JP2023137852A - Thermoplastic elastomer composition, injection molded body and automobile interior part - Google Patents

Abstract

To provide a thermoplastic elastomer composition and the like, the composition having excellent fluidity and flexibility of a molded product and capable of reducing the stickiness of a molded product.SOLUTION: There is provided a thermoplastic elastomer composition which comprises a propylene-based polymer (A), an olefin-based copolymer (B) and a softening agent (C), wherein the (B) contains an ethylene/an α-olefin copolymer (B1) containing ethylene and an α-olefin unit having 3 to 20 carbon atoms and an ethylene/propylene/non-conjugated polyene copolymer (B2), the content of the (B1) in the (B) is 0 to 99 mass%, the content of the (B2) is 1 to 100 mass% [provided that the total of the content of (B1) and (B2) is defined as 100 mass%], the content of the (A) is 25 to 300 pts.mass based on 100 pts.mass of the (B) and the content of the (C) is more than 120 pts.mass and 300 pts.mass or less based on 100 pts.mass of the (C).SELECTED DRAWING: None

Description

The present disclosure relates to a thermoplastic elastomer composition, an injection molded article containing the thermoplastic elastomer composition, and an automobile interior part made of the injection molded article.

A thermoplastic elastomer composition is produced by so-called dynamic crosslinking, in which a resin without radical crosslinking such as polypropylene (PP) and a radical crosslinkable elastomer are crosslinked while melt-kneading in an extruder in the presence of a radical initiator. It is widely used in automobile parts such as interior skin materials.

As such rubber compositions, olefin elastomer compositions using ethylene propylene diene rubber (EPDM) are known (see Patent Document 1 and Patent Document 2). Furthermore, compositions in which hydrogenated rubber is dynamically crosslinked are also known (see Patent Documents 3 and 4). Furthermore, a thermoplastic elastomer composition using a hydrogenated copolymer of an olefin resin, a vinyl aromatic compound, and a conjugated diene compound has been disclosed (see Patent Documents 5 and 6).

Japanese Patent Application Publication No. 8-120127 Japanese Patent Application Publication No. 9-137001 Patent No. 2737251 Japanese Patent Application Publication No. 2004-67798 Japanese Patent Application Publication No. 2001-49051 Japanese Patent Application Publication No. 2005-89656

Thermoplastic elastomer compositions used for automobile interior skin materials are generally required to have high fluidity and, at the same time, are required to have high flexibility in molded products. In order to improve the fluidity of the composition while not impairing the flexibility of the molded product, it is common practice to add a large amount of a softener, but adding a large amount of the softener causes the surface of the molded product to become sticky. There was a tendency for the tactile sensation to be impaired.
In recent years, from the perspective of automobile design, there has been a need to suppress stickiness on the surface of automobile interior skin materials while increasing the flexibility of molded products and the fluidity of compositions, and we have fully satisfied all of these required performances. It is desired to realize a thermoplastic elastomer composition that has the following properties.

In view of the above-mentioned current situation, the present disclosure provides a thermoplastic elastomer composition that has excellent fluidity and flexibility of a molded article and can suppress stickiness of the molded article, an injection molded article containing the composition, and an automobile comprising the injection molded article. The company provides interior parts.

[1]
A propylene polymer (A),
Olefin copolymer (B),
a softener (C);
Contains
The olefin copolymer (B) is
an ethylene/α-olefin copolymer (B1) containing ethylene and an α-olefin unit having 3 to 20 carbon atoms;
Contains an ethylene/propylene/non-conjugated polyene copolymer (B2),
The content of the ethylene/α-olefin copolymer (B1) in the olefin copolymer (B) is 0 to 99% by mass, and the content of the ethylene/α-olefin copolymer (B2) is 0 to 99% by mass. The content is 1 to 100% by mass [however, the total content of (B1) and (B2) is 100% by mass. ] and
The content of the propylene polymer (A) is 25 to 300 parts by mass based on 100 parts by mass of the olefin copolymer (B), and
A thermoplastic elastomer composition, wherein the content of the softener (C) is more than 120 parts by mass and 300 parts by mass or less based on 100 parts by mass of the olefin copolymer (B).

[2]
The content of the ethylene/α-olefin copolymer (B1) in the olefin copolymer (B) is 0 to 95% by mass, and the content of the ethylene/propylene/non-conjugated polyene copolymer ( B2) is 5 to 100% by mass [however, the total content of (B1) and (B2) is 100% by mass. ] and
The thermoplastic elastomer composition according to [1], wherein the content of the softener (C) is more than 120 parts by mass and 290 parts by mass or less based on 100 parts by mass of the olefin copolymer (B).

[3]
The thermoplastic elastomer composition according to [1] or [2], further comprising a hydrogenated block copolymer (D).

[4]
The thermoplastic elastomer composition according to [3], wherein the content of the hydrogenated substance (D) in the block copolymer is 30 to 350 parts by mass based on 100 parts by mass of the olefin copolymer (B). thing.

[5]
According to any one of [1] to [4], the content of the propylene polymer (A) is 25 to 250 parts by mass based on 100 parts by mass of the olefin copolymer (B). thermoplastic elastomer composition.

[6]
The thermoplastic elastomer composition according to any one of [1] to [5], wherein at least a portion of the olefin copolymer (B) is crosslinked.

[7]
An injection molded article comprising the thermoplastic elastomer composition according to any one of [1] to [6].

[8]
An automobile interior part comprising the injection molded article according to [7].

[9]
A propylene polymer (A),
Olefin copolymer (B),
a softener (C);
Contains
The olefin copolymer (B) is
an ethylene/α-olefin copolymer (B1) containing ethylene and an α-olefin unit having 3 to 20 carbon atoms;
Contains an ethylene/propylene/non-conjugated polyene copolymer (B2),
The content of the ethylene/α-olefin copolymer (B1) in the olefin copolymer (B) is 0 to 99% by mass, and the content of the ethylene/α-olefin copolymer (B2) is 0 to 99% by mass. The content is 1 to 100% by mass [however, the total content of (B1) and (B2) is 100% by mass. ] and
The content of the propylene polymer (A) is 25 to 300 parts by mass based on 100 parts by mass of the olefin copolymer (B), and
A method for producing a thermoplastic elastomer composition in which the content of the softener (C) is more than 120 parts by mass and 300 parts by mass or less with respect to 100 parts by mass of the olefin copolymer (B),
The production method includes dynamically heat-treating the propylene polymer (A), the olefin copolymer (B), and the softener (C) in the presence of a crosslinking agent (F). A method for producing a thermoplastic elastomer composition, comprising the step of:

According to the present disclosure, a thermoplastic elastomer composition that has excellent fluidity and flexibility of a molded product and can suppress stickiness of the molded product, an injection molded product containing the composition, and an automobile interior part made of the injection molded product are provided. Can be provided.

In the present disclosure, the descriptions of "XX to YY" and "XX to YY" expressing numerical ranges mean numerical ranges including the lower limit and upper limit, which are the endpoints, unless otherwise specified.
Moreover, when numerical ranges are described in stages, the upper and lower limits of each numerical range can be arbitrarily combined.
Furthermore, the description of "A and/or B" is a concept that includes the case of A, the case of B, and the case of both A and B.

<Propylene polymer (A)>
A propylene polymer (A) which is one of the components of the thermoplastic elastomer composition of the present disclosure [hereinafter may be referred to as "component (A)". ] refers to a polymer in which the content of structural units derived from propylene among the structural units constituting the polymer is 50 mol% or more, and the content of structural units derived from propylene in component (A) is 50 mol% or more. The content is preferably 90 mol% or more.

The number of component (A) according to the present invention may be one, or two or more.
Component (A) according to the present invention may be a propylene homopolymer or a copolymer of propylene and a comonomer other than propylene.

The structure of component (A) according to the present invention is not particularly limited, and for example, the propylene-derived structural unit portion may have an isotactic structure, a syndiotactic structure, or an atactic structure. Further, in the case of the copolymer, it may be of a random type (also referred to as random PP), a block type (also referred to as block PP: bPP), or a graft type.

The comonomer may be any other monomer copolymerizable with propylene, and α-olefins having 2 or 4 to 10 carbon atoms are preferred. Specific examples include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1-decene. , ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, and 1-octene are preferred. One type of comonomer may be used, or two or more types may be used.
The content of the structural unit derived from the comonomer in the copolymer is preferably 10 mol % or less from the viewpoint of heat resistance, mechanical strength, etc.

Component (A) according to the present disclosure may be synthesized by a conventionally known method, or a commercially available product may be used. Examples of commercially available products include polypropylene from Sun Allomer Co., Ltd., Prime Polypro from Prime Polymer Co., Ltd., Novatec from Nippon Polypropylene Co., Ltd., and SCG PP from SCG Plastics.

Component (A) according to the present disclosure may be a crystalline polymer or a non-crystalline polymer. Here, crystallinity means that the melting point (Tm) is observed in differential scanning calorimetry (DSC).
When component (A) according to the present disclosure is a crystalline polymer, its melting point (according to the measurement method of JIS K 7121) is preferably 100°C or higher, more preferably 120°C from the viewpoint of heat resistance. The temperature is preferably 180°C or lower, more preferably 170°C or lower.

The MFR (according to ASTM D 1238-65T measurement method, 230°C, 2.16 kg load) of component (A) according to the present disclosure is preferably 0.1 to 100 g/10 minutes, more preferably 0. It is 1 to 50 g/10 minutes, more preferably 0.1 to 5.0 g/10 minutes.
When the MFR of component (A) according to the present disclosure is within the above range, a composition having excellent heat resistance, mechanical strength, fluidity, and moldability can be easily obtained.

<Olefin copolymer (B)>
Olefin copolymer (B), which is one of the components of the thermoplastic elastomer composition of the present disclosure (hereinafter sometimes referred to as "component B"). ] contains the following ethylene and an ethylene/α-olefin copolymer (B1) containing an α-olefin unit having 3 to 20 carbon atoms, and an ethylene/propylene/non-conjugated polyene copolymer (B2), The content of the ethylene/α-olefin copolymer (B1) in the olefin copolymer (B) is 0 to 99% by mass, preferably 0 to 95% by mass, more preferably 0 to 85% by mass, even more preferably is 0 to 75% by mass, and the content of the ethylene propylene non-conjugated polyene copolymer (B2) is 1 to 100% by mass, preferably 5 to 100% by mass, more preferably 15 to 100% by mass, and Preferably 25 to 100% by mass [provided that the total content of (B1) and (B2) is 100% by mass. ].

Component (B) may be the ethylene/propylene/nonconjugated polyene copolymer (B2) alone, but when component (B) contains the ethylene/α-olefin copolymer (B1), the resulting thermoplastic elastomer composition The product has better stickiness and fluidity.

<Ethylene/α-olefin copolymer (B1)>
Ethylene/α-olefin copolymer (B1), which is one of the components contained in the olefin copolymer (B) according to the present disclosure (hereinafter sometimes referred to as "component (B1)"). ] is an ethylene/α-olefin copolymer containing units derived from ethylene and units derived from α-olefin having 3 to 20 carbon atoms.

Component (B1) according to the present disclosure can be obtained by copolymerizing at least ethylene and an α-olefin having 3 to 20 carbon atoms. Examples of α-olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1- Examples include decene, 1-undecene, 1-dodecene, and the like. Among these, from the viewpoint of imparting flexibility, α-olefins having 3 to 12 carbon atoms are preferred, propylene, 1-butene, and 1-octene are more preferred, and 1-octene is even more preferred.

Component (B1) according to the present disclosure usually has a range of 70 to 99 mol%, preferably 80 to 97 mol% of units derived from ethylene, and 1 unit derived from an α-olefin having 3 to 20 carbon atoms. ~30 mol%, preferably 3~20 mol% [provided that the total amount of units derived from ethylene and units derived from α-olefin having 3 to 20 carbon atoms is 100 mol%. 〕It is in. It is preferable for the content ratio of units derived from ethylene to be within the above range in order to obtain a thermoplastic elastomer composition having excellent mechanical strength.

Component (B1) according to the present disclosure usually has an MFR (ASTM D1238 load 2.16 kg, temperature 190°C) of 0.1 to 20 g/10 minutes, preferably in the range of 0.3 to 10 g/10 minutes. It is in.
By setting component (B1) according to the present disclosure to have an MFR within the above range, a thermoplastic elastomer composition with better balance between fluidity and mechanical strength can be obtained.
Component (B1) according to the present disclosure usually has a density in the range of 0.8 to 0.9 g/cm ³ .

Component (B1) according to the present disclosure can be produced using, for example, a known polymerization catalyst such as a Ziegler-Natta catalyst, a vanadium catalyst, or a metallocene catalyst. The polymerization method is not particularly limited, and liquid phase polymerization methods such as solution polymerization method, suspension polymerization method, and bulk polymerization method, gas phase polymerization method, and other known polymerization methods can be used. Moreover, these copolymers are not limited as long as they exhibit the effects of the present invention, and can be obtained as commercially available products. Commercially available products include, for example, Engage 8842 (ethylene/1-octene copolymer) manufactured by Dow Chemical Company, Vistalon (registered trademark) manufactured by ExxonMobil, and Espren (registered trademark) manufactured by Sumitomo Chemical Co., Ltd. ), Tafmer P (registered trademark), Tafmer A (registered trademark), and the like.

<Ethylene/propylene/non-conjugated polyene copolymer (B2)>
Ethylene-propylene-nonconjugated polyene copolymer (B2), which is one of the components contained in the olefin copolymer (B) according to the present disclosure [hereinafter may be referred to as "component (B2)". ] is obtained by copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a nonconjugated polyene.
Component (B2) according to the present disclosure is a copolymer having a constitutional unit derived from ethylene, a constitutional unit derived from an α-olefin having 3 to 20 carbon atoms, and a constitutional unit derived from a non-conjugated polyene.
Component (B2) according to the present disclosure may be used alone or in combination of two or more.

Specifically, the α-olefin having 3 to 20 carbon atoms constituting component (B2) according to the present disclosure includes propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9- Examples include methyl-1-decene, 11-methyl-1-dodecene and 12-ethyl-1-tetradecene.
The α-olefin having 3 to 20 carbon atoms is preferably an α-olefin having 3 to 12 carbon atoms, more preferably propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene, and more preferably Propylene is preferred.
The α-olefin having 3 to 20 carbon atoms may be used alone or in combination of two or more.

Specifically, the non-conjugated polyene constituting component (B2) according to the present disclosure includes 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, and 5-methyl-1,4-hexadiene. Chain nonconjugated dienes such as methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, and 7-methyl-1,6-octadiene; methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 5-vinyl-2-norbornene, 5-iso Cyclic non-conjugated dienes such as propenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclopentadiene and norbornadiene; 8-methyl-4-ethylidene-1,7-nonadiene, 4-ethylidene-1,7-undecadiene, 2 , 3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, 4-ethylidene-8-methyl-1,7-nonadiene, etc. Examples include. Among them, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene are preferred.
These non-conjugated polyenes may be used alone or in combination of two or more.

As the component (B2) according to the present disclosure, ethylene/propylene/5-ethylidene-2-norbornene random copolymer, ethylene/propylene/5-ethylidene-2-norbornene/5-vinyl-2-norbornene random copolymer For example,
Component (B2) according to the present disclosure is a molar ratio of ethylene and an α-olefin having 3 to 20 carbon atoms (ethylene/α-olefin), in other words, a structural unit derived from ethylene and an α-olefin having 3 to 20 carbon atoms. The molar ratio with the structural unit derived from olefin is usually 50/50 to 90/10, preferably 50/50 to 85/15.

Component (B2) according to the present disclosure contains structural units derived from non-conjugated polyene, usually 1.0 to 25.0% by mass, preferably 3.0 to 20% by mass, more preferably 4.0 to 15% by mass. Included within the range of %.

The iodine value of component (B2) according to the present disclosure is preferably 1 to 50 g/100 g, more preferably 3.0 to 40.0 g/100 g, even more preferably 5.0 to 35.0 g/100 g. It is. When the iodine value is within the above range, a crosslinked product with a high crosslinking density can be obtained and the oil retention of the thermoplastic elastomer composition can be improved, which is preferable.

Component (B2) according to the present disclosure usually has an intrinsic viscosity [η] of preferably 0.5 to 7.0 dl/g, more preferably 1.0 to 5.0 dl/g, as measured in decalin at 135°C. 0 dl/g, more preferably 1.0 to 4.0 dl/g. It is preferable that the limiting viscosity is within the above range because it provides a good balance between physical properties and processability.

As the component (B2) according to the present disclosure, a commercially available component may be used, or a polymer obtained by polymerization may be used.

<<Production method of ethylene/propylene/non-conjugated polyene copolymer (B2)>>
Component (B2) according to the present disclosure is disclosed in JP-A-9-71617, JP-A-9-71618, JP-A-9-208615, JP-A-10-67823, JP-A-10-67824, It can be prepared by a conventionally known method such as that described in JP-A-10-110054, and is not particularly limited, but it is preferably produced by the following method, for example.

Component (B2) according to the present disclosure contains a vanadium compound represented by the following general formula (I-a) or the following general formula (I-b) and an organoaluminium compound represented by the following general formula (II) as main components. of a non-conjugated polyene and ethylene in the presence of a catalyst that Obtained by random copolymerization of ethylene, an α-olefin having 3 to 20 carbon atoms, and a nonconjugated polyene at a molar ratio of supply amount (nonconjugated polyene/ethylene) of 0.01 to 0.2. It will be done. Preferably, the copolymerization is carried out in a hydrocarbon medium.

[Vanadium compound]
The vanadium compound is a component soluble in the hydrocarbon medium of the polymerization reaction system, and specifically,
VO(OR) _a X _b ...(I-a) or V(OR) _c X _d ...(I-b)
(In the formula, R is a hydrocarbon group, ≦c+d≦4)
Typical examples include vanadium compounds represented by or electron donor adducts thereof.

More specifically, VOCl ₃ , VO(OC ₂ H ₅ )Cl ₂ , VO(OC ₂ H ₅ ) ₂ Cl, VO(O-iso-C ₃ H ₇ )Cl ₂ , VO(O-n-C _Examples include _4H9 ) _Cl2 , VO( _OC2H5 ) ₃ , _{VOBr3 , VCl4 , VOCl3} , VO(O-n _{- C4H9} ) ₃ , _{VCl3.2OC6H12OH} , _etc. be able to.

[Organic aluminum compound]
The organoaluminum compound is a compound represented by the following general formula (II).
R' _m AlX' _3-m ...(II)
(In the formula, R' is a hydrocarbon group, X' is a halogen atom, and m is 1 to 3.)

Specific examples of organoaluminum compounds include trialkylaluminums such as triethylaluminum, tributylaluminium, and triisopropylaluminium; dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide. Alkylaluminum sesquialkoxides such as R ¹ _0.5 Al(OR 1 ) 0.5; partially alkoxylated alkylaluminums having an average composition such as R 1 0.5 Al(OR ¹ ) _0.5 ; dialkylaluminum halides such as diethylaluminium chloride, dibutylaluminum chloride, diethylaluminum bromide, etc. ; partially halogenated alkyls such as alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide, alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide; Aluminum; partially hydrogenated alkyl aluminum such as dialkyl aluminum hydride such as diethylaluminum hydride, dibutyl aluminum hydride, alkylaluminum dihydride such as ethyl aluminum dihydride, propyl aluminum dihydride; ethyl aluminum ethoxy chloride, butyl aluminum butoxy Partially alkoxylated and halogenated alkylaluminiums such as chloride, ethylaluminum ethoxybromide, etc. may be mentioned.

In the present disclosure, among the above compound (I-a), a soluble vanadium compound represented by VOCl ₃ and among the above compound (II), Al(OC ₂ H ₅ ) ₂ Cl/Al ₂ (OC ₂ H ₅ ) When a blend with ₃ Cl ₃ (blend ratio (molar ratio) is 1/5 or more) is used as a catalyst component, the insoluble matter after Soxhlet extraction (solvent: boiling xylene, extraction time: 3 hours, mesh: 325) This is preferable because the above-mentioned copolymer rubber (A) can be obtained in which the amount is 1% or less.

Further, as the catalyst used in the copolymerization, a so-called metallocene catalyst, for example, a metallocene catalyst described in JP-A-9-40586 or JP-A-2010-241897 may be used. Further, as the catalyst used in the above-mentioned copolymerization, a non-metallocene catalyst, for example, a transition metal complex catalyst described in WO 2006/121086 may be used.

<Softener (C)>
A softener (C) which is one of the components of the thermoplastic elastomer composition of the present disclosure [hereinafter may be referred to as "component (C)"]. ] is not particularly limited, but a plasticizer commonly used for rubber can be used. From the viewpoint of compatibility with the propylene polymer (A) and the ethylene/α-olefin copolymer (B), process oils made of paraffinic, naphthenic, aromatic, etc. hydrocarbons are preferred. Among these component (C), a process oil mainly composed of paraffinic hydrocarbons is preferred from the viewpoint of weather resistance and colorability, and a process oil mainly composed of naphthenic hydrocarbons is preferred from the viewpoint of compatibility. From the viewpoint of thermal and light stability, the content of aromatic hydrocarbons in the process oil is preferably 10% or less, and 5% or less in terms of the carbon number ratio specified in ASTM D2140-97. is more preferable, and even more preferably 1% or less.

<Hydrogenated product (D) of block copolymer>
Hydrogenated product (D) of a block copolymer that is one of the components of the thermoplastic elastomer composition of the present disclosure [hereinafter may be referred to as "component (D)" or "hydrogenated product (D)"] be. ] is a hydrogenated product of a block copolymer having at least one block each consisting mainly of conjugated diene monomer units and at least one block consisting mainly of vinyl aromatic monomer units.
Component (D) according to the present disclosure is obtained by hydrogenating at least a portion of monomer units derived from a conjugated diene monomer (hereinafter sometimes referred to as "hydrogenation").

Here, the term "vinyl aromatic monomer unit" means a structural unit of a polymer resulting from polymerization of a vinyl aromatic monomer, and its structure is derived from a substituted vinyl group derived from substituted ethylene. This is a molecular structure in which the two carbon atoms of the group serve as bonding sites. Furthermore, the term "conjugated diene monomer unit" refers to a structural unit of a polymer produced as a result of polymerizing a conjugated diene monomer, and its structure consists of two olefins derived from the conjugated diene monomer. This is a molecular structure in which carbon is the bonding site.

In component (D) according to the present disclosure, "containing mainly" means that the copolymer contains monomer units derived from a conjugated diene monomer (or vinyl aromatic monomer) in the copolymer block. It means that the block contains 50 mol% or more, preferably 60 mol% or more, more preferably 65 mol% or more. For example, a block mainly composed of conjugated diene monomer units means that the block contains monomer units derived from conjugated diene monomers in an amount of 50 mol% or more, preferably 60 mol% or more, and more preferably 65 mol%. % or more.

The vinyl aromatic monomer in component (D) according to the present disclosure is not particularly limited, and examples thereof include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N Examples include vinyl aromatic compounds such as -dimethyl-p-aminoethylstyrene and N,N-diethyl-p-aminoethylstyrene. These may be used alone or in combination of two or more. Among these, styrene is preferred from the viewpoint of economy.

The conjugated diene monomer in component (D) according to the present disclosure is a diolefin having a pair of conjugated double bonds, such as 1,3-butadiene (butadiene), 2-methyl-1,3- Examples include butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, and 1,3-hexadiene. Among these, butadiene and isoprene are preferred from the economic point of view. These may be used alone or in combination of two or more.

The arrangement of each block in component (D) according to the present disclosure is not particularly limited, and any suitable arrangement can be adopted as appropriate. For example, if a polymer block made of vinyl aromatic monomer units is represented by S and a polymer block made of conjugated diene monomer units at least partially hydrogenated is represented by B, this block Hydrogenated polymers include SB, S(BS) _n1 (where n1 represents an integer of 1 to 3), and S(BSB) _n2 (where n2 represents an integer of 1 to 2). ), and (SB) _n3 X (where n3 represents an integer of 3 to 6. (represents a residue). Among these, SB type 2 (diblock), SBS type 3 (triblock), and SBSB type 4 (tetrablock) linear block copolymers are preferred.

Here, even if the polymer block B is a polymer block consisting only of conjugated diene monomer units, it mainly contains conjugated diene monomer units and also contains vinyl aromatic monomer units (conjugated diene monomer units). It may be a polymer block in which a monomer unit and a vinyl aromatic monomer unit are copolymerized, and at least a portion of the conjugated diene monomer unit in each polymer block is hydrogenated.

The content of vinyl aromatic monomer units in component (D) according to the present disclosure can be measured by nuclear magnetic resonance spectroscopy (NMR).
From the viewpoint of mechanical strength, the content of the vinyl aromatic monomer unit block in component (D) according to the present disclosure is preferably 10% by mass or more, more preferably 10 to 40% by mass. preferable. Here, the content of the vinyl aromatic compound polymer block in component (D) is determined by a method (I.M. The mass of the vinyl aromatic compound polymer block obtained by the method described in Kolthoff, et al., J. Polym. Here, it is defined by the following formula using (excluding vinyl aromatic compound polymers having an average degree of polymerization of about 30 or less).
Content of vinyl aromatic compound polymer block (mass%) = (mass of vinyl aromatic compound polymer block in copolymer before hydrogenation/mass of copolymer before hydrogenation) x 100

When a plurality of polymer blocks are present in the component (D) according to the present disclosure, the structures such as the molecular weight and composition of each block may be the same or different. For example, component (D) contains a hydrogenated copolymer block containing a conjugated diene monomer unit and a vinyl aromatic monomer unit, and a hydrogenated copolymer block mainly composed of a conjugated diene monomer unit. may exist. The boundaries and edges of each block do not necessarily need to be clearly distinguished. The mode of distribution of the vinyl aromatic monomer units in each polymer block is not particularly limited, and may be uniformly distributed, tapered, stepped, convex, or concave. Good too. Moreover, a crystal part may be present in the polymer block.

The mode of distribution of the vinyl units of the conjugated diene monomer units in each polymer block in component (D) according to the present disclosure is not particularly limited, and for example, the distribution may be biased. Examples of methods for controlling the distribution of vinyl units include adding a vinylizing agent during polymerization and changing the polymerization temperature. Further, the distribution of the hydrogenation rate of the conjugated diene monomer units may be uneven. The hydrogenation rate distribution can be determined by changing the distribution of vinyl units, or by copolymerizing isoprene and butadiene and then hydrogenating them using a hydrogenation catalyst, which will be described later. This can be controlled by a method that utilizes the difference between the two.

From the viewpoint of heat resistance, aging resistance and weather resistance, component (D) according to the present disclosure preferably accounts for 75 mol% or more of the unsaturated bonds contained in the conjugated diene monomer unit before hydrogenation. , more preferably 85 mol% or more, still more preferably 97 mol% or more, is hydrogenated.
The hydrogenation catalyst used for hydrogenation is not particularly limited and is conventionally known.
(1) Supported heterogeneous hydrogenation catalyst in which metals such as Ni, Pt, Pd, and Ru are supported on carbon, silica, alumina, diatomaceous earth, etc.
(2) A so-called Ziegler-type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe, or Cr or a transition metal salt such as an acetylacetone salt and a reducing agent such as an organic aluminum;
(3) Homogeneous hydrogenation catalysts such as so-called organometallic complexes such as organometallic compounds such as Ti, Ru, Rh, and Zr can be used.

Specific hydrogenation catalysts include Japanese Patent Publication No. 42-008704, Japanese Patent Publication No. 43-006636, Japanese Patent Publication No. 63-004841, Japanese Patent Publication No. 01-037970, Japanese Patent Publication No. 01-053851, Hydrogenation catalysts described in Publication No. 02-009041 and the like can be used. Among these, preferred hydrogenation catalysts include reducing organometallic compounds such as titanocene compounds.

As the titanocene compound, for example, the compounds described in JP-A-08-109219 can be used, and specific examples include (substituted ) Examples include compounds having at least one ligand having a cyclopentadienyl skeleton, an indenyl skeleton, or a fluorenyl skeleton.
Examples of the reducing organometallic compound include organic alkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, organozinc compounds, and the like.

The method of polymerizing the block copolymer before hydrogenation in component (D) according to the present disclosure is not particularly limited, and a known method may be employed. For example, JP-A-36-019286, JP-A-43-017979, JP-A-46-032415, JP-A-49-036957, JP-A-48-002423, JP-A-48-004106, Examples include methods described in Japanese Patent Publication No. 56-028925, Japanese Patent Application Laid-open No. 59-166518, and Japanese Patent Application Laid-Open No. 60-186577.

If necessary, component (D) may have a polar group. Examples of polar groups include hydroxyl group, carboxyl group, carbonyl group, thiocarbonyl group, acid halide group, acid anhydride group, thiocarboxylic acid group, aldehyde group, thioaldehyde group, carboxylic acid ester group, amide group, and sulfonic acid group. group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, isothiocyanate group, silicon halide group, an alkoxysilicon group, a tin halide group, a boronic acid group, a boron-containing group, a boronic acid group, an alkoxytin group, a phenyltin group, and the like.

The vinyl bond content in the conjugated diene monomer units in the block copolymer before hydrogenation in component (D) according to the present disclosure is preferably 5 mol% or more from the viewpoint of flexibility and scratch resistance. From the viewpoints of properties, elongation at break, and scratch resistance, the content is preferably 70 mol% or less. The vinyl bond content in the conjugated diene monomer unit is more preferably 10 to 50 mol%, even more preferably 10 to 30 mol%, even more preferably 10 to 25 mol%.
Here, the vinyl bond content refers to the 1,2-bond content of the conjugated diene before hydrogenation, which is incorporated in the bonding modes of 1,2-bond, 3,4-bond, and 1,4-bond. It means the proportion of those incorporated by bonds and 3,4-bonds. Vinyl bond content can be measured by NMR.

The weight average molecular weight of component (D) before crosslinking is not particularly limited, but from the viewpoint of scratch resistance it is preferably 50,000 or more, and from the viewpoint of molding fluidity it is preferably 400,000 or less, more preferably is 50,000 to 300,000. Although the molecular weight distribution (Mw/Mn: weight average molecular weight/number average molecular weight) is not particularly limited, it is preferably a value close to 1 from the viewpoint of scratch resistance. The weight average molecular weight and number average molecular weight were determined by gel permeation chromatography (GPC; manufactured by Shimadzu Corporation, device name: LC-10) using tetrahydrofuran (1.0 mL/min) as a solvent and an oven temperature of 40°C. ), column: TSKgelGMHXL (4.6 mm ID x 30 cm, 2 columns). The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw/Mn) are calculated as polystyrene equivalent molecular weight.

<Polyorganosiloxane (E)>
Polyorganosiloxane (E) is one of the components that may be included in the thermoplastic elastomer composition of the present disclosure [hereinafter sometimes referred to as "component (E)"]. ] is not particularly limited, but preferably has a linear, branched, or crosslinked polymer structure from the viewpoint of abrasion resistance and feel to the touch.

Component (E) according to the present disclosure is not particularly limited, and known components can also be used. Preferred polyorganosiloxanes include polymers containing siloxane units having substituents such as alkyl groups, vinyl groups, and aryl groups. Among these, polyorganosiloxanes having alkyl groups are particularly preferred, and polyorganosiloxanes having methyl groups are particularly preferred. Siloxane is more preferred.

Specific examples of polyorganosiloxanes having methyl groups include polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrogensiloxane, and the like. Among these, polydimethylsiloxane is preferred.

The kinematic viscosity of component (E) according to the present disclosure is not particularly limited, but from the viewpoint of wear resistance and scratch resistance, the kinematic viscosity (25°C) specified in JIS Z8803 is 5000 centistokes (cSt) or more. It is preferable that there be. In addition, from the viewpoint that the dispersibility of component (E) in the resulting thermoplastic elastomer composition tends to improve, the appearance is excellent, and the quality stability during melt extrusion also tends to be further improved, component (E) Preferably, the kinematic viscosity is less than 3 million cSt. The kinematic viscosity of component (E) is more preferably 10,000 cSt or more and less than 3 million cSt, and even more preferably 50,000 cSt or more and less than 3 million cSt.

≪Thermoplastic elastomer composition≫
The thermoplastic elastomer composition of the present disclosure contains the propylene polymer (A), the olefin copolymer (B), and the softener (C), and contains the olefin copolymer (B). ) contains the above ethylene/α-olefin copolymer (B1) and the above ethylene/propylene/non-conjugated polyene copolymer (B2), and contains the above ethylene/α-olefin copolymer (B). The content of the olefin copolymer (B1) is 0 to 99% by mass, and the content of the ethylene/propylene/non-conjugated polyene copolymer (B2) is 1 to 100% by mass [However, (B1) and ( The total content of B2) is 100% by mass. ], and the content of the propylene polymer (A) is 25 to 300 parts by mass, preferably 25 to 250 parts by mass, more preferably 30 parts by mass, based on 100 parts by mass of the olefin copolymer (B). ~230 parts by mass, more preferably 35 to 200 parts by mass, and the content of the softener (C) is more than 120 parts by mass and 300 parts by mass based on 100 parts by mass of the olefin copolymer (B). Hereinafter, the thermoplastic elastomer composition preferably contains more than 120 and less than or equal to 290 parts by mass, more preferably more than 120 and less than or equal to 270 parts by mass, and even more preferably more than 120 and not more than 250 parts by mass.

Since the thermoplastic elastomer composition of the present disclosure contains the above component (A), the above component (B), and the above component (C) in the above ranges, the composition has excellent fluidity, flexibility, and feel. can get.

When the thermoplastic elastomer composition of the present disclosure contains the hydrogenated product (D) of the block copolymer in addition to the above components, a composition with excellent scratch resistance can be obtained.
When the thermoplastic elastomer composition of the present disclosure contains component (D), the content of component (D) is preferably 30 to 350 parts by mass, more preferably 40 parts by mass, based on 100 parts by mass of component (B). The amount is in the range of 330 parts by weight, more preferably 50 to 300 parts by weight.

When the thermoplastic elastomer composition of the present disclosure contains the above polyorganosiloxane (E) in addition to the above components, a composition with excellent wear resistance can be obtained.
When the thermoplastic elastomer composition of the present disclosure contains component (E), the content in the composition as polyorganosiloxane is preferably 0.5 to 10% by mass, more preferably 1 to 8% by mass, More preferably, it is in the range of 1 to 4% by mass.

The thermoplastic elastomer composition of the present disclosure may contain a crosslinking agent (F) [hereinafter sometimes referred to as "component (F)"] as needed. ] is preferably included.
Component (F) according to the present disclosure is obtained by dynamically heat-treating the thermoplastic elastomer composition of the present invention to obtain component (A), component (B), and component of the thermoplastic elastomer composition of the present invention. It acts as a crosslinking initiator for (D). As component (F), a phenol resin crosslinking agent or an organic peroxide crosslinking agent may be used, but an organic peroxide crosslinking agent is preferable.

<Organic peroxide>
Specific examples of organic peroxides that can be used as organic peroxide crosslinking agents include 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, and 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane. -hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, 1,1-bis(t-butylperoxy)cyclododecane, t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)octane, n-butyl-4,4-bis(t-butylperoxy)butane, n-butyl-4,4-bis( Peroxy ketals such as t-butylperoxy)valerate; di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, α,α'-bis(t-butylperoxy-m-isopropyl) ) Benzene, α,α'-bis(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, 2,5-dimethyl-2,5-bis Dialkyl peroxides such as (t-butylperoxy)hexyne-3; acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide oxide, diacyl peroxides such as benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-trioyl peroxide; t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxy- 2-ethylhexanoate, t-butylperoxylaurylate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, Peroxy esters such as t-butyl peroxymaleic acid, t-butyl peroxyisopropyl carbonate, cumyl peroxy octate; t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5- Examples include hydroperoxides such as dimethylhexane-2,5-dihydroperoxide and 1,1,3,3-tetramethylbutyl peroxide.

Among these components (F), from the viewpoint of thermal decomposition temperature and crosslinking performance, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, di-t-butylperoxide, Milperoxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, and 2,5-dimethyl-2,5-bis(t-butylperoxy)hexine-3 are preferred.

The component (F) according to the present disclosure may be used alone or in combination of two or more.
When the thermoplastic elastomer composition of the present disclosure contains component (F), the content is preferably 2 to 10 parts by mass, and more preferably 2 to 10 parts by mass, based on 100 parts by mass of component (B), from the viewpoint of molding fluidity. It preferably contains 2 to 8 parts by mass.
When the thermoplastic elastomer composition of the present disclosure contains component (F), the following crosslinking aid (G) can be used in combination.

<Crosslinking aid (G)>
The crosslinking aid (G) according to the present disclosure includes various known crosslinking aids, specifically monofunctional monomers and polyfunctional monomers. Such crosslinking aids can control the crosslinking reaction rate.
As the monofunctional monomer, for example, radically polymerizable vinyl monomers are preferable, such as aromatic vinyl monomers, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile, acrylic acid ester monomers, Examples include methacrylic acid ester monomers, acrylic acid monomers, methacrylic acid monomers, maleic anhydride monomers, and N-substituted maleimide monomers.

Specific examples of monofunctional monomers include styrene, methylstyrene, chloromethylstyrene, hydroxystyrene, tert-butoxystyrene, acetoxystyrene, chlorostyrene, acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, and acrylic. n-butyl acid, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, maleic anhydride, methylmaleic anhydride, 1,2-dimethylmaleic anhydride , ethylmaleic anhydride, phenylmaleic anhydride, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N-cetylmaleimide and the like. Among these, styrene, acrylonitrile, methacrylonitrile, methyl acrylate, maleic anhydride, N-methylmaleimide and the like are preferred from the viewpoint of ease of reaction and versatility. These monofunctional monomers may be used alone or in combination of two or more.

The polyfunctional monomer is a monomer having a plurality of radically polymerizable functional groups as a functional group, and preferably a monomer having a vinyl group. The number of functional groups in the polyfunctional monomer is preferably two or three.
Specific examples of polyfunctional monomers include divinylbenzene, triallyl isocyanurate, triallyl cyanurate, diacetone diacrylamide, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and trimethylolpropane triacrylate. , ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diisopropenylbenzene, p-quinone dioxime, p,p'-dibenzoylquinone dioxime, phenylmaleimide, allyl methacrylate, N,N'-m -Phenylene bismaleimide, diallyl phthalate, tetraallyloxyethane, 1,2-polybutadiene and the like are preferred, and divinylbenzene and triallyl isocyanurate are more preferred. These polyfunctional monomers may be used alone or in combination of two or more.

When the thermoplastic elastomer composition of the present disclosure contains a crosslinking aid (G), the amount is preferably 1 to 50 parts by weight, more preferably 1 to 30 parts by weight, based on 100 parts by weight of component (F).

<Production method and physical properties of thermoplastic elastomer composition>
By dynamically crosslinking the thermoplastic elastomer composition of the present disclosure, component (A) and component (B) contained in the thermoplastic elastomer composition, and if necessary further component (D), are added. At least a portion of is crosslinked. When performing dynamic crosslinking, it is preferable to perform dynamic heat treatment in the presence of the component (F) or in the presence of the component (F) and the crosslinking aid.

In the present disclosure, "dynamically heat-treating" refers to kneading in a molten state.
Note that for the thermoplastic elastomer composition of the present disclosure, the composition before being dynamically heat-treated may also be referred to as "composition 1", and the composition that has been dynamically heat-treated may also be referred to as "composition 2". be.

The dynamic heat treatment in the present disclosure is preferably performed in a closed-type apparatus, and is preferably performed in an atmosphere of an inert gas such as nitrogen or carbon dioxide gas. The temperature of the heat treatment is in the range of 300°C or less from the melting point of component (A), usually 150 to 270°C, preferably 170 to 250°C. The kneading time is usually 1 to 20 minutes, preferably 1 to 10 minutes. Further, the applied shearing force is usually in the range of 10 to 50,000 s ^-1 , preferably 100 to 10,000 s ^-1 in terms of shear rate.

The Shore A hardness (10 second value) of Composition 2 (according to the measuring method of JIS K 6253) is preferably 50 or more, more preferably 50 to 80.
When the Shore A hardness (10 second value) of Composition 2 is within the above range, it is possible to easily form a molded article having design properties such as touch and high-grade appearance, and scratch resistance.
Specifically, the Shore A hardness (10 second value) can be measured by the method described in the Examples below.

The melt flow rate of Composition 2 (according to the measurement method of JIS K 7210, 230°C, 1.2 kg load) is preferably 30 g/10 minutes or more, more preferably is 55g/10 minutes or more.

In addition to the above component (A), the thermoplastic elastomer composition of the present disclosure may contain an inorganic filler, a plasticizer, and other additives.
Examples of the inorganic filler include calcium carbonate, magnesium carbonate, silica, carbon black, glass fiber, titanium oxide, clay, mica, talc, magnesium hydroxide, aluminum hydroxide, and the like.
Examples of the plasticizer include polyethylene glycol, phthalate esters such as dioctyl phthalate (DOP), and the like.

Examples of other additives include organic and inorganic pigments such as carbon black, titanium dioxide, and phthalocyanine black; 2,6-di-t-butyl-4-methylphenol and n-octadecyl-3-(3,5' - Thermal stabilizers such as di-t-butyl-4-hydroxyphenyl) propionate; Antioxidants such as trisnonylphenyl phosphite and distearyl pentaerythritol diphosphite; 2-(2'-hydroxy-5' methyl UV absorbers such as phenyl)benzotriazole and 2,4-dihydroxybenzophenone; bis-[2,2,6,6-tetramethyl-4-piperidinyl]sebacate, tetrakis(2,2,6,6-tetramethyl- Light stabilizers such as 4-piperidinyl)-1,2,3,4-butanetetracarboxylate; Flame retardants such as ammonium polyphosphate, trioctyl phosphate, and magnesium hydroxide; Silicones such as dimethyl silicone oil and methylphenyl silicone oil. Oil; Anti-blocking agents such as stearic acid amide and erucic acid amide; Foaming agents such as sodium bicarbonate and N,N'-dinitrosopentamethylenetetramine; Antistatic agents such as palmitic acid monoglyceride and stearic acid monoglyceride; Supporting silver ions Examples include antibacterial agents such as zeolite and silver thiosulfite complex.

≪Molded object≫
The molded article according to the present disclosure is not particularly limited as long as it contains the thermoplastic elastomer composition of the present disclosure, and is a molded article molded using any known molding method depending on the application. Examples of the molding method include press molding, injection molding, extrusion molding, calendar molding, blow molding, vacuum molding, and compression molding. From the viewpoint of productivity and the ability to easily form a complicated shape, an injection molded article formed using an injection molding method is preferable.
The thermoplastic elastomer composition of the present disclosure has hardness that satisfies required performance and is excellent in scratch resistance, and is not particularly limited in use. It is suitable for various well-known uses such as electric/electronic parts, sanitary products, films/sheets, foams, and artificial leather, and is particularly suitable for use in automobile parts such as automobile interior parts, and skin materials such as artificial leather.

<Auto parts>
Automotive parts for which the molded article according to the present disclosure can be used include, for example, weather strips, ceiling materials, interior sheets, bumper moldings, side moldings, air spoilers, air duct hoses, cup holders, handbrake grips, shift knob covers, and seat adjustment. Knob, flapper door seal, wire harness grommet, rack and pinion boot, suspension cover boot, glass guide, inner belt line seal, roof guide, trunk lid seal, molded quarter window gasket, corner molding, glass encapsulation, hood seal , glass run channels, secondary seals, various packings, bumper parts, body panels, side shields, glass run channels, instrument panel skins, door skins, ceiling skins, weather stripping materials, hoses, steering wheels, boots, wire harness covers, seats Examples include adjuster covers, among which the thermoplastic elastomer composition of the present disclosure is particularly preferred since it can improve the feel and feel.

<Civil engineering/building materials supplies>
Examples of civil engineering and building materials that can be used with the molded product according to the present disclosure include civil engineering and building materials such as sheets for ground improvement, water supply boards, noise prevention walls, various gaskets and sheets for civil engineering and construction, and water-stopping materials. , joint materials, architectural window frames, etc. Among them, the thermoplastic elastomer composition of the present disclosure is particularly preferable because it can improve the texture and feel.

<Electrical/electronic parts>
Examples of electrical/electronic parts that can be used with the molded article of the present disclosure include electrical/electronic parts such as wire covering materials, connectors, caps, and plugs, and among them, the thermoplastic elastomer composition of the present disclosure can be used. , is particularly preferable because it can improve the texture and feel.

〈Life-related goods〉
Examples of daily life-related goods for which the molded article of the present disclosure can be used include sports shoe soles, ski boots, tennis rackets, ski bindings, sports goods such as bat grips, pen grips, toothbrush grips, hairbrushes, fashion belts, and various other items. Examples include miscellaneous goods such as caps and shoe inner soles, and among them, the thermoplastic elastomer composition of the present disclosure is particularly preferred because it can improve texture and feel.

<Film/sheet>
Films and sheets that can be used for the molded product according to the present disclosure include, for example, infusion bags, medical containers, automobile interior and exterior materials, beverage bottles, clothing cases, food packaging materials, food containers, retort containers, pipes, transparent substrates, Examples include sealants, and among them, the thermoplastic elastomer composition of the present disclosure is particularly preferred because it can improve the texture and feel.

<Artificial leather>
Examples of the artificial leather that can be used in the molded article of the present disclosure include chair skins, bags, school bags, sports shoes such as track and field shoes, marathon shoes, and running shoes, jumpers, coats, and other wear, belts, Examples include sashes, ribbons, notebook covers, book covers, key chains, pencil cases, wallets, business card holders, commuter pass holders, etc. Among them, the thermoplastic elastomer composition of the present disclosure can improve the texture and feel of leather. , particularly preferred.

Hereinafter, the present disclosure will be explained in more detail using Examples and Comparative Examples, but the present disclosure is not limited to these Examples. In addition, in this example, unless otherwise specified, numerical values are based on mass.
The polymers used in Examples and Comparative Examples are shown below.

[Propylene polymer (A)]
(1) As the propylene polymer (A), a propylene homopolymer (A-1) with an MFR of 2.0 g/10 min at 230°C and a 2.16 kg load condition [manufactured by Sun Allomer Co., Ltd., product name Sun Allomer (registered trademark)] PL400A] was used.

[Olefin copolymer (B1)]
(1) As the ethylene/α-olefin copolymer (B1-1), an ethylene/1-octene copolymer (manufactured by Dow Chemical Company, trade name “Engage 8842”) was used. The ethylene content of the copolymer is 55% by mass, the octene content is 45% by mass, and the MFR at 190° C. and a load of 2.16 kg is 1.0 g/10 minutes.

[Ethylene/α-olefin/non-conjugated polyene copolymer (B2)]
(1) As the ethylene/α-olefin/nonconjugated polyene copolymer (B2-1), an ethylene/propylene/5-ethylidene-2-norbornene (ENB) copolymer was used. The ethylene content of this copolymer is 70% by mass, and the ENB content is 4.9% by mass.

[Softener (C)]
(1) As the softener (C-1), paraffin oil (manufactured by Idemitsu Kosan Co., Ltd., trade name "Diana Process Oil PW-100") was used.

[Hydrogenated product (D) of block copolymer]
(1) As the hydrogenated block copolymer (D-1), a hydrogenated styrene-butadiene block copolymer (manufactured by Asahi Kasei Corporation, S.O.E. trade name S1605) was used.
(2) As the hydrogenated block copolymer (D-2), a hydrogenated styrene-butadiene block copolymer (manufactured by Asahi Kasei Corporation, S.O.E. trade name S1606) was used.

[Polyorganosiloxane (E)]
As the polyorganosiloxane (E-1), a masterbatch consisting of 50% by mass of dimethylsiloxane and 50% by mass of polypropylene (manufactured by DuPont-Toray Specialty Materials, trade name "MB50-001") was used.

[Organic peroxide (F)]
As the organic peroxide (F-1), 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane (manufactured by NOF Corporation, trade name "Perhexa 25B") was used.

[Crosslinking aid (G)]
(1) Divinylbenzene (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the crosslinking aid (G-1).

[Examples 1 to 5, Comparative Examples 1 to 5]
As an extruder, a twin-screw extruder (30 mmφ, L/D=74; manufactured by Kobe Steel, "KTX-30") having an oil inlet in the center of the barrel was used. A two-thread screw having kneading sections before and after the injection port was used as the screw. After the polymers other than the softener (C-1) listed in Table 1 were mixed together in the mass parts shown in Table 1, they were introduced into a twin-screw extruder (cylinder temperature 200°C) using a quantitative feeder, and then, The amount of softener (C-1) shown in Table 1 was injected with a pump from the injection port in the center of the extruder, and melt extrusion kneading was performed to obtain a dynamically heat-treated thermoplastic elastomer composition. .
The physical properties of the obtained thermoplastic elastomer composition were evaluated by the following method.
The results are shown in Table 1.

[Fluidity of thermoplastic elastomer composition]
The fluidity of the thermoplastic elastomer composition was evaluated by melt flow rate (MFR). The MFR was measured at 230° C. under a load of 1.2 kg in accordance with JIS K7210. The measurement results were evaluated based on the following criteria.
(Evaluation criteria)
◎: 55g/10 minutes or more ○: 30g/10 minutes or more but less than 55g/10 minutes ×: Less than 30g/10 minutes

[Flexibility (Shore hardness measurement)]
In accordance with JIS K6253, a press sheet with a thickness of 2 mm was produced from a thermoplastic elastomer composition, and the laminated sheet with a thickness of 6 mm obtained by stacking three press sheets was measured using a Shore A hardness meter, The value after 10 seconds (10s value) was determined as Shore hardness.
If the Shore hardness was 50 to 80, it was judged to have excellent flexibility.

[Stickiness (coefficient of kinetic friction (μk)]
A thermoplastic elastomer composition was injection molded using a flat plate mold having dimensions of 15 cm in length and 9 cm in width and subjected to skin texture processing. The injection molding machine used was "M150CL-DM" manufactured by Meiki Seisakusho Co., Ltd. The molding conditions were a resin temperature of 220°C and a mold temperature of 40°C.
The coefficient of dynamic friction of the molded body was evaluated by the measurement method shown below. Using a static/dynamic friction measuring machine (manufactured by Trinity Lab, product name "TL201Ts"), a tactile contact is brought into contact with the molded sample under the conditions of a sliding speed of 100 mm/sec, a vertical load of 50 gf, and a sliding distance of 60 mm. By this, the coefficient of kinetic friction of the sample surface was measured. The measurement results were evaluated based on the following criteria.
(Evaluation criteria)
◎: 0.60μk or less ○: More than 0.60μk and 0.80μk or less ×: More than 0.80μk

As shown in Table 1, the thermoplastic elastomer compositions of Examples 1 to 5 had excellent fluidity, flexibility, and surface feel, and were able to fully satisfy the required performance as a skin material of the present invention. It was confirmed that the overall evaluation was good.
On the other hand, in Comparative Examples 1, 3, and 5, molded products with strong stickiness and excellent texture could not be obtained. Comparative Examples 2 and 4 had low MFR and did not satisfy the high fluidity required for skin materials. From the above, it was found that the compositions of Comparative Examples 1 to 5 were unable to achieve both fluidity and tactility, and the overall evaluation was poor.

Claims (9)

A propylene polymer (A),
Olefin copolymer (B),
a softener (C);
Contains
The olefin copolymer (B) is
an ethylene/α-olefin copolymer (B1) containing ethylene and an α-olefin unit having 3 to 20 carbon atoms;
Contains an ethylene/propylene/non-conjugated polyene copolymer (B2),
The content of the ethylene/α-olefin copolymer (B1) in the olefin copolymer (B) is 0 to 99% by mass, and the content of the ethylene/α-olefin copolymer (B2) is 0 to 99% by mass. The content is 1 to 100% by mass [however, the total content of (B1) and (B2) is 100% by mass. ] and
The content of the propylene polymer (A) is 25 to 300 parts by mass based on 100 parts by mass of the olefin copolymer (B), and
A thermoplastic elastomer composition, wherein the content of the softener (C) is more than 120 parts by mass and 300 parts by mass or less based on 100 parts by mass of the olefin copolymer (B). The content of the ethylene/α-olefin copolymer (B1) in the olefin copolymer (B) is 0 to 95% by mass, and the content of the ethylene/propylene/non-conjugated polyene copolymer ( B2) is 5 to 100% by mass [however, the total content of (B1) and (B2) is 100% by mass. ] and
2. The thermoplastic elastomer composition according to claim 1, wherein the content of the softener (C) is more than 120 parts by mass and 290 parts by mass or less based on 100 parts by mass of the olefin copolymer (B). The thermoplastic elastomer composition according to claim 1 or 2, further comprising a hydrogenated block copolymer (D). The thermoplastic elastomer composition according to claim 3, wherein the content of the hydrogenated substance (D) in the block copolymer is 30 to 350 parts by mass based on 100 parts by mass of the olefin copolymer (B). thing. The heat according to any one of claims 1 to 4, wherein the content of the propylene polymer (A) is 25 to 250 parts by mass based on 100 parts by mass of the olefin copolymer (B). Plastic elastomer composition. The thermoplastic elastomer composition according to any one of claims 1 to 5, wherein at least a portion of the olefin copolymer (B) is crosslinked. An injection molded article comprising the thermoplastic elastomer composition according to any one of claims 1 to 6. An automobile interior part comprising the injection molded article according to claim 7. A propylene polymer (A),
Olefin copolymer (B),
a softener (C);
Contains
The olefin copolymer (B) is
an ethylene/α-olefin copolymer (B1) containing ethylene and an α-olefin unit having 3 to 20 carbon atoms;
Contains an ethylene/propylene/non-conjugated polyene copolymer (B2),
The content of the ethylene/α-olefin copolymer (B1) in the olefin copolymer (B) is 0 to 99% by mass, and the content of the ethylene/α-olefin copolymer (B2) is 0 to 99% by mass. The content is 1 to 100% by mass [however, the total content of (B1) and (B2) is 100% by mass. ] and
The content of the propylene polymer (A) is 25 to 300 parts by mass based on 100 parts by mass of the olefin copolymer (B), and
A method for producing a thermoplastic elastomer composition in which the content of the softener (C) is more than 120 parts by mass and 300 parts by mass or less with respect to 100 parts by mass of the olefin copolymer (B),
The production method includes dynamically heat-treating the propylene polymer (A), the olefin copolymer (B), and the softener (C) in the presence of a crosslinking agent (F). A method for producing a thermoplastic elastomer composition, comprising the step of: