JP2010265473A - Propylene-based copolymer, resin composition consisting of the propylene-based copolymer, and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a propylene-based polymer which gives a molded article in which there is little stickiness, and which is excellent in soft quality and transparency. <P>SOLUTION: The propylene-based polymer satisfies the following requirements (1) and (2). (1) The 25°C hexane soluble content is 0 to 80 mass%. (2) In DSC measurement, no melting point (Tm(°C)) is shown or the Tm and the melting endotherm ΔH satisfy the relationship of ΔH≥6×(Tm-140). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a propylene-based polymer, a resin composition comprising the polymer, a molded body, and a resin modifier. More specifically, the propylene-based polymer provides a molded body with less stickiness and excellent flexibility and transparency. The present invention relates to a polymer, a resin composition comprising the polymer, a molded body, and a resin modifier.

  Conventionally, vinyl chloride resin has been widely used as a soft resin. However, vinyl chloride resin is known to generate harmful substances in the combustion process, and development of alternative products is strongly desired. There is a propylene polymer as an alternative to the soft vinyl chloride resin. Propylene polymers are produced in the presence of various catalysts, but propylene polymers produced using conventional catalyst systems have many sticky components when trying to make them soft (that is, those having a low elastic modulus). There was a drawback of becoming. The APP component that is the cause of the sticky component increases, and the surface properties of the resulting molded article deteriorate. In addition, when a molded body in the form of a sheet or a film is developed for foods, medical uses, various problems may occur. Therefore, a propylene polymer having an improved balance between the low elastic modulus and the amount of the sticky component is desired.

  An object of the present invention is to provide a propylene-based polymer that gives a molded product with less stickiness and excellent flexibility and transparency, a resin composition comprising the polymer, a molded product, and a resin modifier. Is.

  As a result of intensive studies to achieve the above object, the present inventors have (1) the amount of the component eluted in hexane at 25 ° C. is in a specific range, and (2) shows the melting point in DSC measurement. The propylene-based polymer satisfying a specific relationship between the melting point and the melting endotherm when the melting point or the melting point is not found, it is found that the amount of sticky component, the low elastic modulus and the balance of transparency are excellent. It came to complete. That is, the present invention provides the following propylene-based polymer, a resin composition comprising the polymer, a molded product, and a resin modifier.

〔式中、Ｍはチタン、ジルコニウム、ハフニウムから選ばれる金属元素を示し、Ｅ¹及びＥ²はそれぞれ置換シクロペンタジエニル基、インデニル基、置換インデニル基、ヘテロシクロペンタジエニル基、置換ヘテロシクロペンタジエニル基、アミド基、ホスフィド基、炭化水素基及び珪素含有基の中から選ばれた配位子であって、Ａ¹及びＡ²を介して架橋構造を形成しており、またそれらはたがいに同一でも異なっていてもよく、Ｘはα結合性の配位子を示し、Ｘが複数ある場合、複数のＸは同じでも異なっていてもよく、他のＸ、Ｅ¹、Ｅ²又はＹと架橋していてもよい。Ｙはルイス塩基を示し、Ｙが複数ある場合、複数のＹは同じでも異なっていてもよく、他のＹ、Ｅ¹、Ｅ²又はＸと架橋していてもよく、Ａ¹及びＡ²は二つの配位子を結合する二価の架橋基であって、炭素数１〜２０の炭化水素基、炭素数１〜２０のハロゲン含有炭化水素基、珪素含有基、ゲルマニウム含有基、スズ含有基、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ₂−、−Ｓｅ−、−ＮＲ¹−、−ＰＲ¹−、−Ｐ（Ｏ）Ｒ¹−、−ＢＲ¹−又は−ＡｌＲ¹−を示し、Ｒ¹は水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基又は炭素数１〜２０のハロゲン含有炭化水素基を示し、それらはたがいに同一でも異なっていてもよい。ｑは１〜５の整数で〔（Ｍの原子価）−２〕を示し、ｒは０〜３の整数を示す。〕、
１１．上記１〜１０に記載のプロピレン系共重合体と造核剤を含有する樹脂組成物、
１２．造核剤の含有量が１０ｐｐｍ以上である上記１１に記載の樹脂組成物、
１３．上記１１又は１２に記載の樹脂組成物がさらに酸化防止剤、中和剤、スリップ剤、アンチロッキング剤、防曇剤、帯電防止剤から選ばれる添加剤を含有する樹脂組成物、
１４．上記１〜１０のいずれかに記載のプロピレン系共重合体又は上記１１〜１３のいずれかに記載のプロピレン系樹脂組成物を成形してなる成形体、
１５．上記１〜１０のいずれかに記載のプロピレン系共重合体からなるプロピレン系樹脂改質剤 1. A propylene-based copolymer satisfying the following (1) to (4).
(1) The component amount (H25) eluted in hexane at 25 ° C. is 0 to 80% by mass.
(2) In DSC measurement, the melting point (Tm (° C.)) is not shown, or when Tm is shown, Tm and the melting endotherm ΔH (J / g) satisfy the following relationship:
ΔH ≧ 6 × (Tm−140)
(3) The amount of components (W25) eluting at 25 ° C. or lower in the temperature rising chromatography is 20 to 100% by mass,
(4) The stereoregularity index (P) by ¹³ C-NMR measurement is 55 to 90 mol%. 2. The propylene-based copolymer according to 1, wherein the molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) method is 4 or less,
3. The propylene-based copolymer according to 1 or 2 above, wherein the intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 0.5 to 15.0 deciliter / g,
4). The propylene-based copolymer according to any one of the above 1 to 3, wherein the melting endotherm ΔH by DSC measurement is 20 J / g or less,
5). The propylene-based copolymer according to any one of the above 1 to 4, wherein Tm by DSC measurement is 100 ° C or lower,
6). The propylene-based copolymer according to any one of 1 to 5 above, wherein the boiling diethyl ether extract amount is 5% by mass or more,
7). The propylene-based copolymer according to any one of 1 to 6 above, which has a tensile modulus of 100 MPa or less,
8). The propylene-based copolymer according to any one of 1 to 7 above, wherein the propylene-based copolymer is a random copolymer,
9. The propylene-based copolymer according to any one of 1 to 8 above, wherein the structural unit obtained from propylene is 90 mol% or more,
10. (A) It reacts with the transition metal compound represented by the following general formula (I), and (B) (B-1) the transition metal compound of the component (A) or a derivative thereof to form an ionic complex. 1 to 9 obtained by copolymerizing propylene with ethylene and / or an α-olefin having 4 to 20 carbon atoms in the presence of a polymerization compound containing a compound selected from the group consisting of the compound and (B-2) aluminoxane. The propylene-based copolymer according to any one of the above.

[Wherein, M represents a metal element selected from titanium, zirconium and hafnium, and E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, and a substituted heterocyclo group, respectively. A ligand selected from a pentadienyl group, an amide group, a phosphide group, a hydrocarbon group and a silicon-containing group, which forms a crosslinked structure via A ¹ and A ² , and May be the same or different, X represents an α-bonding ligand, and when there are a plurality of X, the plurality of X may be the same or different, and other X, E ¹ , E ² or It may be cross-linked with Y. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, may be cross-linked with other Y, E ¹ , E ² or X, and A ¹ and A ² are A divalent bridging group that binds 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, a germanium-containing group, a tin-containing group , -O -, - CO -, - S -, - SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 - or -AlR ¹ - R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 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 [(M valence) -2], and r represents an integer of 0 to 3. ],
11. A resin composition containing the propylene-based copolymer described in 1 to 10 above and a nucleating agent;
12 The resin composition as described in 11 above, wherein the content of the nucleating agent is 10 ppm or more,
13. The resin composition according to 11 or 12, further comprising an additive selected from an antioxidant, a neutralizing agent, a slip agent, an antilocking agent, an antifogging agent, and an antistatic agent,
14 A molded product obtained by molding the propylene-based copolymer according to any one of 1 to 10 or the propylene-based resin composition according to any one of 11 to 13,
15. A propylene resin modifier comprising the propylene copolymer according to any one of 1 to 10 above.

  The propylene-based polymer of the present invention, the resin composition comprising the polymer, and the molded product have little stickiness, are excellent in softness and transparency, and are used as films, sheets, containers, automobile interior materials, housing materials for home appliances, etc. Is preferred. Examples of the film include a food packaging film and an agricultural film, and examples of the container include a transparent case, a transparent box, and a cosmetic box. Moreover, it can be conveniently used as a soft vinyl chloride resin substitute resin. The resin modifier of the present invention gives a molded article that is flexible and has little stickiness and excellent compatibility with the polyolefin resin.

Hereinafter, the propylene polymer [1], the production method [2], the propylene resin composition [3], the molded product [4] and the propylene resin modifier [5] of the present invention will be described in detail.
[1] Propylene polymer The propylene polymer of the present invention is a polymer having the following (1) and (2) as requirements.
(1) The amount of component (H25) eluted in hexane at 25 ° C. is 0 to 80% by mass. (2) In DSC measurement, the melting point (Tm (° C.)) is not shown, or when Tm is shown, Tm The melting endotherm ΔH (J / g) satisfies the following relationship: ΔH ≧ 6 × (Tm−140)
In the propylene polymer of the present invention, the component amount (H25) eluted in hexane at 25 ° C. is 0 to 80% by mass. Preferably, it is 0-50 mass%, Most preferably, it is 0-25 mass%. H25 is an index indicating whether the amount of the so-called sticky component that causes stickiness, a decrease in transparency, or the like is large or small, and the higher this value, the larger the amount of sticky component. When H25 exceeds 80% by mass, the amount of the sticky component is large, and the blocking resistance and transparency are lowered, so that it cannot be used for food or medical products.

Note that the H25, the mass of the propylene polymer and (W ₀₎ of the polymer in hexane 200 mL, and measuring the 25 ° C., 3 days or more after standing, the mass after drying (W _1), It is the mass reduction rate calculated by the following formula. H25 = [(W ₀ −W ₁ ) / W ₀ ] × 100 (%)
Furthermore, the propylene polymer of the present invention does not show a melting point (Tm (° C.)) in DSC measurement, or when Tm is shown, Tm and the melting endotherm ΔH satisfy the following relationship.

ΔH ≧ 6 × (Tm−140)
More preferably,
ΔH ≧ 3 × (Tm−120)
Particularly preferably,
ΔH ≧ 2 × (Tm−100)
Meet.

  Tm and ΔH are obtained by DSC measurement. That is, using a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer), 10 mg of a sample was melted at 230 ° C. for 3 minutes in a nitrogen atmosphere, and then cooled to 0 ° C. at 10 ° C./min. Furthermore, after maintaining at 0 ° C. for 3 minutes, the peak top of the maximum peak of the melting endotherm curve obtained by raising the temperature at 10 ° C./min is the melting point: Tm, and the melting endotherm in this case is ΔH. .

  By satisfying the above relationship, the propylene-based polymer of the present invention is excellent in the balance between the amount of sticky components such as the obtained molded article, the low elastic modulus, and the transparency. That is, it has a low elastic modulus and excellent softness (also referred to as flexibility), has little sticky component, and excellent surface characteristics (for example, less migration of sticky component to bleed and other products), and There is an advantage of excellent transparency.

As the propylene polymer of the present invention, in addition to the above requirements, the component amount (W25) of the propylene polymer that elutes at 25 ° C. or less in the temperature rising chromatography is preferably 20 to 100% by mass. More preferably, it is 30-100 mass%, Most preferably, it is 50-100 mass%. W25 is an index indicating whether or not the propylene-based polymer is soft. When this value is increased, it means that the component having a high elastic modulus is increased and / or the nonuniformity of the stereoregularity distribution is widened. In the present invention, if W25 is less than 20%, flexibility may be lost, which may be undesirable. Note that W25 is the amount of a component that elutes without being adsorbed by the packing material at a TREF column temperature of 25 ° C. in an elution curve obtained by measurement by temperature-enhanced chromatography with the following operation method, apparatus configuration and measurement conditions. (Mass%).
(A) Method of operation The sample solution is introduced into a TREF column adjusted to a temperature of 135 ° C., then gradually cooled to 0 ° C. at a temperature decrease rate of 5 ° C./hour, held for 30 minutes, and the sample is crystallized on the surface of the filler. Let Thereafter, the column is heated to 135 ° C. at a temperature increase rate of 40 ° C./hour to obtain an elution curve.
(B) Apparatus configuration TREF column: Silica gel column (4.6φ × 150 mm) manufactured by GL Science
Flow cell: GL Science Co., Ltd., optical path length 1 mm KBr cell Liquid feed pump: Senshu Kagaku Co., Ltd. SSC-3100 pump Valve oven: GL Science Co., Ltd. MODEL 554 oven (high temperature type)
TREF oven: manufactured by GL Science Co., Ltd. Two series temperature controller: manufactured by Rigaku Kogyo Co., Ltd. REX-C100 temperature controller Detector: infrared detector for liquid chromatography
MIRAN 1A CVF made by FOXBORO
10-way valve: Barco Electric valve Loop: Barco 500 microliter loop (c) Measurement conditions Solvent: o-dichlorobenzene Sample concentration: 7.5 g / liter Injection amount: 500 microliter Pump flow rate: 2.0 ml / Min Detection wave number: 3.41 μm
Column packing material: Chromosolve P (30-60 mesh)
Column temperature distribution: within ± 0.2 ° C. The propylene polymer of the present invention is not particularly limited as long as it satisfies the above requirements, and includes a propylene homopolymer and a propylene copolymer. Especially, the above-mentioned propylene polymer of the present invention is more preferably realized by the following [a] propylene homopolymer or [a ′] propylene copolymer.

[A] Propylene Homopolymer The propylene homopolymer of the present invention is a polymer having the following (1) to (3) as requirements.
(1) Mesopentad fraction (mmmm) is 20 to 60 mol%,
(2) Racemic pentad fraction (rrrr) and (1-mmmm) satisfy the following relationship, and
[Rrrr / (1-mmmm)] ≦ 0.1
(3) The amount of component (W25) eluting at 25 ° C. or lower in temperature rising chromatography is 20 to 100% by mass. When the propylene homopolymer of the present invention satisfies the above relationship, the resulting molded article or the like is sticky. Excellent balance between the amount of ingredients and low elasticity and transparency. That is, it has a low elastic modulus and excellent softness (also referred to as flexibility), has little sticky component, and excellent surface characteristics (for example, less migration of sticky component to bleed and other products), and There is an advantage of excellent transparency.

The meso-pentad fraction (mmmm fraction) used in the present invention is a ¹³ C-NMR spectrum based on the method proposed by A. Zambelli et al. In “Macromolecules, 6, 925 (1973)”. It is a meso fraction in the pentad unit in the polypropylene molecular chain measured by the signal of the methyl group. When this becomes large, it means that stereoregularity becomes high. When the mesopentad fraction (mmmm) of the propylene homopolymer of the present invention is less than 20 mol%, stickiness is caused. If it exceeds 60 mol%, the elastic modulus increases, which is not preferable. Similarly, the racemic pendant fraction (rrrr fraction) is a racemic fraction in a pentad unit in a polypropylene molecular chain. [Rrrr / (1-mmmm)] is an index representing the uniformity of the regular distribution of the propylene homopolymer, which is obtained from the fraction of the pentad unit. When this value is increased, the distribution of regularity is widened, which means that a mixture of highly ordered PP and APP is obtained like conventional polypropylene produced using an existing catalyst system, and stickiness is increased and transparency is lowered. If [rrrr / (1-mmmm)] of the propylene homopolymer of the present invention exceeds 0.1, stickiness is caused. The ¹³ C-NMR spectrum is measured according to the following apparatus and conditions according to the attribution of peaks proposed by “Macromolecules, 8, 687 (1975)” by A. Zambelli et al.

Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. Method: Complete proton decoupling method Concentration: 220 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 Next, the meaning of W25 and the measurement method for the propylene homopolymer in the present invention are the same as those in the propylene polymer [1]. When W25 of the propylene homopolymer in the present invention is less than 20%, flexibility is lost.

The propylene homopolymer of the present invention has the following (4) mesopentad fraction (mmmm) of 30 to 50% among the above requirements, and (5) racemic pentad fraction (rrrr) and (1-mmmm): ) Satisfies the following relationship,
[Rrrr / (1-mmmm)] ≦ 0.08
And (6) It is further more preferable to satisfy | fill that the component amount (W25) eluted at 25 degrees C or less in a temperature rising chromatography is 30-100 mass%, (7) Racemic pentad fraction (rrrr) and (1 −mmmm) satisfies the following relationship:
It is particularly preferable that [rrrr / (1-mmmm)] ≦ 0.06 and (8) the amount of component (W25) eluting at 25 ° C. or lower in the temperature-programmed chromatography is 50 to 100% by mass. (9) Racemic pentad fraction (rrrr) and (1-mmmm) satisfy the following relationship:
[Rrrr / (1-mmmm)] ≦ 0.05
And (10) It is most preferable when it satisfy | fills that the component amount (W25) eluted at 25 degrees C or less in a temperature rising chromatography is 60-100 mass%.

The propylene homopolymer of the present invention preferably has a pentad fraction (rmrm) exceeding 2.5 mol%. When the pentad fraction (rmrm) exceeds 2.5 mol%, the randomness increases and the transparency is further improved. Furthermore, it is preferable that the mesotriad fraction (mm), the racemic triad fraction (rr), and the triad fraction (mr) satisfy the following relationship.
(Mm) × (rr) / (mr) ² ≦ 2.0

  This relationship represents an index of randomness of the polymer, and the closer to 1, the higher the randomness, the more transparent, and the better balance between flexibility and elastic recovery. As the propylene homopolymer of the present invention, the value of the left side of the above formula is usually 2 or less, preferably 1.8 to 0.5, more preferably 1.5 to 0.5. The triad fraction is determined by the same method as the pentad fraction.

  In addition to the above requirements, the propylene homopolymer of the present invention has a molecular weight distribution (Mw / Mn) measured by gel permeation (GPC) method of 4 or less and / or an intrinsic viscosity measured at 135 ° C. in a tetralin solvent. [Η] is preferably 0.5 to 15.0 deciliter / g, Mw / Mn is 3.5 or less and / or [η] is more preferably 1.0 to 5.0 deciliter / g, and Mw / Mn is 3 or less and / or [η] is particularly preferably 1.0 to 3.0 deciliter / g. Among them, [η] is more preferably 1.5 to 3.0 deciliter / g, particularly preferably 2.0 to 2.5 deciliter / g. If the molecular weight distribution (Mw / Mn) exceeds 4, stickiness may occur, and if the intrinsic viscosity [η] is less than 0.5 deciliter / g, stickiness may occur. Moreover, when it exceeds 15.0 deciliter / g, fluidity | liquidity falls and a moldability may become inferior.

In addition, said Mw / Mn is the value computed from the weight average molecular weight Mw and number average molecular weight Mn of polyethylene conversion measured with the following apparatus and conditions with the gel permeation chromatograph (GPC) method.
GPC measurement 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 / ml Injection volume: 160 microliter Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)
Furthermore, in addition to the above requirements, the propylene homopolymer of the present invention preferably has excellent flexibility when the melting endotherm ΔH by DSC measurement is 20 J / g or less. ΔH is an index indicating whether or not it is soft, and when this value increases, it means that the elastic modulus is high and the softness is lowered. ΔH is determined by the above method.

  Furthermore, the propylene homopolymer in the present invention may or may not have a melting point (Tm) and a crystallization temperature (Tc), but it is not soft or has a low value, particularly about Tm of 100 ° C. or less. It is preferable that Tm and Tc are obtained by DSC measurement. That is, using a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer), 10 mg of a sample was melted at 230 ° C. for 3 minutes in a nitrogen atmosphere, and then cooled to 0 ° C. at 10 ° C./min. The peak top of the maximum peak of the crystallization exothermic curve obtained at this time is the crystallization temperature: Tc. Furthermore, after maintaining at 0 ° C. for 3 minutes, the peak top of the maximum peak of the melting endothermic curve obtained by raising the temperature at 10 ° C./min is the melting point: Tm.

By the way, in general, during the polymerization of propylene, the carbon atom on the methylene side of the propylene monomer is bonded to the active site of the catalyst, and the so-called 1,2 insertion polymerization in which the propylene monomer is sequentially coordinated and polymerized in the same manner. Is usually performed, but there are rarely 2, 1 insertion or 1, 3 insertion (also called abnormal insertion). The homopolymer of the present invention preferably has a small amount of this 2,1 insertion or 1,3 insertion. Moreover, the ratio of these insertions is the following relational expression (1)
[(M−2, 1) + (r−2, 1) + (1, 3)] ≦ 5.0 (%) (1)
Wherein, (m-2,1) is meso measured by ¹³ C-NMR -2,1 insert content (%), racemic-2 was measured by (r-2,1) is ¹³ C-NMR, 1 Insertion content (%) and (1,3) indicate 1,3 insertion content (%) measured by ¹³ C-NMR. ]
Is preferable, and the relational expression (2)
[(M−2, 1) + (r−2, 1) + (1, 3)] ≦ 1.0 (%) (2)
It is more preferable to satisfy the above. Especially relational expression (3)
[(M−2, 1) + (r−2, 1) + (1, 3)] ≦ 0.1 (%) (3)
The most preferable one is satisfied. If this relational expression (1) is not satisfied, the crystallinity may be lowered more than expected, which may cause stickiness.

In addition, (m-2,1), (r-2,1) and (1,3) are the reports of Grassi et al. (Macromolecules, 21, p.617 (1988)) and the reports of Busico et al. (Macromolecules, 27, p. 7538 (1994)), the peak content of the ¹³ C-NMR spectrum was determined, and each insertion content was determined from the integrated intensity of each peak. That is, (m-2,1) is the meso-2,1 insertion content (calculated from the ratio of the integrated intensity of peaks attributed to Pα and γthreo appearing near 17.2 ppm relative to the integrated intensity in the entire methyl carbon region ( %). (R-2,1) is the racemic-2,1 insertion content (%) calculated from the ratio of the integrated intensity of peaks attributed to Pα and γthreo appearing around 15.0 ppm relative to the integrated intensity in the entire methyl carbon region. It is. (1,3) is the 1,3 insertion content (%) calculated from the ratio of the integrated intensity of the peaks attributed to Tβ and γ + appearing around 31.0 ppm with respect to the integrated intensity in the entire methine carbon region.

Further, the propylene homopolymer of the present invention is more preferably one in which a peak attributed to the molecular chain end (n-butyl group) derived from 2,1 insertion is not substantially observed in the measurement of ¹³ C-NMR spectrum. . Regarding the molecular chain end derived from this 2,1 insertion, the peak of ¹³ C-NMR spectrum based on the report of Jungling et al. (J. Polym. Sci .: Part A: Po1ym. Chem., 33, p1305 (1995)). Is determined, and each insertion content is calculated from the integrated intensity of each peak. In isotactic polypropylene, a peak appearing in the vicinity of 18.9 ppm is attributed to the unterminated methyl group carbon of the n-butyl group. Further, ¹³ C-NMR measurement relating to abnormal insertion or molecular chain end measurement may be carried out using the above-mentioned apparatus and conditions.

  In addition to the above requirements, the propylene homopolymer of the present invention preferably further has a boiling diethyl ether extract amount of 5% by mass or more as an index of elastic modulus. In addition, the measurement of boiling diethyl ether extraction amount is measured on condition of the following using a Soxhlet extractor.

Extraction sample: 1-2g
Sample shape: Powder (The pelletized material is crushed and used as a powder)
Extraction solvent: Diethyl ether extraction Time: 10 hours Number of extractions: 180 times or more Extraction amount calculation method: Calculated by the following formula.
[Extraction amount to diethyl ether (g) / Mass of charged powder (g)] × 100
In addition to the above, the propylene homopolymer in the present invention preferably further has a tensile modulus of 100 MPa or less, more preferably 70 MPa or less.

[A ′] Propylene-based copolymer The propylene-based copolymer of the present invention is a copolymer of propylene and ethylene and / or an α-olefin having 4 to 20 carbon atoms, which satisfies the following (1) to (2). It is a coalescence.
(1) The stereoregularity index (P) by ¹³ C-NMR measurement is 55 to 90 mol%, and (2) the amount of component (W25) eluted at 25 ° C. or less in the temperature rising chromatography is 20 to 100 mass. % When the propylene-based copolymer of the present invention satisfies the above relationship, the balance of the amount of sticky component, the low elastic modulus and the transparency of the resulting molded article is excellent. That is, it has a low elastic modulus and excellent softness (also referred to as flexibility), has little sticky component, and excellent surface characteristics (for example, less migration of sticky component to bleed and other products), and It is characterized by excellent transparency. The stereoregularity index (P) in the present invention was measured using the above-mentioned JNM-EX400 type NMR apparatus manufactured by JEOL Ltd., and the ¹³ C-NMR spectrum was measured in the same manner as described above, and propylene-linked mesotriad (mm). It is the value obtained by measuring the fraction. A larger value means higher stereoregularity. As the propylene-based copolymer of the present invention, the stereoregularity index (P) is more preferably 65 to 80 mol%. If the stereoregularity index (P) is less than 55 mol%, the elastic modulus is too low and the moldability becomes poor. Moreover, when it exceeds 90 mol%, it will become hard and will not be soft. Moreover, it is more preferable in W25 being 30-100 mass%, and it is especially preferable in it being 50-100 mass%. When W25 is less than 20%, flexibility is lost. The meaning of W25 and the measurement method are the same as described above.

  Further, the propylene copolymer of the present invention has a molecular weight distribution (Mw / Mn) measured by gel permeation (GPC) method of 4 or less and / or 135 ° C. in a tetralin solvent in addition to the above requirements. The intrinsic viscosity [η] is preferably 0.5 to 15.0 deciliter / g, Mw / Mn is 3.5 or less, and / or [η] is more preferably 1.0 to 5.0 deciliter / g, Mw Particularly preferred is / Mn of 3 or less and / or [η] of 1.0 to 3.0 deciliter / g. If the molecular weight distribution (Mw / Mn) exceeds 4, stickiness may occur. If the intrinsic viscosity [η] is less than 0.5 deciliter / g, stickiness may occur, and if it exceeds 15.0 deciliter / g, the fluidity may decrease and the moldability may be poor. The method for measuring Mw / Mn is the same as described above.

  Furthermore, in addition to the above requirements, the propylene-based copolymer of the present invention preferably has excellent flexibility when the melting endotherm ΔH by DSC measurement is 20 J / g or less. Furthermore, the melting point (Tm) and the crystallization temperature (Tc) may or may not be present, but it is preferable that the melting point (Tm) and the low value, particularly Tm, are 100 ° C. or less. In addition, the measuring method of (DELTA) H, Tm, and Tc is the same as the above.

  In addition to the above-described requirements, the propylene-based copolymer of the present invention preferably further has a boiling diethyl ether extract amount, which is an index of elastic modulus, of 5% by mass or more. In addition, the measurement of boiling diethyl ether extraction amount is the same as the above.

  Moreover, it is preferable that a tensile elasticity modulus is 100 Mpa or less, More preferably, it is 70 Mpa or less.

  Regarding the propylene-based copolymer in the present invention, examples of the α-olefin having 4 to 20 carbon atoms include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-octene, Examples include decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicocene. In the present invention, one or more of these can be used.

  Furthermore, the propylene-based copolymer of the present invention is preferably a random copolymer. Further, the structural unit obtained from propylene is preferably 90 mol% or more, more preferably 95 mol% or more.

[Producing method of propylene homopolymer (a) and propylene copolymer (a ′)]
The method for producing the propylene homopolymer (a) and the propylene copolymer (a ′) in the present invention is a method of homopolymerizing propylene using a catalyst system called a metallocene catalyst, or propylene and ethylene and / or carbon number. The method of copolymerizing 4-20 alpha olefins is mentioned. Examples of the metallocene catalyst include JP-A-58-19309, JP-A-61-130314, JP-A-3-163088, JP-A-4-300787, JP-A-4-21694, and special tables. Transition metal compounds having one or two cyclopentadienyl groups, substituted cyclopentadienyl groups, indenyl groups, substituted indenyl groups, etc. as described in JP-A-1-502036, and the like Examples thereof include a catalyst obtained by combining a transition metal compound having a geometrically controlled ligand and a promoter.

  In the present invention, among metallocene catalysts, the ligand is preferably composed of a transition metal compound that forms a crosslinked structure via a crosslinking group, and in particular, the crosslinked structure is formed via two crosslinking groups. More preferable is a method of homopolymerizing propylene using a metallocene catalyst obtained by combining a transition metal compound and a cocatalyst formed, or a method of copolymerizing propylene and ethylene and / or an α-olefin having 4 to 20 carbon atoms. .

Specifically, (A) the general formula (I)

[In the formula, M represents a group 3-10 of the periodic table or a lanthanoid series metal element, and E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, and a heterocyclopentadienyl group, respectively. A ligand selected from a substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group, and a silicon-containing group, which forms a cross-linked structure through A ¹ and A ² And they may be the same or different, X represents an α-bonding ligand, and when there are a plurality of X, the plurality of X may be the same or different, and other X, E ¹ , E ² or Y may be cross-linked. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, may be cross-linked with other Y, E ¹ , E ² or X, and A ¹ and A ² are A divalent bridging group that binds 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, a germanium-containing group, a tin-containing group , -O -, - CO -, - S -, - SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 - or -AlR ¹ - R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 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 [(M valence) -2], and r represents an integer of 0 to 3. And (B) a compound capable of forming an ionic complex by reacting with the transition metal compound of component (B-1) (A) or a derivative thereof, and (B-2) Examples thereof include a method of homopolymerizing propylene in the presence of a polymerization catalyst containing a component selected from aluminoxane, or a method of copolymerizing propylene with ethylene and / or an α-olefin having 4 to 20 carbon atoms.

In the above general formula (I), M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium. Among them, titanium, zirconium and hafnium are preferable from the viewpoint of olefin polymerization activity. E ¹ and E ² are respectively substituted cyclopentadienyl group, indenyl group, substituted indenyl group, heterocyclopentadienyl group, substituted heterocyclopentadienyl group, amide group (—N <), phosphine group (—P <), Hydrocarbon group [>CR-,> C <] and silicon-containing group [>SiR-,> Si <] (where R is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing group. A ligand selected from (A) and a cross-linked structure is formed 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 preferable.

X represents a σ-binding ligand, and when there are a plurality of X, the plurality of X may be the same or different and may be cross-linked with other X, E ¹ , E ² or Y. . Specific examples of X include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, and carbon. Examples thereof include a silicon-containing group having 1 to 20 carbon atoms, a phosphide group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms. On the other hand, Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other 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 two ligands, which are a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and a silicon-containing group. 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 —, wherein R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and they are identical to each other. But it can be different.

Examples of such a bridging group include a general formula

(R ² and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and they may be the same or different, and may be bonded to each other to form a ring structure. e represents an integer of 1 to 4.)
Specific examples thereof include methylene group, ethylene group, ethylidene group, propylidene group, isopropylidene group, cyclohexylidene group, 1,2-cyclohexylene group, vinylidene group (CH ₂ = C =), a dimethylsilylene group, a diphenylsilylene group, a methylphenylsilylene group, a dimethylgermylene group, a dimethylstannylene group, a tetramethyldisylylene group, and a diphenyldisilylene group. Among these, an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.

In the transition metal compound represented by the general formula (I), when E ¹ and E ² are a substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group, the bond between the bridging groups of A ¹ and A ² is A (1,2 ′) (2,1 ′) double-crosslinking type is preferred.

で表される二重架橋型ビスシクロペンタジエニル誘導体を配位子とする遷移金属化合物が好ましい。 Among the transition metal compounds represented by the general formula (I), the general formula (II)

The transition metal compound which makes the ligand the double bridge type biscyclopentadienyl derivative represented by these is preferable.

In the above general formula (II), M, A ¹ , A ² , q and r are the same as described 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 examples as those exemplified in the description of X in formula (I). Y ¹ represents a Lewis base, if Y ¹ is plural, Y ¹ may be the same or different, may be crosslinked with other Y ¹ or X ^1. Specific examples of Y ¹ are 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, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a heteroatom-containing group. One must not be a hydrogen atom. R ^{4 to} R ⁹ may be the same as or different from each other, and adjacent groups may be bonded to each other to form a ring. Among these, it is preferable that R ⁶ and R ⁷ form a ring and R ⁸ and R ⁹ form a ring. As R ⁴ and R ⁵ , a group containing a hetero atom such as oxygen, halogen, or silicon is preferable because of high polymerization activity.

The transition metal compound having the double-bridged biscyclopentadienyl derivative as a ligand is preferably a (1,2 ′) (2,1 ′) double-bridged ligand. 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)- (5,6-dimethylindenyl) zirconium dichloride, (1,2'-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'-me Len) (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'-dimethylsilyl) ) (2,1′-dimethylsilylene) bis (3-phenylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,5-benzoindenyl) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4-isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) Bis (5,6-dimethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4,7-di-i-propylindenyl) zirconium dichloride, (1 , 2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4-phenylindenyl) zirconium dichloride, 1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-methyl-4-i-propylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethyl Silylene) bis (5,6-benzoindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1′-isopropylidene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-i-propylindenyl) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-n-butylindenyl) zirco Nium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) Ridene) -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) zyl Nium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene ) -Bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2'-diphenyl) Silylene) (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 dichrome (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′-dimethyl) Lucylylene) (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 Chloride, (1,2'-isopropylidene) (2,1'-isopropylidene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) ) (2,1′-dimethylsilylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) 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-dimethylcyclopenta Dienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ′ , 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-isopropylidene) (2,1′-isopropylidene) (3,4-dimethylcyclopentadiene) Enyl) (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, ( , 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′-phenylcyclopentadienyl) 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-propylcyclopen Dienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclo) Pentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadiene) Enyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) (3-methyl-5-ethylcyclopentadienyl) (3'-methyl-5'-ethylcyclopentadienyl) zirconium Dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) (3-methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'- - propyl cyclopentadienyl) zirconium



Mudichloride, (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-propyl cycl Lopentadienyl) zirconium dichloride, (1,2'-methylene) (2,1'-methylene) (3-methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'-i-propylcyclopenta Dienyl) zirconium dichloride, (1,2'-methylene) (2,1'-isopropylidene) (3-methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'-i-propyl) And cyclopentadienyl) zirconium dichloride and those obtained by substituting zirconium in these compounds with titanium or hafnium. Of course, it is not limited to these. Further, it may be an analogous compound of another group or a lanthanoid series metal element.

Next, as the component (B-1) in the component (B), any component can be used as long as it can form an ionic complex by reacting with the transition metal compound of the component (A). The following general formulas (III) and (IV) can be used.
([L ¹ −R ¹⁰ ] ^{k +} ) _a ([Z] ⁻ ) _b (III)
([L ² ] ^{k +} ) _a ([Z] ⁻ ) _b (IV)
(However, L ² is ^{M 2, R 11 R 12 M} 3, R 13 3 C or R ¹⁴ M ^3.)
[In the formulas (III) and (IV), L ¹ is a Lewis base, [Z] ⁻ is a non-coordinating anion [Z ¹ ] ⁻ and [Z ² ] ⁻ , where [Z ¹ ] ⁻ is a plurality of Anion in which the group is bonded to the element, that is, [M ¹ G ¹ G ² ... G ^f ] ⁻ (where M ¹ is a group 5-15 element of the periodic table, preferably a group 13-15 element of the periodic table) G ^{1 to} G ^f are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkyl group having 6 to 20 carbon atoms. Aryl group, aryloxy group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, 1 to 20 carbon atoms An acyloxy group, an organic metalloid group, or a heteroatom-containing hydrocarbon group having 2 to 20 carbon atoms Two or more of G ^{1 to} G ^f may form a ring, f is an integer of [(valence of central metal M ¹ ) +1]), [Z ² ] ⁻ is It represents a conjugate base of a Bronsted acid alone or a combination of Bronsted acid and 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. In addition, a Lewis base may be coordinated. 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, and R ¹¹ and R ¹² are each a cyclopentadienyl group or a substituted group. cyclopentadienyl group, an indenyl group or a fluorenyl group, R ¹³ represents an alkyl group, an aryl group, alkylaryl group or arylalkyl group having 1 to 20 carbon atoms. R ¹⁴ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. k is an ionic valence of [L ¹ −R ¹⁰ ], [L ² ], an integer of 1 to 3, a is an integer of 1 or more, and b = (k × a). M ² includes elements in groups 1 to 3, 11 to 13 and 17 of the periodic table, and M ³ represents elements in groups 7 to 12 of the periodic table. What is represented by this can be used conveniently.

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

Specific examples of R ¹⁰ include hydrogen, methyl group, ethyl group, benzyl group, and trityl group. Specific examples of R ¹¹ and R ¹² include cyclopentadienyl group and methylcyclopentadienyl group. And ethylcyclopentadienyl group, pentamethylcyclopentadienyl group, and the like. Specific examples of R ¹³ include a phenyl group, a p-tolyl group, and a p-methoxyphenyl group. Specific examples of R ¹⁴ include 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, Fe, Co, Ni, and Zn. And so on.

In [Z ¹ ] ⁻ , that is, [M ¹ G ¹ G ² ... G ^f ], specific examples of M ¹ include B, Al, Si, P, As, Sb, etc., preferably B and Al. Can be mentioned. Specific examples of G ¹ and G ^{2 to} G ^f include a dimethylamino group and a diethylamino group as a dialkylamino group, a methoxy group, an ethoxy group, an n-butoxy group, a phenoxy group as an alkoxy group or an aryloxy group, and the like. Hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-octyl, n-eicosyl, phenyl, p-tolyl, benzyl, 4-t -Butylphenyl group, 3,5-dimethylphenyl group, etc., fluorine, chlorine, bromine, iodine as halogen atoms, p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group as heteroatom-containing hydrocarbon groups, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoro Oromechiru) phenyl group, such as bis (trimethylsilyl) methyl group, pentamethyl antimony group as organic metalloid group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexyl antimony group, such as diphenyl boron and the like.

Specific examples of a non-coordinating anion, that is, a Bronsted acid alone having a pKa of −10 or less or a conjugate base [Z ² ] ⁻ of a combination of Bronsted acid and Lewis acid include a trifluoromethanesulfonate anion ( CF ₃ SO ₃ ) ⁻ , bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (ClO ₄ ) ⁻ , trifluoroacetate anion (CF ₃ CO ₂ ) ⁻ , hexafluoroantimony anion (SbF ₆ ) ⁻ , fluorosulfonic acid anion (FSO ₃ ) ⁻ , chlorosulfonic acid anion (ClSO ₃ ) ⁻ , fluorosulfonic acid anion / 5-antimony fluoride (FSO ₃ / SbF) ₅₎ ^-, anion fluorosulfonic acid / 5-fluoride arsenic ^{_{(FSO 3 / AsF 5) -}} , trifluoromethanesulfonic acid / antimony pentafluoride _{(CF 3 SO 3 / SbF 5} ) - and the like.

Specific examples of the ionic compound that reacts with the transition metal compound of the component (A) to form an ionic complex, that is, (B-1) component compounds include triphenylammonium tetraphenylborate, tetraphenyl Tri-n-butylammonium borate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyl tetraphenylborate Diphenylammonium, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, tetraphenylborate Methyl ruborate (2-cyanopyridinium), tetrakis (pentafluorophenyl) triethylammonium borate, tetrakis (pentafluorophenyl) tri-n-butylammonium borate, tetrakis (pentafluorophenyl) triphenylammonium borate, tetrakis (pentafluorophenyl) ) Tetra-n-butylammonium borate, Tetrakis (pentafluorophenyl) tetraethylammonium borate, Tetrakis (pentafluorophenyl) benzyl benzyl (tri-n-butyl) borate, Tetrakis (pentafluorophenyl) methyldiphenylammonium borate, Tetrakis (penta Fluorophenyl) triphenyl (methyl) ammonium borate, tetrakis (pentafluorophenyl) methylanilinium borate Dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, methylpyridinium tetrakis (pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), methyl tetrakis (pentafluorophenyl) borate (4-cyanopyridinium), tetrakis (pentafluorophenyl) triphenylphosphonium borate, tetrakis [ Bis (3,5-ditrifluoromethyl) phenyl] dimethylanilinium borate, ferrocenium tetraphenylborate, tetrafer Silver nylborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) ) Decamethylferrocenium borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) lithium borate, tetrakis (pentafluorophenyl) lithium borate, tetrakis (pentafluorophenyl) sodium borate, tetrakis (pentafluorophenyl) Teoraphenylporphyrin manganese borate, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate, silver perchlorate, silver trifluoroacetate, Examples thereof include silver trifluoromethanesulfonate.
(B-1) may be used singly or in combination of two or more.

On the other hand, as an aluminoxane of the component (B-2),
General formula (V)

(Wherein R ¹⁵ represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group or arylalkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms or a halogen atom, and w represents an average degree of polymerization. Usually, it is an integer of 2 to 50, preferably 2 to 40. Note that each R ¹⁵ may be the same or different.
A chain aluminoxane represented by:

Formula (VI)

(In the formula, R ¹⁵ and w are the same as those in the general formula (V).)
The cyclic aluminoxane shown by these can be mentioned.

Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the means is not particularly limited and may be reacted according to a known method. For example, (1) a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, (2) a method in which an organoaluminum compound is initially added during polymerization, and water is added later, (3) a metal There are a method of reacting crystallization water contained in a salt or the like, water adsorbed on an inorganic or organic material with an organoaluminum compound, and (4) a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum and further reacting with water. . The aluminoxane may be insoluble in toluene.
These aluminoxanes may be used alone or in combination of two or more.

  The use ratio of (A) catalyst component to (B) catalyst component is preferably 10: 1 to 1: 100 in molar ratio when (B-1) compound is used as (B) catalyst component. Preferably, the range of 2: 1 to 1:10 is desirable, and if it deviates from the above range, the catalyst cost per unit mass polymer increases, which is not practical. When the compound (B-2) is used, the molar ratio is preferably 1: 1 to 1: 1000000, more preferably 1:10 to 1: 10000. When deviating from this range, the catalyst cost per unit mass polymer becomes high, which is not practical. Moreover, (B-1) and (B-2) can also be used individually or in combination of 2 or more types as a catalyst component (B).

The polymerization catalyst in the production method of the present invention can use an organoaluminum compound as the component (C) in addition to the components (A) and (B). Here, as the organoaluminum compound of component (C), the general formula (VII)
R ¹⁶ _v AlJ _3-v (VII)
[Wherein, R ¹⁶ represents an alkyl group having 1 to 10 carbon atoms, J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom, and v represents 1 to 3 carbon atoms. (It is an integer)
The compound shown by these is used.

  Specific examples of the compound represented by the general formula (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 production method of the present invention, the preliminary contact can be performed using the above-mentioned component (A), component (B) and component (C). The preliminary contact can be performed by bringing the component (A) into contact with the component (B), for example. However, 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 catalytic activity and reducing the proportion of the (B) 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 seen together with the above effect. The preliminary contact temperature is usually -20 ° C to 200 ° C, preferably -10 ° C to 150 ° C, more preferably 0 ° C to 80 ° C. In the preliminary contact, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, or the like can be used as a 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: 10000, more preferably 1: 5 to 1: 2000, still more preferably 1:10 to 1 in terms of molar ratio. : The range of 1000 is desirable. By using the catalyst component (C), the polymerization activity per transition metal can be improved. However, if the amount is too large, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable.

  In the present invention, at least one of the catalyst components can be supported on a suitable carrier and used. 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 preferable.

Specific examples of the inorganic oxide carrier include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ and mixtures thereof. Examples thereof include silica alumina, zeolite, ferrite, and glass fiber. Of these, SiO ₂ and Al ₂ O ₃ are particularly preferable. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate and the like.

On the other hand, as a carrier other than the above, a magnesium compound represented by the general formula MgR ¹⁷ _x X ¹ _y typified by MgCl ₂ , Mg (OC ₂ H ₅ ) ₂ , or a complex salt thereof can be given. Here, R ¹⁷ represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, X ¹ represents a halogen atom or an alkyl group having 1 to 20 carbon atoms, x is 0 to 2, y is 0 to 2, and x + y = 2. Each R ¹⁷ and each X ¹ may be the same or different.

  Examples of the organic carrier include polymers such as polystyrene, styrene-divinylbenzene copolymer, polyethylene, polypropylene, substituted polystyrene, and polyarylate, starch, and carbon.

As the carrier used in the present invention, MgCl ₂ , MgCl (OC ₂ H ₅ ), Mg (OC ₂ H ₅ ) ₂ , SiO ₂ , Al ₂ O _{3 and the} like are preferable. The properties of the carrier vary depending on the type and production method, but the average particle size is usually 1 to 300 μm, preferably 10 to 200 μm, more preferably 20 to 100 μm.

If the particle size is small, fine powder in the polymer increases, and if the particle size is large, coarse particles in the polymer increase, which causes a decrease in bulk density and clogging of the hopper. The specific surface area of the carrier is usually 1 to 1000 m ² / g, preferably 50 to 500 m ² / g, and the pore volume is usually 0.1 to ⁵ cm ³ / g, preferably 0.3 to ³ cm ³ / g. is there.

  When either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and pore volume can be determined, for example, from the volume of nitrogen gas adsorbed according to the BET method (Journal of the American Chemical Society, Vol. 60, p. 309 (1983). )reference).

  Furthermore, it is desirable that the carrier is used after being usually fired at 150 to 1000 ° C, preferably 200 to 800 ° C. When at least one kind of catalyst component is supported on the carrier, it is desirable to support at least one of (A) catalyst component and (B) catalyst component, preferably both (A) catalyst component and (B) catalyst component. .

  The method for supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited. For example, the method of mixing at least one of the component (A) and the component (B) with the carrier, the carrier After treating with an organoaluminum compound or a halogen-containing silicon compound and mixing with at least one of component (A) and component (B) in an inert solvent, carrier, component (A) and / or component (B) A method of reacting 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 with the component (B) or the component (A); A method of mixing the contact reaction product with the component (B) with the carrier, a method of allowing the carrier to coexist in the contact reaction between the component (A) and the component (B), and the like can be used.

  In the above and other reactions, the organoaluminum compound (C) can also be added. In the present invention, when contacting the (A), (B), and (C), the catalyst may be prepared by irradiating elastic waves. Examples of the elastic wave include a normal sound wave, particularly preferably an ultrasonic wave. Specifically, an ultrasonic wave having a frequency of 1 to 1000 kHz, preferably an ultrasonic wave having a frequency of 10 to 500 kHz can be mentioned.

  The catalyst thus obtained may be used for polymerization after removing the solvent once as a solid and may be used for polymerization as it is. Moreover, in this invention, a catalyst can be produced | generated by performing the carrying | support operation to the support | carrier of at least one of (A) component and (B) component within 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, and an olefin such as ethylene is added at normal pressure to 2 MPa (gauge), and -20 to 20 A method of preliminarily polymerizing at 200 ° C. for about 1 minute to 2 hours to produce catalyst particles can be used.

  In the present invention, the use ratio of the component (B-1) to the carrier is preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500 in terms of mass ratio. -2) The use ratio of the component and the carrier is preferably 1: 0.5 to 1: 1000, more preferably 1: 1 to 1:50, in terms of mass ratio. When using 2 or more types as a component (B), it is desirable that the use ratio of each component (B) and the carrier is within the above range in terms of mass ratio. In addition, the ratio of the component (A) to the carrier used is, by mass ratio, preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500.

If the ratio of component (B) [component (B-1) or component (B-2)] and the carrier, or component (A) and carrier is outside the above range, the activity may decrease. is there. The average particle size of the polymerization catalyst of the present invention thus prepared is usually 2 to 200 μm, preferably 10 to 150 μm, particularly preferably 20 to 100 μm, and the specific surface area is usually 20 to 1000 m ² / g. , Preferably it is 50-500 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. When the specific surface area is less than 20 m ² / g, the activity may decrease, and when it exceeds 1000 m ² / g, the bulk density of the polymer may decrease. In the catalyst of the present invention, the amount of transition metal in 100 g of the support is preferably 0.05 to 10 g, particularly preferably 0.1 to 2 g. If the amount of transition metal is outside the above range, the activity may be lowered.

  In this way, a polymer having an industrially advantageous high bulk density and an excellent particle size distribution can be obtained by supporting it on a carrier. The propylene polymer used in the present invention is produced by homopolymerizing propylene or copolymerizing propylene and ethylene and / or an α-olefin having 4 to 20 carbon atoms using the above-described polymerization catalyst. .

  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, or a suspension polymerization method may be used. A polymerization method is particularly preferred.

About polymerization conditions, superposition | polymerization temperature is -100-250 degreeC normally, Preferably it is -50-200 degreeC, More preferably, it is 0-130 degreeC. The ratio of the catalyst to the reaction raw material is preferably 1 to 10 ⁸ , particularly 100 to 10 ⁵ , preferably from raw material monomer / component (A) (molar ratio). Furthermore, the polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is preferably normal pressure to 20 MPa (gauge), more preferably normal pressure to 10 MPa (gauge).

  Examples of the method for adjusting the molecular weight of the polymer include selection of the type, amount used, and polymerization temperature of each catalyst component, and further polymerization in the presence of hydrogen. When using a polymerization solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane, and aliphatic hydrocarbons such as pentane, hexane, heptane, and octane , Halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. Moreover, you may use monomers, such as an alpha olefin, as a solvent. Depending on the polymerization method, it can be carried out without solvent.

  In the polymerization, prepolymerization can be performed using the polymerization catalyst. The prepolymerization can be performed, for example, by bringing a small amount of olefin into contact with the solid catalyst component, but the method is not particularly limited, and a known method can be used. The olefin used for the prepolymerization is not particularly limited, and examples thereof include those similar to those exemplified above, for example, ethylene, an α-olefin having 3 to 20 carbon atoms, or a mixture thereof. It is advantageous to use the same olefin as that used.

  Moreover, prepolymerization temperature is -20-200 degreeC normally, Preferably it is -10-130 degreeC, More preferably, it is 0-80 degreeC. In the prepolymerization, an inert hydrocarbon, aliphatic hydrocarbon, aromatic hydrocarbon, monomer or the like can be used as a solvent. Of these, aliphatic hydrocarbons are particularly preferred. Moreover, you may perform prepolymerization without a solvent.

  In the prepolymerization, the intrinsic viscosity [η] (measured in decalin at 135 ° C.) of the prepolymerized product is 0.2 deciliter / g or more, particularly 0.5 deciliter / g or more, and per 1 millimole of transition metal component in the catalyst. It is desirable to adjust the conditions so that the amount of the prepolymerized product is 1 to 10000 g, particularly 10 to 1000 g.

[3] Propylene-based resin composition The propylene-based resin composition of the present invention includes a nucleating agent in the propylene-based polymer [1], the propylene homopolymer [a], or the propylene-based copolymer [a ′]. Is a resin composition obtained by adding In general, crystallization of a propylene-based polymer consists of two processes, a crystal nucleation process and a crystal growth process. In the crystal nucleation process, the temperature difference from the crystallization temperature, the state of molecular chain orientation, etc. It is said to affect the generation rate. In particular, it is known that the rate of crystal nucleation is significantly increased when a substance having an effect of promoting molecular chain orientation exists through molecular chain adsorption or the like. Any nucleating agent in the present invention may be used as long as it has an 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 molecular chains of polymers.

  Specific examples of the nucleating agent in the present invention 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 phosphate compound or a metal salt thereof, dibenzylidene sorbitol or a derivative thereof, Examples include rosin acid partial metal salts, inorganic fine particles, imides, amides, quinacridones, quinones, and mixtures thereof.

  Examples of the high melting point polymer include polyolefins such as polyethylene and polypropylene, polyvinylcycloalkanes such as polyvinylcyclohexane and polyvinylcyclopentane, syndiotactic polystyrene, poly-3-methylpentene-1, poly-3-methylbutene-1, and polyalkenylsilane. Can be mentioned.

  Examples of the metal salt include aluminum benzoate, aluminum pt-butylbenzoate, sodium adipate, sodium thiophenecarboxylate, and sodium pyrolecarboxylate.

  Dibenzylidene sorbitol or derivatives 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 etc. are mentioned. Specific examples include Gelall MD, Gelall MD-R (trade name) manufactured by Shin Nippon Rika Co., Ltd., and the like.

  Examples of the rosin acid partial metal salt include Pine Crystal KM1600, Pine Crystal KM1500, Pine Crystal KM1300 (trade name) manufactured by Arakawa Chemical Industries, Ltd.

  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 stone Examples thereof include powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, and molybdenum sulfide.

  Examples of the amide compound include adipic acid dianilide, speric acid dianilide and the like. One type of these nucleating agents may be used, or two or more types may be used in combination.

  In the propylene-based resin composition of the present invention, it is preferable to use inorganic fine particles such as an organic phosphate metal salt and / or talc represented by the following general formula as a nucleating agent with less generation of odor. This propylene-based resin composition is suitable for food applications.

(In the formula, R ¹⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹⁹ and R ²⁰ represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group, respectively. M represents any one of alkali metal, alkaline earth metal, aluminum and zinc, m represents 0 when M is an alkali metal, n represents 1, and M represents an alkaline earth metal or zinc n is 1 or 2, m is 1 when n is 1, m is 0 when n is 2, m is 1 when M is aluminum, and n is 2.)
Specific examples of the organic phosphate metal salt include ADK STAB NA-11 and ADK STAB NA-21 (Asahi Denka Co., Ltd.).

  Further, as the propylene-based resin composition of the present invention, it is preferable to use inorganic fine particles such as talc as a nucleating agent because, when formed into a film, it is excellent in slip properties and properties such as printing properties are improved. . Furthermore, it is preferable to use the dibenzylidene sorbitol or a derivative thereof as a nucleating agent because of excellent transparency. Furthermore, it is preferable to use the amide compound as a nucleating agent because of its excellent rigidity.

  The propylene-based resin composition of the present invention comprises a propylene-based polymer [1], the propylene homopolymer [a] or the propylene-based copolymer [a ′], a nucleating agent, and various types used as desired. The additive may be dry blended using a Henschel mixer or the like. Alternatively, it may be melt kneaded using a single or twin screw extruder, a Banbury mixer, or the like. Alternatively, when a high melting point polymer is used as the nucleating agent, the high melting point polymer may be added simultaneously or sequentially in the reactor at the time of producing the propylene polymer. Examples of various additives used as desired include an antioxidant, a neutralizing agent, a slip agent, an antiblocking agent, an antifogging agent, and an antistatic agent.

  The addition amount of the nucleating agent in the present invention is usually 10 ppm or more, preferably 10 with respect to the propylene polymer [1], the propylene homopolymer [a] or the propylene copolymer [a ′]. It is the range of -10000 ppm, More preferably, it is the range of 10-5000 ppm, More preferably, it is 10-2500 ppm. If it is less than 10 ppm, improvement of the moldability is not observed, and on the other hand, even if an amount exceeding 10,000 ppm is added, the preferable effect may not increase.

[4] Molded body The molded body of the present invention is the propylene polymer [1], the propylene homopolymer [a], the propylene copolymer [a ′] or the propylene resin composition [3]. ] Is a molded body obtained by molding. The molded article of the present invention has softness (also referred to as flexibility), high elastic recovery rate (property that returns to its original state even when pulled), softness, that is, low elasticity and low stickiness and transparency. It is characterized by being excellent.

  Examples of the molded body of the present invention include a film, a sheet, a container, an automobile interior material, and a housing material for an electrical product. Examples of the film include a food packaging film and an agricultural film (an example of a greenhouse). As a container, since it is excellent in transparency, a transparent case, a transparent box, a decorative box, etc. are mentioned.

  Examples of the molding method include an injection molding method, 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 temperature conditions allow the resin to melt and flow, and can usually be performed at a resin temperature of 50 ° C. to 300 ° C. and a mold temperature of 60 ° C. or less. When forming a film as the molded article of the present invention, it can be performed by a general compression molding method, extrusion molding method, blow molding method, cast molding method or the like. The film may or may not be stretched. In the case of stretching, biaxial stretching is preferred. Examples of the biaxial stretching conditions include the following conditions. Molding conditions at the time of sheet molding Resin temperature 50 to 200 ° C., Chill roll temperature 50 ° C. or less Longitudinal stretch condition Stretch ratio 3 to 7 times, Stretch temperature 50 to 100 ° C. Stretch ratio 6 to 12 times stretch ratio, Stretch temperature 50 to 100 ° C. Moreover, the film may process the surface as needed, may enlarge surface energy, or may make the surface polar. For example, the treatment method includes corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone and ultraviolet irradiation treatment, and the like. Examples of the surface unevenness method include a sand blast method and a solvent treatment method.

  The film can be blended with an antioxidant, a neutralizing agent, a slip agent, an antiblocking agent, an antifogging agent, an antistatic agent, or the like as required. Furthermore, since films containing inorganic fine particles such as talc are excellent in slipping properties, secondary processability such as bag making and printing is improved, and it can be applied to all general-purpose packaging films in high-speed production equipment such as various automatic filling and packaging laminates. Is preferred.

  A film formed by molding a propylene-based resin composition containing the 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.

  A film formed by molding a propylene-based resin composition containing the amide compound as a nucleating agent is particularly excellent in rigidity and hardly causes problems such as curling in high-speed bag making. Suitable as a packaging film.

[5] Propylene Resin Modifier The propylene resin modifier of the present invention is based on the propylene polymer [1], the propylene homopolymer [a] or the propylene copolymer [a ′]. It is a resin modifier. The propylene-based resin modifier of the present invention is characterized in that it is flexible and can give a molded article with little stickiness and excellent compatibility with a polyolefin resin. That is, as described above, the propylene-based resin modifier of the present invention is a specific propylene homopolymer or propylene-based polymer, and in particular, since there are some crystalline portions in the polypropylene chain portion, Less sticky than soft polyolefin resin as a modifier. Furthermore, the propylene-based resin modifier of the present invention is excellent in compatibility with polyolefin-based resins, particularly polypropylene-based resins. As a result, compared with the case where ethylene-based rubber or the like, which is a conventional modifier, is used, the surface characteristics (such as stickiness) are less deteriorated and the transparency is high. Due to the above characteristics, the propylene-based resin modifier of the present invention can be suitably used as a physical property improving agent having flexibility and transparency.

  Hereinafter, the present invention will be described more specifically based on examples. However, the present invention is not limited to these examples.

First, a method for evaluating resin properties and physical properties of the polymer of the present invention will be described.
(1) Measurement of [η] Measurement was performed at 135 ° C. in a tetralin solvent using a VMR-053 type automatic viscometer manufactured by Kosei Co., Ltd.
(2) Measurement of pentad fraction, triad fraction and abnormal insertion fraction The measurement was performed by the method described in the text of the specification. That is, the mesopend fraction (mmmm fraction), the triad fraction and the racemic pentad fraction (rrrr fraction) were proposed in “Macromolecules, 6, 925 (1973)” by A. Zambelli et al. The methyl group signal in the ¹³ C nuclear magnetic resonance spectrum was measured to determine the meso fraction, racemic fraction and triad fraction (mm, rr, mr) in the pentad unit in the polypropylene molecular chain. It was. (M-2,1), (r-2,1) and (1,3) are reported by Grassi et al. (Macromolecules, 21, p. 617 (1988)) and Busico et al. (Macromolecules, 27, p. 7538 (1994)), ¹³ C-NMR spectrum peak assignments were determined, and each insertion content was calculated from the integrated intensity of each peak. (M-2,1) was calculated as the meso-2,1 insertion content (%) as the ratio of the integrated intensity of the peak attributed to Pα, γthreo appearing near 17.2 ppm to the integrated intensity in the entire methyl carbon region. . (R-2,1) was calculated as a racemic-2,1 insertion content (%) as a ratio of the integrated intensity of the peak attributed to Pα, γthreo appearing near 15.0 ppm to the integrated intensity in the entire methyl carbon region. . For (1, 3), the ratio of the integrated intensity of the peak attributed to Tβ, γ + appearing in the vicinity of 31.0 ppm to the integrated intensity in the entire methine carbon region was calculated as 1,3 insertion content (%). If the peak to be attributed to meso-2,1 insertion, racemic-2,1 insertion, or 1,3 insertion cannot be identified because it is hidden in noise, etc., each heterogeneous bond content (m -2,1), (r-2,1) or (1,3) was regarded as 0.

^{The 13} C nuclear magnetic resonance spectrum was measured by the following apparatus and conditions.
Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. Method: Proton complete decoupling method Concentration: 220 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

(3) Comonomer unit content in copolymer (mol%) Using a JNM-EX400 type NMR apparatus manufactured by JEOL Ltd., ¹³ C-NMR spectrum was measured under the following conditions and calculated by the following method. .
Sample concentration: 220 mg / NMR solvent 3 ml
NMR solvent: 1,2,4-trichlorobenzene / benzene-d ₆ (90/10 vol%)
Measurement temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 10 seconds Integration count: 4000 times

(A) The chemical shift and attribution of each signal of the spectrum measured by ¹³ C-NMR for the random copolymer of ethylene unit propylene and ethylene are shown in Table 1.

The ethylene unit content (α (mol%)) in the copolymer was determined by the following formula (1) from the spectrum measured by ¹³ C-NMR.
α = E / S × 100 (1)
Here, S and E are respectively S = I _EPE + I _PPE + I _EEE + I _PPP + I _PEE + I _PEP E = I _EEE +2/3 (I _PEE + I _EPE ) +1/3 (I _PPE + I _PEP ) _EPE = I (12)
I _PPE = I (15) + I (11) + (I (14) −I (11)) / 2 + I (10)
I _EEE = I (18) / 2 + I (17) / 4
I _PPP = I (19) + (I (6) + I (7)) / 2 + I (3) + I (13) + I (11) + (I (14) -I (11)) / 2
I _PEE = I (20)
I _PEP = (I (8) + I (9) −2 × I (11)) / 4 + I (21)
It is.

Moreover, the isotactic triad fraction of the PPP chain was determined as the stereoregularity index (P (mol%)) of the copolymer by the following formula (2).
P = Im / I × 100 (2)
Here, Im and I are respectively Im = I (22)
I = I (22) + I (23) + I (24) − {(I (8) + I (9)) / 2 + I (10) + 3/2 × I (11) + I (12) + I (13) + I (15 )}
It is.
Here, I (1), I (2)... Indicate the intensity of the signals 1, 2,.

(4) Measurement of molecular weight distribution (Mw / Mn) Mw / Mn was measured by the method described in the specification text. That is, Mw / Mn is a value calculated from the weight average molecular weight Mw and the number average molecular weight Mn in terms of polyethylene 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 / ml Injection volume: 160 microliter calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver. 1.0)

(5) DSC measurement It measured by the method described in the specification text. That is, using a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer), 10 mg of a sample was melted at 230 ° C. for 3 minutes in a nitrogen atmosphere, then cooled to 0 ° C. at 10 ° C./min, and further 0 The melting endotherm obtained by holding at 3 ° C. for 3 minutes and then raising the temperature at 10 ° C./min was defined as ΔH. The peak top of the maximum peak of the melting endothermic curve obtained at this time was defined as the melting point: Tm. Further, after holding at 230 ° C. for 3 minutes, the temperature is lowered to 0 ° C. at 10 ° C./min. The peak top of the maximum peak of the crystallization exothermic curve obtained at this time was defined as the crystallization temperature: Tc.

(6) Temperature rising fractionation chromatograph The amount W25 (mass%) of the component that elutes without being adsorbed by the packing material at the TREF column temperature of 25 ° C. in the elution curve was determined as follows.
(A) Method of operation The sample solution is introduced into a TREF column adjusted to a temperature of 135 ° C., then gradually cooled to 0 ° C. at a temperature decrease rate of 5 ° C./hour, held for 30 minutes, and the sample is adsorbed on the filler. Thereafter, the column was heated to 135 ° C. at a temperature rising rate of 40 ° C./hour to obtain an elution curve.
(B) Apparatus configuration TREF column: Silica gel column (4.6 φ × 150 mm) manufactured by GL Science
Flow cell: manufactured by GL Science Co., Ltd. Optical path length: 1 mm KBr cell feed pump: manufactured by Senshu Scientific Co., Ltd. SSC-3100 pump valve oven: manufactured by GL Science Co., Ltd. MODEL 554 oven (high temperature type)
TREF oven: GL Science 2 series temperature controller: Rigaku Kogyo REX-C100 temperature controller Detector: Liquid chromatography infrared detector FOXBORO MIRAN 1A CVF
10-way valve: Barco Electric valve loop: Barco 500 microliter loop (c) Measurement conditions Solvent: o-dichlorobenzene Sample concentration: 7.5 g / liter Injection amount: 500 microliter pump flow rate: 2.0 ml / Min Detection wave number: 3.41 μm
Column packing material: Chromosolve P (30-60 mesh)
Column temperature distribution: Within ± 0.2 ° C

(7) Tensile elastic modulus A test piece was prepared by press-molding a propylene polymer and measured by a tensile test in accordance with JIS K-7113.
-Test piece (No. 2 dumbbell) Thickness: 1mm
・ Crosshead speed: 50mm / min
・ Load cell: 100kg

(8) Internal haze A propylene polymer was press-molded to prepare a test piece, which was measured by a test based on JIS K-7105. The smaller this value, the better the transparency.
Test piece: 15 cm × 15 cm × 1 mm (test piece thickness = 1 mm)

(9) Elastic recovery rate It was carried out in the same manner as described in JP-A-5-132590. That is, a propylene-based polymer was press-molded to prepare a JIS-2 dumbbell as a test piece.
Mark of 25mm intervals in the constant-width portion of the dumbbell, which was used as a L _0. The test piece was stretched at a pulling speed of 50 mm / min from a chuck-to-chuck distance of 80 mm to 160 mm with a tensile tester, then returned to the initial distance at −50 mm / min, and a mark attached to the dumbbell after 1 minute. measuring the distance, which was used as a L _1. The elastic recovery rate was calculated by the following formula. When this value was 0 or less, it was determined as “no recovery”.
・ [(2L ₀ −L ₁ ) / L ₀ ] × 100
L ₀ : Initial length of the mark attached to the dumbbell L ₁ : Length after extension of the mark attached to the dumbbell

(10) Anti-blocking property After a propylene polymer was press-molded to prepare a test piece and bonded under the following conditions, the peel strength was measured with a tensile tester.
・ Test piece: 15 mm × 62.5 mm × 2 mm
Adhesion conditions: Adhesion temperature 40 ° C., Adhesion area 15 mm × 31 mm, Crimp load 0.7 kg, 3 hours Shear peeling condition: Crosshead speed 50 mm / min

(11) Izod impact strength A test piece was prepared by press-molding a propylene polymer, and measured according to JIS K-7110, at a test piece thickness of 3 mm and an ambient temperature of -5 ° C.

(12) Amount of component eluted in hexane (H25)
H25 was determined by measurement under the following measurement conditions.
Sample: 0.1-5g
Sample shape: Powder (The pelletized material is crushed and used as a powder)
Solvent: Hexane elution conditions: 25 ° C., standing for 3 days or more Method for calculating elution amount: Calculated by the following formula.
H25 = [(W ₀ −W ₁ ) / W ₀ ] × 100 (%)

(13) Measurement of boiling diethyl ether extract amount Using a Soxhlet extractor, measure under the following conditions.
Sample: 1-2g
Sample shape: Powder (The pelletized material is crushed and used as a powder)
Extraction solvent: diethyl ether extraction time: 10 hours Extraction frequency: 180 times or more Extraction amount calculation method: Calculated by the following formula.
[Extraction amount to diethyl ether (g) / Mass of charged powder (g)] × 100

[Example 1] Propylene homopolymer (1) Preparation of catalyst Synthesis of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-n-butylindenyl) zirconium dichloride Schlenk bottle Into this, 0.83 g (2.4 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (indene) and 50 mL of ether are added. After cooling to −78 ° C. and adding 3.1 mL (5.0 mmol) of n-BuLi (hexane solution 1.6 M), the mixture is stirred at room temperature for 12 hours. The solid obtained by distilling off the solvent was washed with 20 mL of hexane to obtain 1.1 g (2.3 mmol) of a lithium salt as an ether adduct. This lithium salt is dissolved in 50 mL of THF and cooled to -78 ° C. 0.57 mL (5.3 mmol) of n-butyl bromide is slowly added dropwise and stirred at room temperature for 12 hours. After removing the solvent and extracting with 50 mL of hexane, the solvent was removed, and 0.81 g (1 ') of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-n-butylindene) was obtained. .77 mmol). (Yield 74%)
Next, 0.81 g of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-n-butylindene) obtained above in a Schlenk bottle under a nitrogen stream. 77 mmol) and 100 mL of ether. After cooling to −78 ° C. and adding 2.7 mL (4.15 mmol) of n-BuLi (hexane solution 1.54 M), the mixture is stirred at room temperature for 12 hours. The solvent was distilled off, and the resulting solid was washed with hexane to obtain 0.28 g (1.43 mmol) of a lithium salt as an ether adduct.

The lithium salt obtained above is dissolved in 50 mL of toluene under a nitrogen stream. The solution is cooled to −78 ° C., and a suspension of toluene (50 mL) in 0.33 g (1.42 mmol) of zirconium tetrachloride previously cooled to −78 ° C. is added dropwise thereto. After dropping, the mixture is stirred at room temperature for 6 hours. Thereafter, the mixture is filtered, and the solvent of the filtrate is distilled off. Recrystallization from dichloromethane yielded 0.2 g (0.32 mmol) of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-n-butylindenyl) zirconium dichloride. . (Yield 22%)
As a result of measurement by ¹ H-NMR (90 MHz, CDCl ₃ ),
: Δ 0.88, 0.99 (12H, dimethylsilylene), 0.7-1.0, 1.1-1.5 (18H, n-Bu), 7.0-7.6 (8H, benzene ring) Proton).

(2) Polymerization of propylene 6 l of heptane, 6 mmol of triisobutylaluminum, 5 mmol of methylaluminoxane (manufactured by Albemarle), and 1,2'-dimethylsilylene obtained above ) A catalyst component in which 5 μmol of (2,1′-dimethylsilylene) -bis (3-n-butylindenyl) zirconium dichloride was pre-contacted in toluene for 5 minutes was charged. Here, after introducing 0.05 MPa (gauge) of hydrogen, propylene gas was introduced up to 0.8 MPa (gauge) in total pressure, and propylene was supplied by a pressure regulator so that the pressure during polymerization was constant. After performing the polymerization at a polymerization temperature of 50 ° C. for 30 minutes, the content was taken out and dried under reduced pressure to obtain a propylene homopolymer. The obtained polymer was evaluated for the resin properties, and the results are shown in Table 2.

(3) Blending and kneading The following additives were formulated into the polypropylene homopolymer obtained above, and extruded and granulated with a single-screw extruder (manufactured by Tsukada Juki Seisakusho: TLC35-20 type) to obtain pellets. It was.
(Additive formulation)
・ Phenolic antioxidant: Ciba Specialty Chemicals Co., Ltd. Irganox 1010 1000ppm
・ Phosphorus antioxidant: P-EPQ 500ppm
・ Neutralizing agent: calcium stearate; 500ppm
-Neutralizer: DHT-4A; 500 ppm

(4) Physical property evaluation It evaluated by the above-mentioned evaluation method. The results obtained are shown in Table 3.

[Example 2]
The same procedure as in Example 1 was conducted except that the propylene homopolymer was produced without hydrogenation of the propylene homopolymer. The obtained results are shown in Tables 2 and 3.

Example 3
(1) Synthesis of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-methylindenyl) zirconium dichloride (1,2′-dimethylsilylene) obtained in the above in a Schlenk bottle ) 4,4 g (12.8 mmol) of (2,1′-dimethylsilylene) -bis (indene) and 100 mL of ether are added. After cooling to −78 ° C. and adding 16.1 mL (25.7 mmol) of n-BuLi (hexane solution 1.6 M), the mixture is stirred at room temperature for 12 hours. The solid obtained by distilling off the solvent is washed with 20 mL of hexane to quantitatively obtain the lithium salt. This lithium salt is dissolved in 100 mL of THF and cooled to -78 ° C. 7.4 g (52.0 mmol) of methyl iodide is slowly added dropwise and stirred at room temperature for 12 hours. After removing the solvent and extracting with 50 mL of hexane, the solvent was removed and 4.5 g (12 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-methylindene) was added. Obtained. (Yield 94%)
Next, 2.0 g (5.4 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-methylindene) obtained above in a Schlenk bottle under a nitrogen stream was obtained. Add 100 mL of ether. After cooling to −78 ° C. and adding 13.5 mL (21.6 mmol) of n-BuLi (hexane solution 1.6 M), the mixture is stirred at room temperature for 12 hours. The solvent was distilled off, and the resulting solid was washed with hexane to obtain 1.1 g (2.9 mmol) of a lithium salt. Under a nitrogen stream, the lithium salt obtained above is dissolved in 100 mL of toluene. The solution is cooled to -78 ° C, and a suspension of 0.7 g (3.0 mmol) of zirconium tetrachloride preliminarily cooled to -78 ° C in toluene (100 mL) is added dropwise thereto. After dropping, the mixture is stirred at room temperature for 6 hours. Thereafter, filtration was performed, and the precipitate was extracted from dichloromethane. Recrystallization from dichloromethane / hexane gave 0.5 g (0.94 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-methylindenyl) zirconium dichloride. It was. (Yield 32%)
As a result of measurement by ¹ H-NMR (CDCl ₃ ),
: Δ 0.95, 1.05 (12H, dimethylsilylene), 2.50 (6H, CH ₃ ), 7.2-7.7 (8H, Ar—H).

(2) Propylene homopolymerization In a 1 liter stainless steel autoclave, 400 mL of heptane, 0.5 mmol of triisobutylaluminum, and 0.5 mmol of methylaluminoxane (Albemarle) were obtained as described above (1,2 A catalyst component in which 0.5 micromol of '-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-methylindenyl) zirconium dichloride was preliminarily contacted in toluene for 5 minutes was charged. Here, after introducing 0.03 MPa (gauge) of hydrogen, propylene gas was introduced to 0.8 MPa (gauge) at the total pressure, and propylene was supplied by a pressure regulator so that the pressure during polymerization was constant. After performing polymerization at a polymerization temperature of 70 ° C. for 1 hour, the content was taken out and dried under reduced pressure to obtain a propylene homopolymer. The obtained polymer was evaluated for the resin properties, and the results are shown in Table 2.

(3) Blending and kneading The same procedure as in Example 1 was conducted except that the propylene homopolymer obtained above was blended according to the following additive formulation.
(Additive formulation)
・ Phenolic antioxidant: Ciba Specialty Chemicals Co., Ltd. Irganox 1010 1000ppm
Phosphorous antioxidant: Ciba Specialty Chemicals, Inc. Irgafos 168 1000 ppm

(4) Evaluation of physical properties It carried out similarly to Example 1 (4). The results obtained are shown in Table 3.

[Example 4] Propylene-based copolymer (1) Preparation of catalyst (a) Production of (1,2'-ethylene) (2,1'-ethylene) -bis (3-methylindene) 1.12 g (3.94 mmol) of 1,2′-ethylene) (2,1′-ethylene) -bis (indene) was dissolved in 50 ml of dehydrated ether. After cooling to −78 ° C., 5.01 ml of a hexane solution having a concentration of 1.57 mol / l of n-butyllithium (n-butyllithium: 7.87 mmol) was added dropwise over 30 minutes, and the temperature was lowered to room temperature. Raised and stirred for 8 hours. The ether solvent was distilled off under reduced pressure, and the residue was washed with hexane to obtain 1.12 g (3.02 mmol) of dilithium salt as an ether adduct. This dilithium salt was dissolved in 50 ml of dehydrated tetrahydrofuran and cooled to -78 ° C. To this solution, 10 ml of a tetrahydrofuran solution containing 0.42 ml (6.74 mmol) of methyl iodide was added dropwise over 20 minutes, and then the temperature was raised to room temperature, followed by stirring for 8 hours. After evaporating the solvent under reduced pressure, the residue was extracted with ethyl acetate. The extracted solution was washed with water, and the organic layer was dried over anhydrous magnesium sulfate and filtered. The filtrate was dried under reduced pressure to obtain (1,2′-ethylene) (2,1 ′ -Ethylene) -bis (3-methylindene) 0.87 g (2.78 mmol) was obtained with a yield of 70.5%.
This existed as an isomer mixture of double bonds of the five-membered ring moiety.

(B) Production of dilithium salt of (1,2'-ethylene) (2,1'-ethylene) -bis (3-methylindene) (1,2'-ethylene) (2,1'- Ethylene) -bis (3-methylindene) 0.87 g (2.78 mmol) was dissolved in 35 mmol ether and cooled to -78 ° C. To this solution, 3.7 ml of hexane solution having a concentration of 1.57 mol / liter of n-butyllithium (n-butyllithium: 5.81 mmol) was dropped over 30 minutes, and then the temperature was raised to room temperature and 8 hours. Stir. After distilling off the solvent under reduced pressure, the residue was washed with hexane to obtain 1.03 g (2.58 mmol) of dilithium salt as an ether adduct in a yield of 92.8%.
When ¹ H-NMR of this product was determined, the following results were obtained.
¹ H-NMR (THF-d ₈ )
(Δ, ppm): 2.20 (6H, s), 3.25 (8H, s), 6.0 to 7.4 (8H, m)

(C) Production of (1,2'-ethylene) (2,1'-ethylene) -bis (3-methylindenyl) zirconium dichloride (1,2'-ethylene) (2,1'-ethylene) -bis 1.03 g (2.58 mmol) of an ether adduct of (3-methylindene) dilithium salt was suspended in 25 ml of toluene and cooled to -78 ° C. To this, a suspension of 0.60 g (2.58 mmol) of zirconium tetrachloride in toluene (20 ml) was added over 20 minutes, the temperature was raised to room temperature and stirred for 8 hours, and then the toluene supernatant was filtered off. The residue was extracted twice with 50 ml of dichloromethane. After distilling off the solvent under reduced pressure, the residue was recrystallized from dichloromethane / hexane to give (1,2'-ethylene) (2,1'-ethylene) -bis (3-methylindenyl) zirconium dichloride. 0.21 g was obtained with a yield of 17.3%.
When ¹ H-NMR of this product was determined, the following results were obtained.
¹ H-NMR (CDCl ₃ ): 2.48 (6H, s), 3.33 to 3.85 (8H, m), 6.9 to 7.6 (8H, m)

(2) Copolymerization of propylene / ethylene 1.2 l of toluene, 1.5 mmol of triisobutylaluminum, 10 (Al) mmol of methylaluminoxane (manufactured by Albemarle), (1,2 ') in a 2 liter stainless steel autoclave -Ethylene) (2,1'-ethylene) -bis (3-methylindenyl) zirconium dichloride (20 micromol) was added, the temperature was raised to 30 ° C., and an ethylene / propylene mixed gas (ethylene / propylene molar ratio = 1 / 100). Excess gas was discharged so that the total pressure was 0.7 MPa (gauge), and after polymerization for 60 minutes while keeping the gas composition ratio in the system uniform, the contents were taken out and dried under reduced pressure to obtain a propylene system. A copolymer was obtained.
Compounding and kneading, and evaluation of resin properties and physical properties were performed in the same manner as in Example 1. The obtained results are shown in Tables 2 and 3.

[Comparative Example 1] Propylene Homopolymer (1) Preparation of Magnesium Compound A glass reactor equipped with a stirrer with an internal volume of about 6 liters was thoroughly replaced with nitrogen gas. Was heated while stirring and reacted under reflux conditions until no hydrogen gas was generated from the system to obtain a solid reaction product. The magnesium compound was obtained by drying the reaction liquid containing this solid product under reduced pressure.
(2) Preparation of solid catalyst component (A) In a glass reactor having an internal volume of 5 liters sufficiently substituted with nitrogen gas, 160 g of the magnesium compound obtained in (1) above (not crushed) and 80 ml of purified heptane Then, 24 ml of silicon tetrachloride and 23 ml of diethyl phthalate were charged, the system was kept at 80 ° C., 770 ml of titanium tetrachloride was added while stirring and reacted at 110 ° C. for 2 hours, and then the solid components were separated and purified at 90 ° C. Washed with heptane. Further, 1220 ml of titanium tetrachloride was added and reacted at 110 ° C. for 2 hours, and then thoroughly washed with purified heptane to obtain a solid catalyst component (A).

(3) Gas phase polymerization of propylene In a polymerization tank having an internal volume of 200 liters, 6.0 g / hour of the solid catalyst component obtained in the above (2), 0.2 mol / hour of triisobutylaluminum (TIBA), 1-allyl -3,4-dimethoxybenzene (ADMB) 0.012 mol / hour, cyclohexylmethyldimethoxysilane (CHMDMS) 0.012 mol / hour, propylene 37 kg / hour, supplied at 70 ° C. and 2.8 MPa (gauge) Was done.
(4) Formulation and kneading 2,5-dimethyl-2,5-di- (t-butylperoxy) -hexane was mixed with the obtained polypropylene powder, and the same additive formulation as in Example 1 was further performed. Extrusion was performed with a 40 mmΦ extruder to obtain pellets.
(5) Evaluation of resin characteristics and physical properties It was carried out in the same manner as in Example 1. The obtained results are shown in Tables 2 and 3.

[Reference Example] Affinity PL1880
The physical properties of pellets of affinity PL1880 (trade name) manufactured by Dow Chemical Japan Co., Ltd. were evaluated in the same manner as in Example 1 (4). The results obtained are shown in Table 3.

Comparative Example 2 Propylene Homopolymer A stainless steel autoclave with an internal volume of 1 liter, 400 mL of heptane, 0.5 mmol of triisobutylaluminum, 2 micromol of dimethylanilinium (pentafluorophenyl) borate, A catalyst component prepared by subjecting (tertiary butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride 1 micromole prepared in the same manner as in Example 1 of Japanese Patent No. 163088 to toluene for 5 minutes in toluene I put it in. Here, after introducing 0.03 MPa (gauge) of hydrogen, propylene gas was introduced to 0.8 MPa (gauge) at the total pressure, and propylene was supplied by a pressure regulator so that the pressure during polymerization was constant. After performing polymerization at a polymerization temperature of 70 ° C. for 1 hour, the content was taken out and dried under reduced pressure to obtain a propylene homopolymer. Compounding and kneading, resin characteristics and physical properties were evaluated in the same manner as in Example 1. The obtained results are shown in Tables 2 and 3.

[Example 5] Addition of nucleating agent
¹ H The same procedure as in Example 1 was conducted except that the propylene homopolymer obtained in Example 1 was subjected to the following additive formulation. The results obtained are shown in Table 4.
(Additive formulation)
・ Phenolic antioxidant: Ciba Specialty Chemicals Co., Ltd. Irganox 1010 1000ppm
・ Phosphorus antioxidant: P-EPQ 500ppm
・ Neutralizing agent: calcium stearate; 500ppm
-Neutralizer: DHT-4A; 500 ppm
・ Nucleating agent: Shin-Nihon Riken Co., Ltd .: Gelol MD; 1000 ppm

[Example 6] Addition of nucleating agent Shin-Nippon Rikagaku Co., Ltd., a nucleating agent: The same procedure as in Example 5 was carried out except that the amount of gelol MD added was 2000 ppm. The results obtained are shown in Table 4.
[Example 7] Addition of nucleating agent The same procedure as in Example 1 was performed except that the propylene homopolymer obtained in Example 1 was formulated with the following additive. The results obtained are shown in Table 4.
・ Phenolic antioxidant: Ciba Specialty Chemicals Co., Ltd. Irganox 1010 1000ppm
Phosphorous antioxidant: Ciba Specialty Chemicals, Inc. Irgafos 168 1000 ppm
・ Nucleating agent: Shin-Nihon Riken Co., Ltd .: Gelol MD; 5000 ppm
[Example 8] Addition of nucleating agent Shin-Nippon Rikagaku Co., Ltd., a nucleating agent: The same procedure as in Example 7 was carried out except that the amount of gelol MD added was 10000 ppm. The results obtained are shown in Table 4.
[Example 9] Nucleating agent addition Nucleating agent of Example 7: Shin-Nihon Rikagaku Co., Ltd .: Gelol MD: 5000 ppm was changed from Asahi Denka Co., Ltd .: NA-11: 2000 ppm. went. The results obtained are shown in Table 4.

[Example 10] Effect of modifiers 70% by mass of the pellet obtained in Example 1 was blended with Idemitsu Petrochemical Polypropylene E105GM into a single-screw extruder (manufactured by Tsukada Tree Machine Co., Ltd .: TLC35-20). To give pellets. The physical properties were evaluated in the same manner as in Example 1 (4). The results obtained are shown in Table 5.
[Example 11] Effect of modifying agent The same effect as in Example 10 was performed except that the blending ratio of the pellets obtained in Example 1 was changed to 60% by mass. The results obtained are shown in Table 5.
[Example 12] Effect of modifying agent The same effect as in Example 10 was performed except that the blending ratio of the pellets obtained in Example 1 was changed to 30% by mass. The obtained results are shown in Table 5.
[Comparative Example 3]
For polypropylene E105GM manufactured by Idemitsu Petrochemical Co., Ltd., physical properties were evaluated in the same manner as in Example 1 (4). The obtained results are shown in Table 5.
[Comparative Example 4]
The same operation as in Example 10 was conducted except that 50% by mass of the polymer obtained in Comparative Example 2 was blended with Idemitsu Petrochemical Polypropylene E105GM. The obtained results are shown in Table 5.

[Example 13] Propylene homopolymer A 1 L stainless steel pressure-resistant autoclave equipped with a stirrer was heated to 80 ° C. and sufficiently dried under reduced pressure, and then returned to atmospheric pressure with dry nitrogen and cooled to room temperature. Under a dry nitrogen stream, 400 mL of dry deoxygenated heptane and 0.5 mL (1.0 mmol) of a heptane solution of triisobutylaluminum (2.0 M) were added and stirred at 350 rpm for a while. On the other hand, cyclohexane (10 mL) and triisobutylaluminum heptane solution (2 M, 0.5 mL, 1.0 mmol) were introduced into a 50 mL Schlenk tube fully nitrogen-substituted under a nitrogen stream, and dimethylanilinium tetrakis (pentafluorophenyl). Borate in cyclohexane (4M, 1.0 mL, 4.0 mmol) and (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-n-butylindenyl) obtained in Example 1 ) 4 micromoles of zirconium dichloride was added and stirred at room temperature for 60 minutes. Then, the catalyst slurry was quickly charged into the autoclave. And hydrogen was supplied to 0.03 MPa (gauge). Thereafter, stirring was started at 400 rpm, and propylene was slowly pressurized to a total pressure of 0.8 MPa (gauge), and at the same time, the temperature was slowly raised to 50 ° C. Polymerization was carried out for 30 minutes.
After completion of the reaction, unreacted propylene was removed by depressurization. The reaction mixture was poured into 2 L of methanol to precipitate polypropylene, which was filtered and dried to obtain polypropylene. The results obtained in the same manner as in Example 1 are shown in Tables 6 and 7.

[Example 14] Propylene homopolymer A 1 L stainless steel pressure-resistant autoclave equipped with a stirrer was heated to 80 ° C and sufficiently dried under reduced pressure, and then returned to atmospheric pressure with dry nitrogen and cooled to room temperature. Under a dry nitrogen stream, 400 mL of dry deoxygenated heptane, 1.0 mL (2.0 mmol) of a heptane solution of triisobutylaluminum (2.0 M) and a heptane slurry of dimethylanilinium tetrakis (pentafluorophenyl) borate (2.0 μmol, 0.8 mL, 1.6 μmol), and stirred at 350 rpm at room temperature for 5 minutes. Then, and after adding 4 micromoles of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-n-butylindenyl) zirconium dichloride obtained above, the pressure of hydrogen was increased. It charged until it became 0.03 MPa (gauge). Thereafter, stirring was started at 400 rpm, and propylene was slowly pressurized to a total pressure of 0.8 MPa (gauge), and at the same time, the temperature was slowly raised to 50 ° C. Polymerization was carried out for 30 minutes. After completion of the reaction, unreacted propylene was removed by depressurization. The reaction mixture was poured into 2 L of methanol to precipitate polypropylene, which was filtered and dried to obtain polypropylene. The results obtained in the same manner as in Example 1 are shown in Tables 6 and 7.

Example 15
Synthesis of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride (1,2'-dimethylsilylene) (2,1'- 3.0 g (6.97 mmol) of the lithium salt of dimethylsilylene) -bis (indene) is dissolved in 50 mL of THF and cooled to -78 ° C. Iodomethyltrimethylsilane (2.1 mL, 14.2 mmol) is slowly added dropwise and stirred at room temperature for 12 hours. Evaporate the solvent, add 50 mL of ether and wash with saturated ammonium chloride solution. After liquid separation, the organic phase was dried to remove the solvent, and 3.04 g (5.88 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) Got. (Yield 84%)
Next, 3.04 g (5.88 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) obtained above in a Schlenk bottle under a nitrogen stream. ) And 50 mL of ether. After cooling to −78 ° C. and adding 7.6 mL (11.7 mmol) of n-BuLi (hexane solution 1.54 M), the mixture is stirred at room temperature for 12 hours. The solvent was distilled off, and the resulting solid was washed with 40 mL of hexane to obtain 3.06 g (5.07 mmol) of the lithium salt as an ether adduct. (Yield 73%)
As a result of measurement by ¹ H-NMR (90 MHz, THF-d ₈ ),
: Δ 0.04 (s, 18H, trimethylsilyl), 0.48 (s, 12H, dimethylsilylene), 1.10 (t, 6H, methyl), 2.59 (s, 4H, methylene), 3.38 ( q, 4H, methylene), 6.2-7.7 (m, 8H, Ar-H).

The lithium salt obtained above is dissolved in 50 mL of toluene under a nitrogen stream. The mixture is cooled to -78 ° C, and a suspension of 1.2 g (5.1 mmol) of zirconium tetrachloride preliminarily cooled to -78 ° C in toluene (20 mL) is added dropwise. After dropping, the mixture is stirred at room temperature for 6 hours. The solvent of the reaction solution is distilled off. The obtained residue was recrystallized from dichloromethane to obtain 0.9 g (1. 1'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride. 33 mmol) was obtained. (Yield 26%)
As a result of measurement by ¹ H-NMR (90 MHz, CDCl ₃ ),
: Δ0.0 (s, 18H, trimethylsilyl), 1.02, 1.12 (s, 12H, dimethylsilylene), 2.51 (dd, 4H, methylene), 7.1-7.6 (m, 8H) , Ar-H).

(2) Homopolymerization (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-n-butylindenyl) zirconium dichloride instead of (1,2'-dimethylsilylene) (2 , 1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride was used for polymerization in the same manner as in Example 1 (2). The results obtained in the same manner as in Example 1 are shown in Tables 6 and 7.

Example 16
Synthesis of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-ethoxymethylindenyl) zirconium dichloride (1,2'-dimethylsilylene) (2,1'- 4.1 g (9.50 mmol) of lithium salt of dimethylsilylene) -bis (indene) is dissolved in 50 mL of THF and cooled to -78 ° C. Chloromethyl ethyl ether (1.9 mL, 20.5 mmol) is slowly added dropwise and stirred at room temperature for 12 hours. Evaporate the solvent, add 50 mL of ether and hydrolyze with saturated ammonium chloride solution. After liquid separation, the organic phase was dried to remove the solvent, and 3.43 g (7.40 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-ethoxymethylindene) was obtained. Got. (Yield 78%)
Next, 3.43 g (7.40 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-ethoxymethylindene) obtained above in a Schlenk bottle under a nitrogen stream. ) And 50 mL of ether. After cooling to −78 ° C. and adding 9.4 mL (14.8 mmol) of n-BuLi (hexane solution 1.57 M), the mixture is stirred at room temperature for 12 hours. The solvent was distilled off, and the resulting solid was washed with 50 mL of hexane to obtain 1.07 g (1.96 mmol) of a lithium salt as an ether adduct. (Yield 26%)
The lithium salt obtained above is dissolved in 50 mL of toluene under a nitrogen stream. After cooling to -78 ° C, a suspension of 0.46 g (1.96 mmol) of zirconium tetrachloride preliminarily cooled to -78 ° C in toluene (20 mL) is added dropwise. After dropping, the mixture is stirred at room temperature for 6 hours. The solvent of the reaction solution is distilled off. By extracting the obtained residue with 40 mL of hexane, 0.24 g (0.39 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-ethoxymethylindenyl) zirconium dichloride was obtained. ) (Yield 20%)

(2) Homopolymerization (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-n-butylindenyl) zirconium dichloride instead of (1,2'-dimethylsilylene) (2 , 1′-dimethylsilylene) -bis (3-ethoxymethylindenyl) zirconium dichloride was used for polymerization in the same manner as in Example 1 (2). The results obtained in the same manner as in Example 1 are shown in Tables 6 and 7.

  The propylene-based polymer of the present invention, the resin composition comprising the polymer, and the molded product have little stickiness, are excellent in softness and transparency, and are used as films, sheets, containers, automobile interior materials, housing materials for home appliances, etc. Is preferred. Examples of the film include a food packaging film and an agricultural film, and examples of the container include a transparent case, a transparent box, and a cosmetic box. Moreover, it can be conveniently used as a soft vinyl chloride resin substitute resin. The resin modifier of the present invention gives a molded article that is flexible and has little stickiness and excellent compatibility with the polyolefin resin.

Claims (15)

A propylene-based copolymer satisfying the following (1) to (4).
(1) The component amount (H25) eluted in hexane at 25 ° C. is 0 to 80% by mass.
(2) In DSC measurement, the melting point (Tm (° C.)) is not shown, or when Tm is shown, Tm and the melting endotherm ΔH (J / g) satisfy the following relationship:
ΔH ≧ 6 × (Tm−140)
(3) The amount of components (W25) eluting at 25 ° C. or lower in the temperature rising chromatography is 20 to 100% by mass,
(4) The stereoregularity index (P) by ¹³ C-NMR measurement is 55 to 90 mol%.   The propylene copolymer according to claim 1, wherein the molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) method is 4 or less.   The propylene-based copolymer according to claim 1 or 2, wherein the intrinsic viscosity [η] measured in a tetralin solvent at 135 ° C is 0.5 to 15.0 deciliter / g.   The propylene-based copolymer according to any one of claims 1 to 3, wherein a melting endotherm ΔH by DSC measurement is 20 J / g or less.   The propylene-based copolymer according to any one of claims 1 to 4, wherein Tm by DSC measurement is 100 ° C or lower.   The propylene copolymer according to any one of claims 1 to 5, wherein the amount of boiling diethyl ether extracted is 5% by mass or more.   The propylene-based copolymer according to any one of claims 1 to 6, which has a tensile modulus of 100 MPa or less.   The propylene-based copolymer according to any one of claims 1 to 7, wherein the propylene-based copolymer is a random copolymer.   The structural unit obtained from propylene is 90 mol% or more, The propylene-type copolymer in any one of Claims 1-8. (A) It reacts with the transition metal compound represented by the following general formula (I), and (B) (B-1) the transition metal compound of the component (A) or a derivative thereof to form an ionic complex. And (B-2) obtained by copolymerizing propylene with ethylene and / or an α-olefin having 4 to 20 carbon atoms in the presence of a polymerization catalyst containing a component selected from (B-2) aluminoxane. 10. The propylene copolymer according to any one of 9 above.

[Wherein, M represents a metal element selected from titanium, zirconium and hafnium, and E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, and a substituted heterocyclo group, respectively. A ligand selected from a pentadienyl group, an amide group, a phosphide group, a hydrocarbon group and a silicon-containing group, which forms a crosslinked structure via A ¹ and A ² , and May be the same or different, X represents an α-bonding ligand, and when there are a plurality of X, the plurality of X may be the same or different, and other X, E ¹ , E ² or It may be cross-linked with Y. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, may be cross-linked with other Y, E ¹ , E ² or X, and A ¹ and A ² are A divalent bridging group that binds 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, a germanium-containing group, a tin-containing group , -O -, - CO -, - S -, - SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 - or -AlR ¹ - R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 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 [(M valence) -2], and r represents an integer of 0 to 3. ]   The resin composition containing the propylene-type copolymer of Claims 1-10, and a nucleating agent.   The resin composition according to claim 11, wherein the content of the nucleating agent is 10 ppm or more.   The resin composition according to claim 11 or 12, further comprising an additive selected from an antioxidant, a neutralizing agent, a slip agent, an antilocking agent, an antifogging agent, and an antistatic agent.   The molded object formed by shape | molding the propylene-type copolymer in any one of Claims 1-10, or the propylene-type resin composition in any one of Claims 11-13.   The propylene-type resin modifier which consists of a propylene-type copolymer in any one of Claims 1-10.