absorbers, antistatic agents, lubricants, nucleating agents, pressure-sensitive adhesives, antifogging agents, and antiblocking agents. Examples of other resins include high-density polyethylene, linear low-density polyethylene, low-density polyethylene, and elastomers that are copolymers of ethylene and α-olefin, which are manufactured using heterogeneous catalysts. Alternatively, it may be produced with a homogeneous catalyst (for example, a metallocene catalyst). Further, an elastomer such as a styrene copolymer rubber obtained by hydrogenating a styrene-butadiene-styrene copolymer or a styrene-isoprene-styrene copolymer may be added.

The film of the present invention preferably has a thickness of 10 to 500 μm, and more preferably 10 to 100 μm.

The film of the present invention may be a single layer film or a multilayer film including at least one layer composed of the film of the present invention. The film of the present invention may be an unstretched film or a stretched stretched film. Preferably, it is an unstretched film.

The production method of the film of the present invention is not particularly limited. For example, a method of forming a film independently using a commonly used inflation method, T-die method, calendar method, or the like, or at least one layer of a multilayer film The method of forming a film is mentioned. Examples of the method for producing the multilayer film include a co-extrusion method, an extrusion laminating method, a heat laminating method, and a dry laminating method.

The film of the present invention may be subjected to a surface treatment such as corona discharge treatment, flame treatment, plasma treatment, ozone treatment, etc., by a method usually employed industrially.

The application of the film of the present invention is not particularly limited, and examples thereof include packaging applications, and examples thereof include packaging applications such as foods, fibers and sundries. A matte film having a moist and high-quality appearance is preferable.

Hereinafter, although the present invention is explained using an example and a comparative example, the range of the present invention is not limited only to an example. The detailed description of the invention and the measured values of each item in the examples and comparative examples were measured by the following methods.
(1) MFR (unit: g / 10 minutes)
According to JIS K7210, the temperature was 230 ° C. and the load was 2.16 kgf.
(2) Intrinsic viscosity ([η], unit: dL / g)
The measurement was performed in 135 ° C. tetralin using an Ubbelohde viscometer.
(3) Weight ratio χ (unit:% by weight) of component B to the entire polypropylene copolymer
Polymerization ratio: χ of the polymer component (component B) of propylene, ethylene, and α-olefin having 4 or more carbon atoms to the entire polypropylene copolymer containing component A and component B was calculated by the following method. .
χ = 1−ΔH _B / ΔH _A
ΔH _A : Polymer part (component A) whose structural unit derived from propylene is the main component (component A) heat of fusion of polymer after polymerization (J / g)
ΔH _B : Polymer component of propylene, ethylene and α-olefin having 4 or more carbon atoms (component B) Heat of fusion of polymer after polymerization (J / g)
(4) Content of structural unit derived from ethylene of component B (Y) and content of structural unit derived from 1-butene (Z) (unit: wt%)
Content of structural unit derived from ethylene (C2 ′ (T)) in polypropylene-based copolymer containing component A and component B and content of structural unit derived from 1-butene (C4 ′ (T) ) Was determined by the method described on pages 616 to 619 of the Polymer Handbook (1995, published by Kinokuniya Shoten).
Next, C2 ′ (T), C4 ′ (T) and χ described in the above (5) are derived from the content (Y) of structural unit derived from ethylene of component B and 1-butene by the following method. The content (Z) of the structural unit was calculated.
Y = C2 ′ (T) / χ × 100
Z = C4 ′ (T) / χ × 100

(5) Gross (Unit:%)
It measured according to JIS K7105.
(6) Blocking resistance (unit: g / 100 cm ² )
Using 225 mm × 50 mm film, the films were overlapped, and the condition of 100 mm × 50 mm was adjusted at 60 ° C. for 3 hours under a load of 40 g / cm ² . Thereafter, the sample was left in an atmosphere of 23 ° C. and 50% humidity for 30 minutes or more, and the strength required for peeling the sample was measured at a peeling rate of 20 g / min using a Shimadzu blocking tester.
(7) Rigidity (Young's modulus, unit: MPa)
Using an autostrain manufactured by Yasuda Seiki Seisakusho, under an atmosphere of 23 ° C. and a humidity of 50%, using a 120 mm × 30 mm film (collected so that the film forming direction (MD) and the long side direction coincide). A tensile test was performed at a grip interval of 60 mm and a tensile speed of 5 mm / min, and the initial elastic modulus was measured from the tangent at the zero point of the tensile-stress curve.
(8) Impact resistance (unit: kJ / m)
The film was placed in a thermostat set at a predetermined temperature, and the impact strength of the film was measured using a film impact tester manufactured by Toyo Seiki, using a hemispherical impact head having a diameter of 15 mm.

Reference Example 1 Production of Polypropylene Copolymer (BCPP1) [Synthesis of Solid Components]
Into a reactor equipped with a nitrogen-substituted stirrer, 800 liters of hexane, 6.8 kg of diisobutyl phthalate, 350 kg of tetraethoxysilane and 38.8 kg of tetrabutoxytitanium were charged and stirred. Next, 900 liters of dibutyl ether solution of butylmagnesium chloride (concentration 2.1 mol / liter) was added dropwise to the stirred mixture over 5 hours while maintaining the reactor temperature at 7 ° C. After completion of the dropwise addition, the mixture was stirred at 20 ° C. for 1 hour and then filtered. The obtained solid was washed with 1100 liters of toluene three times, and toluene was added so that the total volume of the slurry was 625 liters. Thereafter, the resulting slurry was heat-treated at 70 ° C. for 1 hour with stirring and cooled to room temperature.
A part of the obtained solid component was taken and dried under reduced pressure. The composition analysis of the obtained solid component revealed that the solid component contained 2.1% by weight of titanium atoms, 38.9% by weight of ethoxy groups, and 3.4% by weight of butoxy groups. Moreover, the valence of the titanium atom in this solid component was trivalent.
[Synthesis of solid catalyst components]
After a 100 ml flask equipped with a stirrer, a dropping funnel and a thermometer was replaced with nitrogen, the solid component slurry obtained above was charged in an amount containing 8 g of the dry solid component, and the total volume of the slurry was 26. The supernatant liquid was extracted to 5 ml. A mixture of 16.0 ml of titanium tetrachloride and 0.8 ml of dibutyl ether was added at 40 ° C., and a mixture of 2.0 ml of phthalic acid chloride and 2.0 ml of toluene was added dropwise over 5 minutes. After completion of the dropwise addition, the reaction mixture was stirred at 115 ° C. for 4 hours. Thereafter, solid-liquid separation was performed at the same temperature, and washing was performed 3 times at 115 ° C. with 40 ml of toluene.
After washing, toluene was added so that the volume of the slurry was 26.5 ml. Thereto was added a mixture of 0.8 ml of dibutyl ether, 0.45 ml of diisobutyl phthalate and 6.4 ml of titanium tetrachloride, and the mixture was stirred at 105 ° C. for 1 hour. Thereafter, solid-liquid separation was performed at the same temperature, and washing was performed twice at 105 ° C. with 40 ml of toluene.
Next, toluene was added so that the volume of the slurry was 26.5 ml, and the temperature was 105 ° C. Thereto was added a mixture of 0.8 ml of dibutyl ether and 6.4 ml of titanium tetrachloride, and the mixture was stirred at 105 ° C. for 1 hour. Thereafter, solid-liquid separation was performed at the same temperature, and washing was performed twice at 105 ° C. with 40 ml of toluene.
Furthermore, toluene was added to 105 ° C. so that the volume of the slurry was 26.5 ml. Thereto was added a mixture of 0.8 ml of dibutyl ether and 6.4 ml of titanium tetrachloride, and the mixture was stirred at 105 ° C. for 1 hour. Thereafter, solid-liquid separation was performed at the same temperature, and washing was performed 6 times with 40 ml of toluene at 105 ° C. and 3 times with 40 ml of hexane at room temperature. This was dried under reduced pressure to obtain a solid catalyst component.
The solid catalyst component contained 1.6% by weight of titanium atoms, 7.6% by weight of diethyl phthalate, 0.8% by weight of ethyl normal butyl phthalate, and 2.5% by weight of diisobutyl phthalate.
[Preliminary polymerization]
To a SUS autoclave with a stirrer with an internal volume of 3 L, 1.5 L of fully dehydrated and degassed n-hexane, 30 mmol of triethylaluminum, 3.0 mmol of cyclohexylethyldimethoxysilane and 16 g of the above solid catalyst component were added, After preliminarily polymerizing 32 g of propylene while continuously maintaining the temperature in the autoclave at about 3 to 20 ° C. over about 40 minutes, the prepolymerized slurry was transferred to a 200-liter SUS autoclave with a stirrer. Then, 132 L of liquid butane was added to prepare a slurry of a prepolymerized catalyst component.
Polymerization of component A [polymerization step (1)]
A slurry of propylene, hydrogen, triethylaluminum, cyclohexylethyldimethoxysilane and a prepolymerization catalyst component was continuously fed using a vessel type reactor having an internal volume of 40 L with a stirrer, polymerization temperature: 78 ° C., stirring speed: 150 rpm, Reactor liquid level: 18 L, propylene: 25 kg / hr, hydrogen: 19 NL / hr, triethylaluminum feed: 41 mmol / hr, cyclohexylethyldimethoxysilane feed: 6.15 mmol / hr, prepolymerization Supply amount of catalyst component slurry: Continuous polymerization was carried out for 0.27 hours under the condition of 0.43 g / hour in terms of solid catalyst component. The discharged polymer was 2.3 kg / hour.
[Polymerization step (2)]
The slurry discharged from the polymerization step (1) is continuously transferred to a vessel type reactor different from the polymerization step (1), and propylene and hydrogen are continuously supplied. Polymerization temperature: 73 ° C., stirring speed : 150 rpm, liquid level of the reactor: 44 L was maintained, and continuous polymerization was further performed for 0.46 hours under the conditions of propylene: 15 kg / hour, hydrogen: 10 NL / hour. The discharged polymer was 3.4 kg / hour.
[Polymerization step (3)]
The slurry discharged from the polymerization step (2) is continuously transferred to a vessel type reactor different from the polymerization steps (1) and (2), polymerization temperature: 68 ° C., stirring speed: 150 rpm, reactor liquid Level: 44 L was maintained, and continuous polymerization was further performed for 0.50 hours. The discharged polymer was 3.2 kg / hour.
[Polymerization step (4)]
The slurry discharged from the polymerization step (3) is continuously transferred to a fluidized bed reactor with an internal volume of 1 m ³ and equipped with a stirrer, and propylene and hydrogen are continuously supplied. Polymerization temperature: 80 ° C., polymerization pressure: 1 Polymerization was performed for 3.1 hours at a ratio of propylene and hydrogen in the reactor gas of .8 MPa and a concentration ratio of 99.04 vol% / 0.96 vol% (propylene concentration / hydrogen concentration). The discharged polymer component (component A) was 7.3 kg / hour, and the intrinsic viscosity [η] A of the obtained polymer component was 1.7 dL / g.
Polymerization of component B [polymerization step (5)]
The polymer component (component A) discharged from the polymerization step (4) is continuously transferred to a fluidized bed reactor with a stirrer having an internal volume of 1 m ³ different from the reactor used in the polymerization step (4). Propylene, ethylene, 1-butene and hydrogen are continuously fed, polymerization temperature: 70 ° C., polymerization pressure: 1.4 MPa, concentration ratio of propylene, ethylene, 1-butene and hydrogen in the reactor gas: 27.77 Volume% / 50 volume% / 20.3 volume% / 1.93 volume% (propylene concentration / ethylene concentration / 1-butene concentration / hydrogen concentration), as a molar ratio of triethylaluminum supplying oxygen as a deactivator Polymerization was performed for 2.5 hours under the condition of adding 0.006. The discharged polymer component (component B) was 4.1 kg / hour, and the intrinsic viscosity [η] B of the obtained polymer component (component B) was 4.4 dL / g.
Table 1 shows the analysis results of each component of the produced polypropylene copolymer.

Reference Example 2 Production of Polypropylene Copolymer (BCPP2) The solid catalyst component and prepolymerization were carried out in the same steps as in Reference Example 1.
Polymerization of component A [polymerization step (1)]
A slurry of propylene, hydrogen, triethylaluminum, cyclohexylethyldimethoxysilane and a prepolymerization catalyst component was continuously fed using a vessel type reactor having an internal volume of 40 L with a stirrer, polymerization temperature: 78 ° C., stirring speed: 150 rpm, Reactor liquid level: 18 L, propylene: 25 kg / hr, hydrogen: 20 NL / hr, triethylaluminum feed: 41 mmol / hr, cyclohexylethyldimethoxysilane feed: 6.15 mmol / hr, prepolymerization Supply amount of catalyst component slurry: Continuous polymerization was carried out for 0.26 hours under the condition of 0.59 g / hour in terms of solid catalyst component. The discharged polymer was 2.7 kg / hour.
[Polymerization step (2)]
The slurry discharged from the polymerization step (1) is continuously transferred to a vessel type reactor different from the polymerization step (1), and propylene and hydrogen are continuously supplied. Polymerization temperature: 73 ° C., stirring speed : 150 rpm, liquid level of the reactor: 44 L was maintained, and continuous polymerization was further performed for 0.45 hours under the conditions of propylene: 15 kg / hour and hydrogen: 11 NL / hour. The discharged polymer was 3.2 kg / hour.
[Polymerization step (3)]
The slurry discharged from the polymerization step (2) is continuously transferred to a vessel type reactor different from the polymerization steps (1) and (2), the polymerization temperature: 68 ° C., the stirring speed: 150 rpm, the reactor liquid Level: 44 L was maintained, and further continuous polymerization was performed for 0.49 hours. The discharged polymer was 2.9 kg / hour.
[Polymerization step (4)]
The slurry discharged from the polymerization step (3) is continuously transferred to a fluidized bed reactor with an internal volume of 1 m ³ and equipped with a stirrer, and propylene and hydrogen are continuously supplied. Polymerization temperature: 80 ° C., polymerization pressure: 1 Polymerization was carried out for 2.8 hours at a concentration ratio of propylene and hydrogen in the reactor gas of 0.8 MPa: 98.96 vol% / 1.04 vol% (propylene concentration / hydrogen concentration). The discharged polymer component (component A) was 11.1 kg / hour, and the intrinsic viscosity [η] A of the obtained polymer component (component A) was 1.8 dL / g.
Polymerization of component B [polymerization step (5)]
The polymer component (component A) discharged from the polymerization step (4) is continuously transferred to a fluidized bed reactor with a stirrer having an internal volume of 1 m ³ different from the reactor used in the polymerization step (4). Propylene, ethylene and hydrogen are continuously supplied, polymerization temperature: 70 ° C., polymerization pressure: 1.4 MPa, concentration ratio of propylene, ethylene and hydrogen in the reactor gas: 36.45% by volume / 60% by volume / 3 Polymerization was carried out for 1.5 hours under the condition of adding .55 volume% (propylene concentration / ethylene concentration / hydrogen concentration) and 0.023 as a molar ratio of triethylaluminum supplying oxygen as a deactivator. The discharged polymer component (component B) was 6.3 kg / hour, and the intrinsic viscosity [η] B of the obtained polymer component (component B) was 3.0 dL / g.
Table 1 shows the analysis results of each component of the produced polypropylene polymer.

Example 1
Hydrotalcite (DHT4C, manufactured by Kyowa Chemical Industry Co., Ltd.) 0.01 parts by weight, erucamide (Neutron-S, Nippon Seika Co., Ltd.) with respect to 100 parts by weight of the polypropylene copolymer (BCPP1) 0.10 parts by weight, Sumilizer GP (2,4,8,10-tetra-tert-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [ d, f] [1,3,2] dioxaphosphepine, manufactured by Sumitomo Chemical Co., Ltd.) 0.075 parts by weight, Sumilizer GS (2,4-di-t-amyl-6- [1- (3 , 5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd.) 0.075 parts by weight, 2,5-dimethyl-2,5-di (tarsha) as the organic peroxide Ributylperoxy) f Add 0.03 part by weight of sun, melt and knead at 250 ° C. using a 40 mm single screw extruder (VS40-28 type, Tanabe Plastics Machine Co., Ltd., with full flight type screw), MFR = 6.5 A polypropylene resin composition (g / 10 min) was obtained.
The obtained polypropylene resin composition was melt-extruded at a resin temperature of 250 ° C. using a 50 mmT die film forming apparatus (V-50-F600 type film forming apparatus manufactured by Tanabe Plastics Co., Ltd., with a 400 mm wide T die). went. The melt-extruded product was cooled with a cooling roll through which cooling water of 50 ° C. was passed to obtain a film having a thickness of 30 μm. The properties of the obtained film are shown in Table 3.

Comparative Example 1
MFR = 7.8 (g) by the same method as in Example 1 except that BCPP2 described in Reference Example 2 was used as the polypropylene copolymer and the amount of the organic peroxide was 0.037 parts by weight. / 10 minutes) of the polypropylene resin composition.
The obtained polypropylene resin composition was extruded in the same manner as in Example 1 to obtain a film. The properties of the obtained film are shown in Table 3.

Comparative Example 2
Sumikacene F102-0 (manufactured by Sumitomo Chemical Co., Ltd., density = 0.922 g / cm ³ , MFR = 0.4 g / 10 min) as an ethylene polymer with respect to 90% by weight of the polypropylene copolymer (BCPP2). 10% by weight was mixed uniformly. With respect to 100 parts by weight of the mixture, 0.01 parts by weight of hydrotalcite (DHT4C, manufactured by Kyowa Chemical Industry Co., Ltd.), erucic acid amide (Nutron-S, manufactured by Nippon Seika Co., Ltd.) 0.10 parts by weight Part, Sumilizer GP (2,4,8,10-tetra-tert-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [1 , 3,2] dioxaphosphepine (Sumitomo Chemical Co., Ltd.) 0.075 parts by weight, Sumilizer GS (2,4-di-t-amyl-6- [1- (3,5-di-t) -Amyl-2-hydroxyphenyl) ethyl] phenyl acrylate, manufactured by Sumitomo Chemical Co., Ltd.) 0.075 parts by weight, 2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexane as the organic peroxide Add 0.042 parts by weight Using a 40 mm single-screw extruder (VS40-28, manufactured by Tanabe Plastics Machinery Co., Ltd., with full flight screw), melt-kneaded at 250 ° C., and MFR = 5.8 (g / 10 min) polypropylene system A resin composition was obtained.
The obtained polypropylene resin composition was extruded in the same manner as in Example 1 to obtain a film. The properties of the obtained film are shown in Table 3.

Comparative Example 3
Propylene homopolymer portion having an intrinsic viscosity of 2.3 dL / g was produced in the first step using a Ziegler-Natta type catalyst, and then the intrinsic viscosity was 3.6 dL / g and the ethylene content was 37 in the second step. A polypropylene copolymer (BCPP3) was obtained by producing a copolymer part of propylene and ethylene by weight%. The content of the copolymer portion of propylene and ethylene was 16% by weight.
For 100 parts by weight of the obtained polypropylene copolymer (BCPP3), 0.01 parts by weight of hydrotalcite (DHT4C, manufactured by Kyowa Chemical Industry Co., Ltd.), erucic acid amide (Neutron-S, Nippon Seikai) 0.10 parts by weight, Sumitizer GP (2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5-t-butylphenyl) propoxy) ] Dibenzo [d, f] [1,3,2] dioxaphosphin, manufactured by Sumitomo Chemical Co., Ltd.) 0.075 parts by weight, Sumilizer GS (2,4-di-t-amyl-6- [1 -(3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate, manufactured by Sumitomo Chemical Co., Ltd.) 0.075 parts by weight, 2,5-dimethyl-2,5-as the organic peroxide Di (tertiary butyl peru Ii) Add 0.04 part by weight of hexane, melt and knead at 250 ° C. using a 40 mm single screw extruder (VS40-28 type, manufactured by Tanabe Plastics Machine Co., Ltd., with full flight type screw), MFR = 6 .8 (g / 10 min) of a polypropylene resin composition was obtained.
The obtained polypropylene resin composition was extruded in the same manner as in Example 1 to obtain a film. The properties of the obtained film are shown in Table 3.

Comparative Example 4
80% by weight of a polypropylene copolymer (BCPP3), and as an ethylene polymer, Sumikasen F411-0 (Sumitomo Chemical Co., Ltd., density = 0.925 g / cm ³ , MFR = 4.8 g / 10 min) 20 In the same manner as in Comparative Example 2 except that the amount of 2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexane was changed to 0.055 parts by weight, MFR = 7.3 A polypropylene resin composition (g / 10 min) was obtained.
The obtained polypropylene resin composition was extruded in the same manner as in Example 1 to obtain a film. The properties of the obtained film are shown in Table 3.

Comparative Example 5
Propylene homopolymer portion having an intrinsic viscosity of 2.8 dL / g was produced in the first step using a Ziegler-Natta type catalyst, and then in the second step, an intrinsic viscosity of 2.8 dL / g and an ethylene content of 36 A propylene copolymer (BCPP4) was obtained by producing a copolymer portion of propylene and ethylene by weight%. The content of the copolymer portion of propylene and ethylene was 21% by weight.
Sumicacene F218-0 (manufactured by Sumitomo Chemical Co., Ltd., density = 0.919 g / cm ³ , MFR = 0.9 g / m) as an ethylene polymer with respect to 95% by weight of the obtained propylene copolymer (BCPP4). 10 minutes) 5% by weight was uniformly mixed. With respect to 100 parts by weight of the mixture, 0.01 parts by weight of hydrotalcite (DHT4C, manufactured by Kyowa Chemical Industry Co., Ltd.), erucic acid amide (Nutron-S, manufactured by Nippon Seika Co., Ltd.) 0.10 parts by weight Part, Sumilizer GP (2,4,8,10-tetra-tert-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [1 , 3,2] dioxaphosphepine (Sumitomo Chemical Co., Ltd.) 0.075 parts by weight, Sumilizer GS (2,4-di-t-amyl-6- [1- (3,5-di-t) -Amyl-2-hydroxyphenyl) ethyl] phenyl acrylate, manufactured by Sumitomo Chemical Co., Ltd.) 0.075 parts by weight, 2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexane as the organic peroxide Add 0.050 parts by weight Using a 40 mm single-screw extruder (VS40-28, manufactured by Tanabe Plastics Machine Co., Ltd., with full flight screw), melt-kneaded at 250 ° C., and MFR = 5.9 (g / 10 min) polypropylene system A resin composition was obtained.
The obtained polypropylene resin composition was extruded in the same manner as in Example 1 to obtain a film. The properties of the obtained film are shown in Table 3.

Table 1

Table 2

Table 3

Claims (4)

Polymer component (component A) having a structural unit derived from propylene as a main component (component A) is 50 to 95% by weight, and the content (X) of the structural unit derived from propylene is 10 ≦ X <50% by weight. The content (Y) of the derived structural unit is 50 <Y ≦ 70% by weight, and the content (Z) of the structural unit derived from the α-olefin having 4 or more carbon atoms is 0 <Z ≦ 20% by weight. (However, the total of X, Y and Z is 100% by weight) The content of structural units derived from α-olefins having 4 or more carbon atoms (Z) relative to the content (X) of structural units derived from propylene (Z A polypropylene copolymer containing 5 to 50% by weight of a polymer component (component B) of propylene, ethylene and an α-olefin having 4 or more carbon atoms, wherein the weight ratio of Obtained by melt-kneading in the presence of Polypropylene resin composition characterized by flow rate is 5.0 g / 10 minutes or more. The polypropylene resin composition according to claim 1, wherein 0.001 to 5 parts by weight of an organic peroxide is added to 100 parts by weight of the polypropylene copolymer. The polypropylene resin composition according to claim 1 or 2, wherein the α-olefin having 4 or more carbon atoms is 1-butene. A matte film comprising the polypropylene resin composition according to any one of claims 1 to 3.