JP2002053710A - Resin composition for calender-molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for calender-molding friendly to the environment as less sticking and excellent in a soft property and transparency. SOLUTION: A resin composition for calender-molding comprises 1-99 mass % of propylene polymer [I] fulfilling the following (1) and (2): (1) a mesopentad fraction (mmmm) is 0.2-0.6; and (2) a racemic pentad fraction (rrrr) and (1-mmmm) fulfil the following relationship: [rrrr/(1-mmmm)]<=0.1, and 99-1 mass % of olefinic resin [II].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for calender molding and a molded article thereof, and more particularly, to a resin composition excellent in moldability, easy to recycle, and capable of containing hydrogen chloride gas or dioxin at the time of disposal or incineration. It is friendly to the global environment with less danger of poisonous gas and less sticky,
The present invention relates to a calender-forming resin composition that provides a molded article having excellent flexibility and transparency, and a molded article obtained by calendering the composition.

[0002]

2. Description of the Related Art Conventionally, molded articles obtained by a calendar molding method have been used as tapes, sheets, agricultural goods, home electric and OA equipment parts, automobile interior and exterior parts, housing and building material parts, medical supplies, food supplies, and packaging supplies. It is widely used in the form of film, leather, etc.

As these materials, soft vinyl chloride resins are widely used because of their excellent properties such as flexibility and deformation recovery. However, vinyl chloride resin is known to generate harmful substances such as hydrogen chloride gas and dioxin in the combustion process, and development of alternative resins is strongly desired. As an alternative resin, a molded product obtained by calender molding a resin composition comprising a specific α-olefin / polyene copolymer and an olefin polymer is disclosed (JP-A-5-202237). It was as high as 98 mol% and was inferior in flexibility. In recent years, olefin-based polymers produced using metallocene catalysts, for example, copolymers of ethylene and α-olefins have been proposed. However, when this copolymer is made soft, the disadvantage that sticky components increase. There is. Furthermore, there was a problem that transparency and surface characteristics were inferior, and it was not sufficient.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a calender-forming resin composition capable of forming a molded article which is friendly to the global environment, has low stickiness, and is excellent in flexibility and transparency, with good moldability. It is an object of the present invention to provide a molded product obtained by calender molding.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, it has been found that a composition comprising a specific propylene polymer and an olefin polymer can achieve the object. And completed the present invention. That is, the present invention provides the following calender molding resin composition and a molded article thereof.

[1] A propylene polymer [I] satisfying the following (1) and (2): 1 to 99% by mass, and (1) a mesopentad fraction (mmmm) of 0.2 to 0.
(2) The racemic pentad fraction (rrrr) and (1-mm
mm) that satisfies the following relationship: [rrrr / (1-mmmm)] ≦ 0.1 and 99 to 1% by mass of the olefin-based polymer [II].

[2] The resin composition for calender molding according to the above [1], wherein the propylene polymer [I] is a propylene polymer satisfying the following (3). (3) The intrinsic viscosity [η] measured at 135 ° C. in tetralin is 1.0 to 3.0 deciliter / g. [3] The propylene polymer [I] is a propylene polymer satisfying the following (4). A certain resin composition for calender molding according to the above [1] or [2]. (4) The component amount (W25) eluted at 25 ° C. or lower in the temperature raising chromatography is 20 to 100% by mass. [4] The propylene polymer [I] forms a crosslinked structure via two crosslinking groups. The calender-forming resin composition according to any one of the above [1] to [3], which is polymerized using a metallocene catalyst comprising a transition metal compound and a co-catalyst.

[5] A molded product obtained by calendering the calender-forming resin composition according to any one of the above [1] to [4].

[0009]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a propylene polymer [I] of 1 to 99% by mass and an olefin polymer [I].
I] A calender molding resin composition comprising 99 to 1% by mass and a molded article obtained by calender molding the calender molding resin composition.

Hereinafter, the resin composition for calender molding of the present invention and the molded article thereof will be described in detail. The specific propylene polymer [I] used in the resin composition for calender molding of the present invention is a propylene polymer satisfying the following (1) and (2). (1) The meso pentad fraction (mmmm) is 0.2 to 0.1.
(2) The racemic pentad fraction (rrrr) and (1-mm
mm) satisfies the following relationship: [rrrr / (1-mmmm)] ≦ 0.1 As the propylene polymer in the present invention, the above-mentioned (1)
And (2), but the mesopentad fraction (m
mmm) is preferably 0.3 to 0.6, and 0.4 to 0.5
Is more preferable, and the racemic pentad fraction (rrrr)
And (1-mmmm) preferably satisfy [rrrr / (1-mmmm)] ≦ 0.08, and [rrrr / (1-mmmm)] ≦ 0.0
6 is more preferable, and [rrrr / (1-m
mmm)] ≦ 0.05 is particularly preferred.

When the propylene polymer [I] satisfies the above relationship, the resulting molded article has an excellent balance between the amount of the sticky component, the low elastic modulus and the transparency. In other words, it has a low elastic modulus, is excellent in softness (also called flexibility), has few sticky components, and has excellent surface characteristics (e.g., represented by little transfer of sticky components to bleed and other products), and There is an advantage that transparency is also excellent.

If the propylene polymer has a mesopentad fraction (mmmm) of less than 0.2, it causes stickiness. If it exceeds 0.6, the elastic modulus increases, which is not preferable.
[Rrrr / (1-mmm) of the propylene polymer
m)] exceeds 0.1, causing stickiness.

The mesopentad fraction (mmmm fraction) used in the present invention refers to A. Zamberli (A. Za).
"Macromolecule"
s, 6, 925 (1973) ", and is a meso fraction in pentad units in a polypropylene molecular chain measured by a signal of a methyl group in a ¹³ C-NMR spectrum. When this is increased, it means that stereoregularity is increased. Similarly, the racemic pentad fraction (rrrr fraction) is a racemic fraction in pentad units in a polypropylene molecular chain. [Rrrr / (1
-Mmmm)] is an index obtained from the above-mentioned fraction in the pentad unit and representing the uniformity of the stereoregularity distribution of the propylene polymer. When this value is increased, the stereoregularity distribution is expanded, and a mixture of high stereoregularity PP and APP is obtained as in the case of conventional polypropylene produced using an existing catalyst system, meaning that stickiness increases and transparency decreases. I do. The measurement of the ¹³ C-NMR spectrum was performed by A.
"Macr" by A. Zambelli and others.
Omolecules, 8, 687 (1975) ", according to the following apparatus and conditions.

Apparatus: JNM-EX40 manufactured by JEOL Ltd.
Type 0 ¹³ C-NMR apparatus Method: Proton complete decoupling method Concentration: 220 mg / ml Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C. Pulse width: 45 ° Pulse repetition time: 4 seconds Integration: 10000 times In addition to the above requirements, the propylene polymer of the present invention has (3) an intrinsic viscosity [η] of 1.0 to 3.0 measured in tetralin at 135 ° C. It is preferably 0 deciliter / g. Among them, more preferably 1.0 to 2.5
It is deciliter / g, particularly preferably 1.2 to 2.2 deciliter / g. If the intrinsic viscosity [η] is less than 1.0 deciliter / g, stickiness may occur. If it exceeds 3.0 deciliters / g, the fluidity will be reduced, and the moldability may be poor.

Furthermore, in addition to the requirements of (1), (2) and (3), (4) 25
It is preferable that the component amount (W25) eluted at a temperature of not more than 20 ° C is 20 to 100% by mass, more preferably 30 to 100% by mass, particularly preferably 50 to 100% by mass, and 60 to 100% by mass.
100% by weight is most preferred. W25 refers to the T in the elution curve obtained by measuring the temperature, using the operating method, apparatus configuration, and measurement conditions described in Examples.
It is the amount (% by mass) of the component that is eluted without being adsorbed by the packing material at the REF column temperature of 25 ° C. W25 is an index indicating whether or not the propylene polymer is soft.
When this value is increased, it means that the component having a low elastic modulus is increased and / or the non-uniformity of the stereoregularity distribution is widened. In the present invention, W25 is 20%
If the amount is less than the above range, flexibility may be lost, which is not preferable.

The propylene polymer according to the present invention preferably further satisfies any of the following requirements. The molecular weight distribution (Mw / Mn) measured by the gel permeation (GPC) method is 4 or less, more preferably 3.5 or less, particularly preferably 3 or less. If the molecular weight distribution (Mw / Mn) exceeds 4, stickiness may occur. The above Mw / Mn is determined by gel permeation chromatography (GP) described in Examples.
C) It is determined by the method. When the melting endothermic amount ΔH by DSC measurement is 30 J / g or less, flexibility is excellent and preferable. ΔH is an index indicating whether the material is soft or not, and as this value increases, the elastic modulus increases,
It means that the softness is reduced. The melting point (Tm) and the crystallization temperature (Tc) may or may not be present, but it is preferable not to have a softness point or to have a low value, especially the Tm is 100 ° C. or less.
Note that ΔH, Tm, and Tc are D
Determined by SC measurement. The tensile modulus is preferably 100 MPa or less, more preferably 70 MPa or less.

The propylene polymer used in the present invention may be any one satisfying the above (1) and (2), and a comonomer other than propylene is preferably used in an amount of 2% by mass or less within a range not to impair the object of the present invention. It may be polymerized. Comonomer includes ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1
-Tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. In the present invention, one or more of these can be used.

The method for producing the propylene polymer [I] used in the present invention comprises the steps of (A) combining a transition metal compound forming a crosslinked structure via two crosslinking groups with (B) a cocatalyst. A method of polymerizing or copolymerizing propylene using the obtained metallocene catalyst is preferred. Specifically, the general formula (I)

[0019]

Embedded image

[Wherein, M is a member of Groups 3 to 10 of the periodic table or La
E represents a tanthanoid metal element ¹And E^TwoIs it
Substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, heterocyclopentadienyl group,
Telocyclopentadienyl group, amide group, phosphide
Ligand selected from the group consisting of a group, a hydrocarbon group and a silicon-containing group
And A¹And A^TwoTo form a crosslinked structure via
And they may be the same or different
X represents a σ-binding ligand, and when there are a plurality of Xs,
A plurality of X may be the same or different, and other X,
E¹, E^TwoAlternatively, it may be crosslinked with Y. Y is Lewis salt
A plurality of Y are the same or different
Other Y, E¹, E^TwoOr cross-linked with X
May be, A¹And A^TwoIs the two that binds the two ligands
A divalent crosslinking group, a hydrocarbon group having 1 to 20 carbon atoms,
A halogen-containing hydrocarbon group having a prime number of 1 to 20, a silicon-containing group,
Germanium-containing groups, tin-containing groups, -O-, -CO-,
-S-, -SO_Two-, -Se-, -NR¹-, -PR¹
-, -P (O) R¹-, -BR¹-Or-AlR¹-
And R¹Is a hydrogen atom, a halogen atom, a carbon number of 1 to 20
A hydrocarbon group or a halogen-containing hydrocarbon having 1 to 20 carbon atoms
Denote radicals, which may be the same or different
Good. q is an integer of 1 to 5 and represents ((valence of M) -2).
And r represents an integer of 0 to 3. And a transition metal compound (A) represented by the following formula:
Reacts with transition metal compounds or their derivatives to form ionic complexes
(B-1) capable of forming a body and aluminoxane
Weight containing the co-catalyst component (B) selected from (B-2)
Polymerize or copolymerize propylene in the presence of a combined catalyst
Method.

Specific examples of the transition metal compound represented by the general formula (I) include (1,2′-dimethylsilylene)
(2,1′-dimethylsilylene) bis (3-n-butylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium Dichloride, (1,2′-dimethylsilylene) (2,
1′-dimethylsilylene) bis (3-phenylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,5
-Benzoindenyl) zirconium dichloride, (1,
2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4-isopropylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2
1′-dimethylsilylene) bis (5,6-dimethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,7-di-i-propylindenyl) ) Zirconium dichloride, (1,2′-dimethylsilylene) (2,
1'-dimethylsilylene) bis (4-phenylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-methyl-4-i-propylindenyl) zirconium Dichloride, (1,2'-dimethylsilylene) (2,1'-
Dimethylsilylene) bis (5,6-benzoindenyl)
Zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis ( 3-
Methylindenyl) zirconium dichloride, (1,
2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-i-propylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2
1'-isopropylidene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride , Etc. and those obtained by substituting zirconium in these compounds with titanium or hafnium.

Next, the component (B-1) of the component (B) includes triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, Examples thereof include methyl tetraphenylborate (tri-n-butyl) ammonium and benzyltetraphenylborate (tri-n-butyl) ammonium.

(B-1) may be used alone or in a combination of two or more. On the other hand, as the aluminoxane of the component (B-2), methylaluminoxane,
Ethyl aluminoxane, isobutyl aluminoxane and the like can be mentioned. These aluminoxanes may be used alone or in a combination of two or more.

As the polymerization catalyst, an organoaluminum compound can be used as the component (C) in addition to the components (A) and (B). Here, as the organoaluminum compound of the component (C), trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride,
Examples include methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, and ethylaluminum sesquichloride.

These organoaluminum compounds may be used alone or in combination of two or more. Here, in the polymerization of propylene, at least one of the catalyst components can be used by being supported on a suitable carrier.

The polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, and a suspension polymerization method may be used. Legitization is particularly preferred.

The polymerization temperature is usually -100 to 250 ° C., and the ratio of the catalyst to the reaction raw material is preferably raw material monomer / component (A) (molar ratio) of preferably 1 to 10 ⁸ , more preferably 1 to 10 ⁸ .
It is preferable to be 00-10 ^5. Further, the polymerization time is usually from 5 minutes to 10 hours, and the reaction pressure is usually from normal pressure to 20M.
Pa (gage).

Examples of the olefin polymer [II] used in the resin composition for calender molding of the present invention include polypropylene, propylene-ethylene copolymer, propylene-ethylene-diene copolymer, polyethylene, ethylene / α-olefin. Copolymers, ethylene-vinyl acetate copolymers, hydrogenated styrene-based elastomers and the like can be mentioned.

The resin composition for calender molding of the present invention comprises:
It is composed of 1 to 99% by mass of the propylene polymer [I] and 99 to 1% by mass of the olefin polymer [II]. Preferably, it comprises 10 to 80% by mass of the propylene polymer [I] and 90 to 20% by mass of the olefin polymer [II].
More preferably, the propylene polymer [I] 25 to
75% by mass and 75 to 25% by mass of the olefin polymer [II]. Particularly preferably, 40 to 75% by mass of the propylene polymer [I] and the olefin polymer [II]
It consists of 60-25 mass%. (Manufacturing method of the resin composition for calender molding) The resin composition for calender molding of the present invention comprises 1 to 99% by mass of the propylene polymer [I] and the olefin polymer [II] 9.
9-1% by mass, and various additives used as desired are dry-blended using a Henschel mixer or the like,
It is melt-kneaded with a single-screw or twin-screw extruder, a Banbury mixer or the like. Various additives used as desired include softeners, inorganic fillers, pigments, foaming agents,
Flame retardants and the like. 2. Molded body The molded body of the present invention is a molded body obtained by calendering the above-described resin composition for calendering. In general, calendering is a molding method in which a softened resin is rolled between two or more rolls to form a film-shaped or sheet-shaped molded body having a certain thickness. As the calender molding method, a conventionally known apparatus and molding conditions can be adopted. For example, as a device for calendering, a serial type, an L type, an inverted L type, a Z type and the like can be mentioned. The molding conditions include a resin temperature of 80 ° C to 300 ° C, and the molded article of the present invention preferably has a resin temperature of 100 ° C to 300 ° C, more preferably 120 ° C to 28 ° C.
It is preferable that it is calendered at 0 ° C.

In molding, a film, paper, or cloth is fed to produce artificial leather, waterproof cloth, or various laminated products. The molded article of the present invention is not particularly limited, but may be a film, a sheet, specifically, artificial leather or a waterproof cloth, various laminated products, or an automobile part (interior material, etc.), a home appliance (a refrigerator lining, etc.), or the like. Is mentioned.

The molded article of the present invention is characterized in that it is easy to recycle, has little risk of generating toxic gases and the like at the time of disposal and incineration, and is friendly to the global environment. In addition, it has softness (also called flexibility), high elastic recovery (property to return to the original state even when pulled), and has softness, that is, low stickiness but low transparency and excellent transparency. There are features.

[0032]

[Production of propylene polymer (P1)]

(1) Synthesis of complex Synthesis of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride (1,2′-dimethylsilylene) in a Schlenk bottle (2,
3.0 g (6.97 mmol) of lithium salt of 1′-dimethylsilylene) -bis (indene) was added to 50 mL of THF.
And cooled to -78 ° C. 2.1 mL (14.2 mmol) of iodomethyltrimethylsilane is slowly added dropwise and stirred at room temperature for 12 hours. The solvent is distilled off and ether 5
Add 0 mL and wash with saturated ammonium chloride solution.
After liquid separation, the organic phase was dried and the solvent was removed to give (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) in 3.04.
g (5.88 mmol) were obtained. (Yield: 84%) Next, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) obtained above was placed in a Schlenk bottle under a nitrogen stream. .04 g (5.88 mmol) and ether 5
Add 0 mL. After cooling to −78 ° C., 7.6 mL (11.7 mmol) of n-BuLi (hexane solution 1.54 M) was added.
l) After addition, stir at room temperature for 12 hours. The solvent was distilled off, and the obtained solid was washed with 40 mL of hexane to obtain 3.06 g of a lithium salt as an ether adduct.
(5.07 mmol) was obtained. (Yield 73%) The result of measurement by ¹ H-NMR (90 MHz, THF-d ₈ ) is: δ 0.04 (s, 18H, trimethylsilyl), 0.48 (s, 12H, dimethylsilylene), 1 .10 (t, 6H, methyl), 2.59 (s,
4H, methylene), 3.38 (q, 4H, methylene),
6.2-7.7 (m, 8H, Ar-H).

The lithium salt obtained above is dissolved in 50 mL of toluene under a nitrogen stream. 1.2 g of zirconium tetrachloride cooled to −78 ° C. and previously cooled to −78 ° C.
A suspension of (5.1 mmol) in toluene (20 mL) is added dropwise. After the addition, the mixture is stirred at room temperature for 6 hours. The solvent of the reaction solution is distilled off. The obtained residue was recrystallized from dichloromethane to give 0.9 g of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride (1. 33 mmol) were obtained. (Yield 2
6%) ¹ H-NMR (90 MHz, CDCl ₃ ) gives the following results: δ 0.0 (s, 18H, trimethylsilyl), 1.02, 1.12 (s, 12H, dimethylsilylene), 2. 51 (dd, 4H, methylene), 7.1-
7.6 (m, 8H, Ar-H). (2) Polymerization of propylene In a stainless steel autoclave with a stirrer and having an internal volume of 10 liters, 4 liters of n-heptane, 2 mmoles of triisobutylaluminum, and 2 mmoles of methylaluminoxane (manufactured by Albemarle Co.) were obtained as described above.
2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl)
2 micromoles of zirconium dichloride were charged sequentially. Next, after introducing 0.06 MPa (gauge) of hydrogen, propylene gas was introduced up to 0.8 MPa (gauge) at a total pressure while increasing the temperature to 60 ° C. During the polymerization, propylene was supplied by a pressure regulator so that the total pressure became 0.8 MPa (gauge). After conducting the polymerization at a polymerization temperature of 60 ° C. for 30 minutes, the contents were taken out and dried under reduced pressure to obtain a propylene polymer (P1). Table 1 shows the results obtained by the “method for evaluating resin properties of propylene polymer” shown below. "Method for Evaluating Resin Properties of Propylene Polymer" (1) Measurement of [η] It was measured at 135 ° C. in a tetralin solvent using a VMR-053 automatic viscometer manufactured by Rigo Co., Ltd. (2) Measurement of Pentad Fraction It was measured by the method described in the text of the specification. (3) Measurement of melt flow rate (MFR) 230 ° C., load 21.
Measured at 18N. (4) Measurement of molecular weight distribution (Mw / Mn) Mw / Mn was measured by an apparatus described below. GPC measuring device Column: TOSO GMHHR-H (S) HT Detector: RI detector for liquid chromatogram WATERS 150C Measurement conditions Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C. Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / milliliter Injection amount: 160 microliter Calibration curve: Universal Calibration Analysis program: HT-GPC (Ver. 1.0) (5) DSC measurement Differential scanning calorimeter (Perkin-Elmer, DSC) −
7) Using a 10 mg sample at 220 ° C. in a nitrogen atmosphere for 3
After melting for 1 minute, the peak top of the maximum peak of the crystallization exothermic curve obtained when the temperature was lowered to -40 ° C at 1 ° C / minute was defined as crystallization temperature: Tc. Furthermore, after holding at −40 ° C. for 3 minutes, the melting endotherm obtained by increasing the temperature at 10 ° C./min was defined as ΔH. In addition, the peak top of the maximum peak of the melting endothermic curve obtained at this time is defined as melting point:
Tm. (6) Elevated Temperature Separation Chromatograph The amount W25 (% by mass) of the component eluted without being adsorbed by the filler at the TREF column temperature of 25 ° C. in the elution curve was determined as follows. (A) Operation method A sample solution is introduced into a TREF column adjusted to a temperature of 135 ° C., and then gradually cooled to 0 ° C. at a rate of 5 ° C./hour, held for 30 minutes, and the sample is adsorbed on a filler. Thereafter, the column was heated at a rate of 40 ° C./hour to 135 columns.
The temperature was raised to ℃ to obtain an elution curve. (B) Apparatus configuration TREF column: Silica gel column (4.6φ x 150mm) manufactured by GL Sciences Flow cell: 1mm optical path length KBr cell manufactured by GL Sciences Pump: SSC-3100 pump manufactured by Senshu Kagaku Valve oven: GL Sciences Model 554 oven (high temperature type) TREF oven: GL Science's two-line temperature controller: Rigaku Corporation REX-C100 temperature controller Detector: Infrared detector for liquid chromatography FOXBORO's MIRAN 1A CVF 10-way valve : Barco electric valve loop: Barco 500 microliter loop (c) Measurement conditions Solvent: o-dichlorobenzene Sample concentration: 7.5 g / liter Injection volume: 500 microliter Pump flow rate: 2.0 ml / min Detection Wave number: 3. 1 μm Column filler: Chromosolve P (30-60 mesh) Column temperature distribution: within ± 0.2 ° C. [Example 1] The following additives are formulated into the propylene polymer (P1) obtained above, and the single-screw extrusion is performed. Machine (made by Tsukada Juki Seisakusho):
TLC (Model 35-20) for extrusion granulation to produce pellets. (Additive formulation)-Phenolic antioxidant: 500 ppm of Irganox 1010 manufactured by Ciba Specialty Chemicals Co.-Phosphorus antioxidant: 1,000 ppm of Irgafos 168 70% by mass of P1 pellets obtained above, Idemitsu Oil Chemical IDEMITSUPP F-704NP (hereinafter referred to as B
1) at a ratio of 30% by mass, and heated roll temperature = 180 ° C., cooled roll temperature = 60 by a rolling molding machine (3 inch two rolls manufactured by NISHIMURA).
The sheet was molded as a calender molded body at a molding temperature of 40 ° C. and a take-up speed of 40 m / min. Table 2 shows the results obtained by the “evaluation method for calender molded article” described below. "Evaluation method of calender molded body" (1) Tensile elastic modulus Measured by a tensile test based on JIS K 7127.

Crosshead speed: 50 mm / min Load cell: 100 kg Measurement direction: machine direction (MD direction) (2) Transparency The molded product was visually evaluated.

◎: extremely transparent, ：: transparent, Δ: slightly fogging, ×: severely fogging (3) Moldability Evaluation was made on the surface condition.

：: extremely smooth, ：: smooth, Δ: slightly shark skin, ×: severe shark skin (4) Stickiness The molded product was touched by hand and evaluated by its touch.

◎: No stickiness at all, ○: No stickiness, Δ: Severe stickiness, ×: Severe stickiness [Example 2] In Example 1, instead of (B1),
Idemitsu Petrochemical Idemitsusupp F-744N
The same operation as in Example 1 was performed except that P (hereinafter, also referred to as B2) was used, and the temperature of the heating roll was set to 160 ° C. Table 2 shows the obtained results. [Example 3] In Example 2, P1 pellets were mixed with 50 pellets.
The procedure was performed in the same manner as in Example 2 except that the amount was changed to 50% by mass and (B2) was changed to 50% by mass. Table 2 shows the obtained results. Example 4 In Example 1, the P1 pellets were
Mass%, and instead of (B1), an affinity PL1880 manufactured by Dow Chemical Japan (hereinafter, referred to as A1)
B3), and the heating roll temperature = 1
The procedure was performed in the same manner as in Example 1 except that the temperature was 30 ° C. Table 2 shows the obtained results. [Production of Propylene Polymer] (1) Preparation of Magnesium Compound A glass reactor with an internal volume of about 6 liters equipped with a stirrer was sufficiently replaced with nitrogen gas, and ethanol was added to the reactor.
30 g, 16 g of iodine and 160 g of metallic magnesium were charged, heated with stirring, and reacted under reflux conditions until hydrogen gas was not generated from the inside of the system to obtain a solid reaction product. The reaction solution containing the solid product was dried under reduced pressure to obtain a magnesium compound. (2) Preparation of solid catalyst component (A) 160 g of the magnesium compound (not pulverized) obtained in the above (1) and 80 ml of purified heptane were placed in a glass reactor having an internal volume of 5 liter which was sufficiently substituted with nitrogen gas. ,
After charging 24 ml of silicon tetrachloride and 23 ml of diethyl phthalate, maintaining the inside of the system at 80 ° C., adding 770 ml of titanium tetrachloride with stirring and reacting at 110 ° C. for 2 hours, the solid component was separated and purified heptane at 90 ° C. And washed. Further, 1220 ml of titanium tetrachloride was added, and 110
After reacting at 2 ° C. for 2 hours, it was sufficiently washed with purified heptane to obtain a solid catalyst component (A). (3) Gas phase polymerization of propylene In a polymerization tank having an internal volume of 200 liters, 6.0 g / h of the solid catalyst component obtained in the above (2), 0.2 mol / h of triisobutylaluminum (TIBA), 1-allyl −
0.014 mol / h of 3,4-dimethoxybenzene (ADMB), cyclohexylmethyldimethoxysilane (C
HMDMS) 0.012 mol / h, propylene 37k
g / hour, 70 ° C., 2.8 MPa (gaug
Polymerization was performed in e) to produce a propylene polymer. 2,5-dimethyl-2,2 was added to the obtained propylene powder.
5-Di- (t-butylperoxy) -hexane was mixed, the following additive formulation was performed, and the mixture was extruded and granulated with a single screw extruder (manufactured by Tsukada Juki Seisakusho Co., Ltd .: TLC 35-20). Pellets were produced. Obtained pellet (P2)
Table 1 shows the results obtained by the above “Method for evaluating resin properties of propylene polymer”. (Additive formulation) ・ Phenolic antioxidant: Ciba Specialty Chemicals Co., Ltd. Irganox 1010 1,000 ppm ・ Phosphorus antioxidant: P-EPQ 500 ppm ・ Neutralizer: calcium stearate: 500 ppm ・ Neutralizer : DHT-4A: 500 ppm [Comparative Example 1] In Example 1, the pellet of P1 was replaced with P2.
The procedure was performed in the same manner as in Example 1 except that the pellets were changed. Table 2 shows the obtained results. [Production of propylene polymer (P3)] 400 mL of heptane was placed in a stainless steel autoclave having an internal volume of 1 liter.
0.5 mmol of triisobutylaluminum, and
Dimethylanilinium (pentafluorophenyl) borate (2 μmol) and (tertiary butylamide) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) produced in the same manner as in Example 1 of JP-A-3-16388. A catalyst component obtained by pre-contacting 1 micromol of silane titanium dichloride in toluene for 5 minutes was added. Here, after introducing 0.03 MPa (gauge) of hydrogen,
Propylene gas was introduced up to 0.8 MPa (gauge) at a total pressure, and propylene was supplied by a pressure regulator so that the pressure during polymerization was constant. After polymerization was performed at a polymerization temperature of 70 ° C. for 1 hour, the content was taken out and dried under reduced pressure to obtain a propylene polymer (P3). "Evaluation method of resin properties of propylene polymer" was performed in the same manner as in Example 1, and the obtained results are shown in Table 1. Comparative Example 2 The same procedure as in Example 1 was carried out except that P1 in Example 1 was changed to the propylene polymer P3 obtained above. Table 2 shows the obtained results.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

According to the present invention, the moldability is excellent, the recycling is easy, the toxic gas and the like are not generated at the time of disposal or incineration, the environment is gentle, the stickiness is small, the flexibility and the transparency are low. Thus, a resin composition for calender molding excellent in heat resistance and a molded article obtained by calender molding the composition can be obtained.

Claims (5)

[Claims] 1. A propylene polymer [I] satisfying the following (1) and (2): 1 to 99% by mass, and (1) a mesopentad fraction (mmmm) of 0.2 to 0.
(2) The racemic pentad fraction (rrrr) and (1-mm
mm) that satisfies the following relationship: [rrrr / (1-mmmm)] ≦ 0.1 and 99 to 1% by mass of the olefin-based polymer [II]. 2. The propylene polymer [I] has the following (3)
The calender molding resin composition according to claim 1, which is a propylene polymer satisfying the following. (3) The intrinsic viscosity [η] measured in tetralin at 135 ° C. is 1.0 to 3.0 deciliter / g. 3. The propylene polymer [I] is represented by the following (4):
The resin composition for calendar molding according to claim 1 or 2, which is a propylene polymer satisfying the following. (4) The component amount (W25) eluted at 25 ° C. or lower in the temperature raising chromatography is 20 to 100% by mass. 4. The propylene polymer [I] is polymerized using a metallocene catalyst comprising a transition metal compound having a crosslinked structure via two crosslinking groups and a cocatalyst. 3. The resin composition for calendar molding according to any one of 3. 5. A molded product obtained by subjecting the resin composition for calender molding according to claim 1 to calender molding.