JP5626246B2 - Thermoplastic elastomer composition and method for producing the same - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a thermoplastic elastomer composition, and more specifically, a thermoplastic elastomer composition having excellent molding processability, flexibility, rubber elasticity, scratch resistance, a smooth surface and less flaws, and production thereof Regarding the method.

  In recent years, thermoplastic elastomers such as styrene-based, olefin-based, polyester-based, polyamide-based, polyurethane-based, which are rubber-like soft materials that do not require a vulcanization step and have the same moldability as thermoplastic resins However, it is attracting attention from the viewpoint of process rationalization and recyclability, and is widely used in the fields of automobile parts, home appliance parts, medical equipment parts, packaging materials, civil engineering and building materials, electric wires, and miscellaneous goods. Styrenic thermoplastic elastomers composed of aromatic vinyl-conjugated diene block copolymers or hydrogenated products thereof are excellent in flexibility, rubber elasticity, etc., crystalline propylene resins and ethylene-α-olefins. Olefin-based thermoplastic elastomer, which is a partially crosslinked product obtained by dynamically heat-treating a copolymer rubber with an organic peroxide to crosslink the latter rubber Tomers are excellent in weather resistance and softening bleed resistance, etc., and are relatively inexpensive and economically advantageous. And is used in various fields.

As a thermoplastic composition having improved environmental degradation resistance and excellent mechanical properties such as wear resistance, Patent Document 1 has a density in the range of 0.858 to 0.915 g / cm ³ , In addition, weight-average molecular weight (hereinafter abbreviated as “Mw”) and number average molecular weight calculated by gel permeation chromatography (hereinafter abbreviated as “GPC” where appropriate). (Number-average molecular weight: hereinafter abbreviated as “Mn” where appropriate). The molecular weight distribution (Mw / Mn) is less than 3.0, and ethylene and an α-olefin having 3 to 12 carbon atoms. There has been proposed a thermoplastic composition obtained by crosslinking 25 to 100% by mass of at least one olefin-based polymer with a radical initiator and / or a polyfunctional unsaturated compound.

JP-A-9-104787

  However, the composition described in Patent Document 1 has a sharp molecular weight distribution (Mw / Mn) and excellent scratch resistance. However, when injection molding is performed, a flow mark is generated and the molding appearance is poor. There was a problem that it was difficult to form the profile extrusion when trying to mold.

  The present invention is intended to solve the problems associated with the above-described prior art, and is excellent in profile extrusion processability, excellent in flexibility, rubber elasticity, and scratch resistance, and has a smooth surface. It is an object of the present invention to provide a thermoplastic elastomer composition having less lumps and a method for producing the same.

As a result of intensive studies to achieve the above object, the inventor of the present invention has an ethylene / α-olefin copolymer 2 composed of ethylene and one or more α-olefins and having a molecular weight distribution (Mw / Mn) of less than 3. consists or more, density of 0.850~0.900g / cm ^3, an olefin-based copolymer group is the molecular weight distribution is 3.0 or more, a density of 0.900 g / cm ³ greater than the olefin The present invention has been completed by finding that the above-mentioned problems can be solved by using it as an essential component together with a polymer.

That is, the gist of the present invention is a thermoplastic elastomer composition crosslinked by dynamic heat treatment of the following components (a) to (c) in the presence of a crosslinking agent, wherein the components (a) and ( to the total weight of b), component (a) mass ratio is more than 10%, and 90% or less, the component (b) mass ratio is 90% or less, der least 10% is, and components (a) and The thermoplastic elastomer composition is characterized in that the component (c) is 50 parts by mass or less with respect to 100 parts by mass of the total amount of the component (b) (Claim 1).
(A) density of 0.850 g / cm ³ or more and 0.900 g / cm ³ or less, a gel permeation chromatography (hereinafter referred to as "GPC".) Molecular weight distribution by method {weight-average molecular weight (Mw) / number average The molecular weight (Mn)} is an olefin copolymer group having a molecular weight of 3.0 or more, and the olefin copolymer group is composed of the following two or more types of ethylene / α-olefin copolymers.
It is composed of ethylene and one or more α-olefins having 3 to 12 carbon atoms, and has a molecular weight distribution {mass average molecular weight (Mw) / number average molecular weight (Mn)} by GPC method of less than 3.0. Two or more types of ethylene / α-olefin copolymers (b) Olefin polymers having a density greater than 0.900 g / cm ³ .
(C) Styrenic thermoplastic elastomer having a mass average molecular weight of 80,000 or more and 500,000 or less.

Here, the component (a) is preferably an ethylene / butene-1 copolymer (Claim 2).
Further, it is preferable to further contain Ingredient following (d) (claim 3).
( D) A hydrocarbon rubber softener.

  Moreover, it is preferable that the said component (a) is manufactured using the metallocene catalyst (Claim 4).

  Moreover, it is preferable that the said component (b) is a propylene-type polymer (Claim 5).

  Moreover, it is preferable that carbon number of the alpha-olefin which comprises the ethylene-alpha-olefin copolymer in the said component (a) is 4 or more (Claim 6).

Moreover, it is preferable that the melt flow rate (MFR) of the said component (a) is 0.05 g / 10min or more and 100 g / 10min or less (Claim 7).
Another gist of the present invention is a method for producing a thermoplastic elastomer composition in which the above components (a) to (c) are crosslinked by dynamic heat treatment in the presence of a crosslinking agent, The mass ratio of component (a) to the total mass of (a) and (b) is 10% or more and 90% or less, the mass ratio of component (b) is 90% or less, 10% or more, and the component ( A method for producing a thermoplastic elastomer composition, wherein the crosslinking is performed by mixing so that the component (c) is 50 parts by mass or less with respect to 100 parts by mass of the total amount of a) and the component (b). (Claim 8 ).
Still another subject matter of the present invention resides in an extrusion-molded product obtained by profile extrusion of the above thermoplastic elastomer composition (claim 9 ).

  The thermoplastic elastomer composition of the present invention is excellent in profile extrusion molding processability, and is excellent in flexibility, rubber elasticity, scratch resistance, a smooth surface, and an extrusion-molded product with little fluff. Moreover, according to the manufacturing method of the thermoplastic elastomer composition of this invention, it is possible to obtain such a thermoplastic elastomer composition efficiently.

It is a figure which shows typically the cross-sectional shape of the nozzle | cap | die of a single screw extruder used for evaluation of the profile extrusion moldability of the thermoplastic elastomer composition of each Example and a comparative example.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following description, and various modifications can be made within the scope of the gist of the present invention.

  The thermoplastic elastomer composition of the present invention contains at least the following components (a) and (b). Specifically, the total content of components (a) and (b) in the thermoplastic elastomer composition of the present invention is usually 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass or more. It is a range.

  In the thermoplastic elastomer composition of the present invention, the mass ratio of the component (a) to the total mass of the components (a) and (b) is 10% or more and 90% or less, and the mass ratio of the component (b). Is 90% or less, 10% or more, and is crosslinked.

(A) two or more kinds of ethylene / polyethylene which are composed of ethylene and one or more α-olefins having 3 to 12 carbon atoms and have a molecular weight distribution (Mw / Mn) by GPC method of less than 3.0 consists α- olefin copolymer, density 0.850 g / cm ³ or more and 0.900 g / cm ³ or less, the molecular weight distribution by GPC molecular weight distribution (Mw / Mn) of 3.0 or more, olefinic Copolymer group.
(B) An olefin polymer having a density greater than 0.900 g / cm ³ .

In the thermoplastic elastomer composition of the present invention, the component (a) functions as a soft segment of the thermoplastic elastomer, and the component (b) functions as a hard segment of the thermoplastic elastomer.
Hereinafter, each feature will be described in detail.

[Component (a)]
The olefin copolymer group of the component (a) used in the thermoplastic elastomer composition of the present invention is composed of two or more kinds of ethylene / α-olefin copolymers. Here, each ethylene / α-olefin copolymer is composed of ethylene and an α-olefin having 3 to 12 carbon atoms. A polymer consisting only of ethylene or a polymer consisting only of α-olefin may form crystals.

  The olefin copolymer group of component (a) may contain other components as long as the effects of the present invention are not significantly impaired. Examples of the other components include rubber having a molecular weight distribution (Mw / Mn) by GPC method of 3.0 or more. However, the proportion of the two or more ethylene / α-olefin copolymers in the olefin copolymer group of component (a) is usually preferably 80% by mass or more.

  The type of α-olefin having 3 or more and 12 or less carbon atoms is arbitrary as long as the effects of the present invention are not significantly impaired. For example, propylene, butene-1, pentene-1, hexene-1, octene-1 and the like can be used. Can be mentioned. When an ethylene / α-olefin copolymer containing an α-olefin having 12 or less carbon atoms is used, the sheet surface of the laminate becomes sticky or bleed particularly when a hydrocarbon rubber softening agent described later is blended. It tends to be difficult to cause. On the other hand, the lower limit of the carbon number of the α-olefin is 3 or more as described above, and among these, 4 or more is preferable.

  In particular, as a constituent element of the olefin copolymer group of component (a), an ethylene / butene-1 copolymer composed of ethylene and butene-1 is preferable since the stickiness of the surface formed into a sheet shape is small.

  Further, the ethylene / α-olefin copolymer constituting the olefin copolymer group of the component (a) is a ratio of the mass average molecular weight (Mw) and the number average molecular weight (Mn) calculated by the GPC method. The molecular weight distribution (Mw / Mn) is usually less than 3.0, preferably less than 2.8. An ethylene / α-olefin copolymer having a molecular weight distribution (Mw / Mn) smaller than the upper limit is preferable in terms of scratch resistance. On the other hand, the lower limit of the molecular weight distribution (Mw / Mn) of the ethylene / α-olefin copolymer is not particularly limited, but is usually 1.5 or more.

  The “mass average molecular weight” in the present invention is a mass average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) under the conditions shown in Table 1 below.

  The olefin copolymer group of the component (a) can be obtained, for example, by mixing an ethylene / α-olefin copolymer constituting the component.

  The ethylene / α-olefin copolymers constituting the component (a) olefin copolymer group can be produced using a known metallocene catalyst.

  Metallocene catalysts generally consist of cyclopentadienyl derivatives of Group 4 metals such as titanium and zirconium and cocatalysts, and are not only highly active as polymerization catalysts, but also compared with conventional Ziegler catalysts. Thus, the molecular weight distribution of the obtained polymer is narrow, and the distribution of the α-olefin having 3 to 12 carbon atoms, which is a comonomer in the copolymer, is uniform. Therefore, the olefin elastomer produced by the metallocene catalyst is significantly different from the conventional polymer using a Ziegler catalyst or the like.

The olefin copolymer group of component (a) has a density of usually 0.850 g / cm ³ or more, preferably 0.853 g / cm ³ or more, particularly preferably 0.855 g / cm ³ or more, usually 0.900 g / cm ³ or less, preferably 0.890 g / cm ³ or less, particularly preferably 0.880 g / cm ³ or less. Those having a density equal to or higher than the lower limit are preferable from the viewpoint of strength of the thermoplastic elastomer composition, and those having a density equal to or lower than the upper limit are preferable from the viewpoint of flexibility of the thermoplastic elastomer composition. In addition, the density of an olefin type copolymer group can be measured based on JISK7112.

  The component (a) olefin copolymer group needs to have a molecular weight distribution (Mw / Mn) of generally 3.0 or more, preferably 3.1 or more, throughout the copolymer group. When the molecular weight distribution (Mw / Mn) is equal to or more than the lower limit, a flow mark is hardly generated when the thermoplastic elastomer composition is injection-molded, the molding appearance is good, and the profile is deformed during profile extrusion molding. Since the shape of extrusion is easy to come out, it is preferable. The upper limit of the molecular weight distribution (Mw / Mn) of the entire copolymer group is not particularly limited, but is preferably 10.0 or less. Those below the upper limit are preferred from the viewpoint of scratch resistance of the thermoplastic elastomer composition.

  The component (a) olefin copolymer group has a melt flow rate (hereinafter abbreviated as “MFR” where appropriate) measured at 190 ° C. and a load of 21 N in accordance with JIS K7210. It is preferably in the range of 10 minutes or more, especially 0.1 g / 10 minutes or more, usually 100 g / 10 minutes or less, especially 80 g / 10 minutes or less, and more preferably 60 g / 10 minutes or less. This range is preferred from the viewpoint of moldability of the thermoplastic elastomer composition.

[Component (b)]
Component (b) used in the thermoplastic elastomer composition of the present invention is an olefin polymer having a density greater than 0.900 g / cm ³ . An olefin polymer having a density greater than 0.900 g / cm ³ is excellent in terms of heat resistance.

  The kind of the olefin polymer of component (b) is not particularly limited. Examples include propylene resins, ethylene resins, crystalline polybutene-1 resins, ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid ester copolymers, etc. Among them, propylene resins are preferably used. Specific examples of the propylene resin include a propylene homopolymer, a propylene-ethylene random copolymer resin containing propylene as a main component, and a propylene-ethylene block copolymer resin. Any polymerization method may be adopted as long as a resinous material is obtained.

As described above, the density of the olefin polymer of component (b) is usually 0.900 g / cm ³ or more, preferably 0.901 g / cm ³ or more, particularly preferably 0.902 g / cm ³ or more. is there. Those having a density equal to or higher than the lower limit are preferred from the viewpoint of excellent heat resistance. The upper limit of the density is not particularly limited, but usually 0.970 g / cm ³ or less, among others 0.965 g / cm ³ or less. Those having a density equal to or less than the above upper limit are preferable in that the moldability of the resulting thermoplastic composition is excellent. The density of the olefin copolymer can be measured by the same method as that described in the above [Component (a)] column.

  The melt flow rate (MFR) of the olefin polymer of component (b) is a value measured under conditions of 230 ° C. and 21.2 N load in accordance with JIS K7210, and is usually 0.05 g / 10 min or more, especially 0 It is preferably in the range of 1 g / 10 min or more, usually 200 g / 10 min or less, and more preferably 100 g / 10 min or less. Those having a melt flow rate within the above range are preferred from the viewpoint of injection moldability and extrusion moldability of the thermoplastic elastomer composition.

[Mass ratio of components (a) and (b)]
The mass ratio of components (a) and (b) in the thermoplastic elastomer composition of the present invention is as follows. The ratio of the component (a) to the total amount (100% by mass) of the components (a) and (b) is usually 10% by mass or more, preferably 15% by mass or more, particularly preferably 20% by mass or more, Usually 90% by mass or less, preferably 85% by mass or less, particularly preferably 80% by mass or less, and the proportion of component (b) is usually 90% by mass or more, preferably 85% by mass or more, particularly preferably 80% by mass. It is in the range of not less than mass%, usually not more than 10 mass%, preferably not more than 15 mass%, particularly preferably not more than 20 mass%. When the ratio of the component (a) is not less than the lower limit (that is, the ratio of the component (b) is not more than the upper limit), it is preferable from the viewpoint of flexibility of the resulting thermoplastic elastomer composition, and the ratio of the component (a) is When the ratio is not more than the upper limit (that is, the ratio of the component (b) is not less than the lower limit), it is preferable in terms of injection moldability and extrusion moldability of the thermoplastic elastomer composition.

[Other ingredients]
The thermoplastic elastomer composition of the present invention may contain components other than the above-mentioned components (a) and (b) within the range not impairing the object of the present invention.

  Examples of components other than components (a) and (b) include styrene thermoplastic elastomers, hydrocarbon rubber softeners, various thermoplastic resins and rubbers, and glass fibers, plasticizers, carbon fibers, potassium titanate. Fillers such as fiber, talc, mica, silica, titania, calcium carbonate, carbon black, as well as antioxidants, heat stabilizers, light stabilizers, UV absorbers, neutralizers, lubricants, antifogging agents, petroleum resins Antiblocking agents, antistatic agents, dispersants, flame retardants, conductivity imparting agents, molecular weight regulators, antibacterial agents, antifungal agents, fluorescent whitening agents, colorants, and the like. Among these, it is preferable to contain a styrene-based thermoplastic elastomer (hereinafter referred to as “component (c)”) and / or a hydrocarbon-based rubber softener (hereinafter referred to as “component (d)”). These components (c) and (d) will be described in detail later.

  Components other than these components (a) and (b) may be preliminarily contained in either component (a) or component (b), and each component is uniformly mixed, melt kneaded or You may mix | blend at the time of dynamic heat processing. Further, it may be added after the crosslinking treatment.

[Component (c)]
The thermoplastic elastomer composition of the present invention preferably contains a styrenic thermoplastic elastomer as the component (c) from the viewpoint of improving strength, improving appearance, and the like. The styrenic thermoplastic elastomer generally represents a vinyl aromatic hydrocarbon-elastomeric polymer block copolymer described below.

  The vinyl aromatic hydrocarbon-elastomeric polymer block copolymer is composed of a vinyl aromatic hydrocarbon polymer block and an elastomeric polymer block, and the vinyl aromatic hydrocarbon polymer block has hard segments. Each of the elastomeric polymer blocks constitutes a soft segment, and is typically a vinyl aromatic hydrocarbon polymer block-elastomeric polymer block or a vinyl aromatic hydrocarbon polymer block-elastomeric polymer. A block copolymer having a copolymer structure represented by a block-vinyl aromatic hydrocarbon polymer block, wherein the double bond of the elastomeric polymer block may be partially or completely hydrogenated. In general, it is known as a styrenic thermoplastic elastomer.

  Examples of the vinyl aromatic hydrocarbon in the styrene-based thermoplastic elastomer include styrene, α-methylstyrene, o-, m-, p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, vinylanthracene, and the like. It is done. Of these, styrene is preferred. Further, the elastomeric polymer block is not particularly limited as long as it exhibits elastomeric properties, but conjugated dienes are preferable. Examples of the conjugated diene include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. Among these, butadiene or isoprene, or a mixture of butadiene and isoprene in a mass ratio of 2/8 to 6/4 is preferable.

  In the present invention, the styrene-based thermoplastic elastomer has an aromatic vinyl content of usually 10% by mass or more, especially 15% by mass or more, more preferably 20% by mass or more, and usually 50% by mass or less, especially 45%. It is preferably in the range of not more than mass%, more preferably not more than 40 mass%. Those having an aromatic vinyl content of not less than the lower limit are preferable in terms of mechanical strength and heat resistance of the thermoplastic elastomer composition, and those having an upper limit of not more than the upper limit are excellent in flexibility and rubber elasticity. It is preferable from the viewpoint that bleeding of the softener for hydrocarbon rubber described later hardly occurs. The content of aromatic vinyl in the styrene thermoplastic elastomer can be measured by a technique such as a nuclear magnetic resonance (NMR) method.

In addition, when only butadiene is used as the conjugated diene, from the aspect of improving the tactile sensation as a laminate, 1,2-bond produced by polymerization of butadiene in the conjugated diene polymer block of the styrene-based thermoplastic elastomer { The ratio (mass ratio) of 1,2-bonds in the sum of —CH ₂ —CH (CH═CH ₂ ) —} and 1,4-bonds {—CH ₂ —CH═CH—CH ₂ —} is usually A range of 20% or more, especially 25% or more, and usually 50% or less, particularly 45% or less is preferable. The content of aromatic vinyl in the styrene-based thermoplastic elastomer can be measured by a technique such as NMR method.

  In addition, the hydrogenation rate of the double bond of the conjugated diene polymer block of the styrene-based thermoplastic elastomer is usually 30% or more, particularly 50% or more, more preferably 90% or more, in terms of the molar ratio to the total double bonds. Some are preferred. Those having a hydrogenation rate within the above range are preferable in terms of the weather resistance and heat resistance of the thermoplastic elastomer composition. In addition, the hydrogenation rate of the double bond in the styrene-based thermoplastic elastomer can be measured by a technique such as an NMR method.

  In the present invention, the mass average molecular weight (Mw) of the styrenic thermoplastic elastomer is a value in terms of polystyrene measured by GPC, and is usually 80,000 or more, especially 100,000 or more, further 150,000 or more, and usually 500,000 or less. It is preferably 450,000 or less, more preferably 400,000 or less. Those having a mass average molecular weight equal to or more than the above lower limit are preferred in that the thermoplastic elastomer composition is excellent in rubber elasticity and mechanical strength and has excellent extrusion processability. On the other hand, it is preferable in terms of extrusion molding processability and those below the upper limit.

  As a manufacturing method of the styrene-based thermoplastic elastomer used in the present invention, any manufacturing method may be used as long as the above structure and physical properties can be obtained. For example, it can be obtained by performing block polymerization in an inert solvent using a lithium catalyst or the like by the method described in Japanese Patent Publication No. 40-23798. The hydrogenation treatment of these block copolymers is described in, for example, JP-B-42-8704, JP-B-43-6636, JP-A-59-133203, and JP-A-60-79005. The process described can be carried out in the presence of a hydrogenation catalyst in an inert solvent. Examples of such commercially available block copolymers include “KRATON-G” (Clayton Polymer Co., Ltd.), “Septon” (Kuraray Co., Ltd.), and “Tuftec” (Asahi Kasei Co., Ltd.). It can also be obtained by polymerizing styrene or a derivative thereof and then an elastomeric block and coupling it with a coupling agent. It can also be obtained by polymerizing an elastomeric block using a dilithium compound as an initiator and then successively polymerizing styrene or a derivative thereof.

  The amount of the styrene-based thermoplastic elastomer used as the component (c) is usually 100 parts by weight or less, preferably 50 parts by weight or less when the total amount of the components (a) and (b) is 100 parts by weight. It is.

[Component (d)]
The thermoplastic elastomer composition of the present invention preferably contains a hydrocarbon-based rubber softener as the component (d) from the viewpoint of improving flexibility and moldability. Examples of hydrocarbon rubber softeners include paraffinic, naphthenic, aromatic mineral oil hydrocarbons, and synthetic resin hydrocarbons such as polybutenes, low molecular weight compounds such as polybutadienes, etc. Of these, mineral oil hydrocarbons are preferred. Further, it is preferable that the mass average molecular weight (Mw) is a value in terms of polypropylene measured by GPC and is usually 300 or more, particularly 500 or more, and usually 2000 or less, especially 1500 or less.

  Rubber softeners made of mineral oil hydrocarbons are generally a mixture of aromatic hydrocarbons, naphthene hydrocarbons, and paraffin hydrocarbons, and the carbon number of paraffin hydrocarbons is 50% of the total carbon number. Paraffinic oils account for more than 30% of the total carbon number of naphthenic hydrocarbons are naphthenic oils and 30% or more of the total number of carbons of aromatic hydrocarbons. Are referred to as aromatic oils. In the present invention, paraffinic oils are particularly preferred from the viewpoint of excellent weather resistance, heat resistance, and color tone.

  The mineral oil-based hydrocarbon as a rubber softening agent preferably has a kinematic viscosity at 40 ° C. of usually 20 cst or more, particularly 50 cst or more, and usually 800 cst or less, especially 600 cst. The pour point is usually −40 ° C. or higher, preferably −30 ° C. or higher, and usually 0 ° C. or lower. Further, the flash point is usually 200 ° C. or higher, particularly 250 ° C. or higher, Usually, it is preferably 400 ° C. or lower, particularly 350 ° C. or lower. Mineral oil-based hydrocarbons that satisfy these characteristics are preferred in that they are excellent in bleed resistance.

  The amount of the hydrocarbon-based rubber softener used as the component (d) is usually 200 parts by weight or less, preferably 150 parts by weight or less when the total amount of the components (a) and (b) is 100 parts by weight. Range.

[Other thermoplastic resins]
Examples of the thermoplastic resin that the thermoplastic elastomer composition of the present invention may contain in addition to the above-described components (a) to (d) include, for example, polyamide systems such as polyphenylene ether resins, nylon 6 and nylon 66 Examples thereof include resins, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyoxymethylene resins such as polyoxymethylene homopolymers and polyoxymethylene copolymers, polymethyl methacrylate resins, and polystyrene resins.

[Other rubbers]
Examples of the rubber that the thermoplastic elastomer composition of the present invention may contain in addition to the components (a) to (d) described above include, for example, ethylene / propylene copolymer rubbers other than essential components, ethylene · Examples thereof include olefin rubbers such as propylene / non-conjugated diene copolymer rubber, polybutadiene, and styrene copolymer rubber.

[Crosslinking]
The thermoplastic elastomer composition of the present invention is characterized by containing the above-mentioned components and being crosslinked. The method for crosslinking is not particularly limited, but usually, from the viewpoint of improving rubber elasticity and extrusion moldability, it is preferable to dynamically heat-treat (dynamic crosslinking) in the presence of a crosslinking agent.

  Here, the dynamic heat treatment (dynamic heat treatment) means kneading in a molten state or a semi-molten state. Usually, the dynamic heat treatment is carried out by uniformly mixing the above-mentioned components and then melt-kneading them in the presence of a crosslinking agent and a crosslinking aid used as necessary. As the mixing device, a Henschel mixer, a ribbon blender, a V-type blender or the like is used, and as the kneading device, a mixing roll, a kneader, a Banbury mixer, a Brabender plastograph, a single or twin screw extruder, or the like is used.

  As the crosslinking agent, organic peroxides, maleimide-based crosslinking agents, sulfur, phenol-based crosslinking agents, oximes, polyamines and the like are used, and organic peroxides, maleimide-based crosslinking agents, and phenol-based crosslinking agents are preferable. An organic peroxide is particularly preferable from the viewpoint that a composition having an appropriate degree of crosslinking can be obtained.

  Specific examples of the organic peroxide particularly preferable as the crosslinking agent include di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butyl). Peroxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-di (t- Dialkyl peroxides such as butylperoxy) -3,3,5-trimethylcyclohexane, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) ) Peroxyesters such as hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexyne-3, acetyl par Kishido, lauroyl peroxide, benzoyl peroxide, p- chlorobenzoyl peroxide, 2,4-diacyl peroxides such as benzoyl peroxide and the like, hydroperoxides and the like, such as diisopropylbenzene hydroperoxide and the like. Among these, an organic peroxide having a one-minute half-life temperature of 140 ° C. or more is preferable from the viewpoint that a composition having an appropriate degree of crosslinking can be obtained. Examples of such an organic peroxide include 1, 3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) ) Hexin-3 and the like.

  As a use ratio of the crosslinking agent, when the total amount of the components (a) and (b) is 100 parts by mass, usually 0.05 parts by mass or more, preferably 0.07 parts by mass or more, and usually 3 parts by mass. Part or less, preferably 1 part by weight or less.

  Examples of the crosslinking aid include peroxide crosslinking aids such as sulfur, p-quinonedioxime, p-dinitrosobenzene, 1,3-diphenylguanidine, m-phenylenebismaleimide, divinylbenzene, triallylsia. Polyfunctional vinyl compounds such as nurate, triallyl isocyanurate, diallyl phthalate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl ( Although polyfunctional (meth) acrylate compounds, such as (meth) acrylate, etc. are mentioned, Divinylbenzene and a trimethylol propane tri (meth) acrylate are especially preferable.

  The proportion of the crosslinking aid used is usually 0 parts by mass or more, preferably 0.01 parts by mass or more, and usually 3 parts by mass or less when the total amount of components (a) and (b) is 100 parts by mass. The range is preferably 1 part by mass or less.

  The kneading temperature of the dynamic heat treatment is usually 100 ° C. or higher, preferably 110 ° C. or higher, and usually 300 ° C. or lower, preferably 280 ° C. or lower. The kneading time of the dynamic heat treatment is usually 10 seconds or longer, preferably 20 seconds or longer, and usually 30 minutes or shorter, preferably 20 minutes or shorter. The state of the material during the dynamic heat treatment varies depending on the type of material used and the temperature of the dynamic heat treatment, and is usually in a semi-molten state or a molten state, but is not particularly limited. In kneading, in addition to a method of kneading the components all at once, a multi-stage division kneading method in which an arbitrary component is kneaded and then the other remaining components are added and kneaded may be employed.

[Molding method]
The thermoplastic elastomer composition of the present invention can be molded by a known method as necessary and used as a molded body. Examples of the molding method include molding methods usually used for thermoplastic elastomers, such as injection molding, extrusion molding, hollow molding, and compression molding. Moreover, you may perform secondary processes, such as lamination molding and thermoforming, after that. The thermoplastic elastomer composition of the present invention may be formed as a single body or may be combined with other materials to form a laminate.

[Characteristics and applications]
The thermoplastic elastomer composition of the present invention is excellent in profile extrusion processability, has excellent properties such as flexibility, rubber elasticity, scratch resistance, a smooth surface and a reduced amount of fluff.

  From the above-mentioned characteristics, the thermoplastic elastomer composition of the present invention is molded into a desired shape, such as automobile parts, home appliance parts, medical equipment parts, packaging materials, civil engineering and building materials, electric wires, and miscellaneous goods. Used as a material in a wide range of fields.

EXAMPLES Hereinafter, although this invention is demonstrated still in detail using an Example and a comparative example, this invention is not limited to a following example, unless the summary is exceeded.
The materials, molding methods and evaluation methods used in Examples and Comparative Examples are as follows.

[material]
[Component (a): Ethylene / α-olefin copolymer]
As the component (a) in each Example and Comparative Example, the following components (a-1), (a-2) and / or (A) were mixed and used in combinations and ratios shown in Table 2 described later. . Table 2 shows Mw / Mn of the whole component (a) in each Example and Comparative Example.

-Component (a-1): Copolymer of ethylene and butene-1 A copolymer of ethylene and butene-1 (Tafmer A0250S manufactured by Mitsui Chemicals, Inc.) was used as the component (a-1). . The polymerization catalyst was a metallocene system, the density was 0.860 g / cm ³ , Mw / Mn = 2.2, and MFR (190 ° C., 21 N load) = 0.2 g / 10 min. That is, this component (a-1) corresponds to an ethylene / α-olefin copolymer which is a component of the component (a) defined in the present invention.

-Component (a-2): Copolymer of ethylene and butene-1 As component (a-2), a copolymer of ethylene and butene-1 (Tafmer A1050S manufactured by Mitsui Chemicals, Inc.) was used. . The polymerization catalyst was a metallocene system, the density was 0.860 g / cm ³ , Mw / Mn = 2.2, and MFR (190 ° C., 21 N load) = 1.5 g / 10 min. That is, this component (a-2) corresponds to an ethylene / α-olefin copolymer which is a constituent element of the component (a) defined in the present invention.

-Component (A): Ethylene-propylene-ethylidene norbornene copolymer As the component (A), an ethylene-propylene-ethylidene norbornene copolymer (EP57C manufactured by JSR Corporation) was used. The polymerization catalyst was a Ziegler system, the ethylene content was 66% by mass, the ethylidene norbornene content was 4.5% by mass, the density was 0.860 g / cm ³ , and Mw / Mn = 3.2. That is, this component (A) does not correspond to the olefin copolymer which becomes a component of the component (a) prescribed | regulated to this invention.

[Component (b): Olefin polymer]
As the component (b) in each example and comparative example, a propylene polymer was used (hereinafter referred to as “component (b-1)”). The density was 0.905 g / cm ³ and MFR (230 ° C., 21.2 N load) = 0.9 g / 10 min.

[Component (c): Vinyl aromatic hydrocarbon-elastomeric polymer block copolymer]
As a component (c) in each Example and Comparative Example, a hydrogenated product of a styrene-butadiene block copolymer having a copolymer structure of styrene block-butadiene block-styrene block (G1651 manufactured by Kraton Polymer Co., Ltd.) was used (this) (Hereinafter referred to as “component (c-1)”). The styrene content was 33% by mass, the hydrogenation rate was 98% or more, the mass average molecular weight was 245000, and the proportion of 1,2-bonds was 37%.

[Component (d): Softener for hydrocarbon rubber]
Paraffinic oil (PW90 manufactured by Idemitsu Kosan Co., Ltd.) was used as the component (d) in each example and comparative example (hereinafter referred to as “component (d-1)”). The weight average molecular weight was 539, the kinematic viscosity at 40 ° C. was 96 cSt, the pour point was −15 ° C., and the flash point was 272 ° C.

[Crosslinking agent]
2,5-dimethyl-2,5-di (t-butylperoxy) hexane (hereinafter abbreviated as “POX”) was used as a crosslinking agent.

[Crosslinking aid]
Divinylbenzene (hereinafter abbreviated as “DVB”) was used as a crosslinking aid.

[Examples 1 to 4 and Comparative Examples 1 to 4]
The components (c) and (d) in the amounts shown in Table 2 below were mixed for 1 minute using a Henschel mixer. Further, the components (a), (b), POX and DVB in the amounts shown in Table 2 below were added and further mixed for 1 minute using a Henschel mixer. This mixture is fed at a rate of 30 kg / hour to the first supply port of the same direction twin screw extruder (“KTX44” manufactured by Kobe Steel, L / D = 41, number of cylinder blocks = 11) having two raw material supply ports. The resulting mixture was dynamically heat treated by melting and kneading at 110 to 220 ° C. During the heat treatment, an amount of component (d) shown in Table 2 below was supplied from a second supply port provided in the middle of the extruder cylinder. After the heat treatment, the product was extruded in a strand form from a die and cut to obtain pellets of a thermoplastic elastomer composition (the thermoplastic elastomer compositions of Examples 1 to 4 and Comparative Examples 1 to 4 respectively). . Here, the combined density of component (a-1) and component (a-2) in Examples 1 to 4 is 0.860 g / cm ³ .

[Evaluation method]
The pellets of the thermoplastic elastomer compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were used for evaluation by the following method.

(1) Evaluation of profile extrusion formability:
A 40 mmφ single screw extruder (manufactured by Mitsubishi Heavy Industries, Ltd.) was used, and the thermoplasticity of each of the examples and comparative examples was obtained from a die having a cross-sectional shape shown in FIG. The shape of the molded product obtained by extruding the pellet of the elastomer composition was evaluated. The reflectivity of the die shape and the surface state of the molded product were visually determined, and those having problems such as uneven thickness and edge breakage were determined to be “bad”, and those having no such problems were determined to be “good”.

(2) to (4) Evaluation of scratch resistance, hardness, rubber elasticity:
From the pellets of the thermoplastic elastomer composition of each Example and Comparative Example, using an in-line screw type injection molding machine (“IS130G” manufactured by Toshiba Machine Co., Ltd.), injection pressure 500 kg / cm ² , injection temperature 220 ° C., mold temperature Under the condition of 30 ° C., a sheet having a width of 120 mm, a length of 80 mm, and a thickness of 2 mm was injection molded. The obtained sheet was punched in the lateral direction as necessary to prepare a sample. Using the obtained sample, scratch resistance, hardness and rubber elasticity (compression set) were measured by the following methods.

(2) Scratch resistance:
The surface of the above sample was scratched with a tungsten carbide cutter using a Toyo Seiki Co., Ltd. (Tavers Scratch Tester) at a load of 300 g, and the surface was visually observed in three stages as shown below. evaluated.
○: Not scratched △: Almost scratched ×: Scratched

(3) Hardness:
Duro hardness A was measured according to JIS K6253.

(4) Compression set:
Based on JIS K6262, it measured by 70 degreeC, 22 hours, and 25% compression.

(5) to (6) Evaluation of surface roughness Ra and roughness:
The pellets of the thermoplastic elastomer composition of each Example and Comparative Example were extruded into a sheet shape having a width of 250 mm and a thickness of 0.35 mm from a T die of a 45 mmφ extruder (single flight type screw) manufactured by Watanabe Machine. Using the obtained sheet as a sample, surface roughness Ra and roughness were evaluated.

(5) Evaluation of surface roughness Ra:
About the surface of the said sample, based on JISB0601, centerline average roughness Ra was measured using the Toyo Seimitsu Co., Ltd. surface roughness meter (Surfcom 570A).

(6) Evaluation of irregularities in the extruded sheet:
The sheet skin of the sample was visually observed, and was evaluated in the following three stages based on the number of bumps in the range of the sample sheet length of 1.5 m and the size of the bumps.
○: Excellent △: Good ×: Bad

[Evaluation results]
The evaluation results of the thermoplastic elastomer compositions of each Example and each Comparative Example obtained by the above-described method are shown in Table 2 below.

  As is clear from the results in Table 2 above, the thermoplastic elastomer compositions of Examples 1 to 4 having the prescribed composition of the present invention have profile extrusion moldability, scratch resistance, hardness, compression set, and surface roughness. Good results are shown for both evaluations of Ra and Botsu.

  On the other hand, the thermoplastic elastomer compositions of Comparative Examples 1 and 2 using only one type of ethylene / α-olefin copolymer that satisfies the provisions of the present invention as the component of component (a) are profile extrusion molding. The evaluation result of the property is “defect”, and the evaluation result of the butt is also “good”.

  Further, as the component of component (a), the thermoplastic elastomer composition of Comparative Example 3 using only an olefin copolymer that does not satisfy the provisions of the present invention, and an ethylene / α-olefin that satisfies the provisions of the present invention. The thermoplastic elastomer composition of Comparative Example 4 in which one type of copolymer was used in combination with an olefin copolymer that does not satisfy the provisions of the present invention has a "bad" evaluation result of profile extrusion moldability and roughness. Also, the scratch resistance remains “good”. Further, the surface roughness Ra also shows a high value.

  From the above results, the thermoplastic elastomer compositions of Examples 1 to 4 are superior to the thermoplastic elastomer compositions of Comparative Examples 1 to 4 in excellent profile extrusion processability, and are flexible, rubber elastic, and scratch resistant. It is clear that the surface of the extrusion-molded product is smooth and has few irregularities.

  The thermoplastic elastomer composition of the present invention can be formed into a desired shape and processed into a wide range of automotive parts, home appliance / OA equipment parts, medical equipment parts, packaging materials, civil engineering and building materials, electric wires, miscellaneous goods and the like. It can be suitably used as a material in various fields.

  Specifically, for example, automobile parts include an instrument panel, a console box, an armrest, a headrest, a door trim, a rear panel, a pillar trim, a sun banza, a trunk room trim, a trunk lid trim, an air bag storage box, a seat buckle, and a headliner. , Interior skin materials such as glove boxes, handle pads, steering wheel covers, seats for seats, and ceiling materials.

  Home appliances and OA equipment parts include TV, video, washing machine, dryer, vacuum cleaner, cooler, air conditioner, remote control, microwave oven, toaster, coffee maker, pot, jar, dishwasher, electric razor, hair dryer, microphone, Cover materials for housings such as headphones, beauty equipment, CD / cassette storage boxes, personal computers, typewriters, projectors, telephones, copiers, facsimiles, telexes, etc.

  Examples of the sporting goods include decorative parts for sports shoes, sports equipment such as rackets for various ball games, grips for equipment, saddle skin materials for bicycles, motorcycles and tricycles, and the like.

  For building and housing parts, furniture such as furniture, desks and chairs; skin materials such as gates, doors and walls; wall decoration materials; ceiling decoration materials; curtain wall skin materials; indoors such as kitchens, washrooms and toilets Floor materials for indoor use; floor materials for indoor use such as verandas, terraces, balconies and carports;

Other industrial parts include grips for electric tools, hoses, and skin materials thereof; packing materials and the like. In addition, stationery such as bags, cases, files, notebooks, albums, etc .; camera bodies; skin materials such as toys such as dolls, outer frames of the forehead and skin materials thereof.

Claims (9)

A thermoplastic elastomer composition crosslinked by subjecting the following components (a) to (c) to dynamic heat treatment in the presence of a crosslinking agent,
The mass ratio of component (a) to the total mass of components (a) and (b) is 10% or more and 90% or less, and the mass ratio of component (b) is 90% or less and 10% or more, and The thermoplastic elastomer composition, wherein the component (c) is 50 parts by mass or less with respect to 100 parts by mass of the total amount of the component (a) and the component (b).
(A) density of 0.850 g / cm ³ or more and 0.900 g / cm ³ or less,
A group of olefin copolymers having a molecular weight distribution {mass average molecular weight (Mw) / number average molecular weight (Mn)} by a gel permeation chromatography (hereinafter referred to as “GPC”) method of 3.0 or more,
The olefin copolymer group is composed of the following two or more types of ethylene / α-olefin copolymers.
It is composed of ethylene and one or more α-olefins having 3 to 12 carbon atoms, and has a molecular weight distribution {mass average molecular weight (Mw) / number average molecular weight (Mn)} by GPC method of less than 3.0. Two or more types of ethylene / α-olefin copolymers (b) Olefin polymers having a density greater than 0.900 g / cm ³ .
(C) Styrenic thermoplastic elastomer having a mass average molecular weight of 80,000 or more and 500,000 or less.   The thermoplastic elastomer composition according to claim 1, wherein the component (a) is an ethylene / butene-1 copolymer. The thermoplastic elastomer composition according to claim 1 or 2, further comprising the following component (d):
(D) A hydrocarbon rubber softener. The thermoplastic elastomer composition according to any one of claims 1 to 3, wherein the component (a) is produced using a metallocene catalyst. The thermoplastic elastomer composition according to any one of claims 1 to 4, wherein the component (b) is a propylene-based polymer. The heat according to any one of claims 1 to 5, wherein the α-olefin constituting the ethylene / α-olefin copolymer in the component (a) has 4 or more carbon atoms. Plastic elastomer composition.   The melt flow rate (MFR) of the component (a) is 0.05 g / 10 min or more and 100 g / 10 min or less.
The thermoplastic elastomer composition according to any one of claims 1 to 6, wherein the composition is a thermoplastic elastomer composition. A method for producing a thermoplastic elastomer composition in which the following components (a) to (c) are crosslinked by dynamic heat treatment in the presence of a crosslinking agent,
The mass ratio of component (a) to the total mass of components (a) and (b) is 10% to 90%, the mass ratio of component (b) is 90% to 10%, and Production of a thermoplastic elastomer composition, wherein the crosslinking is performed by mixing so that the component (c) is 50 parts by mass or less with respect to 100 parts by mass of the total amount of (a) and the component (b). Method.
(A) density of 0.850 g / cm ³ or more and 0.900 g / cm ³ or less,
A group of olefin copolymers having a molecular weight distribution {mass average molecular weight (Mw) / number average molecular weight (Mn)} by a gel permeation chromatography (hereinafter referred to as “GPC”) method of 3.0 or more,
The olefin copolymer group is composed of the following two or more types of ethylene / α-olefin copolymers.
It is composed of ethylene and one or more α-olefins having 3 to 12 carbon atoms, and has a molecular weight distribution {mass average molecular weight (Mw) / number average molecular weight (Mn)} by GPC method of less than 3.0. Two or more types of ethylene / α-olefin copolymers (b) Olefin polymers having a density greater than 0.900 g / cm ³ .
(C) Styrenic thermoplastic elastomer having a mass average molecular weight of 80,000 or more and 500,000 or less. An extrusion-molded product obtained by profile-extrusion of the thermoplastic elastomer composition according to any one of claims 1 to 7 .

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