JP2002371162A - 1-butene polymer composition and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a 1-butene polymer composition excellent in transparency and flexibility and improved in crystalline stabilization rate, and provide a molded product comprising the 1-butene polymer composition. SOLUTION: This 1-butene polymer composition is obtained by adding a nucleating agent to a 1-butene polymer having (1) a melting point which is not observed or 0-10 deg.C, (2) <=20 stereoregularity index [(mmmm)/(mmrr+rmmr)], (3) <=4.0 molecular weight distribution (Mw/Mn) and (4) 10,000-1,000,000 weight average molecular weight(Mw) or (6) or 1-butene homopolymer or a 1-butene copolymer obtained by polymerizing 1-butene with ethylene and/or a 3-20C α-olefin (except 1-butene) and having >=90 mole % structural unit derived from 1-butene and (7) having <=50% II type crystal fraction (CII) obtained by X-ray diffraction method after melting the polymer at 190 deg.C for 5 minutes, rapidly cooling to solidify with ice water and subsequently standing for at a room temperature for 1 hour. This molded product is obtained by molding the 1-butene polymer composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a 1-butene resin composition and a molded article thereof, and more particularly, to a 1-butene resin composition having excellent transparency and flexibility and an improved crystal stabilization rate. And a molded article thereof.

[0002]

2. Description of the Related Art 1-butene polymer (polybutene-1)
Has been used as a general-purpose resin for a wide variety of applications because it is tough, has excellent heat resistance, and is inexpensive. For example, 1-butene-based polymer is used as a cast film such as a biaxially stretched film or a laminated film because it has features such as extremely transparent, strong stiffness, heat resistance, and low moisture absorption. . Crystallinity 1
-Butene polymer films are widely used as packaging films, taking advantage of their excellent rigidity, transparency and moisture-proof properties. However, the 1-butene-based polymer film requires a large degree of supercooling to initiate crystallization and has a low crystallization temperature even at the same melting point, as compared with the ethylene-based polymer.
This is particularly noticeable in copolymers having low crystallinity, such as copolymers and polymers having low stereoregularity. Therefore, molding becomes difficult, and resin properties, low-temperature heat sealability, elastic modulus, impact resistance, and the like are reduced.

[0003] By the way, the 1-butene polymer has been produced by using a magnesium-supported titanium catalyst (JP-A-7-145205). Had an adverse effect. Regarding this point, in recent years, 1-butene polymers having a uniform composition have been obtained with metallocene catalysts (Japanese Patent Application Laid-Open Nos. 62-119214, 62-121708, 62-121707, 62-121707, 62-71). -119213, JP-A-8-225605). However, the homopolymers disclosed in these prior arts have high stereoregularity and lack flexibility. Therefore, in order to enhance flexibility, a copolymer of 1-butene and another α-olefin has been proposed. However, even when using a metallocene catalyst,
In the case of a simple 1-butene-based copolymer, the composition distribution may be widened, and it was not possible to effectively prevent crystal deformation, stickiness, and a decrease in transparency. In addition, it is generally known that 1-butene-based polymer shows different crystal states called type I crystal and type II crystal by X-ray diffraction analysis. The conventional 1-butene polymer is
The transition from the type II crystal state to the type I crystal state gradually occurs,
It has an inconvenience as a product such as shrinkage of a molded product.

[0004]

SUMMARY OF THE INVENTION The present invention provides a 1-butene resin composition having excellent transparency and flexibility and an improved crystal stabilization rate, and a molded article comprising the 1-butene resin composition. It is intended to do so.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and have found that (1) melting point, (2) stereoregularity index ｛(mmmm) / (mmrr)
+ Rmmr)｝, (3) molecular weight distribution (Mw / Mn),
(4) 1-weight-average molecular weight (Mw) in a specific range
It has been found that a composition obtained by adding a nucleating agent to a butene-based polymer has excellent transparency, flexibility and a crystal stabilization rate, and (5) a structural unit derived from 1-butene;
(6) The present inventors have found that a 1-butene-based polymer having a type II crystal fraction (CII) within a specific range has no change with time in the physical properties due to the crystal modification, and completed the present invention.

That is, the present invention provides the following 1-butene resin composition and a molded article thereof. 1. A 1-butene-based resin composition obtained by adding a nucleating agent to a 1-butene-based polymer satisfying the following (1) to (4) in an amount of 10 ppm or more. (1) Using a differential scanning calorimeter (DSC), the sample was melted at 190 ° C. for 5 minutes in a nitrogen atmosphere, and then −1 at 5 ° C./min.
After cooling down to 0 ° C, keeping at -10 ° C for 5 minutes,
The melting point (TmP) defined as the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained by raising the temperature at
Crystalline resin at 00 ° C. (2) Stereoregularity index ｛(mmmm) / (mmrr + r
(3) Gel permeation chromatograph (GPC)
Molecular weight distribution (Mw / Mn) measured by GPC method is 4.0 or less. (4) Weight average molecular weight (Mw) measured by GPC method.
Is a 10,000-1,000,000 2.1-butene-based polymer is a 1-butene homopolymer, and its mesopentad fraction (mmmm) is 20-90.
%, Which satisfies the following formula (1): 1-butene-based resin composition as described in 1 above. (Mmmm) ≦ 90−2 × (rr) (1) (rr is a racemic triad fraction) Using a differential scanning calorimeter (DSC), the sample was melted at 190 ° C. for 5 minutes in a nitrogen atmosphere, and then -10 at 5 ° C./min.
Temperature, and kept at -10 ° C for 5 minutes.
The melting point (Tm) (° C.) defined as the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained by raising the temperature in minutes, and a differential scanning calorimeter (DS)
Using C), the sample is melted at 190 ° C. for 5 minutes in a nitrogen atmosphere, and then rapidly cooled to 25 ° C. When the temperature is kept at 25 ° C., a crystallization exothermic peak is obtained from the time when the temperature is lowered to 25 ° C. The 1-butene-based resin composition according to the above 1 or 2, wherein the crystallization time (t) (minute) defined as the time until the satisfies the following formula (2). t ≦ 40−0.34 × Tm (2) 4.1 Melting point (Tm) (° C.) and crystallization time (t) (minute) of 1-butene resin composition and melting point (TmP) of 1-butene polymer ) (° C.) and crystallization time (tP) (minutes) (where tP is a value obtained by melting the sample at 190 ° C. for 5 minutes in a nitrogen atmosphere, rapidly lowering the temperature to 25 ° C., and maintaining the temperature at 25 ° C.) Is the time from when the temperature is lowered to 25 ° C. until the crystallization exothermic peak is obtained.)
The 1-butene-based resin composition according to any one of the above items 1 to 3, which satisfies (5). 0 ≦ Tm ≦ 100 (3) Tm−TmP ≦ 8 (4) t−tP ≦ −4 (5) A 1-butene-based resin composition obtained by adding 10 ppm or more of a nucleating agent to a 1-butene-based polymer satisfying the following (6) and (7). (6) 1-butene homopolymer or 1 obtained by copolymerizing 1-butene with ethylene and / or an α-olefin having 3 to 20 carbon atoms (excluding 1-butene).
-A butene-based copolymer, in which the structural unit derived from 1-butene is 90 mol% or more. 5. The type II crystal fraction (CII) obtained by analyzing from X-ray diffraction is 50% or less. 6. The 1-butene-based resin composition according to the above 5, wherein the weight average molecular weight (Mw) measured by GPC method is 10,000 to 1,000,000. 7. A molded article obtained by molding the 1-butene-based resin composition according to any one of the above 1 to 6.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION [1] 1-butene-based polymer, [2] Method for producing 1-butene-based polymer, [3] 1-
The butene-based resin composition and the molded article [4] will be sequentially described in detail.

[1] 1-Butene Polymer The 1-butene polymer used in the present invention includes a 1-butene homopolymer obtained by homopolymerizing 1-butene,
-There is a 1-butene copolymer obtained by copolymerizing butene with ethylene or an α-olefin having 3 to 20 carbon atoms (excluding 1-butene), and a 1-butene homopolymer is preferably used. As the α-olefin other than 1-butene constituting the 1-butene copolymer, ethylene, propylene,
1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1
-Eicosene, etc., and one or more of these can be used. As the 1-butene copolymer in the present invention, a random copolymer is preferred.
Further, the structural unit obtained from 1-butene is preferably at least 90 mol%, more preferably at least 95 mol%, particularly preferably at least 98 mol%. 1-
When the structural unit obtained from butene is less than 90 mol%, the surface of the molded product may be sticky or the transparency may be reduced.

The 1-butene-based polymer used in the present invention is a polymer which requires the following (1) to (4) or (6) to (7). (1) Using a differential scanning calorimeter (DSC), the sample was melted at 190 ° C. for 5 minutes in a nitrogen atmosphere, and then −1 at 5 ° C./min.
After cooling down to 0 ° C, keeping at -10 ° C for 5 minutes,
The melting point (TmP) defined as the peak top of the peak observed at the highest temperature of the melting endothermic curve obtained by raising the temperature at
Crystalline resin at 00 ° C. (2) Stereoregularity index ｛(mmmm) / (mmrr + r
(3) Gel permeation chromatograph (GPC)
Molecular weight distribution (Mw / Mn) measured by GPC method is 4.0 or less. (4) Weight average molecular weight (Mw) measured by GPC method.
(10) 1-butene homopolymer, or copolymerization of 1-butene with ethylene and / or an α-olefin having 3 to 20 carbon atoms (excluding 1-butene). 1 obtained
-A butene-based copolymer, in which the structural unit derived from 1-butene is 90 mol% or more. (7) After melting at 190 ° C for 5 minutes, solidifying rapidly with ice water, and leaving at room temperature for 1 hour, The type II crystal fraction (CII) obtained by analysis from X-ray diffraction is 50% or less

[0010] The 1-butene polymer in the present invention is a crystalline compound having at least a substantially melting point. The melting point (TmP) is usually observed with a differential scanning calorimeter (DSC). In the present invention, having a melting point substantially means
It means that a crystal melting peak is substantially observed in DSC measurement. The crystal melting peak is, for example, the TmP
Alternatively, it refers to TmD described later, and a peak is observed under at least one of the measurement conditions. The 1-butene-based polymer in the present invention satisfies the above-mentioned relationship, and thus has an excellent balance between the amount of the sticky component of the obtained molded article and the like, the low elastic modulus and the transparency. That is, the elastic modulus is low, the softness (also referred to as flexibility) is excellent, the sticky component is small, and the surface characteristics (for example, the transfer of the sticky component to bleed and other products are small) are excellent, and There is an advantage that transparency is also excellent.

The 1-butene polymer used in the present invention has no melting point (TmP) from the viewpoint of softness, or has a melting point (TmP) of 0 to 100 ° C., preferably 0 to 80 ° C. It is necessary that The melting point (TmP) of the 1-butene polymer is determined by DSC measurement. That is, using a differential scanning calorimeter (DSC-7, manufactured by Perkin-Elmer Co., Ltd.), previously melt 10 mg of a sample in a nitrogen atmosphere at 190 ° C. for 5 minutes, and then lower the temperature to −10 ° C. at 5 ° C./min. The heat of crystallization obtained by the above is ΔHc. Further, after holding at −10 ° C. for 5 minutes, the endothermic amount obtained by increasing the temperature at 10 ° C./min is defined as ΔH, and the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained at this time is defined as ΔH. Melting point (TmP).

Further, the 1-butene polymer used in the present invention may be a crystalline resin having a melting point (TmD) of 0 to 100 ° C. by a differential scanning calorimeter (DSC) from the viewpoint of softness. . TmD is preferably from 0 to 80C. Note that TmD is determined by DSC measurement. That is, a differential scanning calorimeter (manufactured by Perkin-Elmer, DSC-7)
Then, after holding 10 mg of the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, the melting endotherm obtained by increasing the temperature at 10 ° C./min is defined as ΔHD. In addition, the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained at this time is the melting point (TmD).

Such a 1-butene polymer is a crystalline resin satisfying the following (1 ′) to (4 ′). (1 ′) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min. (2 ') Stereoregularity index ｛(mmmm) / (mmrr +)
rmmr)｝ is 20 or less. (3 ′) Gel permeation chromatograph (GP
3. The molecular weight distribution (Mw / Mn) measured by the method C) is 4.
0 or less (4 ′) Weight average molecular weight (M
w) is in the range of 10,000 to 1,000,000 The 1-butene polymer used in the present invention has excellent flexibility and preferably 10 J / g or less when the melting endotherm ΔHD measured by DSC is 50 J / g or less. Is more preferable. ΔHD is an index indicating whether the material is soft or not, and when this value is large, the elastic modulus is high and the softness is low.

In the 1-butene homopolymer used in the present invention, the stereoregularity index ｛(mmmm) / (mmrr + rmmr) obtained from the (mmmm) fraction and the (mmrr + rmmr) fraction of the 1-butene chain portion. }But,
It is 20 or less, preferably 18 or less, more preferably 15 or less. When the stereoregularity index exceeds 20, the flexibility, the low-temperature heat sealing property, and the hot tack property are reduced.

[0015] In the 1-butene polymer used in the present invention, the mesopentad fraction (mmmm) and the abnormal insertion content (1,4 insertion fraction) are determined according to V.I. "Macromol. Chem. Phy reported by Busico et al.
s. , 198, 1257 (1997) ". That is, the signals of methylene group and methine group are measured using ¹³ C nuclear magnetic resonance spectrum, and the fraction of mesopentad and the content of abnormal insertion in the poly (1-butene) molecule are determined. The measurement of the ¹³ C nuclear magnetic resonance spectrum is performed using the following apparatus and conditions. Apparatus: JNM-EX400 type ¹³ CN manufactured by JEOL Ltd.
MR apparatus Method: Proton complete decoupling method Concentration: 230 mg / mL Solvent: 90:10 (volume ratio) of 1,2,4-trichlorobenzene and heavy benzene Mixed solvent Temperature: 130 ° C Pulse width: 45 ° Pulse repetition time: 4 seconds integration: 10,000 times Stereoregularity index ｛(mmmm) / (mmrr + rmm)
r)｝ is (mmmm), (mmm
r) and (rmmr) are calculated from the measured values, and the racemic triad fraction (rr) is also calculated by the above method.

The 1-butene polymer of the present invention has a molecular weight distribution (Mw / Mw /
Mn) is 4 or less, preferably 3.5 or less, particularly preferably 3.0 or less. Molecular weight distribution (Mw / Mn)
Exceeds 4, stickiness may occur. Also,
In the present invention, the 1-butene-based polymer has a G
The weight average molecular weight measured by the PC method is 100,00
0-1,000,000, preferably 100,000-
1,000,000. If Mw is less than 100,000, stickiness may occur. Also, 1,00
If it exceeds 000, the fluidity will be reduced and the moldability may be poor.

The above molecular weight distribution (Mw / Mn)
Is a value calculated from the mass average molecular weight Mw and the number average molecular weight Mn in terms of polystyrene measured by the GPC method using the following apparatus and conditions. 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)

In addition to the above requirements, the 1-butene polymer of the present invention has a melting endotherm ΔH of 50 J measured by DSC.
/ G or less is preferred because of excellent flexibility.
/ G or less. ΔH is an index indicating whether the material is soft or not, and when this value is large, it means that the elastic modulus is high and the softness is low. Note that ΔH
Is determined by the method described above.

The 1-butene polymer of the present invention preferably has a mesopentad fraction (mmmm) of 20 to 90%, more preferably 30 to 85%, and more preferably 30 to 85%.
Most preferably, it is で 80%. If the mesopentad fraction is less than 20%, the surface of the molded product may be sticky or the transparency may be reduced. On the other hand, if it exceeds 90%, the flexibility, the low-temperature heat sealing property, and the hot tack property may be reduced. The 1-butene homopolymer in the present invention is (mmmm) ≦ 90−2 × (rr)
Preferably, the relationship of (mmmm) ≦
More preferably, the relationship of 87-2 × (rr) is satisfied. If this relationship is not satisfied, the surface of the molded article may be sticky or the transparency may be reduced.

The 1-butene polymer or 1-butene resin composition of the present invention has a component (H25) eluting in hexane at 25 ° C. of 0 to 80% by weight. It is preferably from 0 to 60% by weight, particularly preferably from 0 to 50% by weight. H25 is an index indicating whether the amount of a so-called sticky component that causes stickiness, a decrease in transparency, or the like is large or small. The higher this value is, the larger the amount of the sticky component is. When H25 exceeds 80% by weight, the amount of the sticky component is large, blocking is reduced, and it may not be used for food or medical use. Note that H2
5 means the weight (W ₀ ) (0.9 to 1.1 g) of the 1-butene-based polymer or 1-butene-based resin composition and the polymer in 200 mL of hexane at 25 ° C. for 4 days The weight loss (W ₁ ) after the standing and drying was measured and calculated according to the following equation. W25 = [(W ₀ −W ₁ ) / W ₀ ] × 100 (%)

In the case of requirements (6) to (7), ie, 1-
Butene homopolymer, or 1-butene and ethylene and / or an α-olefin having 3 to 20 carbon atoms (however,
-Butene) obtained by copolymerizing 1-butene, wherein the structural unit derived from 1-butene is 90%.
In the case of not less than mol%, it was melted at 190 ° C. for 5 minutes, quenched and solidified with ice water, left at room temperature for 1 hour, and then analyzed by X-ray diffraction to obtain a type II crystal fraction. (CII) must be 50% or less, preferably 20% or less, more preferably 0%. In the present invention, the type II crystal fraction (CII) is determined according to A.I. Turner J
"Polymer, 7, 2" reported by ones et al.
3 (1966) ".
That is, the peak of the type I crystal state and the peak of the type II crystal state were measured by X-ray diffraction analysis, and the type II crystal fraction (CII) in the crystal of the 1-butene homopolymer was determined. X-ray diffraction analysis (WAXD) was performed using the anti-cathode type rotor flex RU-200 manufactured by Rigaku Denki KK under the following conditions. Sample condition: Melted at 190 ° C for 5 minutes, quenched and solidified with ice water, then left at room temperature for 1 hour Output: 30 kV, 200 mA Detector: PSPC (Position-sensitive proportional counter) Integration time: 200 seconds

In the case of requirements (6) and (7), GPC
Weight average molecular weight (Mw) is 10,000
It is preferably from 0 to 1,000,000. It is more preferably from 100,000 to 1,000,000, and still more preferably from 100,000 to 500,000.
If Mw is less than 10,000, stickiness may occur. On the other hand, when it exceeds 1,000,000, the fluidity is reduced and the moldability may be poor. The method of measuring Mw / Mn and Mw is the same as described above.

[2] Method for Producing 1-Butene Polymer The method for producing 1-butene polymer in the present invention includes a method of homopolymerizing 1-butene using a catalyst system called a metallocene catalyst or a method of producing 1-butene. Butene and ethylene and / or
Alternatively, a method of copolymerizing an α-olefin having 3 to 20 carbon atoms (excluding 1-butene) may be used. Examples of metallocene catalysts include JP-A-58-19309, JP-A-61-130314, and JP-A-3-16308.
8, JP-A-4-300887, JP-A-4-30087
Transition having one or two ligands such as a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group as described in JP-A No. 211694, JP-T No. 1-50203 and the like. Examples include a metal compound and a catalyst obtained by combining a promoter with a transition metal compound in which the ligand is geometrically controlled, and these are called highly ordered metallocene catalysts.

The method for producing the 1-butene polymer of the present invention is preferably a metallocene catalyst in which the ligand comprises a transition metal compound having a crosslinked structure via a crosslinking group. However, a method of homopolymerizing 1-butene using a metallocene catalyst (highly-ordered metallocene catalyst) obtained by combining a transition metal compound forming a crosslinked structure via two crosslinking groups with a cocatalyst, or A method of copolymerizing 1-butene with ethylene and / or an α-olefin having 3 to 20 carbon atoms (excluding 1-butene) is more preferable. Specifically, (A) the general formula (I)

[0025]

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[Wherein M represents a metal element belonging to Groups 3 to 10 of the periodic table or a lanthanoid series, and E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentade group, respectively. A ligand selected from a dienyl group, a substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group and a silicon-containing group, forming a crosslinked structure via A ¹ and A ² 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,
It may be crosslinked with E ¹ , E ² or Y. Y represents a Lewis base, if Y is plural, the plurality of Y may be the same or different, other Y, it may be crosslinked E ^1, E ² or X, A ¹ and A ² A divalent cross-linking group bonding two ligands, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group,
Germanium-containing group, tin-containing group, -O-, -CO-,
_{-S -, - SO 2 -,} - Se -, - NR 1 -, - PR 1
-, - P (O) R 1 -, - BR 1 - or -AlR ¹ - are shown, R ¹ represents a hydrogen atom, a halogen atom, having from 1 to 20 carbon atoms
Or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. q represents an integer of 1 to 5 and represents ((valence of M) -2), and r represents an integer of 0 to 3. (B) (B-1) a compound capable of reacting with the transition metal compound of the component (A) or a derivative thereof to form an ionic complex; and (B-2) A method of homopolymerizing 1-butene in the presence of a polymerization catalyst containing a component selected from aluminoxane, or 1-butene and ethylene and / or an α-olefin having 3 to 20 carbon atoms (excluding 1-butene) ) Is copolymerized.

In the above general formula (I), M represents a metal element belonging to Groups 3 to 10 of the periodic table or a lanthanoid series;
Specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium, and lanthanoid-based metals. It is suitable. E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, an amide group (-N <), and a phosphine group (-P <),
Hydrocarbon group [>CR-,> C <] and silicon-containing group [> S
iR-,> Si <] (where R is hydrogen or carbon number 1-2)
0 is a hydrocarbon group or a hetero atom-containing group), and forms a crosslinked structure via A ¹ and A ² . E ¹ and E ² may be the same or different. As E ¹ and E ² , a substituted cyclopentadienyl group, an indenyl group and a substituted indenyl group are preferred.

X represents a σ-binding ligand. When there are a plurality of X's, a plurality of X's may be the same or different and are cross-linked to other X, E ¹ , E ² or Y. You may.
Specific examples of X include a halogen atom and a carbon atom having 1 to 20 carbon atoms.
Hydrocarbon group, C1-20 alkoxy group, C6-20 aryloxy group, C1-20 amide group, C1-20 silicon-containing group, C1-20 phosphide Group, sulfide group having 1 to 20 carbon atoms, 1 carbon atom
And 20 acyl groups. On the other hand, Y represents a Lewis base, and when there are a plurality of Ys, the plurality of Ys may be the same or different, and may be cross-linked to another Y, E ¹ , E ² or X. Specific examples of the Lewis base of Y include amines, ethers, phosphines, thioethers and the like.

Next, A ¹ and A ² are divalent bridging groups for bonding the two ligands, and include a hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group containing 1 to 20 carbon atoms. , Silicon-containing group, germanium-containing group, tin-containing group, -O-, -C
O -, - S -, - SO 2 -, - Se -, - NR 1 -, -
PR ^1- , -P (O) R ^1- , -BR ¹ -or -AlR
¹ - shows a, R ¹ represents a hydrogen atom, a hydrocarbon group having a halogen atom or having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, they may be the same with or different from each other. As such a crosslinking group, for example, a general formula

[0030]

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(D is carbon, silicon or tin, R ² and R
³ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, each of which may be the same or different, and which may be bonded to each other to form a ring structure. e shows the integer of 1-4. ). Specific examples thereof include a methylene group, an ethylene group, an ethylidene group, a propylidene group, an isopropylidene group, a cyclohexylidene group, a 1,2-cyclohexylene group, a vinylidene group (CH ₂ = C =), dimethylsilylene group, diphenylsilylene group, methylphenylsilylene group, dimethylgermylene group, dimethylstannylene group, tetramethyldisilylene group, diphenyldisilylene group, and the like. Among them, an ethylene group, an isopropylidene group and a dimethylsilylene group are preferred. q represents an integer of 1 to 5 and represents ((valence of M) -2), and r represents an integer of 0 to 3. Among such transition metal compounds represented by general formula (I), general formula (II)

[0032]

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A transition metal compound having a double-bridged biscyclopentadienyl derivative represented by the following formula as a ligand is preferable. In the general formula (II), M, A ¹ , A ² , q and r are the same as above. X ¹ represents a σ-bonding ligand, and when plural X ^1, a plurality of X ¹ may be the same or different, may be crosslinked with other X ¹ or Y ^1. Specific examples of X ¹ include the same as those exemplified in the description of X in the general formula (I). Y
¹ represents a Lewis base, and when there are a plurality of Y ¹ ,
¹ may be the same or different, and may be crosslinked with another Y ¹ or X ¹ . Specific examples of Y ¹ include the same as those exemplified in the description of Y in the general formula (I). R ^{4 to} R ⁹ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
The halogen-containing hydrocarbon group, silicon-containing group or heteroatom-containing group, at least one of which must not be a hydrogen atom. Further, R ^{4 to} R ⁹ may be the same or different, and adjacent groups may be bonded to each other to form a ring. Among them, it is preferable that R ⁶ and R ⁷ form a ring, and that R ⁸ and R ⁹ form a ring. As R ⁴ and R ⁵ , groups containing a heteroatom such as oxygen, halogen, silicon and the like are preferable because of their high polymerization activity.

The transition metal compound having the double-bridged biscyclopentadienyl derivative as a ligand preferably contains silicon in a bridging group between the ligands. Specific examples of the transition metal compound represented by the general formula (I) include (1,2′-
Ethylene) (2,1′-ethylene) -bis (indenyl) zirconium dichloride, (1,2′-methylene)
(2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,2′-isopropylidene)
(2,1′-isopropylidene) -bis (indenyl)
Zirconium dichloride, (1,2'-ethylene)
(2,1′-ethylene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-ethylene)
(2,1′-ethylene) -bis (4,5-benzoindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4-isopropylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (5,6-dimethylindenyl) zirconium dichloride, (1,2′-ethylene)
-Ethylene) (2,1'-ethylene) -bis (4,7-
Diisopropylindenyl) zirconium dichloride,
(1,2′-ethylene) (2,1′-ethylene) -bis (4-phenylindenyl) zirconium dichloride,
(1,2′-ethylene) (2,1′-ethylene) -bis (3-methyl-4-isopropylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-
Ethylene) -bis (5,6-benzoindenyl) zirconium dichloride, (1,2′-ethylene) (2,1 ′
-Isopropylidene) -bis (indenyl) zirconium dichloride, (1,2'-methylene) (2,1'-ethylene) -bis (indenyl) zirconium dichloride, (1,2'-methylene) (2,1'- Isopropylidene) -bis (indenyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-methylindenyl) ) Zirconium dichloride, (1,2′-dimethylsilylene)
(2,1′-dimethylsilylene) bis (3-n-butylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-i-propylindenyl) Zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene ) Screw (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 ) Screw (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, (1,2′-dimethylsilylene) (2,1′-isopropylidene) ) -Bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-
Isopropylidene) -bis (3-phenylindenyl)
Zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene)
(2,1′-methylene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) -bis (3-i-propylindenyl) zirconium dichloride , (1,2 '
-Dimethylsilylene) (2,1′-methylene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) -bis (3-trimethylsilylmethyl (Indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) -bis (3-trimethylsilylindenyl) zirconium dichloride,
2'-diphenylsilylene) (2,1'-methylene)-
Bis (indenyl) zirconium dichloride, (1,
2'-diphenylsilylene) (2,1'-methylene)-
Bis (3-methylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) -bis (3-i-propylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) )
(2,1′-methylene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) -bis (3-trimethylsilylmethylindenyl) zirconium Dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) ( 3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3 '-Methylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-ethylene) ( 3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene)
(2,1′-methylene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-
Isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-methylene) (3-methylcyclopentadienyl) (3'-
Methylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride,
(1,2′-isopropylidene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3 ′
-Methylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) (Enyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,
2'-dimethylsilylene) (2,1'-ethylene)
(3,4-dimethylcyclopentadienyl) (3 ′,
4'-dimethylcyclopentadienyl) zirconium dichloride, (1,2'-ethylene) (2,1'-methylene) (3,4-dimethylcyclopentadienyl)
(3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1 ′
-Isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-methylene)
(2,1′-methylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropyl) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride,
2'-isopropylidene) (2,1'-isopropylidene) (3,4-dimethylcyclopentadienyl)
(3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene)
(2,1′-dimethylsilylene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, ( 1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-isopropylcyclopentadienyl) (3′-
Methyl-5'-isopropylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-methyl-5
-N-butylcyclopentadienyl) (3'-methyl-
5′-n-butylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,
1'-dimethylsilylene) (3-methyl-5-phenylcyclopentadienyl) (3'-methyl-5'-phenylcyclopentadienyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, ( 1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5-i-propylcyclopentadienyl) (3′-
Methyl-5'-i-propylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) (3-methyl-5
-N-butylcyclopentadienyl) (3'-methyl-
5′-n-butylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,
1'-isopropylidene) (3-methyl-5-phenylcyclopentadienyl) (3'-methyl-5'-phenylcyclopentienyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-ethylcyclopentadienyl)
(3′-methyl-5′-ethylcyclopentadienyl)
Zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-i-propylcyclopentadienyl) (3′-methyl-5′-
i-propylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-
Ethylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride, (1,2′-
Dimethylsilylene) (2,1′-ethylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) ) (2,
1′-methylene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′- Methylene) (3-methyl-
5-i-propylcyclopentadienyl) (3'-methyl-5'-i-propylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene)
(2,1′-methylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-methylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride, (1 , 2'-Ethylene) (2,1'-methylene) (3-methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'-
i-propylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-isopropylidene) (3-methyl-5-i-propylcyclopentadienyl) (3′-methyl-5 '-I-propylcyclopentadienyl) zirconium dichloride, (1,
2′-methylene) (2,1′-methylene) (3-methyl-5-i-propylcyclopentadienyl) (3′-methyl-5′-i-propylcyclopentadienyl) zirconium dichloride, (1 , 2'-methylene) (2,
1'-isopropylidene) (3-methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'-i
-Propylcyclopentadienyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) bisindenylzirconium dichloride, (1,1′-diphenylsilylene) (2,2′-dimethyl (Silylene) bisindenyl zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) bisindenyl zirconium dichloride, (1,1′-diisopropylsilylene) (2,2 ′)
-Dimethylsilylene) bisindenylzirconium dichloride, (1,1′-dimethylsilylene) (2,2′-
(Diisopropylsilylene) bisindenyl zirconium dichloride, (1,1′-dimethylsilyleneindenyl) (2,2′-dimethylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1 ′
-Diphenylsilyleneindenyl) (2,2'-diphenylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1'-diphenylsilyleneindenyl) (2,2'-dimethylsilylene-3-trimethylsilylindenyl) Zirconium dichloride,
(1,1′-dimethylsilylene) (2,2′-dimethylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,1′-diphenylsilylene) (2,2′-diphenylsilylene) ( Indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,1′-diphenylsilylene)
(2,2′-dimethylsilylene) (indenyl) (3-
Trimethylsilylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-diphenylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,1′-
Diisopropylsilylene) (2,2′-dimethylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-diisopropylsilylene) (indenyl) (3-trimethylsilyl (Indenyl) zirconium dichloride, (1,1′-diisopropylsilylene) (2,2′-diisopropylpropylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2 ,
2′-dimethylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1′-diphenylsilylene) (2,2′-diphenylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium Dichloride,
(1,1′-diphenylsilylene) (2,2′-dimethylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1 ′
-Dimethylsilylene) (2,2′-diphenylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1′-diisopropylsilylene) (2,2′-dimethylsilylene) (indenyl) (3 -Trimethylsilylmethylindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-diisopropylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1'-diisopropylsilylene) Examples thereof include (2,2′-diisopropylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride and those obtained by substituting zirconium in these compounds with titanium or hafnium. Of course, it is not limited to these. Further, a similar compound of a metal element of another group or a lanthanoid series may be used. In the above compound, (1,1 ′-) (2,2′-) is replaced with (1,2′-)
(2,1′-), and (1,2 ′-) (2,
1′-) may be (1,1 ′-) (2,2′-).

Next, as the component (B-1) of the component (B), any compound capable of reacting with the transition metal compound of the component (A) to form an ionic complex can be used. The following general formulas (III), (IV) ([L ¹ −R ¹⁰ ] ^{k +} ) _a ([Z] ⁻ ) _b ... (III) ([L ² ] ^{k +} ) _a ([Z] ^-) _b ··· (IV) (provided that, L ² is ^{M 2, R 11 R 12 M} 3, R 13 3 C or R
A ¹⁴ M ^3. In the formulas (III) and (IV), L ¹ is a Lewis base, and [Z] ⁻ is
Non-coordinating anion [Z ^{1] -} and [Z ^{2] -,} wherein [Z ^{1] -} anion in which a plurality of groups are bonded to the element ^{[M 1 G 1 G 2 ··· G} f ] ^- ( Here, M ¹ is an element belonging to Groups 5 to 15 of the periodic table, preferably ^{13 to 1} of the periodic table.
Shows Group 5 elements. G ^{1 to} G ^f each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon atom having 2 to 4 carbon atoms.
0 dialkylamino group, C1-C20 alkoxy group, C6-C20 aryl group, C6-C20 aryloxy group, C7-C40 alkylaryl group, C7-C40 Arylalkyl group, 1 to 1 carbon atoms
A halogen-substituted hydrocarbon group of 20; an acyloxy group of 1 to 20 carbon atoms; an organic metalloid group; or a heteroatom-containing hydrocarbon group of 2 to 20 carbon atoms. 2 out of G ^{1 to} G ^f
One or more may form a ring. f is [(center metal M
Represents an integer of ¹ valence) +1]. ), [Z ² ] ^-
A conjugate base of a Bronsted acid alone or a combination of a Bronsted acid and a Lewis acid having a logarithm (pKa) of the reciprocal of the acid dissociation constant of −10 or less, or a conjugate base of an acid generally defined as a super strong acid is shown. Further, a Lewis base may be coordinated. Also, R ¹⁰ 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, R ¹¹ and R ¹²
Represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ¹³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. R ¹⁴ represents a macrocyclic ligand such as tetraphenylporphyrin and phthalocyanine. k is an ionic valence of [L ¹ -R ¹⁰ ] and [L ² ], an integer of 1 to 3, a is an integer of 1 or more, and b = (k × a). M ² contains an element from Groups 1 to ³ , 11 to 13, and 17 of the periodic table, and M ³ represents an element from Groups 7 to 12 of the periodic table. ] Can be suitably used.

Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, and triethylphosphine Phosphines such as triphenylphosphine and diphenylphosphine; thioethers such as tetrahydrothiophene; esters such as ethyl benzoate; and nitriles such as acetonitrile and benzonitrile.

Specific examples of R ¹⁰ include hydrogen, methyl group, ethyl group, benzyl group, and trityl group. Specific examples of R ¹¹ and R ¹² include cyclopentadienyl group, methylcyclopentane Examples thereof include a dienyl group, an ethylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Specific examples of R ¹³ include a phenyl group, a p-tolyl group, a p-methoxyphenyl group and the like, and specific examples of R ¹⁴ include a tetraphenylporphine, phthalocyanine, allyl, methallyl and the like. . Specific examples of M ² include Li, Na, K, Ag, Cu, Br, I, and I _3. Specific examples of M ³ include Mn, F
e, Co, Ni, Zn and the like.

[Z ¹ ] ⁻ , that is, [M ¹ G ¹ G
² ... G ^f ], B and A are specific examples of M ^1.
l, Si, P, As, Sb, etc., preferably B and Al
Is mentioned. Specific examples of G ¹ , G ^{2 to} G ^f include dimethylamino and diethylamino as dialkylamino groups, and methoxy, ethoxy, n-butoxy groups as alkoxy or aryloxy groups.
Methyl, ethyl, n-propyl, isopropyl, n-butyl, etc.
Fluorine, chlorine, bromine, halogen atoms such as isobutyl group, n-octyl group, n-eicosyl group, phenyl group, p-tolyl group, benzyl group, 4-t-butylphenyl group and 3,5-dimethylphenyl group; Iodine, p-fluorophenyl group as a hetero atom-containing hydrocarbon group, 3,5
-Difluorophenyl group, pentachlorophenyl group,
Organic metalloid groups such as 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group, bis (trimethylsilyl) methyl group, etc. as pentamethylantimony group, trimethylsilyl group, trimethyl Examples include a germyl group, a diphenylarsine group, a dicyclohexylantimony group, and diphenylboron.

Further, a non-coordinating anion, ie, pKa
Specific examples of the conjugated base [Z ² ] ⁻ of a Brönsted acid alone or a combination of a Brönsted acid and a Lewis acid having a -10 or less are trifluoromethanesulfonic acid anion (CF ₃ SO ₃ ) ⁻ , bis (trifluoromethanesulfonyl) ) Methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (Cl
O ₄ ) ^- , trifluoroacetic acid anion (CF ₃ CO ₂ )
^- , Hexafluoroantimony anion (Sb
F ₆ ) ^- , fluorosulfonic acid anion (FS
O ₃ ) ^- , chlorosulfonic acid anion (ClS
O ₃ ) ^- , fluorosulfonate anion / 5-antimony fluoride (FSO ₃ / SbF ₅ ) ^- , fluorosulfonate anion / 5-arsenic fluoride (FSO ₃ / As)
F ₅₎ ^-, trifluoromethanesulfonic acid / antimony pentafluoride _{(CF 3 SO 3 / SbF 5} ) - and the like.

Specific examples of the ionic compound forming an ionic complex by reacting with the transition metal compound of the component (A), that is, the compound of the component (B-1) include
Triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyltetraphenylborate (tri-n- Butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyl 2-phenylopyridinium Triethylammonium, tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate ) Tri-n-butylammonium borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetra-n-butylammonium tetrakis (pentafluorophenyl) borate, tetraethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Benzyl (tri-n-butyl) ammonium borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, methylanilinium tetrakis (pentafluorophenyl) borate, tetrakis (pentane) Dimethylanilinium fluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, tetrakis Methylpyridinium pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate, benzyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate, tetrakis ( Methyl pentafluorophenyl) borate (4-cyanopyridinium), triphenylphosphonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate, ferrocenium tetraphenylborate, tetraphenyl Silver borate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, tetrakis (pentafluorophenyl) borate Rosenium, tetrakis (pentafluorophenyl)
(1,1'-dimethylferrocenium borate), decamethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Lithium borate, sodium tetrakis (pentafluorophenyl) borate, tetraphenylporphyrin manganese tetrakis (pentafluorophenyl) borate, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate,
Silver perchlorate, silver trifluoroacetate, silver trifluoromethanesulfonate and the like can be mentioned. (B-1) may be used alone, or two or more kinds may be used in combination. On the other hand, as the aluminoxane of the component (B-2), the general formula (V)

[0041]

Embedded image

(Wherein R ¹⁵ represents an alkyl group, alkenyl group, aryl group having 1 to 20, preferably 1 to 12 carbon atoms,
It represents a hydrocarbon group such as an arylalkyl group or a halogen atom, w represents an average degree of polymerization, and is usually an integer of 2 to 50, preferably 2 to 40. In addition, each R ¹⁵ may be the same or different. Aluminoxane represented by the general formula (VI):

[0043]

Embedded image

(In the formula, R ¹⁵ and w are the same as those in the above formula (V).)

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. The means is not particularly limited, and the reaction may be carried out according to a known method. For example,
A method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, a method in which an organoaluminum compound is initially added during polymerization and water is added later, water of crystallization contained in a metal salt, etc., inorganic substances Reacting water adsorbed on organic substances with organic aluminum compounds,
There is a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum and then reacting with water. The aluminoxane may be insoluble in toluene.

These aluminoxanes may be used alone or in combination of two or more. When the (B-1) compound is used as the (B) catalyst component, the molar ratio of the (A) catalyst component to the (B) catalyst component is preferably from 10: 1 to 1: 100, Preferably 2: 1
If the ratio deviates from the above range, the catalyst cost per unit mass polymer increases,
Not practical. When the compound (B-2) is used, the molar ratio is preferably 1: 1 to 1: 1,000,000,
More preferably, the range is from 1:10 to 1: 10000. If the ratio is out of this range, the cost of the catalyst per unit mass polymer increases, which is not practical. As the catalyst component (B), (B-1) and (B-2) may be used alone or in combination of two or more.

As the polymerization catalyst for producing the 1-butene polymer, 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), a compound represented by the general formula (VII): R ¹⁶ _v AlJ _3-v (VII) wherein R ¹⁶ is an alkyl group having 1 to 10 carbon atoms, and J is Hydrogen atom, alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
And v is an integer of 1 to 3]. Specific examples of the compound represented by the general formula (VII) 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. In the method for producing a 1-butene-based polymer, preliminary contact can also be performed using the above-mentioned components (A), (B) and (C). The preliminary contact is carried out by adding the component (A) to, for example,
It can be performed by contacting the component (B),
The method is not particularly limited, and a known method can be used. These preliminary contacts are effective in reducing the catalyst cost, such as improving the catalyst activity and reducing the proportion of the component (B) used as a promoter. Further, by bringing the component (A) and the component (B-2) into contact with each other, an effect of improving the molecular weight can be observed in addition to the above effects. The pre-contact temperature is usually -20C to 200C, preferably -10C to 1C.
The temperature is 50 ° C, more preferably 0 ° C to 80 ° C. In the preliminary contact, an aliphatic hydrocarbon, an aromatic hydrocarbon, or the like can be used as the inert hydrocarbon of the solvent. Particularly preferred among these are aliphatic hydrocarbons.

The use ratio of the catalyst component (A) to the catalyst component (C) is preferably 1: 1 to 1: 1000 in molar ratio.
0, more preferably 1: 5 to 1: 2000, and still more preferably 1:10 to 1: 1000.
By using the catalyst component (C), the polymerization activity per transition metal can be improved. However, if it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable. In the production of the 1-butene polymer, at least one of the catalyst components can be used by being supported on a suitable carrier. The type of the carrier is not particularly limited, and any of inorganic oxide carriers, other inorganic carriers and organic carriers can be used,
In particular, inorganic oxide carriers or other inorganic carriers are preferred.

As the inorganic oxide carrier, specifically, S
iO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , F
e ₂ O ₃ , B ₂ O ₃ , CaO, ZnO, BaO, ThO
₂ and mixtures thereof, for example, silica alumina, zeolite, ferrite, glass fiber and the like.
Among them, SiO ₂ and Al ₂ O ₃ are particularly preferable. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate, or the like.

On the other hand, as a carrier other than the above, MgC
general formula M represented by l ₂ , Mg (OC ₂ H ₅ ) _2, etc.
gR magnesium compound or a complex salt represented by the ¹⁷ _X X ¹ _y can be exemplified. Here, R ¹⁷ has 1 carbon atom.
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 ¹⁷ and each X
¹ may be the same or different. As the organic carrier, polystyrene, styrene-divinylbenzene copolymer, polyethylene, poly 1-
Examples thereof include polymers such as butene, substituted polystyrene, and polyarylate, starch, and carbon.

A catalyst used for producing a 1-butene-based polymer
As the carrier of the medium, MgCl_Two, MgCl (OC
_TwoH_Five), Mg (OC_TwoH_Five)_Two, SiO_Two, Al_TwoO
_ThreeAre preferred. The nature of the carrier depends on its type and
The average particle size is usually 1 to 300 μm,
Preferably 10 to 200 μm, more preferably 20 to 10
0 μm. Fine powder in polymer increases with small particle size
When the particle size is large, the coarse particles in the polymer increase and the bulk density increases.
Of the hopper and clogging of the hopper. In addition, the carrier
The specific surface area is usually 1 to 1000 m^Two/ G, preferably 5
0-500m^Two/ G, pore volume is usually 0.1-5 cm^Three
/ G, preferably 0.3-3 cm ^Three/ G.

If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and the pore volume can be determined, for example, from the volume of nitrogen gas adsorbed according to the BET method. further,
When the carrier is an inorganic oxide carrier, usually 150
It is desirable to use it after firing at 1000 to 1000C, preferably 200 to 800C. When at least one of the catalyst components is supported on the carrier, it is desirable that at least one of the catalyst component (A) and the catalyst component (B), and preferably both the catalyst component (A) and the catalyst component (B) be supported. .

The method for supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited. For example, at least one of the components (A) and (B) is mixed with the carrier. Method, a method of treating a carrier with an organoaluminum compound or a halogen-containing silicon compound, and then mixing the carrier with at least one of the component (A) and the component (B) in an inert solvent.
Or a method of reacting the component (B) with an organoaluminum compound or a halogen-containing silicon compound, a method of supporting the component (A) or the component (B) on a carrier, and then mixing the component (B) or the component (A). And a method of mixing the contact reactant of the components (A) and (B) with the carrier, and a method of coexisting the carrier during the contact reaction between the components (A) and (B).

In the above and methods,
An organoaluminum compound as the component (C) may be added. In the production of the catalyst used for producing the 1-butene polymer, the catalyst may be prepared by irradiating an elastic wave when the above (A), (B) and (C) are brought into contact.
Examples of the elastic wave include a 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 is used.

The catalyst thus obtained may be subjected to solvent distillation once, taken out as a solid, and then used for polymerization, or may be used for polymerization as it is. Also, 1-
In the production of a butene-based polymer, a catalyst can be generated by performing an operation of loading at least one of the component (A) and the component (B) on a carrier in a polymerization system.
For example, at least one of the component (A) and the component (B), a carrier and, if necessary, the organoaluminum compound of the component (C) are added.
A method may be used in which pre-polymerization is performed at −20 to 200 ° C. for about 1 minute to 2 hours in addition to MPa (gauge) to generate catalyst particles.

The use ratio of the component (B-1) and the carrier in the catalyst used for producing the 1-butene polymer is as follows:
The mass ratio is preferably from 1: 5 to 1: 10000, more preferably from 1:10 to 1: 500, and (B
-2) The use ratio of the component to the carrier is preferably 1: 0.5 to 1: 1000, more preferably 1: 1 to 1: by mass ratio.
It is desirable to set it to 50. When two or more of the components (B) are used as a mixture, it is desirable that the use ratio of each component (B) to the carrier be within the above range in terms of mass ratio. Also,
The use ratio of the component (A) to the carrier is preferably 1: 5 to 1: 10000, more preferably 1:10 to 1 by mass.
It is desirable to set 1: 500.

Component (B) [Component (B-1) or (B-
When the usage ratio of the (2) component] and the carrier or the usage ratio of the component (A) and the carrier deviates from the above range, the activity may be reduced. The average particle size of the polymerization catalyst thus prepared is usually 2 to 200 μm, preferably 10 to 15 μm.
0 μm, particularly preferably 20 to 100 μm, and the specific surface area is usually 20 to 1000 m ² / g, preferably 50
５００500 m ² / g. If the average particle size is less than 2 μm, fine powder in the polymer may increase, and if it exceeds 200 μm, coarse particles in the polymer may increase. If the specific surface area is less than 20 m ² / g, the activity may decrease, and if it exceeds 1000 m ² / g, the bulk density of the polymer may decrease. In the catalyst used for producing the 1-butene-based polymer, the amount of the transition metal in 100 g of the carrier is usually 0.05 to 10 g, and particularly preferably 0.1 to 2 g. If the amount of the transition metal is outside the above range, the activity may be reduced.

By supporting on a carrier as described above, a polymer having a high bulk density and excellent particle size distribution, which are industrially advantageous, can be obtained. The 1-butene polymer used in the present invention is obtained by homopolymerizing 1-butene or 1-butene and ethylene and / or an α-olefin having 3 to 20 carbon atoms using the above-described polymerization catalyst (provided that (Excluding 1-butene). In this case, 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. The polymerization method is particularly preferred.

Regarding the polymerization conditions, the polymerization temperature is usually -1.
00 to 250 ° C, preferably -50 to 200 ° C, more preferably
Preferably it is 0-130 degreeC. In addition,
The ratio of the catalyst used is determined by the ratio of the starting monomer / component (A)
Ratio is preferably 1 to 10. ⁸, Especially 100 to 10^FiveWhen
Preferably, The polymerization time is usually 5 minutes to 10 hours,
The reaction pressure is preferably from normal pressure to 20 MPa (gaug).
e), more preferably normal pressure to 10 MPa (gaug)
e).

The method for adjusting the molecular weight of the polymer includes selection of the type and amount of each catalyst component used, the polymerization temperature, and polymerization in the presence of hydrogen. When a polymerization solvent is used, 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 And halogenated hydrocarbons such as chloroform and dichloromethane. These solvents may be used alone or in a combination of two or more. Further, a monomer such as an α-olefin may be used as the solvent. In addition, depending on the polymerization method, it can be carried out without a solvent.

In the polymerization, preliminary polymerization can be performed using the polymerization catalyst. The prepolymerization can be performed by, for example, 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 may be the same as those exemplified above, for example, ethylene, α-α having 3 to 20 carbon atoms.
An olefin or a mixture thereof can be used, but it is advantageous to use the same olefin as the olefin used in the polymerization.

The prepolymerization temperature is usually from -20 to 20.
0 ° C, preferably -10 to 130 ° C, more preferably 0 ° C.
８０80 ° C. In the prepolymerization, an aliphatic hydrocarbon, an aromatic hydrocarbon, a monomer, or the like can be used as a solvent. Of these, aliphatic hydrocarbons are particularly preferred. Further, the prepolymerization may be performed without a solvent. In the prepolymerization, the intrinsic viscosity [η] (measured in decalin at 135 ° C.) of the prepolymerized product is 0.2 deciliter / g or more, especially 0.5 deciliter / g or more, and per 1 mmol of transition metal component in the catalyst. It is desirable to adjust the conditions so that the amount of the prepolymerized product is from 1 to 10,000 g, especially from 10 to 1000 g.

[3] 1-butene-based resin composition A 1-butene-based polymer is produced by the above method, and a 1-butene-based resin composition is obtained by adding a nucleating agent thereto. Generally, crystallization of a 1-butene polymer is composed of two processes, a crystal nucleation process and a crystal growth process.
In the crystal nucleus generation process, it is said that the state such as the temperature difference from the crystallization temperature and the orientation of the molecular chains influence the crystal nucleus generation rate. In particular, it is known that the presence of a substance having an effect of promoting molecular chain orientation through molecular chain adsorption or the like significantly increases the crystal nucleation rate. Any nucleating agent may be used as long as it has the effect of improving the progress rate of the crystal nucleation process. Substances that have the effect of improving the progress rate of the crystal nucleation process include substances that have the effect of promoting molecular chain orientation through the process of adsorbing the molecular chains of the polymer.

Specific examples of the nucleating agent include a high melting point polymer, an organic carboxylic acid or a metal salt thereof, an aromatic sulfonate or a metal salt thereof, an organic phosphoric acid compound or a metal salt thereof, dibenzylidene sorbitol or a derivative thereof. , Rosin acid partial metal salts, inorganic fine particles, imides, amides, quinacridones, quinones or mixtures thereof. One of these nucleating agents may be used, or two or more of them may be used in combination.

As the high melting point polymer, polyethylene,
Polyolefin such as polypropylene, polyvinylcyclohexane, polyvinylcycloalkane such as polyvinylcyclopentane, syndiotactic polystyrene, poly3-methylpentene-1, poly3-methylbutene-1,
And polyalkenylsilane. Examples of the metal salt include aluminum benzoate, aluminum pt-butyl benzoate, sodium adipate, sodium thiophenecarboxylate, sodium pyrrolecarboxylate and the like.

A film formed by molding a 1-butene polymer composition containing dibenzylidene sorbitol or a derivative thereof as a nucleating agent is particularly suitable for packaging toys, stationery, etc. because of its excellent transparency and large display effect. It is. Examples of dibenzylidene sorbitol or a derivative thereof include dibenzylidene sorbitol, 1,3: 2,4-bis (o-
3,4-dimethylbenzylidene) sorbitol, 1,
3: 2,4-bis (o-2,4-dimethylbenzylidene) sorbitol, 1,3: 2,4-bis (o-4-ethylbenzylidene) sorbitol, 1,3: 2,4-bis (o- 4-chlorobenzylidene) sorbitol, 1,
3: 2,4-dibenzylidene sorbitol and the like. Further, specifically, Gelol MD and Gelol MD-R (trade name) manufactured by Shin Nippon Rika (manufactured by) are also included.
Examples of the rosin acid partial metal salt include Pine Crystal KM1600 and Pine Crystal KM1 manufactured by Arakawa Chemical Industries, Ltd.
500 and Pine Crystal KM1300 (trade name).

The 1-butene-based resin composition is preferably formed by using the above-mentioned inorganic fine particles such as talc as a nucleating agent, since when formed into a film, the film has excellent slip properties and improves properties such as printing properties. . Inorganic fine particles include talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, alumina, silica, diatomaceous earth, titanium oxide, magnesium oxide, pumice Powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate,
Barium sulfate, calcium sulfite, molybdenum sulfide and the like can be mentioned.

In the 1-butene-based resin composition of the present invention, it is preferable to use inorganic fine particles such as an organic metal phosphate and / or talc represented by the following general formula, because they generate less odor. This 1-butene-based resin composition is suitable for use in food products. Specific examples of metal organic phosphates include:
ADK STAB NA-11 and ADK STAB NA-21 (manufactured by Asahi Denka Co., Ltd.).

[0070]

Embedded image

(Wherein R ¹⁸ is a hydrogen atom or a carbon atom having 1 to 4 carbon atoms)
R ¹⁹ and R ²⁰ are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group,
It represents an aryl group or an aralkyl group. M represents any one of an alkali metal, an alkaline earth metal, aluminum and zinc. When M is an alkali metal, m is 0, n
Represents 1, n represents 1 or 2 when M is an alkaline earth metal or zinc, m represents 1 when n is 1, m represents 0 when n is 2, m when aluminum is aluminum Represents 1 and n represents 2. )

Further, 1 containing an amide compound as a nucleating agent
-A film formed by molding a butene-based polymer composition is particularly excellent in rigidity and hardly causes problems such as winding wrinkles in high-speed bag-making. Examples of the amide compound include dianilide adipate and dianilide sperate.

The amount of the nucleating agent to be added is usually 10 ppm or more, preferably 50 ppm, based on the 1-butene polymer.
３3000 ppm. If the amount is less than 10 ppm, the moldability is not improved, and on the other hand, even if the amount of the nucleating agent is increased, the effect corresponding thereto may not be obtained. Also,
Although it depends on the type of nucleating agent, generally, from the viewpoint of the transparency and impact resistance of the 1-butene polymer composition, the amount of the nucleating agent added is preferably 1000 ppm or less, and more preferably 500 ppm or less. preferable. As a more specific addition amount, as sorbidol-based nucleating agent, dibenzylidene sorbitol is preferably 3000 ppm or less, more preferably 1500 ppm or less, and particularly preferably 500 ppm or less. For bis (p-methylbenzylidene) sorbitol and bis (dimethylbenzylidene) sorbitol, the content is preferably 1200 ppm or less, more preferably 600 ppm or less, and particularly preferably 300 ppm or less. In the case of a sodium salt of organic phosphate, which is a metal salt of organic phosphate, the concentration is preferably 500 ppm or less, more preferably 250 ppm or less, and particularly preferably 125 ppm or less. In the organic phosphoric acid Al salt, 1900 ppm or less, further 150
It is preferably at most 0 ppm, particularly preferably at most 500 ppm. As talc, manufactured by Asada Flour Milling Co., Ltd., talc MMR is 4000 ppm or less, further 2000 ppm or less,
In particular, it is preferably 1000 ppm or less. Nester NU manufactured by Nippon Rika Co., Ltd. as an amide compound
At -100, 3000 ppm or less, and 1500p
pm or less, particularly preferably 500 ppm or less.

The 1-butene resin composition of the present invention comprises
(1) a method of dry-blending a butene-based polymer with the above-mentioned nucleating agent and various additives used as desired using a Henschel mixer or the like; (2) a single-screw or twin-screw extruder, Banbury A method of melt-kneading using a mixer or the like. (3) When using a high-melting polymer as a nucleating agent, at the time of producing a 1-butene polymer, add the high-melting polymer simultaneously or sequentially in a reactor. It is manufactured by a manufacturing method or the like. Various additives used as desired include antioxidants, neutralizing agents, slip agents, antiblocking agents, antifogging agents, and antistatic agents.

In the 1-butene resin composition of the present invention, the relationship between the melting point Tm (° C.) and the crystallization time t (min) is 0 ≦ Tm ≦ 100 and t ≦ 40−0.34 × Tm. Is preferably satisfied, and more preferably t ≦ 35−0.34 × Tm is satisfied. t ≦ 40−0.34 × Tm
Is not satisfied, the balance between the melting point and the crystallization time is poor, and in particular, the secondary workability such as heat-sealing and hot tack deteriorates.

Further, the 1-butene resin composition of the present invention has a melting point Tm (° C.) and a crystallization time t (min) of the 1-butene resin composition and a melting point Tm of the 1-butene polymer.
The relationship between P (° C.) and the crystallization time tP (min) is expressed by T
It is preferable that m-TmP ≦ 8 and t−tP ≦ −4 are satisfied, and it is more preferable that Tm−TmP ≦ 4 and t−tP ≦ −6 be satisfied. Further, it is more preferable that Tm−TmP ≦ 2 and t−tP ≦ −8 are satisfied. This relationship represents a balance between the deterioration of the secondary workability due to the increase in the melting point due to the effect of adding the nucleating agent and the moldability due to the improvement of the crystallization rate.

[4] Molded Article The molded article of the present invention is a molded article obtained by molding the above 1-butene resin composition. The molded article of the present invention is characterized by being excellent in transparency and flexibility and having a high crystal stabilization rate. As the molded article of the present invention, films, sheets,
Containers, interior materials for automobiles, housing materials for home electric appliances, and the like. Examples of the film include a food packaging film and an agricultural film (an example of a greenhouse). Examples of the container include a case, a box, a decorative box, and the like.

The molding method of the molded article includes an injection molding method,
Examples include a compression molding method, an injection compression molding method, a gas assist injection molding method, an extrusion molding method, and a blow molding method. The molding conditions are not particularly limited as long as the resin is at a temperature at which the resin melts and flows. Usually, the resin temperature is 50 ° C to 300 ° C,
It can be performed at a mold temperature of 60 ° C. or less. When a film is formed as the molded article of the present invention, a general compression molding method, an extrusion molding method, a blow molding method, a cast molding method, or the like can be used. Further, the film obtained by molding the 1-butene resin composition of the present invention may or may not be stretched. When stretching, biaxial stretching is preferred. The conditions for biaxial stretching include the following conditions. Molding conditions during sheet molding Resin temperature 50 to 200 ° C, chill roll temperature 50 ° C or less Longitudinal stretching condition 3 to 7 times stretching ratio, 50 to 100 ° C stretching temperature Horizontal stretching condition 6 to 12 times stretching ratio, 50 to 100 ° C stretching temperature

The film obtained by molding the 1-butene resin composition of the present invention may be treated, if necessary, to increase the surface energy or polarize the surface. Good. For example, examples of the treatment method include a corona discharge treatment, a chromic acid treatment, a flame treatment, a hot air treatment, and an ozone or ultraviolet irradiation treatment. Examples of the method for making the surface uneven include a sand blast method and a solvent treatment method. The film obtained by molding the 1-butene-based resin composition of the present invention contains a commonly used antioxidant, a neutralizing agent,
A slip agent, an anti-blocking agent, an anti-fogging agent, an antistatic agent and the like can be added as required. Further, the film containing inorganic fine particles such as talc has excellent slip properties, so that secondary processing properties such as bag making and printing are improved, and various general-purpose packaging films in high-speed production equipment such as various automatic filling packaging laminations. It is suitable for.

Further, a multilayer film can be produced from the 1-butene resin composition according to the present invention. The method for producing the 1-butene-based resin multilayer laminate is not particularly limited, and examples thereof include a method for producing by a melt coextrusion molding method. Among them, a T-die cast molding method, which enables high-speed molding by a large molding machine, is particularly preferable. The take-up speed is usually 50 m / min or more, and may be a high-speed film forming condition. The thickness of the multilayer laminate is not particularly limited, but is usually about 10 to 5000 μm. The molded article (press molding) of the 1-butene-based resin composition of the present invention has excellent transparency and flexibility, has an improved crystal stabilization speed, and has a film of the 1-butene-based resin composition of the present invention. Is excellent in low-temperature heat sealability, heat sealability and antiblocking property.

[0081]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. First, the resin properties of the 1-butene-based polymer and the 1-butene-based resin composition of the present invention and the method for evaluating the physical properties of the molded article will be described.

(Resin Properties) (1) Mesopentad Fraction, Racemic Triad Fraction, Abnormal Insertion Amount, and Stereoregularity Index Measured by the method described in the specification. (2) Weight average molecular weight (Mw) and molecular weight distribution (Mw /
Mn) It was measured by the method described in the specification text. (3) DSC measurement (3-1) DSC measurement of 1-butene polymer Differential scanning calorimeter (manufactured by Perkin-Elmer, DSC-
7) Using 10 mg of sample in advance in a nitrogen atmosphere
After melting at 90 ° C. for 5 minutes, the crystallization exotherm obtained by lowering the temperature to −10 ° C. at 5 ° C./min was defined as ΔHc. The peak top of the maximum peak of the crystallization exothermic curve obtained at this time was defined as the crystallization temperature Tc (° C.). Further, after holding at −10 ° C. for 5 minutes, the endothermic amount obtained by increasing the temperature at 10 ° C./min was defined as ΔH. The peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained at this time was defined as the melting point (TmP). (3-2) DSC measurement of 1-butene resin composition Differential scanning calorimeter (manufactured by Perkin-Elmer, DSC-
7) Using 10 mg of sample in advance in a nitrogen atmosphere
After melting at 90 ° C. for 5 minutes, the crystallization exotherm obtained by lowering the temperature to −10 ° C. at 5 ° C./min was defined as ΔHc. The peak top of the maximum peak of the crystallization exothermic curve obtained at this time was defined as the crystallization temperature Tc (° C.). Further, after holding at −10 ° C. for 5 minutes, the endothermic amount obtained by increasing the temperature at 10 ° C./min was defined as ΔH. The peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained at this time was defined as the melting point (Tm). (4) Crystallization time (4-1) Crystallization time of 1-butene polymer Differential scanning calorimeter (manufactured by Perkin-Elmer, DSC-
7) Using 10 mg of sample in advance in a nitrogen atmosphere
After melting at 90 ° C for 5 minutes, the temperature was rapidly lowered to 25 ° C,
It was kept at 25 ° C. The time from this point until the crystallization exothermic peak was obtained was defined as the crystallization time (tP). (4-2) Crystallization time of 1-butene resin composition Differential scanning calorimeter (manufactured by Perkin-Elmer, DSC-
7) Using 10 mg of sample in advance in a nitrogen atmosphere
After melting at 90 ° C for 5 minutes, the temperature was rapidly lowered to 25 ° C,
It was kept at 25 ° C. The time from this point until the crystallization exothermic peak was obtained was defined as the crystallization time (t). (5) Type II crystal fraction (CII) It was measured by the method described in the specification.

(Evaluation of Physical Properties of Press-Molded Body) (5) Tensile Modulus A pellet of the resin composition was press-molded to prepare a test piece, which was measured under the following conditions in accordance with JIS K-7113. -Crosshead speed: 50 mm / min (6) Internal haze It was measured by a test based on JIS K-7105.

Production Example 1 (Preparation of polymerization catalyst) (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethyl) used as a catalyst in the production of a polymer by the following method Indenyl) zirconium dichloride was produced. In a Schlenk bottle, 3.0 g (6.97 mmol) of a lithium salt of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (indene) was dissolved in 50 ml of THF and cooled to −78 ° C. Then, 2.1 ml (14.2 mmol) of iodomethyltrimethylsilane was slowly dropped, and the mixture was stirred at room temperature for 12 hours. The solvent was distilled off, 50 ml of ether was added, and the mixture was washed with a saturated ammonium chloride solution. After liquid separation, the organic phase was dried and the solvent was removed, and 3.04 g (5.88 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) was obtained. Was obtained (yield 84%). Next, the (1,2′-dimethylsilylene) (2, obtained above) was placed in a Schlenk bottle under a nitrogen stream.
3.04 g (5.88 mmol) of 1'-dimethylsilylene) -bis (3-trimethylsilylmethylindene)
And 50 ml of ether, cooled to −78 ° C., and a hexane solution of n-BuLi (1.54 M,
7.6 ml (1.7 mmol)) were added dropwise.
After raising the temperature to room temperature and stirring for 12 hours, ether was distilled off. The solid thus obtained was washed with 40 ml of hexane to convert the lithium salt into an ether adduct of 3.06 g.
(5.07 mmol) was obtained (yield 73%). ¹ H N
As a result of measurement by MR (90 MHz, THF-d ₈ ), δ was 0.04 (s, 18H, trimethylsilyl);
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 in a nitrogen stream was dissolved in 50 ml of toluene, cooled to −78 ° C., and 1.2 g (5.1 mmol) of zirconium tetrachloride previously cooled to −78 ° C. in toluene (20 ml) ) The suspension was added dropwise. After dripping,
After stirring at room temperature for 6 hours, the solvent of the reaction solution was distilled off. The resulting residue was recrystallized from dichloromethane to give 0.9 g (1 .
33 mmol) (26% yield). ¹ H NMR
(90 MHz, CDCl ₃ ) showed that δ was 0.0 (s, 18H, trimethylsilyl); 1.02
1.12 (s, 12H, dimethylsilylene); 2.51
(Dd, 4H, methylene); 7.1-7.6 (m, 8
H, Ar-H).

Production Example 2 (Production of 1-butene-based polymer) 1.6 L of heptane, 2 kg of 1-butene and 10 mmol of methylaluminoxane were added to a heated and dried 10-liter autoclave, and hydrogen was further added at 0.03 MPa.
Introduced. After the temperature was raised to 50 ° C. with stirring, (1,2′-dimethylsilylene) of the catalyst prepared in Production Example 1 was used.
(2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride (10 μmol) was added and polymerized for 60 minutes. After the completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 850 g of a 1-butene polymer.

Example 1 To a 1-butene polymer obtained in Production Example 2 was added 1000 ppm of an antioxidant Irganox 1010 and 1000 ppm of a nucleating agent Gelol MD, and a single screw extruder (TLC35 manufactured by Tsukada Juki Seisakusho, Ltd.) -20) and extruded and granulated.
Pellets of the butene-based resin composition were obtained. The evaluation results of the obtained 1-butene-based resin composition and the press-formed product are shown in the first section.
It is shown in the table.

Reference Example 1 The procedure of Example 1 was repeated without adding a nucleating agent to the 1-butene polymer obtained in Production Example 2. Table 1 shows the evaluation results of the obtained 1-butene-based polymer and the press-formed product.

[0088]

[Table 1]

In Table 1, since Reference Example 1 does not add a nucleating agent to the 1-butene polymer, the melting point of Reference Example 1 is TmP, the crystallization time is tP, and the formula (3)
It can be seen that this satisfies (5).

[0090]

The molded article comprising the 1-butene-based resin composition of the present invention has excellent transparency and flexibility and a high crystal stabilization rate, and thus can be used for films, sheets, containers, automobile interior materials, and home electric appliances. It can be suitably used as a housing material of the above, and can be produced industrially advantageously. Further, since resin compositions having different properties can be obtained by the nucleating agent added in the present invention, molded articles for various uses can be obtained by adding the nucleating agent according to the purpose.

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[Procedure amendment]

[Submission date] November 2, 2001 (2001.11.
2)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 5

[Correction method] Change

[Correction contents]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction contents]

That is, the present invention provides the following 1-butene resin composition and a molded article thereof. 1. A 1-butene-based resin composition obtained by adding a nucleating agent to a 1-butene-based polymer satisfying the following (1) to (4) in an amount of 10 ppm or more. (1) Using a differential scanning calorimeter (DSC), the sample was melted at 190 ° C. for 5 minutes in a nitrogen atmosphere, and then −1 at 5 ° C./min.
After cooling down to 0 ° C, keeping at -10 ° C for 5 minutes,
The melting point (TmP) defined as the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained by raising the temperature at
Crystalline resin at 00 ° C. (2) Stereoregularity index ｛(mmmm) / (mmrr + r
(3) Gel permeation chromatograph (GPC)
Molecular weight distribution (Mw / Mn) measured by GPC method is 4.0 or less. (4) Weight average molecular weight (Mw) measured by GPC method.
Is a 10,000-1,000,000 2.1-butene-based polymer is a 1-butene homopolymer, and its mesopentad fraction (mmmm) is 20-90.
%, Which satisfies the following formula (1): 1-butene-based resin composition as described in 1 above. (Mmmm) ≦ 90−2 × (rr) (1) (rr is a racemic triad fraction) Using a differential scanning calorimeter (DSC), the sample was melted at 190 ° C. for 5 minutes in a nitrogen atmosphere, and then -10 at 5 ° C./min.
Temperature, and kept at -10 ° C for 5 minutes.
The melting point (Tm) (° C.) defined as the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained by raising the temperature in minutes, and a differential scanning calorimeter (DS)
Using C), the sample is melted at 190 ° C. for 5 minutes in a nitrogen atmosphere, and then rapidly cooled to 25 ° C. When the temperature is kept at 25 ° C., a crystallization exothermic peak is obtained from the time when the temperature is lowered to 25 ° C. The 1-butene-based resin composition according to the above 1 or 2, wherein the crystallization time (t) (minute) defined as the time until the satisfies the following formula (2). t ≦ 40−0.34 × Tm (2) 4.1 Melting point (Tm) (° C.) and crystallization time (t) (minute) of 1-butene resin composition and melting point (TmP) of 1-butene polymer ) (° C.) and crystallization time (tP) (minutes) (where tP is a value obtained by melting the sample at 190 ° C. for 5 minutes in a nitrogen atmosphere, rapidly lowering the temperature to 25 ° C., and maintaining the temperature at 25 ° C.) Is the time from when the temperature is lowered to 25 ° C. until the crystallization exothermic peak is obtained.)
The 1-butene-based resin composition according to any one of the above items 1 to 3, which satisfies (5). 0 ≦ Tm ≦ 100 (3) Tm−TmP ≦ 8 (4) t−tP ≦ −4 (5) A 1-butene-based resin composition obtained by adding 10 ppm or more of a nucleating agent to a 1-butene-based polymer satisfying the following (6) and (7). (6) 1-butene homopolymer or 1 obtained by copolymerizing 1-butene with ethylene and / or an α-olefin having 3 to 20 carbon atoms (excluding 1-butene).
-A butene-based copolymer, in which the structural unit derived from 1-butene is 90 mol% or more. , II-type crystal fraction obtained in more analyzed X-ray diffraction (CII) is less than 50% 6. 6. The 1-butene-based resin composition according to the above 5, wherein the weight average molecular weight (Mw) measured by GPC method is 10,000 to 1,000,000. 7. A molded article obtained by molding the 1-butene-based resin composition according to any one of the above 1 to 6.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction contents]

The 1-butene-based polymer used in the present invention is a polymer which requires the following (1) to (4) or (6) to (7). (1) Using a differential scanning calorimeter (DSC), the sample was melted at 190 ° C. for 5 minutes in a nitrogen atmosphere, and then −1 at 5 ° C./min.
After cooling down to 0 ° C, keeping at -10 ° C for 5 minutes,
The melting point (TmP) defined as the peak top of the peak observed at the highest temperature of the melting endothermic curve obtained by raising the temperature at
Crystalline resin at 00 ° C. (2) Stereoregularity index ｛(mmmm) / (mmrr + r
(3) Gel permeation chromatograph (GPC)
Molecular weight distribution (Mw / Mn) measured by GPC method is 4.0 or less. (4) Weight average molecular weight (Mw) measured by GPC method.
(10) 1-butene homopolymer, or copolymerization of 1-butene with ethylene and / or an α-olefin having 3 to 20 carbon atoms (excluding 1-butene). 1 obtained
-A butene-based copolymer, in which the structural unit derived from 1-butene is 90 mol% or more. , II-type crystal fraction obtained in more analyzed X-ray diffraction (CII) is 50% or less

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction contents]

The 1-butene polymer used in the present invention has a melting point (TmP) from the viewpoint of softness .
Alternatively, the melting point (TmP) needs to be 0 to 100 ° C, preferably 0 to 80 ° C. In addition, this 1
-The melting point (TmP) of the butene polymer is determined by DSC measurement. That is, a differential scanning calorimeter (Perkin
Using Elmer, DSC-7), prepare sample 1 in advance.
0 mg was melted at 190 ° C. for 5 minutes under a nitrogen atmosphere,
The crystallization exotherm obtained by lowering the temperature to −10 ° C. at 5 ° C./min is defined as ΔHc. Further, after holding at −10 ° C. for 5 minutes, the endothermic amount obtained by increasing the temperature at 10 ° C./min is defined as ΔH, and the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained at this time is defined as ΔH. Melting point (TmP).

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction contents]

The 1-butene polymer of the present invention has a molecular weight distribution (Mw / Mw /
Mn) is 4 or less, preferably 3.5 or less, particularly preferably 3.0 or less. Molecular weight distribution (Mw / Mn)
Exceeds 4, stickiness may occur. Also,
In the present invention, the 1-butene-based polymer has a G
The weight average molecular weight measured by the PC method is 10,000
~ 1,000,000, preferably 100,000 ~ 1,
1,000,000. If Mw is less than 10,000 ,
Stickiness may occur. Also, 1,000,000
If it exceeds 0, the moldability may be poor because the fluidity is reduced.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0030

[Correction method] Change

[Correction contents]

[0030]

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Claims (7)

[Claims] 1. A 1-butene-based resin composition obtained by adding a nucleating agent to a 1-butene-based polymer satisfying the following (1) to (4) in an amount of 10 ppm or more. (1) Using a differential scanning calorimeter (DSC), the sample was melted at 190 ° C. for 5 minutes in a nitrogen atmosphere, and then −1 at 5 ° C./min.
After cooling down to 0 ° C, keeping at -10 ° C for 5 minutes,
The melting point (TmP) defined as the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained by raising the temperature at
Crystalline resin at 00 ° C. (2) Stereoregularity index ｛(mmmm) / (mmrr + r
(3) Gel permeation chromatograph (GPC)
Molecular weight distribution (Mw / Mn) measured by GPC method is 4.0 or less. (4) Weight average molecular weight (Mw) measured by GPC method.
Is 10,000-1,000,000 2. The 1-butene polymer is a 1-butene homopolymer and has a mesopentad fraction (mmmm) of 20.
The 1-butene-based resin composition according to claim 1, wherein the composition satisfies the following formula (1). (Mmmm) ≦ 90−2 × (rr) (1) (rr is a racemic triad fraction) 3. Using a differential scanning calorimeter (DSC), melt the sample at 190 ° C. for 5 minutes in a nitrogen atmosphere,
The temperature is defined as the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained by lowering the temperature to −10 ° C. in minutes, holding at −10 ° C. for 5 minutes, and then increasing the temperature at 10 ° C./min. Using a melting point (Tm) (° C.) and a differential scanning calorimeter (DSC), the sample was heated at 190 ° C. in a nitrogen atmosphere.
After melting for 5 minutes, the temperature was rapidly lowered to 25 ° C.
The crystallization time (t) (minute) defined as the time from when the temperature is lowered to 25 ° C. to when a crystallization exothermic peak is obtained when the temperature is kept at 5 ° C., satisfies the following formula (2).
Or the 1-butene resin composition according to claim 2. t ≦ 40−0.34 × Tm (2) 4. Melting point (Tm) of 1-butene resin composition
(° C) and crystallization time (t) (min), melting point (TmP) (° C) and crystallization time (tP) of 1-butene polymer
(Min) (Here, tP was measured at 190 ° C. in a nitrogen atmosphere.
After melting for 5 minutes, the temperature was rapidly lowered to 25 ° C.
This is the time from when the temperature is lowered to 25 ° C. when the crystallization exothermic peak is obtained when the temperature is kept at 5 ° C. ) Satisfies the following formulas (3) to (5): 1-butene-based resin composition according to claim 1. 0 ≦ Tm ≦ 100 (3) Tm−TmP ≦ 8 (4) t−tP ≦ −4 (5) 5. A 1-butene-based resin composition comprising a 1-butene-based polymer satisfying the following (6) and (7) and a nucleating agent added in an amount of 10 ppm or more. (6) 1-butene homopolymer or 1 obtained by copolymerizing 1-butene with ethylene and / or an α-olefin having 3 to 20 carbon atoms (excluding 1-butene).
-A butene-based copolymer, in which the structural unit derived from 1-butene is 90 mol% or more. (7) After melting at 190 ° C for 5 minutes, solidifying rapidly with ice water, and leaving at room temperature for 1 hour, The type II crystal fraction (CII) obtained by analysis from X-ray diffraction is 50% or less 6. The 1-butene resin composition according to claim 5, wherein the weight average molecular weight (Mw) measured by the GPC method is 10,000 to 1,000,000. 7. A molded article obtained by molding the 1-butene-based resin composition according to claim 1.