JP2017014449A - Polyolefin resin composition for extrusion laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyolefin resin composition without losing transparency by additive's bleeding out to a surface even by blending at high concentration when proceeded to a film or a sheet and without causing change of additive concentration even with long term use, therefore excellent in long term weather resistance and excellent in whitening resistance, color fastness and extrusion laminate processability.SOLUTION: There is provided a polyolefin resin composition for extrusion laminate containing (A) a propylene resin, (B) a polypropylene resin having a branched structure, (C) a triaryltriazine compound, (D) a hindered amine-based photostabilizer and (E) a dialkylhydroxylamine-based compound and having MFR of 2 to 10 g/10 min. with percentages of (A), (B), (C), (D) and (E) based on 100 wt.% of the total amount of (A) to (E) of 50 to 96.89 wt.%, 3 to 50 wt.%, 0.1 to 5 wt.%, 0.005 to 1 wt.% and 0.005 to 1 wt.% respectively.SELECTED DRAWING: None

Description

  The present invention is excellent in extrusion laminating processability, and even when a weathering agent is blended at a high concentration, the weathering agent is prevented from bleed-out bleed-out when laminated, and there is no decrease in transparency or long-term weathering performance. The present invention also relates to a polyolefin resin composition for extrusion lamination having excellent whitening resistance and discoloration resistance.

In order to improve the weather resistance of a polyolefin-based thermoplastic resin sheet or film, blending a hindered amine-based light stabilizer or ultraviolet absorber is widely practiced.
In particular, high weather resistance is required for films and sheets for agricultural film, architecture, and civil engineering. Various weather resistance stabilizers are blended in the resin used for such a film or sheet based on polyethylene or polypropylene. With respect to weather resistance, various developments have been made in order to prevent deterioration of films and sheets, and to obtain films and sheets having a longer life and better performance.

Films and sheets are deteriorated by ultraviolet rays in sunlight in the presence of oxygen in the air, and the strength and elongation are reduced and are damaged. In order to improve this, various weathering stabilizers are blended. The weather resistance stabilizer to be blended is roughly classified into an ultraviolet absorber and a light stabilizer. Conventionally, the ultraviolet absorbers have been mainly nickel compounds, but in recent years, ultraviolet absorbers such as benzophenone, benzotriazole, and triazine have been developed and applied to various applications. Also, sterically hindered amine compounds have been developed for light stabilizers, and these have become the mainstream of current weathering stabilizers due to their excellent performance.
These weather resistance stabilizers are used singly or in combination. Especially when the film or sheet is a laminate with another base material or the contained material needs to be protected from light deterioration, light It is necessary to use a stabilizer and a UV absorber in combination. However, when both the above UV absorber and light stabilizer are used for a long period of time, they bleed out from the surface of the resin and are washed away from the surface of the film or sheet. As a result, only unsatisfactory performance was obtained. Therefore, when long-term weather resistance is required, it is necessary to blend a high concentration light stabilizer and ultraviolet absorber in advance, but with the ultraviolet absorber and light stabilizer bleed out on the surface of the film or sheet, There was also a problem that transparency was impaired such as the film or sheet becoming cloudy white. In particular, when used by being laminated with other polyolefin-based substrate films or sheets, there has been a problem that the interfacial adhesive strength with the substrate is lowered due to bleeding out of the additive.

For example, as shown in Patent Document 1 and the like, the above problem is considerably improved by adding a specific triaryltriazine type ultraviolet absorber, but it is inferior in whitening resistance and causes a problem particularly in bending at a low temperature. It was happening.
For example, as shown in Patent Document 2, the weather resistance and the whitening resistance were improved by adding a specific polypropylene, an ultraviolet absorber and a light stabilizer, but the discoloration resistance was poor.

JP 2004-43596 A Japanese Patent Laid-Open No. 11-147981

  In view of the above-mentioned problems, the object of the present invention is to add even if it is used for a long time without losing transparency because the additive bleeds to the surface even when blended in a high concentration when processed into a film or sheet It is an object of the present invention to provide a polyolefin resin composition that does not change the agent concentration, and therefore has excellent long-term weather resistance, and also has excellent whitening resistance, discoloration resistance, and extrusion laminate processability.

As a result of intensive studies to solve the above-mentioned problems, the present inventors contain a specific light stabilizer, a specific ultraviolet absorber and a dialkylhydroxylamine compound in a specific polyolefin resin composition, and further, if necessary, By blending with organic peroxide and melt-kneading, it is excellent in extrusion lamination processability, and even if processed into a film or sheet, the additive bleeds out and does not impair transparency, and it is weather resistant even after long-term use It was found that a polyolefin resin composition for extrusion laminating excellent in whitening resistance and discoloration resistance was obtained, and the present invention was completed.
The present invention provides a polyolefin resin composition for extrusion lamination having the following constitution.

[1] A melt flow rate (hereinafter referred to as “ MFR ”may be abbreviated as“ MFR ”.) Is a resin composition of 2 to 10 g / 10 min, and the components (A), (B), ( The ratio of C), (D), and (E) is 50 to 96.89% by weight, 3 to 50% by weight, 0.1 to 5% by weight, 0.005 to 1% by weight, and 0.005 to 1, respectively. A polyolefin resin composition for extrusion lamination, characterized in that the content is% by weight.
(A) Propylene resin having MFR of 1 to 50 g / 10 min (B) Polypropylene resin having a branched structure satisfying the following characteristics (i) to (iv) (i) MFR of 0.1 to 30 g / 10 Minute (ii) In the molecular weight distribution by GPC, Mw / Mn is 3.0 to 10.0.
(Iii) The branching index g ′ at an absolute molecular weight Mabs of 1 million is 0.30 or more and less than 1.00 (iv) Melt tension (MT) (unit: g)
log (MT) ≧ −0.9 × log (MFR) +0.7, or MT ≧ 15
Satisfy one of the following.
(C) at least one compound selected from the group of triaryltriazine compounds represented by formula (1)

（式中、Ｒ^１はイソオクチル基）
（Ｄ）ヒンダードアミン系光安定剤
（Ｅ）ジアルキルヒドロキシルアミン系化合物

(Wherein R ¹ is an isooctyl group)
(D) Hindered amine light stabilizer (E) Dialkylhydroxylamine compound

[2] The polyolefin resin composition for extrusion lamination according to [1], wherein the polypropylene resin (B) having a branched structure satisfies the following property (v):
(V) The 25 ° C. paraxylene soluble component amount (CXS) is less than 5.0% by weight based on the total amount of the polypropylene resin (B) [3] The polypropylene resin (B) having a branched structure has the following (vi) The polyolefin resin composition for extrusion lamination according to [1], which satisfies the characteristics.
(Vi) The propylene unit tri-linked mm fraction by ¹³ C-NMR is 95% or more. [4] The propylene-based resin (A) is a propylene / α-olefin copolymer having a melting point of 110 to 155 ° C. The polyolefin resin composition for extrusion lamination according to [1].
[5] The polyolefin resin composition for extrusion lamination according to [4], wherein the propylene resin (A) is a propylene / ethylene copolymer polymerized using a metallocene catalyst.
[6] Further, the organic peroxide (F) is blended by 0.005 to 0.1 parts by weight with respect to a total of 100 parts by weight of (A) to (E), and melt kneaded. The polyolefin resin composition for extrusion lamination according to any one of [1] to [5].

  The polyolefin resin composition of the present invention is a bleedout by combining a specific propylene resin and a polypropylene resin having a specific structure with a specific triaryltriazine UV absorber, a hindered amine light stabilizer and a dialkylhydroxylamine compound. Excellent in transparency and long-term weather resistance, in addition, excellent in extrusion laminating properties, excellent in whitening resistance and discoloration resistance, has a good surface appearance, extruded into a film or sheet, It is suitable for laminating with other base materials to make a laminate molded product.

Hereinafter, each component, a manufacturing method, and an application are demonstrated.
[Propylene resin (A): polypropylene, propylene random copolymer]
As the propylene-based resin (A), polypropylene and / or propylene random copolymer having an MFR of 1 to 50 g / 10 min is used.
The propylene-based resin (A) may be a polypropylene homopolymer, a copolymer of propylene and ethylene and / or an α-olefin having 4 to 20 carbon atoms, or a plurality thereof. A mixture of these components may also be used. When a copolymer of propylene and ethylene and / or an α-olefin having 4 to 20 carbon atoms is used, the weight fraction of ethylene or α-olefin as a comonomer is preferably up to 5% by weight, more preferably 8%. Those up to% by weight are preferably used.

  The MFR of the propylene-based resin (A) needs to be 1 to 50 g / 10 minutes, preferably 3 to 40 g / 10 minutes, and more preferably 5 to 30 g / 10 minutes. MFR in the range of 1 to 50 g / 10 min makes it compatible with polypropylene resin (B), has excellent processability for extrusion laminating, has excellent spreadability, and enables extrusion lamination at high speed. It becomes.

The melting point of the propylene-based resin (A) is preferably 130 to 170 ° C., more preferably 135 to 168 ° C., and the molecular weight distribution is preferably Mw / Mn, preferably 3.0 to 10.0, more preferably 3.2. The thing of the range of -8.0 can be used conveniently.
The melting point was determined by using differential operation calorimetry (DSC), once the temperature was raised to 200 ° C. to erase the thermal history, the temperature was lowered to 40 ° C. at a temperature lowering rate of 10 ° C./min, and the temperature rising rate was 10 again. The temperature at the top of the endothermic peak when measured at ° C / min. Mw / Mn is obtained by the same method as described later.

  The production method of the propylene-based resin (A) is not limited, and the propylene-based resin (A) may be produced using a Ziegler-Natta catalyst or may be produced using a metallocene catalyst.

  Ziegler-Natta catalysts are described in, for example, “Polypropylene Handbook” Edward P. Moore Jr. It is a catalyst system as outlined in Section 2.3.1 (pages 20-57) of the edited by Tetsuo Yasuda and Satoshi Sakuma, supervised by the Industrial Research Council (1998). For example, titanium trichloride and halogen A titanium trichloride catalyst composed of organoaluminum fluoride, a solid catalyst component containing magnesium chloride, titanium halide, and an electron donating compound as essential components, a magnesium-supported catalyst composed of organoaluminum and an organosilicon compound, and a solid catalyst component It refers to a catalyst in which an organoaluminum compound component is combined with an organosilicon treatment solid catalyst component formed by contacting organoaluminum and an organosilicon compound.

  The metallocene catalyst includes (i) a transition metal compound belonging to Group 4 of the periodic table (so-called metallocene compound) containing a ligand having a cyclopentadienyl skeleton, and (ii) a stable ionic state by reacting with the metallocene compound. A catalyst comprising an activatable cocatalyst and, if necessary, (iii) an organoaluminum compound, any known catalyst can be used. The metallocene compound is preferably a bridged metallocene compound capable of stereoregular polymerization of propylene, and more preferably a bridged metallocene compound capable of isoregular polymerization of propylene.

  Examples of (i) metallocene compounds include JP-A-60-35007, JP-A-63-130314, JP-A-63-295607, JP-A-1-275609, JP-A-2-41303, and JP-A-2-41303. JP-A-2-131488, JP-A-2-76887, JP-A-3-163888, JP-A-4-30087, JP-A-4-21694, JP-A-5-43616, JP-A-5-209913, JP-A-6 No. 239914, JP-A-7-504934, JP-A-8-85708, etc. can be preferably used.

  More specifically, methylene bis (2-methylindenyl) zirconium dichloride, ethylenebis (2-methylindenyl) zirconium dichloride, ethylene 1,2- (4-phenylindenyl) (2-methyl-4-phenyl) -4H-azulenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (4-methylcyclopentadienyl) (3-t-butylindenyl) zirconium dichloride, dimethylsilylene (2- Methyl-4-t-butyl-cyclopentadienyl) (3′-t-butyl-5′-methyl-cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (4,5 6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene bis [1- (2-methyl-4-phenylindenyl)] zirconium dichloride, dimethylsilylene bis [1- (2-ethyl-4-phenylindenyl)] Zirconium dichloride, dimethylsilylenebis [4- (1-phenyl-3-methylindenyl)] zirconium dichloride, dimethylsilylene (fluorenyl) t-butylamidozirconium dichloride, methylphenylsilylenebis [1- (2-methyl-4, (1-naphthyl) -indenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-methyl-4,5-benzoindenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-methyl-4-phenyl-) 4H-azuleni ] Zirconium dichloride, dimethylsilylenebis [1- (2-ethyl-4- (4-chlorophenyl) -4H-azulenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-ethyl-4-naphthyl-4H-azurenyl) ] Zirconium dichloride, diphenylsilylene bis [1- (2-methyl-4- (4-chlorophenyl) -4H-azulenyl)] zirconium dichloride, dimethylsilylene bis [1- (2-ethyl-4- (3-fluorobiphenyl) Ryl) -4H-azurenyl)] zirconium dichloride, dimethylgermylenebis [1- (2-ethyl-4- (4-chlorophenyl) -4H-azurenyl)] zirconium dichloride, dimethylgermylenebis [1- (2-ethyl) -4-phenylindenyl)] zirconium di Zirconium compounds such as chloride can be exemplified.

In the above, compounds in which zirconium is replaced with titanium or hafnium can be used in the same manner. It is also preferable to use a mixture of a zirconium compound and a hafnium compound. Further, the chloride can be replaced with other halogen compounds, hydrocarbon groups such as methyl, isobutyl and benzyl, amide groups such as dimethylamide and diethylamide, alkoxide groups such as methoxy group and phenoxy group, hydride groups and the like.
Of these, metallocene compounds obtained by crosslinking an indenyl group or an azulenyl group with a silicon or germyl group are particularly preferable.

The metallocene compound may be used by being supported on an inorganic or organic compound carrier. The carrier is preferably an inorganic or organic porous compound. Specifically, ion-exchange layered silicate, zeolite, SiO ₂ , Al ₂ O ₃ , silica alumina, MgO, ZrO ₂ , TiO ₂ , B Examples include inorganic compounds such as ₂ O ₃ , CaO, ZnO, BaO, and ThO ₂ , organic compounds composed of porous polyolefin, styrene / divinylbenzene copolymer, olefin / acrylic acid copolymer, and the like, or a mixture thereof. It is done.

  (Ii) As a co-catalyst that can be activated to a stable ionic state by reacting with a metallocene compound, an organoaluminum oxy compound (for example, an aluminoxane compound), an ion-exchange layered silicate, a Lewis acid, a boron-containing compound, an ionic compound Preferred examples include fluorine-containing organic compounds.

  (Iii) Examples of the organoaluminum compound include trialkylaluminum such as triethylaluminum, triisopropylaluminum, and triisobutylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, alkylaluminum dihalide, alkylaluminum hydride, and organoaluminum alkoxide. Preferably mentioned.

  Of these, polypropylene is preferably produced with a Ziegler-Natta catalyst, and the propylene random copolymer is preferably produced with a metallocene catalyst.

  The production method of the propylene-based resin (A) is not particularly limited and can be produced by any of the conventionally known slurry polymerization method, bulk polymerization method, gas phase polymerization method, and the like, and within the range, a multistage It is also possible to produce a polypropylene and a propylene random copolymer using a polymerization method.

[Polypropylene resin (B)]
The polypropylene resin (B) used in the present invention is a polypropylene resin having a branched structure and satisfies the characteristics (i) to (iv).
Each of the above characteristics and a method for producing the polypropylene resin (B) will be specifically described below.

Characteristic (i): MFR
The melt flow rate (MFR) of the polypropylene resin (B) used in the present invention needs to be in the range of 0.1 to 30 g / 10 minutes, preferably 0.3 to 20.0 g / 10 minutes, Preferably it is 0.5-10.0 g / 10min. If it is 0.1 g / 10 min or more, the fluidity will be sufficient and problems such as excessive load on the extruder during extrusion laminating will not occur. On the other hand, if it is 30 g / 10 min or less, the tension will be sufficient. It is suitable for the characteristics as a high melt tension material.
The method for controlling the MFR value is well known and can be easily adjusted by adjusting the temperature and pressure, which are the polymerization conditions of the polypropylene resin (B), or by controlling the amount of hydrogen added during polymerization of a chain transfer agent such as hydrogen. Can be performed.
In the present invention, the MFR of the propylene-based resin is JIS K7210: 1999 “Method of plastic-thermoplastic melt mass flow rate (MFR) and test method for melt volume flow rate (MVR)”, condition M (230 ° C, 2.16 kg load), and the unit is g / 10 minutes.

Characteristic (ii): Molecular weight distribution by GPC In addition, the polypropylene resin (B) needs to have a relatively wide molecular weight distribution, and the molecular weight distribution Mw / Mn obtained by gel permeation chromatography (GPC) (where, It is necessary that Mw is a weight average molecular weight and Mn is a number average molecular weight) of 3.0 or more and 10.0 or less. The molecular weight distribution Mw / Mn of the polypropylene resin (B) is preferably in the range of 3.5 to 8.0, more preferably 4.1 to 6.0.
Furthermore, it is preferable that Mz / Mw (where Mz is the Z average molecular weight) is 2.5 or more and 10.0 or less as a parameter that more significantly represents the width of the molecular weight distribution. A more preferable range of Mz / Mw is 2.8 to 8.0, and more preferably 3.0 to 6.0.
As the molecular weight distribution is wider, the molding processability is improved, but those having Mw / Mn and Mz / Mw in this range are particularly excellent in extrusion laminate processability.

The definitions of Mn, Mw, and Mz are described in “Basics of Polymer Chemistry” (Edited by Polymer Society, Tokyo Kagaku Dojin, 1978) and can be calculated from molecular weight distribution curves by GPC.
And the specific measuring method of GPC is as follows.
Apparatus: GPC manufactured by Waters (ALC / GPC 150C)
Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: Showa Denko AD806M / S (3 in series)
-Mobile phase solvent: orthodichlorobenzene (ODCB)
・ Measurement temperature: 140 ℃
・ Flow rate: 1.0 ml / min
・ Injection volume: 0.2ml
Sample preparation: Prepare a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolve it at 140 ° C. for about 1 hour.

Conversion from the retention capacity obtained by GPC measurement to the molecular weight is performed using a calibration curve prepared in advance by standard polystyrene (PS). The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve is created by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximation by the least square method.
In addition, the following numerical value is used for the viscosity formula [η] = K × M ^α used for conversion to molecular weight.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78

  In order to set Mw / Mn to 3.0 or more and 10.0 or less and Mz / Mw to 2.5 or more and 10.0 or less, the temperature and pressure conditions of propylene polymerization are changed, or as the most general technique Can be easily adjusted by a method in which a chain transfer agent such as hydrogen is added during propylene polymerization. Furthermore, when using 2 or more types of the metallocene catalyst mentioned later and a catalyst, it can control by changing the quantity ratio.

Characteristic (iii): Branch index g ′
As a direct indicator that the polypropylene resin (B) used in the present invention has long-chain branching, a branching index g ′ can be mentioned. g ′ is given by the ratio of the intrinsic viscosity [η] lin of the linear polymer having the same molecular weight as the intrinsic viscosity [η] br of the polymer having a long chain branched structure, that is, [η] br / [η] lin. When a long chain branched structure is present, the value is smaller than 1.
The definition is described in, for example, “Developments in Polymer Characterization-4” (JV Dawkins ed. Applied Science Publishers, 1983), and is an index known to those skilled in the art.

The branching index g ′ can be obtained as a function of the absolute molecular weight Mabs by using, for example, a GPC equipped with a light scatterometer and a viscometer as described below.
The polypropylene resin (B) used in the present invention has a g ′ of 0.30 or more and less than 1.00, preferably 0.55 or more and 0.98 or less, when the absolute molecular weight Mabs determined by light scattering is 1,000,000. More preferably, they are 0.75 or more and 0.96 or less, More preferably, they are 0.78 or more and 0.95 or less.
The polypropylene resin (B) used in the present invention is considered to preferably have a comb chain as a molecular structure. When the branching index g ′ is less than 0.30, the main chain is few and the side chain is The ratio is extremely large. In such a case, the melt tension may not be improved or a gel may be formed, which is not preferable in the extrusion laminating process. On the other hand, when it is 1.00, this means that there is no long-chain branching, and the melt tension tends to be insufficient, which is not suitable for extrusion laminating.

The lower limit of g ′ is preferably the above value for the following reason.
According to the document “Encyclopedia of Polymer Science and Engineering vol. 2” (John Wiley & Sons 1985 p. 485), the g ′ value of the comb polymer is represented by the following formula.

Here, g is a branching index defined by the rotation radius ratio of the polymer, and ε is a constant determined by the shape of the branched chain and the solvent. According to Table 3 of 487, a value of about 0.7 to 1.0 is reported for the comb chain in a good solvent. λ is the ratio of the main chain in the comb chain, and p is the average number of branches. According to this equation, the number of branches is extremely large for a comb chain, that is, p is infinite, and g ′ = g ^ε = λ ^ε , which is not less than the value of λ ^ε. In general, there will be a lower limit.

On the other hand, the formula of a conventionally known random branched chain that is considered to occur in the case of electron beam irradiation or peroxide modification is given by the formula (19) on page 485 in the same document. In the chain, as the number of branch points increases, the g ′ and g values monotonously decrease, especially without the lower limit. That is, in the present invention, the fact that the g ′ value has a lower limit means that the polypropylene resin (B) having a long chain branched structure used in the present invention has a structure close to a comb chain. Therefore, the distinction from the random branched chain generated by the conventional electron beam irradiation or peroxide modification becomes clearer.
In the branched polymer having a structure close to a comb chain in which g ′ is in the above range, the degree of decrease in melt tension when kneading is repeated is small, and in the process of industrially producing sheets and films, For example, when an end material or the like generated by cutting the end portion is subjected to molding again as a recycled material, deterioration in physical properties and moldability is reduced.

A specific method for calculating the branching index g ′ is as follows.
Waters Alliance GPCV2000 is used as a GPC apparatus equipped with a differential refractometer (RI) and a viscosity detector (Viscometer). As the light scattering detector, a DAWN-E manufactured by WYatt Technology, a multi-angle laser light scattering detector (MALLS) is used. The detectors are connected in the order of MALLS, RI, and Viscometer. The mobile phase solvent is 1,2,4-trichlorobenzene (added with an antioxidant Irganox 1076 manufactured by BASF Japan Ltd. at a concentration of 0.5 mg / mL).
The flow rate is 1 mL / min, and two columns of Tosoh Corporation GMHHR-H (S) HT are connected and used. The temperature of the column, sample injection section, and each detector is 140 ° C. The sample concentration is 1 mg / mL and the injection volume (sample loop volume) is 0.2175 mL.

In order to obtain the absolute molecular weight (Mabs) obtained from MALLS, the mean square inertia radius (Rg), and the intrinsic viscosity ([η]) obtained from Viscometer, data processing software ASTRA (version 4.73.04) attached to MALLS is used. The calculation is performed with reference to the following documents.
1. “Developments in Polymer Characterization-4” (JV Dawkins ed. Applied Science Publishers, 1983. Chapter 1.)
2. Polymer, 45, 6495-6505 (2004).
3. Macromolecules, 33, 2424-2436 (2000).
4). Macromolecules, 33, 6945-6925 (2000).

The branching index g ′ is a ratio of the intrinsic viscosity ([η] br) obtained by measuring a sample with the above Viscometer and the intrinsic viscosity ([η] lin) obtained separately by measuring a linear polymer ([[ η] br / [η] lin).
When a long-chain branched structure is introduced into a polymer molecule, the radius of inertia becomes smaller than that of a linear polymer molecule having the same molecular weight. Since the intrinsic viscosity becomes smaller as the inertia radius becomes smaller, the intrinsic viscosity ([η] br) of the branched polymer with respect to the intrinsic viscosity ([η] lin) of the linear polymer having the same molecular weight as the long-chain branched structure is introduced. The ratio ([η] br / [η] lin) becomes smaller.
Therefore, when the branch index (g ′ = [η] br / [η] lin) is a value smaller than 1, it means that a branch is introduced. Here, as a linear polymer for obtaining [η] lin, a commercially available homopolypropylene (Novatech PP (registered trademark), grade name: FY6 manufactured by Nippon Polypro Co., Ltd.) is used. The fact that the logarithm of [η] lin of a linear polymer has a linear relationship with the logarithm of molecular weight is known as the Mark-Houwink-Sakurada equation, so [η] lin is appropriately set on the low molecular weight side or the high molecular weight side. Extrapolation can be used to obtain numerical values.

  In order to make the branching index g ′ 0.30 or more and less than 1.00, it is achieved by introducing many long-chain branches, selection of preferred metallocene catalysts described later, a combination thereof, a quantitative ratio thereof, and prepolymerization This can be achieved by controlling the conditions for polymerization.

Characteristic (iv): Melt tension (MT)
Furthermore, the polypropylene resin (B) used in the present invention has the following relational expression between melt tension (MT) and MFR:
log (MT) ≧ −0.9 × log (MFR) +0.7
Or MT ≧ 15
You need to meet one of the following:
Here, MT is Capillograph 1B manufactured by Toyo Seiki Seisakusho Co., Ltd. Capillary: 2.0 mm in diameter, 40 mm in length, cylinder diameter: 9.55 mm, cylinder extrusion speed: 20 mm / min, take-off speed: 4. The melt tension when measured under the conditions of 0 m / min and temperature: 230 ° C. is expressed in grams. However, when the MT of the polypropylene resin (B) is extremely high, the resin may be broken at a take-up speed of 4.0 m / min. In such a case, the take-up speed can be lowered to take off the resin. Let MT be the tension at the highest speed. The measurement conditions and units of MFR are as described above.

This rule is an index for the polypropylene resin (B) having a branched structure to have a sufficient melt tension for extrusion laminating. Generally, MT has a correlation with MFR. It is described by the relational expression.
Thus, the method of defining the melt tension MT with the relational expression with MFR is a normal method for those skilled in the art. For example, JP 2003-25425 discloses the definition of polypropylene having a high melt tension as follows: The following relational expression has been proposed.
log (MS)> − 0.61 × log (MFR) +0.82
(Here, MS is synonymous with MT.)
Japanese Unexamined Patent Application Publication No. 2003-64193 proposes the following relational expression as a definition of polypropylene having a high melt tension.
11.32 × MFR ^−0.7854 ≦ MT
Furthermore, Japanese Patent Laid-Open No. 2003-94504 proposes the following relational expression as a definition of polypropylene having a high melt tension.
MT ≧ 7.52 × MFR ^−0.576

In the present invention, the polypropylene resin (B) having a branched structure is represented by the relational formula:
log (MT) ≧ −0.9 × log (MFR) +0.7 or MT ≧ 15
If any of the above is satisfied, it can be said that the resin has a sufficiently high melt tension and is useful for extrusion laminating.
The polypropylene resin (B) has the following relational expression:
log (MT) ≧ −0.9 × log (MFR) +0.9 or MT ≧ 15
It is more preferable to satisfy | fill, and it is still more preferable to satisfy | fill the following relational expressions.
log (MT) ≧ −0.9 × log (MFR) +1.1 or MT ≧ 15
Although it is not necessary to provide the upper limit value of MT in particular, when MT exceeds 40 g, the take-up speed is remarkably slowed by the measurement method described above, and measurement becomes difficult. In such a case, since it is considered that the spreadability of the resin is also deteriorated, it is preferably 40 g or less, more preferably 35 g or less, and most preferably 30 g or less.

  In order to satisfy the relational expression of MT and MFR described above, the long chain branching amount of the polypropylene resin (B) may be increased to increase the melt tension. This can be achieved by controlling the amount ratio and prepolymerization conditions to introduce a large amount of long chain branches.

Characteristic (v): 25 ° C. Paraxylene soluble component amount (CXS)
The polypropylene resin (B) used in the present invention has a high stereoregularity, and it is preferable that there are few low crystalline components that cause stickiness and bleed-out when it becomes a laminated product. This low crystalline component is evaluated by the amount of xylene soluble component (CXS) at 25 ° C., which is preferably less than 5.0% by weight, more preferably 3.0%, based on the total amount of the polypropylene resin (B). % By weight or less, more preferably 1.0% by weight or less, and particularly preferably 0.5% by weight or less. The lower limit is not particularly limited, but is usually 0.01% by weight or more, preferably 0.03% by weight or more.

The details of the CXS measurement method are as follows.
A 2 g sample is dissolved in 300 ml of p-xylene (containing 0.5 mg / ml BHT) at 130 ° C. to make a solution, and then left at 25 ° C. for 12 hours. Thereafter, the precipitated polymer is separated by filtration, p-xylene is evaporated from the filtrate, and further dried under reduced pressure at 100 ° C. for 12 hours to recover room temperature xylene-soluble components. The ratio (% by weight) of the weight of the recovered component to the charged sample weight is defined as CXS.

  In order to make CXS less than 5.0% by weight, it is possible to produce by using a metallocene catalyst as described later. In addition to keeping the purity of the catalyst above a certain level, It is necessary that the reaction conditions during the polymerization are not extremely high and that the amount ratio of the organoaluminum compound to the metallocene complex is not excessively increased.

Characteristic (vi): mm fraction of three chain of propylene units by ¹³ C-NMR The polypropylene resin (B) used in the present invention is characterized by high stereoregularity. Stereoregularity of the ^height 13 that can be evaluated by ^{C-NMR, 13 C-NMR} mm fraction of the propylene unit triad sequences obtained by it is preferably 95% or more.
As for the mm fraction, the upper limit of the ratio of three propylene unit chains in which the direction of methyl branching in each propylene unit is the same in any three propylene unit chains composed of head-to-tail bonds in the polymer chain is 100%. This mm fraction is a value indicating that the steric structure of the methyl group in the polypropylene molecular chain is controlled isotactically, and the higher the value, the higher the degree of control. If the mm fraction is greater than this value, the mechanical properties tend to be improved.
Accordingly, the mm fraction is preferably 95% or more, more preferably 96% or more, and still more preferably 97% or more.

In addition, the detail of the measuring method of mm fraction of the propylene unit 3 chain | strand by ¹³ C-NMR is as follows.
A sample of 375 mg is completely dissolved in 2.5 ml of deuterated 1,1,2,2-tetrachloroethane in an NMR sample tube (10φ), and then measured at 125 ° C. by a proton complete decoupling method. The chemical shift sets the central peak of the three peaks of deuterated 1,1,2,2-tetrachloroethane to 74.2 ppm. The chemical shift of other carbon peaks is based on this.
Flip angle: 90 degrees Pulse interval: 10 seconds Resonance frequency: 100 MHz or more Integration frequency: 10,000 times or more Observation range: -20 ppm to 179 ppm
Number of data points: 32768
The analysis of the mm fraction is performed using the measured ¹³ C-NMR spectrum.
The spectrum is assigned with reference to Macromolecules, (1975) 8 pp. 687 and Polymer, 30, vol. 1, 1350 (1989).
Note that a more specific method for determining the mm fraction is described in detail in paragraphs [0053] to [0065] of Japanese Patent Laid-Open No. 2009-275207, and the present invention is performed according to this method. .

  The mm fraction can be 95% or more by using a polymerization catalyst that achieves a highly crystalline polymer, and by using a preferred metallocene catalyst described later for polymerization.

[Other characteristics of polypropylene resin (B) having a branched structure]
As a further additional feature of the polypropylene resin (B) having a branched structure according to the present invention, the strain hardening degree (λmax (0.1)) in the measurement of the extensional viscosity at a strain rate of 0.1 s ⁻¹ is 6.0. It is mentioned above.
The strain hardening degree (λmax (0.1)) is an index representing the strength at the time of melting, and when this value is large, there is an effect of improving the melt tension. As a result, neck-in during extrusion laminating can be suppressed, and the strain hardening degree is preferably 6.0 or more, more preferably 8.0 or more.

Details of the calculation method of λmax (0.1) are as follows.
The elongational viscosity at a temperature of 180 ° C. and the strain rate = 0.1 s ⁻¹ is plotted on a logarithmic graph with the horizontal axis representing time t (seconds) and the vertical axis representing elongational viscosity η _E (Pa · seconds). On the log-log graph, the viscosity immediately before strain hardening is approximated by a straight line.
Specifically, first, the slope at each time when the extensional viscosity is plotted against time is obtained. In this case, considering that the measurement data of the extensional viscosity is discrete, various averaging methods are used. Is used. For example, there is a method of obtaining the slope of adjacent data and taking a moving average of several surrounding points.
The elongational viscosity is a simple increasing function in the low strain region, gradually approaches a constant value, and if there is no strain hardening, it agrees with the Truton viscosity after a sufficient amount of time. From about 1 strain amount (= strain rate × time), the extensional viscosity starts to increase with time. That is, the slope tends to decrease with time in the low strain region, but tends to increase from about 1 strain, and there is an inflection point on the curve when the extensional viscosity is plotted against time. . Therefore, a point where the slope of each time obtained above takes the minimum value in the range of the distortion amount of about 0.1 to 2.5 is obtained, and a tangent line is drawn at the point, and the straight line has a distortion amount of 4.0. Extrapolate until The maximum value (ηmax) of the extensional viscosity η _E until the strain amount becomes 4.0 is obtained, and the viscosity on the approximate straight line up to that time is η lin. ηmax / ηlin is defined as λmax (0.1).

[Method for producing polypropylene resin (B) having a branched structure]
The polypropylene resin (B) having a branched structure is not particularly limited as long as it satisfies the above characteristics (i) to (iv). However, as described above, the amount of low low crystalline component is high. A preferred production method for satisfying all the conditions of stereoregularity, relatively wide molecular weight distribution, range of branching index g ′, and high melt tension is a method using a macromer copolymerization method using a combination of metallocene catalysts. . As an example of such a method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 2009-57542 can be given.
This method produces a polypropylene having a long-chain branched structure using a catalyst in which a catalyst component having a specific structure having macromer-producing ability and a catalyst component having a specific structure having high molecular weight and macromer copolymerization ability are combined. According to this, industrially effective methods such as bulk polymerization and gas phase polymerization, particularly single-stage polymerization under practical pressure-temperature conditions, and using hydrogen as a molecular weight regulator. It is possible to produce a polypropylene resin having a long-chain branched structure having the desired physical properties.

In the past, it was necessary to increase the branching efficiency by lowering the crystallinity by using a polypropylene component having a low stereoregularity. However, in the above method, a polypropylene component having a sufficiently high stereoregularity is required. The above (vi) and (v) relating to high stereoregularity and low amount of low crystalline component, which can be introduced into the side chain by a simple method and is preferable as the polypropylene resin (B) used in the present invention. It is suitable for satisfying these characteristics.
Moreover, if the said method is used, molecular weight distribution can be widened by using two types of catalysts from which a superposition | polymerization characteristic differs greatly, and the said (ii)-required for the polypropylene resin (B) which has a branched structure used for this invention It is possible and preferable to satisfy the characteristic (iv) at the same time.

Then, the preferable manufacturing method of the polypropylene resin (B) which has the branched structure used for this invention is described in detail below.
As a preferred method for producing the polypropylene resin (B) having a branched structure, a method for producing a propylene polymer using the following catalyst components (G), (H) and (I) as a propylene polymerization catalyst can be mentioned.
(G): at least one kind from component [G-1] which is a compound represented by the following general formula (g1);
A transition metal compound belonging to Group 4 of the periodic table of at least one kind from Component [G-2], which is a compound represented by General Formula (g2) described later.
(H): Ion exchange layered silicate (I): Organoaluminum compound

Hereinafter, the catalyst components (G), (H) and (I) will be described in detail.
(1) Catalyst component (G)
(I) Component [G-1]: Compound represented by the following general formula (g1)

(In the general formula (g1), R ¹¹ and R ¹² each independently represent a heterocyclic group containing nitrogen, oxygen or sulfur having 4 to 16 carbon atoms. Moreover, each of R ¹³ and R ¹⁴ represents Independently, an aryl group having 6 to 16 carbon atoms and nitrogen having 6 to 16 carbon atoms, which may contain halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a plurality of heteroelements selected from these And X ¹¹ and Y ¹¹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or silicon having 1 to 20 carbon atoms. Represents a containing hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, Q ¹¹ is C1-C20 divalent hydrocarbon Represents a base group, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms.)

The heterocyclic group containing nitrogen, oxygen or sulfur having 4 to 16 carbon atoms of R ¹¹ and R ¹² is preferably a 2-furyl group, a substituted 2-furyl group, a substituted 2-thienyl group, It is a substituted 2-furfuryl group, and more preferably a substituted 2-furyl group.
Moreover, as a substituted 2-furyl group, a substituted 2-thienyl group, and a substituted 2-furfuryl group, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and a propyl group, Examples include halogen atoms such as fluorine atom and chlorine atom, alkoxy groups having 1 to 6 carbon atoms such as methoxy group and ethoxy group, and trialkylsilyl groups. Of these, a methyl group and a trimethylsilyl group are preferable, and a methyl group is particularly preferable.
Further, R ¹¹ and R ¹² are particularly preferably a 2- (5-methyl) -furyl group. R ¹¹ and R ¹² are preferably the same as each other.
Carbon atoms 6 to 16 of the R ¹³ and R ^14, halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or may contain a plurality of hetero elements selected from these, the aryl group In the range of 6 to 16 carbon atoms, one or more hydrocarbon group having 1 to 6 carbon atoms, silicon-containing hydrocarbon group having 1 to 6 carbon atoms, 1 to 6 carbon atoms on the aryl cyclic skeleton It may have a halogen-containing hydrocarbon group as a substituent.

At least one of R ¹³ and R ¹⁴ is preferably a phenyl group, a 4-methylphenyl group, a 4-i-propylphenyl group, a 4-t-butylphenyl group, a 4-trimethylsilylphenyl group, or 2,3-dimethyl. A phenyl group, 3,5-di-t-butylphenyl group, 4-phenyl-phenyl group, chlorophenyl group, naphthyl group, or phenanthryl group, more preferably a phenyl group, 4-i-propylphenyl group, 4- t-butylphenyl group, 4-trimethylsilylphenyl group, 4-chlorophenyl group. Further, it is preferable that R ¹³ and R ¹⁴ are the same.

In the general formula (g1), X ¹¹ and Y ¹¹ are auxiliary ligands, and react with the cocatalyst of the catalyst component (H) to generate an active metallocene having olefin polymerization ability. Therefore, as long as this object is achieved, X ¹¹ and Y ¹¹ are not limited in the type of ligand, and are independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. A C1-C20 silicon-containing hydrocarbon group, a C1-C20 halogenated hydrocarbon group, a C1-C20 oxygen-containing hydrocarbon group, an amino group, or a C1-C20 nitrogen-containing hydrocarbon Indicates a group.

In general formula (g1), Q ¹¹ is a silylene having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms, which bonds two five-membered rings. Represents either a group or a germylene group. When two hydrocarbon groups are present on the silylene group or the germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ¹¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, di ( n-propyl) silylene, di (i-propyl) silylene, alkylsilylene groups such as di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; tetra An alkyl oligosilylene group such as methyldisilylene; a germylene group; an alkylgermylene group in which the silicon of the above-mentioned divalent hydrocarbon group having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) germylene Group; arylgermylene group And so on. In these, the silylene group which has a C1-C20 hydrocarbon group, or the germylene group which has a C1-C20 hydrocarbon group is preferable, and an alkylsilylene group and an alkylgermylene group are especially preferable.

Of the compounds represented by the general formula (g1), specific examples of preferable compounds are given below.
Dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-thienyl) -4-phenyl -Indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-diphenylsilylenebis {2 -(5-Methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl} ] Hafnium, dichloro [1,1'-dimethylgermylenebis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium, dic B [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5- Trimethylsilyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-phenyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [ 1,1′-dimethylsilylenebis {2- (4,5-dimethyl-2-furyl) -4-phenyl-indenyl}] hafnium dichloride, dichloro [1,1′-dimethylsilylenebis {2- (2-benzofuryl) ) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- ( -Methylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-ipropylphenyl) -indenyl}] hafnium, dichloro [ 1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trimethylsilylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2 -Furfuryl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-fluorophenyl) -indenyl}] Hough , Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trifluoromethylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylene Bis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4 -(1-Naphtyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1 ′ -Dimethylsilylenebis {2- (2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (2-furyl) -4- (9-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (1-naphthyl) -indenyl}] hafnium, Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- ( 5-methyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (9- Phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (1-naphthyl) -indenyl}] ha Nitrogen, dichloro [1,1′-dimethylsilylenebis {2- (5-tert-butyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-t-butyl-2- Furyl) -4- (9-phenanthryl) -indenyl}] hafnium.

  Of these, more preferred are dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylene. Bis {2- (5-methyl-2-furyl) -4- (4-methylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-ipropylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trimethylsilylphenyl) -indenyl} ] Hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -indenyl}] hafni Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2 -(5-Methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium.

  Particularly preferred is dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2- (5-Methyl-2-furyl) -4- (4-ipropylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl)- 4- (4-Trimethylsilylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} ] Hafnium.

(Ii) Component [G-2]: Compound represented by the general formula (g2)

(In General Formula (g2), R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 6 carbon atoms, and R ²³ and R ²⁴ are each independently halogen, silicon, oxygen, An aryl group having 6 to 16 carbon atoms, which may contain sulfur, nitrogen, boron, phosphorus, or a plurality of heteroelements selected from these, X ²¹ and Y ²¹ each independently represent a hydrogen atom, A halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, amino Represents a group or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, Q ²¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, or a silylene that may have a hydrocarbon group having 1 to 20 carbon atoms. ^{.M 21} represents a group or a germylene group Is a zirconium or hafnium.)

R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, and preferably methyl. , Ethyl, n-propyl.

R ²³ and R ²⁴ each independently contain a halogen having 6 to 16 carbon atoms, preferably 6 to 12 carbon atoms, halogen, silicon, or a plurality of hetero elements selected from these. It is a good aryl group. Preferable examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4 -(2-fluoro-4-biphenylyl), 4- (2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3, Examples include 5-dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dichloro-4-trimethylsilylphenyl, and the like.

X ²¹ and Y ²¹ are auxiliary ligands that react with the co-catalyst of the catalyst component (H) to produce an active metallocene having olefin polymerization ability. Therefore, as long as this object is achieved, X ²¹ and Y ²¹ are not limited in the type of ligand, and are independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, C1-C20 silicon-containing hydrocarbon group, C1-C20 halogenated hydrocarbon group, C1-C20 oxygen-containing hydrocarbon group, amino group, or C1-C20 nitrogen-containing hydrocarbon group Indicates.

Q ²¹ is a binding group that bridges two conjugated five-membered ring ligands, and has a divalent hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms. A silylene group or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms, preferably a substituted silylene group or a substituted germylene group. The substituent bonded to silicon and germanium is preferably a hydrocarbon group having 1 to 12 carbon atoms, and two substituents may be linked.

Specific examples of Q ²¹ include methylene, dimethylmethylene, ethylene-1,2-diyl, dimethylsilylene, diethylsilylene, diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylsilylene, Examples include diethylsilylene, diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylgermylene, diethylgermylene, diphenylgermylene, methylphenylgermylene, and the like.

Further, M ²¹ is zirconium or hafnium, preferably hafnium.

Preferred examples of the metallocene compound represented by the general formula (g2) include the following.
However, in the following, only representative exemplary compounds are described avoiding many complicated examples, and in the method for producing a polypropylene resin (B) having a branched structure used in the present invention, component [G-2] It is obvious that various ligands, cross-linking groups, or auxiliary ligands can be arbitrarily used. In the following, a compound in which the central metal is hafnium is described, but a compound substituted for zirconium is also treated as disclosed in the present specification.

  Dichloro {1,1′-dimethylsilylenebis (2-methyl-4-phenyl-4-hydroazurenyl)} hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4 -Hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2-methyl-4- (4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chloro-4-t-butylphenyl)- 4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- ( -Methyl-4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl} ] Hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2 -Methyl-4- (1-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [ 1,1′-dimethylsilylenebis {2-methyl-4- (4-chloro-2-naphthyl)- -Hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-Methyl-4- (2-chloro-4-biphenylyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (9-phenanthryl) -4-hydroazurenyl] }] Hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chlorophenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-n-propyl -4- (3-Chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] huff Nitrogen, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-chloro-4-tert-butylphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2-ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2-methyl-4- (2-fluoro-4-biphenylyl) ) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2-methyl-4- (4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′- (9-silafluorene-9,9-diyl) bis {2-ethyl-4- (4-chlorophenyl) -4-hydroazurenyl}] Funium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl -4- (2-fluoro-4-biphenylyl) -4-hydroazulenyl}] hafnium, dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3 5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium and the like.

  Of these, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- Methyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4 -Hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-Ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] ha Dichloro, [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, is there.

  Particularly preferably, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl -4- (2-Fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4- Hydroazurenyl}] hafnium, dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] Hafnium.

(2) Catalyst component (H)
The catalyst component (H) preferably used for producing the polypropylene resin (B) is an ion-exchange layered silicate.
(I) Types of ion-exchanged layered silicates Ion-exchanged layered silicates (hereinafter sometimes simply referred to as silicates) are surfaces formed by ionic bonds or the like that are parallel to each other with a binding force. A silicate compound having a stacked crystal structure and containing exchangeable ions. Most silicates are mainly produced as a main component of clay minerals in nature, and therefore often contain impurities (quartz, cristobalite, etc.) other than ion-exchanged layered silicates. Good. Depending on the type, amount, particle size, crystallinity, and dispersion state of these impurities, it may be preferable to pure silicate, and such a complex is also included in the catalyst component (B).
The silicate to be used is not limited to a natural product, and may be an artificial synthetic product or may contain them.

Specific examples of the silicate include the following layered silicates described in Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1995).
That is, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stemite and other smectites, vermiculite and other vermiculites, mica, illite, sericite and sea chlorite and other mica, attapulgite, sepiolite and palygorskite , Bentonite, pyrophyllite, talc, chlorite group, etc.
The silicate is preferably a silicate in which the main component silicate has a 2: 1 type structure, more preferably a smectite group, and particularly preferably montmorillonite. The type of interlayer cation is not particularly limited, but a silicate containing an alkali metal or an alkaline earth metal as a main component of the interlayer cation is preferable from the viewpoint of being relatively easy and inexpensive to obtain as an industrial raw material.

(Ii) Chemical treatment of ion-exchangeable layered silicate The ion-exchangeable layered silicate of the catalyst component (Y) can be used as it is without any particular treatment, but is preferably subjected to chemical treatment. Here, the chemical treatment of the ion-exchange layered silicate may be any of a surface treatment for removing impurities adhering to the surface and a treatment that affects the structure of the clay. Treatment, alkali treatment, salt treatment, organic matter treatment and the like.

<Acid treatment>:
In addition to removing impurities on the surface, the acid treatment can elute some or all of cations such as Al, Fe, Mg, etc. in the crystal structure.
The acid used in the acid treatment is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and oxalic acid.
Two or more salts (described in the next section) and acid may be used for the treatment. The treatment conditions with salts and acids are not particularly limited. Usually, the salt and acid concentrations are 0.1 to 50% by weight, the treatment temperature is room temperature to boiling point, and the treatment time is 5 minutes to 24 hours. It is preferable to carry out the process under the condition of selecting and eluting at least a part of the substance constituting at least one compound selected from the group consisting of ion-exchangeable layered silicates. In addition, salts and acids are generally used in an aqueous solution.
In addition, you may use what combined the following acids and salts as a processing agent. Moreover, the combination of these acids and salts may be sufficient.

<Salt treatment>:
Cations that are preferably 40% or more, more preferably 60% or more, of the exchangeable Group 1 metal cations contained in the ion-exchange layered silicate before being treated with salts, dissociated from the salts shown below. It is preferable to perform ion exchange.
The salt used in the salt treatment for the purpose of ion exchange is a group consisting of a cation containing at least one atom selected from the group consisting of group 1 to 14 atoms, a halogen atom, an inorganic acid, and an organic acid. A compound comprising at least one anion selected from the group consisting of at least one anion selected from the group consisting of group 2 to 14 atoms, Cl, Br, I, F, PO ₄ , SO ₄ , NO ₃ , CO ₃ , C ₂ O ₄ , ClO ₄ , OOCCH ₃ , CH ₃ COCHCOCH ₃ , OCl ₂ , O (NO ₃ ) ₂ , O (ClO ₄ ) ₂ , O (SO ₄ ) At least one anion selected from the group consisting of OH, O ₂ Cl ₂ , OCl ₃ , OOCH, OOCCH ₂ CH ₃ , C ₂ H ₄ O ₄ and C ₅ H ₅ O ₇ Is a compound consisting of

Preferred examples of such _{salts, LiF, LiCl, LiBr, LiI} , Li 2 SO 4, Li (CH 3 COO), LiCO 3, Li (C 6 H 5 O 7), LiCHO 2, LiC 2 O ₄ , LiClO ₄ , Li ₃ PO ₄ , CaCl ₂ , CaSO ₄ , CaC ₂ O ₄ , Ca (NO ₃ ) ₂ , Ca ₃ (C ₆ H ₅ O ₇ ) ₂ , MgCl ₂ , MgBr ₂ , MgSO ₄ , Mg (PO ₄ ) ₂ , Mg (ClO ₄ ) ₂ , MgC ₂ O ₄ , Mg (NO ₃ ) ₂ , Mg (OOCCH ₃ ) ₂ , MgC ₄ H ₄ O _{4 and the} like.

Further, Ti (OOCCH ₃ ) ₄ , Ti (CO ₃ ) ₂ , Ti (NO ₃ ) ₄ , Ti (SO ₄ ) ₂ , TiF ₄ , TiCl ₄ , Zr (OOCCH ₃ ) ₄ , Zr (CO ₃ ) ₂ , Zr (NO ₃ ) ₄ , Zr (SO ₄ ) ₂ , ZrF ₄ , ZrCl ₄ , ZrOCl ₂ , ZrO (NO ₃ ) ₂ , ZrO (ClO ₄ ) ₂ , ZrO (SO ₄ ), HF (OOCCH ₃ ) ₄ , HF (CO ₃ ) ₂ , HF (NO ₃ ) ₄ , HF (SO ₄ ) ₂ , HFOCl ₂ , HFF ₄ , HFCl ₄ , V (CH ₃ COCHCOCH ₃ ) ₃ , VOSO ₄ , VOCl ₃ , VCl ₃ , VCl ₄ , VBr _{3 and the} like.

Also, Cr (CH ₃ COCHCOCH ₃ ) ₃ , Cr (OOCCH ₃ ) ₂ OH, Cr (NO ₃ ) ₃ , Cr (ClO ₄ ) ₃ , CrPO ₄ , Cr ₂ (SO ₄ ) ₃ , CrO ₂ Cl ₂ , CrF ₃ , CrCl ₃ , CrBr ₃ , CrI ₃ , Mn (OOCCH ₃ ) ₂ , Mn (CH ₃ COCHCOCH ₃ ) ₂ , MnCO ₃ , Mn (NO ₃ ) ₂ , MnO, Mn (ClO ₄ ) ₂ , MnF ₂ , MnCl ₂ , Fe (OOCCH ₃ ) ₂ , Fe (CH ₃ COCHCOCH ₃ ) ₃ , FeCO ₃ , Fe (NO ₃ ) ₃ , Fe (ClO ₄ ) ₃ , FePO ₄ , FeSO ₄ , Fe ₂ (SO ₄ ) ₃ , FeF ₃ FeCl ₃ , FeC ₆ H ₅ O _{7 and the} like.

In addition, Co (OOCCH ₃ ) ₂ , Co (CH ₃ COCHCOCH ₃ ) ₃ , CoCO ₃ , Co (NO ₃ ) ₂ , CoC ₂ O ₄ , Co (ClO ₄ ) ₂ , Co ₃ (PO ₄ ) ₂ , CoSO ₄ , CoF ₂ , CoCl ₂ , NiCO ₃ , Ni (NO ₃ ) ₂ , NiC ₂ O ₄ , Ni (ClO ₄ ) ₂ , NiSO ₄ , NiCl ₂ , NiBr _{2 and the} like.
Furthermore, Zn (OOCCH ₃ ) ₂ , Zn (CH ₃ COCHCOCH ₃ ) ₂ , ZnCO ₃ , Zn (NO ₃ ) ₂ , Zn (ClO ₄ ) ₂ , Zn ₃ (PO ₄ ) ₂ , ZnSO ₄ , ZnF ₂ , ZnCl ₂ , AlF ₃ , AlCl ₃ , AlBr ₃ , AlI ₃ , Al ₂ (SO ₄ ) ₃ , Al ₂ (C ₂ O ₄ ) ₃ , Al (CH ₃ COCHCOCH ₃ ) ₃ , Al (NO ₃ ) ₃ , AlPO ₄ , GeCl ₄ , GeBr ₄ , GeI _{4 and the} like.

<Alkali treatment>:
In addition to acid and salt treatment, the following alkali treatment or organic matter treatment may be performed as necessary. Examples of the treating agent used in the alkali treatment include LiOH, NaOH, KOH, Mg (OH) ₂ , Ca (OH) ₂ , Sr (OH) ₂ , Ba (OH) _{2 and the} like.

<Organic treatment>:
Examples of the organic treatment agent used for the organic treatment include trimethylammonium, triethylammonium, N, N-dimethylanilinium, triphenylphosphonium, and the like.
Examples of the anion constituting the organic treatment agent include hexafluorophosphate, tetrafluoroborate, and tetraphenylborate other than the anion exemplified as the anion constituting the salt treatment agent. However, it is not limited to these.

Moreover, these processing agents may be used independently and may be used in combination of 2 or more types. These combinations may be used in combination for the treatment agent added at the start of the treatment, or may be used in combination for the treatment agent added during the treatment. The chemical treatment can be performed a plurality of times using the same or different treatment agents.
These ion-exchange layered silicates usually contain adsorbed water and interlayer water. In the present invention, it is preferable to remove these adsorbed water and interlayer water and use them as the catalyst component (H).

  The heat treatment method of the ion-exchange layered silicate adsorbed water and interlayer water is not particularly limited, but it is necessary to select conditions so that interlayer water does not remain and structural destruction does not occur. The heating time is 0.5 hour or longer, preferably 1 hour or longer. At that time, when the moisture content of the catalyst component (H) after removal was 0 wt% when dehydrated for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 1 mmHg (0.13 kPa), It is preferably 3% by weight or less, preferably 1% by weight or less.

  As mentioned above, what is particularly preferable as the catalyst component (H) is an ion-exchange layered silicate having a water content of 3% by weight or less, obtained by performing a salt treatment and / or an acid treatment.

  The ion-exchange layered silicate is preferable because it can be treated with a catalyst component (I) of an organoaluminum compound described later before use as a catalyst or as a catalyst. Although there is no restriction | limiting in the usage-amount of catalyst component (I) with respect to 1g of ion-exchange layered silicate, Usually, 20 mmol or less, Preferably it is 0.5 mmol or more and 10 mmol or less. There is no limitation on the treatment temperature and time, the treatment temperature is usually 0 ° C. or more and 70 ° C. or less, and the treatment time is 10 minutes or more and 3 hours or less. It is also possible and preferable to wash after the treatment. As the solvent, the same hydrocarbon solvent as that used in the preliminary polymerization and slurry polymerization described later is used.

The catalyst component (H) is preferably a spherical particle having an average particle size of 5 μm or more. If the particle shape is spherical, a natural product or a commercially available product may be used as it is, or a particle whose particle shape and particle size are controlled by granulation, sizing, fractionation, or the like may be used.
Examples of the granulation method used here include agitation granulation method and spray granulation method, but commercially available products can also be used.
Moreover, you may use organic substance, an inorganic solvent, inorganic salt, and various binders in the case of granulation.
The spherical particles obtained as described above desirably have a compressive fracture strength of 0.2 MPa or more, particularly preferably 0.5 MPa or more, in order to suppress crushing and generation of fine powder in the polymerization process. In the case of such particle strength, the effect of improving the particle properties is effectively exhibited especially when prepolymerization is performed.

(3) Catalyst component (I)
The catalyst component (I) is an organoaluminum compound. As the organoaluminum compound used as the catalyst component (I), a compound represented by the general formula: (AlR ³¹ _q Z _3-q ) _p is appropriate.
In this invention, it cannot be overemphasized that the compound represented by this formula can be used individually, in mixture of multiple types or in combination. In this formula, R ³¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and Z represents a halogen, hydrogen, an alkoxy group or an amino group. q represents an integer of 1 to 3, and p represents an integer of 1 to 2, respectively.
R ³¹ is preferably an alkyl group, and Z is a chlorine atom when it is a halogen atom, a C 1-8 alkoxy group when it is an alkoxy group, and a C 1 atom when it is an amino group. Eight amino groups are preferred.

Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethylaluminum. Examples thereof include sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, and diisobutylaluminum chloride.
Of these, trialkylaluminum and alkylaluminum hydride having p = 1 and q = 3 are preferable. More preferably, it is trialkylaluminum in which R ³¹ is an alkyl group having 1 to 8 carbon atoms.

(4) Catalyst Formation / Preliminary Polymerization The catalyst contacts each of the above catalyst components (G) to (I) in the (preliminary) polymerization tank, simultaneously or continuously, or once or multiple times. Can be formed.
The contacting of each component is usually performed in an aliphatic hydrocarbon or aromatic hydrocarbon solvent. Although a contact temperature is not specifically limited, It is preferable to carry out between -20 degreeC and 150 degreeC. As the contact order, any desired combination can be used, but particularly preferable ones for each component are as follows.
When the catalyst component (I) is used, the catalyst component (G), the catalyst component (H), or the catalyst component (G) and the catalyst are brought into contact with each other before the catalyst component (G) and the catalyst component (H) are brought into contact with each other. Contacting catalyst component (I) with both components (H), or contacting catalyst component (I) simultaneously with contacting catalyst component (G) and catalyst component (H), or catalyst component Although it is possible to contact the catalyst component (I) after contacting the catalyst component (H) with (G), it is preferable to contact the catalyst component (H) before contacting the catalyst component (G) with the catalyst component (H). It is a method of contacting any of the component (I).
Moreover, after making each component contact, it is possible to wash | clean with an aliphatic hydrocarbon or an aromatic hydrocarbon solvent.

The amount of catalyst components (A), (B) and (C) used is arbitrary. For example, the amount of the catalyst component (A) used relative to the catalyst component (B) is preferably in the range of 0.1 μmol to 1,000 μmol, particularly preferably 0.5 μmol to 500 μmol, relative to 1 g of the catalyst component (B). The amount of the catalyst component (C) relative to the catalyst component (A) is preferably a transition metal molar ratio of preferably 0.01 to 5 × 10 ⁶ , particularly preferably within a range of 0.1 to 1 × 10 ^4. .

The component [G-1] (compound represented by the general formula (g1)) and the component [G-2] (compound represented by the general formula (g2)) are used in a proportion of the polypropylene resin (B). The molar ratio of the transition metal of [G-1] to the total amount of the components [G-1] and [G-2] is preferably within a range that satisfies the above characteristics, but is preferably 0.30 or more, 0.0. 99 or less.
By changing this ratio, it is possible to adjust the balance between melt physical properties and catalyst activity. That is, from the component [G-1], a low molecular weight terminal vinyl macromer is produced, and from the component [G-2], a high molecular weight body obtained by copolymerizing a part of the macromer is produced. Therefore, by changing the ratio of the component [G-1], the average molecular weight, molecular weight distribution, deviation of the molecular weight distribution toward the high molecular weight side, very high molecular weight component, branch (amount, length, Distribution) can be controlled, whereby the melt properties such as branching index g ′, strain hardening degree λmax, melt tension, and spreadability can be controlled.

In order to produce the polypropylene resin (B), the molar ratio is preferably 0.30 or more, more preferably 0.40 or more, and further preferably 0.5 or more. Further, the upper limit is preferably 0.99 or less, and in order to efficiently obtain a polypropylene resin (B) with high catalytic activity, it is preferably 0.95 or less, and more preferably 0.90 or less. It is.
Further, by using the component [G-1] within the above range, it is possible to adjust the balance between the average molecular weight and the catalyst activity with respect to the hydrogen amount.

  The catalyst is preferably subjected to a prepolymerization treatment which consists of contacting it with an olefin and polymerizing it in a small amount. By performing the prepolymerization treatment, gel formation can be prevented when the main polymerization is performed. The reason is considered to be that long-chain branches can be uniformly distributed among the polymer particles when the main polymerization is performed, and the melt physical properties can be improved thereby.

The olefin used in the prepolymerization is not particularly limited, but propylene, ethylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, Styrene and the like can be exemplified. The olefin feed method may be any method such as a feed method for maintaining the olefin at a constant speed or in a constant pressure state, a combination thereof, or a stepwise change.
The prepolymerization temperature and time are not particularly limited, but are preferably in the range of −20 ° C. to 100 ° C. and 5 minutes to 24 hours, respectively. The amount of prepolymerization is preferably 0.01 to 100, more preferably 0.1 to 50 in terms of weight ratio of the prepolymerized polymer to the catalyst component (H). Moreover, catalyst component (I) can also be added or added at the time of prepolymerization. It is also possible to wash after the prepolymerization.

  In addition, a method of coexisting a polymer such as polyethylene or polypropylene, or a solid of an inorganic oxide such as silica or titania, at the time of contacting or after contacting each of the above components is also possible.

(5) Use of catalyst / propylene polymerization Any polymerization method can be used as long as the olefin polymerization catalyst including the catalyst component (G), the catalyst component (H) and the catalyst component (I) is in efficient contact with the monomer. Can be adopted.
Specifically, a slurry method using an inert solvent, a so-called bulk method, a solution polymerization method, or a substantially liquid solvent without using an inert solvent as a solvent. A gas phase method can be used. Moreover, the method of performing continuous polymerization and batch type polymerization is also applied. In addition to single-stage polymerization, it is possible to carry out multistage polymerization of two or more stages.
In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, toluene, or the like is used alone or as a polymerization solvent.

The polymerization temperature is usually 0 ° C. or higher and 150 ° C. or lower. In particular, when bulk polymerization is used, the temperature is preferably 40 ° C or higher, more preferably 50 ° C or higher. The upper limit is preferably 80 ° C. or lower, and more preferably 75 ° C. or lower.
Furthermore, when using vapor phase polymerization, 40 degreeC or more is preferable, More preferably, it is 50 degreeC or more. The upper limit is preferably 100 ° C. or lower, more preferably 90 ° C. or lower.
The polymerization pressure is preferably 1.0 MPa or more and 5.0 MPa or less. In particular, when bulk polymerization is used, the pressure is preferably 1.5 MPa or more, more preferably 2.0 MPa or more. The upper limit is preferably 4.0 MPa or less, more preferably 3.5 MPa or less.

Furthermore, when using vapor phase polymerization, 1.5 MPa or more is preferable, and 1.7 MPa or more is more preferable. Further, the upper limit is preferably 2.5 MPa or less, and more preferably 2.3 MPa or less.
Furthermore, as a molecular weight regulator and for an activity improving effect, hydrogen is supplementarily in a molar ratio with respect to propylene, preferably in the range of 1.0 × 10 ⁻⁶ or more and 1.0 × 10 ⁻² or less. Can be used.

Also, by changing the amount of hydrogen used, in addition to the average molecular weight of the polymer to be produced, the molecular weight distribution, the deviation of the molecular weight distribution toward the high molecular weight side, very high molecular weight components, branching (amount, length, Distribution) can be controlled, whereby the melt physical properties characterizing polypropylene having a long chain branching structure such as MFR, branching index, strain hardening degree, melt tension MT, and spreadability can be controlled.
Therefore, hydrogen should be used at a molar ratio to propylene of 1.0 × 10 ⁻⁶ or more, preferably 1.0 × 10 ⁻⁵ or more, more preferably 1.0 × 10 ⁻⁴ or more. Is good. Moreover, regarding an upper limit, it is good to use at 1.0 * 10 ^<-2> or less, Preferably it is 0.9 * 10 ^<-2> or less, More preferably, it is 0.8 * 10 ^<-2> or less.

In addition to the propylene monomer, copolymerization using an α-olefin comonomer having 2 to 20 carbon atoms excluding propylene, for example, ethylene and / or 1-butene as a comonomer may be performed depending on the application.
Therefore, in order to obtain a polypropylene resin (B) used in the present invention having a good balance between catalytic activity and melt properties, ethylene and / or 1-butene should be used at 15 mol% or less with respect to propylene. Is more preferable, it is 10 mol% or less, More preferably, it is 7 mol% or less.

  When propylene is polymerized using the catalyst and polymerization method exemplified here, one end of the polymer is mainly propenyl from an active species derived from the catalyst component [G-1] by a special chain transfer reaction generally called β-methyl elimination. The structure is shown and so-called macromers are produced. This macromer can generate a higher molecular weight and is taken into the active species derived from the catalyst component [G-2] having better copolymerizability, and it is considered that the macromer copolymerization proceeds. Therefore, it is considered that the comb chain is the main branch structure of the polypropylene resin having a long chain branch structure to be generated.

[Triaryltriazine compound (C)]
The triaryltriazine compound (C) used in the present invention is an ultraviolet absorber and is at least one compound selected from the group of triaryltriazine compounds represented by the formula (1).

ここで、式（１）中、Ｒ^１はイソオクチル基である。かかる特定構造の紫外線吸収剤は、従来ポリオレフィン系樹脂には使用されていなかったが、本発明ではこれをポリオレフィン系樹脂に含有することにより、ポリオレフィン系樹脂に一般的に使用されているベンゾトリアゾール系やベンゾフェノン系、更には上記式（１）においてＲ^１がノルマルオクチル基であるようなトリアリールトリアジン系の紫外線吸収剤を用いた場合に比べて、高濃度でも格段にブリードアウトを抑制することができる。上記式（１）において、Ｒ^１がノルマルオクチル基では、超長期ではブリードアウトによる白化が生じやすくなるので好ましくなく、イソオクチル基以外のイソアルキル基でも、紫外線吸収性能とブリード性のバランスが得られないので好ましくない。

Here, in Formula (1), R ¹ is an isooctyl group. Such an ultraviolet absorber having a specific structure has not been conventionally used for polyolefin resins, but in the present invention, by containing this in a polyolefin resin, a benzotriazole-based resin generally used for polyolefin resins. Compared with the case of using a triaryltriazine-based UV absorber in which R ¹ is a normal octyl group in the above formula (1) or benzophenone-based, the bleedout can be remarkably suppressed even at a high concentration. it can. In the above formula (1), when R ¹ is a normal octyl group, whitening due to bleed out is likely to occur in the ultra-long term, and an isoalkyl group other than an isooctyl group is not preferable, and a balance between ultraviolet absorption performance and bleed property cannot be obtained. Therefore, it is not preferable.

As the triaryltriazine type ultraviolet absorber represented by the above formula (1), R ¹ may be one type of isooctyl group or a mixture of two or more types of isooctyl groups, but two or more types of isooctyl groups may be used. A mixture of groups is preferred. Examples of the isooctyl group used include 2-octyl group, 2-methyl-1-heptyl group, 3-methyl-1-heptyl group, 4-methyl-1-heptyl group, 5-methyl-1-heptyl group, 6- Methyl-1-heptyl group, 3-octyl group, 2-ethyl-1-hexyl group, 3-ethyl-1-hexyl group, 4-ethyl-1-hexyl group, 4-octyl group, 2-propyl-1- Pentyl group, 2-methyl-3-heptyl group, 2-isopropyl-1-pentyl group, 2-methyl-2-heptyl group, 3-methyl-2-heptyl group, 4-methyl-2-heptyl group, 5- Methyl-2-heptyl group, 6-methyl-2-heptyl group, 2,2-dimethyl-1-hexyl group, 2,3-dimethyl-1-hexyl group, 2,4-dimethyl-1-hexyl group, 2 , 5-Dimethyl-1-hex Group, 3,3-dimethyl-1-hexyl group, 3,4-dimethyl-1-hexyl group, 3,5-dimethyl-1-hexyl group, 4,4-dimethyl-1-hexyl group, 4,5 -Dimethyl-1-hexyl group, 5,5-dimethyl-1-hexyl group, 3-methyl-3-heptyl group, 3-ethyl-2-hexyl group, 4-ethyl-2-hexyl group, 2-methyl- 2-ethyl-1-pentyl group, 2-methyl-3-ethyl-1-pentyl group, 3-methyl-3-ethyl-1-pentyl group, 4-methyl-3-heptyl group, 5-methyl-3- Heptyl group, 6-methyl-3-heptyl group, 2-ethyl-3-methyl-1-pentyl group, 2-ethyl-4-methyl-1-pentyl group, 3-ethyl-4-methyl-1-pentyl group 3-ethyl-3-hexyl group, 4-ethyl-3-hexyl Sil group, 2,2-diethyl-1-butyl group, 4-methyl-4-heptyl group, 3-methyl-4-heptyl group, 2-methyl-4-heptyl group, 2,3-dimethyl-3-hexyl Group, 2,4-dimethyl-3-hexyl group, 2,5-dimethyl-3-hexyl group, 2,3-dimethyl-2-ethyl-1-butyl group, 2-isopropyl-3-methyl-1-butyl Group, 3,3,4-trimethyl-1-pentyl group, 2-methyl-3-heptyl group and the like.
The triaryltriazine-based compound represented by the above formula (1) can be easily synthesized by an ordinary triaryltriazine synthesis method. For example, 2,4,6-trichlorotriazine may be added with 2 moles of xylene and 1 mole of 3-alkoxyphenol in the presence of a Lewis acid catalyst, or 2,6-dimethylbenzamidine hydrohalide 2-Hydroxy-4,6-diaryltriazine was synthesized from formate and halogenated formate, then treated with thionyl chloride to give 2-chloro-4,6-diaryltriazine, then reacted with 3-alkoxyphenol with Lewis acid catalyst May be.
Moreover, a commercially available thing can also be used for the triaryl triazine type compound represented by the said Formula (1).

The triaryltriazine compound used in the present invention includes a triaryltriazine compound that is an alkyl group other than an isooctyl group, an alkenyl group, or an alkynyl group as R ¹ as long as the effects of the present invention are not inhibited. It doesn't matter. The allowable amount of a triaryltriazine compound that is an alkyl group other than an isooctyl group, an alkenyl group, or an alkynyl group as R ¹ varies depending on the type of triaryltriazine compound, but is approximately 30 for all triaryltriazine compounds. Less than mol%.

[Hindered amine light stabilizer (D)]
The light stabilizer used in the present invention is a compound containing a hindered piperidine structure, which is bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl-1- (2-hydroxyethyl) succinate. -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate 2,2,6,6-tetramethyl-4-piperidinylbenzoate, bis- (1,2,6,6-tetramethyl-4-piperidinyl) -2- (3,5-di-t-butyl -4-hydroxybenzyl) -2-n-butylmalonate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 1,1 '-(1,2-ethanediyl) Screw (3,3,5,5-tetramethylpiperazinone), (mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, (Mixed 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, mixed {2,2,6,6-tetramethyl-4- Piperidyl / β, β, β ′, β′-tetramethyl-3-9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butane Tetracarboxylate, mixed {1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3-9- [2,4,8,10-tetra Oxaspiro (5,5) undecane] diethyl -1,2,3,4-butanetetracarboxylate, N, N′-bis (3-aminopropyl) ethylenediamine-2-4-bis [N-butyl-N- (1,2,2,6,6) -Pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and Condensate with 1,2-dibromoethane, [N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-2- (2,2,6,6-tetramethyl-4 -Piperidyl) imino] propionamide, poly {[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [[(2,2 , 6,6-tetramethyl-4-piperidyl) imino] hex Methylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]}, and the like. These light stabilizers may be used alone or as a mixture of two or more.
Specific examples of such hindered amine light stabilizers include trade names of BASF Corporation: Tinuvin 622, Chimassorb 944, Chimassorb 119, Chimassorb 2020, Tinuvin 765, Tinuvin 144, Tinuvin 123, Sanol LS 2626, Uvinul 4049H, Examples include Uvinul 4050H, Uvinul 5050H, Cytex Cyasorb 3346, and Cyasorb UV 500.

[Dialkylhydroxylamine compound (E)]
The dialkylhydroxylamine compound used in the present invention is preferably N, N-dialkylhydroxylamine, and is represented by the general formula R ¹ R ² NOH (wherein R ¹ and R ² each independently represents alkyl). It is the compound shown. In the formula, preferable R ¹ or R ² is preferably a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, or a heptadecyl group. Particularly preferred dialkylhydroxylamines are N, N-dioctadecylhydroxylamine and N, N-dihexadecylhydroxylamine or a mixture thereof. As commercially available products, Irgastab FS042 (manufactured by BASF), Irgastab FS301 (phosphorus antioxidant) For example, a 1: 1 (weight ratio) blend of the agent and FS042, manufactured by BASF).

[Organic peroxide (F)]
In the polyolefin resin composition of this invention, an organic peroxide (E) can be mix | blended as needed. By blending and kneading the organic peroxide (E), the MFR and swell ratio of the polyolefin resin composition of the present invention can be easily controlled within a specific range.
Examples of the organic peroxide (E) include those included in the hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, and ketone peroxide group. Specifically, for example, the hydroperoxide group includes cumene hydroperoxide, tertiary butyl hydroperoxide, etc., and the dialkyl peroxide group includes dicumyl peroxide, ditertiary butyl peroxide, etc. The peroxide group includes lauryl peroxide, benzoyl peroxide and the like. Similarly, the peroxyester group includes tertiary peroxyacetate and tertiary butyl peroxybenzoate, and the ketone peroxide group includes cyclohexanone peroxide. You may use simultaneously 1 type, or several types in the organic peroxide illustrated by these.

[Other ingredients]
In addition to the ultraviolet absorber and the light stabilizer described above, other additional components can be blended in the polyolefin resin composition of the present invention within a range that does not significantly impair the effects of the present invention. Examples of such optional components include antioxidants, crystal nucleating agents, clearing agents, lubricants, antiblocking agents, antistatic agents, antifogging agents, neutralizing agents, and metal inertness used in ordinary polyolefin resin materials. Examples thereof include an agent, a colorant, a dispersant, a peroxide, a filler, and an optical brightener.

(7) Mixing ratio of each component The mixing ratio of each of the above components in the polyolefin resin composition of the present invention is in the following range with respect to 100% by weight of the total amount of (A) to (E).
The content rate of propylene-type resin (A) is 50 to 96.89 weight%, Preferably it is 60 to 90 weight%. If the ratio of (A) is in the above range, it is preferable because weather resistance and extrusion lamination processability are excellent.
The content ratio of the polypropylene resin (B) having a branched structure is 3 to 50% by weight, preferably 5 to 40% by weight. If the ratio of (B) is within the above range, it is preferable because molding processability is excellent.
The content ratio of the triaryltriazine compound (C) is preferably 0.1 to 5% by weight. If the ratio of (C) is within the above range, weather resistance is excellent, which is preferable, and also preferable in terms of hue and economy.
The content ratio of the hindered amine light stabilizer (D) is preferably 0.005 to 1% by weight, more preferably 0.01 to 0.5% with respect to 100% by weight of the components (A) to (E). % By weight. When the content is within the above range, the weather resistance is sufficient, and the blooming phenomenon on the film surface is less likely to occur.
The content ratio of the dialkylhydroxylamine compound is preferably 0.005 to 1% by weight with respect to 100% by weight of the components (A) to (E). When the content is within the above range, the thermal stability at the time of melt processing and the resistance to discoloration at the time of electron beam irradiation are excellent, which is also preferable in terms of economy. A more preferable content is 0.01 to 0.5% by weight.
The blending ratio of the organic peroxide (F) is preferably 0.005 to 0.1 parts by weight, more preferably 0.01 to 0.05 parts by weight with respect to 100 parts by weight as a total of (A) to (E). Part. A ratio of (E) within the above range is preferable because high-speed moldability at the time of extrusion laminating is excellent, and the material strength is improved and neck-in at the time of extrusion laminating is reduced, which is preferable.

(8) Production of polyolefin resin composition The polyolefin resin composition of the present invention comprises the above essential components (A) to (E), a component (F) blended as necessary, and an additional component, and is melted. It is obtained by kneading. For melt kneading, for example, each component in the form of powder, pellets, etc., kneading machines such as uniaxial or biaxial extruders, Banbury mixers, kneader blenders, Brabender plastographs, small batch mixers, continuous mixers, mixing rolls, etc. To do. The kneading temperature is generally 180 to 270 ° C. Moreover, a kneader can also combine 2 or more types of what was mentioned above.
The melt kneading with the addition of the organic peroxide (E) can be performed at the same time when the components (A) to (E) are blended. Furthermore, (C), (D), (E) and additional components can be added after (F) is added to (A) and (B) and melt-kneaded for modification.

(9) Physical properties of polyolefin resin composition The polyolefin resin composition of the present invention obtained as described above has the following physical properties.
The MFR (value measured according to JIS-K6921-2: 1997 appendix (230 ° C., 2.16 kg load)) is 2 to 10 g / 10 minutes, preferably 4 to 10 g / 10 minutes. If the MFR is within the above range, it is preferable from the standpoint that good extrusion laminate processability is obtained and transparency is good. Moreover, it is preferable in terms of easy adjustment of the thickness in the T-die width direction, difficulty in adhering to the pressure-bonding roll during processing, improving workability, and improving material strength.

  Resin materials having high MFR generally have low mechanical strength and tend to be inferior in long-term weather resistance. On the other hand, a resin material having a low MFR is excellent in mechanical strength and long-term weather resistance, but has a poor resin flowability, a low processing speed, and an inferior extrusion laminate processability. On the other hand, the polyolefin resin composition of the present invention is a resin composition having a low MFR and excellent swell ratio and a good neck-in extrusion lamination processability, and this resin composition is high. It is a resin material having a good balance of mechanical strength, long-term weather resistance, and extrusion lamination processability.

(10) Use of polyolefin resin composition The polyolefin resin composition of the present invention is excellent in extrusion laminate processability and blended with a weathering agent that hardly bleeds out, so it has excellent long-term weather resistance and whitening resistance. In addition, it has excellent discoloration resistance and a good surface appearance. Therefore, it is suitable for extrusion into a film or sheet and laminating with another base material to obtain a laminate molded product.

  Any conventionally known method may be employed as a method for extrusion lamination. For example, after the raw material resin is heated, melted and kneaded with an extruder, it is extruded into a film form from a T-die, and the film surface resin is coated on the surface of the base material fed out from the base material raw material, and a rubber roll and a cooling roll And a method of obtaining the three-layer coating sandwiched with the film-like resin by passing the second base material from the cooling roll side, or two units Examples thereof include a tandem method in which both sides are coated by using an extruder at the same time. The substrate to be laminated is not particularly limited, and examples thereof include cellophane, paper, other resin materials, and metals.

  In addition, the polyolefin resin composition of the present invention can further improve weather resistance and discoloration resistance while suppressing bleed-out by combining a specific ultraviolet absorber, light stabilizer and dialkylhydroxylamine compound. Can do. Therefore, it is possible not only to prevent deterioration of the film or sheet itself made of the polyolefin resin composition, but also to effectively prevent deterioration of the laminated substrate due to light transmitted through the film or sheet. Moreover, when a laminated molded product is used as a packaging material, it is possible to effectively prevent degradation of the inclusion. Therefore, the effects of the present invention are particularly exhibited in such applications. In addition, there is an advantage that bleed-out is suppressed and adhesiveness with the base material is not lowered.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In addition, the characteristic evaluation method of the resin composition in an Example and resin used in the Example are as follows.

1. Evaluation method (1) MFR: Measured according to JIS-K6921-2: 1997 appendix (230 ° C., 2.16 kg load).
(2) Extrusion laminating processability (take-off speed, neck-in): Cooling using an extrusion laminating apparatus (extruder 90 mmφ) in which the temperature of the resin extruded from the T-die is 250 ° C. When the roll surface temperature is 25 ° C., the die width is 560 mm, the die lip opening is 0.7 mm, and the take-off processing speed is 80 m / min, the extrusion amount is adjusted so that the coating thickness becomes 80 μm, the extrusion is performed, and the width 500 mm and the thickness 25 μm. Extrusion laminating is performed on a biaxially stretched polypropylene film while the take-up speed is increased from 20 m / min, and the maximum processing speed at which stable coating can be performed is measured. The processing speed is 80 m / min and the coating thickness is 80 μm. The neck-in at the time was measured. As the extrusion laminating property, it is desirable that the maximum take-up speed in this evaluation is 130 m / min or more and the neck-in is 100 mm or less.
(3) Weather resistance 1: A sheet prepared from a polyolefin resin composition as a raw material was irradiated with a sunshine weather meter (black panel temperature in the tank: 63 ° C., JIS-B7753). % Until the cracks occurred. The long-term weather resistance is desirably 4000 hours or longer in this evaluation.
(4) Weather resistance 2: A sheet prepared using a polyolefin resin composition as a raw material was irradiated with a sunshine weather meter in the same manner as in (2), and the UV absorbance of the sheet after 2000 to 5000 hours was measured using a UV spectrophotometer (Shimadzu Corporation) Measured in the range of 500 to 250 nm with a UV1600PC (manufactured by the company), and evaluated with ○ to × according to the following evaluation criteria. As long-term weather resistance, it is desirable that the evaluation is ○ even for 5000 hours.
○: The ratio of the maximum absorbance after irradiation to the maximum absorbance before irradiation is 95% or more. Δ: The ratio of the maximum absorbance after irradiation to the maximum absorbance before irradiation is less than 70 to 95%. X: The maximum absorbance after irradiation. The ratio to the maximum absorbance before irradiation is less than 70%. (5) Transparency: A sheet prepared from a polyolefin resin composition as a raw material is irradiated with a sunshine weather meter in the same manner as in (2), and a sheet after 2000 hours to 5000 hours The haze was measured by a plastic optical property test method (JIS-K7105 haze A method), and evaluated according to the following evaluation criteria: ○ to ×. As long-term weather resistance, it is desirable that it is ◯ even after 5000 hours in this evaluation.
○: Haze change from before irradiation is less than 3% Δ: Haze change from before irradiation is from 3 to less than 5%.
X: Haze change from before irradiation is 5% or more.
(6) Whitening resistance: A sheet prepared using a polyolefin resin composition as a raw material was cut into 10 cm × 10 cm. The cut sheet was folded in two at 0 ° C. atmosphere. The crease was rubbed 10 times on a glass plate with a metal plate weighing 2 kg. After returning the fold to a flat surface, it was observed at a magnification of 20 times using a polarizing microscope, and the state of the fold was judged according to the following criteria for whitening resistance evaluation. The whitening resistance is preferably ◯ in this evaluation.
○: The crease is not whitened
Δ: The crease is slightly whitened
X: The crease is markedly whitened (7) Discoloration resistance: A sheet prepared using a polyolefin resin composition as a raw material is placed in an oven at 40 ° C., and the discoloration state after one month is evaluated according to the following evaluation criteria: Visual evaluation was made with ×. The discoloration resistance is desirably ◯ in this evaluation.
○: No discoloration.
Δ: Slightly discolored.
X: Remarkably discolored.

2. Sample [component (A)]
A-1: Nippon Polypro Co., Ltd., trade name: Novatec EA9H [Propylene homopolymer with Ziegler-Natta catalyst]
MFR = 1.3 (230 ° C., 2.16 kg load, JIS-K6921-2: 1997 appendix), Tm = 165 ° C.
A-2; manufactured by Nippon Polypro Co., Ltd., trade name: Novatec EG7F [propylene-ethylene random copolymer with Ziegler-Natta catalyst]
MFR = 1.4, Tm = 143 ° C
A-3; manufactured by Nippon Polypro Co., Ltd., trade name: Wintech WFX6 [propylene-ethylene random copolymer with metallocene catalyst]
MFR = 2.0, Tm = 125 ° C

[(PE) component]
PE-1; manufactured by Nippon Polyethylene Co., Ltd., trade name: “NOVATEC LD / LC604”
MFR (190 ° C.) = 8 g / 10 min (190 ° C., 2.16 kg load, JIS-K6922-2: 1997 appendix), melting point = 107 ° C.

[Component (C)]
C-1; made by Cytec Co., Ltd., trade name “Siasorb UV-1164G”
49 mol% of the derivative in which R ¹ in the formula (1) is a 3-ethyl-1-hexyl group, 20 mol% of a derivative in which the 4-methyl-1-heptyl group is used, and a 3-ethyl-4-methyl-1-pentyl group The total amount of the derivative composition and isooctyl derivative containing 19 mol% of the derivative and 10 mol% of the derivative which is a 2-ethyl-1-hexyl group is 98 mol%.

[(D) component]
D-1; “Chimassorb2020” manufactured by BASF
D-2: “Chimassorb944” manufactured by BASF
D-3; “Tinuvin 622” manufactured by BASF

[(LS) component]
LS-1; “Uvinul 3034” manufactured by BASF (benzotriazole light stabilizer)
[(E) component]
E-1: “FS301” manufactured by BASF
[(F) component]
F-1; Di-t-butyl peroxide

[Production Example 1 (Production of polypropylene resin B1)]
<Synthesis example 1 of catalyst component (G)>
Synthesis of dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl}] hafnium (component [G-1] (complex 1) ):
(I) Synthesis of 4- (4-i-propylphenyl) indene To a 500 ml glass reaction vessel, 15 g (91 mmol) of 4-i-propylphenylboronic acid and 200 ml of dimethoxyethane (DME) were added, and 90 g of cesium carbonate ( 0.28 mol) and 100 ml of water were added, 13 g (67 mmol) of 4-bromoindene and 5 g (4 mmol) of tetrakistriphenylphosphinopalladium were added in this order, and the mixture was heated at 80 ° C. for 6 hours.
After allowing to cool, the reaction solution was poured into 500 ml of distilled water, transferred to a separatory funnel, and extracted with diisopropyl ether. The ether layer was washed with saturated brine and dried over sodium sulfate. Sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column to obtain 15.4 g (yield 99%) of 4- (4-i-propylphenyl) indene as a colorless liquid.

(Ii) Synthesis of 2-bromo-4- (4-i-propylphenyl) indene In a 500 ml glass reaction vessel, 15.4 g (67 mmol) of 4- (4-i-propylphenyl) indene, 7.2 ml of distilled water DMSO: 200 ml was added, and 17 g (93 mmol) of N-bromosuccinimide was gradually added thereto. The mixture was stirred at room temperature for 2 hours, poured into 500 ml of ice water, and extracted three times with 100 ml of toluene. The toluene layer was washed with saturated brine, 2 g (11 mmol) of p-toluenesulfonic acid was added, and the mixture was heated to reflux for 3 hours while removing moisture. The reaction mixture was allowed to cool, washed with saturated brine, and dried over sodium sulfate. Sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column to obtain 19.8 g (yield 96%) of 2-bromo-4- (4-i-propylphenyl) indene as a yellow liquid. .

(Iii) Synthesis of 2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indene In a 500 ml glass reaction vessel, 6.7 g (82 ml mol) of 2-methylfuran, DME: 100 ml And cooled to -70 ° C in a dry ice-methanol bath. To this, 51 ml (81 mmol) of a 1.59 mol / L n-butyllithium-n-hexane solution was added dropwise and stirred as it was for 3 hours. The solution was cooled to −70 ° C., and a solution of 20 ml (87 mmol) of triisopropyl borate and 50 ml of DME was added dropwise thereto. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
The reaction solution was hydrolyzed with 50 ml of distilled water, and then a solution of 223 g of potassium carbonate and 100 ml of water and 19.8 g (63 mmol) of 2-bromo-4- (4-i-propylphenyl) indene were added in that order at 80 ° C. The mixture was heated and reacted for 3 hours while removing low-boiling components.
After allowing to cool, the reaction solution was poured into 300 ml of distilled water, transferred to a separatory funnel and extracted three times with diisopropyl ether. The ether layer was washed with saturated brine and dried over sodium sulfate. Sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column to obtain 19.6 g of 2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indene as a colorless liquid ( Yield 99%).

(Iv) Synthesis of dimethylbis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) silane In a 500 ml glass reaction vessel, 2- (2-methyl-5- Furyl) -4- (4-i-propylphenyl) indene (9.1 g, 29 mmol) and THF (200 ml) were added, and the mixture was cooled to -70 ° C in a dry ice-methanol bath. To this, 17 ml (28 mmol) of a 1.66 mol / L n-butyllithium-hexane solution was dropped, and the mixture was stirred as it was for 3 hours. The mixture was cooled to −70 ° C., 0.1 ml (2 mmol) of 1-methylimidazole and 1.8 g (14 mmol) of dimethyldichlorosilane were sequentially added, and the mixture was stirred overnight while gradually returning to room temperature.
Distilled water was added to the reaction solution, transferred to a separatory funnel and washed with brine until neutral, and sodium sulfate was added to dry the reaction solution. Sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column, and dimethylbis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) silane was diluted lightly. 8.6 g (88% yield) of a yellow solid was obtained.

(V) Synthesis of dimethylsilylenebis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) hafnium dichloride Into a 500 ml glass reaction vessel, dimethylbis (2- (2 -Methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) silane (8.6 g, 13 mmol) and diethyl ether (300 ml) were added, and the mixture was cooled to -70 ° C in a dry ice-methanol bath. Thereto was added dropwise 15 ml (25 mmol) of a 1.66 mol / L n-butyllithium-n-hexane solution, and the mixture was stirred for 3 hours. The solvent of the reaction solution was distilled off under reduced pressure, 400 ml of toluene and 40 ml of diethyl ether were added, and the solution was cooled to −70 ° C. in a dry ice-methanol bath. Thereto was added 4.0 g (13 mmol) of hafnium tetrachloride. Thereafter, the mixture was stirred overnight while gradually returning to room temperature.
The solvent was distilled off under reduced pressure and recrystallized from dichloromethane-hexane to obtain a racemic dimethylsilylenebis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) hafnium dichloride. As a yellow crystal, 7.6 g (yield 65%) was obtained.

The identified value by ^{1 H-NMR} of the obtained racemates are described below.
¹ H-NMR (C ₆ D ₆ ) identification result:
Racemate: δ 0.95 (s, 6H), δ 1.10 (d, 12H), δ 2.08 (s, 6H), δ 2.67 (m, 2H), δ 5.80 (d, 2H), δ6. 37 (d, 2H), δ 6.74 (dd, 2H), δ 7.07 (d, 2H), δ 7.13 (d, 4H), δ 7.28 (s, 2H), δ 7.30 (d, 2H) ), Δ 7.83 (d, 4H).

<Synthesis example 2 of catalyst component (G)>
rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium (synthesis of component [A-2] (complex 2)):
The synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium is carried out according to the method described in Example 1 of JP-A-11-240909. It carried out like.

<Catalyst synthesis example 1>
(I) Chemical treatment of ion-exchange layered silicate In a separable flask, 96% sulfuric acid (668 g) was added to 2,264 g of distilled water, and then montmorillonite (trade name Benclay SL, manufactured by Mizusawa Chemical Co., Ltd.) as layered silicate 400 g) was added. The slurry was heated at 90 ° C. for 210 minutes. When 4,000 g of distilled water was added to the reaction slurry and filtered, 810 g of a cake-like solid was obtained.
Next, 432 g of lithium sulfate and 1,924 g of distilled water were added to the separable flask to make a lithium sulfate aqueous solution, and the entire amount of the cake-like solid was charged. The slurry was reacted at room temperature for 120 minutes. 4 L of distilled water was added to this slurry, followed by filtration, and further washing with distilled water to pH 5-6, followed by filtration to obtain 760 g of a cake-like solid.
The obtained solid was preliminarily dried overnight at 100 ° C. under a nitrogen stream, and then coarse particles of 53 μm or more were removed, followed by drying under reduced pressure at 200 ° C. for 2 hours to obtain 220 g of chemically treated smectite.
The composition of this chemically treated smectite is Al: 6.45 wt%, Si: 38.30 wt%, Mg: 0.98 wt%, Fe: 1.88 wt%, Li: 0.16 wt%, Al / Si = 0.175 [mol / mol].

(Ii) Catalyst preparation and prepolymerization In a three-necked flask (volume: 1 L), 20 g of the chemically treated smectite obtained above was added, and heptane (132 mL) was added to form a slurry, which was triisobutylaluminum (25 mmol: concentration) 143 mg / mL heptane solution (68.0 mL) was added, and the mixture was stirred for 1 hour, washed with heptane until the residual liquid ratio became 1/100, and heptane was added so that the total volume became 100 mL.
In another flask (volume: 200 mL), complex 1 of the catalyst component [G-1] prepared in Synthesis Example 1 of the catalyst component (G), rac-dichloro [1,1′-dimethylsilylenebis { 2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl}] hafnium (210 μmol) was dissolved in toluene (42 mL) (solution 1), and another flask (volume 200 mL) was added. ), The catalyst component [G-2] complex 2 produced in Synthesis Example 2 of the catalyst component (G), rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4 -Chlorophenyl) -4-hydroazurenyl}] hafnium (90 μmol) was dissolved in toluene (18 mL) (solution 2).

Triisobutylaluminum (0.84 mmol: 1.2 mL of a heptane solution with a concentration of 143 mg / mL) was added to a 1 L flask containing the chemically treated smectite, and then the above solution 1 was added and stirred at room temperature for 20 minutes. Thereafter, triisobutylaluminum (0.36 mmol: 0.50 mL of a heptane solution having a concentration of 143 mg / mL) was added, and then the above solution 2 was added and stirred at room temperature for 1 hour.
Thereafter, 338 mL of heptane was added, and this slurry was introduced into a 1 L autoclave.
After the internal temperature of the autoclave was set to 40 ° C., propylene was fed at a rate of 10 g / hour, and prepolymerization was performed while maintaining the temperature at 40 ° C. for 4 hours. Thereafter, propylene feed was stopped and residual polymerization was carried out for 1 hour. After removing the supernatant of the resulting catalyst slurry by decantation, triisobutylaluminum (6 mmol: 17.0 mL of a heptane solution having a concentration of 143 mg / mL) was added to the remaining portion and stirred for 5 minutes.
This solid was dried under reduced pressure for 1 hour to obtain 52.8 g of a dry prepolymerized catalyst. The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 1.64.
Hereinafter, this is referred to as “preliminary polymerization catalyst 1”.

<Polymerization>
After sufficiently replacing the inside of the stirring autoclave having an internal volume of 200 liters with propylene, 45 kg of sufficiently dehydrated liquefied propylene was introduced. To this was added 4.4 liters of hydrogen (as a standard volume) and 470 ml (0.12 mol) of a triisobutylaluminum / n-heptane solution, and the internal temperature was raised to 70 ° C. Next, 2.4 g of the prepolymerized catalyst 1 (by weight excluding the prepolymerized polymer) was injected with argon to initiate polymerization, and the internal temperature was maintained at 70 ° C. After 2 hours, 100 ml of ethanol was injected, purged of unreacted propylene, and the inside of the autoclave was purged with nitrogen to terminate the polymerization.
The obtained polymer was dried for 1 hour under a nitrogen stream at 90 ° C. to obtain 16.5 kg of a propylene polymer (hereinafter referred to as “B1”).
The catalytic activity was 6880 (g-PP / g-cat). The MFR was 1.0 g / 10 minutes.

[Production of Pellet (B-1) of Polypropylene Resin B1]
Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxy), which is a phenolic antioxidant, with respect to 100 parts by weight of the polypropylene resin (B1) produced in Production Example 1 above. Phenyl) propionate] methane (trade name: IRGANOX 1010, manufactured by BASF Japan Ltd.) 0.125 parts by weight, tris (2,4-di-t-butylphenyl) phosphite (product) Name: IRGAFOS 168, manufactured by BASF Japan Ltd.) 0.125 parts by weight, mixed for 3 minutes at room temperature using a high-speed stirring mixer (Henschel mixer, trade name), then melted in a twin screw extruder By kneading, a pellet (B-1) of polypropylene resin (B) was obtained.
For the twin screw extruder, KZW-25 manufactured by Technobel was used, the screw rotation speed was 400 RPM, and the kneading temperature was 80, 160, 210, 230 from the bottom of the hopper (hereinafter, the same temperature up to the die outlet). did.

Various evaluations described above were performed on this pellet (B-1).
MFR = 1.0 g / 10 min, CXS = 0.1 wt%, mm = 98.4%, Mw / Mn = 4.2, Mz / MW = 3.7, branching index g ′ = 0 when Mabs is 1 million .85, melt tension (MT) = 23.3 g, log (MT) = 1.37, −0.9 × log (MFR) + 0.7 = 0.70.

[Example 1]
Propylene resin (A-1) 69.1% by weight, branched polypropylene resin (B-1) 30% by weight, triaryltriazine compound (C-1) 0.5% by weight, hindered amine light stabilizer (D-1) 0.08 parts by weight of organic peroxide (F-1) per 100 parts by weight of a composition comprising 0.2% by weight of dialkylhydroxylamine compound (E-1) ) Was mixed well with a blender, and then melt extruded and pelletized. The obtained pellet was MFR = 7 g / 10 min. The obtained pellets were melt extruded at a resin temperature of 250 ° C. and a width of 600 mm from a T die attached to an extruder having a diameter of 65 mm, and the maximum take-up speed was evaluated and the take-up speed was 80 m / min and the wall thickness was 80 μm. A sheet for evaluating neck-in was created. The weather resistance 1, weather resistance 2, and transparency were evaluated by the above methods. The evaluation results are shown in Table 1.

[Example 2]
Propylene resin (A-2) 69.1% by weight, branched polypropylene resin (B-1) 30% by weight, triaryltriazine compound (C-1) 0.5% by weight, hindered amine light stabilizer (D-1) 0.08 parts by weight of organic peroxide (F-1) per 100 parts by weight of a composition comprising 0.2% by weight of dialkylhydroxylamine compound (E-1) ) Was mixed well with a blender, and then melt extruded and pelletized. The obtained pellet was MFR = 8 g / 10 min. The obtained pellets were melt extruded at a resin temperature of 250 ° C. and a width of 600 mm from a T die attached to an extruder having a diameter of 65 mm, and the maximum take-up speed was evaluated and the take-up speed was 80 m / min and the wall thickness was 80 μm. A sheet for evaluating neck-in was created. The weather resistance 1, weather resistance 2, and transparency were evaluated by the above methods. The evaluation results are shown in Table 1.

[Example 3]
Propylene resin (A-3) 69.1% by weight, branched polypropylene resin (B-1) 30% by weight, triaryltriazine compound (C-1) 0.5% by weight, hindered amine light stabilizer (D-1) 0.07 parts by weight of organic peroxide (F-1) per 100 parts by weight of the composition comprising 0.2% by weight of dialkylhydroxylamine compound (E-1) ) Was mixed well with a blender, and then melt extruded and pelletized. The obtained pellet was MFR = 8 g / 10 min. The obtained pellets were melt extruded at a resin temperature of 250 ° C. and a width of 600 mm from a T die attached to an extruder having a diameter of 65 mm, and the maximum take-up speed was evaluated and the take-up speed was 80 m / min and the wall thickness was 80 μm. A sheet for evaluating neck-in was created. The weather resistance 1, weather resistance 2, and transparency were evaluated by the above methods. The evaluation results are shown in Table 1.

[Example 4]
Propylene resin (A-2) 69.1% by weight, branched polypropylene resin (B-1) 30% by weight, triaryltriazine compound (C-1) 0.5% by weight, hindered amine light stabilizer (D-2) 0.08 parts by weight of organic peroxide (F-1) with respect to 100 parts by weight of a composition comprising 0.2% by weight and 0.2 parts by weight of dialkylhydroxylamine compound (E-1) ) Was mixed well with a blender, and then melt extruded and pelletized. The obtained pellet was MFR = 8 g / 10 min. The obtained pellets were melt extruded at a resin temperature of 250 ° C. and a width of 600 mm from a T die attached to an extruder having a diameter of 65 mm, and the maximum take-up speed was evaluated and the take-up speed was 80 m / min and the wall thickness was 80 μm. A sheet for evaluating neck-in was created. The weather resistance 1, weather resistance 2, and transparency were evaluated by the above methods. The evaluation results are shown in Table 1.

[Example 5]
Propylene resin (A-2) 69.1% by weight, branched polypropylene resin (B-1) 30% by weight, triaryltriazine compound (C-1) 0.5% by weight, hindered amine light stabilizer (D-3) 0.08 parts by weight of organic peroxide (F-1) with respect to 100 parts by weight of a composition comprising 0.2% by weight and 0.2 parts by weight of dialkylhydroxylamine compound (E-1) ) Were mixed well with a blender, and then melt extruded and pelletized. The obtained pellet was MFR = 8 g / 10 min. The obtained pellets were melt extruded at a resin temperature of 250 ° C. and a width of 600 mm from a T die attached to an extruder having a diameter of 65 mm, and the maximum take-up speed was evaluated and the take-up speed was 80 m / min and the wall thickness was 80 μm. A sheet for evaluating neck-in was created. The weather resistance 1, weather resistance 2, and transparency were evaluated by the above methods. The evaluation results are shown in Table 1.

[Comparative Example 1]
Propylene resin (A-2) 95.3 wt%, polyethylene resin (PE-1) 4 wt%, triaryltriazine compound (C-1) 0.5 wt%, hindered amine light stabilizer (D-1 ) With respect to 100 parts by weight of the composition comprising 0.2% by weight, 0.05 part by weight of the organic peroxide (F-1) was thoroughly mixed with a blender, and then melt-extruded and pelletized. The obtained pellet was MFR = 6 g / 10 min. The obtained pellets were melt extruded at a resin temperature of 250 ° C. and a width of 600 mm from a T die attached to an extruder having a diameter of 65 mm, and the maximum take-up speed was evaluated and the take-up speed was 80 m / min and the wall thickness was 80 μm. A sheet for evaluating neck-in was created. The weather resistance 1, weather resistance 2, and transparency were evaluated by the above methods. The evaluation results are shown in Table 1.

[Comparative Example 2]
Propylene resin (A-2) 69.3% by weight, branched polypropylene resin (B-1) 30% by weight, triaryltriazine compound (C-1) 0.5% by weight, hindered amine light stabilizer (D-1) To 100 parts by weight of a composition composed of 0.2% by weight, 0.08 part by weight of organic peroxide (F-1) was mixed well with a blender, and then melt extruded and pelletized. . The obtained pellet was MFR = 8 g / 10 min. The obtained pellets were melt extruded at a resin temperature of 250 ° C. and a width of 600 mm from a T die attached to an extruder having a diameter of 65 mm, and the maximum take-up speed was evaluated and the take-up speed was 80 m / min and the wall thickness was 80 μm. A sheet for evaluating neck-in was created. The weather resistance 1, weather resistance 2, and transparency were evaluated by the above methods. The evaluation results are shown in Table 1.

[Comparative Example 3]
Propylene resin (A-2) 69.1% by weight, branched polypropylene resin (B-1) 30% by weight, triaryltriazine compound (C-1) 0.5% by weight, benzotriazole-based light stability 0.08 parts by weight of organic peroxide (F--) with respect to 100 parts by weight of the composition comprising 0.2% by weight of agent (LS-1) and 0.2 parts by weight of dialkylhydroxylamine compound (E-1) After mixing well with 1) with a blender, it was melt extruded and pelletized. The obtained pellet was MFR = 8 g / 10 min. The obtained pellets were melt extruded at a resin temperature of 250 ° C. and a width of 600 mm from a T die attached to an extruder having a diameter of 65 mm, and the maximum take-up speed was evaluated and the take-up speed was 80 m / min and the wall thickness was 80 μm. A sheet for evaluating neck-in was created. The weather resistance 1, weather resistance 2, and transparency were evaluated by the above methods. The evaluation results are shown in Table 1.

  As apparent from Table 1, Examples 1 to 5 were excellent in extrusion lamination processability, weather resistance, transparency, whitening resistance and discoloration resistance. On the other hand, when polyethylene is used, the whitening resistance is poor (Comparative Example 1). If a hindered amine light stabilizer is used and a dialkylhydroxylamine compound is not used, discoloration resistance is poor (Comparative Example 2). Moreover, the polyolefin resin composition using a benzotriazole-based light stabilizer was inferior in weather resistance, transparency, and discoloration resistance (Comparative Example 3).

Claims (6)

Contains the following components (A), (B), (C), (D), and (E) and is compliant with JIS K7210 (230 ° C., 2.16 kg load) (hereinafter referred to as “MFR”). 2) to 10 g / 10 minutes, and the components (A), (B), (C), and (A) to (E) with respect to a total amount of 100% by weight. The ratio of (D) and (E) is 50 to 96.89 wt%, 3 to 50 wt%, 0.1 to 5 wt%, 0.005 to 1 wt%, and 0.005 to 1 wt%, respectively. A polyolefin resin composition for extrusion lamination, which is characterized in that it exists.
(A) Propylene resin having MFR of 1 to 50 g / 10 min (B) Polypropylene resin having a branched structure satisfying the following characteristics (i) to (iv) (i) MFR of 0.1 to 30 g / 10 Minute (ii) In the molecular weight distribution by GPC, Mw / Mn is 3.0 to 10.0.
(Iii) The branching index g ′ at an absolute molecular weight Mabs of 1 million is 0.30 or more and less than 1.00 (iv) Melt tension (MT) (unit: g)
log (MT) ≧ −0.9 × log (MFR) +0.7, or MT ≧ 15
Satisfy one of the following.
(C) at least one compound selected from the group of triaryltriazine compounds represented by formula (1)

(Wherein R ¹ is an isooctyl group)
(D) Hindered amine light stabilizer (E) Dialkylhydroxylamine compound The polyolefin resin composition for extrusion lamination according to claim 1, wherein the polypropylene resin (B) having a branched structure satisfies the following property (v).
(V) 25 ° C. paraxylene soluble component amount (CXS) is less than 5.0% by weight based on the total amount of polypropylene resin (B) The polyolefin resin composition for extrusion lamination according to claim 1, wherein the polypropylene resin (B) having a branched structure satisfies the following property (vi).
(Vi) mm fraction of propylene unit 3 chain by ¹³ C-NMR is 95% or more   The polyolefin resin composition for extrusion lamination according to claim 1, wherein the propylene-based resin (A) is a propylene / α-olefin copolymer having a melting point of 110 to 155 ° C.   The polyolefin resin composition for extrusion lamination according to claim 4, wherein the propylene resin (A) is a propylene / ethylene copolymer polymerized using a metallocene catalyst.   Furthermore, 0.005-0.1 part by weight of the organic peroxide (F) is blended with respect to a total of 100 parts by weight of (A) to (E), and melt kneaded. Item 6. The polyolefin resin composition for extrusion lamination according to any one of Items 1 to 5.