JP2020100725A - Olefinic polymer composition and artificial leather using the same - Google Patents

Abstract

To provide a polyolefinic artificial leather more lightweight than polyvinyl chloride products, excellent in wear resistance and having a tactile impression equivalent to that of the polyvinyl chloride products, and to provide an olefinic polymer composition suitable for a raw material of the artificial leather.SOLUTION: An olefinic polymer composition is characterized by including: (A) a propylene-based polymer having a syndiotactic pentad fraction (rrrr fraction) of 85% or more and including a constitutional unit induced from propylene of 90-100 mol%; (B) a propylene-based copolymer including a propylene-derivative constitutional unit of 40-89 mol% and a 2-20C α-olefin-derivative constitutional unit of 11-60 mol%; (C) an aromatic vinyl block copolymer or a hydrogenated material thereof; (D) a hydrogenated petroleum resin; and (E) a softener.SELECTED DRAWING: None

Description

The present invention relates to an olefin polymer composition and its use. More specifically, the present invention relates to an olefin polymer composition that can be suitably used for producing synthetic leather, and synthetic leather using the same.

Synthetic leather is used for various purposes such as ornaments, bags, stationery, various cases, packaging, furniture, building interior materials, and automobile interior materials.
BACKGROUND ART Synthetic leather in which a layer made of polyvinyl chloride (vinyl chloride) resin is formed on the surface of a base cloth or a base material layer has been widely used from the past. Polyvinyl chloride resin is inexpensive, and synthetic leather having a wide range of hardness can be manufactured by adjusting the amount of the plasticizer blended. However, since such vinyl chloride has problems such as elution of plasticizers and incineration, there is a need for de-vinyl chloride (substitute for vinyl chloride) depending on the application, and a material replacing vinyl chloride is required.

In recent years, as a raw material for synthetic leather replacing PVC, a polyurethane resin has come to be used because of its excellent elastic modulus, load resistance and mechanical strength over a wide hardness range. In the case of polyurethane, an attempt has been made to secure the tactile sensation by, for example, foaming the skin layer (see Patent Document 1).

In Patent Document 2, a synthetic leather having a surface layer of polyurethane resin formed on the surface of a wet microporous layer of polyurethane resin integrally formed with a fibrous base material has a wet microporous layer and thus has an excellent tactile sensation and an appearance. The upper part will be similar to natural leather, and the appearance and texture can be further improved by forming a polyurethane skin layer on the surface of the wet microporous layer of the polyurethane resin from which the film formed has been removed. Have been described.
Although it is expected to use a polyolefin resin, there is a problem that the synthetic leather obtained by using a soft olefin resin such as an olefin thermoplastic elastomer as a raw material does not have sufficient abrasion resistance.

JP, 2010-255163, A JP-A-5-44173

By the way, in recent years, olefin polymers have been attracting attention as a substitute material for PVC due to its light weight. However, in the field of olefin polymers, the inventors of the present invention have considered that there is still room for improvement in terms of tactile sensation compared to PVC, although some have been found that can be used for synthetic leather.
The present invention is a polyolefin synthetic leather, which is lighter in weight than a PVC product, has excellent abrasion resistance, and has a texture equivalent to that of a PVC product, and an olefin polymer composition suitable as a raw material for the synthetic leather. The challenge is to provide.

The gist of the present invention relates to the following items [1] to [6].
[1] (A) A propylene-based polymer having a syndiotactic pentad fraction (rrrr fraction) measured by ¹³ C-NMR of 85% or more and containing 90 to 100 mol% of a structural unit derived from propylene. Coalescence: 5-10 parts by mass,
(B) A propylene-based copolymer containing 40 to 89 mol% of a propylene-derived structural unit and 11 to 60 mol% of a C2 to C20 α-olefin-derived structural unit and satisfying the following requirement (b): : 25 to 50 parts by mass,
(C) A block copolymer containing a block composed of a structural unit derived from an aromatic vinyl compound and a block composed of a structural unit derived from a conjugated diene compound or a hydrogenated product thereof: 10 to 40 parts by mass,
(D) Hydrogenated petroleum resin: 10 to 30 parts by mass, and
(E) Softening agent having a kinematic viscosity at 40° C. in the range of 30 to 200 mm ² /sec: 5 to 15 parts by mass (provided (A), (B), (C), (D) and (E). ) Is 100 parts by mass)
An olefin-based polymer composition comprising:
Requirement (b): The intrinsic viscosity [η] (dl/g) measured in decalin at 135° C. and the MFR (g/10 min) measured at 230° C. and a load of 2.16 kg satisfy the following relational expression. ..
1.50 x MFR ^(-0.20) ≤ [η] ≤ 2.65 x MFR ^(-0.20)

[2] A block copolymer containing a block composed of a structural unit derived from an aromatic vinyl compound (C) and a block composed of a structural unit derived from a conjugated diene compound or a hydrogenated product thereof is derived from an aromatic vinyl compound. A block copolymer comprising a block composed of a structural unit, a block composed of a structural unit derived from a conjugated diene compound, and a block composed of a structural unit derived from a polymer of an aromatic vinyl compound, or a hydrogenated product thereof, wherein: 1] The olefin-based polymer composition as described above.

[3] A styrene-ethylene-butylene-based block copolymer or a hydrogenated product thereof containing a block composed of a structural unit derived from an aromatic vinyl compound (C) and a block composed of a structural unit derived from a conjugated diene compound. -The olefin polymer composition according to the above [1] or [2], which is a styrene block copolymer.

[4] Furthermore, 0.1 to 10 parts by mass of (F) silicone-modified polypropylene is contained with respect to 100 parts by mass of the total of (A), (B), (C), (D) and (E). The olefin polymer composition according to any one of [1] to [3] above.
[5] The olefin polymer composition according to any one of [1] to [4] above, which is used for producing synthetic leather.
[6] Synthetic leather including a layer composed of the olefin polymer composition according to any one of [1] to [5].

The olefin polymer composition of the present invention can be used as a raw material for various molded articles, is lighter in weight than a vinyl chloride product, and is excellent in abrasion resistance even though it is an olefin type synthetic leather having good tactile sensation. It is suitable as a raw material. Further, the synthetic leather of the present invention is lighter in weight than vinyl chloride products, and is excellent in abrasion resistance despite being olefinic, and has a good tactile sensation.

<Olefin-based polymer composition>
Propylene polymer (A)
The propylene-based polymer (A) constituting the olefin-based polymer composition of the present invention has a syndiotactic pentad fraction (rrrr fraction) measured by ¹³ C-NMR of 85% or more, preferably 90%. Or more, more preferably 93% or more, further preferably 94% or more, and a propylene system containing 90 to 100 mol%, preferably 92 to 100 mol%, more preferably 95 to 100 mol% of a structural unit derived from propylene. It is a polymer.

The propylene-based polymer (A) having a rrrr fraction in the above range is excellent in moldability, heat resistance and transparency, and has better properties as crystalline polypropylene. Further, by using the propylene-based polymer (A), crystallization suppression and fine spheronization occur, so that the obtained olefin-based polymer composition of the present invention has high transparency and surface gloss. ..

When the propylene polymer in the above range is used as the propylene polymer (A) according to the present invention, an olefin polymer composition having particularly excellent heat resistance can be obtained.
The syndiotactic pentad fraction (rrrr fraction) of the propylene-based polymer (A) according to the present invention is measured as follows.

The rrrr fraction is P _rrrr in the ¹³ C-NMR spectrum (absorption intensity derived from the methyl group of the third unit at the site where 5 units of propylene units are continuously syndiotacticly bonded) and P _w (total of propylene units). It is determined by the following formula (1) from the absorption intensity of (absorption intensity derived from methyl group).

rrrr fraction (%)=100×P _rrrr /P _w (1)
The NMR measurement is performed, for example, as follows. That is, 0.35 g of the sample is heated and dissolved in 2.0 ml of hexachlorobutadiene. After filtering this solution through a glass filter (G2), 0.5 ml of deuterated benzene is added and charged into an NMR tube having an inner diameter of 10 mm. Then, ¹³ C-NMR measurement is performed at 120° C. using a GX-500 type NMR measuring device manufactured by JEOL Ltd. The total number of times is 8,000 or more.

Examples of the propylene-based polymer (A) according to the present invention include propylene homopolymers and copolymers of propylene and α-olefins having 2 to 20 carbon atoms. Examples of the α-olefin include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene. , 1-octadecene, 1-eicosene, and the like, and ethylene or an α-olefin having 4 to 10 carbon atoms is preferable. The α-olefin copolymerized with propylene may be one kind or two or more kinds.

The propylene polymer (A) according to the present invention preferably has a heat of fusion (ΔH _A ) obtained by a differential scanning calorimeter (DSC) measurement of 20 J/g or more, more preferably 40 J/g or more, and further preferably It is a propylene-based polymer of 50 J/g or more. The upper limit of the heat of fusion (ΔH _A ) is not particularly limited, but is usually 120 J/g or less.

The propylene polymer (A) according to the present invention preferably has a melting point (Tm) obtained by a differential scanning calorimeter (DSC) measurement of 145° C. or higher, more preferably 147° C. or higher, still more preferably 150° C. or higher. And particularly preferably 155°C or higher. The upper limit of Tm is not particularly limited, but is usually 170° C. or lower, for example. The propylene-based polymer (A) having a melting point (Tm) in the above range is excellent in moldability, heat resistance and mechanical properties.

The propylene polymer (A) according to the present invention preferably has an intrinsic viscosity [η] measured in decalin at 135° C. of 0.5 to 10 dl/g, more preferably 1.0 to 6 dl/g, It is preferably in the range of 1.0 to 4 dl/g, and when the intrinsic viscosity is in such a range, good fluidity is exhibited, it is easy to mix with other components, and the olefin polymer obtained is obtained. Molded articles having excellent mechanical strength tend to be obtained from the composition.

The MFR of the propylene-based polymer (A) according to the present invention is not particularly limited as long as the olefin-based polymer composition obtained by blending the propylene-based polymer (A) can be molded and processed, but is usually 230°C. The MFR measured under a load of 2.16 kg is in the range of 0.001 to 50 g/10 minutes, preferably 0.1 to 30 g/10 minutes, and more preferably 0.1 to 10 g/10 minutes.

The propylene-based polymer (A) according to the present invention can be obtained by various known production methods such as the production method described in International Publication No. WO2006/123759.

Propylene copolymer (B)
The propylene-based copolymer (B) that constitutes the olefin-based polymer composition of the present invention contains 40 to 89 mol%, preferably 50 to 89 mol%, and more preferably 55 to 89 mol% of a propylene-derived structural unit. , 11 to 60 mol%, preferably 11 to 50 mol%, more preferably 11 to 45 mol% of a structural unit derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) (provided that propylene is used). The total of the constituent units derived from and the constituent units derived from the α-olefin having 2 to 20 carbon atoms (however, excluding propylene) is 100 mol %), and a propylene-based co-polymer satisfying the following requirement (b). It is united.

Requirement (b): The intrinsic viscosity [η] (dl/g) measured in decalin at 135° C. and the MFR (g/10 min) measured at 230° C. and a load of 2.16 kg are expressed by the following relational expression (2). ) Is satisfied.
1.50 x MFR ^(-0.20) ≤ [η] ≤ 2.65 x MFR ^(-0.20) (2)
Preferably, the intrinsic viscosity [η] (dl/g) measured in decalin at 135° C. and the MFR (g/10 min) measured at 230° C. under a load of 2.16 kg have the following relational expression (2′). Meet
1.80 x MFR ^(-0.20) ≤ [η] ≤ 2.50 x MFR ^(-0.19) (2')
The propylene-based polymer (B) satisfying the formula (2) of the requirement (b), preferably the formula (2′) has the same intrinsic viscosity [η] as compared with the conventional isotactic propylene-based copolymer. Shows a small MFR.

This is because, as described in Macromolecules 31, 1335-1340 (1998), the molecular weight between entanglement points of isotactic polypropylene (reported as Me=6900 (g/mol) in the paper) and syndiotactic polypropylene. It is considered to be due to the difference with the molecular weight between entanglement points (reported as Me=2170 (g/mol) in the paper). That is, it is considered that the same intrinsic viscosity [η] has a syndiotactic structure, so that the material having an isotactic structure has more entanglement points and a smaller MFR.

As described above, the propylene-based polymer satisfying the above-mentioned formula (2) of the requirement (b) is a polymer having stereoregularity different from that of the propylene-based polymer having an isotactic structure, and is a so-called syndyne. It is considered to have an tactic structure. By containing such a propylene-based copolymer (B), the olefin-based polymer composition according to the present invention has excellent wear resistance.

Examples of the propylene-based copolymer (B) according to the present invention include a copolymer of propylene and an α-olefin having 2 to 20 carbon atoms. Examples of the α-olefin include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene. , 1-octadecene, 1-eicosene, and the like, and ethylene or an α-olefin having 4 to 10 carbon atoms is preferable. The α-olefin copolymerized with propylene may be one kind or two or more kinds.

The propylene-based copolymer (B) according to the present invention preferably has a heat of fusion (ΔH _B ) obtained by DSC measurement of 10 J/g or less, more preferably 5 J/g or less, still more preferably 1 J/g or less. It is a propylene-based copolymer.

The propylene-based copolymer (B) according to the present invention is preferably a polymer having a melting point of less than 90°C, more preferably 80°C or less, still more preferably no melting point, which is obtained by DSC measurement. In the present invention, the absence of a melting point means that the heat of fusion ΔH due to the melting peak is 1 J/g or less.

The MFR of the propylene-based copolymer (B) according to the present invention satisfies the above requirement (b), and an olefin-based polymer composition obtained by mixing the propylene-based copolymer (B) can be molded and processed. It is not particularly limited as long as it is, but usually, MFR measured at 230° C. under a load of 2.16 kg is 0.01 to 100 g/10 minutes, preferably 0.01 to 50 g/10 minutes, more preferably 0.1 to 30 g. /10 minutes, particularly preferably 0.1 to 10 g/10 minutes.

The intrinsic viscosity [η] of the propylene-based copolymer (B) according to the present invention is not particularly limited as long as the above requirement (b) is satisfied, but the intrinsic viscosity [η] measured in 135° C. decalin is usually 0. It is desirable to be in the range of 0.01 to 10 dl/g, preferably 0.05 to 10 dl/g, and more preferably 0.1 to 5 dl/g. When the propylene-based polymer (B) having an intrinsic viscosity [η] in the above range is used, the obtained olefin-based polymer composition has excellent fluidity during molding and mechanical properties of the obtained molded body are also excellent. ..

The propylene-based polymer (B) according to the present invention usually has an Mw/Mn (in terms of polystyrene) measured by GPC of 1.2 to 3.5, more preferably 1.5 to 3.0.
In the propylene-based copolymer (B) according to the present invention, as shown below, the measured syndiotactic triad fraction (rr fraction) measured by ¹³ C-NMR takes a value within a specific range. It may be one. Preferably, the rr fraction is 40% or more, more preferably 45% or more.

The rr fraction is P _rr in the ¹³ C-NMR spectrum (absorption intensity derived from the methyl group of the second unit in the site where three propylene units are continuously syndiotacticly bonded) and P _w (total propylene units). It is determined by the following formula (3) from the absorption intensity of the absorption intensity derived from the methyl group).
rr fraction (%)=100×P _rr /P _w (3)

Here, when determining the rr fraction, the absorption derived from mr (absorption derived from at least both syndiotactic bond and isotactic bond among 3 units of propylene unit, used for determining Pmr (absorption intensity)) ), absorption derived from _rr (absorption derived from the methyl group of the second unit at the site where three propylene units are continuously syndiotacticly bonded, used to determine P _rr (absorption intensity)), or mm derived Absorption (absorption derived from the methyl group of the second unit at the site where three propylene units are continuously isotactically bonded, used to determine P _mm (absorption intensity)) overlaps with absorption derived from the comonomer. In this case, the contribution of the comonomer component is not subtracted and the value is calculated as it is.

The rr fraction is specifically [0018] among the descriptions of the method for obtaining the "syndiotacticity parameter (SP value)" described in [0018] to [0031] of JP-A-2002-097325. ]-[0023] according to the attributions, it is calculated by the above formula (3) from the integrated intensities of the signals in the first region, the second region and the third region.

In the measurement of rr fraction, ¹³ C-NMR measurement is performed as follows, for example. That is, 0.35 g of the sample is heated and dissolved in 2.0 ml of hexachlorobutadiene. After filtering this solution through a glass filter (G2), 0.5 ml of deuterated benzene is added and charged into an NMR tube having an inner diameter of 10 mm. Then, ¹³ C-NMR measurement is performed at 120° C. using a GX-400 type NMR measurement device manufactured by JEOL Ltd. The total number of times is 8,000 or more.

The rr fraction is an index indicating that the component (B) has a higher proportion of a so-called syndiotactic structure, and is an index having a similar meaning to satisfying the requirement (b) described above.

The propylene-based polymer (B) according to the present invention has a constitutional unit derived from propylene, for example, 40 to 89 mol%, preferably 50 to 89 mol%, more preferably 55 to 80 mol%, and a constitutional unit derived from ethylene, for example. 1 to 35 mol %, preferably 1 to 30 mol %, more preferably 5 to 20 mol %, and for example, 10 to 45 mol %, preferably a constituent unit derived from an α-olefin having 4 to 20 carbon atoms. Propylene/ethylene/α-olefin copolymer having 4 to 20 carbon atoms (B1) in the range of 10 to 40 mol%, more preferably 15 to 40 mol% is desirable (provided that propylene-derived constitutional unit, ethylene-derived And the total of the structural unit derived from the α-olefin having 4 to 20 carbon atoms is 100 mol %.).

Further, in this case, the total amount of the constituent units derived from propylene, the constituent units derived from ethylene and the constituent units derived from α-olefin having 4 to 20 carbon atoms in the content of the constituent unit derived from α-olefin having 4 to 20 carbon atoms. (Pb2-2) and the content of ethylene-derived constitutional units, the total amount of propylene-derived constitutional units, ethylene-derived constitutional units, and α-olefin-derived constitutional units having 4 to 20 carbon atoms. The ratio (mol%) to (Pb2-1) preferably satisfies the relationship of Pb2-2>Pb2-1, and more preferably (Pb2-2)-(Pb2-1)≧1 mol%. ..

As the propylene-based polymer (B) according to the present invention, in addition to the propylene/ethylene/C4-20 α-olefin copolymer (B1), a propylene-derived structural unit is, for example, 50 to 89 mol%. , Preferably 55 to 89 mol %, more preferably 65 to 85 mol %, propylene containing a structural unit derived from ethylene, for example, 11 to 50 mol %, preferably 11 to 45 mol %, more preferably 15 to 35 mol %. An ethylene copolymer (B2) can also be mentioned (however, the total of the propylene-derived constitutional unit and the ethylene-derived constitutional unit is 100 mol %). Comparing the copolymers (B1) and (B2), the propylene/ethylene/α-olefin copolymer (B1) is preferable.

The propylene-based polymer (B) according to the present invention can be produced by various known production methods. For example, it can be obtained by copolymerizing propylene and α-olefin with a catalyst capable of producing syndiotactic propylene. More specifically, for example, it can be produced by the method described in WO 2008-059895, but the method is not limited thereto.

A block copolymer containing a block composed of a structural unit derived from an aromatic vinyl compound and a block composed of a structural unit derived from a conjugated diene compound, or a hydrogenated product thereof (C)
A block copolymer comprising a block composed of a structural unit derived from an aromatic vinyl compound and a block composed of a structural unit derived from a conjugated diene compound, which constitutes the olefin polymer composition of the present invention, or a hydrogenated product thereof (C ) Is usually a thermoplastic elastomer. Here, “consisting of” means that other structural unit may be contained within a range that does not affect the present invention.

Preferably, it is a block copolymer containing a block composed of a constituent unit derived from an aromatic vinyl compound, a block composed of a constituent unit derived from a conjugated diene compound, and a block composed of a constituent unit derived from an aromatic vinyl compound. A triblock copolymer is particularly preferred.

Examples of the aromatic vinyl compound that constitutes the block composed of the aromatic vinyl compound-derived structural unit include styrene, α-methylstyrene, p-methylstyrene, vinylxylene, vinylnaphthalene, and mixtures thereof. Particularly preferred is styrene. Examples of the conjugated diene compound contained in the block composed of the structural unit derived from the conjugated diene compound include butadiene, isoprene, pentadiene, isobutylene, and mixtures thereof. Among them, butadiene, isoprene and mixtures thereof are preferred. However, butadiene is more preferable.

A typical example of such a (C) block copolymer and hydrogenated product thereof is a block copolymer containing a block composed of a structural unit derived from an aromatic vinyl compound and a block composed of a structural unit derived from a conjugated diene compound. Examples include coalesced products and hydrogenated products thereof. More specifically, for example, a block copolymer consisting of a block obtained by polymerizing styrene and a block obtained by polymerizing butadiene and a hydrogenated product thereof, and a block obtained by polymerizing styrene and butadiene are polymerized. And a hydrogenated product of the block obtained by polymerizing styrene with a block obtained by polymerizing styrene, and a block copolymer comprising a block obtained by polymerizing styrene and a block obtained by polymerizing isoprene. Polymers and hydrogenated products thereof, triblock copolymers composed of blocks obtained by polymerizing styrene and blocks obtained by polymerizing isoprene, and blocks obtained by polymerizing styrene, and hydrogenated products thereof, and the like. To be

Here, for example, hydrogenation of a block copolymer composed of three blocks of a polymer block segment obtained by polymerizing styrene, a block segment obtained by polymerizing butadiene, and a polymer block segment obtained by polymerizing styrene The thing is sometimes called styrene/ethylene/butylene/styrene block copolymer (SEBS).

Derived from an aromatic vinyl compound in a block copolymer containing a block composed of a constitutional unit derived from an aromatic vinyl compound and a block composed of a constitutional unit derived from a conjugated diene compound or a hydrogenated product (C) thereof according to the present invention. The content of the segment is not particularly limited, but is preferably in the range of 5 to 40% by weight based on the total weight of the block copolymer or the hydrogenated product (C) thereof in view of flexibility and rubber elasticity.

The MFR of a block copolymer or a hydrogenated product (C) thereof comprising a block composed of a constitutional unit derived from an aromatic vinyl compound and a block composed of a constitutional unit derived from a conjugated diene compound according to the present invention is a mixture thereof. The olefin polymer composition thus obtained is not particularly limited as long as it can be molded and processed, but the MFR measured under a load of 2.16 kg at 230° C. according to JIS K-7210 is usually 0. It is in the range of 01 to 100 g/10 minutes, preferably 0.01 to 50 g/10 minutes, more preferably 0.1 to 30 g/10 minutes, and particularly preferably 0.1 to 10 g/10 minutes.

One or two types of block copolymers or hydrogenated products (C) thereof according to the present invention, each containing a block composed of a structural unit derived from an aromatic vinyl compound and a block composed of a structural unit derived from a conjugated diene compound. The above may be used in combination, or a commercially available product may be used.

Hydrogenated petroleum resin (D)
The hydrogenated petroleum resin (D) constituting the olefin polymer composition of the present invention means a product obtained by hydrogenating a petroleum resin. Petroleum resin is a C ₅ fraction (a fraction containing mainly hydrocarbons having 5 carbon atoms) and/or a C ₉ fraction among the remaining fractions obtained by collecting the necessary fractions from the cracked oil of petroleum naphtha. It is a resin obtained by polymerizing a (fraction containing mainly a hydrocarbon having 9 carbon atoms) as a raw material.

Specific examples of the hydrogenated petroleum resin using the C ₅ fraction as a raw material include isoprene, trans-1,3-pentadiene, cis-1,3-pentadiene, cyclopentadiene, dicyclopentadiene, methyldicyclopentadiene, dimethyl. Examples include hydrogenated resins obtained by polymerizing conjugated diolefinic unsaturated hydrocarbons having 4 to 6 carbon atoms represented by dicyclopentadiene and the like. Among them, hydrogenated compounds of dicyclopentadiene resin are preferable.

As a hydrogenated petroleum resin using a C ₉ fraction as a raw material, a hydrogenated resin obtained from a C ₉ fraction containing an aromatic hydrocarbon as a main component is preferable. Preferred are hydrogenated compounds obtained by partially or completely hydrogenating an aromatic petroleum resin containing C ₉ fraction as a main raw material and a copolymerized petroleum resin thereof, and specific examples thereof include styrene and isopropenyltoluene. , Vinyltoluene, α-methylstyrene, hydrogenated C ₉ aromatic petroleum resin obtained by polymerizing indene, and among them, those obtained by polymerization of styrene and α-methylstyrene are preferable, Those obtained by polymerization of α-methylstyrene are more preferable. The aromatic petroleum resin includes C ₅ /C ₉ copolymerized petroleum resin (resin obtained by copolymerizing C ₅ fraction and C ₉ fraction of naphtha cracked oil), styrenes of tar naphtha fraction, indenes, Coumalone indene resin containing coumarone, other dicyclopentadiene, etc., alkylphenol resin represented by condensate of p-tertiarybutylphenol and acetylene, ο-xylene, p-xylene or m-xylene formalin A xylene-based resin obtained by reacting with is also included. Among these, hydrogenated compounds of C ₉ aromatic petroleum resins and hydrogenated compounds of C ₅ /C ₉ copolymerized petroleum resins are preferable, and hydrogenated compounds of C ₉ aromatic petroleum resins are particularly preferable.
In the present invention, among these hydrogenated petroleum resins (D), hydrogenated resins obtained from aromatic hydrocarbons are preferably used.

The hydrogenated petroleum resin (D) according to the present invention preferably satisfies at least one of the following requirements (d1) and (d2), and more preferably both of them.

(Requirement (d1))
The hydrogenated petroleum resin (D) has a softening point of preferably 100°C or higher, more preferably 100 to 250°C.
Here, the softening point is a temperature measured as follows. The softening point is measured by the ring and ball method according to JIS K-2207. In other words, the sample was packed in a specified ring, supported horizontally in a water bath or glycerin bath, a specified ball was placed in the center of the sample, the bath temperature was raised at a rate of 5°C/min, and the sample enclosing the ball was The softening point is the temperature when the bottom plate of the ring base is touched.

(Requirement (d2))
The weight average molecular weight (Mw) of the hydrogenated petroleum resin (D) measured by GPC is preferably 400 or more, more preferably 400 to 10000, and further preferably 400 to 5000.

The hydrogenated petroleum resin (D) according to the present invention is not particularly limited in the content of constituent units derived from the main monomer constituting the hydrogenated petroleum resin (D), but is preferably 50 to 100 mol based on the total amount of the hydrogenated petroleum resin (D). %, more preferably 75 to 100 mol %.

The hydrogenated petroleum resin (D) may contain a monomer other than the above-mentioned main monomer, and the other monomer is not particularly limited, but may be, for example, a C ₅ fraction or a C ₉ fraction. Examples thereof include monomers selected from saturated hydrocarbons.

The hydrogenated petroleum resin (D) may be used alone or in combination of two or more.
Further, the hydrogenated petroleum resin (D) may be appropriately produced by a conventional method, or a commercially available product may be used. Examples of commercially available products include, for example, α-methylstyrene hydrogenated resin, trade name “Regalrez” manufactured by Eastman Chemical Co., Ltd., and C ₉ aromatic hydrocarbon-based hydrogenated resins include Arakawa Chemical Co., Ltd. Company name "Alcon", Idemitsu Kosan Co., Ltd. product name "I Marve", ExxonMobil Co., Ltd. product name "Opera", "Escorets", Eastman Chemical Co., Ltd. product name "Plastolyn", etc. Examples of the C5 hydrocarbon-based hydrogenated resin include a product name “Eastotac” manufactured by Eastman Chemical Co., Ltd., and the like.

Softener (E)
The softening agent (E) constituting the olefin polymer composition of the present invention is a softening agent having a kinematic viscosity at 40° C. of 30 to 200 mm ² /sec, preferably 50 to 180 mm ² /sec. Here, the kinematic viscosity of the softening agent is a value measured according to JIS K2283.

As the softening agent (E), a softening agent usually used for rubber can be used. Specifically, petroleum-based substances such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and petrolatum; coal tar. , Coal tar such as coal tar pitch; fatty oils such as castor oil, linseed oil, rapeseed oil, soybean oil and coconut oil; waxes such as tall oil, beeswax, carnauba wax, lanolin; ricinoleic acid, palmitic acid, stearin Acids, fatty acids such as barium stearate and calcium stearate, or metal salts thereof; synthetic polymer substances such as petroleum resin, coumarone indene resin and atactic polypropylene; ester plasticizers such as dioctyl phthalate, dioctyl adipate and dioctyl sebacate; Other examples include microcrystalline wax, sub (factice), liquid polybutadiene, modified liquid polybutadiene, and liquid thiocol. Among these softeners, oils are preferable, and process oil is particularly preferable.

Silicone modified polypropylene (F)
The olefin polymer composition of the present invention also preferably contains a silicone-modified polypropylene (F) as an optional component. The silicone-modified polypropylene (F) is not particularly limited as long as polypropylene is modified with silicone, but it is usually a component obtained by graft-polymerizing silicone with polypropylene or a propylene-based polymer. is there. Examples of silicones include one selected from polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane.

The amount of silicone in the silicone-modified polypropylene (F) can be appropriately adjusted in consideration of the resin strength, the required degree of antifouling property, and the like. The molecular weight or MFR (230° C., 2.16 kg) of the silicone-modified polypropylene (F) is not particularly limited, but normally, the MFR is generally 2 g/10 min to 70 g/10 min, It is preferably 9 g/10 minutes to 70 g/10 minutes.

The silicone-modified polypropylene (F) can be obtained by binding to the polypropylene chain, for example, a silicone resin in which both ends of the molecular chain are blocked with dimethylvinylsiloxane groups. Specific manufacturing methods and the like are known, and can be obtained, for example, according to the description in JP-A-8-127660.

Moreover, as the silicone-modified polypropylene (F), a commercially available silicone-grafted polypropylene can be used. Examples of commercially available silicone-grafted polypropylenes include X-22-2101 (Shin-Etsu Chemical Co., Ltd.) and BY27-201 (Toray Dow Corning Co., Ltd.).

Other components The olefin polymer composition of the present invention may contain components other than the above-mentioned (A) to (F) within a range not impairing the object of the present invention. For example, the olefin-based polymer composition of the present invention may contain an inorganic filler, if necessary, and includes a nucleating agent, an antioxidant, a flame retardant, an antistatic agent, a pigment, a dye, and a rust inhibitor. You may contain additives, such as.

Representative examples of the inorganic filler include, for example, calcium carbonate, talc, glass fiber, magnesium carbonate, mica, kaolin, calcium sulfate, barium sulfate, titanium white, white carbon, carbon black, aluminum hydroxide, aluminum oxide, and hydroxide. Magnesium, silica, clay, zeolite and the like can be mentioned, and these can be used alone or in admixture of two or more.

Representative examples of the nucleating agent include, for example, sodium benzoate, bisbenzylidene sorbitol, bis(p-methylbenzylidene) sorbitol, bis(p-ethylbenzylidene) sorbitol, sodium-2,2-methylenebis(4,6-dibenzyl). -T-butylphenyl)phosphite, talc, titanium oxide, aluminum hydroxydi-pt-butylbenzoate and the like can be mentioned, and these can be used alone or in admixture of two or more kinds.

Typical examples of the antioxidant include pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] and triethylene glycol-bis[3-(3-t -Butyl-5-methyl-4-hydroxyphenyl)propionate] and the like, and phenolic antioxidants such as tris(monononylphenyl)phosphite and tris(2,4-di-t-butylphenyl)phosphite Examples thereof include antioxidants and sulfur-based antioxidants such as dilaurylthiodipropionate, and these may be used alone or in combination of two or more.

Typical examples of the flame retardant include magnesium hydroxide, calcium hydroxide, and phosphorus compounds, and these can be used alone or in combination of two or more.

Olefin-based polymer composition The olefin-based polymer composition of the present invention,
5 to 10 parts by mass, preferably 5 to 9 parts by mass of the propylene-based polymer (A),
25 to 50 parts by mass, preferably 27 to 45 parts by mass of the propylene-based copolymer (B),
10 to 40 parts by mass, preferably 15 to 35 parts by mass of the aromatic vinyl block copolymer or its hydrogenated product (C),
10 to 30 parts by mass, preferably 15 to 25 parts by mass of the hydrogenated petroleum resin (D), and
It is a composition containing the softening agent (E) in an amount of 5 to 15 parts by mass, preferably 6 to 14 parts by mass (however, the total of (A), (B), (C), (D) and (E). Is 100 parts by mass).

In the olefin polymer composition of the present invention, the silicone-modified polypropylene (F) is further added to 100 parts by mass of the total of (A), (B), (C), (D) and (E). , Usually 0.05 to 10 parts by mass, preferably 0.1 to 10 parts by mass, more preferably 3 to 10 parts by mass. A molded product made of a composition containing the silicone-modified polypropylene in such an amount is preferable because it has excellent abrasion resistance.
Further, the olefin polymer composition of the present invention may contain the above-mentioned inorganic filler. When an inorganic filler is contained, it is usually 0.01 to 10 parts by mass, preferably 100 parts by mass with respect to the total 100 parts by mass of (A), (B), (C), (D) and (E). It is preferably in the range of 0.01 to 5 parts by mass, more preferably 0.01 to 1 part by mass.

Production of Olefin-Based Polymer Composition The olefin-based polymer composition of the present invention can be obtained by sequentially or simultaneously melt-kneading the above-mentioned components. In the preparation of the olefin polymer composition, for example, using a conventional kneader such as roll, Banbury mixer, single-screw extruder, twin-screw extruder, etc., each raw material is introduced sequentially or simultaneously and melt-kneaded. , A method of preparing the composition can be used. It is preferable that the raw materials to be simultaneously introduced into the kneader be mixed in advance. The obtained olefin polymer composition is usually preferably pelletized.

<Molding method and application of olefin polymer composition>
INDUSTRIAL APPLICABILITY The olefin polymer composition of the present invention can be widely used for conventionally known polyolefin applications, and can be used by molding it into molded articles of various shapes including, for example, sheets, unstretched or stretched films, filaments and the like. it can.

Specific examples of the molded article include molding obtained by known thermoforming methods such as calendar molding, extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, and foam molding. The body.

The molded body will be described below with several examples. When the molded product according to the present invention is, for example, a calendar molded product, its shape and product type are not particularly limited, and examples thereof include a sheet, a film (unstretched), a pipe, a hose, a wire coating, and a filament, and particularly a sheet. , Films and filaments are preferred.

When the olefin polymer composition of the present invention is extrusion-molded, conventionally known extruders and molding conditions can be adopted. For example, a single screw extruder, a kneading extruder, a ram extruder, a gear extruder. The molten olefin polymer composition of the present invention can be extruded from a T-die or the like to form a sheet or film (unstretched).

Sheet Molding The olefin polymer composition of the present invention is particularly referred to as a sheet [generally, a sheet having a large thickness is referred to as a sheet and a sheet having a thin thickness is referred to as a film, but in the present invention, the sheet and the film are collectively referred to as a “sheet”. Call. ] Suitable for molding. When a sheet is formed using the olefin polymer composition of the present invention, (Step 1): a step of heating and melting the olefin polymer composition, and (Step 2): a heat-melted olefin polymer composition. Can be performed in the step of forming a sheet.
Further, a step of kneading the heat-melted olefin polymer composition may be included between the (step 1) and (step 2).

Calender molding The olefin polymer composition of the present invention is particularly suitable for calender molding. When calendering using the olefin polymer composition of the present invention, (step 1): a step of heating and melting the olefin polymer composition, and (step 2-1): calendering to form a sheet. Can be done in process.

Further, a step of kneading the heat-melted olefin polymer composition may be included between the (step 1) and (step 2-1).
Further, the (step 2) may include a step of obtaining a laminate by (step 2-2): a step of simultaneously forming a sheet by calendering and laminating the following base material.

Synthetic Leather Molding Synthetic leather (artificial leather) can be molded by (step 2-1) calendering to form a sheet, or (step 2-2) calendering to form a sheet and sticking the following base material. A method of obtaining a laminated body in a step of performing the matching at the same time is preferable, but the sheets obtained in the above-mentioned (Step 1) and (Step 2) may be taken out and separately bonded to a base material.

Further, an embossing step of forming a pattern on the surface of the sheet by heat fusion, needle punching or the like may be added at an appropriate stage in the production process of the sheet or laminate of the present invention.
That is, embossing may be performed directly on the sheet of the present invention, a laminated body may be manufactured by bonding the sheet after embossing and a substrate, or embossing may be performed after forming the laminated body. Good.

Laminated body The sheet obtained from the olefin polymer composition of the present invention may be laminated with various known base materials depending on the application.

The substrate that can be laminated is a woven fabric, a knitted fabric, a non-woven fabric, or a silver surface layer made of at least one of synthetic fiber, natural fiber, inorganic fiber, or a mixture thereof.
Examples of synthetic fibers include synthetic fibers made of polypropylene, polyethylene, polyester, nylon, acrylic, polyurethane, polyvinyl chloride, silicone, and the like.

Examples of natural fibers include cotton, hemp, silk, and wool.
Examples of the inorganic fiber include glass fiber and carbon fiber.
Further, as the woven cloth, for example, a woven fabric or a knitted fabric made of a fibrous material can be used. Examples of the non-woven fabric include a fibrous material entangled by a chemical method, a mechanical method, or a combination thereof to form a web.
In addition, examples of the base material that can be laminated include foams such as foam sheets. Examples of the foam include polyolefins such as urethane, polyethylene and polypropylene, and foams made of polystyrene.

Synthetic Leather The olefin polymer composition of the present invention can be suitably used for synthetic leather (artificial leather) applications. The synthetic leather of the present invention may be a sheet-like material obtained from the olefin-based polymer composition of the present invention, and a sheet-like material obtained from the olefin-based polymer composition and another substrate are laminated. It may be one that has been subjected to processing such as embossing. The synthetic leather according to the present invention is preferably a laminate including a layer made of the olefin polymer composition of the present invention. Here, the layer comprising the olefin polymer composition of the present invention is preferably a surface layer (outermost layer). Synthetic leather can be used in various fields such as automobiles (including motorcycles), sports, home appliances, stationery, sundries, furniture, clothing, gardening, and building materials.

Specific examples of applications of the synthetic leather according to the present invention include automobile flooring materials, ceiling materials, instrument panels, door trims, interior seats, seat leathers, seat backs, bicycle saddles, deck boards, floor mats, and non-slip. Mats, leisure sheets, gaskets, tarpaulins, chair skins, bags, school bags, athletics shoes and marathon shoes, running shoes, basket shoes, tennis shoes, golf shoes, walking shoes, jumpers, coats, safety wear, gloves , Ski wear, mountaineering clothes for winter, obi, plow, ribbon, mobile phone strap, switch plate, jacket, name tag, golf bag, watch belt, bag grip, golf club grip, boots, notebook cover, book cover, key chain, ashtray Cases, cigarette cases, cellphone cases, pen cases, pen grips, wallets, business card holders, pass cases, tatami mats, wallpaper, shoulder straps, sandals, slippers, boats, water beds, tent fabrics, albums, address book covers, care products (Bed cover), baseball ball, basketball, handball, dodge ball, table cloth, accordion curtain, lighting equipment, stuffed animal, underlay, desk cover, picture frame, harness, belt, hat, parachute, kayak, sofa, cushion cover, ball skin, Examples include but are not limited to mouse pads, patches, badges, bracelets, necklaces, storage boxes, greenhouse sheets, chests, tables, tissue boxes and the like.

The synthetic leather according to the present invention is excellent in abrasion resistance, scratch resistance and the like, water resistance and weight reduction, from the viewpoint of good recyclability, automobile flooring materials, ceiling materials, instrument panels, door trims, interior sheets, It is especially suitable for automotive interior parts such as seat leather.

Further, since it is water resistant, lightweight, and has no odor or color transfer, it is particularly suitable for sports equipment such as mats, tatami mats, running shoes, mountaineering shoes, balls, kayaks, and ski wear.

The synthetic leather according to the present invention includes the layer made of the above-described olefin polymer of the present invention, and thus has excellent abrasion resistance and flexibility, and exhibits a touch similar to that of a synthetic leather made of vinyl chloride. .. Conventionally, in synthetic leather made of resin other than PVC, in order to achieve a texture close to that made of PVC, it relies on ingenuity in processing such as foaming the skin layer or laminating a cushion layer under the skin layer. In many cases, it was unavoidable, but with synthetic leather using the olefin-based polymer composition of the present invention, a tactile sensation equivalent to that of vinyl chloride synthetic leather can be achieved without modification by processing or structure. The degree of freedom in designing synthetic leather and products using the synthetic leather becomes higher. Further, the product can be reduced in weight because it can be sufficiently used in a form having no cushion layer or the like.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
The physical properties and the like in Examples and Comparative Examples were measured by the following methods.

(1) MFR
The MFR was measured according to JIS K-7210 (1999) at 230° C. under a load of 2.16 kg.
(2) Density (kg/m ³ )
The density measurement was performed using a density gradient tube using the product pellet as a sample.

(3) Intrinsic viscosity [η] (dl/g)
It is a value measured at 135° C. using a decalin solvent. That is, about 20 mg of polymer powder, pellets or resin lumps were dissolved in 15 ml of decalin, and the specific viscosity η _SP was measured in an oil bath at 135°C. To this decalin solution, 5 ml of decalin solvent was added and diluted, and then the specific viscosity η _SP was measured in the same manner. This dilution operation was repeated twice more, and the value of η _SP /C when the solute concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity (see the following formula).
[Η]=lim(η _SP /C) (C→0)

(4) Molecular weight distribution (Mw/Mn)
The molecular weight distribution (Mw/Mn) was measured as follows using a gel permeation chromatograph Alliance GPC-2000 type manufactured by Waters. The separation columns were two TSKgel GNH6-HT and two TSKgel GNH6-HTL, the column sizes were 7.5 mm in diameter and 300 mm in length, the column temperature was 140° C., and the mobile phase was o. -Using dichlorobenzene (Wako Pure Chemical Industries, Ltd.) and BHT (dibutylhydroxytoluene, Takeda Yakuhin) 0.025% by weight as an antioxidant, moving at 1.0 ml/min, the sample concentration was 15 mg/10 mL, and sample injection The amount was 500 microliters and a differential refractometer was used as a detector. The standard polystyrene was manufactured by Tosoh Corporation when the molecular weight was Mw<1000 and Mw>4×10 ⁶ , and was manufactured by Pressure Chemical Corporation when 1000≦Mw≦4×10 ⁶ .

(5) Content of ethylene, propylene and α-olefin in each polymer Quantification of the content of ethylene, propylene and α-olefin was performed using a JNM GX-400 type NMR measuring device manufactured by JEOL Ltd. as follows. Was measured. A sample (0.35 g) was dissolved by heating in 2.0 ml of hexachlorobutadiene. After this solution was filtered through a glass filter (G2), 0.5 ml of deuterated benzene was added and charged into an NMR tube having an inner diameter of 10 mm to perform ¹³ C-NMR measurement at 120°C. The number of times of integration was 8,000 or more. The composition of ethylene, propylene and α-olefin was quantified by the obtained ¹³ C-NMR spectrum.

(6) Stereoregularity (rrrr fraction, rr fraction, and mmmm fraction)
The stereoregularity was quantified by ¹³ C-NMR measurement under the same conditions as above.
The syndiotactic pentad fraction (rrrr fraction) is P _rrrr in the ¹³ C-NMR spectrum (absorption intensity derived from the methyl group of the third unit in the site where 5 units of propylene units are continuously syndiotacticly bonded). ) And P _w (absorption intensity derived from all the methyl groups of the propylene unit) were obtained from the following formula (1).
rrrr fraction (%)=100×P _rrrr /P _w (1)

The syndiotactic triad fraction (rr fraction) is P _rr in the ¹³ C-NMR spectrum (absorption intensity derived from the second methyl unit at the site where three propylene units are continuously syndiotacticly bonded). And the absorption intensity of P _w (absorption intensity derived from all methyl groups of the propylene unit) were calculated by the following formula (3).
rr fraction (%)=100×P _rr /P _w (3)
The mmmm fraction was measured by the method described in JP-A-2003-147135.

(7) Melting point (Tm) and heat of fusion (ΔH) (J/g)
Using Seiko Instruments DSC, about 5 mg of the sample was packed in an aluminum pan for measurement, heated to 230° C. at 50° C./min, held at 230° C. for 5 minutes, and then -100 at 10° C./min. The temperature was lowered to 0° C., and then the temperature was held for 5 minutes, and then the temperature was raised to 200° C. at 10° C./min. The melting point (Tm) and the heat of fusion (ΔH) were determined from the endothermic curve at the time of this final temperature rise.

(8) Durometer A Hardness As a sample for measuring the durometer A hardness, a 1 mm thick press sheet was molded using a propylene-based polymer composition using a hydraulic heat press machine manufactured by Shindo Metal Industry Co., Ltd. set at 200°C. At this time, the residual heat is applied for about 5 to 7 minutes and pressurized at 10 MPa for 1 to 2 minutes, then, using another hydraulic heat press manufactured by Shindo Metal Industry Co., Ltd. set at 20° C., compressed at 10 MPa and cooled for about 5 minutes. Then, a measurement sample was prepared. A brass plate having a thickness of 5 mm was used as the hot plate.
The obtained press sheet was left standing at 23° C. for 24 hours for conditioning, and then used for measurement. According to JIS K-7215, the retention time was 5 seconds.

(9) Abrasion resistance (Taber abrasion test)
As a sample, using a press sheet obtained by conditioning, according to JIS K-7204, 23° C., wear wheel; H-22, rotation speed; 60 rotations/minute (60 rpm), number of rotations; 500 times, load The amount of wear loss (mg) was measured at 1000 g.

(10) Tactile evaluation As a sample, a press sheet obtained by adjusting the condition was used, and the following seven grades were given by sensory evaluation.
1...Returning is very fast and feels firm after rolling and holding 2...Returning is fast and feels firm after rolling and holding 3...Rolling and grasping with hand After returning, it feels a little bit firmer and harder. 4...Returning after rolling and holding with a hand is medium speed, hardness 5...Returning after rolling and holding with a hand is a little slower , Feeling soft 6...Return after rolling and holding by hand is slow 7...Returning after rolling and holding by hand is very slow and feels soft

[Production Example 1] (Production of Propylene Polymer (A-1))
250 ml of toluene was charged into a glass autoclave having an inner volume of 500 ml which had been sufficiently replaced with nitrogen, propylene was passed at a rate of 150 liter/hour, and kept at 25°C for 20 minutes. On the other hand, a magnetic stirrer was placed in a side-armed flask with a content volume of 30 ml that had been sufficiently replaced with nitrogen, and 5.00 mmol of a toluene solution of methylaluminoxane (Al=1.53 mol/l) was added, and then dibenzylmethylene (cyclopentadiene 5.0 μmol of a toluene solution of (enyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride was added, and the mixture was stirred for 20 minutes. This solution was added to a toluene-containing glass autoclave in which propylene was flown to initiate polymerization. Propylene gas was continuously supplied at a rate of 150 liters/hour, polymerization was carried out at 25° C. for 45 minutes under normal pressure, and then a small amount of methanol was added to terminate the polymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer, and the polymer was dried under reduced pressure at 80° C. for 12 hours. As a result, 2.38 g of a polymer was obtained. The polymerization activity was 0.63 kg-PP/mmol-Zr·hr, the intrinsic viscosity [η] of the obtained propylene homopolymer (A-1) was 1.9 dl/g, and Tm=158° C. (Tm1=152 ° C., a Tm2 = 158 ° C.), pentad fraction (rrrr fraction) is 93.5% heat of fusion (△ H _a) is 57J / g, was Mw / Mn = 2.0 .. The MFR (JIS K6721, 230° C., 2.16 kg load) was 6.0 g/10 minutes.

[Production Example 2] (Production of propylene/ethylene/1-butene copolymer (B-1))
In a polymerization apparatus of 2000 ml that had been sufficiently replaced with nitrogen, 833 ml of dry hexane, 120 g of 1-butene and triisobutylaluminum (1.0 mmol) were charged at room temperature, then the temperature inside the polymerization apparatus was raised to 60° C., and propylene was added. After pressurizing the pressure in the system to 0.33 MPa, the pressure in the system was adjusted to 0.63 MPa with ethylene. Then, 0.002 mmol of di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride was contacted with 0.6 mmol of methylaluminoxane (manufactured by Tosoh Finechem Co., Ltd.) in terms of aluminum. The toluene solution was added to the polymerization vessel, polymerization was carried out for 20 minutes while maintaining the internal temperature at 60° C. and the system internal pressure at 0.63 MPa with ethylene, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 2 L of methanol and dried under vacuum at 130° C. for 12 hours. The obtained propylene/ethylene/1-butene copolymer (B-1) was 97 g, and the intrinsic viscosity [η] measured in decalin at 135°C was 2.3 dl/g. MFR (JIS K6721, 230° C., 2.16 kg load) was 1.3 g/10 minutes. That is, the value on the left side of the relational expression (2) of the requirement (b) is 1.50 x (1.3) ^(-0.20) = 1.42, and the value on the right side is 2.65 x (1.3) ^{( Since -0.20)} = 2.51 and the intrinsic viscosity [η] is 2.3 dl/g, it can be seen that the relational expression (2) of the requirement (b) is satisfied. The glass transition point obtained by DSC was −23.8° C., and the heat of fusion (ΔH _B ) was 1 J/g or less.
The composition of the propylene/ethylene/1-butene copolymer (B-1) was such that the constitutional unit derived from propylene was 62 mol %, the constitutional unit derived from ethylene was 10 mol %, and the constitutional unit derived from 1-butene was 28 mol %. there were.

The components used in Examples and Comparative Examples are shown below.
-Propylene-based polymer (A) component The propylene-based polymer (A-1) obtained in Production Example 1 was used.
-Propylene-based copolymer (B) component The propylene/ethylene/1-butene copolymer (B-1) obtained in Production Example 2 was used.
-Aromatic vinyl block copolymer or hydrogenated product (C) component thereof As a hydrogenated product (C-1) of the aromatic vinyl block copolymer, MFR: 4.5 g/10 minutes (temperature: 230°C) , Load: 2.16 kg), Durometer A hardness: 42 hydrogenated styrene block copolymer elastomer (trade name: Tuftec (registered trademark) H1221 manufactured by Asahi Kasei Co., Ltd.) was used.

-Hydrogenated petroleum resin (D) component As hydrogenated petroleum resin (D-1), Arakawa Chemical Co., Ltd. Alcon P-140 (alicyclic saturated hydrocarbon resin, softening point: 140 ± 5°C, Mw: 900) is used. Using.
・Softening agent (E)
Paraffin oil Diana Process Oil PW90 (40° C. kinematic viscosity: 95 mm ² /s) manufactured by Idemitsu Chemical Co., Ltd. was used as the softening agent (E-1).

-Silicone-modified polypropylene (F) component As a grafted silicone polymer (F-1), a grafted silicone polymer (made by Toray Dow Corning Co., Ltd.) having an MFR of 5 g/10 minutes (temperature: 230°C, load: 2.16 kg). The product name BY27-201) was used.
・Soft PVC
Commercially available soft polyvinyl chloride (G-1): (density 1200 kg/m ³ ).

[Examples 1 to 3 and Comparative Examples 1 to 5]
The raw materials of (A-1) to (E-1) and, if necessary, (F-1) were weighed in the amounts (parts by mass) described in Table 1 below to obtain a mixture of the components. It was 0.2 parts by weight of 3,5-di-t-butyl-4-hydroxytoluene was added as an antioxidant to 100 parts by weight of the obtained mixture, and a resin temperature of 200 was obtained using a twin-screw extruder. The pellets of the olefin-based polymer composition were obtained by melt-kneading at 0° C. and granulating.
The physical properties of the obtained olefin polymer composition were measured by the methods described above. The results are shown in Table 1.

The composition of Example 1 had a density of 890 kg/m ³ and a wear resistance (Taber wear loss amount), which is a performance as an index of durability as a synthetic leather, was 5 mg.
The composition of Example 2 had a density of 890 kg/m ³ and an abrasion resistance of 1 mg. The wear resistance was further improved as compared with Example 1.
The polyvinyl chloride of Comparative Example 5 had a density of 1200 kg/m ³ and abrasion resistance of 10 mg.

The olefin polymer composition of the present invention can be suitably used as a raw material for various molded products such as sheets, and can be particularly preferably used for synthetic leather applications. The synthetic leather of the present invention can be used in various fields such as automobiles (including two wheels), sports, home appliances, stationery, sundries, furniture, clothing, gardening, and building materials.

Claims (6)

(A) A propylene-based polymer having a syndiotactic pentad fraction (rrrr fraction) measured by ¹³ C-NMR of 85% or more and containing 90 to 100 mol% of a constitutional unit derived from propylene: 5 -10 parts by mass,
(B) A propylene-based copolymer containing 40 to 89 mol% of a propylene-derived structural unit and 11 to 60 mol% of a C2 to C20 α-olefin-derived structural unit, and satisfying the following requirement (b): : 25 to 50 parts by mass,
(C) A block copolymer containing a block composed of a structural unit derived from an aromatic vinyl compound and a block composed of a structural unit derived from a conjugated diene compound or a hydrogenated product thereof: 10 to 40 parts by mass,
(D) Hydrogenated petroleum resin: 10 to 30 parts by mass, and
(E) Softening agent having a kinematic viscosity at 40° C. in the range of 30 to 200 mm ² /sec: 5 to 15 parts by mass (provided (A), (B), (C), (D) and (E). ) Is 100 parts by mass)
An olefin-based polymer composition comprising:
Requirement (b): The intrinsic viscosity [η] (dl/g) measured in decalin at 135° C. and the MFR (g/10 min) measured at 230° C. and a load of 2.16 kg satisfy the following relational expression. ..
1.50 x MFR ^(-0.20) ≤ [η] ≤ 2.65 x MFR ^(-0.20) A block copolymer or a hydrogenated product thereof comprising the block (C) composed of a structural unit derived from an aromatic vinyl compound and a block composed of a structural unit derived from a conjugated diene compound is prepared from a structural unit derived from an aromatic vinyl compound. An olefinic polymer according to claim 1, which is a block copolymer or a hydrogenated product thereof, which comprises a block consisting of a structural unit derived from a conjugated diene compound, and a block consisting of a structural unit derived from an aromatic vinyl compound. Polymer composition. A block copolymer containing the block (C) composed of a structural unit derived from an aromatic vinyl compound and a block composed of a structural unit derived from a conjugated diene compound or a hydrogenated product thereof is a styrene/ethylene/butylene/styrene block copolymer. The olefin polymer composition according to claim 1 or 2, which is a polymer. Furthermore, 0.1 to 10 parts by mass of (F) silicone-modified polypropylene is contained with respect to 100 parts by mass of the total of (A), (B), (C), (D) and (E). Item 5. The olefin polymer composition according to any one of Items 1 to 3. The olefin polymer composition according to any one of claims 1 to 4, which is used for producing synthetic leather. A synthetic leather comprising a layer comprising the olefin-based polymer composition according to claim 1.