JP5015479B2 - Molded body made of propylene resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molded item such as a film, a sheet, a tube, a hose, an injection-molded article or a laminated product that is improved in stickiness, the change in external appearance with time and the like resulting from a propylene-based soft resin and is excellent in the balance among transparency, flexibility, heat resistance and the like. <P>SOLUTION: The molded item is composed of a resin composition that comprises a propylene-ethylene copolymer having an ethylene unit content of at most 20 mol% and an [EEE] triad chain fraction f<SB>EEE</SB>of at most 0.1 mol%, and gives fractionated components by the temperature-raising elution fractionation method (TREF) that satisfy the requirements below. The component 1 which is soluble at 0&deg;C accounts for 10-80 mass%; the component 2 which is eluted at a temperature higher than 0&deg;C and not higher than 70&deg;C accounts for 10-60 mass%; the component 3 which is eluted at a temperature higher than 70&deg;C and lower than 100&deg;C accounts for 5-50 mass%; and the component 4 which is eluted at a temperature of 100&deg;C or higher accounts for 0-30 mass%, provided that (the component 1)+(the component 2)+(the component 3)+(the component 4)=100 mass%. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention is a molded article having improved balance with transparency, flexibility, heat resistance, etc., in particular, a film, a sheet, a tube, The present invention relates to a molded body such as a hose, an injection molded product, and a laminate.

Conventionally, starting with environmental problems, propylene-based soft resins have been used in a wide range of fields, but as molded articles such as films, transparency, flexibility, low stickiness, heat resistance, etc. Therefore, there has been a demand for a molded article having a balance between these physical properties.
In recent years, with the rapid growth of electronic materials and optical materials, attempts have been made to apply polyolefin-based materials to protective films, process films, etc., but they are applied due to problems such as lack of gloss and transfer of sticky components. Was a difficult situation.

Conventional polypropylene-based soft resins having transparency (polyolefin-based thermoplastic elastomer (TPO)) control the stereoregularity of polypropylene or copolymerize propylene and α-olefin (for example, see Patent Document 1). Although manufactured, the molecular weight of the amorphous component (0 ° C. soluble component in the temperature rising elution fractionation method (TREF)) that exhibits flexibility is small, and the temporal change in transparency is large.
Further, a flexible polypropylene resin composed of an amorphous component and a crystalline component is known (for example, see Patent Document 2), but the elution temperature difference between the two components is large, and the molecular weight of the amorphous component is equal to the molecular weight of the crystalline component. Since it is equivalent or small, the change with time of transparency is large.
A polypropylene resin composed only of a low crystal component is also known. However, sufficient flexibility cannot be obtained by itself, and there is stickiness, which is not satisfactory as a flexible material.

JP-A-5-9214 Japanese Patent Laid-Open No. 9-309982

  The present invention has been made in view of the above circumstances, and has improved stickiness derived from a propylene-based soft resin, improved appearance over time, and the like, and a film and sheet excellent in balance of transparency, flexibility, heat resistance, etc. It aims at providing molded bodies, such as a tube, a hose, an injection molded product, and a laminated body.

As a result of intensive investigations to achieve the above object, the present inventors have found that a molded article comprising a resin composition containing a propylene-ethylene copolymer satisfying specific requirements and satisfying specific requirements is national. It was found that it can be adapted.
The present invention has been completed based on such findings.

That is, the present invention
1. It contains a propylene-ethylene copolymer having an ethylene unit content of 20 mol% or less and a triad chain fraction f _{EEE of} [EEE] of 0.1 mol% or less, and is fractionated by a temperature rising elution fractionation method (TREF). The molded object which consists of a resin composition in which the component to satisfy the following requirements.
Component 1: 10-80% by mass of soluble component at 0 ° C.
Component 2: 10-60 mass% of elution component exceeding 0 degreeC and 70 degrees C or less
Component 3: 5-50 mass% of elution components exceeding 70 degreeC and less than 100 degreeC
Ingredient 4: 0 to 30% by mass of eluted component at 100 ° C. or higher
However, it is the component 1 + component 2 + component 3 + component 4 = 100 mass%.
2. The intrinsic viscosity [η] measured in decalin at a temperature of 135 ° C. for the components fractionated by the temperature rising elution fractionation method (TREF) satisfies component 1 ≧ component 2> component 3, and the intrinsic viscosity of component 3 [ η] is a molded article according to the above 1, comprising a resin composition exceeding 0.6 deciliter / g,
3. The molded article according to 1 or 2 above, wherein the molded article is selected from a film, a sheet, a tube, a hose, an injection molded product, and a laminate.

According to the present invention, films, sheets, tubes, and hoses having excellent flexibility, transparency, and high glossiness that are remarkably improved in stickiness, change in appearance over time, peeling whitening, etc., and retain the initial surface state. In addition, molded articles such as injection molded articles and laminates are obtained.
In addition, since the transition of the amorphous component to the surface of the molded body is slow, the effect of adding surface characteristic expression additives such as antistatic agents and antifogging agents is enhanced.

The propylene-ethylene copolymer of the present invention will be described.
In addition, the measuring method of each characteristic is mentioned later.
First, the ethylene unit content in the copolymer is 20 mol% or less.
The ethylene unit content is preferably 1 to 15 mol%, more preferably 3 to 12 mol%.
When it is 20 mol% or less, heat resistance and transparency are sufficient.
Further, the triad chain fraction f _{EEE of the} copolymer [EEE] is 0.1 (mol%) or less.
f _EEE is preferably 0.08 mol% or less, and more preferably 0.05 mol% or less.
When the _fEEE is 0.1 mol% or less, the transparency is improved.
Since f _EEE increases when manufactured using an Mg / Ti-based catalyst, it is preferable to use the catalyst system of the present invention to be described later in order to make it 0.1 mol% or less.

The ethylene unit content and f _EEE in the copolymer can be determined as follows.
In the propylene (P) -ethylene (E) copolymer of the present invention, the following three chains are represented by A. According to the assignment of the ¹³ C-NMR peak proposed by “Zambelli et al.,“ Macromolecules, 8 , 687 (1975) ”, it can be calculated by the following formula.
EPE = I _{8
PPE = I 9 + (I 10} /2) + I 11
EEE = (EEE / 2) + (PEE / 4) = (I 12/2) + (I 13/4)
_{PPP = I 14 + (I 10} /2)
PEE = I ₁₅
PEP = I ₁₆ + (I ₁₇ + I ₁₈ ) / 4
Here, I ₈ = 33.3 ppm intensity, I ₉ = 31.1 ppm intensity, I ₁₀ = 31.2 ppm intensity, I ₁₁ = 34.1 ppm intensity, I ₁₂ = 30.0 ppm intensity, I ₁₃ = 30.4 ppm intensity, I ₁₄ = 29.2 ppm intensity, I ₁₅ = 27.3 ppm intensity, I ₁₆ = 24.7 ppm intensity, I ₁₇ = 34.9 ppm intensity, I ₁₈ = 34.6 ppm intensity It is strength.
When T = EPE + PPE + EEE + PPP + PEE + PEP, each triad chain fraction (mol%) can be calculated by the following equation.
f _EPE = (EPE / T) x 100
f _PPE = (PPE / T) × 100
f _EEE = (EEE / T) x 100
f _PPP = (PPP / T) × 100
f _PEE = (PEE / T) × 100
f _PEP = (PEP / T) × 100

The dyad chain fraction can be calculated from the above triad chain fraction by the following formula.
f _PP = f _PPP + [f _PPE / 2]
f _PE = f _EPE + f _PEP + [(f _PPE + f _PEE ) / 2]
f _EE = f _EEE + [f _PEE / 2]
The ethylene unit content (mol%) can be calculated by the following formula.
Ethylene unit content (mol%) = f _EE + (f _PE / 2)
[Measurement of ¹³ C-NMR]
220 mg of a sample is taken into a 10 mm diameter NMR sample tube, and 3 mL of 1,2,4-trichlorobenzene / heavy benzene (90/10 vol%) mixed solvent is added.
A ¹³ C-NMR spectrum is measured after uniformly dissolving at 140 ° C. using an aluminum block heater.
The NMR measurement conditions are as follows.
NMR device JEOL EX400 (400MHz NMR device)
Pulse width 7.5μs (45 degree pulse)
Pulse repetition time 4 seconds Integration count 1,000 times Measurement temperature 130 ° C

（式中、Ｅ¹は二つの共役五員環配位子を架橋する結合性基を示す。Ｒ¹及びＲ²は、それぞれ炭化水素基、ハロゲン原子、アルコキシ基、珪素含有炭化水素基、リン含有炭化水素基、窒素含有炭化水素基又は硼素含有炭化水素基を示し、Ｒ³〜Ｒ⁶は、それぞれ水素、炭化水素基、ハロゲン原子、アルコキシ基、珪素含有炭化水素基、リン含有炭化水素基、窒素含有炭化水素基又は硼素含有炭化水素基を示す。Ｍ¹は周期律表４〜６族の遷移金属を示す。また、Ｘ¹，Ｙ¹はそれぞれ共有結合性の配位子を示す。尚、Ｘ¹及びＹ¹は、それぞれ互いに結合して環構造を形成してもよい。）
で表わされる遷移金属化合物が挙げられる。
Ｒ¹〜Ｒ⁶の炭化水素基としては、炭素数１〜２０のものが好ましく、特に炭素数１〜１２のものが好ましい。
この炭化水素基は一価の基として、共役五員環基であるシクロペンタジエニル基と結合していてもよく、又、これが複数個存在する場合には、Ｒ¹、Ｒ³、Ｒ⁴のうちの２個又はＲ²、Ｒ⁵、Ｒ⁶のうちの２個が結合していてもよい。
該共役五員環としては、置換又は非置換のシクロペンタジエニル基、インデニル基及びフルオレニル基である。
ハロゲン原子としては、塩素、臭素、ヨウ素及びフッ素原子が挙げられ、アルコキシ基としては、炭素数１〜１２のものが好ましく挙げられる。
Ｅ¹としては、（１）メチレン基、エチレン基、イソプロピレン基、メチルフェニルメチレン基、ジフェニルメチレン基、シクロヘキシレン基等の炭素数１〜４のアルキレン基、シクロアルキレン基又はその側鎖低級アルキル若しくはフェニル置換体、（２）シリレン基、ジメチルシリレン基、メチルフェニレン基、ジフェニルシリレン基、ジシリレン基、テトラメチルジシリレン基等のシリレン基、オリゴシリレン基又はその側鎖低級アルキル若しくはフェニル置換体、（３）ゲルマニウム、リン、窒素、硼素又はアルミニウムを含む炭化水素基［低級アルキル基、フェニル基、ヒドロカルビルオキシ基（好ましくは低級アルコキシ基）等］、具体的には（ＣＨ₃）₂Ｇｅ基、（Ｃ₆Ｈ₅）₂Ｇｅ基、（ＣＨ₃）Ｐ基、（Ｃ₆Ｈ₅）Ｐ基、（Ｃ₄Ｈ₉）Ｎ基、（Ｃ₆Ｈ₅）Ｎ基、（ＣＨ₃）Ｂ基、（Ｃ₄Ｈ₉）Ｂ基、（Ｃ₆Ｈ₅）Ｂ基、（Ｃ₆Ｈ₅）Ａｌ基、（ＣＨ₃Ｏ）Ａｌ基等が挙げられる。
これらの中で、アルキレン基、シリレン基が好ましい。
Ｍ¹は、周期律表４〜６族の遷移金属を示し、具体的には、チタニウム、ジルコニウム、ハフニウム、ニオブ、モリブデン、タングステン等を挙げることができるが、これらの中でチタニウム、ジルコニウム及びハフニウムが好ましく、特にジルコニウムが好適である。
Ｘ¹及びＹ¹は、それぞれ共有結合性の配位子であり、具体的には、水素原子、ハロゲン原子、炭素数１〜２０、好ましくは１〜１０の炭化水素基、炭素数１〜２０、好ましくは１〜１０のアルコキシ基、アミノ基、炭素数１〜２０、好ましくは１〜１２のリン含有炭化水素基（例えば、ジフェニルホスフィン基等）又は炭素数１〜２０、好ましくは１〜１２の珪素含有炭化水素基（例えば、トリメチルシリル基等）、炭素数１〜２０、好ましくは１〜１２の炭化水素基又はハロゲン含有硼素化合物（例えば、ＢＦ₄，Ｂ（Ｃ₆Ｈ₅）₄）を示す。
これらの中で、ハロゲン原子及び炭化水素基が好ましい。
このＸ¹及びＹ¹は互いに同一であっても異なっていてもよい。 Although there is no restriction | limiting in the manufacturing method of the propylene-ethylene copolymer which concerns on this invention, The mixture of the metallocene catalyst which gives (1) high crystalline polypropylene as a main catalyst component, and (2) the metallocene catalyst which gives low crystalline polypropylene, It is preferable to use a combination of (3) promoter component and (4) porous carrier.
Examples of the metallocene catalyst that gives one of the main catalyst components (1) highly crystalline polypropylene include a mono-bridged metallocene catalyst.
As the mono-bridged metallocene catalyst, the general formula (I)

(In the formula, E ¹ represents a bonding group that bridges two conjugated five-membered ring ligands. R ¹ and R ² are each a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, phosphorus -Containing hydrocarbon group, nitrogen-containing hydrocarbon group or boron-containing hydrocarbon group, wherein R ^{3 to} R ⁶ are hydrogen, hydrocarbon group, halogen atom, alkoxy group, silicon-containing hydrocarbon group, phosphorus-containing hydrocarbon group, respectively. Represents a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group, M ¹ represents a transition metal of Groups 4 to 6 in the periodic table, and X ¹ and Y ¹ each represents a covalent bond ligand. X ¹ and Y ¹ may be bonded to each other to form a ring structure.)
The transition metal compound represented by these is mentioned.
Examples of the hydrocarbon group R ¹ to R ^6, preferably those having 1 to 20 carbon atoms, particularly preferably from 1 to 12 carbon atoms.
This hydrocarbon group may be bonded as a monovalent group to a cyclopentadienyl group which is a conjugated five-membered cyclic group, and when there are a plurality of these, R ¹ , R ³ , R ⁴ Or ^two of R ² , R ⁵ and R ⁶ may be bonded.
The conjugated five-membered ring includes a substituted or unsubstituted cyclopentadienyl group, indenyl group and fluorenyl group.
Examples of the halogen atom include chlorine, bromine, iodine and fluorine atoms, and examples of the alkoxy group preferably include those having 1 to 12 carbon atoms.
E ¹ includes (1) an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, an isopropylene group, a methylphenylmethylene group, a diphenylmethylene group, and a cyclohexylene group, a cycloalkylene group, or a side chain lower alkyl thereof. Or a phenyl-substituted product, (2) a silylene group such as a silylene group, a dimethylsilylene group, a methylphenylene group, a diphenylsilylene group, a disilylene group, or a tetramethyldisylylene group, an oligosilylene group, or a side chain lower alkyl or phenyl-substituted product, (3) a hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum [lower alkyl group, phenyl group, hydrocarbyloxy group (preferably lower alkoxy group) and the like], specifically, (CH ₃ ) ₂ Ge group, (C ₆ H _{5) 2} Ge group, (CH ₃₎ P group, (C ₆ H ₅₎ P group, C ₄ H ₉₎ N group, (C ₆ H ₅₎ N group, (CH ₃₎ B group, (C ₄ H ₉₎ B group, (C ₆ H ₅₎ B group, (C ₆ H ₅₎ Al group , (CH ₃ O) Al group, and the like.
Among these, an alkylene group and a silylene group are preferable.
M ¹ represents a transition metal of groups 4 to 6 of the periodic table, and specific examples include titanium, zirconium, hafnium, niobium, molybdenum, tungsten, etc. Among these, titanium, zirconium, and hafnium Is preferable, and zirconium is particularly preferable.
X ¹ and Y ¹ are each a covalently bonded ligand, specifically, a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 10 carbon atoms, or 1 to 20 carbon atoms. , Preferably an alkoxy group having 1 to 10 carbon atoms, an amino group, 1 to 20 carbon atoms, preferably a phosphorus-containing hydrocarbon group having 1 to 12 carbon atoms (such as a diphenylphosphine group), or 1 to 20 carbon atoms, preferably 1 to 12 A silicon-containing hydrocarbon group (for example, trimethylsilyl group), a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, or a halogen-containing boron compound (for example, BF ₄ , B (C ₆ H ₅ ) ₄ ) Show.
Among these, a halogen atom and a hydrocarbon group are preferable.
X ¹ and Y ¹ may be the same as or different from each other.

Specific examples of the transition metal compound represented by the general formula (I) include the following compounds.
(A) Methylenebis (indenyl) titanium dichloride, ethylenebis (indenyl) titanium dichloride, methylenebis (indenyl) titanium chlorohydride, ethylenebis (indenyl) methyltitanium chloride, ethylenebis (indenyl) methoxychlorotitanium, ethylenebis (indenyl) titanium Diethoxide, ethylenebis (indenyl) dimethyltitanium, ethylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride, ethylenebis (2-methylindenyl) titanium dichloride, ethylenebis (2,4,7 -Trimethylindenyl) titanium dichloride, ethylenebis (2-methyl-4,5-benzoindenyl) titanium dichloride, ethylenebis (2-methyl-4-phenyl) Ruindenyl) titanium dichloride, ethylenebis (2-methyl-4,5,6,7-tetramethylindenyl) titanium dichloride, ethylenebis (2-methyl-5,6-dimethylindenyl) titanium dichloride, ethylenebis (2 -Methyl-4- (1-naphthyl) indenyl) titanium dichloride, ethylenebis (2-methyl-4- (2-naphthyl) indenyl) titanium dichloride, ethylenebis (2-methyl-4-i-propylindenyl) titanium Dichloride, ethylenebis (2-ethyl-4-phenylindenyl) titanium dichloride, ethylenebis (2-methyl-4-tolylindenyl) titanium dichloride, ethylenebis (2,4-dimethylindenyl) titanium dichloride, ethylenebis (2-me Ru-4-trimethylsilylindenyl) titanium dichloride, ethylenebis (2,4-dimethyl-5,6,7-trihydroindenyl) titanium dichloride, ethylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) titanium dichloride, ethylene (2-methyl-4-t-butylcyclopentadienyl) (3′-t-butyl-5′-methylcyclopentadienyl) titanium dichloride, ethylene ( 2,3,5-trimethylcyclopentadienyl) (2 ′, 4 ′, 5′-trimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2-methylindenyl) titanium dichloride, isopropylidenebis (indenyl) Titanium dichloride, isopropylidenebis (2,4- Methylindenyl) titanium dichloride, isopropylidene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) titanium dichloride, isopropylidene (2-methyl-4-t-butylcyclopenta Dienyl) (3′-t-butyl-5′-methylcyclopentadienyl) titanium dichloride, ethylenebis (2-methylbenzoindenyl) titanium dichloride, ethylenebis (benzoindenyl) titanium dichloride, etc. A transition metal compound having two bridged conjugated five-membered ring ligands,
(B) Dimethylsilylenebis (indenyl) titanium dichloride, dimethylsilylenebis (indenyl) methyltitanium chloride, dimethylsilylenebis (indenyl) methoxychlorotitanium, dimethylsilylenebis (indenyl) titanium diethoxide, dimethylsilylenebis (indenyl) Dimethyltitanium, dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride, dimethylsilylenebis (2-methylindenyl) titanium dichloride, dimethylsilylenebis (2,4,7-trimethylindenyl) titanium Dichloride, dimethylsilylenebis (2-methyl-4,5-benzoindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) titani Mudichloride, dimethylsilylenebis (2-methyl-4,5,6,7-tetramethylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-5,6-dimethylindenyl) titanium dichloride, dimethylsilylenebis (2 -Methyl-4- (1-naphthyl) indenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4- (2-naphthyl) indenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-i-propylindenyl) ) Titanium dichloride, dimethylsilylenebis (2-ethyl-4-phenylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-toluylin) Nyl) titanium dichloride, dimethylsilylenebis (2,4-dimethylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-trimethylsilylindenyl) titanium dichloride, dimethyldimethylenebis (2,4-dimethyl-5,6) , 7-trihydroindenyl) titanium dichloride, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylene (2-methyl-4-t) -Butylcyclopentadienyl) (3'-t-butyl-5'-methylcyclopentadienyl) titanium dichloride, dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5 '-Trimethylcyclopentadienyl) titanium di Loride, isopropylidenebis (2-methylindenyl) titanium dichloride, isopropylidenebis (indenyl) titanium dichloride, isopropylidenebis (2,4-dimethylindenyl) titanium dichloride, isopropylidene (2,4-dimethylcyclopentadidi) Enyl) (3 ′, 5′-dimethylcyclopentadienyl) titanium dichloride, isopropylidene (2-methyl-4-t-butylcyclopentadienyl) (3′-t-butyl-5′-methylcyclopentadiene) Transition metal compounds having two silylene group-bridged conjugated five-membered ring ligands such as enyl) titanium dichloride, dimethylsilylenebis (2-methylbenzoindenyl) titanium dichloride, dimethylsilylenebis (benzoindenyl) titanium dichloride,
Further, in the compounds described in the above (a) to (b), those in which the chlorine atom of these compounds is replaced by a bromine atom, an iodine atom, a methyl atom, a phenyl atom or the like, or the central metal of the transition metal compound Can be mentioned in which titanium is replaced with zirconium, hafnium, niobium, tungsten or the like.

（式中、Ｅ²及びＥ³は二つの共役五員環配位子を架橋する結合性基を示す。Ｒ⁹〜Ｒ¹⁸は、それぞれ水素、炭化水素基、ハロゲン原子、アルコキシ基、珪素含有炭化水素基、リン含有炭化水素基、窒素含有炭化水素基又は硼素含有炭化水素基を示し、Ｒ⁷、Ｒ⁸、Ｒ¹⁹及びＲ²⁰は、それぞれ炭化水素基、ハロゲン原子、アルコキシ基、珪素含有炭化水素基、リン含有炭化水素基、窒素含有炭化水素基又は硼素含有炭化水素基を示す。Ｍ²は周期律表４〜６族の遷移金属を示す。また、Ｘ²，Ｙ²はそれぞれ共有結合性の配位子を示す。尚、Ｘ²及びＹ²は、それぞれ互いに結合して環構造を形成してもよい。）
で表わされる遷移金属化合物が挙げられる。
Ｒ⁷〜Ｒ²⁰の炭化水素基としては、炭素数１〜２０のものが好ましく、特に炭素数１〜１２のものが好ましい。
この炭化水素基は一価の基として、共役五員環基であるシクロペンタジエニル基と結合していてもよく、又、これが複数個存在する場合には、一般式（II）式においては、Ｒ⁷とＲ⁹が、又はＲ⁸とＲ¹⁰が結合していてもよく、一般式（III）においては、Ｒ¹¹〜Ｒ¹⁴及びＲ²⁰のうちの２個が、又はＲ¹⁵〜Ｒ¹⁹のうちの２個が結合していてもよい。
該共役五員環としては、置換又は非置換のシクロペンタジエニル基、インデニル基及びフルオレニル基である。
ハロゲン原子としては、塩素、臭素、ヨウ素及びフッ素原子が挙げられ、アルコキシ基としては、炭素数１〜１２のものが好ましく挙げられる。
このＥ²及びＥ³としては、（１）メチレン基、エチレン基、イソプロピレン基、メチルフェニルメチレン基、ジフェニルメチレン基、シクロヘキシレン基等の炭素数１〜４のアルキレン基、シクロアルキレン基又はその側鎖低級アルキル若しくはフェニル置換体、（２）シリレン基、ジメチルシリレン基、メチルフェニレン基、ジフェニルシリレン基、ジシリレン基、テトラメチルジシリレン基等のシリレン基、オリゴシリレン基又はその側鎖低級アルキル若しくはフェニル置換体、（３）ゲルマニウム、リン、窒素、硼素又はアルミニウムを含む炭化水素基［低級アルキル基、フェニル基、ヒドロカルビルオキシ基（好ましくは低級アルコキシ基）等］、具体的には、（ＣＨ₃）₂Ｇｅ基、（Ｃ₆Ｈ₅）₂Ｇｅ基、（ＣＨ₃）Ｐ基、（Ｃ₆Ｈ₅）Ｐ基、（Ｃ₄Ｈ₉）Ｎ基、（Ｃ₆Ｈ₅）Ｎ基、（ＣＨ₃）Ｂ基、（Ｃ₄Ｈ₉）Ｂ基、（Ｃ₆Ｈ₅）Ｂ基、（Ｃ₆Ｈ₅）Ａｌ基、（ＣＨ₃Ｏ）Ａｌ基等が挙げられる。
これらの中で、アルキレン基、シリレン基が好ましい。
Ｅ²及びＥ³は互いに同じでも異なっていてもよい。
Ｍ²は、周期律表４〜６族の遷移金属を示し、具体的には、チタニウム、ジルコニウム、ハフニウム、ニオブ、モリブデン、タングステン等を挙げることができるが、これらの中でチタニウム、ジルコニウム及びハフニウムが好ましく、特にジルコニウムが好適である。
Ｘ²及びＹ²は、それぞれ共有結合性の配位子であり、具体的には、水素原子、ハロゲン原子、炭素数１〜２０、好ましくは１〜１０の炭化水素基、炭素数１〜２０、好ましくは１〜１０のアルコキシ基、アミノ基、炭素数１〜２０、好ましくは１〜１２のリン含有炭化水素基（例えば、ジフェニルホスフィン基等）又は炭素数１〜２０、好ましくは１〜１２の珪素含有炭化水素基（例えば、トリメチルシリル基等）、炭素数１〜２０、好ましくは１〜１２の炭化水素基又はハロゲン含有硼素化合物（例えば、ＢＦ₄，Ｂ（Ｃ₆Ｈ₅）₄）を示す。
これらの中で、ハロゲン原子及び炭化水素基が好ましい。
このＸ²及びＹ²は互いに同一であっても異なっていてもよい。 As the metallocene catalyst that gives another low-crystalline polypropylene, which is another main catalyst component used in the method for producing a propylene-ethylene copolymer of the present invention, includes a bi-bridged metallocene catalyst.
As the bibridged metallocene catalyst, the general formula (II) or the general formula (III)

(In the formula, E ² and E ³ each represent a binding group that bridges two conjugated five-membered ring ligands. R ^{9 to} R ¹⁸ each contain hydrogen, a hydrocarbon group, a halogen atom, an alkoxy group, or silicon. A hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group, wherein R ⁷ , R ⁸ , R ¹⁹ and R ²⁰ are each a hydrocarbon group, a halogen atom, an alkoxy group, or a silicon-containing group A hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, or a boron-containing hydrocarbon group, M ² represents a transition metal of Groups 4 to 6 in the periodic table, and X ² and Y ² are each shared. Represents a binding ligand, wherein X ² and Y ² may be bonded to each other to form a ring structure.)
The transition metal compound represented by these is mentioned.
As a hydrocarbon group of R < ⁷ > -R < ²⁰ >, a C1-C20 thing is preferable and a C1-C12 thing is especially preferable.
This hydrocarbon group may be bonded as a monovalent group to a cyclopentadienyl group which is a conjugated five-membered ring group, and when there are a plurality of these groups, in the formula (II), , R ⁷ and R ⁹ , or R ⁸ and R ¹⁰ may be bonded to each other, and in general formula (III), two of R ^{11 to} R ¹⁴ and R ²⁰ or R ^{15 to} R Two of ¹⁹ may be combined.
The conjugated five-membered ring includes a substituted or unsubstituted cyclopentadienyl group, indenyl group and fluorenyl group.
Examples of the halogen atom include chlorine, bromine, iodine and fluorine atoms, and examples of the alkoxy group preferably include those having 1 to 12 carbon atoms.
Examples of E ² and E ³ include (1) a methylene group, an ethylene group, an isopropylene group, a methylphenylmethylene group, a diphenylmethylene group, a cyclohexylene group, and the like, a cycloalkylene group, or a cycloalkylene group thereof. Side chain lower alkyl or phenyl substituted product, (2) Silylene group such as silylene group, dimethylsilylene group, methylphenylene group, diphenylsilylene group, disilylene group, tetramethyldisilylene group, oligosilylene group or the side chain lower alkyl or Phenyl substituted product, (3) hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum [lower alkyl group, phenyl group, hydrocarbyloxy group (preferably lower alkoxy group) etc.], specifically, (CH ₃ ) ₂ Ge group, (C ₆ H ₅ ) ₂ Ge group, (CH ₃ ) P group, (C ₆ H ₅ ) P group, (C ₄ H ₉ ) N group, (C ₆ H ₅ ) N group, (CH ₃ ) B group, (C ₄ H ₉ ) B group, (C ₆ H ₅ ) B group, ( C ₆ H ₅ ) Al group, (CH ₃ O) Al group and the like.
Among these, an alkylene group and a silylene group are preferable.
E ² and E ³ may be the same or different from each other.
M ² represents a transition metal of groups 4 to 6 in the periodic table, and specific examples include titanium, zirconium, hafnium, niobium, molybdenum, tungsten, etc. Among these, titanium, zirconium, and hafnium Is preferable, and zirconium is particularly preferable.
X ² and Y ² are each a covalently bonded ligand, specifically, a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 10 carbon atoms, or 1 to 20 carbon atoms. , Preferably an alkoxy group having 1 to 10 carbon atoms, an amino group, 1 to 20 carbon atoms, preferably a phosphorus-containing hydrocarbon group having 1 to 12 carbon atoms (such as a diphenylphosphine group), or 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. A silicon-containing hydrocarbon group (for example, trimethylsilyl group), a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, or a halogen-containing boron compound (for example, BF ₄ , B (C ₆ H ₅ ) ₄ ). Show.
Among these, a halogen atom and a hydrocarbon group are preferable.
X ² and Y ² may be the same as or different from each other.

Specific examples of the transition metal compound represented by the general formula (II) include (1,2′-ethylene) (2,1′-ethylene) -bis (3-trimethylsilylcyclopentadienyl) titanium dichloride, (1 , 2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylcyclopentadienyl) titanium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (3 -Trimethylsilyl-4-methylcyclopentadienyl) titanium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilyl-4-methylcyclopentadienyl) titanium dichloride, etc. Is mentioned.
In the compounds described above, those in which the chlorine atom of these compounds is replaced with a bromine atom, an iodine atom, a methyl atom, a phenyl atom, or the like, and the central metal titanium of the transition metal compound is zirconium, hafnium, niobium, tungsten Can be mentioned.

Specific examples of the transition metal compound represented by the general formula (III) include (1,2′-ethylene) (2,1′-ethylene) -bis (3-methylindenyl) titanium dichloride, (1,2 '-Ethylene) (2,1'-ethylene) -bis (3-methyl-4-isopropylindenyl) titanium dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (3-methyl -5,6-benzoindenyl) titanium dichloride, (1,2'-ethylene) (2,1'-isopropylidene) -bis (3-methyl-indenyl) titanium dichloride, (1,2'-methylene) ( 2,1′-ethylene) -bis (3-methyl-indenyl) titanium dichloride, (1,2′-methylene) (2,1′-isopropylidene) -bis (3-methyl-indenyl) titanium dichloride , (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-methyl-indenyl) titanium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene)- Bis (3-n-butylindenyl) titanium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-i-propylindenyl) titanium dichloride, (1,2 ' -Dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) titanium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-phenyl) Indenyl) titanium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-methyl-4,5- Nzoindenyl) titanium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-methyl-4-isopropylpropenyl) titanium dichloride, (1,2'-dimethylsilylene) ( 2,1'-dimethylsilylene) -bis (3,5,6-trimethylindenyl) titanium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-methyl-4 , 7-di-i-propylindenyl) titanium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-methyl-4-phenylindenyl) titanium dichloride, (1 , 2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-methyl-4-i-propylindenyl) titanium dichloride Lido, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-methylindenyl) titanium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -Bis (3-i-propylindenyl) titanium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-n-butylindenyl) titanium dichloride, (1,2 '-Dimethylsilylene) (2,1'-isopropylidene) -bis (3-trimethylsilylmethylindenyl) titanium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3- Trimethylsilylindenyl) titanium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-phenyl) Indenyl) titanium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-methylindenyl) titanium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene ) -Bis (3-i-propylindenyl) titanium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-n-butylindenyl) titanium dichloride, (1,2 '-Dimethylsilylene) (2,1'-methylene) -bis (3-trimethylsilylmethylindenyl) titanium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-trimethylsilylindene Nyl) titanium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -bis (3-methylindenyl) titanium Dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -bis (3-i-propylindenyl) titanium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -Bis (3-n-butylindenyl) titanium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -bis (3-trimethylsilylmethylindenyl) titanium dichloride, (1,2'- And diphenylsilylene) (2,1′-methylene) -bis (3-trimethylsilylindenyl) titanium dichloride.
In the compounds described above, those in which the chlorine atom of these compounds is replaced with a bromine atom, an iodine atom, a methyl atom, a phenyl atom, or the like, and the central metal titanium of the transition metal compound is zirconium, hafnium, niobium, tungsten Can be mentioned.

The mixing ratio (molar ratio) of the metallocene catalyst that gives highly crystalline polypropylene and the metallocene catalyst that gives low crystalline polypropylene is usually 1/1000 to 1000/1, preferably 1/1000 to 100/1, more preferably 1/1000 to 10/1.
Within this range, a propylene-ethylene copolymer having sufficient flexibility can be obtained.

Next, (3) the promoter component includes the following (3-1) catalyst component and / or (3-2) catalyst component, of which (3-1) as the catalyst component, the above (1) Any compound can be used as long as it is a compound capable of reacting with the catalyst component and (2) the transition metal compound of the catalyst component to form an ionic complex, but the following general formula (IV) or (V)
([L ¹ −R ²¹ ] ^{k +} ) _a ([Z] ⁻ ) _b (IV)
([L ² ] ^{k +} ) _a ([Z] ⁻ ) _b (V)
(However, L ² is M ³ , R ²² R ²³ M ⁴ , R ²⁴ ₃ C or R ²⁵ M ^5. )
[In the formulas (IV) and (V), L ¹ is a Lewis base, [Z] ⁻ is a non-coordinating anion [Z ¹ ] ⁻ and [Z ² ] ⁻ , where [Z ¹ ] ⁻ is a plurality of Anion in which the group is bonded to the element, that is, [M ³ G ¹ G ² ... G ^f ] ⁻ (where M ³ is an element of Group 5 to 15 of the periodic table, preferably Group 13 to 15 of the periodic table. G ^{1 to} G ^f are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 6 to 20 carbon atoms. Aryl group having 6 to 20 carbon atoms, alkyl aryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, 1 to carbon atoms 20 represents an acyloxy group, an organic metalloid group, or a heteroatom-containing hydrocarbon group having 2 to 20 carbon atoms. Two or more of G ^{1 to} G ^f may form a ring, and f represents an integer of ((valence of central metal M ³ ) +1).
[Z ² ] ⁻ is defined as a Bronsted acid alone having a logarithm (pKa) of the reciprocal of the acid dissociation constant or a conjugate base of a combination of Bronsted acid and Lewis acid, or generally a super strong acid. Indicates a conjugate base of an acid. In addition, a Lewis base may be coordinated.
R ²¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, and R ²² and R ²³ are each a cyclopentadienyl group, A substituted cyclopentadienyl group, indenyl group or fluorenyl group, R ²⁴ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group.
R ²⁵ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine.
k is an ionic valence of [L ¹ −R ²¹ ], [L ² ], an integer of 1 to 3, a is an integer of 1 or more, and b = (k × a).
M ⁴ contains elements of Group 1 to 3, 11 to 13 and 17 of the periodic table, and M ⁵ represents elements of Group 7 to 12 of the periodic table. ]
What is represented by these can be used conveniently.
Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, Amines such as pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, phosphines such as triethylphosphine, triphenylphosphine, diphenylphosphine, thioethers such as tetrahydrothiophene, benzoic acid Examples thereof include esters such as ethyl acid, and nitriles such as acetonitrile and benzonitrile.
Specific examples of R ²¹ include hydrogen, methyl group, ethyl group, benzyl group, and trityl group. Specific examples of R ²² and R ²³ include cyclopentadienyl group and methylcyclopentadienyl group. , Ethylcyclopentadienyl group, pentamethylcyclopentadienyl group, and the like.
Specific examples of R ²⁴ include phenyl group, p-tolyl group, p-methoxyphenyl group, and specific examples of R ²⁵ include tetraphenylporphine, phthalocyanine, allyl, methallyl, and the like. .
Specific examples of M ⁴ include Li, Na, K, Ag, Cu, Br, I, I _{3 and the} like. Specific examples of M ⁵ include Mn, Fe, Co, Ni, Zn. Etc.
In [Z ¹ ] ⁻ , that is, [M ³ G ¹ G ² ... G ^f ], specific examples of M ³ include B, Al, Si, P, As, Sb, etc., preferably B and Al. Can be mentioned.
Specific examples of G ¹ and G ^{2 to} G ^f include dialkylamino groups such as dimethylamino group and diethylamino group, alkoxy groups or aryloxy groups such as methoxy group, ethoxy group, n-butoxy group, phenoxy group and the like. Hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-octyl, n-eicosyl, phenyl, p-tolyl, benzyl, 4- t-butylphenyl group, 3,5-dimethylphenyl group, etc., halogen, fluorine, chlorine, bromine, iodine, heteroatom-containing hydrocarbon group, p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group , 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromedium ) Phenyl group, bis (trimethylsilyl) methyl group, pentamethyl antimony group as organic metalloid group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexyl antimony group, diphenyl boron, and the like.
Specific examples of a non-coordinating anion, that is, a Bronsted acid alone having a pKa of −10 or less, or a conjugate base [Z ² ] ⁻ of a combination of Bronsted acid and Lewis acid include a trifluoromethanesulfonate anion ( CF ₃ SO ₃ ) ⁻ , bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (ClO ₄ ) ⁻ , trifluoroacetate anion (CF ₃ CO ₂ ) ⁻ , hexafluoroantimony anion (SbF ₆ ) ⁻ , fluorosulfonic acid anion (FSO ₃ ) ⁻ , chlorosulfonic acid anion (ClSO ₃ ) ⁻ , fluorosulfonic acid anion / 5-antimony fluoride (FSO ₃ / SbF) ₅₎ ^-, fluorosulfonic acid anion / - fluoride arsenic ^{_{(FSO 3 / AsF 5) -}} , trifluoromethanesulfonic acid / antimony pentafluoride _{(CF 3 SO 3 / SbF 5} ) - , and the like.

Specific examples of the ionic compound that reacts with the transition metal compound of (1) the catalyst component and (2) the catalyst component to form an ionic complex, ie, (3-1) the catalyst component compound, include tetra Triethylammonium phenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl tetraphenylborate (tri-n-butyl) ) Ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridyl tetraphenylborate Nitrogen, methyl tetraphenylborate (2-cyanopyridinium), tetrakis (pentafluorophenyl) triethylammonium borate, tetrakis (pentafluorophenyl) tri-n-butylammonium borate, tetrakis (pentafluorophenyl) triphenylammonium borate, tetrakis ( Pentafluorophenyl) tetra-n-butylammonium borate, tetraethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) benzyl (tri-n-butyl) ammonium borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, Tetrakis (pentafluorophenyl) borate triphenyl (methyl) ammonium, tetrakis (pentafluorophenyl) boron Methylanilinium, dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, methylpyridinium tetrakis (pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluoro) Phenyl) methyl borate (2-cyanopyridinium), tetrakis (pentafluorophenyl) benzyl borate (2-cyanopyridinium), tetrakis (pentafluorophenyl) methyl borate (4-cyanopyridinium), tetrakis (pentafluorophenyl) triphenyl borate Phosphonium, tetrakis [bis (3,5-ditrifluoromethyl) phenyl] dimethylanilinium borate, tetraphenylborate ferro Cenium, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (1,1′-dimethylferrocenium), tetrakis ( Pentafluorophenyl) decamethylferrocenium borate, silver tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) trityl borate, lithium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) sodium borate, tetrakis (penta Fluorophenyl) borate tetraphenylporphyrin manganese, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate, silver perchlorate, silver Examples thereof include silver trifluoroacetate and silver trifluoromethanesulfonate.
(3-1) One type of catalyst component may be used, or two or more types may be used in combination.

（式中、Ｒ²⁶は、炭素数１〜２０、好ましくは１〜１２のアルキル基，アルケニル基，アリール基，アリールアルキル基等の炭化水素基又はハロゲン原子を示し、ｗは平均重合度を示し、通常２〜５０、好ましくは２〜４０の整数である。
尚、各Ｒ²⁶は同じでも異なっていてもよい。）
で示される鎖状アルミノキサン、及び一般式（VII）

（式中、Ｒ²⁶及びｗは前記一般式（VI）におけるものと同じである。)
で示される環状アルミノキサンを挙げることができる。
前記アルミノキサンの製造法としては、アルキルアルミニウムと水等の縮合剤とを接触させる方法が挙げられるが、その手段については特に限定はなく、公知の方法に準じて反応させればよい。
例えば、（１）有機アルミニウム化合物を有機溶剤に溶解しておき、これを水と接触させる方法、（２）重合時に当初有機アルミニウム化合物を加えておき、後に水を添加する方法、（３）金属塩等に含有されている結晶水、無機物や有機物への吸着水を有機アルミニウム化合物と反応させる方法、（４）テトラアルキルジアルミノキサンにトリアルキルアルミニウムを反応させ、更に水を反応させる方法等がある。
尚、アルミノキサンとしては、トルエン不溶性のものであってもよい。
これらのアルミノキサンは一種用いてもよく、二種以上を組み合わせて用いてもよい。
（１）触媒成分と（２）触媒成分の合計量と（３）触媒成分との使用割合は、（３）触媒成分として（３−１）触媒成分化合物を用いた場合には、モル比で好ましくは１０：１〜１：１００、より好ましくは２：１〜１：１０の範囲が望ましく、上記範囲内であると、単位質量ポリマー当りの触媒コストが安価で、実用的である。
また、（３−２）触媒成分化合物を用いた場合には、モル比で好ましくは１：１〜１：１００００００、より好ましくは１：１０〜１：１００００の範囲が望ましい。
この範囲内であると、単位質量ポリマーあたりの触媒コストが安価で、実用的である。
また、（３）触媒成分としては（３−１）触媒成分，（３−２）触媒成分を単独又は二種以上組み合わせて用いることもできる。 On the other hand, the catalyst component (3-2) is represented by the general formula (VI)

(Wherein R ²⁶ represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group or arylalkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, or a halogen atom, and w represents an average degree of polymerization. In general, it is an integer of 2 to 50, preferably 2 to 40.
Each R ²⁶ may be the same or different. )
A chain aluminoxane represented by the general formula (VII)

(In the formula, R ²⁶ and w are the same as those in the general formula (VI).)
The cyclic aluminoxane shown by these can be mentioned.
Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the means thereof is not particularly limited and may be reacted according to a known method.
For example, (1) a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, (2) a method in which an organoaluminum compound is initially added during polymerization, and water is added later, (3) a metal There are a method of reacting crystallization water contained in a salt or the like, water adsorbed on an inorganic or organic material with an organoaluminum compound, and (4) a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum and further reacting with water. .
The aluminoxane may be insoluble in toluene.
These aluminoxanes may be used alone or in combination of two or more.
The usage ratio of (1) catalyst component, (2) total amount of catalyst component, and (3) catalyst component is the molar ratio when (3-1) catalyst component compound is used as (3) catalyst component. The range of 10: 1 to 1: 100 is more preferable, and the range of 2: 1 to 1:10 is more preferable. When it is within the above range, the catalyst cost per unit mass polymer is low and practical.
When (3-2) a catalyst component compound is used, the molar ratio is preferably 1: 1 to 1: 1000000, more preferably 1:10 to 1: 10000.
Within this range, the catalyst cost per unit mass polymer is inexpensive and practical.
Further, (3-1) the catalyst component and (3-2) the catalyst component can be used alone or in combination of two or more as the catalyst component (3).

In addition to the above (1) catalyst component and (2) catalyst component and (3) catalyst component and (4) porous carrier, the polymerization catalyst for producing the propylene-ethylene copolymer is (5) An organoaluminum compound can be used as the catalyst component.
Here, as the organoaluminum compound of (5) catalyst component, the general formula (VIII)
R ²⁷ _v AlJ _3-v (VIII)
[Wherein R ²⁷ represents an alkyl group having 1 to 10 carbon atoms, J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom, and v represents 1 to 3 carbon atoms. (It is an integer)
The compound shown by these is used.
Specific examples of the compound represented by the general formula (VIII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride. , Diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like.
These organoaluminum compounds may be used alone or in combination of two or more.

(4) Specific examples of the porous carrier include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , Fe ₂ O 3, B ₂ O 3, CaO, ZnO, BaO, ThO ₂ and mixtures thereof. Examples thereof include silica alumina, zeolite, ferrite, glass fiber and the like.
Of these, SiO ₂ and Al ₂ O ₃ are particularly preferable.
The porous carrier may contain a small amount of carbonate, nitrate, sulfate and the like.
On the other hand, as a carrier other than the above, a magnesium compound represented by the general formula MgR ²⁸ _x X ¹ _y typified by MgCl ₂ , Mg (OC ₂ H ₅ ) _2, or a complex salt thereof can be given.
Here, R ²⁸ represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, X ¹ represents a halogen atom or an alkyl group having 1 to 20 carbon atoms, x is 0 to 2, y is 0 to 2, and x + y = 2.
Each R ²⁸ and each X ¹ may be the same or different.
Examples of the organic carrier include polymers such as polystyrene, styrene-divinylbenzene copolymer, polyethylene, poly 1-butene, substituted polystyrene, polyarylate, starch, carbon, and the like.
As the carrier of the catalyst used for the production of the propylene-ethylene copolymer, MgCl ₂ , MgCl (OC ₂ H ₅ ), Mg (OC ₂ H ₅ ) _{2 and the} like are also preferable.
Moreover, although the property of a support | carrier differs with the kind and manufacturing method, an average particle diameter is 1-300 micrometers normally, Preferably it is 10-200 micrometers, More preferably, it is 20-100 micrometers.
If the particle size is small, fine powder in the polymer increases, and if the particle size is large, coarse particles in the polymer increase, which causes a decrease in bulk density and clogging of the hopper.
The specific surface area of the carrier is usually 1 to 1000 m ² / g, preferably 50 to 500 m ² / g, and the pore volume is usually 0.1 to ⁵ cm ³ / g, preferably 0.3 to ³ cm ³ / g. is there.
When the specific surface area or pore volume is in the above range, the catalytic activity increases.
The specific surface area and pore volume can be determined from the volume of nitrogen gas adsorbed according to the BET method, for example.
Further, when the carrier is an inorganic oxide carrier, it is usually desirable to use it after baking at 150 to 1000 ° C, preferably 200 to 800 ° C.

When at least one catalyst component is supported on the carrier, at least one of (1) catalyst component + (2) catalyst component and (3) catalyst component, preferably (1) catalyst component + (2) catalyst component and ( 3) It is desirable to carry both catalyst components.
The method for supporting at least one of (1) catalyst component + (2) catalyst component and (3) catalyst component on the carrier is not particularly limited. For example, (a) (1) catalyst component + (2) catalyst And (3) a method of mixing at least one of the catalyst component and the carrier, (b) after treating the carrier with an organoaluminum compound or a halogen-containing silicon compound, and (1) catalyst component + (2) in an inert solvent Method of mixing with at least one of catalyst component and (3) catalyst component, (c) support and (1) catalyst component + (2) catalyst component, and / or (3) catalyst component and organoaluminum compound or halogen-containing silicon compound (D) (1) catalyst component + (2) catalyst component or (3) after the catalyst component is supported on the carrier, (3) catalyst component or (1) catalyst component + (2) catalyst Mix with ingredients (E) (1) catalyst component + (2) catalyst component and (3) a method of mixing a catalytic reaction product of a catalyst component with a carrier, (f) (1) catalyst component + (2) catalyst component and ( 3) In the contact reaction with the catalyst component, a method in which a carrier coexists can be used.
In the above methods (d), (e) and (f), (5) an organoaluminum compound as a catalyst component may be added.

In the production of the catalyst used for the production of the propylene-ethylene copolymer, the (1) catalyst component + (2) catalyst component, (3) catalyst component, (4) porous carrier, and (5) catalyst component are contacted. When the catalyst is used, the catalyst may be prepared by irradiating elastic waves.
Examples of the elastic wave include a normal sound wave, particularly preferably an ultrasonic wave.
Specifically, an ultrasonic wave having a frequency of 1 to 1000 kHz, preferably an ultrasonic wave having a frequency of 10 to 500 kHz can be mentioned.
The catalyst thus obtained may be used for the polymerization after the solvent is distilled off and taken out as a solid, or may be used for the polymerization as it is.
In the production of the propylene-ethylene copolymer, (1) catalyst component + (2) catalyst component and (3) at least one of the catalyst components, (4) the supporting operation on the porous carrier is carried out in the polymerization system. By doing so, a catalyst can be produced.
For example, at least one of (1) catalyst component + (2) catalyst component and (3) catalyst component, (4) a porous carrier and, if necessary, (5) the organoaluminum compound of the catalyst component, A method can be used in which olefin is added at normal pressure to 2 MPa, and prepolymerization is performed at -20 to 200 ° C. for about 1 minute to 2 hours to generate catalyst particles.
The use ratio of the catalyst component (3-1) and the carrier in the catalyst used for the production of this propylene-ethylene copolymer is preferably 1: 5 to 1: 10000, more preferably 1:10 to 1 in terms of mass ratio. The ratio of the component (3-2) to the carrier is preferably 1: 0.5 to 1: 1000, more preferably 1: 1 to 1:50 in terms of mass ratio. Is desirable.
(3) When two or more kinds are mixed and used as the catalyst component, it is desirable that the use ratio of each (3) catalyst component and the carrier is within the above range in terms of mass ratio.
The ratio of (1) catalyst component + (2) catalyst component and (4) porous carrier is mass ratio, preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500. Is desirable.
(3) catalyst component [(3-1) catalyst component or (3-2) catalyst component] and (4) ratio of use of porous carrier, or (1) catalyst component + (2) catalyst component and carrier When the use ratio is within the above range, the activity increases and the powder morphology is also improved.
The average particle diameter of the polymerization catalyst thus prepared is usually 2 to 200 μm, preferably 10 to 150 μm, particularly preferably 20 to 100 μm, and the specific surface area is usually 20 to 1000 m ² / g, preferably 50-500 m ² / g.
When the average particle size is 2 μm or more, fine powder in the polymer is reduced, and when it is 200 μm or less, coarse particles in the polymer are reduced.
When the specific surface area is 20 m ² / g or more, the activity increases, and when it is 1000 m ² / g or less, the bulk density of the polymer increases.
Moreover, in the catalyst used for the production of the propylene-ethylene copolymer, the amount of transition metal in 100 g of the support is usually 0.05 to 10 g, particularly preferably 0.1 to 2 g.
When the amount of transition metal is within the above range, the activity increases.

When producing the propylene-ethylene copolymer according to the present invention, it is preferable to perform a first step of propylene homopolymerization and a second step of copolymerization of propylene and ethylene.
The homopolymerization of propylene in the first step can be selected from slurry polymerization or bulk polymerization.
The copolymerization of propylene and ethylene in the second step can be selected from slurry, bulk, and gas phase polymerization.
The first step and the second step can be multistage polymerization.
As polymerization conditions in propylene homopolymerization, the polymerization pressure is not particularly limited, and is usually atmospheric pressure to 8 MPa, preferably 0.2 to 5 MPa, and the polymerization temperature is usually 0 to 200 ° C., preferably 30 to 30 ° C. It is appropriately selected within the range of 100 ° C.
The polymerization time is usually about 5 minutes to 20 hours, preferably about 10 minutes to 10 hours.
As polymerization conditions in the copolymerization of propylene and ethylene, the polymerization pressure is not particularly limited, and is usually atmospheric pressure to 8 MPa, preferably 0.2 to 5 MPa, and the polymerization temperature is usually 0 to 200 ° C., preferably It is appropriately selected within the range of 20 to 100 ° C.
The polymerization time is usually about 1 minute to 20 hours, preferably about 1 minute to 10 hours.
The ratio of propylene and ethylene supplied is a molar ratio of 0.01 to 9, preferably 0.05 to 2.3.
The molecular weight of the polymer in the propylene homopolymerization part and the copolymerization part can be adjusted by adding a chain transfer agent, preferably adding hydrogen.
Further, an inert gas such as nitrogen may be present.
When using a polymerization solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane, and aliphatic hydrocarbons such as pentane, hexane, heptane, and octane Halogenated hydrocarbons such as chloroform and dichloromethane can be used.
These solvents may be used alone or in combination of two or more.
Depending on the polymerization method, it can be carried out without solvent.

In the polymerization, prepolymerization can be performed using the polymerization catalyst.
The prepolymerization can be performed, for example, by bringing a small amount of olefin into contact with the solid catalyst component, but the method is not particularly limited, and a known method can be used.
The olefin used for the prepolymerization is not particularly limited, and examples thereof include those similar to those exemplified above, for example, ethylene, an α-olefin having 3 to 20 carbon atoms, or a mixture thereof. It is advantageous to use ethylene or propylene used in the process.
Moreover, prepolymerization temperature is -20-200 degreeC normally, Preferably it is -10-130 degreeC, More preferably, it is 0-80 degreeC.
In the prepolymerization, an aliphatic hydrocarbon, an aromatic hydrocarbon, or the like can be used as a solvent.
Of these, aliphatic hydrocarbons are particularly preferred.
Moreover, you may perform prepolymerization without a solvent.
In the prepolymerization, the preliminarily polymerized product has an intrinsic viscosity [η] (measured in decalin at 135 ° C.) of 0.2 dl / g or more, particularly 0.5 dl / g or more, and preliminarily with respect to 1 mmol of the transition metal component in the catalyst. It is desirable to adjust the conditions so that the amount of the polymerization product is 1 to 10000 g, particularly 10 to 1000 g.

  The higher the ratio of (metallocene catalyst that provides low crystalline polypropylene / metallocene catalyst that provides high crystalline polypropylene) is used, the more ethylene is used, the more flexible propylene-ethylene copolymer is obtained.

In the resin composition containing the propylene-ethylene copolymer of the present invention, the components fractionated by the temperature rising elution fractionation method (TREF) satisfy the following requirements.
Component 1: 10-80% by mass of soluble component (non-crystalline component) at 0 ° C.
Component 2: Elution component (low crystal component) exceeding 0 ° C. and 70 ° C. or less is 10 to 60% by mass
Component 3: 5-50 mass% of elution components exceeding 70 degreeC and less than 100 degreeC
Component 4: 0 to 30% by mass of elution component (crystal component) at 100 ° C. or higher
However, it is the component 1 + component 2 + component 3 + component 4 = 100 mass%.
In Component 1, the soluble component at 0 ° C. is preferably 12 to 70% by mass, more preferably 15 to 60% by mass.
Component 2 has an elution component of more than 0 ° C. and 70 ° C. or less, preferably 12 to 50% by mass, and more preferably 15 to 45% by mass.
Component 3 has an elution component exceeding 70 ° C. and less than 100 ° C., preferably 7 to 45 mass%, more preferably 10 to 40 mass%.
Component 4 is preferably 1 to 25% by mass, more preferably 2 to 20% by mass of an elution component exceeding 100 ° C. or more.
When the components 1 to 4 satisfy the above requirements, the obtained molded article is excellent in transparency, and changes with time such as stickiness and appearance are improved.

  In the present invention, the temperature rising elution fractionation method (TREF) is based on the method described in detail in, for example, Journal of Applied Polymer Science; Applied Polymer Symposium 45, 1-24 (1990). That is, first, a high-temperature polymer solution is introduced into a column using diatomaceous earth as a filler, and the column temperature is gradually decreased to crystallize the filler surface in order from a component having a high melting point. In this method, the elution polymer component is fractionated by gradually elevating the temperature and then eluting in order from the component having the lowest melting point (see Examples).

In addition, the resin composition containing the propylene-ethylene copolymer of the present invention is preferably an intrinsic viscosity [η] measured in decalin at a temperature of 135 ° C. of components to be fractionated by a temperature-temperature elution fractionation method (TREF). However, component 1 ≧ component 2> component 3 is satisfied, and the intrinsic viscosity [η] of component 3 exceeds 0.6 deciliter / g.
When the intrinsic viscosity [η] of the component to be fractionated satisfies the above requirements and the intrinsic viscosity [η] of component 3 exceeds 0.6 deciliter / g, the resulting molded product is further excellent in transparency and stickiness. Changes over time such as appearance are improved.
The intrinsic viscosity [η] of component 3 is preferably more than 1.0 deciliter / g, more preferably more than 1.5 deciliter / g.

The resin composition containing the propylene-ethylene copolymer of the present invention is blended with a propylene-based polymer containing component 4 (crystal component) at 100 ° C. or higher, which is fractionated by a temperature rising elution fractionation method (TREF). Can do.
When a propylene polymer is blended, the formability is further improved by the action of the crystal component.
The compounding quantity of a propylene polymer is 5-25 mass% normally, Preferably it is 7-20 mass%.
Examples of the propylene-based polymer include crystalline polypropylene obtained by homopolymerizing propylene and propylene-α-olefin copolymer obtained by copolymerizing propylene and α-olefin.
These polymers are produced by a general-purpose polymerization method (gas phase, slurry, bulk polymerization, etc.) using a Ziegler catalyst.

In the resin composition of the present invention, the function of each component fractionated by the temperature-temperature elution fractionation method (TREF) is considered as follows.
Component 1 (amorphous component) suppresses the growth of crystallization by closing the crystal growth space of component 3 (crystalline component) in the development of flexibility and crystallization from the molten state, and moreover than component 3 Since the intrinsic viscosity [η] (molecular weight) is large, the transfer rate of the component 1 itself to the surface of the molded product is slowed down.
Component 2 (low crystal component) is involved in the crystal growth of component 3 and is assumed to function as a dispersing material that slows the growth and disperses component 1 that closes the growth space in the vicinity of component 3.
Component 3 plays a role of promoting solidification when forming into a molded body and improving formability and the like.
Component 4 (crystalline component) improves the formability of the molded body.
Therefore, the molded body obtained from the resin composition satisfying the requirements of the above components 1 to 4 is excellent in transparency, and the stickiness and appearance change are remarkably improved.
Further, when flexibility is acceptable, the resin composition containing the propylene-ethylene copolymer contains 50 components 4 (crystal components) of 100 ° C. or higher that are fractionated by a temperature rising elution fractionation method (TREF). Even when 3 to 30% by mass of a propylene-based polymer containing at least mass% is blended, the above effect is not impaired, and a molded product that is flexible and excellent in transparency and has little change with time such as stickiness can be obtained.

As a molded object of this invention, a film, a sheet | seat, a tube, a hose, an injection molded product, and a laminated body are mentioned.
The laminate includes a laminate having at least one layer made of the resin composition of the present invention.
In producing the molded article of the present invention, various known additives can be blended with the corresponding resin composition as desired.
Examples of various additives used as desired include antioxidants, neutralizers, slip agents, antiblocking agents, antifogging agents, lubricants, nucleating agents, and antistatic agents.
These additives may be used alone or in combination of two or more.
For example, examples of the antioxidant include phosphorus antioxidants, phenol antioxidants, sulfur antioxidants, and the like.

  Specific examples of phosphorus antioxidants include trisnonylphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-t -Butylphenyl) pentaerythritol phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphos Phyto, tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylene-di-phosphonite, ADK STAB 1178 (Asahi Denka) Johoku Chemical Co., Ltd.), Adeka Stub 2112 (Asahi Denka Co., Ltd.), JPP-2000 (Johoku Chemical Co., Ltd.) , Weston 618 (GE (manufactured)), ADK STAB PEP-24G (Asahi Denka (manufactured)), ADK STAB PEP-36 (Asahi Denka (manufactured)), ADK STAB HP-10 (Asahi Denka (manufactured)), Sandstab P-EPQ (Sand (Manufactured)), phosphite 168 (Ciba Specialty Chemicals (manufactured)), and the like.

  Specific examples of the phenolic antioxidant include 2,6-di-t-butyl-4-methylphenol and n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl). ) Propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 4 , 4'-butylidenebis- (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) 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, Sumilizer BHT (Sumitomo Chemical Co., Ltd.), Yoshinox BHT (Yoshitomi Pharmaceutical Co., Ltd.), Antage BHT (Kawaguchi Chemical Co., Ltd.), Irganox 1076 (Ciba Specialty Chemicals) (Manufactured)), Irganox 1010 (manufactured by Ciba Specialty Chemicals (manufactured)), Adeka Stub AO-60 (manufactured by Asahi Denka) (manufactured by Asahi Denka), Sumilizer BP-101 (manufactured by Sumitomo Chemical), Tominox TT (manufactured by Yoshitomi Pharmaceutical ( )), TTHP (Toray (made)), Irganox 3114 (Ciba Specialty Chemicals (made)), Adekastab AO-20 (Asahi Denka (made)), Adekastab AO-40 (Asahi Denka (made)), Sumilizer BBM-S (Sumitomo Chemical Co., Ltd.), Yoshinox BB (Yoshitomi Pharmaceutical Co., Ltd.), Antage W 300 (Kawaguchi Chemical Co., Ltd.), Irganox 245 (Ciba Specialty Chemicals Co., Ltd.), Adeka Stub AO-70 (Asahi Denka Co., Ltd.), Tominox 917 (Yoshitomi Pharmaceutical Co., Ltd.), Adeka Stub AO-80 (Asahi Denka (manufactured)), Sumilizer GA-80 (Sumitomo Chemical (manufactured)) and the like.

  Specific examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, pentaerythritol. Tetrakis (3-laurylthiopropionate), Sumilizer TPL (Sumitomo Chemical Co., Ltd.), Yoshinox DLTP (Yoshitomi Pharmaceutical Co., Ltd.), Antix L (Nippon Yushi Co., Ltd.), Sumilizer TPM (Sumitomo Chemical Co., Ltd.) ), Yoshinox DMTP (Yoshitomi Pharmaceutical Co., Ltd.), Antix M (Nippon Oil & Fats Co., Ltd.), Sumilizer TPS (Sumitomo Chemical Co., Ltd.), Yoshinox DSTP (Yoshitomi Pharmaceutical Co., Ltd.), Antix S (Nippon Oil & Fats Co., Ltd.) Adeka Stub AO-412S (Asahi Denka (manufactured)), SEENOX 412S (Cipro Kasei (manufactured)), S Millizer TDP (Sumitomo Chemical Co., Ltd.)

  Among these, Irganox 1010: Substance name: Pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], Irgaphos 168: Substance name: Tris (2,4- Di-t-butylphenyl) phosphite, Irganox 1076: Substance name: Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, Irganox 1330: Substance name: 1, 3, 5-Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, Irganox 3114: Substance name: Tris (3,5-di-t-butyl-4- Hydroxybenzyl) isocyanurate, P-EPQ: substance name: tetrakis (2,4-di-t-butylphenyl) 4,4′-bi Eniren - di - phosphite is particularly preferred.

When an antioxidant is used in the present invention, the antioxidant may be added in an amount of about 0.001 to 1 part by mass with respect to 100 parts by mass of the resin composition.
Thereby, yellowing etc. can be prevented and it is preferable.

If the specific usage example of said antioxidant is given,
Example 1: Irganox 1010 1,000 ppm
PEP-Q 1,000ppm
Example 2: Irganox 1076 1,200 ppm
PEP-Q 600ppm
Irgaphos 168 800ppm
Example 3: Irganox 1010 400-1,000 ppm
Irgaphos 168 700-1500ppm
Etc.

Further, as a neutralizing agent, calcium stearate, zinc stearate, magnesium stearate, hydrotalcite (DHT-4A): Composition formula: Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O, Li ₂ Al ₄ (OH) ₁₂ CO 3 .3H ₂ O (“Mizukarak H-1” from Mizusawa Chemical Co., Ltd.)] and the like are particularly preferable.

  As the anti-blocking agent, “Silicia” manufactured by Fuji Silysia Co., Ltd .: synthetic silica type, “Mizukasil” manufactured by Mizusawa Chemical Industry Co., Ltd .: synthetic silica type and the like are particularly preferable.

  As the slip agent, erucic acid amide, oleic acid amide, stearic acid amide, behenic acid amide, ethylene bis stearic acid amide, ethylene bis oleic acid amide, stearyl erucamide, oleyl palmitoamide are particularly preferable.

Antifogging agents include (di) glycerin mono (di, tri) oleate, (di) glycerin mono (di, tri) stearate, (di) glycerin mono (di) palmitate, (di) glycerin mono (di) laurate Glycerin fatty acid ester compounds such as sorbitan laurate, sorbitan palmitate, sorbitan (tri) stearate, sorbitan fatty acid ester compounds such as sorbitan (tri) oleate, polyoxyethylene alkyl (phenyl) ether, polyoxyethylene sorbitan monooleate, poly Ethylene oxide adducts such as oxyethylene glycerol monostearate, propylene glycol monolaurate, propylene glycol monopalmitate, propylene glycol monostearate, propylene glycol monooleate Propylene glycol fatty acid esters, such bets can be mentioned.
A plurality of these antifogging agents can be used.
By using an antifogging agent, fogging due to steam can be prevented, and the value of the displayed product can be increased by maintaining transparency.

  When using a nucleating agent, the addition amount of the nucleating agent is usually 10 ppm or more, preferably in the range of 10 to 10,000 ppm, more preferably 10 to 5, based on the resin composition of the present invention. The range is 000 ppm, more preferably 10 to 2,500 ppm.

The resin composition of the present invention comprises a propylene-ethylene copolymer having an ethylene unit content of 20 mol% or less and a triad chain fraction f _{EEE of} [EEE] of 0.1 mol% or less, the propylene-ethylene copolymer. And a combination of 3 to 30% by mass of a propylene-based polymer in which a component of 100 ° C. or higher is 50% by mass or more, which is fractionated by a temperature rising elution fractionation method (TREF), and if necessary, various additives are added in predetermined amounts, It can be produced by an ordinary method, for example, a method of pelletizing with a melt kneader such as an extruder or a Banbury mixer.

The molded article of the present invention is a molded article obtained by molding the resin composition pellets obtained as described above by various molding methods such as injection molding, extrusion molding, and thermoforming.
As a method for forming the film and sheet of the present invention using the resin composition pellets obtained as described above, for example, a T-die cast molding method, an inflation molding method, a calendar molding method, or the like can be employed.
In the sheet and film molding method, the resin is heated and extruded at a molding resin temperature of about 190 to 270 ° C., and cooled to form a film.
As a cooling method, either air cooling or water cooling can be employed.

The film and sheet of the present invention have a sufficient function as a film and sheet even when they are not stretched.
However, if necessary, it can be biaxially stretched by a known method.
By this stretching, the cutability of the film and the sheet can be improved.
The thickness of the film and sheet of the present invention is usually 5 to 500 μm, preferably 10 to 300 μm, and more preferably 60 to 120 μm.

The film and sheet of the present invention are based on the single-layer film made of the corresponding resin composition, but may be a multilayer film or sheet having at least one layer made of these resin compositions. .
Moreover, it can also be set as the multilayer film and sheet | seat which consist of one or more layers suitably selected from the resin composition layer which forms the film of this invention, a sheet | seat, and another olefin resin.
In this case, the ratio of the layer made of the resin composition of the present invention is usually in the range of 1 to 99%, preferably 20 to 80%, and this layer may be at least one outer layer. The features of the invention can be utilized, which is preferable.
In addition, as other olefin resin of the multilayer film, polypropylene, propylene-α-olefin copolymer, propylene-ethylene-diene copolymer, high pressure method low density polyethylene, high density polyethylene, density is 0.850-0. 940 g / cm ³ ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer, hydrogenated styrene elastomer and the like.

As a method of forming a laminate comprising at least one layer comprising the tube, hose, injection-molded product of the present invention and the resin composition of the present invention using the resin composition pellets obtained as described above. For example, a general extrusion molding method, T-die casting molding method, inflation molding method, calendar molding method, or the like can be employed.
In the method of forming a tube, hose, injection-molded product, and laminate, the resin is heated to a molding resin temperature of about 200 to 270 ° C., extruded, cooled, and formed into a film.
As a cooling method, either air cooling or water cooling can be employed.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

In the present invention, physical property measurement and evaluation of propylene-ethylene copolymer, propylene-based polymer, resin composition (pellet), and molded product (film, injection-molded product, tube) were performed according to the following methods.
[Physical properties and evaluation methods]
(1) Temperature rising elution fractionation method (TREF)
(A) Method of operation A sample solution in which a sample is completely dissolved in orthodichlorobenzene at a temperature of 140 ° C. is introduced into a TREF column adjusted to a temperature of 135 ° C., and then gradually lowered to 0 ° C. at a cooling rate of 5 ° C./hour. The temperature is lowered and the sample is adsorbed on the filler.
Then, after maintaining at 0 ° C. for 30 minutes, orthodichlorobenzene was allowed to flow through the column, and the components that were not adsorbed by the filler were eluted by maintaining at 0 ° C. for 10 minutes.
Thereafter, the column was heated to 135 ° C. at a rate of temperature increase of 40 ° C./hour while circulating orthodichlorobenzene, the polymer components were sequentially eluted, and the concentration of the eluted polymer was measured to obtain an elution curve.
In addition, when the linear high-density polyethylene (US Department of Commerce National Institute of Standards and Technology, SRM1475) was measured by this method, the elution peak temperature Tp was 100.6 degreeC.
(B) Measuring device TREF column: silica gel column (4.6Φ × 150 mm) manufactured by GL Science
Flow cell: KBr cell manufactured by GL Sciences Inc. Optical path length 1mm
Liquid feed pump: SSC-3100 manufactured by Senshu Science
Valve oven: Model 554 manufactured by GL Sciences
TREF oven: GL Sciences 2 series temperature controller: Rigaku Kogyo REX-C100
Concentration detector: Infrared detector for liquid chromatography MIRAN made by FOXBORO
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 milliliters / Min Detection wave number: 3.41 μm
Column packing: Chromosolv P (30/60 mesh)
Column temperature distribution: within ± 0.2 ° C. (2) Measurement of intrinsic viscosity [η] Measurement was carried out at 135 ° C. in a decalin solvent using a VMR-053 type automatic viscometer manufactured by Koiso Co., Ltd.
70-80 mg of a sample was completely dissolved in decalin at a temperature of 135 ° C., the dissolved solution was placed in a viscometer, allowed to drop naturally, its flow time was determined, and the following formula was calculated.
Relative viscosity [η _rel ] = (Sample solution dropping seconds) / (Blank dropping seconds)
Specific viscosity [η _sp ] = [η _rel ] −1
Intrinsic viscosity [η] = [− 1+ (1 + 4 × 0.35 × [η _sp ]) ^1/2 ] / (2 × 0.35 × D)
0.35: Huggins constant when using decalin
D: Sample concentration (3) Measurement of tensile strength Measured according to JIS Z1702 (MD).
(4) Measurement of total haze It measured based on JISK7105.
(5) Measurement of change over time The obtained film, test piece and tube were stored in a constant temperature bath at 40 ° C. for 2 weeks, and then all haze changes before and after storage were measured.
(6) In the case of an injection-molded product, the evaluation of the change with time after measuring all hazes was visually (O: good transparency, x: poor transparency)
(7) In the case of a tube, the transparency and its change with time were evaluated by visual observation without measuring the total haze (○: transparency was good, Δ: transparency was slightly poor, x: transparency was poor)
(8) Measurement of wettability change Corona treatment was performed during film formation, and using a wetting index standard solution (manufactured by Wako Pure Chemical Industries, Ltd.), the wetting number of the obtained film was adjusted to 52 μm N / m, After storage in a thermostatic bath for 1 week, the change in the number of wettings before and after storage was measured using a wetting reagent.
A small change over time in wettability (change from the number of wetting of 52 μN / m) is considered to be a small shift of component 1 to the film surface.
(9) Flexibility Flexibility when the obtained tube (length: 15 cm) was bent at 180 degrees was evaluated (◯: good, x: poor).
(10) Bending resilience The obtained tube (length: 15 cm) was bent at 180 degrees to evaluate the state of the crease (◯: no crease, x: crease)

Production Example 1 (polymer m-TPO1)
(Catalyst adjustment)
Silica-supported methylmethylaluminoxane (supported MAO, Al supported amount: 14% by mass) and dimethylsilylene bis (2-methyl-benzo [e] indenyl) zirconium (IV) dichloride (complex A) and (1,2'-dimethylsilylene) ) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium (IV) dichloride (complex B) with respect to Al in the supported MAO, the Zr in the complex A is 0. A pre-polymerization was performed for 1 hour at 30 ° C. and a propylene pressure of 0.13 MPa using a catalyst supported so that the Zr in the complex B was 0.001.
(Production of polymer m-TPO1)
Into a 350 L autoclave, 100 L of liquid propylene was charged and 100 mmol of triisobutylaluminum was added. Then, 200 μmol of zirconium was added to the catalyst at 40 ° C. to initiate polymerization.
60 minutes after the start of polymerization, 0.1 MPa of ethylene was charged at a partial pressure, and the temperature was raised to 50 ° C.
Ethylene was continuously added so that the ethylene partial pressure was constant, and polymerization was carried out for 60 minutes.
After completion of the polymerization, the propylene was flushed and dried for 2 hours under a nitrogen stream at 80 ° C.
The obtained polymer had an ethylene unit content of 2.9 mol% and an intrinsic viscosity [η] in decalin at a temperature of 135 ° C. of 5.5 deciliter / g.
In this polymer, as an antioxidant, Irganox 1010 (manufactured by Ciba Specialty Chemicals) 500 ppm, Irgafos 168 (manufactured by Ciba Specialty Chemicals) 1000 ppm, as neutralizing agent, calcium stearate 300 ppm, As a peroxide, 1% by mass of Tr301-10PP (manufactured by Kayaku Akzo Co., Ltd.) was added, and the melt flow rate (MFR: 230 ° C., load 21.18 N) was 4 to 4 at the time of melt kneading in a twin screw extruder. Polymer m-TPO1 adjusted to 6 g / 10 min was obtained.
The physical properties of the obtained polymer m-TPO1 were measured. The results are shown in Table 1.

Production Example 2 (Polymer m-TPO2)
A polymer m-TPO2 was obtained in the same manner as the polymer m-TPO1 except that the ethylene partial pressure was 0.2 MPa.
The obtained polymer had an ethylene unit content of 5.1 mol% and an intrinsic viscosity [η] in decalin at a temperature of 135 ° C. of 5.3 deciliter / g.
With respect to the obtained polymer m-TPO2, the physical properties thereof were measured in the same manner as in Production Example 1.
The results are shown in Table 1.

Production Example 3 (Polymer m-TPO3)
A polymer m-TPO3 was obtained in the same manner as the polymer m-TPO1 except that the ethylene partial pressure was 0.35 MPa.
The obtained polymer had an ethylene unit content of 7.7 mol% and an intrinsic viscosity [η] in decalin at a temperature of 135 ° C. of 5.6 deciliter / g.
The physical properties of the obtained polymer m-TPO3 were measured in the same manner as in Production Example 1.
The results are shown in Table 1.

Production Example 4 (polymer m-TPO4)
A polymer m-TPO4 was obtained in the same manner as the polymer m-TPO1 except that the ethylene partial pressure was 0.4 MPa.
The obtained polymer had an ethylene unit content of 11.8 mol% and an intrinsic viscosity [η] in decalin at a temperature of 135 ° C. of 5.5 deciliter / g.
The physical properties of the obtained polymer m-TPO4 were measured in the same manner as in Production Example 1.
The results are shown in Table 1.

Reference example 1
In the polymer m-TPO1, as an antioxidant, Irganox 1010 (manufactured by Ciba Specialty Chemicals) 500 ppm, Irgafos 168 (manufactured by Ciba Specialty Chemicals) 1000 ppm, as neutralizing agent, calcium stearate As a peroxide, 1% by mass of Tr301-10PP (manufactured by Kayaku Akzo Co., Ltd.) is added as a peroxide, and a melt flow rate (MFR: 230 ° C., load 21.18 N) is applied during melt kneading in a twin screw extruder. Polymer m-TPO1 pellets (resin composition) adjusted to 4 to 6 g / 10 min were obtained.
About the obtained polymer m-TPO1 pellet, the physical property was measured.
The results are shown in Table 2.
Next, the polymer m-TPO1 pellet was extruded using a 40 mmφ cast molding machine at a die outlet resin temperature of 250 ° C. to obtain a 200 μm film. The physical properties of the obtained film were measured.
The results are shown in Table 2.

Reference example 2
Pellets were obtained in the same manner as in Reference Example 1 except that the polymer m-TPO2 was used.
The physical properties of the obtained pellets were measured. The results are shown in Table 2.
Next, a film was obtained in the same manner as in Reference Example 1 except that polymer m-TPO2 pellets were used, and the physical properties thereof were measured. The results are shown in Table 2.

Reference example 3
Pellets were obtained in the same manner as in Reference Example 1 except that the polymer m-TPO3 was used.
The physical properties of the obtained pellets were measured. The results are shown in Table 2.
Next, a film was obtained in the same manner as in Reference Example 1 except that polymer m-TPO3 pellets were used, and the physical properties thereof were measured. The results are shown in Table 2.

Example 4
Pellets were obtained in the same manner as in Reference Example 1 except that the polymer m-TPO4 was used.
The physical properties of the obtained pellets were measured. The results are shown in Table 2.
Next, a film was obtained in the same manner as in Reference Example 1 except that polymer m-TPO4 pellets were used, and the physical properties thereof were measured. The results are shown in Table 2.

Reference Example 5
Polymer m-TPO4 and random polypropylene (random PP) [Polypropylene F-730NV, ethylene unit content: 2.8 mol%, f _EEE : 0.6 mol%, melt flow rate (MFR); 7 g / 10 minutes, tensile modulus: 800 MPa, component 4 of 100 ° C. or higher fractionated by temperature rising temperature elution fractionation method (TREF); 30 mass%] blended at a mass ratio of 70/30, In the same manner as in Reference Example 1, pellets were obtained.
The physical properties of the obtained pellets were measured. The results are shown in Table 2.
Next, a film was obtained in the same manner as in Reference Example 1 except that the blended pellets were used, and the physical properties thereof were measured. The results are shown in Table 2.

Reference Example 6
Polymer m-TPO4 and random polypropylene (random PP) [Polypropylene F-730NV, ethylene unit content: 2.8 mol%, f _EEE : 0.6 mol%, melt flow rate (MFR); 7 g / 10 minutes, tensile elastic modulus: 800 MPa, component 4 of 100 ° C. or higher fractionated by temperature rising temperature elution fractionation method (TREF); 30 mass%] blended at a mass ratio of 50/50, In the same manner as in Reference Example 1, pellets were obtained.
The physical properties of the obtained pellets were measured. The results are shown in Table 2.
Next, a film was obtained in the same manner as in Reference Example 1 except that the blended pellets were used, and the physical properties thereof were measured. The results are shown in Table 2.

Comparative Example 1
Others using random polypropylene (random PP) [TPOJ-5910 manufactured by Prime Polymer Co., Ltd., ethylene unit content: 1.0 mol%, f _EEE : 0.4 mol%, melt flow rate (MFR); 8 g / 10 min] Produced pellets in the same manner as in Reference Example 1.
The physical properties of the obtained pellets were measured. The results are shown in Table 2.
Next, a film was obtained in the same manner as in Reference Example 1 except that J-5910 pellets were used, and the physical properties thereof were measured. The results are shown in Table 2.

Comparative Example 2
Others using random polypropylene (random PP) [TPOJ-5710 manufactured by Prime Polymer Co., Ltd., ethylene unit content: 1.0 mol%, f _EEE : 0.4 mol%, melt flow rate (MFR); 8 g / 10 min] Produced pellets in the same manner as in Reference Example 1.
The physical properties of the obtained pellets were measured. The results are shown in Table 2.
Next, a film was obtained in the same manner as in Reference Example 1 except that J-5710 pellets were used, and the physical properties thereof were measured. The results are shown in Table 2.

Comparative Example 3
Use random polypropylene (random PP) [TPOF-3740 manufactured by Prime Polymer Co., Ltd., ethylene unit content: 4.0 mol%, f _EEE : 1.7 mol%, melt flow rate (MFR); 4.5 g / 10 min] Otherwise, pellets were obtained in the same manner as in Reference Example 1.
The physical properties of the obtained pellets were measured. The results are shown in Table 2.
Next, a film was obtained in the same manner as in Reference Example 1 except that F-3740 pellets were used, and the physical properties thereof were measured. The results are shown in Table 2.

Comparative Example 4
Homopolypropylene (homo PP) [manufactured by Prime Polymer Co., Ltd. Polypropylene F-704NP, ethylene unit content: 0 mol%, f _EEE: 0 mol%, melt flow rate (MFR); 7.0g / 10 min] except for using the In the same manner as in Reference Example 1, pellets were obtained.
The physical properties of the obtained pellets were measured. The results are shown in Table 2.
Next, a film was obtained in the same manner as in Reference Example 1 except that F-704NP pellets were used, and the physical properties thereof were measured. The results are shown in Table 2.

Comparative Example 5
Random polypropylene (random PP) [manufactured by Prime Polymer Co. TPOT-310E, ethylene unit content: 30 mol%, f _EEE: 10 mol%, melt flow rate (MFR); 1.5g / 10 min] except for using the In the same manner as in Reference Example 1, pellets were obtained.
The physical properties of the obtained pellets were measured. The results are shown in Table 2.
Next, a film was obtained in the same manner as in Reference Example 1 except that T-310E pellets were used, and the physical properties thereof were measured. The results are shown in Table 2.

Example 7
The polymer m-TPO1 was molded at a set temperature of 250 ° C. and a mold temperature of 40 ° C. using a Nippon Steel Works 50t injection molding machine to obtain a test piece having a thickness of 1 mmt.
About the obtained test piece, all haze and its time-dependent change were measured.
The results are shown in Table 3.

Example 8
A test piece was obtained in the same manner as in Example 7 except that the polymer m-TPO2 was used, and the total haze and its change with time were measured.
The results are shown in Table 3.

Example 9
A test piece was obtained in the same manner as in Example 7 except that the polymer m-TPO4 was used, and the total haze and its change with time were measured.
The results are shown in Table 3.

Example 10
Polymer m-TPO4 and random polypropylene (random PP) [Polypropylene F-730NV, ethylene unit content: 2.8 mol%, f _EEE : 0.6 mol%, melt flow rate (MFR); 7 g / 10 minutes, tensile modulus: 800 MPa, components of 100 ° C. or higher fractionated by temperature-temperature elution fractionation (TREF); 30% by mass] blended at a mass ratio of 70/30. Test pieces were obtained in the same manner as in Example 7, and all haze and its change with time were measured.
The results are shown in Table 3.

Comparative Example 6
Others using random polypropylene (random PP) [TPOJ-5910 manufactured by Prime Polymer Co., Ltd., ethylene unit content: 1.0 mol%, f _EEE : 0.4 mol%, melt flow rate (MFR); 8 g / 10 min] Obtained the test piece like Example 7, and measured all the haze and its time-dependent change.
The results are shown in Table 3.

Comparative Example 7
Use random polypropylene (random PP) [TPOF-3740 manufactured by Prime Polymer Co., Ltd., ethylene unit content: 4.0 mol%, f _EEE : 1.7 mol%, melt flow rate (MFR); 4.5 g / 10 min] The test piece was obtained in the same manner as in Example 7, and the total haze and its change with time were measured.
The results are shown in Table 3.

Comparative Example 8
Random polypropylene (random PP) [manufactured by Prime Polymer Co. TPOT-310E, ethylene unit content: 30 mol%, f _EEE: 10 mol%, melt flow rate (MFR); 1.5g / 10 min] except for using the Test pieces were obtained in the same manner as in Example 7, and all haze and its change with time were measured.
The results are shown in Table 3.

Example 11
The polymer m-TPO2 was extruded at a set temperature of 230 ° C. using a 20 mmΦ extruder, and a tube having an outer diameter of 10 mmΦ was obtained by a plate sizing method.
The obtained tube was measured for transparency, change with time, bendability, and bend restoration property.
The results are shown in Table 4.

Example 12
A tube was obtained in the same manner as in Example 11 except that the polymer m-TPO3 was used.
The obtained tube was measured for transparency, change with time, bendability, and bend restoration property.
The results are shown in Table 4.

Comparative Example 9
Use random polypropylene (random PP) [TPOF-3740 manufactured by Prime Polymer Co., Ltd., ethylene unit content: 4.0 mol%, f _EEE : 1.7 mol%, melt flow rate (MFR); 4.5 g / 10 min] Otherwise, a tube was obtained in the same manner as in Example 11.
The obtained tube was measured for transparency, change with time, bendability, and bend restoration property.
The results are shown in Table 4.

Comparative Example 10
Other than using random polypropylene (random PP) [TPOT-310E manufactured by Prime Polymer Co., Ltd., ethylene unit content: 30 mol%, f _EEE : 10 mol%, melt flow rate (MFR); 1.5 g / 10 min] A tube was obtained in the same manner as in Example 11.
The obtained tube was measured for transparency, change with time, bendability, and bend restoration property.
The results are shown in Table 4.

  ADVANTAGE OF THE INVENTION According to this invention, the molded object excellent in the balance of transparency, a softness | flexibility, heat resistance, etc. in which the stickiness derived from propylene-type soft resin, the time-dependent change of an external appearance, etc. were improved is obtained. Therefore, application of films, sheets, tubes, hoses, injection-molded articles, laminates and the like utilizing these characteristics is expected in various industrial fields.

Claims (4)

It contains a propylene-ethylene copolymer having an ethylene unit content of 20 mol% or less and a triad chain fraction f _{EEE of} [EEE] of 0.1 mol% or less, and is fractionated by a temperature rising elution fractionation method (TREF). The molded object which consists of a resin composition in which the component to satisfy the following requirements.
Component 1: 0 soluble component at ℃ is 55-80 wt%
Component 2: 10-60 mass% of elution component exceeding 0 degreeC and 70 degrees C or less
Component 3: 5-50 mass% of elution components exceeding 70 degreeC and less than 100 degreeC
Ingredient 4: 0 to 30% by mass of eluted component at 100 ° C. or higher
However, it is the component 1 + component 2 + component 3 + component 4 = 100 mass%.   The intrinsic viscosity [η] measured in decalin at a temperature of 135 ° C. for the components fractionated by the temperature rising elution fractionation method (TREF) satisfies component 1 ≧ component 2> component 3, and the intrinsic viscosity of component 3 [ The molded body according to claim 1, comprising a resin composition in which η] exceeds 0.6 deciliter / g.   The molded article according to claim 1 or 2, wherein the ethylene unit content is 11.8 to 20 mol%. The molded body according to any one of claims 1 to 3, wherein the molded body is selected from a film, a sheet, a tube, a hose, an injection molded product, and a laminate.