JPWO2017018461A1 - Uniaxially stretched molded product and its production method - Google Patents

Abstract

(A) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min. Using an olefin polymer (A) having a melting point (Tm-D) defined as the observed peak top (Tm-D) exceeding 120 ° C. and (b) a differential scanning calorimeter (DSC), the sample was placed in a nitrogen atmosphere − The melting endotherm (ΔH−D) obtained from the melting endotherm curve obtained by holding at 10 ° C. for 5 minutes and then raising the temperature at 10 ° C./min is 0 to 80 J / g, and the molecular weight distribution (Mw / A uniaxially stretched molded product comprising a polyolefin composition containing an olefin polymer (B) having a Mn) of less than 3.0.

Description

  The present invention relates to a uniaxially stretched molded product and a method for producing the same.

  Examples of the uniaxially stretched product include monofilaments, bands, stretched tapes, slit yarns that are slit along the stretching direction (longitudinal direction) and stretched while heating (hereinafter also referred to as “flat yarns”), and blades Examples thereof include a split yarn that is an aggregate fiber in which singles are connected in a mesh pattern to a split made discontinuous by a group (a rotary blade or a rotary brush).

On the other hand, polypropylene resins are excellent in strength, rigidity, heat resistance, chemical stability, and the like. Therefore, uniaxially stretched molded products such as flat yarns, monofilaments, and bands made of polypropylene resin are excellent in mechanical strength and are widely used as industrial materials such as various bags, cross sheets, ropes, nets, and bundles. Yes.
For example, a flat yarn is generally obtained by slitting an unstretched raw fabric and stretching the slit film. Here, when the film is stretched at a high stretch ratio in order to promote molecular orientation and increase the strength, breakage during production due to uneven thickness may occur.
Further, in order to increase the strength, the draw ratio is increased, so that the elongation of the flat yarn itself may deteriorate and the toughness may be impaired. In that case, the woven fabric produced by weaving a flat yarn having a high draw ratio has a drawback of becoming brittle when a large deformation is applied.
In order to improve the elongation of the flat yarn, a method of reducing the draw ratio is usually used. However, in this case, the uneven thickness accuracy and strength are lowered, and therefore it is not appropriate. Therefore, it has been desired to improve the balance between strength and elongation of the flat yarn obtained.

Therefore, for example, as a method of increasing the strength of the uniaxially stretched molded product, a method of stretching at a higher magnification using a higher molecular weight polypropylene has been proposed.
In order to facilitate stretching at a high magnification, it is important to obtain an unstretched original fabric having uniform physical properties. However, when high molecular weight polypropylene is used, the flow resistance at the time of melt extrusion is large, so it is easy to cause surging and melt fracture, and it is difficult to obtain a uniform unstretched raw material such as surface state and crystallinity. .
As an aid to solving the above problem, in Patent Document 1, 0.01 to 0.10 parts by weight of an organic peroxide is added to 100 parts by weight of polypropylene, and 2 ° C. at 180 to 300 ° C. using an extruder or the like. 2-10 parts by weight of crystalline polypropylene (B) having a melt flow rate (hereinafter also referred to as “MFR”) of 3 to 15 g / 10 min and a Q value of 3.5 or less. A polypropylene composition for stretch molding is proposed in which 100 parts by weight of crystalline polypropylene (A) having a melt flow rate of 0.3 to 2.0 g / 10 min and a Q value of 5 to 8 is mixed.

  However, the polypropylene composition for stretch molding contains an organic peroxide, and has a defect that deterioration starts from the organic peroxide. On the other hand, the polypropylene composition for stretch molding is produced. At this time, it is necessary to pay sufficient attention to the handling of the organic peroxide, and there is a problem that the operation becomes complicated.

JP-A-2-308839

  The present invention has been made in view of the above circumstances, and provides a uniaxially stretched molded product excellent in the balance of elastic modulus, elongation at break, rupture strength, and thickness deviation accuracy compared to conventional uniaxially stretched molded products, and a method for producing the same. It is intended.

As a result of intensive studies, the present inventors have achieved the above object by blending the olefin polymer (B) having a specific structure with a relatively low melting endotherm into the polyolefin composition. I found out. The present invention has been completed based on such findings.
That is, the present invention provides the following inventions.
[1] A uniaxially stretched molded article comprising a polyolefin-based composition containing the following components (a) and (b).
(A) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min. Olefin polymer (A) whose melting point (Tm-D) defined as the observed peak top exceeds 120 ° C
(B) Using a differential scanning calorimeter (DSC), the sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 10 ° C./min. Olefin polymer (B) having a calorific value (ΔH-D) of 0 to 80 J / g and a molecular weight distribution (Mw / Mn) of less than 3.0
[2] The [b] component of the polyolefin-based composition is 0.5% by mass or more and less than 50% by mass with respect to 100% by mass of the total amount of the (a) and (b) components. 1].
[3] The uniaxially stretched molded article according to the above [1] or [2], wherein the olefin polymer (A) is a propylene polymer (a1).
[4] Any one of the above [1] to [3], wherein 50 mol% or more of the monomer constituting the olefin polymer (B) is a propylene polymer (b1) composed of a propylene monomer. The uniaxially stretched molded product described in 1.
[5] The uniaxially stretched molded article according to the above [4], wherein the propylene polymer (b1) satisfies the following (i) and / or (ii).
(I) The structural unit of ethylene is contained in excess of 0 mol% and 20 mol% or less.
(Ii) The structural unit of 1-butene is contained in an amount exceeding 0 mol% and not more than 30 mol%.
[6] The uniaxially stretched molded article according to the above [4], wherein the propylene polymer (b1) satisfies the following (1).
(1) Mesopentad fraction [mmmm] is 20 to 60 mol%.
[7] The uniaxially stretched molded product according to any one of [4] to [6], wherein the propylene polymer (b1) satisfies the following (2).
(2) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min. The melting point (Tm-D) defined as the observed peak top is 0-120 ° C.
[8] A flat yarn, monofilament, band, split yarn, or tape comprising the uniaxially stretched molded product according to any one of [1] to [7].
[9] The uniaxially stretched molded article according to any one of the above [1] to [7], which is at least one selected from the group consisting of flat yarn, monofilament, band, split yarn and tape.
[10] A sheet comprising the uniaxially stretched molded product obtained by knitting the uniaxially stretched molded product according to any one of the above [1] to [7].
[11] A sheet made of a knitted uniaxially stretched molded product according to any one of [1] to [7].
[12] A uniaxial film in which both front and back surfaces are made flat using an olefin-based composition containing the following components (a) and (b), the produced film is slit, and the slit film is stretched while being heated. A method for producing a stretched molded product.
(A) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min. Olefin polymer (A) whose melting point (Tm-D) defined as the observed peak top exceeds 120 ° C
(B) Using a differential scanning calorimeter (DSC), the sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 10 ° C./min. Olefin polymer (B) having a calorific value (ΔH-D) of 0 to 80 J / g and a molecular weight distribution (Mw / Mn) of less than 3.0

  According to the present invention, it is possible to provide a uniaxially stretched molded article and a method for producing the same, which are superior in balance of elastic modulus, elongation at break, rupture strength, and thickness accuracy compared to conventional uniaxially stretched molded articles.

  The present invention is described below. In this specification, the term “A to B” relating to the description of numerical values means “A or more and B or less” (when A <B) or “A or less and B or more” (when A> B). . Moreover, in this invention, the combination of a preferable aspect is a more preferable aspect. In the present specification, the component (a) and the olefin polymer (A) are synonymous with the component (b) and the olefin polymer (B).

[Uniaxially stretched molded product]
As described above, the “uniaxially stretched molded product” in the present invention is a “slit yarn” (hereinafter referred to as “slit yarn”) that is slit along the monofilament, band, stretched tape, stretch direction (longitudinal direction) and heated. The term “flat yarn”) and “split yarn” which is an aggregated fiber in which singles are connected in a mesh form to a split made discontinuous by a blade group (rotating blade or rotating brush) are used.

The uniaxially stretched molded product of the present invention comprises a polyolefin-based composition containing the following components (a) and (b).
(A) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min. Olefin polymer (A) whose melting point (Tm-D) defined as the observed peak top exceeds 120 ° C
(B) Using a differential scanning calorimeter (DSC), the sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 10 ° C./min. Olefin polymer (B) having a calorific value (ΔH-D) of 0 to 80 J / g and a molecular weight distribution (Mw / Mn) of less than 3.0

In addition, the uniaxially stretched molded product of the present invention is such that the component (b) of the polyolefin-based composition is 100% by mass with respect to the total amount of the components (a) and (b), and the elastic modulus, elongation at break and fracture. From the viewpoint of improving the balance between strength and uneven thickness accuracy, it is preferably 0.5% by mass or more and less than 50% by mass, more preferably 0.5% by mass or more and less than 20% by mass, and still more preferably 0.5% by mass. It is more than 1 mass% and less than 15 mass%, More preferably, it is 1 mass% or more and less than 10 mass%.
Hereafter, each component used for this invention and a manufacturing method are demonstrated one by one.

<Olefin polymer (A)>
The olefin polymer (A), which is the component (a) used in the present invention, was held at −10 ° C. for 5 minutes in a nitrogen atmosphere using a differential scanning calorimeter (DSC), and then 10 ° C./min. The melting point (Tm-D) defined as the peak top that is observed on the highest temperature side of the melting endothermic curve obtained by raising the temperature at 150 ° C. exceeds 120 ° C. When the melting point (Tm-D) is 120 ° C. or lower, there is a problem that the heat resistance of a molded article using the polyolefin-based composition, for example, a uniaxially stretched molded article, for example, a flat yarn is inferior. From such a viewpoint, the melting point (Tm-D) is preferably 125 ° C. or higher, more preferably 140 ° C. or higher, still more preferably 150 ° C. or higher, and still more preferably 160 ° C. or higher.
In addition, this melting | fusing point (Tm-D) is a value measured by the method as described in the Example mentioned later.

The olefin polymer (A) of the present embodiment is preferably an olefin polymer obtained by polymerizing one or more monomers selected from, for example, ethylene and an α-olefin having 3 to 28 carbon atoms.
Examples of the α-olefin having 3 to 28 carbon atoms include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene and 1- Examples include dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene and 1-icocene. Among these, Preferably it is C3-C24 alpha-olefin, More preferably, it is C3-C12 alpha-olefin, More preferably, it is C3-C6 alpha-olefin, Most preferably, it is C3-C4 An α-olefin, most preferably propylene.
An olefin polymer obtained by polymerizing one of these alone may be used, or an olefin copolymer obtained by copolymerizing two or more of them may be used. In the present specification, the term “olefin polymer” includes an olefin copolymer. Examples of the olefin copolymer include an ethylene polymer in which 50 mol% or more of the monomers constituting the polymer are ethylene monomers, and a propylene polymer in which 50 mol% or more of the monomers constituting the polymer are propylene monomers ( a1), butene-based polymers in which 50 mol% or more of monomers constituting the polymer are butene monomers, and the like, and excellent molded article physical properties from the viewpoint of rigidity and heat resistance, for example, uniaxially stretched molded article The resulting propylene polymer (a1) is more preferred. Furthermore, the propylene polymer (a1) preferably has a mesopentad fraction [mmmm] described later of 70 to 99.5 mol%, more preferably 80 to 99 mol%, from the viewpoint of improving rigidity and heat resistance. More preferably, it is 85-98 mol%, More preferably, it is 87-97 mol%, Most preferably, it is 90-97 mol%.
As propylene polymer (a1), propylene homopolymer, propylene-ethylene block copolymer, propylene-butene block copolymer, propylene-α-olefin block copolymer, propylene-ethylene random copolymer, propylene A propylene-based polymer (a1) selected from a -butene random copolymer, a propylene-α-olefin random copolymer, a propylene-α-olefin graft copolymer, and the like is preferable. Furthermore, the propylene polymer (a1) of the present invention is particularly preferably a propylene-ethylene random copolymer or propylene alone from the viewpoint of the physical properties of the molded body, for example, the physical properties (for example, mechanical properties) of the uniaxially stretched molded product. It is a polymer. The polymer may be a polymer using a petroleum / coal-derived monomer or a polymer using a biomass-derived monomer.

  As content of the olefin polymer (A) in a polyolefin-type composition, it is 50 with respect to the total content of 100 mass% of the olefin polymer (B) mentioned later and the said olefin polymer (A). It is at least mass%. When the content is less than 50% by mass, the uniaxially stretched molded product using the polyolefin-based composition has a problem that heat resistance is lowered. From such a viewpoint, the content of the olefin polymer (A) in the polyolefin composition is 100 total content of the olefin polymer (B) and the olefin polymer (A) described later. Preferably it is 80 mass% or more with respect to the mass%, More preferably, it is 85 mass% or more, More preferably, it is 90 mass%. Further, from the viewpoint of heat resistance of a uniaxially stretched molded product using the polyolefin-based composition, it is preferably 98% by mass or less, more preferably 95% by mass or less.

<Olefin polymer (B)>
The olefin polymer (B), which is the component (b) used in the present invention, was held at −10 ° C. for 5 minutes in a nitrogen atmosphere using a differential scanning calorimeter (DSC), then 10 ° C./min. The melting endotherm (ΔH-D) obtained from the melting endotherm curve obtained by raising the temperature at 0 to 0-80 J / g, and the molecular weight distribution (Mw / Mn) is less than 3.0.
The olefin polymer (B) of the present invention is preferably an olefin polymer (B) obtained by polymerizing one or more monomers selected from ethylene and an α-olefin having 3 to 28 carbon atoms.
Examples of the α-olefin having 3 to 28 carbon atoms include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene and 1- Examples include dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene and 1-icocene. Among these, Preferably it is C3-C24 alpha-olefin, More preferably, it is C3-C12 alpha-olefin, More preferably, it is C3-C6 alpha-olefin, Most preferably, it is C3-C4 An α-olefin, most preferably propylene.
An olefin polymer (B) obtained by polymerizing one of these alone may be used, or an olefin copolymer (B) obtained by copolymerizing two or more in combination. Also good. As the olefin copolymer (B), an ethylene polymer in which 50 mol% or more of the monomers constituting the polymer is an ethylene monomer, or a propylene polymer in which 50 mol% or more of the monomers constituting the polymer is a propylene monomer Examples include polymer (b1), butene-based polymers in which 50 mol% or more of the monomers constituting the polymer are butene monomers, and the like, and excellent molded article properties from the viewpoint of suppressing stretching unevenness, for example, uniaxially stretched molded articles The propylene-based polymer (b1) that can obtain physical properties is more preferable.
As propylene polymer (b1), propylene homopolymer, propylene-ethylene block copolymer, propylene-butene block copolymer, propylene-α-olefin block copolymer, propylene-ethylene random copolymer, propylene It is preferably a propylene polymer (b1) selected from a butene random copolymer, a propylene-α-olefin random copolymer, a propylene-α-olefin graft copolymer, and the like, and in particular, a propylene homopolymer Is preferred.

  Moreover, in the polyolefin-type composition of this invention, when the olefin polymer (A) which is a main component is a propylene-type polymer (a1), a compatible viewpoint with the main component propylene-type polymer (a1). In the case where the propylene polymer (b1) is a copolymer containing an olefin having 2 carbon atoms, the constituent unit of the olefin having 2 carbons (that is, ethylene monomer) is preferably 0 mol%. More than 20 mol%, more preferably more than 0 mol%, less than 18 mol%, still more preferably more than 0 mol%, less than 15 mol%, still more preferably more than 0 mol% and less than 13 mol% It is. In the case of a copolymer containing an olefin having 3 carbon atoms, the constituent unit of the olefin having 3 carbon atoms (that is, propylene monomer) is preferably 50 mol% or more, more preferably 65 mol% or more. More preferably, it is 75 mol% or more, and still more preferably 80 mol% or more. In the case of a copolymer containing an α-olefin having 4 or more carbon atoms, the content of the α-olefin having 4 or more carbon atoms is preferably more than 0 mol% and not more than 30 mol%, more preferably It is more than 0 mol% and not more than 27 mol%, more preferably more than 0 mol% and not more than 20 mol%. Moreover, in the polyolefin-type composition of this invention, when the olefin polymer (A) which is a main component is a propylene-type polymer (a1), a compatible viewpoint with the main component propylene-type polymer (a1). From the above, the olefin polymer (B) of the present invention is most preferably a propylene homopolymer. The polymer may be a polymer using a petroleum / coal-derived monomer or a polymer using a biomass-derived monomer.

Since the polyolefin-based composition of the present invention contains the olefin-based polymer (B), the proportion of the amorphous component is increased, and the yield stress when the polyolefin-based composition is stretched is reduced. And the tenacity of the resulting uniaxially stretched molded product, such as flat yarn, is improved.
In particular, from the viewpoint of greatly improving the uniform stretchability of the polyolefin-based composition, in order to increase the ratio of the amorphous component in the polyolefin-based composition, the content of the olefin-based polymer (B) is The total content of the polymer (B) and the olefin polymer (A) is preferably 100% by mass or more and less than 50% by mass, more preferably 0.5% by mass. % Or more and less than 20% by mass, more preferably 0.5% by mass or more and less than 15% by mass, still more preferably 1% by mass or more and less than 10% by mass.
In particular, when the olefin polymer (A) is a propylene polymer (a1) and the olefin polymer (B) is a propylene polymer (b1), the propylene polymer. The compatibility of the propylene-based polymer (b1) with respect to (a1) becomes better, and a molded product having more excellent stretchability can be obtained.

  The olefin polymer (B) has the following melting endotherm (ΔH-D) and molecular weight distribution (Mw / Mn) from the viewpoint of greatly improving stretchability without affecting the mechanical properties of the molded body. And having the characteristics described later (particularly, in the case of the propylene polymer (b1)), the content of the olefin polymer (B) is in the above-described range. preferable.

(Melting endotherm (ΔH-D))
The melting endotherm (ΔH-D) of the olefin polymer (B) and the propylene polymer (b1) is 0 to 80 J / g. When the melting endotherm (ΔH-D) of the olefin polymer (B) and the propylene polymer (b1) is 0 to 80 J / g, the main component of the polyolefin composition suitable for the uniaxially stretched molded product of the present invention The degree of crystallinity is reduced with respect to the component olefin polymer (A) (particularly when the olefin polymer (A) is a propylene polymer (a1)). Thereby, the number of tie molecules between lamellae and lamellae is reduced. When the number of tie molecules is small during stretching, the initial higher-order structure is uniformly deformed, and as a result, uniform stretchability is improved. From such a viewpoint, the melting endotherm (ΔH-D) is preferably 10 to 70 J / g, more preferably 20 to 60 J / g, and still more preferably 30 to 50 J / g.
The melting endotherm (ΔH−D) can be controlled by appropriately adjusting the monomer concentration and reaction pressure.
The melting endotherm (ΔH-D) is a melting endotherm curve obtained by DSC measurement with a line connecting a point on the low temperature side where there is no change in calorie and a point on the high temperature side where there is no change in calorie as a baseline. It is calculated by obtaining the area surrounded by the line portion including the peak and the base line.

(Molecular weight distribution (Mw / Mn))
The molecular weight distribution (Mw / Mn) of the olefin polymer (B) and the propylene polymer (b1) is preferably less than 3.0 from the viewpoint of high strength. If the molecular weight distribution (Mw / Mn) is less than 3.0, low molecular weight components that adversely affect stretchability and molded article physical properties, for example, physical properties (for example, mechanical properties) of uniaxially stretched molded products are suppressed. The physical properties of the molded product of the present invention, in particular, the deterioration of the physical properties of the uniaxially stretched molded product are suppressed. From such a viewpoint, the molecular weight distribution (Mw / Mn) of the olefin polymer (B) and the propylene polymer (b1) is preferably 2.5 or less, more preferably 1.5 to 2.5. .
In the present invention, the molecular weight distribution (Mw / Mn) is a value calculated from the polystyrene-equivalent weight average molecular weight Mw and number average molecular weight Mn measured by gel permeation chromatography (GPC).

The olefin polymer (B) and the propylene polymer (b1) of the present invention are preferably propylene polymers satisfying either one of the following (1) or (2) or both, and more preferably Satisfies the following (3), more preferably satisfies the following (4) and (5).
(1) Mesopentad fraction [mmmm] is 20 to 60 mol%.
(2) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min. The melting point (Tm-D) defined as the observed peak top is 0-120 ° C.
(3) The value of [rrrr] / (1- [mmmm]) is 0.1 or less.
(4) The racemic meso racemic meso pentad fraction [rmrm] exceeds 2.5 mol%.
(5) The value of [mm] × [rr] / [mr] ² is 2.0 or less.

(1) Mesopentad fraction [mmmm]
The mesopentad fraction [mmmm] is an index representing the stereoregularity of the olefin polymer (B) and the propylene polymer (b1), and the stereoregularity increases as the mesopentad fraction [mmmm] increases.
When the olefin polymer (B) is a propylene homopolymer, the mesopentad fraction [mmmm] is improved in handling properties of the propylene polymer and stretchability when added in a small amount to the olefin polymer (A). From a viewpoint of an effect, Preferably it is 20-60 mol%, More preferably, it is 30-55 mol%, More preferably, it is 40-50 mol%. When the mesopentad fraction [mmmm] is 20 mol% or more, the stretchability can be improved without reducing the rigidity of the olefin polymer (A), which is the main component of the polyolefin composition of the present invention. If it is 60 mol% or less, it is not eutectic with the main component olefin polymer (A), and is compatible with the amorphous part of the main component olefin polymer (A) to be extensible. Can be improved.

(2) Melting point (Tm-D)
The melting point (Tm-D) of the olefin polymer (B) and the propylene polymer (b1) is preferably higher from the viewpoint of strength and moldability. Preferably it is 0-120 degreeC, More preferably, it is 50-100 degreeC, More preferably, it is 55-90 degreeC, More preferably, it is 60-80 degreeC.
In the present invention, a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer Co., Ltd.) is used, and 10 mg of a sample is held at −10 ° C. for 5 minutes in a nitrogen atmosphere and then heated at 10 ° C./min. The peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained by the above is defined as the melting point (Tm-D). The melting point can be controlled by appropriately adjusting the monomer concentration and reaction pressure.

(3) [rrrr] / (1- [mmmm])
The value of [rrrr] / (1- [mmmm]) is obtained from the mesopentad fraction [mmmm] and the racemic pentad fraction [rrrr] and is an index indicating the uniformity of the regularity distribution of polypropylene. When this value of [rrrr] / (1- [mmmm]) is increased, it becomes a mixture of highly stereoregular polypropylene and atactic polypropylene like conventional polypropylene produced using an existing catalyst system. It causes stickiness of the stretched molded product. The unit of [rrrr] and [mmmm] in the above is mol%.
From the standpoint of stickiness, the value of [rrrr] / (1- [mmmm]) in the olefin polymer (B) and the propylene polymer (b1) is preferably 0.1 or less, more preferably 0.8. 001 to 0.05, more preferably 0.001 to 0.04, and particularly preferably 0.01 to 0.04.

Here, the mesopentad fraction [mmmm], the racemic pentad fraction [rrrr], and the racemic mesoracemi mesopentad fraction [rmrm] to be described later are determined according to “Macromolecules, 6, 925 (1973) ”, and meso fraction, racemic fraction, and racemic meso-racemic meso in pentad units in the polypropylene molecular chain measured by the methyl group signal of the ¹³ C-NMR spectrum. It is a fraction. As the mesopentad fraction [mmmm] increases, the stereoregularity increases. Further, triad fractions [mm], [rr] and [mr] described later are also calculated by the above method.

(4) Racemic meso racemic meso pentad fraction [rmrm]
The racemic meso racemic meso pentad fraction [rmrm] is an index representing the randomness of the stereoregularity of polypropylene, and the randomness of polypropylene increases as the value increases.
The racemic meso racemic meso pentad fraction [rmrm] of the olefin polymer (B) and the propylene polymer (b1) is preferably more than 2.5 mol%. When [rmrm] of the olefin polymer (B) and the propylene polymer (b1) exceeds 2.5 mol%, the randomness increases, and the olefin weight which is the main component of the polyolefin composition of the present invention. Copolymerization (A) (especially when the olefin polymer (A) is a propylene polymer (a1)) becomes difficult to eutectify, and as a result, a decrease in heat resistance and rigidity of the polyolefin composition is suppressed. The From such a viewpoint, the racemic meso racemic meso pentad fraction [rmrm] of the olefin polymer (B) and the propylene polymer (b1) is more preferably 2.6 mol% or more, and still more preferably 2. 7 mol% or more. The upper limit is usually preferably about 10 mol%, more preferably 7 mol%, still more preferably 5 mol%, and particularly preferably 4 mol%.

(5) [mm] × [rr] / [mr] ²
The value of [mm] × [rr] / [mr] ² calculated from the triad fraction [mm], [rr] and [mr] represents an index of randomness of the polymer. The olefin polymer (A) which is the main component of the polyolefin composition of the present invention (especially when the olefin polymer (A) is a propylene polymer (a1)) and eutectic crystallized. It does not occur, and the stretchability can be improved efficiently with respect to the main component olefin polymer (A) (particularly propylene polymer (a1)). The value of the above formula of the olefin polymer (B) and the propylene polymer (b1) of the present invention is usually 2.0 or less, preferably 1.8 to 0.5, more preferably 1.5 to 0.00. The range is 5. In addition, the unit of [mm] and [rr] in the above is mol%.

  The propylene polymer (b1) can be produced, for example, using a metallocene catalyst as described in WO2003 / 087172. In particular, those using a transition metal compound in which a ligand forms a cross-linked structure via a cross-linking group are preferred, and in particular, a transition metal compound that forms a cross-linked structure via two cross-linking groups and Metallocene catalysts obtained by combining promoters are preferred.

〔式中、Ｍは周期律表第３〜１０族又はランタノイド系列の金属元素を示し、Ｅ^１及びＥ^２はそれぞれ置換シクロペンタジエニル基、インデニル基、置換インデニル基、ヘテロシクロペンタジエニル基、置換ヘテロシクロペンタジエニル基、アミド基、ホスフィド基、炭化水素基及び珪素含有基の中から選ばれた配位子であって、Ａ^１及びＡ^２を介して架橋構造を形成しており、又それらは互いに同一でも異なっていてもよく、Ｘはσ結合性の配位子を示し、Ｘが複数ある場合、複数のＸは同じでも異なっていてもよく、他のＸ、Ｅ^１、Ｅ^２又はＹと架橋していてもよい。Ｙはルイス塩基を示し、Ｙが複数ある場合、複数のＹは同じでも異なっていてもよく、他のＹ，Ｅ^１、Ｅ^２又はＸと架橋していてもよく、Ａ^１及びＡ^２は二つの配位子を結合する二価の架橋基であって、炭素数１〜２０の炭化水素基、炭素数１〜２０のハロゲン含有炭化水素基、珪素含有基、ゲルマニウム含有基、スズ含有基、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ_２−、−Ｓｅ−、−ＮＲ^１−、−ＰＲ^１−、−Ｐ（Ｏ）Ｒ^１−、−ＢＲ^１−又は−ＡｌＲ^１−を示し、Ｒ^１は水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基又は炭素数１〜２０のハロゲン含有炭化水素基を示し、それらは互いに同一でも異なっていてもよい。ｑは１〜５の整数で〔（Ｍの原子価）−２〕を示し、ｒは０〜３の整数を示す。〕
で表される遷移金属化合物、並びに
（ii）（ii−１）該（ｉ）成分の遷移金属化合物又はその派生物と反応してイオン性の錯体を形成しうる化合物及び（ii−２）アルミノキサンからなる群から選ばれる少なくとも一種の成分
を含有する重合用触媒が挙げられる。For example,
(I) General formula (I)

[In the formula, M represents a group 3-10 of the periodic table or a lanthanoid series metal element, and E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, respectively. A ligand selected from a substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group, and a silicon-containing group, which forms a cross-linked structure via A ¹ and A ² In addition, they may be the same or different from each other, X represents a σ-bonded ligand, and when there are a plurality of X, the plurality of X may be the same or different, and other X, E ¹ , E ² or Y may be cross-linked. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X, and A ¹ and A ² are A divalent bridging group that binds two ligands, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group _{, -O -, - CO -,} - S -, - SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 - or -AlR ¹ - R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same as or different from each other. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3. ]
And (ii) (ii-1) a compound capable of reacting with the transition metal compound of component (i) or a derivative thereof to form an ionic complex, and (ii-2) aluminoxane And a polymerization catalyst containing at least one component selected from the group consisting of:

  As the transition metal compound (i), a ligand is preferably a (1,2 ′) (2,1 ′) double-bridged transition metal compound, such as (1,2′-dimethylsilylene) ( 2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride.

  Specific examples of the compound of component (ii-1) include triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl tetraphenylborate (tri- n-butyl) ammonium, benzyl tetraphenylborate (tri-n-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, tetra Benzylpyridinium phenylborate, methyl tetraphenylborate (2-cyanopyridinium), trikis (tetrafluorophenyl) borate triethyla Monium, tetrakis (pentafluorophenyl) tri-n-butylammonium borate, tetrakis (pentafluorophenyl) triphenylammonium borate, tetrakis (pentafluorophenyl) tetra-n-butylammonium borate, tetraethylammonium tetrakis (pentafluorophenyl) borate Benzyl tetrakis (pentafluorophenyl) ammonium borate (tri-n-butyl), methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) boric acid Methylanilinium, tetrakis (pentafluorophenyl) borate dimethylanilinium, tetrakis (pentafluoropheny L) Trimethylanilinium borate, methyl pyridinium tetrakis (pentafluorophenyl) borate, benzyl pyridinium tetrakis (pentafluorophenyl) borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), methyl tetrakis (pentafluorophenyl) borate (4-cyanopyridinium), triphenylphosphonium tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-ditrifluoromethyl) phenyl] dimethylaniline borate Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, Trakis (pentafluorophenyl) borate ferrocenium, tetrakis (pentafluorophenyl) borate (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) decamethylferrocenium borate, tetrakis (pentafluorophenyl) silver borate, Tetrakis (pentafluorophenyl) triborate borate, tetrakis (pentafluorophenyl) lithium borate, tetrakis (pentafluorophenyl) sodium borate, tetrakis (pentafluorophenyl) borate tetraphenylporphyrin manganese, silver tetrafluoroborate, silver hexafluorophosphate, hexa Examples thereof include silver fluoroarsenate, silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate.

  Examples of the aluminoxane as the component (ii-2) include known chain aluminoxanes and cyclic aluminoxanes.

  Also, trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride, etc. The propylene-based polymer (b1) may be produced using a combination of these organoaluminum compounds.

<Additives>
A preferred embodiment of the polyolefin-based composition suitable for the uniaxially stretched molded product of the present invention comprises the above components (a) and (b). However, the polyolefin-based composition suitable for the uniaxially stretched molded product of the present invention may further include an antioxidant, a heat stabilizer, a weather stabilizer, and an antistatic agent as long as the object of the present invention is not impaired. , Slip agents, antifogging agents, lubricants, nucleating agents, antiblocking agents, dyes, pigments, natural oils, synthetic oils, waxes, fillers, elastomers, and the like.
As the antioxidant, a hindered phenol-based, sulfur-based, lactone-based, organic phosphite-based, organic phosphonite-based antioxidant, or an antioxidant obtained by combining several of these can be used. The antioxidant is preferably blended in the range of 0.01 to 5% by mass with respect to 100% by mass of the total amount of the polyolefin-based composition.
As the antistatic agent, known low molecular type or high molecular type antistatic agents that are generally used can be suitably used.
Examples of the low molecular weight antistatic agent include nonionic antistatic agents such as alkyldiethanolamine, polyoxyethylene alkylamide, monoglycerin fatty acid ester, diglycerin fatty acid ester, sorbitan fatty acid ester, and tetraalkylammonium salt type cationic type. Antistatic agents such as antistatic agents, anionic antistatic agents such as alkylsulfonates, and amphoteric antistatic agents such as alkylbetaines.
Examples of polymer antistatic agents include nonionic antistatic agents such as polyetheresteramide, anionic antistatic agents such as polystyrene sulfonic acid, and cationic antistatic agents such as quaternary ammonium salt-containing polymers. Etc.
The antistatic agent is preferably blended in the range of 0.01 to 5% by mass with respect to 100% by mass of the total amount of the polyolefin-based composition.
As the slip agent, amides of saturated or unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid, stearic acid, erucic acid and behenic acid, or bisamides of these saturated or unsaturated fatty acids can be used. Of these, erucic acid amide and ethylenebisstearic acid amide are preferable. The slip agent is preferably blended in the range of 0.01 to 5% by mass with respect to 100% by mass of the total amount of the polyolefin-based composition.
Antiblocking agents include finely divided silica, finely divided aluminum oxide, finely divided clay, powdered or liquid silicone resin, polytetrafluoroethylene resin, finely crosslinked resin such as crosslinked acrylic resin or methacrylic resin powder Can be mentioned. Of these, finely divided silica and finely powdered crosslinked resin are preferred. It is preferable to mix | blend an antiblocking agent in 0.01-5 mass% with respect to 100 mass% of whole quantity of the said polyolefin-type composition.
As the elastomer, styrene-based, olefin-based, ester-based, soft vinyl chloride-based, urethane-based, amide-based, butadiene-isoprene-based elastomers, or an elastomer obtained by combining several of these can be used. Of these, styrene, olefin, and butadiene / isoprene are preferred. The elastomer is preferably blended in the range of 1 to 20% by mass with respect to 100% by mass of the total amount of the polyolefin-based composition.

<Manufacture of polyolefin-based composition>
The polyolefin-based composition includes the above components (a) and (b), and, if necessary, additives, for example, a high-speed mixer, a Banbury mixer, a continuous kneader, a single or twin screw extruder, a roll, Generally, a method of granulating by heat melting and kneading using an ordinary mixing and kneading machine such as a Brabender plastograph is employed.
The polyolefin-based composition is preferably used for extrusion molding. Further, the above components (a) and (b) may be used (dry blending) immediately before extrusion molding, for example, simultaneously in a hopper on an extruder.

[Flat yarn]
The flat yarn of the present invention is a flat yarn comprising the polyolefin composition.
By using the polyolefin-based composition described above, stretchability is improved and elongation is improved. This is because a predetermined amount of the olefin polymer (B), particularly the propylene polymer (b1) is localized in the olefin polymer (A), particularly the propylene polymer (a1). Thus, it is assumed that the balance between strength and elongation of the obtained flat yarn is improved. More specifically, when the olefin polymer (B) is blended with the olefin polymer (A), the growth of spherulite size is suppressed due to the slow crystallinity while maintaining the melting point. , Spherulite size becomes smaller. Furthermore, when the spherulite occupation area ratio decreases, the neck deformation of the initial deformation is suppressed and the uniform stretchability is improved. By improving the uniform stretchability, the thickness deviation accuracy is improved, the breaking frequency is reduced, and the production stability is increased.

When the flat yarn of the present invention is formed into a sheet by weaving, which will be described later, a flexible container bag, a sandbag bag, an adhesive tape base material, a leisure sheet, a mesh sheet, a design sheet, a track sheet, and other various sheets, a valchip, a net, and a carpet Used for lining materials, bag materials, interior materials, etc.
In addition, the artificial turf can be manufactured using the flat yarn itself of the present invention.

[Monofilament]
The monofilament of the present invention is a monofilament made of the polyolefin-based composition.
Similar to the flat yarn described above, by using the above-described polyolefin-based composition, stretchability is improved and elongation is improved. The mechanism is as described above, and the description is omitted here.

Monofilament refers to a single, untwisted fiber.
The monofilament of the present invention is usually formed by extruding the above-mentioned polyolefin-based composition from an extruder or the like in a molten state, and subjecting it to stretching and relaxation treatment as desired. In addition, the monofilament may be a drawn yarn that has been stretched after being extruded, or may be a stretched yarn that has been subjected to stretching and relaxation after being extruded, or a stretched yarn that has been subjected to stretching and relaxation after being extruded. Is preferred. The monofilament of the present invention is preferably a monofilament having a total draw ratio of 10 times or less, more preferably a monofilament having a total draw ratio of 8 times or less. The total draw ratio of the monofilament may be determined in consideration of a balance of various properties such as wear resistance, tensile strength, elongation, and flexibility. There is no particular lower limit for the total draw ratio, but the total draw ratio is usually 2 times or more, and often 3 times or more.
The monofilament of the present invention has a yarn diameter of 0.01 mm or more and 10 mm or less, preferably 0.02 to 7 mm, more preferably 0.05 to 5 mm, still more preferably 0.05 to 2 mm. .

Further, the yarn used for weaving the fabric is a twisted monofilament. On the other hand, cloths are not only made by weaving yarn, but also non-woven fabrics made by intertwining fibers intricately.
In addition, taking advantage of rigidity, makeup filters such as fishing lines, oil filters, gravel filter filters, fishing nets, aquaculture nets, tennis and badminton rackets, toothbrushes, hair brushes and other toiletry brushes And various industrial brushes.

[band]
The band of the present invention is a band made of the above polyolefin-based composition.
Similar to the flat yarn described above, by using the above-described polyolefin-based composition, stretchability is improved and elongation is improved. The mechanism is as described above, and the description is omitted here.

Examples of the band include a manual band used for packing and a binding band used for fixing an object.
A general band manufacturing method will be described. In a general band production method, a raw material mainly composed of the above-described polyolefin-based composition is melt-extruded from an extruder die and cooled to obtain a strip-shaped raw material. This strip-shaped raw fabric is heated and stretched at a stretch ratio set. The stretched product stretched in the length direction is embossed with a pair of embossing rollers, and an embossed pattern is applied to the front and back surfaces. Next, annealing is performed, and the film is wound after cooling. A packing band is generally manufactured at a stretching ratio of 7 to 20 times, and the strength and rigidity are improved by stretching, and the rigidity contributes to suitability of the packing machine. The raw material may be a small amount of calcium carbonate, pigments and other additives mixed with the above-described polyolefin-based composition as the main raw material. When calcium carbonate is not added, a transparent band is formed, and when it is added, an opaque band is formed, but there is an effect of preventing cracking.

  Note that the width and thickness of the band are appropriately selected according to the use of the band, and the shape, width and thickness of the binding band are similarly selected according to the use.

[Split yarn]
The split yarn of the present invention is a split yarn comprising the above polyolefin composition.
Similar to the flat yarn described above, by using the above-described polyolefin-based composition, stretchability is improved and elongation is improved. The mechanism is as described above, and the description is omitted here.

  A “split yarn” is a fiber structure having a fine mesh. In appearance, it has a structure in which a large number of fine fibers are gathered and the fibers are partially bonded to form a net. The split yarn is usually obtained by passing a uniaxially stretched plastic film between needle blade rolls. In this specification, the formation of fibers by causing a number of tears in the film in this manner is referred to as “splitting” or “split defibration”. In a narrow sense, the split yarn is referred to as a thread-like body obtained by twisting the fiber structure as described above, and a non-twisted one is sometimes referred to as a flat yarn. However, in this specification, the term split yarn is used to encompass both.

The split yarn of the present invention is characterized in that the fibers are connected to each other and have high tensile strength, and is used for packaging materials, industrial materials, curtains, and carpets.
In addition, according to the use of a split yarn, you may form in a network structure or a branched structure suitably, and the long fiber and branch of a split yarn also include a thing with a diameter of 100 micrometers or less.

[tape]
The tape of the present invention is a tape comprising the above polyolefin-based composition.
Similar to the flat yarn described above, by using the above-described polyolefin-based composition, stretchability is improved and elongation is improved. The mechanism is as described above, and the description is omitted here.

Examples of the tape of the present invention include packaging tapes and adhesive tape base tapes.
Here, the manufacturing method of the packaging tape and the manufacturing method of the base material of the adhesive tape are the same as the above-described manufacturing method of the band.
Note that the width and thickness of the tape are appropriately selected according to the application of the tape.

[Sheet]
The sheet | seat of this invention is a sheet | seat which consists of the uniaxially stretched molding which knit the uniaxially stretched molded product mentioned above, and knit.

  In the present invention, the flat yarn is woven and knitted using warp and / or weft to form a sheet. As a weaving method, it can be woven using a known loom such as a circular loom, a slewer loom, a water jet loom, and the woven structure includes various shapes such as plain weave, twill weave and leno weave. Applied. The knitting method may be either flat knitting or warp knitting, and specific examples include tricot knitting, Miranese knitting, and Russell knitting.

  Such a woven and knitted material may be suitably used as a multi-layer sheet with a base material and a polyethylene resin layer laminated on one or both sides. By laminating the polyethylene-based resin layer, waterproof and dustproof properties are imparted, and a beautiful shrink-wrapped product that fits the packaged object is obtained. As a method for laminating the polyethylene resin layer, a known extrusion laminating method is preferably used. The thickness of the layer provided by the extrusion laminating method is preferably 20 to 100 μm, more preferably 30 to 60 μm per side. If it is less than 20 μm, the welding strength in post-processing is insufficient, and if it exceeds 100 μm, flexibility is lost, which is not preferable.

[Method for producing uniaxially stretched molded product]
The polyolefin-based composition is suitably used for a molding method having a stretching process.
Although it does not specifically limit as a stretch molding method, The uniaxial stretch molding method (a roll method, a tubular method, a tenter method, etc.) etc. which are applied to the stretch molding of a general purpose plastics are employ | adopted.

In the method for producing a uniaxially stretched molded product of the present invention, first, an unstretched original fabric made of the polyolefin-based composition is heated in a temperature range of usually 50 ° C. to 280 ° C. to form a flat film (“ (Also referred to as “film formation”). Next, the obtained film is uniaxially stretched in the machine direction (MD) by a roll method, a tenter method, a tubular method, or the like. The stretching temperature is usually in the range of 30 ° C to 200 ° C, preferably 50 ° C to 170 ° C. The draw ratio is usually in the range of 2 to 25 times in the longitudinal direction. Moreover, after extending | stretching, you may perform heat processing, such as the method of spraying a hot air, the method of irradiating infrared rays, the method of irradiating a microwave, and making it contact on a heat roll.
For example, when the uniaxially stretched molded product is a flat yarn, the obtained film may be cut (slit) into strips before being heated and uniaxially stretched in the machine direction (MD). It is not necessary to provide a slit. In the case where no slit is provided, the uniaxially stretched film obtained after uniaxial stretching can be cut (slit) into strips.
The thickness of the uniaxially stretched molded product obtained by such a stretch molding method is arbitrary depending on the application, for example, in the case of a flat yarn, the thickness is usually 3 μm or more and 500 μm or less, Preferably they are 10 micrometers or more and 500 micrometers or less, More preferably, they are 10 micrometers or more and 300 micrometers or less.
A band made of the polyolefin composition is produced in the same manner as the uniaxially stretched molded product, but the stretch ratio is 4 to 8 times that of flat yarn, whereas the band is about 10 to 20 times as high. ing.

  The molded uniaxially stretched molded product has chemical functions, electrical functions, magnetic functions, mechanical functions, friction / wear / lubricating functions, optical functions, thermal functions, biocompatibility and other surface functions. Various purposeful secondary processing can be performed for the purpose of providing the above. Examples of secondary processing include embossing, painting, adhesion, printing, metalizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, Coating) and the like.

  The uniaxially stretched molded product obtained by this embodiment may or may not use an organic solvent. It is preferable because it is excellent in safety. Therefore, if an organic solvent is not used, since it is excellent in safety, it is widely applied as medical uses, food packaging uses, daily necessities, electrical equipment materials, home appliance housings, automobile materials, and the like. In particular, it is useful for packaging substances that are easily affected by oxygen or that may deteriorate, including foods. Moreover, if a residual monomer is also 5,000 ppm or less, durability can be improved and coloring can be reduced.

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

Below, the measuring method of the olefin polymer (A) used in the Example and an olefin polymer (B) is demonstrated.
[DSC measurement]
Using a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer Co.), a melting endotherm obtained by holding 10 mg of a sample at −10 ° C. for 5 minutes in a nitrogen atmosphere and then raising the temperature at 10 ° C./min. It calculated | required as melting endotherm (DELTA) HD from a curve. Moreover, melting | fusing point (Tm-D) was calculated | required from the peak top of the peak observed on the highest temperature side of the obtained melting endothermic curve.
The melting endotherm (ΔH-D) is a differential scanning calorimeter (manufactured by Perkin Elmer Co., Ltd.) with a line connecting a point on the low temperature side where there is no change in heat quantity and a point on the high temperature side where there is no change in heat quantity as the baseline , DSC-7), and calculating the area surrounded by the line portion including the peak of the melting endothermic curve obtained by DSC measurement and the base line.

[Weight average molecular weight (Mw), molecular weight distribution (Mw / Mn) measurement]
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) method to determine the molecular weight distribution (Mw / Mn). For the measurement, the following equipment and conditions were used, and polystyrene-reduced weight average molecular weight and number average molecular weight were obtained. The molecular weight distribution (Mw / Mn) is a value calculated from these weight average molecular weight (Mw) and number average molecular weight (Mn).
<GPC measurement device>
Column: “TOSO GMHHR-H (S) HT” manufactured by Tosoh Corporation
Detector: RI detection for liquid chromatogram "WATERS 150C" manufactured by Waters Corporation
<Measurement conditions>
Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 mL / min Sample concentration: 2.2 mg / mL
Injection volume: 160 μL
Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)

[NMR measurement]
The ¹³ C-NMR spectrum was measured with the following apparatus and conditions. In addition, the attribution of the peak followed the method proposed by A. Zambelli et al. In “Macromolecules, 8, 687 (1975)”.
Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. Method: Proton complete decoupling method Concentration: 220 mg / mL
Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds Integration: 10,000 times

<Calculation formula>
M = m / S × 100
R = γ / S × 100
S = Pββ + Pαβ + Pαγ
S: Signal intensity of side chain methyl carbon atoms of all propylene units Pββ: 19.8 to 22.5 ppm
Pαβ: 18.0 to 17.5 ppm
Pαγ: 17.5 to 17.1 ppm
γ: Racemic pentad chain: 20.7 to 20.3 ppm
m: Mesopentad chain: 21.7-22.5 ppm

The mesopentad fraction [mmmm], the racemic pentad fraction [rrrr] and the racemic mesoracemi mesopentad fraction [rmrm] are described in “Macromolecules, 6, 925 (1973)” by A. Zambelli et al. are those determined in conformity with the proposed method, meso fraction in pentad units in the polypropylene molecular chain as measured by the signal of the methyl groups of the ^{13 C-NMR} spectrum, the racemic fraction and the racemic meso racemic meso It is a fraction. As the mesopentad fraction [mmmm] increases, the stereoregularity increases. The triad fractions [mm], [rr] and [mr] were also calculated by the above method.

[Melt flow rate (MFR) measurement]
Based on JIS K7210, the measurement was performed under conditions of a temperature of 230 ° C. and a load of 2.16 kg.

  The olefin polymer (A) used in the examples will be described below.

<Olefin polymer A>
As the olefin polymer (A), MFR: 4 g / 10 min (temperature 230 ° C., load 2.16 kg), melting point (Tm-D): 163 ° C., melting endotherm (ΔHD): 94 g / J The propylene homopolymer was used.

  Below, the manufacture example of the olefin polymer (B) used in the Example is demonstrated.

Production Example 1 [Production of Olefin Polymer (B)]
In a stainless steel reactor with an internal volume of 20 L equipped with a stirrer, 20 L / hr of n-heptane, 15 mmol / hr of triisobutylaluminum, dimethylanilinium tetrakispentafluorophenylborate, (1,2'-dimethylsilylene) The catalyst component obtained by contacting (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride and triisobutylaluminum with propylene in a mass ratio of 1: 2: 20 in advance is converted into zirconium. At 6 μmol / hr.
Propylene and hydrogen were continuously supplied so as to maintain the total pressure in the reactor at 1.0 MPa · G, the polymerization temperature was appropriately adjusted, and a polymerization solution having a desired molecular weight was obtained.
An olefin polymer (B) was obtained by adding an antioxidant to the resulting polymerization solution so that the content thereof was 1,000 ppm by mass, and then removing n-heptane as a solvent. .

  The olefin polymer (B) obtained in Production Example 1 was measured as described above. The results are shown in Table 1 below.

Production Example 2 [Production of Olefin Polymer (B)]
Only the polymerization temperature of Production Example 1 was changed to obtain a polymerization solution having another desired molecular weight.
An olefin polymer (B) was obtained by adding an antioxidant to the resulting polymerization solution so that the content thereof was 1,000 ppm by mass, and then removing n-heptane as a solvent. .

  The olefin polymer (B) obtained in Production Example 2 was measured as described above. The results are shown in Table 2 below.

<Evaluation of flat yarn that is uniaxially stretched>
By the following measuring method, the physical property of the flat yarn which is the uniaxially stretched material produced by each Example and comparative example mentioned later was evaluated.

(Measuring mechanical properties)
Using a 200 mm × 15 mm strip test piece collected from the flat yarn which is a uniaxially stretched product, a tensile tester (manufactured by Shimadzu Corporation, “Autograph AG-I”) has a tensile speed of 300 mm / in the machine direction. Tensile, min, elastic modulus, breaking strength, breaking elongation were determined.
In each test, measurements were taken five times in the machine direction, and the average value was taken as the measured value. In addition, the test piece of a machine direction means the test piece whose longitudinal direction of the said strip-shaped test piece is a machine direction of a uniaxially stretched product here.
(I) Elastic modulus Using a strip-shaped test piece of 200 mm × 15 mm, a tensile tester was used to pull at a chuck-to-chuck distance of 150 mm, a tensile speed of 300 mm / min, the elongation (strain) as the horizontal axis, and the stress as the vertical axis. A relation line (curve) was drawn on the two-dimensional coordinate axis, and the inclination of the relation line before the yield point was obtained as “elastic modulus”. The higher the modulus of elasticity, the better the rigidity of the film.
<Evaluation criteria>
A: Elastic modulus is 6 GPa or more B: Elastic modulus is 5 GPa or more and less than 6 GPa C: Elastic modulus is 4.5 GPa or more and less than 5 GPa D: Elastic modulus is less than 4.5 GPa

(Ii) Break strength On the relationship line (curve) on the two-dimensional coordinate axis, the maximum tensile stress appearing on the test piece before the test piece broke was determined as “break strength”.
<Evaluation criteria>
A: Break strength is 370 MPa or more B: Break strength is 300 MPa or more and less than 370 MPa C: Break strength is 260 MPa or more and less than 300 MPa D: Break strength is less than 260 MPa

(Iii) Elongation at break Elongation at break (%) = 100 × (L−L ₀ ) / L ₀
(In the formula, L ₀ : length of the test piece before the test, L: length of the test piece at break)
<Evaluation criteria>
A: Breaking elongation is 20% or more B: Breaking elongation is 15% or more and less than 20% C: Breaking elongation is 10% or more and less than 15% D: Breaking elongation is less than 10%

[Evaluation of stretchability]
(I) Thickness distribution measurement The thickness of the flat yarn was measured with a thickness distribution meter ("Millimar C1216" manufactured by Marl). The measurement range was 8 points at 5 cm intervals in each machine direction of the flat yarn. A value obtained by calculating an average value from the obtained measured values was defined as a flat yarn thickness. The standard deviation was calculated from the measured values.
<Evaluation criteria>
A: Standard deviation is less than 8 B: Standard deviation is 8 or more and less than 9 C: Standard deviation is 9 or more and less than 10 D: Standard deviation is 10 or more

Example 1
5% by mass of the olefin polymer (B) of Production Example 1 and the olefin polymer (A) (polypropylene, MFR: 4 g / 10 min (temperature 230 ° C., load 2.16 kg)), melting point (Tm-D) A resin composition comprising: 163 ° C., melting endotherm (ΔH-D): 94 g / J) 95% by mass with a hot press (melting: 200 ° C./5 minutes, cooling: 20 ° C./5 minutes) A 200 μm film was formed. The obtained film was uniaxially drawn in the machine direction at a drawing temperature of 135 ° C. and a draw ratio of 7 times using a table tenter manufactured by Iwamoto Seisakusho to produce a flat yarn, thereby producing a uniaxially drawn yarn. The obtained flat yarn was evaluated for thickness unevenness (also referred to as “standard deviation of stretchability”) and mechanical properties. The results are shown in Table 3.

Comparative Example 1
The same procedure as in Example 1 was performed except that the resin composition of Example 1 was changed to 100% by mass of the olefin polymer (A). The resulting flat yarn was evaluated for thickness unevenness and mechanical properties. The results are shown in Table 3.

Example 2
10% by mass of the olefin polymer (B) of Example 1 and the olefin polymer (A) (polypropylene, MFR: 4 g / 10 min (temperature 230 ° C., load 2.16 kg)), melting point (Tm-D) 163 ° C., melting endotherm (ΔHD): 94 g / J) The same procedure as in Example 1 was performed except that a resin composition consisting of 90% by mass was used. The resulting flat yarn was evaluated for thickness unevenness and mechanical properties. The results are shown in Table 3.

Comparative Examples 2 and 3
The resin composition of Example 1 was changed to 100% by mass of the olefin polymer (A), and the same procedure as in Example 1 was carried out except that the longitudinal stretching ratio and the stretching temperature or the stretching temperature were changed as shown in Table 3. The resulting flat yarn was evaluated for thickness unevenness and mechanical properties. The results are shown in Table 3.

  As can be seen from Table 3, the uniaxially stretched product (flat yarn) containing the olefin polymer (B) has high flat yarn thickness uniformity. It is considered that the uniformity was improved because the yield stress was reduced and neck deformation was suppressed by including the olefin polymer (B). It can be seen that the stretchability is good, the thickness is uniform, and the frequency of fracture is assumed to be reduced, and the mechanical properties are improved in a well-balanced manner. As a result, it can be seen that the production stability is also excellent.

<Evaluation of monofilament>
The physical properties of the monofilaments produced in each Example and Comparative Example described later were evaluated by the following measurement methods.

(Measuring mechanical properties)
The olefin polymer (A) and the olefin polymer (B) are dry blended and wound up with a die width of 0.5 mm, a die nozzle diameter of 0.3 mφ, 24 nozzles, and a first roll and a second roll. Fibers were produced using the apparatus. Spinnability was judged from the state from the nozzle to the first roll, and stretchability was judged from the state of the fibers from the first roll to the second roll. Furthermore, the mechanical properties of the fiber obtained by the above method were evaluated. The results are shown in Table 4.
(I) Spinnability: Judged by the presence or absence of breakage of the fiber obtained from the die to the first roll.
<Evaluation criteria>
A: No break D: With break (ii) Stretchability: Judged by the presence or absence of breakage of fibers from the first roll to the second roll.
<Evaluation criteria>
A: No break D: With break

Example 3
2% by mass of the olefin polymer (B) of Production Example 1 and the olefin polymer (A) (polypropylene, manufactured by Prime Polymer Co., Ltd., trade name “Y2005GP”, MFR: 20 g / 10 min (temperature 230 ° C., load 2.16 kg) ), Melting point (Tm-D): 161 ° C.) 98% by mass, and a die width of 0.5 mm, a die nozzle diameter of 0.3 mφ, 24 nozzles, a first roll and a second roll. The fiber was produced using a winding device. Spinnability was judged from the state from the nozzle to the first roll, and stretchability was judged from the state of the fibers from the first roll to the second roll. Furthermore, the mechanical properties of the fiber obtained by the above method were evaluated. The results are shown in Table 4.

Comparative Example 4
The same procedure as in Example 1 was performed except that the resin composition of Example 3 was changed to 100% by mass of the olefin polymer (A). The spinnability and stretchability of the obtained monofilament were judged. Furthermore, the mechanical properties were evaluated. The results are shown in Table 4.

Example 4
5% by mass of the olefin polymer (B) of Production Example 1 and the olefin polymer (A) (polypropylene, manufactured by Prime Polymer Co., Ltd., trade name “Y2005GP”, MFR: 20 g / 10 min (temperature 230 ° C., load 2.16 kg) And a melting point (Tm-D): 161 ° C.) except that a resin composition consisting of 95% by mass was used in the same manner as in Example 3. The spinnability and stretchability of the obtained monofilament were judged. Furthermore, the mechanical properties were evaluated. The results are shown in Table 4.

Comparative Examples 5 and 6
The same procedure as in Example 1 was performed except that the resin composition of Example 1 was 100% by mass of the olefin polymer (A) and the winding speeds 1 and 2 were changed as shown in Table 4. The spinnability and stretchability of the obtained monofilament were judged. Furthermore, the mechanical properties were evaluated. The results are shown in Table 4.

  As can be seen from Table 4, the fiber containing the olefin polymer (B) has high spinnability and stretchability of the monofilament. This is considered to be an effect of slowing down the crystallization speed by including the olefin polymer (B). It can also be seen that the mechanical properties are also improved in a well-balanced manner. As a result, it can be seen that the production stability is also excellent.

Example 5
2% by mass of the olefin polymer (B) of Production Example 2 and the olefin polymer (A) (polypropylene, manufactured by Prime Polymer Co., Ltd., trade name “Y2000GV”, MFR: 18 g / 10 min (temperature 230 ° C., load 2.16 kg) ), Melting point (Tm-D): 167 ° C.) 98% by mass, and a die width of 0.5 mm, a die nozzle diameter of 0.3 mφ, 24 nozzles, the first roll and the second roll. The fiber was produced using a winding device. Spinnability was judged from the state from the nozzle to the first roll, and stretchability was judged from the state of the fibers from the first roll to the second roll. Furthermore, the mechanical properties of the fiber obtained by the above method were evaluated. The results are shown in Table 5.

Example 6
The same procedure as in Example 5 was performed except that the winding speed 2 was changed as shown in Table 5. The spinnability and stretchability of the obtained monofilament were judged. Furthermore, the mechanical properties were evaluated. The results are shown in Table 5.

Example 7
5% by mass of the olefin polymer (B) of Production Example 1 and the olefin polymer (A) (polypropylene, manufactured by Prime Polymer Co., Ltd., trade name “Y2000GV”, MFR: 18 g / 10 min (temperature 230 ° C., load 2.16 kg) And a melting point (Tm-D): 167 ° C.) 95% by mass, and the same procedure as in Example 5 was carried out except that the winding speed 2 was changed as shown in Table 5. . The spinnability and stretchability of the obtained monofilament were judged. Furthermore, the mechanical properties were evaluated. The results are shown in Table 5.

Comparative Examples 7 and 8
The same procedure as in Example 5 was performed except that the resin composition of Example 5 was changed to 100% by mass of the olefin polymer (A) and the winding speed 2 was changed as shown in Table 5. The spinnability and stretchability of the obtained monofilament were judged. Furthermore, the mechanical properties were evaluated. The results are shown in Table 5.

  As can be seen from Table 5, the fiber containing the olefin polymer (B) has high spinnability and stretchability of the monofilament. This is considered to be an effect of slowing down the crystallization speed by including the olefin polymer (B). It can also be seen that the mechanical properties are also improved in a well-balanced manner. As a result, it can be seen that the production stability is also excellent.

  The uniaxially stretched molded product of the present invention has an excellent balance of elastic modulus, elongation at break, fracture strength, and uneven thickness accuracy. When this uniaxially molded product is a flat yarn, if it is made into a sheet by weaving, a flexible container bag Can be used for sandbag bags, adhesive tape base materials, leisure sheets, mesh sheets, design sheets, track sheets, etc., valchips, nets, carpet lining materials, bag materials, interior materials, etc. Artificial grass can also be produced using the yarn itself.

Claims (10)

A uniaxially stretched molded article comprising a polyolefin-based composition containing the following components (a) and (b).
(A) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min. Olefin polymer (A) whose melting point (Tm-D) defined as the observed peak top exceeds 120 ° C
(B) Using a differential scanning calorimeter (DSC), the sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 10 ° C./min. Olefin polymer (B) having a calorific value (ΔH-D) of 0 to 80 J / g and a molecular weight distribution (Mw / Mn) of less than 3.0   The said (b) component of the said polyolefin-type composition is 0.5 mass% or more and less than 50 mass% with respect to 100 mass% of total amounts with the said (a) and (b) component. Uniaxially stretched molded product.   The uniaxially stretched molded product according to claim 1 or 2, wherein the olefin polymer (A) is a propylene polymer (a1).   The uniaxial stretch molding according to any one of claims 1 to 3, wherein 50 mol% or more of the monomer constituting the olefin polymer (B) is a propylene polymer (b1) composed of a propylene monomer. object. The uniaxially stretched molded product according to claim 4, wherein the propylene polymer (b1) satisfies the following (i) and / or (ii).
(I) A structural unit of ethylene is contained in an amount of more than 0 mol% and 20 mol% or less.
(Ii) The structural unit of 1-butene is contained in an amount of more than 0 mol% and 30 mol% or less. The uniaxially stretched molded product according to claim 4, wherein the propylene polymer (b1) satisfies the following (1).
(1) Mesopentad fraction [mmmm] is 20 to 60 mol%. The uniaxially stretched molded product according to any one of claims 4 to 6, wherein the propylene polymer (b1) satisfies the following (2).
(2) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min. The melting point (Tm-D) defined as the observed peak top is 0-120 ° C.   The uniaxially stretched molded product according to any one of claims 1 to 7, which is at least one selected from the group consisting of flat yarn, monofilament, band, split yarn and tape.   A sheet comprising a knitted uniaxially stretched molded product according to any one of claims 1 to 7. A uniaxially stretched molded product in which front and back surfaces are made flat using an olefin-based composition containing the following components (a) and (b), the produced film is slit, and the slit film is stretched while being heated. Manufacturing method.
(A) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min. Olefin polymer (A) whose melting point (Tm-D) defined as the observed peak top exceeds 120 ° C
(B) Using a differential scanning calorimeter (DSC), the sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 10 ° C./min. Olefin polymer (B) having a calorific value (ΔH-D) of 0 to 80 J / g and a molecular weight distribution (Mw / Mn) of less than 3.0