JP2021191843A - Polypropylene-based resin composition, laminate and method for producing them - Google Patents

Abstract

To provide a polypropylene-based resin composition which has small neck-in in high-temperature extrusion molding of, for example, 290°C or higher, is excellent in extrusion lamination workability at high molding speed of, for example, 200 m/min or higher, and is excellent in transparency, and a laminate using the polypropylene-based resin composition.SOLUTION: A polypropylene-based resin composition contains 2-30 mass% of a polypropylene resin (X1) having specific characteristics, 5-98 mass% of a polypropylene resin (X2) having specific characteristics, and 0-80 mass% of a polypropylene-based resin (Y) having specific characteristics, wherein the total amount of the polypropylene resin (X1), the polypropylene resin (X2) and the polypropylene-based resin (Y) is 100 mass%.SELECTED DRAWING: None

Description

The present invention relates to polypropylene-based resin compositions and laminates and methods for producing them. Specifically, for example, the neck-in in high-temperature extrusion molding at 290 ° C. or higher is small and the spreadability is high, so that the molding speed is, for example, 200 m / min or more. The present invention relates to a polypropylene-based resin composition having excellent transparency of the contents and a laminate using the polypropylene-based resin composition, for example, because it is excellent in high-speed extrusion laminating processability and excellent transparency.

Conventionally, as food packaging materials, industrial materials, building materials, various resin films, sheets, metal foils, boards, papers, etc. In addition, a laminated body obtained by laminating a polyolefin-based resin by a laminating processing method and imparting water vapor blocking property, waterproof property, rust prevention property, and scratch prevention property has been used. Examples of the laminating method include a dry laminating method in which a polyolefin resin is adhered to a base material via an anchor coating agent, and an extrusion lamination method in which a polyolefin resin is melt-extruded and laminated on a base material. Due to the increasing demand for VOC-free, there is a growing demand for the development of polyolefin resins that can be extruded and laminated.
Polypropylene-based resin is superior in transparency, rigidity, surface glossiness, and heat resistance as compared with polyethylene-based resin. On the other hand, the polypropylene-based resin has a linear molecular structure, and the weight average molecular weight cannot be as large as that of the polyethylene-based resin, so that the melt tension is low. In the extrusion laminating method, which is molded at a relatively high temperature, a resin with a high melt tension has a small neck-in (difference between the die width of the extruder and the width of the extruded film), and draw resonance (drawing) even at a high molding speed. (Instability phenomenon due to thickness unevenness or expansion and contraction of the edge portion) that occurs in the taking direction tends to be less likely to occur, but polypropylene-based resin having a low melt tension has been difficult to use for extrusion laminating.

By blending low-density polyethylene or an amorphous ethylene-α-olefin copolymer with polypropylene, the neck-in is solved, but the transparency and heat resistance are inferior, and the upper limit of the molding speed does not generate draw resonance (upper limit of molding speed). Hereinafter, there is a problem that the improvement of high-speed formability) is not sufficient (see Patent Documents 1 and 2).
As a method for improving high-speed moldability, a method of blending oil, polyethylene wax, etc. with a thermoplastic resin composition in which polypropylene is blended with low-density polyethylene (see Patent Documents 3 to 5), and a metallocene catalyst are used. Disclosed is a method for producing an extruded laminated film using a thermoplastic resin composition in which low-density polyethylene is blended with polypropylene produced in (see Patent Document 6). Although these methods improve high-speed moldability, they do not solve the problem of sacrificing transparency and heat resistance, which are the advantages of polypropylene, because polyethylene is used.

On the other hand, a technique for applying melt tension has been developed by focusing on the molecular structure itself of polypropylene resin. For example, Patent Document 7 discloses a technique for improving the melt tension by introducing a long-chain branch into polypropylene by high-energy ionizing radiation. This method is not preferable in terms of cost because it requires large-scale equipment, and has problems such as yellowing and a decrease in melt tension over time.
Further, Patent Document 8 discloses a method of introducing a long chain branch into a polypropylene resin using an organic peroxide. This method has not only problems such as contamination by decomposition products of organic peroxides, odor, and yellowing, but also problems that a large amount of gel is generated and the appearance is significantly deteriorated when the amount of modification is increased in order to obtain high melt tension. was there.

Further, in recent years, a technique for obtaining a polypropylene resin having a long-chain branched structure showing extremely high melt tension by performing propylene polymerization by single-stage polymerization in the presence of a catalyst containing a plurality of specific metallocene catalyst components has been developed. It is disclosed (see Patent Documents 9 and 10).
However, since the polypropylene resin having such a high melt tension is liable to cause a draw resonance phenomenon, it cannot be said that the high-speed moldability is sufficient.
In order to solve this problem, a technique for improving neck-in and high-speed moldability by blending 50 to 97% by mass of a polypropylene resin having an MFR of 1 to 50 g / 10 minutes into a polypropylene resin having a high melt tension has been developed. It is disclosed (see Patent Document 11). In this method, the high-speed moldability is improved as compared with the case where the polypropylene resin itself having a high melt tension is extruded and laminated, but further improvement is required.

Japanese Unexamined Patent Publication No. 8-259752 Japanese Unexamined Patent Publication No. 2006-56914 Special Fair 5-80492 Gazette Special Table 2003-528948 Gazette International Publication No. 2009/069595 Japanese Unexamined Patent Publication No. 2001-323119 Japanese Unexamined Patent Publication No. 62-121704 Japanese Unexamined Patent Publication No. 6-1577666 Japanese Unexamined Patent Publication No. 2009-57542 Japanese Unexamined Patent Publication No. 2009-275207 Japanese Unexamined Patent Publication No. 2014-55252

The object (problem) of the present invention is, in view of the above-mentioned problems of the prior art, that the neck-in is small in high-temperature extrusion molding of, for example, 290 ° C. or higher, and the extrusion laminating workability at a high speed of, for example, 200 m / min or higher. It is an object of the present invention to provide a polypropylene-based resin composition having excellent transparency and excellent transparency, and a laminate using the polypropylene-based resin composition.

As a result of diligent research to solve the above problems, the present inventors have found that the polypropylene-based resin composition containing a specific polypropylene-based resin maintains a high melt tension, resulting in neck-in in high-temperature extrusion molding. We have found that it is small, has excellent high-speed extrusion laminating workability, and has excellent transparency, and has completed the present invention.

The polypropylene-based resin composition of the present invention comprises a polypropylene resin (X1) having the following properties (X1-1) to (X1-6).
Polypropylene resin (X2) having the following characteristics (X2-1) to (X2-6), and
It is characterized by including.
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 80 g / 10 minutes or less.
(X1-2) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by GPC is 2.0 or more and 5.0 or less, and the Z average molecular weight (Mz). The ratio (Mz / Mw) of the weight average molecular weight (Mw) to the weight average molecular weight (Mw) is 2.0 or more and 5.0 or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 0.5% by mass or more.
(X1-4) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirement (Equation 1).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.0 (Equation 1)
(X1-5) The branch index g'(Mz _abs ) measured by GPC is 0.70 or more and 0.95 or less.
(X1-6) ¹³ The triad fraction (mm) of 3 chains of propylene units by C-NMR is 95% or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 80 g / 10 minutes or less.
(X2-2) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by GPC is 2.0 or more and 5.0 or less, and the Z average molecular weight (Mz). The ratio (Mz / Mw) between the weight average molecular weight (Mw) and the weight average molecular weight (Mw) is 2.0 or more and 5.0 or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 0.5% by mass or more.
(X2-4) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirement (Equation 1).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.0 (Equation 1)
(X2-5) The branch index g'(Mz _abs ) measured by GPC is 0.70 or more and 0.95 or less.
(X2-6) ¹³ The triad fraction (mm) of 3 chains of propylene units by C-NMR is 95% or more.
However, MFR of X1 <MFR of X2, W _1M of _{X1 ≧ W 1M of X2.}

The polypropylene-based resin composition of the present invention may further contain a polypropylene-based resin (Y) having the following characteristics (Y-1) to (Y-2).
(Y-1) MFR (230 ° C., load 2.16 kgf) is 10 g / 10 minutes or more and 50 g / 10 minutes or less.
(Y-2) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirements (formula A).
log (MT170 ° C) <-1.1 x log (MFR) +2.0 (Formula A)

The polypropylene-based resin composition of the present invention comprises 5% by mass to 30% by mass of polypropylene resin (X1), 5% by mass to 50% by mass of polypropylene resin (X2), and 20% by mass to 80% by mass of polypropylene-based resin (Y). , May be included. (However, the total amount of the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene-based resin (Y) is 100% by mass.)

In the polypropylene-based resin composition of the present invention, the polypropylene resin (X1) has the following characteristics (X1-1) and (X1-3).
The polypropylene resin (X2) may have the following characteristics (X2-1) and (X2-3).
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 30 g / 10 minutes or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 2.5% by mass or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 30 g / 10 minutes and 80 g / 10 minutes or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion (W _1M ) of the components having a molecular weight of 1 million or more is 0.5% by mass or more and less than 2.5% by mass.

In the polypropylene-based resin composition of the present invention, the polypropylene resin (X1) has the following characteristics (X1-1) and (X1-3).
The polypropylene resin (X2) may have the following characteristics (X2-1) and (X2-3).
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 10 g / 10 minutes or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 3.5% by mass or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 10 g / 10 minutes and 80 g / 10 minutes or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion (W _1M ) of the components having a molecular weight of 1 million or more is 0.5% by mass or more and less than 3.5% by mass.

The polypropylene-based resin composition of the present invention comprises 2% by mass to 30% by mass of polypropylene resin (X1), 5% by mass to 98% by mass of polypropylene resin (X2), and 0% by mass to 80% by mass of polypropylene-based resin (Y). , May be included. (However, the total amount of the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene-based resin (Y) is 100% by mass.)

The polypropylene-based resin composition of the present invention may be used for extrusion laminating.

The method for producing a polypropylene-based resin composition of the present invention is a step of obtaining a polypropylene resin (X1) having the following characteristics (X1-1) to (X1-6).
A step of obtaining a polypropylene resin (X2) having the following characteristics (X2-1) to (X2-6), and a step of mixing or melt-kneading the polypropylene resin (X1) and the polypropylene resin (X2).
It is characterized by having.
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 80 g / 10 minutes or less.
(X1-2) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by GPC is 2.0 or more and 5.0 or less, and the Z average molecular weight (Mz). The ratio (Mz / Mw) between the weight average molecular weight (Mw) and the weight average molecular weight (Mw) is 2.0 or more and 5.0 or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 0.5% by mass or more.
(X1-4) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirement (Equation 1).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.0 (Equation 1)
(X1-5) The branch index g'(Mz _abs ) measured by GPC is 0.70 or more and 0.95 or less.
(X1-6) ¹³ The triad fraction (mm) of 3 chains of propylene units by C-NMR is 95% or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 80 g / 10 minutes or less.
(X2-2) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by GPC is 2.0 or more and 5.0 or less, and the Z average molecular weight (Mz). The ratio (Mz / Mw) between the weight average molecular weight (Mw) and the weight average molecular weight (Mw) is 2.0 or more and 5.0 or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 0.5% by mass or more.
(X2-4) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirement (Equation 1).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.0 (Equation 1)
(X2-5) The branch index g'(Mz _abs ) measured by GPC is 0.70 or more and 0.95 or less.
(X2-6) ¹³ The triad fraction (mm) of 3 chains of propylene units by C-NMR is 95% or more.
However, MFR of X1 <MFR of X2, W _1M of _{X1 ≧ W 1M of X2.}

The method for producing a polypropylene-based resin composition of the present invention further comprises a step of obtaining a polypropylene-based resin (Y) having the following characteristics (Y-1) to (Y-2).
The step of mixing or melt-kneading may be a step of mixing or melt-kneading the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene-based resin (Y).
(Y-1) MFR (230 ° C., load 2.16 kgf) is 10 g / 10 minutes or more and 50 g / 10 minutes or less.
(Y-2) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirements (formula A).
log (MT170 ° C) <-1.1 x log (MFR) +2.0 (Formula A)

In the method for producing a polypropylene-based resin composition of the present invention, the mixing or melt-kneading step comprises 5% by mass to 30% by mass of the polypropylene resin (X1) and 5% by mass to 50% by mass of the polypropylene resin (X2). 20% by mass to 80% by mass of the polypropylene resin (Y) is mixed or melt-kneaded (however, the total amount of the polypropylene resin (X1), the polypropylene resin (X2) and the polypropylene resin (Y) is 100% by mass. It may be a step.

In the method for producing a polypropylene-based resin composition of the present invention, the polypropylene resin (X1) has the following characteristics (X1-1) and (X1-3).
The polypropylene resin (X2) may have the following characteristics (X2-1) and (X2-3).
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 30 g / 10 minutes or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 2.5% by mass or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 30 g / 10 minutes and 80 g / 10 minutes or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion (W _1M ) of the components having a molecular weight of 1 million or more is 0.5% by mass or more and less than 2.5% by mass.

In the method for producing a polypropylene-based resin composition of the present invention, the polypropylene resin (X1) has the following characteristics (X1-1) and (X1-3).
The polypropylene resin (X2) may have the following characteristics (X2-1) and (X2-3).
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 10 g / 10 minutes or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 3.5% by mass or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 10 g / 10 minutes and 80 g / 10 minutes or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion (W _1M ) of the components having a molecular weight of 1 million or more is 0.5% by mass or more and less than 3.5% by mass.

In the method for producing a polypropylene-based resin composition of the present invention, the mixing or melt-kneading step comprises 2% by mass to 30% by mass of the polypropylene resin (X1) and 5% by mass to 98% by mass of the polypropylene resin (X2). The polypropylene resin (Y) 0% by mass to 80% by mass is mixed or melt-kneaded (however, the total amount of the polypropylene resin (X1), the polypropylene resin (X2) and the polypropylene resin (Y) is 100% by mass. It may be a step.

The method for producing a polypropylene-based resin composition of the present invention may be a method for producing a polypropylene-based resin composition for extrusion laminating.

The laminate of the present invention is a laminate including a base material layer and a polypropylene-based resin composition layer.
The polypropylene-based resin composition layer is a polypropylene resin (X1) having the following characteristics (X1-1) to (X1-6) and a polypropylene resin having the following characteristics (X2-1) to (X2-6). It is characterized by including (X2) and.
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 80 g / 10 minutes or less.
(X1-2) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by GPC is 2.0 or more and 5.0 or less, and the Z average molecular weight (Mz). The ratio (Mz / Mw) between the weight average molecular weight (Mw) and the weight average molecular weight (Mw) is 2.0 or more and 5.0 or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 0.5% by mass or more.
(X1-4) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirement (Equation 1).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.0 (Equation 1)
(X1-5) The branch index g'(Mz _abs ) measured by GPC is 0.70 or more and 0.95 or less.
(X1-6) ¹³ The triad fraction (mm) of 3 chains of propylene units by C-NMR is 95% or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 80 g / 10 minutes or less.
(X2-2) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by GPC is 2.0 or more and 5.0 or less, and the Z average molecular weight (Mz). The ratio (Mz / Mw) between the weight average molecular weight (Mw) and the weight average molecular weight (Mw) is 2.0 or more and 5.0 or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 0.5% by mass or more.
(X2-4) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirement (Equation 1).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.0 (Equation 1)
(X2-5) The branch index g'(Mz _abs ) measured by GPC is 0.70 or more and 0.95 or less.
(X2-6) ¹³ The triad fraction (mm) of 3 chains of propylene units by C-NMR is 95% or more.
However, MFR of X1 <MFR of X2, W _1M of _{X1 ≧ W 1M of X2.}

In the laminate of the present invention, the polypropylene-based resin composition layer may further contain a polypropylene-based resin (Y) having the following characteristics (Y-1) to (Y-2).
(Y-1) MFR (230 ° C., load 2.16 kgf) is 10 g / 10 minutes or more and 50 g / 10 minutes or less.
(Y-2) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirements (formula A).
log (MT170 ° C) <-1.1 x log (MFR) +2.0 (Formula A)

In the laminate of the present invention, the polypropylene-based resin composition layer contains 5% by mass to 30% by mass of the polypropylene resin (X1), 5% by mass to 50% by mass of the polypropylene resin (X2), and the polypropylene-based resin (Y). ) 20% by mass to 80% by mass may be contained. (However, the total amount of the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene-based resin (Y) is 100% by mass.)

In the laminated body of the present invention, the polypropylene resin (X1) has the following characteristics (X1-1) and (X1-3).
The polypropylene resin (X2) may have the following characteristics (X2-1) and (X2-3).
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 30 g / 10 minutes or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 2.5% by mass or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 30 g / 10 minutes and 80 g / 10 minutes or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion (W _1M ) of the components having a molecular weight of 1 million or more is 0.5% by mass or more and less than 2.5% by mass.

In the laminated body of the present invention, the polypropylene resin (X1) has the following characteristics (X1-1) and (X1-3).
The polypropylene resin (X2) may have the following characteristics (X2-1) and (X2-3).
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 10 g / 10 minutes or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 3.5% by mass or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 10 g / 10 minutes and 80 g / 10 minutes or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion (W _1M ) of the components having a molecular weight of 1 million or more is 0.5% by mass or more and less than 3.5% by mass.

In the laminate of the present invention, the polypropylene-based resin composition layer contains 2% by mass to 30% by mass of the polypropylene resin (X1), 5% by mass to 98% by mass of the polypropylene resin (X2), and the polypropylene-based resin (Y). ) 0% by mass to 80% by mass may be contained. (However, the total amount of the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene-based resin (Y) is 100% by mass.)

The method for producing a laminate of the present invention is a method for producing a laminate including a base material layer and a polypropylene-based resin composition layer.
A polypropylene resin (X1) having the following characteristics (X1-1) to (X1-6) and a polypropylene resin having the following characteristics (X2-1) to (X2-6) on at least one surface of the base material layer (X2-1) to (X2-6). It is characterized by having a step of forming the polypropylene-based resin composition layer by extruding and laminating a mixture of X2) and a melt-kneaded product.
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 80 g / 10 minutes or less.
(X1-2) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by GPC is 2.0 or more and 5.0 or less, and the Z average molecular weight (Mz). The ratio (Mz / Mw) between the weight average molecular weight (Mw) and the weight average molecular weight (Mw) is 2.0 or more and 5.0 or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 0.5% by mass or more.
(X1-4) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirement (Equation 1).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.0 (Equation 1)
(X1-5) The branch index g'(Mz _abs ) measured by GPC is 0.70 or more and 0.95 or less.
(X1-6) ¹³ The triad fraction (mm) of 3 chains of propylene units by C-NMR is 95% or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 80 g / 10 minutes or less.
(X2-2) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by GPC is 2.0 or more and 5.0 or less, and the Z average molecular weight (Mz). The ratio (Mz / Mw) between the weight average molecular weight (Mw) and the weight average molecular weight (Mw) is 2.0 or more and 5.0 or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 0.5% by mass or more.
(X2-4) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirement (Equation 1).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.0 (Equation 1)
(X2-5) The branch index g'(Mz _abs ) measured by GPC is 0.70 or more and 0.95 or less.
(X2-6) ¹³ The triad fraction (mm) of 3 chains of propylene units by C-NMR is 95% or more.
However, MFR of X1 <MFR of X2, W _1M of _{X1 ≧ W 1M of X2.}

In the method for producing a laminate of the present invention, the step of forming the polypropylene-based resin composition layer includes the polypropylene resin (X1), the polypropylene resin (X2), and the following on at least one surface of the base material layer. Even in the step of forming the polypropylene-based resin composition layer by extrusion-laminating a mixture or melt-kneaded product of the polypropylene-based resin (Y) having the characteristics (Y-1) to (Y-2) of. good.
(Y-1) MFR (230 ° C., load 2.16 kgf) is 10 g / 10 minutes or more and 50 g / 10 minutes or less.
(Y-2) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirements (formula A).
log (MT170 ° C) <-1.1 x log (MFR) +2.0 (Formula A)

In the method for producing a laminate of the present invention, the steps for forming the polypropylene-based resin composition layer are 5% by mass to 30% by mass of the polypropylene resin (X1) and 5% by mass to 50% by mass of the polypropylene resin (X2). %, A mixture of 20% by mass to 80% by mass of the polypropylene-based resin (Y), or a melt-kneaded product (however, the total amount of the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene-based resin (Y)). Is 100% by mass.) May be a step of forming the polypropylene-based resin composition layer by extrusion laminating.

In the method for producing a laminate of the present invention, the polypropylene resin (X1) has the following characteristics (X1-1) and (X1-3).
The polypropylene resin (X2) may have the following characteristics (X2-1) and (X2-3).
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 30 g / 10 minutes or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 2.5% by mass or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 30 g / 10 minutes and 80 g / 10 minutes or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion (W _1M ) of the components having a molecular weight of 1 million or more is 0.5% by mass or more and less than 2.5% by mass.

In the method for producing a laminate of the present invention, the polypropylene resin (X1) has the following characteristics (X1-1) and (X1-3).
The polypropylene resin (X2) may have the following characteristics (X2-1) and (X2-3).
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 10 g / 10 minutes or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 3.5% by mass or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 10 g / 10 minutes and 80 g / 10 minutes or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion (W _1M ) of the components having a molecular weight of 1 million or more is 0.5% by mass or more and less than 3.5% by mass.

In the method for producing a laminate of the present invention, the steps for forming the polypropylene-based resin composition layer are 2% by mass to 30% by mass of the polypropylene resin (X1) and 5% by mass to 98% by mass of the polypropylene resin (X2). %, And 0% by mass to 80% by mass of the polypropylene-based resin (Y), or a melt-kneaded product (however, the total amount of the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene-based resin (Y)). Is 100% by mass.) May be a step of forming the polypropylene-based resin composition layer by extrusion laminating.

The polypropylene-based resin composition of the present invention has a small neck-in in high-temperature extrusion molding at, for example, 290 ° C. or higher, and is excellent in extrusion-lamination processability at a high-speed molding speed of, for example, 200 m / min or higher. The laminate obtained by using the polypropylene-based resin composition is excellent in transparency.

Hereinafter, embodiments of the present invention will be described in detail for each item. In addition, in this specification, "~" indicating a numerical range is used in the meaning of including the numerical values described before and after it as a lower limit value and an upper limit value. The description of the constituent elements described below is an example of the embodiment of the present invention, and the present invention is not limited to these contents.

1. 1. Polypropylene resin composition The polypropylene resin composition of the present invention comprises a polypropylene resin (X1) having the following characteristics (X1-1) to (X1-6).
Polypropylene resin (X2) having the following characteristics (X2-1) to (X2-6), and
It is characterized by including.
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 80 g / 10 minutes or less.
(X1-2) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by GPC is 2.0 or more and 5.0 or less, and the Z average molecular weight (Mz). The ratio (Mz / Mw) between the weight average molecular weight (Mw) and the weight average molecular weight (Mw) is 2.0 or more and 5.0 or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 0.5% by mass or more.
(X1-4) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirement (Equation 1).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.0 (Equation 1)
(X1-5) The branch index g'(Mz _abs ) measured by GPC is 0.70 or more and 0.95 or less.
(X1-6) ¹³ The triad fraction (mm) of 3 chains of propylene units by C-NMR is 95% or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 80 g / 10 minutes or less.
(X2-2) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by GPC is 2.0 or more and 5.0 or less, and the Z average molecular weight (Mz). The ratio (Mz / Mw) between the weight average molecular weight (Mw) and the weight average molecular weight (Mw) is 2.0 or more and 5.0 or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 0.5% by mass or more.
(X2-4) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirement (Equation 1).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.0 (Equation 1)
(X2-5) The branch index g'(Mz _abs ) measured by GPC is 0.70 or more and 0.95 or less.
(X2-6) ¹³ The triad fraction (mm) of 3 chains of propylene units by C-NMR is 95% or more.
However, MFR of X1 <MFR of X2, W _1M of _{X1 ≧ W 1M of X2.}
The difference between the MFR of X2 and the MFR of X1 may be adjusted as appropriate, but from the viewpoint of easily obtaining the effect of the present invention, it may be 9.5 g / 10 minutes or more, and may be 12 g / 10 minutes or more. , 20 g / 10 minutes or more, 29.5 g / 10 minutes or more, while 60 g / 10 minutes or less.

The polypropylene-based resin composition of the present invention may further contain a polypropylene-based resin (Y) having the following characteristics (Y-1) to (Y-2).
(Y-1) MFR (230 ° C., load 2.16 kgf) is 10 g / 10 minutes or more and 50 g / 10 minutes or less.
(Y-2) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirements (formula A).
log (MT170 ° C) <-1.1 x log (MFR) +2.0 (Formula A)

Both the polypropylene resin (X1) and the polypropylene resin (X2) having the above-mentioned characteristics are long-chain branched polypropylene resins having high stereoregularity and containing a specific amount of high-molecular-weight components, and satisfy the above formula (1). Has sufficient melt tension from. In such a polypropylene resin having sufficient melt tension, a polypropylene resin (X1) having a relatively large amount of high molecular weight components and low fluidity within a specific range and a polypropylene resin having a relatively small amount of high molecular weight components and high fluidity. By mixing (X2), the polypropylene-based resin composition of the present invention can impart fluidity while maintaining a high melt tension, so that neck-in in high-temperature extrusion molding tends to be small, and the neck-in in high-temperature extrusion molding tends to be small, and the speed is high. It is easy to have excellent extruded laminating processability, and it is easy to have excellent transparency. A polypropylene resin (X2) having a relatively small amount of high molecular weight component and high fluidity can be a fluidity-imparting component.
The fluidity-imparting component does not have to be a long-chain branched polypropylene resin containing a specific amount of high molecular weight component. By further combining and mixing the polypropylene resin (Y) as a fluidity-imparting component, high-speed moldability tends to be improved.

1-1. Polypropylene resin (X1)
The polypropylene resin (X1) has each property of (X1-1) to (X1-6).

1-1-1. Characteristics (X1-1): MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 80 g / 10 minutes or less. However, the MFR of the polypropylene resin (X1) is less than the MFR of the polypropylene resin (X2).
As for the characteristic (X1-1), as a preferred embodiment, the MFR (230 ° C., load 2.16 kgf) may be larger than 0.5 g / 10 min and 30 g / 10 min or less, and as a further preferred embodiment, the MFR ( 230 ° C., load 2.16 kgf) may be more than 0.5 g / 10 minutes and 10 g / 10 minutes or less.
MFR is an index showing melt fluidity, and this value decreases as the molecular weight of the polymer increases. On the other hand, as the molecular weight decreases, this value increases.
The MFR of X1 is larger than 0.5 g / 10 minutes, preferably 1 g / 10 minutes or more, and 2 g / 10 minutes from the viewpoint that the melt fluidity becomes good and the load of the extruder is easily suppressed with respect to extrusion molding. Above, more preferably 3 g / 10 minutes or more. The MFR may be greater than 8 g / 10.
On the other hand, the MFR of X1 may be 30 g / 10 minutes or less, preferably 25 g / 10 minutes or less, more preferably 25 g / 10 minutes or less, from the viewpoint that the melt tension becomes good and the moldability such as extrusion laminate moldability becomes good. It is 20 g / 10 minutes or less, more preferably 10 g / 10 minutes or less, still more preferably 9.5 g / 10 minutes or less, and particularly preferably 9 g / 10 minutes or less.
In the present invention, the melt flow rate (MFR) is based on JIS K7210 "Test method for melt mass flow rate (MFR) and melt volume flow rate (MVR) of plastic-thermoplastic plastic", and the test condition is 230 ° C. , It is a value measured with a load of 2.16 kgf.
The melt flow rate (MFR) can be easily adjusted by changing the temperature and pressure of the polymerization, or by a general method of adding a chain transfer agent such as hydrogen at the time of polymerization.

1-1-2. Characteristic (X1-2): The ratio (Mw / Mn) of the weight average molecular weight (Mw) obtained by GPC to the number average molecular weight (Mn) is 2.0 or more and 5.0 or less, and the Z average molecular weight (Z average molecular weight). The ratio (Mz / Mw) of Mw) to the weight average molecular weight (Mw) is 2.0 or more and 5.0 or less.

Mw / Mn is an index showing the spread of the molecular weight distribution, and the larger this value is, the wider the molecular weight distribution is. If Mw / Mn is too small, the low molecular weight component may decrease and the melt fluidity may deteriorate. Therefore, Mw / Mn is 2.0 or more, preferably 2.1 or more, and more preferably 2.2 or more. On the other hand, if Mw / Mn is too large, the amount of the high molecular weight component may increase relatively and the melt fluidity may deteriorate. Therefore, Mw / Mn is 5.0 or less, preferably 4.9 or less. Mw / Mn may be 4.6 or less, or 4.2 or less.
Similarly, Mz / Mw is an index showing the spread of the molecular weight distribution, and is an index showing the spread on the high molecular weight side as compared with Mw / Mn. The larger these values are, the wider the molecular weight distribution is toward the high molecular weight side. If Mz / Mw is too small, the high molecular weight component may decrease and the melt tension may decrease. Therefore, Mz / Mw is 2.0 or more, preferably 2.1 or more, and more preferably 2.2 or more. On the other hand, if Mz / Mw is too large, the amount of the high molecular weight component may increase relatively and the melt fluidity may deteriorate. Therefore, Mz / Mw is 5.0 or less, preferably 4.0 or less, and more preferably 3.6 or less. Mz / Mw may be 3.5 or less.
The average molecular weight and molecular weight distribution (Mz, Mw, Mn, Mw / Mn, Mz / Mw) measured by GPC of polypropylene resin (X1) can be changed by changing the temperature and pressure conditions of propylene polymerization, or by the most common method. It can be easily adjusted by a method of adding a chain transfer agent such as hydrogen at the time of propylene polymerization. Further, the type of metallocene complex to be used, and when two or more types of complexes are used, control can be performed by changing the amount ratio.
The polypropylene resin (X1) of the present invention preferably has Mw of 200,000 or more and 500,000 or less from the viewpoint of the balance between melt fluidity and melt tension. From the viewpoint of melt tension, Mw is preferably 230,000 or more, more preferably 250,000 or more, and from the viewpoint of melt fluidity, it is preferably 450,000 or less, further preferably 40 or less.

1-1-3. Characteristic (X1-3): In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 0.5% by mass or more. Provided that _{W 1M} of _{W 1M} ≧ polypropylene resin polypropylene resin (X1) (X2). As a preferred embodiment, the characteristic (X1-3) may have a proportion of components having a molecular weight of 1 million or more (W _1M ) of 2.5% by mass or more in the integrated molecular weight distribution curve obtained by GPC, which is more preferable. As an embodiment, it may be 3.5% by mass or more.

As described above, when the amount of the high molecular weight component is small, the melt tension becomes small. Therefore, W _1M of X1 is 0.5% by mass or more, may be 2.5% by mass or more, preferably 3.0% by mass or more, more preferably 3.5% by mass or more, and particularly. It is preferably 4.0% by mass or more. The upper limit of W _1M of X1 is not particularly limited, but may be 10.0% by mass or less from the viewpoint of melt fluidity.
In the present invention, W _1M sets the integral value up to 1 million (log (M) = 6.0) in the integrated molecular weight distribution curve (normalized to 1 for the total amount) obtained by GPC. It is defined as a value obtained by multiplying the value subtracted from the value by 100.
W _1M is, for example, in a method using a catalyst containing a plurality of metallocene complexes, as one of the metallocene complexes to be used, one that can produce a high molecular weight polymer is selected, and then the other metallocene that produces a low molecular weight side. It can be easily adjusted by controlling the amount ratio to the complex, the amount of hydrogen added at the time of polymerization, and the polymerization temperature.

The values of Mz, Mw, Mn, Mw / Mn, Mz / Mw, and W _1M defined above are all obtained by gel permeation chromatography (GPC), and the measuring method and measuring instrument thereof. The details of are as follows.
Equipment: Waters GPC (ALC / GPC, 150C)
Detector: FOXBORO MIRAN, 1A, IR detector (measurement wavelength: 3.42 μm)
Column: Showa Denko AD806M / S (3)
Mobile phase solvent: o-dichlorobenzene (ODCB)
Measurement temperature: 140 ° C
Flow rate: 1.0 mL / min Injection volume: 0.2 mL
The sample is prepared by preparing a 1 mg / mL solution using the sample and ODCB (containing 0.5 mg / mL dibutylhydroxytoluene (BHT)) and dissolving it at 140 ° C. for about 1 hour. ..
Further, the conversion from the holding capacity obtained by GPC measurement to the molecular weight is performed using a calibration curve using standard polystyrene prepared in advance. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
Brands: F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve is created by injecting 0.2 mL of 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 approximating with the least squares method.
Viscosity formula used for conversion to molecular weight: [η] = K × M ^α uses the following numerical values.
PS: K = 1.38 × 10 ^-4 , α = 0.7
PP: K = 1.03 × 10 ^-4 , α = 0.78

1-1-4. Characteristics (X1-4): The melt tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirements (Equation 1).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.0 (Equation 1)

Here, at MT170 ° C., using Capillograph 1B manufactured by Toyo Seiki Seisakusho Co., Ltd., capillary: diameter 2.0 mm, length 40 mm, cylinder diameter: 9.55 mm, cylinder extrusion speed: 20 mm / min, take-up speed: 4. It represents the melt tension when measured under the conditions of 0 m / min and temperature: 170 ° C., and the unit is grams. Note that MT230 ° C., which is shown in Examples described later, represents the melting tension when measured under the condition of temperature: 230 ° C. under the above-mentioned measurement conditions. However, if the MT of the sample is extremely high, the resin may break at a pick-up speed of 4.0 m / min. In such a case, the pick-up speed is reduced to the maximum speed at which the sample can be picked up. Let the tension be MT. The measurement conditions and units of MFR are as described above.
This regulation is an index for polypropylene resin (X1) to have sufficient melt tension, and since MT generally has a correlation with MFR, it is described by a relational expression with MFR.
If the polypropylene resin (X1) satisfies the above (Equation 1), not only the effect of reducing neck-in can be obtained, but also the stress propagates uniformly to the molten film, so that the film thickness is not good, which is called a resonance phenomenon. The uniform phenomenon and the unstable phenomenon due to the expansion and contraction of the edge portion are suppressed.
Further, it is more preferable to satisfy the following (Equation 2), and further preferably to satisfy (Equation 3).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.3 (Equation 2)
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.5 (Equation 3)

It is not necessary to set the upper limit value of MT in particular, but when MT exceeds 50 g, the taking-up speed becomes remarkably slow in the above measurement method, and measurement becomes difficult. In such a case, it is considered that the ductility of the resin is also lowered, so that it is preferably 45 g or less, 40 g or less, more preferably 35 g or less, and further preferably 30 g or less.
In order to satisfy the above condition (Equation 1), for example, the amount of long-chain branching of the polypropylene resin (X1) may be increased to increase the melt tension. This is possible by controlling the quantity ratio and the prepolymerization conditions to introduce many long-chain branches.

1-1-5. Characteristic (X1-5): The branch index g'(Mz _abs ) measured by GPC is 0.70 or more and 0.95 or less.

As a direct index that the polypropylene resin (X1) has a branch, the branch 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. , If a long-chain branched structure is present, it takes a value less than 1. That is, polypropylene with g'<1 means "long-chain branched polypropylene".
Definitions are described, for example, in "Developments in Polymer Charactization-4" (JV Dawkins ed. Applied Science Publics, 1983) and are known to those of skill in the art.

g'can be obtained as a function of absolute molecular weight Mabs, for example, by using a GPC equipped with a light scatterometer and a viscometer as described below in the detector.
The polypropylene resin (X1) used in the present invention has a g'(Mz _{abs ) at a Z average molecular weight Mz abs} of absolute molecular weight Mabs determined by light scattering, preferably 0.72 or more, more preferably 0.75 or more. It is more preferably 0.80 or more, preferably 0.90 or less, more preferably 0.89 or less, still more preferably 0.88 or less.

Further, since the degree of decrease in the melt tension when kneading at a high temperature of 290 ° C. or higher or when kneading is repeated is small, the extruded laminate formability is deteriorated (increased neck-in and resonance phenomenon occurs at low speed take-up). A branched polymer having a comb-shaped chain structure is preferable because it is difficult to use.
The specific method for calculating g'is as follows.
An Alliance GPCV2000 manufactured by Waters is used as a GPC apparatus equipped with a differential refractometer (RI) and a viscosity detector (Viscometer). As the light scattering detector, a multi-angle laser light scattering detector (MALLS) DAWN-E manufactured by Waitt Technology is used. The detectors are connected in the order of MALLS, RI, and Viscometer. The mobile phase solvent is 1,2,4-trichlorobenzene (addition of the antioxidant Irganox 1076 manufactured by BASF Japan, Inc. at a concentration of 0.5 mg / mL).
The flow rate is 1 mL / min, and the column is used by connecting two GMHHR-H (S) HTs manufactured by Tosoh Corporation. The temperature of the column, the sample injection part and each detector is 140 ° C. The sample concentration is 1 mg / mL, and the injection amount (sample loop volume) is 0.2175 mL.
The data processing software ASTRA (version 4.73.04) attached to MALLS is used to calculate the absolute molecular weight (Mabs) obtained from MALLS, the root mean square radius (Rg), and the limit viscosity ([η]) obtained from Viscometer. Then, calculate with reference to the following documents.
References:
1. 1. "Developments in Polymer Charactization-4" (JV Dawkins ed. Applied Science Publishers, 1983. Chapter 1.)
2. 2. Polymer, 45, 6495-6505 (2004)
3. 3. Macromolecules, 33, 2424-2436 (2000)
4. Macromolecules, 33, 6945-6952 (2000)

[Calculation of branch index (g')]
The branching index (g') is the ratio of the extreme viscosity ([η] br) obtained by measuring the sample with the above Viscometer to the extreme viscosity ([η] lin) obtained by separately measuring the linear polymer. It is calculated as ([η] br / [η] lin).
When a long-chain branched structure is introduced into a polymer molecule, the radius of inertia becomes smaller as compared with a linear polymer molecule having the same molecular weight. As the radius of inertia decreases, the limit viscosity decreases. Therefore, as the long-chain branched structure is introduced, the limit viscosity of the branched polymer ([η] lin) with respect to the limit viscosity ([η] lin) of the linear polymer having the same molecular weight. The ratio of br) ([η] br / [η] lin) becomes smaller.
Therefore, when the branching index (g'= [η] br / [η] lin) is smaller than 1, it means that it has a long-chain branching structure.
Here, as the linear polymer for obtaining [η] lin, commercially available homopolypropylene (Novatec PP (registered trademark) grade name: FY6 manufactured by Japan Polypropylene Corporation) is used. Since it is known as the Mark-Howwink-Sakurada equation that the logarithm of [η] lin of a linear polymer has a linear relationship with the logarithm of molecular weight, [η] lin is appropriately used on the low molecular weight side and the high molecular weight side. It can be extrapolated to get a numerical value.

The branching index g'to be 0.70 or more and 0.95 or less is achieved by introducing a large number of long-chain branches, for example, selection of a preferable metallocene catalyst, a combination thereof, and an amount ratio thereof, and prepolymerization. This is possible by controlling the conditions and polymerizing.

1-1-6. (X1-6): The triad fraction (hereinafter, may be referred to as mm fraction ^{) of the propylene unit 3 chain by 13 C-NMR is 95% or more.}

The polypropylene resin (X1) used in the present invention preferably has high stereoregularity. Stereoregularity of the ^height, can be evaluated by 13 ^C-NMR, propylene unit triad sequence of mm fraction is good to have a 95% stereoregularity obtained by 13 C-NMR.
The mm fraction is the ratio of 3 chains of propylene units in which the direction of the methyl branch in each propylene unit is the same in any 3 chains of propylene units consisting of a head-tail bond in the polymer chain, so the upper limit is 100%. Is. This mm fraction is a value indicating that the three-dimensional structure of the methyl group in the polypropylene molecular chain is isotropically controlled, and the higher the value, the higher the control. When the mm fraction is smaller than this value, the elastic modulus of the product is lowered, and the surface scratch resistance imparting effect of the polypropylene-based resin composition layer of the laminate tends to be inferior.
Therefore, the mm fraction is 95% or more, more preferably 96% or more, and further preferably 97% or more.

The details of the method for measuring the mm fraction of 3 chains of propylene units by ^{13 C-NMR are as follows.}
After 375 mg of the sample is completely dissolved in 2.5 ml of deuterated 1,1,2,2-tetrachloroethane in an NMR sample tube (10φ), the measurement is carried out at 125 ° C. by the 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. Chemical shifts of other carbon peaks are based on this.
・ Flip angle: 90 degrees ・ Pulse interval: 10 seconds ・ Resonance frequency: 100 MHz or more ・ Number of integrations: 10,000 times or more ・ Observation range: -20 ppm to 179 ppm
-Number of data points: 32768

Mm fraction of propylene unit triad sequences is the integrated intensity of the measured 13C signal by ^{13 C-NMR} measurement is obtained by substituting the following equation.
mm (%) = Imm × 100 / (Imm + 3 × Imrmrm)
Here, it is the amount shown by Imm = I _{23.6 to 21.1} and Imrm = I _{19.8 to 19.7.}
^{The 13} C-NMR measurement method for obtaining the mm fraction of 3 chains of propylene units can be carried out by the same method as the above measurement.
Spectrum attribution can be made with reference to Polymer Journal, Vol. 16, pp. 717 (1984), Asakura Shoten, Macromolecules, 8 卷, pp. 687 (1975), and Polymer, Vol. 30, pp. 1350 (1989). can.

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

1-1-7. Method for Producing Polypropylene Resin (X1) The polypropylene resin (X1) is not particularly limited as long as it satisfies the above-mentioned characteristics (X1-1) to (X1-6), but as described above, it is not particularly limited. A preferred production method for satisfying conditions such as high stereoregularity, relatively wide molecular weight distribution, branch index g'(Mz _abs ) range, and high melt tension is a macromer copolymerization method using a combination of metallocene catalysts. This is the method used. Examples of such a method include the methods disclosed in JP-A-2009-57542. This method is a method for producing polypropylene having a long-chain branched structure by using a catalyst in which a catalyst component having a specific structure having a macromer-forming ability and a catalyst component having a specific structure having a 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 modifier, are used for the purpose. It is possible to produce a polypropylene resin having a long-chain branched structure having physical properties.

The polypropylene resin (X1) according to the present invention is an α-olefin comonomer having 2 to 20 carbon atoms excluding the propylene monomer and propylene, for example, ethylene, even if it is a propylene homopolymer obtained by homopolymerizing a propylene monomer. And / or a propylene / α-olefin copolymer obtained by copolymerizing with 1-butene may be used.
The shape of the polypropylene resin (X1) is not particularly limited, and may be in the form of powder or particles which are granulated products thereof.

The polypropylene resin (X1) according to the present invention is obtained by mixing other additional components described later as necessary with a Henshell mixer, V blender, ribbon blender, tumbler blender or the like, and if necessary, a single shaft. The granulated product may be kneaded by a kneader such as an extruder, a multi-screw extruder, a kneader, or a Bambari mixer.

1-2. Polypropylene resin (X2)
The polypropylene resin (X2) has the properties (X2-1) to (X2-6).

1-2-1. Characteristics (X2-1): MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 80 g / 10 minutes or less. However, the MFR of the polypropylene resin (X1) is less than the MFR of the polypropylene resin (X2). As for the characteristic (X2-1), as a preferred embodiment, the MFR (230 ° C., load 2.16 kgf) may be more than 10 g / 10 minutes and 80 g / 10 minutes or less, and as a further preferred embodiment, the MFR (230 ° C., The load 2.16 kgf) may exceed 30 g / 10 minutes and may be 80 g / 10 minutes or less.
MFR is an index showing melt fluidity, and this value decreases as the molecular weight of the polymer increases. On the other hand, as the molecular weight decreases, this value increases.
The MFR of X2 is more than 0.5 g / 10 minutes, preferably larger than 10 g / 10 minutes, more preferably, from the viewpoint that the melt fluidity becomes good and the load of the extruder is easily suppressed with respect to extrusion molding. Greater than 15 g / 10 min, more preferably greater than 30 g / 10 min, and particularly preferably greater than 40 g / 10 min.
On the other hand, the MFR of X2 is 80 g / 10 minutes or less, preferably 70 g / 10 minutes or less, and more preferably 65 g / 10 minutes, from the viewpoint that the melt tension becomes good and the moldability such as extrusion laminating formability becomes good. It is as follows.
In the present invention, the melt flow rate (MFR) was measured by the same method as that used for the polypropylene resin (X1). The melt flow rate (MFR) can be easily adjusted by changing the temperature and pressure of the polymerization, or by a general method of adding a chain transfer agent such as hydrogen at the time of polymerization.

1-2-2. Characteristic (X2-2): The ratio (Mw / Mn) of the weight average molecular weight (Mw) obtained by GPC to the number average molecular weight (Mn) is 2.0 or more and 5.0 or less, and the Z average molecular weight (Z average molecular weight). The ratio (Mz / Mw) of Mw) to the weight average molecular weight (Mw) is 2.0 or more and 5.0 or less.

Mw / Mn is an index showing the spread of the molecular weight distribution, and the larger this value is, the wider the molecular weight distribution is. If Mw / Mn is too small, the low molecular weight component is reduced and the melt fluidity is deteriorated. Therefore, Mw / Mn is 2.0 or more, preferably 2.1 or more, and more preferably 2.2 or more. On the other hand, if Mw / Mn is too large, the amount of the high molecular weight component is relatively increased, and the melt fluidity is deteriorated. Therefore, Mw / Mn is 5.0 or less, preferably 4.6 or less, and more preferably 4.2 or less.
Similarly, Mz / Mw is an index showing the spread of the molecular weight distribution, and is an index showing the spread on the high molecular weight side as compared with Mw / Mn. The larger these values are, the wider the molecular weight distribution is toward the high molecular weight side. If Mz / Mw is too small, the high molecular weight component is reduced and the melt tension is reduced. Therefore, Mz / Mw is 2.0 or more, preferably 2.1 or more, and more preferably 2.2 or more. On the other hand, if Mz / Mw is too large, the amount of the high molecular weight component is relatively increased, and the melt fluidity is deteriorated. Therefore, Mz / Mw is 5.0 or less, preferably 4.3 or less, and more preferably 4.0 or less. Mz / Mw may be 3.5 or less.
The average molecular weight and molecular weight distribution (Mz, Mw, Mn, Mw / Mn, Mz / Mw) measured by GPC of polypropylene resin (X2) can be changed by changing the temperature and pressure conditions of propylene polymerization, or by the most common method. It can be easily adjusted by a method of adding a chain transfer agent such as hydrogen at the time of propylene polymerization. Further, the type of metallocene complex to be used, and when two or more types of complexes are used, control can be performed by changing the amount ratio.
The polypropylene resin (X2) of the present invention preferably has Mw of 150,000 or more and 200,000 or less from the viewpoint of the balance between melt fluidity and melt tension. Mw is preferably 160,000 or more from the viewpoint of melt tension, and preferably 190,000 or less from the viewpoint of melt fluidity.

1-2-3. Characteristic (X2-3): In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 0.5% by mass or more. Provided that _{W 1M} of _{W 1M} ≧ polypropylene resin polypropylene resin (X1) (X2). The characteristic (X2-3) is preferably such that the proportion of components having a molecular weight of 1 million or more (W _1M ) is 0.5% by mass or more and less than 3.5% by mass in the integrated molecular weight distribution curve obtained by GPC. It may be present, and more preferably, in the integrated molecular weight distribution curve obtained by GPC, the proportion (W _1M ) of the components having a molecular weight of 1 million or more is 0.5% by mass or more and less than 2.5% by mass. May be good.

As described above, when the amount of the high molecular weight component is small, the melt tension becomes small. Therefore, W _1M of X2 is 0.5% by mass or more, preferably 1.0% by mass or more, and more preferably 1.5% by mass or more. On the other hand, as W _1M increases, the melt fluidity decreases. Therefore, W _1M of X2 is preferably less than 3.5% by mass, more preferably 3.0% by mass or less, still more preferably less than 2.5% by mass, and particularly preferably 2.0% by mass. It is as follows.
In the present invention, W _1M sets the integral value up to 1 million (log (M) = 6.0) in the integrated molecular weight distribution curve (normalized to 1 for the total amount) obtained by GPC. It is defined as a value obtained by multiplying the value subtracted from the value by 100.
W _1M is, for example, in a method using a catalyst containing a plurality of metallocene complexes, as one of the metallocene complexes to be used, one that can produce a high molecular weight polymer is selected, and then the other metallocene that produces a low molecular weight side. It can be easily adjusted by controlling the amount ratio to the complex, the amount of hydrogen added at the time of polymerization, and the polymerization temperature.

The values of Mz, Mw, Mn, Mw / Mn, Mz / Mw, and W _1M defined above are all obtained by gel permeation chromatography (GPC), and the measuring method and measuring instrument thereof. Is the same as that used for the polypropylene resin (X1).

1-2-4. Characteristics (X2-4): The melt tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirement (Equation 1).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.0 (Equation 1)

Here, MT170 ° C. and MT230 ° C. are melt tensions when measured by the same method as the measurement method used for the polypropylene resin (X1), and the measurement conditions and units are as described above.
This regulation is an index for polypropylene resin (X2) to have sufficient melt tension, and since MT generally has a correlation with MFR, it is described by a relational expression with MFR.
If the polypropylene resin (X2) satisfies the above (Equation 1), not only the effect of reducing neck-in can be obtained, but also the stress propagates uniformly to the molten film, so that the film thickness is not good, which is called a resonance phenomenon. The uniform phenomenon and the unstable phenomenon due to the expansion and contraction of the edge portion are suppressed.
Further, it is more preferable to satisfy the following (Equation 2), and further preferably to satisfy (Equation 3).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.3 (Equation 2)
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.5 (Equation 3)

It is not necessary to set the upper limit value of MT in particular, but when MT exceeds 40 g, the taking-up speed becomes remarkably slow in the above measurement method, and measurement becomes difficult. In such a case, it is considered that the ductility of the resin is also lowered, so that it is preferably 40 g or less, more preferably 35 g or less, and further preferably 30 g or less.
In order to satisfy the above condition (Equation 1), for example, the amount of long-chain branching of the polypropylene resin (X2) may be increased to increase the melt tension. This is possible by controlling the quantity ratio and the prepolymerization conditions to introduce many long-chain branches.

1-2-5. Characteristic (X2-5): The branch index g'(Mz _abs ) measured by GPC is 0.70 or more and 0.95 or less.

As a direct index that the polypropylene resin (X2) has a branch, the branch index g'can be mentioned as in the polypropylene resin (X1), and the same applies to the calculation method of g'.
The branching index g'to be 0.70 or more and 0.95 or less is achieved by introducing a large number of long-chain branches, for example, selection of a preferable metallocene catalyst, a combination thereof, and an amount ratio thereof, and prepolymerization. This is possible by controlling the conditions and polymerizing.
The polypropylene resin (X2) used in the present invention has a g'(Mz _{abs ) at a Z average molecular weight Mz abs} of absolute molecular weight Mabs determined by light scattering, preferably 0.72 or more, more preferably 0.75 or more. It is more preferably 0.80 or more, preferably 0.90 or less, more preferably 0.88 or less, still more preferably 0.85 or less.

1-2-6. (X2-6): ¹³ The mm fraction of 3 chains of propylene units by C-NMR is 95% or more.

The polypropylene resin (X2) used in the present invention preferably has high stereoregularity. The high ^{degree of stereoregularity can be evaluated by 13} C-NMR, and it is preferable that ^{the mm fraction of the propylene unit 3 chain obtained by 13} C-NMR has a stereoregularity of 95% or more, and the effect thereof. Is the same as the polypropylene resin (X1).

1-2-7. Method for Producing Polypropylene Resin (X2) The polypropylene resin (X2) is not particularly limited as long as it satisfies the above-mentioned characteristics (X2-1) to (X2-6), but as described above, it is not particularly limited. A preferred production method for satisfying conditions such as high stereoregularity, relatively wide molecular weight distribution, branch index g'(Mz _abs ) range, and high melt tension is a macromer copolymerization method using a combination of metallocene catalysts. This is the method used. Examples of such a method include the methods disclosed in JP-A-2009-57542. This method is a method for producing polypropylene having a long-chain branched structure by using a catalyst in which a catalyst component having a specific structure having a macromer-forming ability and a catalyst component having a specific structure having a 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 modifier, are used for the purpose. It is possible to produce a polypropylene resin having a long-chain branched structure having physical properties.

The polypropylene resin (X2) according to the present invention is an α-olefin comonomer having 2 to 20 carbon atoms excluding the propylene monomer and propylene, for example, ethylene, even if it is a propylene homopolymer obtained by homopolymerizing a propylene monomer. And / or a propylene / α-olefin copolymer obtained by copolymerizing with 1-butene may be used.
The shape of the polypropylene resin (X2) is not particularly limited, and may be in the form of powder or particles that are granulated products thereof.

The polypropylene resin (X2) according to the present invention is obtained by mixing other additional components described later as necessary with a Henshell mixer, V blender, ribbon blender, tumbler blender or the like, and if necessary, a single shaft. The granulated product may be kneaded by a kneader such as an extruder, a multi-screw extruder, a kneader, or a Bambari mixer.

1-3. Polypropylene resin (Y)
The polypropylene-based resin (Y) has the properties (Y-1) to (Y-2).

1-3-1. Characteristic (Y-1): MFR (230 ° C., load 2.16 kgf) is 10 g / 10 minutes or more and 50 g / 10 minutes or less.
The MFR of the polypropylene-based resin (Y) is 10 g / 10 minutes or more, preferably 15 g / 10 minutes or more, from the viewpoint of improving the fluidity of the polypropylene-based resin composition and suppressing the resonance phenomenon during extrusion laminating molding. Is. On the other hand, the MFR of the polypropylene-based resin (Y) is 50 g / 10 minutes or less, preferably 45 g / 10 minutes or less, from the viewpoint that the melt tension becomes good and the production efficiency of the product becomes good.

The MFR of the polypropylene-based resin (Y) is easily adjusted by changing the temperature and pressure conditions of the propylene polymerization or by adding a chain transfer agent such as hydrogen at the time of polymerization.

Further, the polypropylene-based resin (Y) may be one in which the MFR is adjusted by reducing the organic peroxide after polymerizing the polypropylene-based resin.
The organic peroxide used at that time is benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, 1,1-bis- (t-butyl peroxide)-. 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t-butyl) Peroxy) Valerate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2 , 5-Di (t-butylperoxy) -3-hexine, 1,3-bis (t-butylperoxyisopropyl) benzene, α, α'-bis (t-butylperoxyisopropyl) benzene, t-butyl -Hydroperoxide, cumenehydroperoxide, lauroyl peroxide, di-t-butyl-diperoxyphthalate, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, isopropylpercarbonate and the like can be mentioned.
These are not limited to one type, and two or more types can be used in combination. Among these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, 1,3 -Bis (t-butylperoxyisopropyl) benzene and α, α'-bis (t-butylperoxyisopropyl) benzene are particularly preferable.

The reduction method for adjusting MFR uses organic peroxides, preferably 0.005 parts by mass to 0.1 parts by mass per 100 parts by mass of the resin or resin composition, and both are above the melting temperature of the resin. It may be kneaded by heating at a temperature of, for example, 180 ° C. to 300 ° C., and any method can be adopted as the method, but it is particularly preferable to carry out the kneading in an extruder. Further, both may be sufficiently mixed using a mixer such as a Henschel mixer or a ribbon blender in advance before heating and kneading the two so that the organic peroxide is uniformly dispersed in the polypropylene resin. Further, in order to improve the dispersibility of the organic peroxide, a mixture of the organic peroxide in an appropriate medium can also be used. It can be used in the present invention by satisfying the requirements for the characteristic physical characteristics of the polypropylene-based resin (Y) in the present invention after adjusting the MFR by reducing the organic peroxide.

1-3-2. Characteristic (Y-2): Melt tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirements (formula A).
log (MT170 ° C) <-1.1 x log (MFR) +2.0 (Formula A)

Here, MT170 ° C. is the melt tension when measured by the same method as the measurement method used for the polypropylene resin (X1), and the measurement conditions and units are as described above.
This regulation is an index for indicating the melt tension of the polypropylene-based resin (Y), and since MT generally has a correlation with MFR, it is described by a relational expression with MFR.
By satisfying the above (formula A), the polypropylene-based resin (Y) imparts fluidity when blended with the polypropylene resins (X1) and (X2), and reduces molding defects such as film rupture during molding. be able to.

1-3-3. Method for Producing Polypropylene Resin (Y) The polypropylene resin (Y) is not limited in its production method, and may be produced by a Ziegler-Natta catalyst or a metallocene catalyst.
The Ziegler-Natta catalyst is, for example, "Polypropylene Handbook" Edward P. Moore Jr. It is a catalytic system as outlined in Section 2.3.1 (pages 20-57) of the Industrial Research Council (1998), edited by Tetsuo Yasuda and supervised by Nobu Sakuma. For example, titanium trichloride and halogen. A titanium trichloride catalyst made of organic aluminum, a solid catalyst component containing magnesium chloride, titanium halide, and an electron donating compound, a magnesium-supporting catalyst made of organic aluminum and an organic silicon compound, and a solid catalyst component made of organic aluminum. It refers to a catalyst in which an organic aluminum compound component is combined with an organic silicon-treated solid catalyst component formed by contacting an organic silicon compound.

Further, as the metallocene catalyst, (i) a transition metal compound (so-called metallocene compound) of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton and (ii) a stable ion by reacting with the metallocene compound. It is a catalyst composed of a co-catalyst that can be activated into a state and, if necessary, an organic aluminum compound (iii), and any known catalyst can be used. The metallocene compound is preferably a crosslinked metallocene compound capable of stereoregular polymerization of propylene, and more preferably a crosslinked metallocene compound capable of isoregular polymerization of propylene.

Examples of the (i) metallocene compound include JP-A-60-35007, JP-A-61-130314, JP-A-63-295607, JP-A 1-275609, JP-A-2-41303, and Japanese Patent Publication No. 2-41303. Kaihei 2-131488, JP-A-2-76887, JP-A-3-163088, JP-A-4-300878, JP-A-4-211694, JP-A-5-43616, JP-A-5-209013, JP-A. Those disclosed in JP-A-6-239914, JP-A-7-504934, and JP-A-8-85708 can be preferably used.

More specifically,
Methylenebis (2-methylindenyl) zirconium dichloride, ethylenebis (2-methylindenyl) zirconium dichloride,
Ethylene 1,2- (4-phenylindenyl) (2-methyl-4-phenyl-4H-azurenyl) zirconium dichloride,
Isopropyridene (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,
Dimethylsilylenebis [1- (2-methyl-4-phenylindenyl)] zirconium dichloride,
Dimethylsilylenebis [1- (2-ethyl-4-phenylindenyl)] zirconium dichloride,
Dimethylsilylenebis [4- (1-phenyl-3-methylindenyl)] zirconium dichloride,
Dimethylsilylene (fluorenyl) t-butylamide zirconium 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-azurenyl)] zirconium dichloride,
Dimethylsilylenebis [1- (2-ethyl-4- (4-chlorophenyl) -4H-azurenyl)] zirconium dichloride,
Dimethylsilylenebis [1- (2-ethyl-4-naphthyl-4H-azurenyl)] zirconium dichloride,
Diphenylsilylenebis [1- (2-methyl-4- (4-chlorophenyl) -4H-azurenyl)] zirconium dichloride,
Dimethylsilylenebis [1- (2-ethyl-4- (3-fluorobiphenylyl) -4H-azurenyl)] zirconium dichloride,
Dimethylgelmilenebis [1- (2-ethyl-4- (4-chlorophenyl) -4H-azurenyl)] zirconium dichloride,
Zirconium compounds such as dimethylgelmilenebis [1- (2-ethyl-4-phenylindenyl)] zirconium dichloride can be exemplified.

In the above, a compound 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 another halogen compound, a hydrocarbon group such as methyl, isobutyl or benzyl, an amide group such as dimethylamide or diethylamide, an alkoxide group such as a methoxy group or a phenoxy group, or a hydride group.
Of these, a metallocene compound in which an indenyl group or an azulenyl group is crosslinked with a silicon or gelmil group is particularly preferable.
Further, the metallocene compound may be used by supporting it on a carrier of an inorganic or organic compound.
The carrier is preferably a porous compound of an inorganic or organic compound, and specifically, ion-exchangeable layered silicate, zeolite, SiO ₂ , Al ₂ O ₃ , silica alumina, MgO, ZrO ₂ , TiO ₂ , B. include _{2 O 3, CaO, ZnO,} BaO, ThO 2, inorganic compounds such as polyolefin porous, styrene-divinylbenzene copolymer, an organic compound comprising an olefin-acrylic acid copolymers, or mixtures thereof Be done.

Further, examples of the co-catalyst capable of reacting with the (ii) metallocene compound and activating it into a stable ionic state include organoaluminum oxy compounds (for example, aluminoxane compounds), ion-exchangeable layered silicates, Lewis acids, and boron-containing compounds. Ionic compounds, fluorine-containing organic compounds and the like are preferably mentioned.

Further, examples of the (iii) organoaluminum compound include trialkylaluminum such as triethylaluminum, triisopropylaluminum, and triisobutylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, alkylaluminum dihalide, alkylaluminum hydride, and organoaluminum alcoholic acid. The side and the like are preferably mentioned.

Of the above, the polypropylene homopolymer is preferably produced by a Ziegler-Natta catalyst, and the propylene random copolymer is preferably produced by a metallocene catalyst.

The method for producing the polypropylene-based resin (Y) is not particularly limited, and any conventionally known slurry polymerization method, bulk polymerization method, gas phase polymerization method, or the like can be used, and if it is within the range, it can be produced in multiple stages. It is also possible to produce polypropylene and propylene-based random copolymers by using a polymerization method.

The polypropylene-based resin (Y) may be a propylene homopolymer obtained by homopolymerizing a propylene monomer, or a propylene / ethylene copolymer obtained by copolymerizing a propylene monomer and an ethylene comonomer. May be. The polypropylene-based resin (Y) preferably contains 0% by mass to 6.0% by mass of ethylene as a comonomer. More preferably, it contains 0% by mass to 5.0% by mass of ethylene, and more preferably 0% by mass to 4.0% by mass of ethylene. If the ethylene content exceeds 6.0% by mass, the crystallinity may decrease and the heat resistance may decrease.
The shape of the polypropylene-based resin (Y) is not particularly limited, and may be in the form of powder or particles that are granulated products thereof.

The polypropylene-based resin (Y) according to the present invention is obtained by mixing other additional components described later as necessary with a Henshell mixer, V blender, ribbon blender, tumbler blender or the like, and if necessary, a single shaft. It is obtained by a method of kneading with a kneader such as an extruder, a multi-screw extruder, a kneader, and a Bambari mixer.

1-4. Polypropylene resin composition 1-4-1. Ratio of Polypropylene Resin (X1), Polypropylene Resin (X2), Polypropylene Resin (Y) The polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene resin (Y) in the polypropylene resin composition of the present invention. The ratio of (X1), (X2) and (Y) is 100% by mass in total, preferably 2% by mass to 30% by mass of polypropylene resin (X1) and 5% by mass to 98% by mass of polypropylene resin (X2). And polypropylene resin (Y) 0% by mass to 80% by mass, more preferably polypropylene resin (X1) 2% by mass to 30% by mass, polypropylene resin (X2) 5% by mass to 80% by mass, and polypropylene resin ( Y) 10% by mass to 80% by mass, more preferably 5% by mass to 30% by mass of polypropylene resin (X1), 5% by mass to 50% by mass of polypropylene resin (X2), and 20% by mass of polypropylene resin (Y). -80% by mass, more preferably 5% by mass to 25% by mass of polypropylene resin (X1), 15% by mass to 45% by mass of polypropylene resin (X2), and 30% by mass to 70% by mass of polypropylene-based resin (Y). It is particularly preferable that the polypropylene resin (X1) is 5% by mass to 20% by mass, the polypropylene resin (X2) is 20% by mass to 40% by mass, and the polypropylene resin (Y) is 40% by mass to 65% by mass.
The polypropylene resin (X1) may be 2% by mass or more, 2.5% by mass or more, or 5% by mass based on a total of 100% by mass of (X1), (X2) and (Y). % Or more, 30% by mass or less, 25% by mass or less, or 20% by mass or less.
The polypropylene resin (X2) may be 5% by mass or more, 15% by mass or more, or 20% by mass or more based on a total of 100% by mass of (X1), (X2) and (Y). It may be 98% by mass or less, 80% by mass or less, 50% by mass or less, 45% by mass or less, 40% by mass or less. May be.
The polypropylene-based resin (Y) may be 0% by mass or more, 10% by mass or more, or 20% by mass based on a total of 100% by mass of (X1), (X2), and (Y). It may be more than or equal to 30% by mass, may be 40% by mass or more, may be 80% by mass or less, may be 70% by mass or less, and may be 65% by mass. It may be as follows.
Within the above range, for example, the neck-in in high-temperature extrusion molding at 290 ° C. or higher is small and the ductility is high, so that a molded product having excellent high-speed extrusion laminating workability and excellent transparency can be obtained. A resin composition that can be obtained is obtained.

As a preferred first embodiment of the polypropylene-based resin composition of the present invention,
Polypropylene resin (X1) having the following characteristics (X1-1) to (X1-6) is 2% by mass to 30% by mass, and
Polypropylene resin (X2) having the following characteristics (X2-1) to (X2-6) is 5% by mass to 98% by mass, and
Contains 0% by mass to 80% by mass of a polypropylene-based resin (Y) having the following characteristics (Y-1) to (Y-2) (however, polypropylene resin (X1), polypropylene resin (X2), and polypropylene-based resin. The total amount with the resin (Y) is 100% by mass.) Polypropylene-based resin composition can be mentioned. The preferred range of each ratio and each characteristic may be the same as described above.
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 10 g / 10 minutes or less.
(X1-2) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by GPC is 2.0 or more and 5.0 or less, and the Z average molecular weight (Mz). The ratio (Mz / Mw) between the weight average molecular weight (Mw) and the weight average molecular weight (Mw) is 2.0 or more and 5.0 or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 3.5% by mass or more.
(X1-4) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirement (Equation 1).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.0 (Equation 1)
(X1-5) The branch index g'(Mz _abs ) measured by GPC is 0.70 or more and 0.95 or less.
(X1-6) ¹³ The triad fraction (mm) of 3 chains of propylene units by C-NMR is 95% or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 10 g / 10 minutes and 80 g / 10 minutes or less.
(X2-2) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by GPC is 2.0 or more and 5.0 or less, and the Z average molecular weight (Mz). The ratio (Mz / Mw) between the weight average molecular weight (Mw) and the weight average molecular weight (Mw) is 2.0 or more and 5.0 or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion (W _1M ) of the components having a molecular weight of 1 million or more is 0.5% by mass or more and less than 3.5% by mass.
(X2-4) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirement (Equation 1).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.0 (Equation 1)
(X2-5) The branch index g'(Mz _abs ) measured by GPC is 0.70 or more and 0.95 or less.
(X2-6) ¹³ The triad fraction (mm) of 3 chains of propylene units by C-NMR is 95% or more.
(Y-1) MFR (230 ° C., load 2.16 kgf) is 10 g / 10 minutes or more and 50 g / 10 minutes or less.
(Y-2) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirements (formula A).
log (MT170 ° C) <-1.1 x log (MFR) +2.0 (Formula A)

Further, as a preferred second embodiment of the polypropylene-based resin composition of the present invention,
Polypropylene resin (X1) having the following characteristics (X1-1) to (X1-6) is 5% by mass to 30% by mass, and
Polypropylene resin (X2) having the following characteristics (X2-1) to (X2-6) is 5% by mass to 50% by mass, and
Contains 20% by mass to 80% by mass of a polypropylene-based resin (Y) having the following characteristics (Y-1) to (Y-2) (however, polypropylene resin (X1), polypropylene resin (X2), and polypropylene-based resin. The total amount with the resin (Y) is 100% by mass.) Polypropylene-based resin composition can be mentioned. The preferred range of each ratio and each characteristic may be the same as described above.
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 30 g / 10 minutes or less.
(X1-2) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by GPC is 2.0 or more and 5.0 or less, and the Z average molecular weight (Mz). The ratio (Mz / Mw) between the weight average molecular weight (Mw) and the weight average molecular weight (Mw) is 2.0 or more and 5.0 or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 2.5% by mass or more.
(X1-4) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirement (Equation 1).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.0 (Equation 1)
(X1-5) The branch index g'(Mz _abs ) measured by GPC is 0.70 or more and 0.95 or less.
(X1-6) ¹³ The triad fraction (mm) of 3 chains of propylene units by C-NMR is 95% or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 30 g / 10 minutes and 80 g / 10 minutes or less.
(X2-2) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by GPC is 2.0 or more and 5.0 or less, and the Z average molecular weight (Mz). The ratio (Mz / Mw) between the weight average molecular weight (Mw) and the weight average molecular weight (Mw) is 2.0 or more and 5.0 or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion (W _1M ) of the components having a molecular weight of 1 million or more is 0.5% by mass or more and less than 2.5% by mass.
(X2-4) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirement (Equation 1).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.0 (Equation 1)
(X2-5) The branch index g'(Mz _abs ) measured by GPC is 0.70 or more and 0.95 or less.
(X2-6) ¹³ The triad fraction (mm) of 3 chains of propylene units by C-NMR is 95% or more.
(Y-1) MFR (230 ° C., load 2.16 kgf) is 10 g / 10 minutes or more and 50 g / 10 minutes or less.
(Y-2) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirements (formula A).
log (MT170 ° C) <-1.1 x log (MFR) +2.0 (Formula A)

1-4-2. Other Ingredients The polypropylene-based resin composition of the present invention can be used by adding the following various components other than the above-mentioned polypropylene resin (X1), polypropylene resin (X2), and polypropylene-based resin (Y), if necessary. ..

1-4-2-1. Additives Additives such as antioxidants that can be added to polypropylene resins can be appropriately added to the polypropylene resin composition of the present invention as long as the effects of the present invention are not significantly impaired.
Specifically, 2,6-di-t-butyl-p-cresol (BHT), tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (BASF Japan) Made by the company, with the product name "IRGANOX 1010") and n-octadecyl-3- (4'-hydroxy-3,5'-di-t-butylphenyl) propionate (manufactured by BASF Japan, product name "IRGANOX 1076"). Phenolic stabilizers such as bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite and tris (2,4-di-t-butylphenyl) phosphite. Stabilizers, lubricants typified by higher fatty acid amides and higher fatty acid esters, antistatic agents such as glycerin esters, sorbitanoic acid esters, polyethylene glycol esters of fatty acids with 8 to 22 carbon atoms, silica, calcium carbonate, talc, etc. An anti-blocking agent or the like may be added.

Further, an ultraviolet absorber and a light stabilizer can be added to the polypropylene-based resin composition of the present invention in order to impart weather resistance.
The ultraviolet absorber is a compound having an absorption band in the ultraviolet region, and is known to be triazole-based, benzophenone-based, salicylate-based, cyanoacrylate-based, nickel chelate-based, inorganic fine particle-based, and the like. The most commonly used of these is the triazole system.
Hereinafter, typical compounds are exemplified as ultraviolet absorbers.
Among triazole-based compounds, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole (trade name: Sumisorb 200, TinuvinP), 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole (Product names: Sumisorb 340, Tinuvin399), 2- (2'-hydroxy-3', 5'-di-t-butylphenyl) benzotriazole (trade names: Sumisorb 320, Tinuvin320), 2- (2'-hydroxy) -3', 5'-di-t-amylphenyl) Benzotriazole (trade name: Sumisorb 350, Tinuvin328), 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5 Chlorobenzotriazole (trade name: Sumisorb 300, Tinuvin 326) can be exemplified.
Examples of the benzophenone-based compound include 2-hydroxy-4-methoxybenzophenone (trade name: Sumisorb 110) and 2-hydroxy-4-n-octoxybenzophenone (trade name: Sumisorb 130).
As the salicylate-based compound, 4-t-butylphenyl salicylate (trade name: Seasorb 202) can be exemplified.
As the cyanoacrylate compound, ethyl (3,3-diphenyl) cyanoacrylate (trade name: Seasove 501) can be exemplified.
As the nickel chelate compound, nickel dibutyldithiocarbamate (trade name: Antigen NBC) can be exemplified.
Examples of the inorganic fine particle-based compound include TiO ₂ , ZnO ₂ , and CeO _2.

As the light stabilizer, it is common to use a hindered amine compound, which is called HALS. HALS has a 2,2,6,6-tetramethylpiperidine skeleton and cannot absorb ultraviolet rays, but suppresses photodegradation by a wide variety of functions. It is said that its three main functions are the capture of radicals, the decomposition of hydroxyperoxide compounds, and the capture of heavy metals that accelerate the decomposition of hydroxyperoxide.

Hereinafter, representative compounds as HALS will be exemplified.
For sebacate-type compounds, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (trade name: Adecastab LA-77, Sanol LS-770), bis (1,2,2,6,6) −Pentamethyl-4-piperidyl) sebacate (trade name: Sanol LS-765) can be exemplified.
Among the butane tetracarboxylate type compounds, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate (trade name: Adecastab LA-57), tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate (trade name: Adecastab LA-52), 1,2,3,4-butanetetra Condensation of carboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and tridecyl alcohol (trade name: Adecastab LA-67), 1,2,3,4-butanetetracarboxylic acid and 1, A condensate of 2,2,6,6-pentamethyl-4-piperidinol and tridecyl alcohol (trade name: Adecastab LA-62) can be exemplified.
In the succinic acid polyester type compound, a condensed polymer of succinic acid and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine can be exemplified. For triazine-type compounds, 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 (trade name: Chimasorb199), poly {6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2 , 4-Diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino} (trade name: Chimasorb944) ), Poly (6-morpholino-s-triazine-2,4-diyl) {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetra) Methyl-4-piperidyl) imino} (trade name: Chimasorb 3346) can be exemplified.

1-4-2-2. Other Polymers To the polypropylene-based resin composition of the present invention, a modifier such as an elastomer or a polyethylene-based resin that can be added to the polypropylene-based resin can be appropriately added.
Among the above, the elastomer includes an ethylene-α-olefin copolymer, a binary random copolymer resin of propylene and an α-olefin having 4 to 12 carbon atoms, and propylene and ethylene and an α-olefin having 4 to 12 carbon atoms. A ternary random copolymer resin with an olefin can be mentioned.

Further, a styrene-based elastomer can also be added, and the styrene-based elastomer can be appropriately selected and used from commercially available ones. For example, Clayton as a hydrogenated additive for a styrene-butadiene block copolymer. Under the trade name of "Clayton G" from Polymer Japan Co., Ltd. and under the trade name of "Tough Tech" from Asahi Chemicals Co., Ltd. As a hydrogen additive for a styrene-vinylized polyisoprene block copolymer, under the trade name of "Hyblur" from Kuraray Co., Ltd., as a hydrogen additive for a styrene-butadiene random copolymer, JSR Co., Ltd. It is sold under the trade name of "Polymeron", and may be appropriately selected and used from these product groups.

Examples of the polyethylene-based resin include ethylene / α-olefin copolymers such as low-density polyethylene and linear low-density polyethylene, and the density thereof is in the range of ^{0.860 g / cm 3 to} 0.910 g / cm ^3. preferably ^there, more preferably ^{0.870g / cm 3 ~0.905g / cm 3} , further preferably ^{0.875g / cm 3 ~0.895g / cm 3} . If it exceeds the above range, transparency may decrease.
The density is a value measured at 23 ° C. in accordance with JIS K7112.
The α-olefin used in the ethylene / α-olefin copolymer is preferably an α-olefin having 3 to 18 carbon atoms. Specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-methyl-pentene-1, 4-methyl-hexene-1, 4,4-dimethylpentene- The first prize can be mentioned. Further, the α-olefin may be one kind or a combination of two or more kinds.
Examples of such ethylene / α-olefin copolymers include ethylene-based elastomers and ethylene-propylene-based rubbers. In particular, an ethylene / α-olefin copolymer called metallocene-based polyethylene produced by using a metallocene-based catalyst with less decrease in transparency is suitable.

The amount of the polyethylene resin or the like to be blended is preferably 5 parts by mass to 35 parts by mass, more preferably 6 parts by mass, based on 100 parts by mass of the total of (X1), (X2) and (Y). It is about 30 parts by mass, more preferably 7 parts by mass to 25 parts by mass.

The polypropylene-based resin composition of the present invention contains a total of 100 parts by mass of the above (X1), (X2), and (Y), or, if necessary, other components that do not impair the effects of the present invention. As a mixing method of these components, a method of mixing with a Henschel mixer, a V blender, a ribbon blender, a tumbler blender, etc., and, if necessary, a kneader such as a single-screw extruder, a multi-screw extruder, a kneader, a Bambari mixer, etc. Two types of kneading methods are given as examples. In either case, the mixing method is not particularly limited as long as the effect of the present invention is not impaired.

1-4-3. Applications of Polypropylene Resin Composition The polypropylene resin composition of the present invention is appropriately desired by means such as pressure molding, film molding, vacuum molding, extrusion molding, extrusion laminating molding, foam molding, hollow molding, injection molding and the like. It can be used to manufacture various molded products by molding into the shape of.

The polypropylene-based resin composition of the present invention is particularly preferably used for extrusion laminating.
The polypropylene-based resin composition of the present invention is melt-extruded and laminated (extruded and laminated) on the surface of a base material, and is suitably used for producing a laminated laminate.
Extrusion laminating is a molding method in which a molten resin film extruded from a T-die is continuously coated and pressure-bonded onto the surface of a prefabricated base material, and the coating and adhesion are performed at the same time. .. Normally, it is laminated on one side surface of the base material, but it can also be laminated on both sides if necessary.

2. 2. Method for Producing Polypropylene Resin Composition The method for producing a polypropylene resin composition of the present invention is a step of obtaining a polypropylene resin (X1) having the above-mentioned characteristics (X1-1) to (X1-6).
Having a step of obtaining a polypropylene resin (X2) having the above-mentioned characteristics (X2-1) to (X2-6), and a step of mixing or melt-kneading the polypropylene resin (X1) and the polypropylene resin (X2). It is characterized by.
The method for producing a polypropylene-based resin composition of the present invention further comprises, as a preferred embodiment, a step of obtaining a polypropylene-based resin (Y) having the above-mentioned characteristics (Y-1) to (Y-2).
The step of mixing or melt-kneading may be a step of mixing or melt-kneading the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene-based resin (Y).
In the step of mixing or melt-kneading, more preferably, the polypropylene resin (X1) is 2% by mass to 30% by mass, the polypropylene resin (X2) is 5% by mass to 98% by mass, and the polypropylene resin (Y) is 0% by mass. Even in the step of mixing or melt-kneading% to 80% by mass (however, the total amount of the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene-based resin (Y) is 100% by mass). good. In this case, the polypropylene resin (X1) and the polypropylene resin (X2) may be the same as the polypropylene resin (X1) and the polypropylene resin (X2) in the above-mentioned "Preferable first embodiment of the polypropylene resin composition". good.
In the step of mixing or melt-kneading, more preferably, the polypropylene resin (X1) is 5% by mass to 30% by mass, the polypropylene resin (X2) is 5% by mass to 50% by mass, and the polypropylene resin (Y) is 20% by mass. Even in the step of mixing or melt-kneading% to 80% by mass (however, the total amount of the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene-based resin (Y) is 100% by mass). good. In this case, the polypropylene resin (X1) and the polypropylene resin (X2) may be the same as the polypropylene resin (X1) and the polypropylene resin (X2) in the above-mentioned "Preferable second embodiment of the polypropylene resin composition". good.

The method for obtaining the polypropylene resin (X1) is not particularly limited, and the polypropylene resin (X1) can be produced by the method described in the above-mentioned "Method for producing polypropylene resin (X1)".
The method for obtaining the polypropylene resin (X2) is not particularly limited, and the polypropylene resin (X2) can be produced by the method described in the above-mentioned "Method for producing polypropylene resin (X2)".
The method for obtaining the polypropylene-based resin (Y) is not particularly limited, and the polypropylene-based resin (Y) can be produced by the method described in the above-mentioned "Method for producing the polypropylene resin (Y)".
The method of further mixing the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene resin (Y) as needed is not particularly limited, and a method of mixing with a henshell mixer, a V blender, a ribbon blender, a tumbler blender, or the like is used. Can be mentioned.
The method of melt-kneading the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene resin (Y) as needed is not particularly limited, and a single-screw extruder, a multi-screw extruder, a kneader, a Banvari mixer, etc. Examples thereof include a method of melt-kneading with a kneader.
The ratio of the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene-based resin (Y) is the ratio described in the above-mentioned "Ratio of polypropylene resin (X1), polypropylene resin (X2), polypropylene-based resin (Y)". Can be mentioned.
The use of the polypropylene-based resin composition thus produced may be the same as the above-mentioned "use of polypropylene-based resin composition".

3. 3. Laminated body The laminated body of the present invention is a laminated body containing a base material layer and a polypropylene-based resin composition layer, and the polypropylene-based resin composition layer has the above-mentioned characteristics (X1-1) to (X1-6). The polypropylene resin (X1) having the above-mentioned characteristics (X2-1) to (X2-6) is contained.
In the laminate of the present invention, the polypropylene-based resin composition layer may further contain the polypropylene-based resin (Y) having the above-mentioned properties (Y-1) to (Y-2) as a preferred embodiment.
In a more preferable embodiment, the polypropylene-based resin composition layer has 2% by mass to 30% by mass of the polypropylene resin (X1), 5% by mass to 98% by mass of the polypropylene resin (X2), and 0% by mass of the polypropylene-based resin (Y). % To 80% by mass, and may be contained. (However, the total amount of the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene-based resin (Y) is 100% by mass.) In this case, the polypropylene resin (X1) and the polypropylene resin (X2) are used. It may be the same as the polypropylene resin (X1) and the polypropylene resin (X2) of the above-mentioned "preferable first embodiment of the polypropylene resin composition".
As a more preferable embodiment, the polypropylene-based resin composition layer has 5% by mass to 30% by mass of the polypropylene resin (X1), 5% by mass to 50% by mass of the polypropylene resin (X2), and 20% by mass of the polypropylene-based resin (Y). % To 80% by mass, and may be contained. (However, the total amount of the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene-based resin (Y) is 100% by mass.) In this case, the polypropylene resin (X1) and the polypropylene resin (X2) are used. It may be the same as the polypropylene resin (X1) and the polypropylene resin (X2) of the above-mentioned "preferable second embodiment of the polypropylene resin composition".

The ratio of the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene-based resin (Y) is the ratio described in the above-mentioned "Ratio of polypropylene resin (X1), polypropylene resin (X2), polypropylene-based resin (Y)". Can be mentioned.

The base material used as the base material layer is polyester resin such as polyethylene terephthalate and polybutylene terephthalate, ethylene / vinyl acetate copolymer satanized product, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, and poly-4-methyl-1-pentene. , Polyvinyl resin, polyamide 6, polyamide 66, polyamide 6.66, polyamide 12, and other thermoplastic resin films or sheets, paper, and metal foils such as aluminum and iron.
Further, the thermoplastic resin film or sheet may be uniaxially or biaxially stretched, and a biaxially stretched polypropylene film is particularly preferable. Further, it is also preferable that this is laminated with paper.
The thickness of the base material layer is usually about 5 μm to 100 μm.
Examples of the laminating method of the base material layer and the polypropylene-based resin composition layer include an extrusion laminating method, a co-pressing film method, a dry laminating method, a wet laminating method, a hot melt laminating method, and a thermal laminating method.

The form of the base material is not limited to a film or a sheet, and may be a shape such as a woven fabric or a non-woven fabric. Further, the base material may have a single-layer structure or a multi-layer structure. The method for producing the base material having a multi-layer structure is not particularly limited, and examples thereof include a co-press film method, a dry laminating method, a wet laminating method, a hot melt laminating method, an extrusion laminating method, and a thermal laminating method.
Further, these base materials may be subjected to various film processing treatments such as anchor coating processing, metal vapor deposition processing, corona discharge processing processing, and printing processing in advance.

The laminate of the present invention can be suitably used for various foods and beverages, pharmaceuticals / medical products, cosmetics, clothing, stationery, building materials, battery packaging, paper product packaging and other packaging applications such as industrial materials and industrial materials. ..

4. Method for Producing Laminated Body The method for producing a laminated body of the present invention is a method for producing a laminated body including a base material layer and a polypropylene-based resin composition layer.
A polypropylene resin (X1) having the above-mentioned characteristics (X1-1) to (X1-6) and a polypropylene resin (X2) having the above-mentioned characteristics (X2-1) to (X2-6) on at least one surface of the base material layer. It is characterized by having a step of forming the polypropylene-based resin composition layer by extruding and laminating a mixture of and.
The step of forming the polypropylene-based resin composition layer preferably comprises the polypropylene resin (X1), the polypropylene resin (X2), and the above-mentioned characteristics (Y-1) to the above-mentioned characteristics (Y-1) on at least one surface of the base material layer. It may be a step of forming the polypropylene-based resin composition layer by extruding and laminating a mixture or a melt-kneaded product of the polypropylene-based resin (Y) having (Y-2).
The steps for forming the polypropylene-based resin composition layer are more preferably 2% by mass to 30% by mass of the polypropylene resin (X1), 5% by mass to 98% by mass of the polypropylene resin (X2), and the polypropylene-based resin. The total amount of the mixture or melt-kneaded resin (Y) of 0% by mass to 80% by mass (however, the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene-based resin (Y) is 100% by mass. ) May be a step of forming the polypropylene-based resin composition layer by extrusion laminating. In this case, the polypropylene resin (X1) and the polypropylene resin (X2) may be the same as the polypropylene resin (X1) and the polypropylene resin (X2) in the above-mentioned "Preferable first embodiment of the polypropylene resin composition". good.
The step of forming the polypropylene-based resin composition layer is more preferably 5% by mass to 30% by mass of the polypropylene resin (X1), 5% by mass to 50% by mass of the polypropylene resin (X2), and the polypropylene-based resin. The total amount of the mixture or melt-kneaded resin (Y) of 20% by mass to 80% by mass (however, the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene-based resin (Y) is 100% by mass. ) May be a step of forming the polypropylene-based resin composition layer by extrusion laminating. In this case, the polypropylene resin (X1) and the polypropylene resin (X2) may be the same as the polypropylene resin (X1) and the polypropylene resin (X2) in the above-mentioned "Preferable second embodiment of the polypropylene resin composition". good.

As the base material layer, the base material layer described in the above "3. Laminated body" can be exemplified.
The method for mixing the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene-based resin (Y) and the melt-kneading method can be exemplified by the method described in the above "2. Method for producing a polypropylene-based resin composition". ..
The ratio of the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene-based resin (Y) is the ratio described in the above-mentioned "Ratio of polypropylene resin (X1), polypropylene resin (X2), polypropylene-based resin (Y)". Can be mentioned.

When the polypropylene-based resin composition of the present invention containing the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene-based resin (Y) is extruded and laminated on the base material layer, the melt extrusion temperature of the resin composition is usually set. The temperature is 180 ° C to 320 ° C, preferably 200 ° C to 310 ° C. If the temperature exceeds 320 ° C., the moldability may decrease.
Since the extrusion laminating molding speed is directly related to productivity, it is preferably molded at 200 m / min or more, and more preferably 210 m / min or more.
Further, the surface of the molten film of the polypropylene-based resin composition of the present invention can be treated with ozone for the purpose of introducing a polar group. Ozone treatment amount is preferably carried out at a 0.01g ^{/ m 2} ~1g ^/ m 2 of the surface area of the molten film.

Extrusion laminating is usually done on one side of the substrate layer, but can be extruded on both sides if desired.
The thickness of the formed polypropylene-based resin composition layer is usually 1 μm to 250 μm, preferably 3 μm to 200 μm, and particularly preferably 5 μm to 150 μm.
The laminate obtained by the extrusion laminating process can be further subjected to various film processing processes such as metal vapor deposition processing, corona discharge processing processing, and printing processing.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
The evaluation methods and resins used in Examples and Comparative Examples are as follows.

1. 1. Evaluation method (1) Melt flow rate (MFR):
Measured according to ISO 1133: 1997 Connections M. The unit is g / 10 minutes.
(2) Molecular weight distribution (Mw / Mn and Mz / Mn):
It was determined by GPC measurement according to the method described above.
(3) Melt tension (MT):
According to the above-mentioned method, the measurement was carried out under the following conditions using a capillograph 1B manufactured by Toyo Seiki Seisakusho.
・ Capillary: diameter 2.0 mm, length 40 mm
・ Cylinder diameter: 9.55 mm
・ Cylinder extrusion speed: 20 mm / min ・ Pick-up speed: 4.0 m / min ・ Temperature: 170 ° C 230 ° C
If the MT is extremely high, the resin may break at a pick-up speed of 4.0 m / min. In such a case, the pick-up speed is reduced and the tension at the maximum pick-up speed is MT. And. The unit is grams (g).
(4) Branch index (g'(Mz _abs )):
According to the method described above, it was determined by a GPC equipped with a differential refractometer (RI), a viscosity detector (Viscometer), and a light scattering detector (MALLS) as detectors.
(5) mm fraction:
Obtained according to the method described above. The unit is%.
(6) Ethylene content:
¹³ C-NMR using GSX-400 manufactured by JEOL Ltd. or an equivalent device (carbon nuclear resonance frequency 100 MHz or more) according to the method described in paragraphs [0120] to [0125] of JP2013-199642A. It is a value obtained by analyzing the spectrum. The unit is mass%.
(7) Melting point:
Using a differential operating calorimeter (DSC), the temperature was once raised to 200 ° C., left for 5 minutes, the temperature was lowered to 40 ° C. at a temperature lowering rate of 10 ° C./min, and the temperature was measured again at a temperature rise rate of 10 ° C./min. The temperature at the top of the endothermic peak was taken as the melting point. The unit is ° C.

2. 2. Extruded laminate formability (1) Ductility:
Using an extrusion laminating device in which the temperature of the resin extruded from the T-die mounted on an extruder having a diameter of 90 mmφ is set to 290 ° C., the polypropylene-based resin composition has an air gap of 100 mm, a cooling roll surface temperature of 25 ° C., A craft with ^{a width of 505 mm and a basis weight of 50 g / m 2} is extruded by adjusting the extrusion amount so that the coating thickness is 20 μm when the die width is 560 mm, the die lip opening is 0.7 mm, and the take-up processing speed is 80 m / min. Extrusion laminating was performed on the paper while increasing the take-up speed from 80 m / min, and the maximum processing speed (unit: m / min) at which draw resonance did not occur was made ductile.
Those having a ductility of 200 m / min or more have excellent extrusion lamination formability.
(2) Neck-in:
Using the above-mentioned extrusion laminating device, a laminate having an extrusion laminate coating thickness of 20 μm was prepared on kraft paper having a processing speed of 80 m / min and a basis weight of 50 g / m ^{2, and the die width was obtained.} The difference in width (unit: mm) of the resin composition layer was taken as the neck-in. The smaller the neck-in, the wider the effective product width and the better the extrusion laminating workability.

3. 3. Film properties (1) Creation of film for evaluation of physical properties:
Using the above-mentioned extrusion laminating apparatus, a laminate having an extrusion laminate coating thickness of 40 μm was prepared on a biaxially stretched PET film having a processing speed of 40 m / min and a thickness of 12 μm.
By peeling the biaxially stretched PET film from the obtained laminate, a film for evaluating physical properties was obtained.
(2) HAZE:
The HAZE of the physical characteristic evaluation film obtained in (1) above was measured according to JIS K7105. The smaller the haze value (unit:%), the better the transparency.

4. Materials used (1) Polypropylene resin (X1)
The polymer (X1-1) produced in Production Example 1 below was used.

[Manufacturing Example 1 (Manufacturing of PP-1)]
<Catalyst synthesis example 1>
(1) Complex synthesis (1-a) rac-dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl}] hafnium Synthesis:
rac-dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl}] hafnium was synthesized from JP2012-149160. It was synthesized according to the method of Example 1.

(1-b) rac-dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] Hafnium synthesis:
rac-dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium was synthesized according to the method of Example 7 of JP-A-11-240909. did.

(2) Preparation of catalyst (2-a) Chemical treatment of ion-exchangeable layered silicate In a 1 L three-necked flask equipped with a stirring blade and a reflux device, 645.1 g of distilled water and 82.6 g of 98% sulfuric acid were placed. In addition, the temperature was raised to 95 ° C.
Commercially available montmorillonite (Benclay KK manufactured by Mizusawa Industrial Chemicals, Al = 9.78% by mass, Si = 31.79% by mass, Mg = 3.18% by mass, Al / Si (molar ratio) = 0.320, An average particle size of 14 μm) was added, and the mixture was reacted at 95 ° C. for 320 minutes. After 320 minutes, 0.5 L of distilled water was added to stop the reaction, and the mixture was filtered to obtain 255 g of a cake-like solid.
1 g of this cake contained 0.31 g of chemically treated montmorillonite (intermediate). The chemical composition of the chemically treated montmorillonite (intermediate) was Al = 7.68% by mass, Si = 36.05% by mass, Mg = 2.13% by mass, and Al / Si (molar ratio) = 0.222.
1545 g of distilled water was added to the cake to form a slurry, and the temperature was raised to 40 ° C. 5.734 g of lithium hydroxide / hydrate was added as a solid and reacted at 40 ° C. for 1 hour. After 1 hour, the reaction slurry was filtered and washed 3 times with 1 L of distilled water to obtain a cake-like solid again.
When the recovered cake was dried, 80 g of chemically treated montmorillonite was obtained. The chemical composition of this chemically treated montmorillonite is Al = 7.68% by mass, Si = 36.05% by mass, Mg = 2.13% by mass, Al / Si (molar ratio) = 0.222, Li = 0.53. It was% by mass.

(2-b) ^{Prepolymerization In a reactor having an internal volume of 1 m 3} , 150 kg of the chemically treated montmorillonite obtained as described above was placed, and 2832 L of hexane was added to form a slurry, which was 74.4 kg (375 mol) of triisobutylaluminum. Was added over 85 minutes and stirred for 60 minutes. After that, it was washed with hexane to 1/32, and the total volume was set to 900 L.
The slurry solution containing the chemically treated montmorillonite was kept at 50 ° C., and 0.65 kg of triisobutylaluminum (4.257 kg 3.28 mol of a hexane solution having a concentration of 15.3% by mass) was added thereto.
After stirring for 5 minutes, add 0.657 kg (0.81 mol) of rac-dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium and 96 L of toluene. , Continued stirring for 60 minutes.
Then, 9.758 kg (26.61 mol) of trinormal octyl aluminum was added and stirred for 6 minutes, and then 0.064 kg of triisobutylaluminum (concentration: 0.648 mass%) of toluene was added to 240 L of toluene in a container with another stirring device. To the place where 9.88 kg, 0.32 mol) was added, rac-dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl. }] The prepared solution was added by adding 1.768 kg (1.89 mol) of phenylium, 100 L of toluene was added, and stirring was continued for another 20 minutes.
After that, 2387 L of hexane was added to bring the internal temperature of the reactor to 40 ° C., and then 328.1 kg of propylene was fed over 240 minutes to perform prepolymerization while maintaining 40 ° C.
Then, the propylene feed was stopped and residual polymerization was carried out at 40 ° C. for 80 minutes.
After the completion of the residual polymerization, stirring was stopped and the contents were allowed to settle and settled. The supernatant was removed so that the solution volume became 1500 L, 12.7 kg of triisobutylaluminum was added, 3974 L of hexane was added again, and the mixture was stirred and then settled, and the supernatant was removed until the solution volume reached 1500 L.
To this, 8.9 kg of triisobutylaluminum (42.9 kg of a hexane solution having a concentration of 20.8 mass%) and 205 L of hexane were added.
Then, the reaction solution was transferred to a dryer and dried at 40 ° C. for 9 hours.
Then, 465 kg of the dry prepolymerization catalyst was obtained. The prepolymerization ratio (value obtained by dividing the amount of prepolymer by the amount of solid catalyst) was 2.10. This prepolymerization catalyst was designated as catalyst 1.

<Polymerization>
The 20 L autoclave was heated and dried well in advance by circulating nitrogen, and then the inside of the tank was replaced with propylene and cooled to room temperature. Triisobutylaluminum solution in heptane (140mg / mL) 18.7mL, after introducing the liquid propylene 5000g of _{H 2} after 0.85N (normal) L introduced, the temperature was raised to 63 ° C.. Then, 230 mg of the catalyst 1 excluding the prepolymerized polymer was pressure-fed to the polymerization tank with high-pressure argon to start polymerization, and the temperature was rapidly raised to 70 ° C. The temperature was maintained at 70 ° C., and 1 hour after the start of polymerization, unreacted propylene was quickly purged to terminate the polymerization. As a result, about 1730 g of polymer powder (PP-1) was obtained.
The catalytic activity was 7520 g-PP / g-catalyst. The MFR was 8.5 g / 10 minutes.

[Manufacturing Example 2 (Manufacturing of PP-2)]
<Polymerization>
The 20 L autoclave was heated and dried well in advance by circulating nitrogen, and then the inside of the tank was replaced with propylene and cooled to room temperature. Triisobutylaluminum solution in heptane (140mg / mL) 18.7mL, after introducing the liquid propylene 5000g of _{H 2} after 0.68N (normal) L introduced, the temperature was raised to 63 ° C.. Then, 310 mg of the catalyst 1 excluding the prepolymerized polymer was pressure-fed to the polymerization tank with high-pressure argon to start polymerization, and the temperature was rapidly raised to 70 ° C. The temperature was maintained at 70 ° C., and 1 hour after the start of polymerization, unreacted propylene was quickly purged to terminate the polymerization. As a result, about 22170 g of polymer powder (PP-2) was obtained.
The catalytic activity was 7000 g-PP / g-catalyst. The MFR was 3.1 g / 10 minutes.

<Manufacturing of pellets>
[Manufacturing of (X1-1)]
Tetrakiss [methylene-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propione-, which is a phenolic antioxidant, based on 100 parts by mass of the polymer powder (PP-1). G] methane (trade name: IRGANOX1010, manufactured by BASF Japan Co., Ltd.) 0.125 parts by mass, tris (2,4-di-t-butylphenyl) phosphite (trade name: IRGAFOS 168), which is a phosphite-based antioxidant. , BASF Japan Co., Ltd.) 0.125 parts by mass was mixed, mixed at room temperature for 3 minutes using a high-speed stirring mixer (Henshell mixer, trade name), and then melt-kneaded with a twin-screw extruder. Pellets (X1-1) of polypropylene resin (X1) were obtained.
For the twin-screw extruder, KZW-25 manufactured by Technobel Co., Ltd. is used, the screw rotation speed is 400 RPM, and the kneading temperature is 80 ° C, 160 ° C, 210v, 230 ° C from the bottom of the hopper (hereinafter, the same temperature up to the die outlet). It was set as.

[Manufacturing of (X1-2)]
Pellets (X1-2) were obtained by the same production method as (X1-1) except that the polymer powder (PP-2) was used.

The pellets (X1-1) and (X1-2) were evaluated for MFR, ¹³ C-NMR, GPC, branching index g', and melt tension (MT). The evaluation results are shown in Table 1.

(2) Polypropylene resin (X2)
Any of the polymers (X2-1) to (X2-3) produced in Production Examples 3 to 5 below was used.

[Manufacturing Example 3 (Manufacturing of PP-3)]
In Production Example 1, _{the same polymerization was carried out except that H 2} was 1.28 N (normal) L and the catalyst 1 had a mass of 220 mg excluding the prepolymerized polymer. As a result, about 2508 g of polymer powder (PP-3) was obtained.
The catalytic activity was 11400 g-PP / g-catalyst. The MFR was 60 g / 10 minutes.

[Manufacturing Example 4 (Manufacturing of PP-4)]
In Production Example 4, the following polymerization was carried out instead of the polymerization in Production Example 1. In a stirred high-pressure reactor having an internal volume of ^{100m 3 (L / D = 1.2} ), liquefied propylene 2 × ¹⁰ 4 kg / hr, triisobutylaluminum 80kg / hr, _{H 2} and 0.13 kg / hr, pre The polymerization catalyst 1 is continuously charged with a flow rate of 1.00 kg / hr as the mass excluding the prepolymerized polymer, the temperature is maintained at 70 ± 0.1 ° C., and the polymer slurry concentration in the polymerization reactor is 40 mass. Continuous polymerization was carried out so as to be maintained at%. Then, a polymer powder (PP-4) was obtained. The production amount of the polymer powder (PP-4) was 8.0 × 10 ³ kg / hr.

[Manufacturing Example 5 (Manufacturing of PP-5)]
In Production Example 3, _{the same polymerization was carried out except that H 2} was 1.105 N (normal) L and the catalyst 1 was 190 mg in mass excluding the prepolymerized polymer. As a result, about 1997 g of polymer powder (PP-5) was obtained.
The catalytic activity was 10510 g-PP / g-catalyst. The MFR was 32 g / 10 minutes.

<Manufacturing of pellets>
[Manufacturing of (X2-1)]
Tetrakiss [methylene-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propione-, which is a phenolic antioxidant, based on 100 parts by mass of the polymer powder (PP-3). G] methane (trade name: IRGANOX1010, manufactured by BASF Japan Co., Ltd.) 0.125 parts by mass, tris (2,4-di-t-butylphenyl) phosphite (trade name: IRGAFOS 168), which is a phosphite-based antioxidant. , BASF Japan Co., Ltd.) 0.125 parts by mass was mixed, mixed at room temperature for 3 minutes using a high-speed stirring mixer (Henshell mixer, trade name), and then melt-kneaded with a twin-screw extruder. Pellets (X2-1) of polypropylene resin (X2) were obtained.
For the twin-screw extruder, KZW-25 manufactured by Technobel Co., Ltd. is used, the screw rotation speed is 400 RPM, and the kneading temperature is 80 ° C, 160 ° C, 210 ° C, 230 ° C from the bottom of the hopper (hereinafter, the same temperature up to the die outlet). ) Was set.

[Manufacturing of (X2-2)]
Pellets (X2-2) were obtained by the same production method as (X2-1) except that the polymer powder (PP-4) was used.
[Manufacturing of (X2-3)]
Pellets (X2-3) were obtained by the same production method as (X2-1) except that the polymer powder (PP-5) was used.

The pellets (X2-1) to (X2-3) were evaluated for MFR, ¹³ C-NMR, GPC, branch index g', and melt tension (MT). The evaluation results are shown in Table 2.

(3) Polypropylene resin (Y)
As the polypropylene-based resin (Y), any of the following polypropylenes (Y-1) to (Y-4) was used. The MFR and melt tension (MT170 ° C.) of these (Y-1) to (Y-4) were evaluated. The evaluation results and the catalyst used are shown in Table 3. In Table 3, MT170 ° C. of (Y-1) to (Y-4) was below the detection limit, so it was set to less than 0.1.

(Y-1) [Production Example 3 (Production of Y-1)]: Nippon Polypro Co., Ltd., trade name "Wintech (registered trademark) WSX03", metallocene-catalyzed propylene-ethylene random copolymer (containing ethylene) Amount = 3.2% by mass, MFR = 25g / 10 minutes, Tm = 125 ° C.) 100 parts by mass of organic peroxide (2,5-dimethyl-2,5-di (t-butylperoxy) hexane) ) Add 0.05 parts by mass and mix with a Henshell mixer, then use a technobel "KZW-25" twin-screw extruder with a screw diameter of 25 mm, screw rotation speed of 300 rpm, and kneading temperature from under the hopper to C1 /. Pellets with Tm = 125 ° C. and MFR = 45 g / 10 minutes were obtained by melt extrusion at C2 / C3 to C7 / head / die = 150 ° C./180 ° C./230 ° C./230 ° C./180 ° C.

(Y-2): Made by Japan Polypropylene Corporation, trade name "Novatec (registered trademark) SA08", propylene homopolymer catalyzed by Ziegler-Natta, MFR = 80 g / 10 minutes, Tm = 161 ° C.
(Y-3): Made by Japan Polypropylene Corporation, trade name "Wintech (registered trademark) WSX03", metallocene-catalyzed propylene homopolymer, MFR = 25 g / 10 minutes, Tm = 125 ° C.
(Y-4): Made by Japan Polypropylene Corporation, trade name "Wintech (registered trademark) WFX4", metallocene-catalyzed propylene homopolymer, MFR = 7 g / 10 minutes, Tm = 125 ° C.

[Example 1]
1. 1. Blending Polypropylene resin (X1) is 10% by mass of (X1-1), polypropylene resin (X2) is 40% by mass of (X2-1), and polypropylene resin (Y) is 50% by mass of (Y-1). It was weighed in such a manner, put into a Henchel mixer, and stirred and mixed for 3 minutes.
2. 2. Using a technobel "KZW-25" twin-screw extruder with a granulation screw diameter of 25 mm, the screw rotation speed is 300 rpm, and the kneading temperature is C1 / C2 / C3 to C7 / head / die = 150 ° C / 180 ° C from the bottom of the hopper. Melting and kneading at / 230 ° C / 230 ° C / 180 ° C, the molten resin extruded from the strand die is taken up while being cooled and solidified in a cooling water tank, and the strand is cut into a diameter of 3 mm and a length of 2 mm using a strand cutter. As a result, pellets of the polypropylene-based resin composition were obtained. The MFR of the obtained pellets was evaluated.
3. 3. Production of Film The pellets of the obtained polypropylene-based resin composition were extruded from a T-die having a width of 560 mm mounted on an extruder having a diameter of 90 mmφ at a resin temperature of 290 ° C. to obtain a film. The extruded laminate moldability of the polypropylene resin composition and the physical characteristics of the film were evaluated.

[Example 2]
In Example 1, (X1-1) was 10% by mass as the polypropylene resin (X1), (X2-1) was 20% by mass as the polypropylene resin (X2), and (Y-1) was used as the polypropylene resin (Y). The film was produced in the same manner as in Example 1 except that the content was 70% by mass.

[Example 3]
In Example 1, (X1-1) was 10% by mass as the polypropylene resin (X1), (X2-1) was 80% by mass as the polypropylene resin (X2), and (Y-1) was used as the polypropylene resin (Y). The film was produced in the same manner as in Example 1 except that the content was 10% by mass.

[Example 4]
In Example 1, (X1-1) was 10% by mass as the polypropylene resin (X1), (X2-1) was 40% by mass as the polypropylene resin (X2), and (Y-3) was used as the polypropylene resin (Y). The film was produced in the same manner as in Example 1 except that the content was 50% by mass.

[Example 5]
In Example 1, (X1-1) was 20% by mass as the polypropylene resin (X1), (X2-1) was 30% by mass as the polypropylene resin (X2), and (Y-1) was used as the polypropylene resin (Y). The film was produced in the same manner as in Example 1 except that the content was 50% by mass.

[Example 6]
In Example 1, (X1-2) is 5% by mass as the polypropylene resin (X1), (X2-1) is 45% by mass as the polypropylene resin (X2), and (Y-1) is used as the polypropylene resin (Y). The film was produced in the same manner as in Example 1 except that the content was 50% by mass.

[Example 7]
In Example 1, (X1-2) was 2.5% by mass as the polypropylene resin (X1), (X2-2) was 27.5% by mass as the polypropylene resin (X2), and (Y) was the polypropylene resin (Y). The film was produced in the same manner as in Example 1 except that -1) was 70% by mass.

[Example 8]
In Example 1, (X1-2) was 5% by mass as the polypropylene resin (X1), (X2-3) was 25% by mass as the polypropylene resin (X2), and (Y-1) was used as the polypropylene resin (Y). The film was produced in the same manner as in Example 1 except that the content was 70% by mass.

[Comparative Example 1]
In Example 1, the film is formed in the same manner as in Example 1 except that (X1-1) is 30% by mass as the polypropylene resin (X1) and (Y-2) is 70% by mass as the polypropylene resin (Y). Was manufactured.

[Comparative Example 2]
In Example 1, the same method as in Example 1 is used except that (X2-1) is 50% by mass as the polypropylene resin (X2) and (Y-4) is 50% by mass as the polypropylene resin (Y). Manufactured the film.

Table 4 shows the evaluation results of the ratio of each resin of Examples and Comparative Examples, the MFR of the pellets of the polypropylene-based resin composition, the extruded laminate moldability, and the physical properties of the film.

As for the extruded laminate moldability of Examples 1 to 8, the polypropylene resin (X1), the polypropylene resin (X2) and the polypropylene resin (Y) contained in the polypropylene resin composition all satisfy the specific physical properties of the present invention. Therefore, the spreadability was good. In addition, both neck-in and transparency were excellent.
Comparative Example 1 does not contain polypropylene resin (X2) and does not have a polypropylene component having a highly fluid branched structure. Therefore, even if it is mixed with highly fluid polypropylene resin (Y-2), it has ductility. The result was low, insufficient melt tension, and large neck-in. In Comparative Example 2, since the polypropylene resin (X1) was not contained and the fluidity of the polypropylene resin (Y-4) was low, the neck-in was good, but the ductility was extremely low. rice field.

Claims (26)

Polypropylene resin (X1) having the following characteristics (X1-1) to (X1-6), and
Polypropylene resin (X2) having the following characteristics (X2-1) to (X2-6), and
Polypropylene resin composition containing.
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 80 g / 10 minutes or less.
(X1-2) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by GPC is 2.0 or more and 5.0 or less, and the Z average molecular weight (Mz). The ratio (Mz / Mw) of the weight average molecular weight (Mw) to the weight average molecular weight (Mw) is 2.0 or more and 5.0 or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 0.5% by mass or more.
(X1-4) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirement (Equation 1).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.0 (Equation 1)
(X1-5) The branch index g'(Mz _abs ) measured by GPC is 0.70 or more and 0.95 or less.
(X1-6) ¹³ The triad fraction (mm) of 3 chains of propylene units by C-NMR is 95% or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 80 g / 10 minutes or less.
(X2-2) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by GPC is 2.0 or more and 5.0 or less, and the Z average molecular weight (Mz). The ratio (Mz / Mw) of the weight average molecular weight (Mw) to the weight average molecular weight (Mw) is 2.0 or more and 5.0 or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion (W _1M ) of the components having a molecular weight of 1 million or more is 0.5% by mass or more.
(X2-4) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirement (Equation 1).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.0 (Equation 1)
(X2-5) The branch index g'(Mz _abs ) measured by GPC is 0.70 or more and 0.95 or less.
(X2-6) ¹³ The triad fraction (mm) of 3 chains of propylene units by C-NMR is 95% or more.
However, MFR of X1 <MFR of X2, W _1M of _{X1 ≧ W 1M of X2.} The polypropylene-based resin composition according to claim 1, further comprising a polypropylene-based resin (Y) having the following characteristics (Y-1) to (Y-2).
(Y-1) MFR (230 ° C., load 2.16 kgf) is 10 g / 10 minutes or more and 50 g / 10 minutes or less.
(Y-2) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirements (formula A).
log (MT170 ° C) <-1.1 x log (MFR) +2.0 (Formula A) It contains 5% by mass to 30% by mass of polypropylene resin (X1), 5% by mass to 50% by mass of polypropylene resin (X2), and 20% by mass to 80% by mass of polypropylene resin (Y) (however, polypropylene resin (X1). ), The polypropylene resin (X2) and the polypropylene resin (Y) are 100% by mass.), The polypropylene resin composition according to claim 2. The polypropylene resin (X1) has the following characteristics (X1-1) and (X1-3).
The polypropylene-based resin composition according to any one of claims 1 to 3, wherein the polypropylene resin (X2) has the following characteristics (X2-1) and (X2-3).
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 30 g / 10 minutes or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 2.5% by mass or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 30 g / 10 minutes and 80 g / 10 minutes or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion (W _1M ) of the components having a molecular weight of 1 million or more is 0.5% by mass or more and less than 2.5% by mass. The polypropylene resin (X1) has the following characteristics (X1-1) and (X1-3).
The polypropylene-based resin composition according to claim 1 or 2, wherein the polypropylene resin (X2) has the following characteristics (X2-1) and (X2-3).
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 10 g / 10 minutes or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 3.5% by mass or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 10 g / 10 minutes and 80 g / 10 minutes or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion (W _1M ) of the components having a molecular weight of 1 million or more is 0.5% by mass or more and less than 3.5% by mass. It contains 2% by mass to 30% by mass of polypropylene resin (X1), 5% by mass to 98% by mass of polypropylene resin (X2), and 0% by mass to 80% by mass of polypropylene resin (Y) (however, polypropylene resin (X1). ), The polypropylene resin (X2) and the polypropylene resin (Y) are 100% by mass.), The polypropylene resin composition according to claim 1, 2 or 5. The polypropylene-based resin composition according to any one of claims 1 to 6, which is used for extrusion laminating. A step of obtaining a polypropylene resin (X1) having the following characteristics (X1-1) to (X1-6),
A step of obtaining a polypropylene resin (X2) having the following characteristics (X2-1) to (X2-6), and a step of mixing or melt-kneading the polypropylene resin (X1) and the polypropylene resin (X2).
A method for producing a polypropylene-based resin composition having the above.
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 80 g / 10 minutes or less.
(X1-2) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by GPC is 2.0 or more and 5.0 or less, and the Z average molecular weight (Mz). The ratio (Mz / Mw) between the weight average molecular weight (Mw) and the weight average molecular weight (Mw) is 2.0 or more and 5.0 or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 0.5% by mass or more.
(X1-4) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirement (Equation 1).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.0 (Equation 1)
(X1-5) The branch index g'(Mz _abs ) measured by GPC is 0.70 or more and 0.95 or less.
(X1-6) ¹³ The triad fraction (mm) of 3 chains of propylene units by C-NMR is 95% or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 80 g / 10 minutes or less.
(X2-2) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by GPC is 2.0 or more and 5.0 or less, and the Z average molecular weight (Mz). The ratio (Mz / Mw) between the weight average molecular weight (Mw) and the weight average molecular weight (Mw) is 2.0 or more and 5.0 or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion (W _1M ) of the components having a molecular weight of 1 million or more is 0.5% by mass or more.
(X2-4) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirement (Equation 1).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.0 (Equation 1)
(X2-5) The branch index g'(Mz _abs ) measured by GPC is 0.70 or more and 0.95 or less.
(X2-6) ¹³ The triad fraction (mm) of 3 chains of propylene units by C-NMR is 95% or more.
However, MFR of X1 <MFR of X2, W _1M of _{X1 ≧ W 1M of X2.} Further, the step of obtaining a polypropylene-based resin (Y) having the following characteristics (Y-1) to (Y-2) is included.
The polypropylene-based product according to claim 8, wherein the mixing or melt-kneading step is a step of mixing or melt-kneading the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene-based resin (Y). A method for producing a resin composition.
(Y-1) MFR (230 ° C., load 2.16 kgf) is 10 g / 10 minutes or more and 50 g / 10 minutes or less.
(Y-2) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirements (formula A).
log (MT170 ° C) <-1.1 x log (MFR) +2.0 (Formula A) In the step of mixing or melt-kneading, the polypropylene resin (X1) is 5% by mass to 30% by mass, the polypropylene resin (X2) is 5% by mass to 50% by mass, and the polypropylene resin (Y) is 20% by mass to 80% by mass. % Is mixed or melt-kneaded (however, the total amount of the polypropylene resin (X1), the polypropylene resin (X2) and the polypropylene-based resin (Y) is 100% by mass), according to claim 9. A method for producing a polypropylene-based resin composition. The polypropylene resin (X1) has the following characteristics (X1-1) and (X1-3).
The method for producing a polypropylene-based resin composition according to any one of claims 8 to 10, wherein the polypropylene resin (X2) has the following characteristics (X2-1) and (X2-3).
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 30 g / 10 minutes or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 2.5% by mass or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 30 g / 10 minutes and 80 g / 10 minutes or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion (W _1M ) of the components having a molecular weight of 1 million or more is 0.5% by mass or more and less than 2.5% by mass. The polypropylene resin (X1) has the following characteristics (X1-1) and (X1-3).
The method for producing a polypropylene-based resin composition according to claim 8 or 9, wherein the polypropylene resin (X2) has the following characteristics (X2-1) and (X2-3).
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 10 g / 10 minutes or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 3.5% by mass or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 10 g / 10 minutes and 80 g / 10 minutes or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion (W _1M ) of the components having a molecular weight of 1 million or more is 0.5% by mass or more and less than 3.5% by mass. In the mixing or melt-kneading step, the polypropylene resin (X1) is 2% by mass to 30% by mass, the polypropylene resin (X2) is 5% by mass to 98% by mass, and the polypropylene resin (Y) is 0% by mass to 80% by mass. % Is mixed or melt-kneaded (however, the total amount of the polypropylene resin (X1), the polypropylene resin (X2) and the polypropylene-based resin (Y) is 100% by mass), claim 8 and 9. Or the method for producing a polypropylene-based resin composition according to 12. The method for producing a polypropylene-based resin composition according to any one of claims 8 to 13, which is used for extrusion laminating. A laminate containing a base material layer and a polypropylene-based resin composition layer.
The polypropylene-based resin composition layer is a polypropylene resin (X1) having the following characteristics (X1-1) to (X1-6) and a polypropylene resin having the following characteristics (X2-1) to (X2-6). A laminate comprising (X2) and.
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 80 g / 10 minutes or less.
(X1-2) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by GPC is 2.0 or more and 5.0 or less, and the Z average molecular weight (Mz). The ratio (Mz / Mw) between the weight average molecular weight (Mw) and the weight average molecular weight (Mw) is 2.0 or more and 5.0 or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 0.5% by mass or more.
(X1-4) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirement (Equation 1).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.0 (Equation 1)
(X1-5) The branch index g'(Mz _abs ) measured by GPC is 0.70 or more and 0.95 or less.
(X1-6) ¹³ The triad fraction (mm) of 3 chains of propylene units by C-NMR is 95% or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 80 g / 10 minutes or less.
(X2-2) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by GPC is 2.0 or more and 5.0 or less, and the Z average molecular weight (Mz). The ratio (Mz / Mw) between the weight average molecular weight (Mw) and the weight average molecular weight (Mw) is 2.0 or more and 5.0 or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion (W _1M ) of the components having a molecular weight of 1 million or more is 0.5% by mass or more.
(X2-4) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirement (Equation 1).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.0 (Equation 1)
(X2-5) The branch index g'(Mz _abs ) measured by GPC is 0.70 or more and 0.95 or less.
(X2-6) ¹³ The triad fraction (mm) of 3 chains of propylene units by C-NMR is 95% or more.
However, MFR of X1 <MFR of X2, W _1M of _{X1 ≧ W 1M of X2.} The laminate according to claim 15, wherein the polypropylene-based resin composition layer further contains a polypropylene-based resin (Y) having the following characteristics (Y-1) to (Y-2).
(Y-1) MFR (230 ° C., load 2.16 kgf) is 10 g / 10 minutes or more and 50 g / 10 minutes or less.
(Y-2) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirements (formula A).
log (MT170 ° C) <-1.1 x log (MFR) +2.0 (Formula A) The polypropylene-based resin composition layer comprises 5% by mass to 30% by mass of the polypropylene resin (X1), 5% by mass to 50% by mass of the polypropylene resin (X2), and 20% by mass to 80% by mass of the polypropylene-based resin (Y). % (However, the total amount of the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene-based resin (Y) is 100% by mass), according to claim 16. The polypropylene resin (X1) has the following characteristics (X1-1) and (X1-3).
The laminate according to any one of claims 15 to 17, wherein the polypropylene resin (X2) has the following characteristics (X2-1) and (X2-3).
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 30 g / 10 minutes or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 2.5% by mass or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 30 g / 10 minutes and 80 g / 10 minutes or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion (W _1M ) of the components having a molecular weight of 1 million or more is 0.5% by mass or more and less than 2.5% by mass. The polypropylene resin (X1) has the following characteristics (X1-1) and (X1-3).
The laminate according to claim 15 or 16, wherein the polypropylene resin (X2) has the following characteristics (X2-1) and (X2-3).
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 10 g / 10 minutes or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 3.5% by mass or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 10 g / 10 minutes and 80 g / 10 minutes or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion (W _1M ) of the components having a molecular weight of 1 million or more is 0.5% by mass or more and less than 3.5% by mass. The polypropylene-based resin composition layer has 2% by mass to 30% by mass of the polypropylene resin (X1), 5% by mass to 98% by mass of the polypropylene resin (X2), and 0% by mass to 80% by mass of the polypropylene-based resin (Y). % (However, the total amount of the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene-based resin (Y) is 100% by mass), according to claim 15, 16 or 19. body. A method for producing a laminate including a base material layer and a polypropylene-based resin composition layer.
A polypropylene resin (X1) having the following characteristics (X1-1) to (X1-6) and a polypropylene resin having the following characteristics (X2-1) to (X2-6) on at least one surface of the base material layer (X2-1) to (X2-6). A method for producing a laminate, which comprises a step of forming the polypropylene-based resin composition layer by extruding and laminating a mixture of X2) and a melt-kneaded product.
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 80 g / 10 minutes or less.
(X1-2) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by GPC is 2.0 or more and 5.0 or less, and the Z average molecular weight (Mz). The ratio (Mz / Mw) between the weight average molecular weight (Mw) and the weight average molecular weight (Mw) is 2.0 or more and 5.0 or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 0.5% by mass or more.
(X1-4) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirement (Equation 1).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.0 (Equation 1)
(X1-5) The branch index g'(Mz _abs ) measured by GPC is 0.70 or more and 0.95 or less.
(X1-6) ¹³ The triad fraction (mm) of 3 chains of propylene units by C-NMR is 95% or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 80 g / 10 minutes or less.
(X2-2) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by GPC is 2.0 or more and 5.0 or less, and the Z average molecular weight (Mz). The ratio (Mz / Mw) between the weight average molecular weight (Mw) and the weight average molecular weight (Mw) is 2.0 or more and 5.0 or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion (W _1M ) of the components having a molecular weight of 1 million or more is 0.5% by mass or more.
(X2-4) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirement (Equation 1).
log (MT170 ° C) ≧ −1.1 × log (MFR) +2.0 (Equation 1)
(X2-5) The branch index g'(Mz _abs ) measured by GPC is 0.70 or more and 0.95 or less.
(X2-6) ¹³ The triad fraction (mm) of 3 chains of propylene units by C-NMR is 95% or more.
However, MFR of X1 <MFR of X2, W _1M of _{X1 ≧ W 1M of X2.} In the step of forming the polypropylene-based resin composition layer, the polypropylene resin (X1), the polypropylene resin (X2), and the following characteristics (Y-1) to (Y) are further formed on at least one surface of the base material layer. The method for producing a laminate according to claim 21, which is a step of forming the polypropylene-based resin composition layer by extruding and laminating a mixture or a melt-kneaded product of the polypropylene-based resin (Y) having -2). ..
(Y-1) MFR (230 ° C., load 2.16 kgf) is 10 g / 10 minutes or more and 50 g / 10 minutes or less.
(Y-2) The melting tension (MT170 ° C.) (unit: g) measured at 170 ° C. satisfies the following requirements (formula A).
log (MT170 ° C) <-1.1 x log (MFR) +2.0 (Formula A) In the step of forming the polypropylene-based resin composition layer, the polypropylene resin (X1) is 5% by mass to 30% by mass, the polypropylene resin (X2) is 5% by mass to 50% by mass, and the polypropylene resin (Y) is formed. Extruded a mixture or melt-kneaded product of 20% by mass to 80% by mass (however, the total amount of the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene-based resin (Y) is 100% by mass). The method for producing a laminated body according to claim 22, which is a step of forming the polypropylene-based resin composition layer by laminating. The polypropylene resin (X1) has the following characteristics (X1-1) and (X1-3).
The method for producing a laminate according to any one of claims 21 to 23, wherein the polypropylene resin (X2) has the following characteristics (X2-1) and (X2-3).
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 30 g / 10 minutes or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 2.5% by mass or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 30 g / 10 minutes and 80 g / 10 minutes or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion (W _1M ) of the components having a molecular weight of 1 million or more is 0.5% by mass or more and less than 2.5% by mass. The polypropylene resin (X1) has the following characteristics (X1-1) and (X1-3).
The method for producing a laminate according to claim 21 or 22, wherein the polypropylene resin (X2) has the following characteristics (X2-1) and (X2-3).
(X1-1) MFR (230 ° C., load 2.16 kgf) is more than 0.5 g / 10 minutes and 10 g / 10 minutes or less.
(X1-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion of components having a molecular weight of 1 million or more (W _1M ) is 3.5% by mass or more.
(X2-1) MFR (230 ° C., load 2.16 kgf) is more than 10 g / 10 minutes and 80 g / 10 minutes or less.
(X2-3) In the integrated molecular weight distribution curve obtained by GPC, the proportion (W _1M ) of the components having a molecular weight of 1 million or more is 0.5% by mass or more and less than 3.5% by mass. The steps for forming the polypropylene-based resin composition layer include the polypropylene resin (X1) of 2% by mass to 30% by mass, the polypropylene resin (X2) of 5% by mass to 98% by mass, and the polypropylene-based resin (Y). Extruded a mixture of 0% by mass to 80% by mass or a melt-kneaded product (however, the total amount of the polypropylene resin (X1), the polypropylene resin (X2), and the polypropylene-based resin (Y) is 100% by mass). The method for producing a laminate according to claim 21, 22 or 25, which is a step of forming the polypropylene-based resin composition layer by laminating.