WO2007024025A1

WO2007024025A1 - Thermoplastic elastomer composition and process for producing the same

Info

Publication number: WO2007024025A1
Application number: PCT/JP2006/317287
Authority: WO
Inventors: Kentarou Kanae; Hideo Nakanishi; Minoru Maeda; Minoru Tanaka
Original assignee: Jsr Corporation
Priority date: 2005-08-25
Filing date: 2006-08-25
Publication date: 2007-03-01
Also published as: JPWO2007024025A1

Abstract

A thermoplastic elastomer composition having a sea-island structure which comprises (i) a sea phase comprising a first polymer serving as a matrix and a second polymer present in the matrix and (ii) an island phase comprising a third polymer in a particulate state. The composition has satisfactory foamability, is reduced in compression set, has excellent rubber elasticity, and has a satisfactory balance among these properties.

Description

Thermoplastic elastomer composition and process for producing the same

Technical field

[0001] The present invention relates to a thermoplastic elastomer composition and a method for producing the same, and more particularly, has good foamability, small compression set, excellent rubber elasticity, and a good balance of these properties. The present invention relates to a provided thermoplastic elastomer composition and a method for producing the same. '' Background technology

[0002] In recent years, foam-molded products obtained by foam-molding resin materials have been widely used as cushioning materials against vibration and noise of weather strips such as automobiles, home appliances, and information equipment. In particular, as a resin material that can be easily foamed and can be easily molded into a desired shape, a dynamically crosslinked thermoplastic elastomer composition can be mentioned.

[0003] As a related prior art, a thermoplastic elastomer composition in which crystalline polyethylene constitutes a three-dimensional network structure in a matrix made of ethylene / α-olefin copolymer is disclosed (for example, patent document) 1). This thermoplastic elastomer composition has excellent foamability. In addition, when compared with a normal non-crosslinked thermoplastic elastomer, the rubber elasticity is improved because the compression set is small. However, the improved level of rubber elasticity (compression set) is still not satisfactory and there was a need for further improvements.

[0004] On the other hand, a thermoplastic elastomer composition having improved rubber elasticity (compression set) has also been developed (see, for example, Patent Documents 2 and 3). However, these thermoplastic elastomer compositions are constituted by a matrix (sea phase) force S thermoplastic resin! For this reason, it cannot be said that the foaming property is good, and the texture of the obtained foamed molded product is not good! / There was a habit problem.

[0005] Patent Document 1: Pamphlet of International Publication No. 01 064784

Patent Document 2: Japanese Patent No. 2140072

Patent Document 3: JP-A-10-182901 Disclosure of the invention

[0006] The present invention has been made in view of such problems of the prior art, and the problem is that the foaming property is good, the compression set is small, and the rubber elasticity is excellent. Another object of the present invention is to provide a thermoplastic elastomer composition having a good balance of these characteristics and a method for producing the same.

[0007] As a result of intensive studies to achieve the above-mentioned problems, the present inventors have dispersed island phases having different polymer forces in a sea phase composed of two or more kinds of polymers into a specific network structure. The present inventors have found that the above-described problems can be achieved by constructing a so-called multiple structure, and have completed the present invention.

[0008] That is, according to the present invention, the following thermoplastic elastomer composition and a method for producing the same are provided.

[0009] [1] (ii) a sea phase containing a first polymer and a second polymer, wherein the second polymer is present in a matrix that is a force of the first polymer, and (mouth) particles A thermoplastic elastomer composition having a sea-island structure comprising:

[0010] [2] The thermoplastic elastomer composition according to [1], wherein the second polymer forms a three-dimensional network structure in the matrix having the first polymer force.

[0011] [3] The first polymer is an ethylene 'a-olefin copolymer (A), the second polymer is a crystalline ethylene resin (B), and the third polymer The thermoplastic elastomer composition according to the above [1] or [2], wherein the polymer is a crosslinked rubber (C).

[0012] [4] (ii)

1, 2—Bends consisting of conjugated gen polymer blocks having a Biel bond content of 25% or less, and 1, 2—intermediate blocks having a conjugated gen polymer block force of more than 25% bulge bond content The thermoplastic elastomer composition according to the above [3], further comprising a hydrogenated block copolymer (D) obtained by hydrogenating the block copolymer.

[0013] [5] The thermoplastic elastomer composition according to [3] or [4], wherein the crosslinked rubber (C) has a particle size of 20 μm or less.

[6] The thermoplastic elastomer composition according to any one of [3] to [5] above, further containing a foaming agent (E). [7] [7] The crosslinked rubber (C) is at least selected from the group consisting of ethylene a-olefin copolymer rubber, unsaturated nitrile-conjugated rubber, butadiene rubber, and acrylic rubber. The thermoplastic elastomer composition according to any one of the above [3] to [6]

[8] [8] further containing a softening agent (F),

The thermoplasticity according to [3] to [7], wherein the content of the softening agent (F) is 200 parts by mass or less with respect to 100 parts by mass of the crosslinked rubber (C). Elastomer composition.

[9] The softening agent (F) is a mineral oil-based softening agent (F-1), and the content ratio of the mineral oil-based softening agent (F-11) is the ethylene 'α-olefin-based The thermoplastic elastomer composition according to the above [8], which is 200 parts by mass or less with respect to 100 parts by mass of the copolymer (Α).

[0018] [10] An ethylene'-olefin-based copolymer (A) and a crystalline ethylene-based resin (B), and the crystalline structure of the ethylene'-olefin-based copolymer (A) in the matrix It is obtained by dynamically heat-treating a mixture containing a first composition containing an ethylene-based resin (B), a rubber (G), and a thermoplastic resin (H) in the presence of a crosslinking agent. And a heat phase having a sea-island structure composed of ¾Γ ^ and a sea phase composed of the particulate crosslinked rubber (C). A process for producing a thermoplastic elastomer composition comprising obtaining a plastic elastomer composition.

[0019] [11] A molded product obtained by molding the thermoplastic elastomer composition according to any one of the above [1] to [9].

[0020] [12] From the above [1:] to [9]! / A foam-molded product obtained by foam-molding the thermoplastic elastomer composition described in any one of the above.

[0021] The thermoplastic elastomer composition of the present invention has excellent foaming properties, small compression set, excellent rubber elasticity, and powerfully having these characteristics in a well-balanced manner. is there.

[0022] Furthermore, according to the method for producing a thermoplastic elastomer composition of the present invention, foamability is good, compression set is small, rubber elasticity is excellent, and these properties are well balanced. A provided thermoplastic elastomer composition can be produced.

[0023] The molded article of the present invention has a good compression set and good rubber elasticity! It has such an effect. In addition, the foamed molded article of the present invention is well foamed with a good texture, has a small compression set and is excellent in rubber elasticity.

Brief Description of Drawings

FIG. 1 is an electron micrograph (low magnification) showing the microstructure of the thermoplastic elastomer composition of Example 1.

FIG. 2 is an electron micrograph (high magnification) showing the microstructure of the thermoplastic elastomer composition of Example 1.

FIG. 3 is an electron micrograph showing the microstructure of the thermoplastic elastomer composition of Comparative Example 2.

FIG. 4 is an electron micrograph showing the microstructure of a foam produced using the thermoplastic elastomer composition of Example 1.

FIG. 5 is an electron micrograph showing the microstructure of a foam produced by using the thermoplastic elastomer composition of Comparative Example 2.

BEST MODE FOR CARRYING OUT THE INVENTION

[0025] The best mode for carrying out the present invention will be described below. However, the present invention is not limited to the following embodiment, and is within the scope of the gist of the present invention. Based on the above, it should be understood that modifications and improvements as appropriate to the following embodiments also fall within the scope of the present invention.

[0026] 1. Thermoplastic † Raw Elastomer E

One embodiment of the thermoplastic elastomer composition of the present invention comprises (i) a first polymer and a second polymer, wherein the second polymer is in a matrix of the first polymer. It has a sea-island structure including a sea phase constituting a three-dimensional network structure and an island phase such as (mouth) particulate third polymer shell. The details will be described below.

[0027] (ii) Sea phase

The sea phase of the thermoplastic elastomer composition of this embodiment is a phase having a first polymer and a second polymer. This sea phase is constituted by the presence of the second polymer in the matrix of the first polymer force. More specifically, the second The sea phase is formed by forming a three-dimensional network structure in the matrix of the first polymer. The first polymer is made of, for example, a non-crosslinked elastomer, has flexibility, and has a property of foaming with various foaming agents. The second polymer is made of, for example, a resin, has thermoplasticity (thermoplastic resin), and has a property of foaming with various foaming agents.

[0028] (Mouth) Island Minister

The island phase of the thermoplastic elastomer composition of this embodiment is a phase comprising a particulate third polymer. More specifically, this (mouth) island phase is a phase that exists in the (ii) sea phase. The third polymer is made of, for example, a crosslinked elastomer and has rubber elasticity and flexibility.

[0029] Next, each component constituting the thermoplastic elastomer composition of the present embodiment will be specifically described. As the first polymer constituting the matrix of the sea phase of the thermoplastic elastomer composition of the present embodiment, an ethylene 'a-olefin copolymer (A) (hereinafter referred to as “E AO copolymer (A ) "Or!" (A) component "))) can also be mentioned as preferred examples. In addition, a preferred example of the second polymer that forms a three-dimensional network structure in the sea phase is a crystalline ethylene resin (B) (hereinafter also referred to as “component (B)”). Furthermore, a preferred example of the third polymer constituting the island phase is crosslinked rubber (C) (hereinafter also referred to as “component (C)”). Details of each component will be described below.

[0030] (Ethylene α-olefin copolymer (A))

The component (ii) is an ethylene 'a-olefin copolymer. This component (A) is a copolymer mainly composed of ethylene and α-olefin having 3 to L carbon atoms excluding ethylene. The content of the structural unit derived from ethylene in the component (ii) is 50 to 90 mol% when the total of the structural unit derived from ethylene and the structural unit derived from α-olefin is 100 mol%. It is preferable that When the content is more than 90 mol%, the resulting thermoplastic elastomer composition tends to be insufficient in flexibility. On the other hand, when the content is less than 50 mol%, the mechanical strength of the obtained thermoplastic elastomer composition tends to be insufficient.

[0031] Specific examples of α-olefin having 3 to 3 carbon atoms: propylene, 1-butene, 1- Examples include pentene, 4-methyl monopentene 1, 1-hexene, 1-heptene, 1-octene, 1-decene. Of these, propylene, 1-butene, 1-hexene and 1-octene are preferable, and propylene and 1-butene are more preferable. These compounds can be used as a single worm or in combination of two or more. When _α -olefin having 10 or less carbon atoms is used, the copolymerizability of this 0-olefin with other monomers is improved. (Alpha) in the component, the content of structural units derived from one Orefin is, when the total of the constitutional unit derived from the structural units and a- Orefuin derived from ethylene and 100m _O l%, 5~50mol% 10 to 45 mol% is more preferable, and 15 to 40 mol% is particularly preferable. If the content of the structural unit derived from α-olefin is less than 5 mol%, it tends to be difficult to obtain the rubber elasticity required for the thermoplastic elastomer composition. On the other hand, when the content of the structural unit derived from α-olefin is more than 50 mol%, the durability of the resulting thermoplastic elastomer composition tends to be low.

In addition, the component (A) may contain a constituent unit derived from non-conjugated gen at a ratio of 0 to 10 mol% if necessary. When the content ratio of the structural unit derived from this gen is more than 10 mol ° / ₀ , durability of the obtained thermoplastic elastomer composition tends to be lowered. Specific examples of non-conjugated gens include linear acyclic gens such as 1,4-hexagen, 1,6-hexagen, 1,5-hexagen; 5-methyl-1,4-hexagen, 3 , 7-Dimethylolene 1, 6-octagen, 5, 7-dimethylocta-1, 6, 6-gen, 3, 7-dimethyl 1, 7, 7-octagen, 7-methylocta 1, 6-gen, dihydromyrcene, etc. Acyclic gen; tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, bicyclo [2. 2. 1] —hepta-1,5-gen, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, Alicyclic gens such as 5-propenyl-2-norbornene, 5-isopropylidene-2-carebornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, etc. Door can be. Of these, 1,4-monohexagen, dicyclopentagen, and 5-ethylidene-2-norbornene are preferred. These compounds can be used as a single insect or a combination of two or more. [0033] The intrinsic viscosity [η] of component (A) measured at 135 ° C in a decalyte medium is preferably 3.5 to 6.8 dl / g. 4.0 to 6.8 dlZg It is more preferable that it is 4.3 to 6.8 dl / g. If this intrinsic viscosity [] is less than 3.5 dlZg, the rubber elasticity of the thermoplastic elastomer composition tends to decrease. On the other hand, if it exceeds 6.8 dlZg, the moldability tends to decrease.

[0034] As the component (A), in addition to the above-described binary copolymers and ternary copolymers, some of the hydrogen atoms in these copolymers are halogens such as chlorine atoms and bromine atoms. Halogen copolymer substituted with atoms; butyl chloride, vinyl acetate, (meth) acrylic acid, (meth) acrylic acid derivatives (methyl (meth) acrylate, glycidyl (meth) acrylate, (meth) Acrylic monomers, etc.), maleic acid, maleic acid derivatives (maleic anhydride, maleimide, dimethyl maleate, etc.), conjugation monomers (butadiene, isoprene, black mouthprene, etc.) and other unsaturated monomers. Or a terpolymer, or a graft copolymer obtained by graft polymerization with respect to the halogenated copolymer or the like. These copolymers can be used singly or in combination of two or more.

[0035] As the component (A), an oil-extended rubber (X) obtained by adding a mineral oil softener (F-1) to the EAO copolymer (A) can also be used. This oil-extended rubber (X) is preferred because it is easy to handle in producing the thermoplastic elastomer composition of this embodiment. Here, the content ratio of the EAO copolymer (A) and the mineral oil softener (F-1) in the oil-extended rubber (X) is preferably 20 to 80% by mass, respectively. More preferably, it is 25 to 75% by mass, and particularly preferably 30 to 70% by mass. The form of the EAO copolymer (A) and the oil-extended rubber (X) may be any form of bale, crumb, pellet, and powder (including vano-crushed product).

[0036] Component (A) is used, for example, in the presence of a catalyst comprising a Ziegler-Natta catalyst, a soluble vanadium compound, and a solvent containing an organic aluminum compound, ethylene, aolefin, and as required. Such a non-conjugated diene can be produced by a method of polymerizing hydrogen as a quantity adjusting agent if necessary (a polymerization method using a medium-low pressure method) or the like. This polymerization can be carried out by a gas phase method (fluidized bed or stirred bed) or a liquid phase method (slurry method or solution method). [0037] Examples of the soluble vanadium compound include VOC1 and

3 Z or να and alcohol

Four

It is preferable to use the reaction product of Examples of the alcohol include methanol, ethanol, η-propanol, isopropanol, η-butanol, sec-butanol, teptanol mono-ole, n-hexanol, n-octanol, 2-ethino hexanol, n-decanol, n —Dodecanol or the like can be used. Of these, alcohols having 3 to 8 carbon atoms are preferably used.

[0038] Examples of the organoaluminum compound include triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, jetylaluminum monochloride, diisobutylaluminum monochloride, ethyluranoium sesquioxide, butyl aluminum sesquioxide. Methyl aluminoxane, which is a reaction product of trimethylaluminum and water, can be mentioned. Among these, ethylaluminum sesquichloride, butylaluminum sesquichloride, a mixture of ethylaluminum sesquichloride and triisobutylaluminum, and a mixture of triisoptylaluminum and butynolealuminum sesquichloride are preferably used. It is done.

[0039] Further, as the solvent, a hydrocarbon is preferably used. Of these, n-pentane, n-hexane, n-heptane, n-octane, isooctane, and cyclohexane are more preferably used. These hydrocarbons can be used singly or in combination of two or more.

[0040] The content ratio of component (A) in the sea phase constituting the thermoplastic elastomer composition of the present embodiment is 20 when the total of component (A) and component (B) is 100 parts by mass. It is preferable to set it to -90 mass parts, It is more preferable to set it as 25-85 mass parts, It is especially preferable to set it as 30-80 mass parts. If the content of component (A) is outside the above numerical range, the rubber elasticity, flexibility, and moldability of the resulting thermoplastic elastomer composition, and the oil predability tends to decrease when a softener is added. is there.

[0041] (Crystalline ethylene resin (B))

The component (B) is a crystalline ethylene resin. This component (B) is composed mainly of ethylene, and the content ratio of structural units derived from ethylene is 90 to 100 mol. %. The crystallinity of the component (B) is preferably 10% or more. When the degree of crystallinity is less than 10%: ^, the resulting thermoplastic elastomer composition tends to have poor mechanical strength. Furthermore, it is preferable that the melting peak temperature of the component (B) measured by a differential scanning calorimeter (DSC) is 100 ° C. or higher. When the melting peak temperature is less than 100 ° C., the heat resistance of the obtained thermoplastic elastomer composition tends to decrease and the compression set tends to increase.

[0042] Specific examples of the component (B) include polyethylene, ethylene content of 90 mol% or more, carbon number such as propylene, butene-1, 1, 4-methinolepentene, 1, hexene-1, octene-1, etc. And copolymers with hyolein having a valence of 3-6. These polymers can be used in one job or in combination of two or more. Polyethylene may be obtained by a high pressure method or a low pressure method or by a displacement method.

[0043] The content ratio of component (B) in the sea phase constituting the thermoplastic elastomer composition of the present embodiment is 1 when the total of component (A) and component (B) is 100 parts by mass. It is preferable to set it as -40 mass parts, It is still more preferable to set it as 3-35 mass parts, It is especially preferable to set it as 5-30 mass parts. When the content ratio of the component (B) is outside the above numerical range, the rubber elasticity, flexibility, and moldability of the resulting thermoplastic elastomer composition, and the tendency to decrease the oil bleeding property when a softening agent is added. It is in.

[0044] (Crosslinked rubber (C))

Component (C) is a crosslinked rubber and is present in the form of particles dispersed in the aforementioned sea phase. Component (C) consists of (C-1) ethylene · "one-olefin copolymer rubber (hereinafter also referred to as" (C-1) component "), (C-2) unsaturated nitrile rubber (hereinafter , “(C-2) component”), (C-3) butadiene rubber (hereinafter also referred to as “(C-13) component”), and (C-4) acrylic rubber (hereinafter referred to as “(C — It is preferable that “4) component” is at least one selected from the group consisting of V ヽぅ).

[0045] (C-1) Ethylene 'a-olefin copolymer rubber

The component (C-1) is ethylene 'a-olefin copolymer rubber. Specific examples of the component (C-1) include the same components as the component (A) described above.

[0046] (C-2) Unsaturated nitrile-conjugated gen rubber Component (C-2) is an unsaturated nitrile mono-conjugated rubber. As this (C-2) component, for example, a copolymer rubber of unsaturated nitrile and conjugated gen, a polar group-containing copolymerizable monomer other than unsaturated nitrile, conjugated gen and unsaturated nitrile, and And a partially crosslinked copolymer rubber obtained by partially crosslinking these copolymer rubbers, and a copolymer rubber that is partially hydrogenated after polymerization. The content ratio of the structural unit derived from unsaturated nitrile in the component (C-2) is preferably 10 to 70% by mass! /.

[0047] Conjugated diene (hereinafter also referred to as "(C-2-1) component") constituting component (C-2) includes, for example, butadiene, isoprene, 1,3-hexagen, 2-methyl 1,3-butadiene, 2,3-dimethylbutadiene, 2-trimethoxysilyl-1,3-butadiene, 1,3-pentane, 2,4-dimethyl-1,3-butadiene, etc. . Of these, butadiene and isoprene are preferred. These compounds can be used singly or in combination of two or more.

[0048] Unsaturated nitrile (hereinafter, also referred to as "(C-2-2-2) component") constituting component (C-2) includes, for example, acrylonitrile, methacrylonitrile, ethylacrylonitrile, isopropyl alcohol. Lilonitrile, black mouth acrylonitrile, fluoroacrylonitrile and the like can be mentioned. Of these, acrylonitrile is preferable. These compounds can be used alone or in combination of two or more.

[0049] Examples of (C-2) component-containing polar group-containing copolymerizable monomer other than unsaturated-tolyl (hereinafter, also referred to as "(C-2-3) component") include, for example, acrylic Methyl acrylate, Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, s_butyl acrylate, 2-methyl butyl acrylate, 3-methyl butyl acrylate, n-acrylate —Hexyl, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, acrylamide, N-hydroxymethyl (meth) acrylamide, N— (2-hydroxyethyl) (meth) Acrylamide, N, N-bis (2-hydroxyethynole) (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) atalyte , Crotonic acid 2-hydroxyethyl, Crotonic acid 2-hydroxypropinole, Cay cinnamate 2-hydroxyethyl, Cay cinnamate 2-hydroxypropyl, Crotonic acid N-Hydroxymethylamide, Crotonic acid N- (2 —Hydroxyethyl) amide, Kaycin acid N-hydroxy Methyl amide, cinnamate N— (2-hydroxyethyl) amide, aryl alcohol, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, ethylene glycol mono (meth) acrylate, propylene glycol mono (meta ) Atalylate, vinylinamine, arylamine, o_aminostyrene, m-aminostyrene, p-aminostyrene, 2-aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, glycidyl (meth) acrylate , Aryl glycidyl ether, acrolein, butyl methyl ketone, divinino phthalate, diaryl phthalate,, N-methylenebis (meth) acrylamide, N, N-ethylenebis (meth) acrylamide,, N-hexamethylenebis (meta ) Acrylamide, (meth) a Kurylic acid, Crotonic acid, Kaycin acid, Itaconic acid, Maleic acid, Fumaric acid, Citraconic acid, Mesaconic acid, (Meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid, Methacrylic acid 2-hydroxyptyl, (Meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxybutyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid dimethylenaminoethyl, (meth) acrylic acid jetylamino Ethyl, _ω -carboxy-poly-polyprolactone mono (meth) acrylate, tetrahydrofurfuryl acrylate, polyalkylene glycol of polyethylene glycol (number of alkylene glycol units is 2 to 23, for example), di (meth) acrylate, polypropylene Polyalkylene glycol (alkylene glycol) The number of call units is, for example, 2 to

23) Di (meth) acrylate and the like. Of these, acrylic acid, ethyl acrylate, η-butyl acrylate, t-butyl acrylate, and s-butyl acrylate are preferred. These compounds can be used individually by 1 type or in combination of 2 or more types.

[0050] The content ratio of the structural unit derived from the (C—2-1) component in the (C) component is (C-2-D + (C—2-2—2) + (C—2—3) = is 100 mass ^_0/0, it is good Mashiku 15 to 75 wt%, the content of the constituent unit to be between 20 and 70 mass% derived from more preferable. (C- 2- 1) component If it is less than 15% by mass, the rubber elasticity of the resulting thermoplastic elastomer composition tends to decrease, whereas if it exceeds 75% by mass, the oil resistance of the obtained thermoplastic elastomer composition is low. Tend to be bad.

[0051] The content of the structural unit derived from the component (C-2-2) is (C-2-1) + (C-2 -2) + (C-2-3) = 100% by mass When it is, it is preferable that it is 15-50 mass%, and it is still more preferable that it is 16-45 mass%. (C-2-2) of structural unit derived from component If the content is less than 15% by mass, the oil resistance of the resulting thermoplastic elastomer composition tends to be lowered. On the other hand, if it exceeds 50% by mass, the rubber elasticity of the obtained thermoplastic elastomer composition tends to decrease.

[0052] The content ratio of the structural unit derived from the component (C-2-3) was (C-2-1) + (C-2-2-2) + (C-2-3) = 100% by mass. In this case, it is preferably 0 to 60% by mass, more preferably 0 to 50% by mass. When the content ratio of the structural unit derived from the component (C-2-3) is more than 60% by mass, the rubber elasticity of the obtained thermoplastic elastomer composition tends to be lowered.

[0053] (C-3) Butadiene rubber

Component (C-3) is butadiene rubber. This (C-3) component should be a polymer polymerized using a rare earth element compound-based catalyst mainly composed of structural units derived from butadiene! / V.

[0054] (C-4) Acrylic rubber

Component (C-4) is acrylic rubber. Examples of the component (C-4) include an acrylic rubber mainly composed of a known alkyl acrylate and / or an alkoxyalkyl acrylate, or a copolymer of the acrylic rubber and an unsaturated acrylonitrile monomer. Acrylic nitrile acrylic rubber can be mentioned.

[0055] The alkyl acrylate constituting the component (C-4) (hereinafter also referred to as "(C-4-1) component") includes, for example, methylolacrylate, ethyl acrylate, propyl acrylate. Rate, butyl acrylate, octyl acrylate and the like. Of these, ethyl acrylate, propyl acrylate, and butyl acrylate are preferable. Examples of the alkoxyalkyl acrylate which constitutes the component (C-4) include methoxymethyl acrylate, methoxychetyl acrylate, ethoxy ethynoleate acrylate, butoxetyl acrylate, methoxy catechol. Examples include shetila acrylate. Of these, methoxyethyl acrylate, ethoxyethyl acrylate and the like are preferable. These alkynole acrylates and alkoxy alkynole acrylates can be used singly or in combination of two or more.

[0056] The content of the structural unit derived from the component (C-4-1-) in the component (C-4) is 20 to 99 It is preferably 99% by mass, more preferably 60-94.98% by mass, particularly preferably 70-90% by mass. If this ratio is less than 20% by mass, the resulting thermoplastic elastomer composition may have an excessive hardness and may not have a suitable inertial state. On the other hand, if this ratio exceeds 99.99 mass ° / ₀ , the resulting thermoplastic elastomer composition tends to have poor oil resistance.

As the monomer (C-4-2) that can be copolymerized with each monomer component to introduce a crosslinking group into the structure of component (C-4), for example, dihydrodiacrylate Cyclopentenyl, dihydrodicyclopentenyl methacrylate, dihydrodicyclopentenyl itaconate, dihydrodicyclopentyl maleate, dihydrodicyclopentenyl fumarate, dihydrodicyclopentenyl oxateyl acrylate (DCPEA), methacryl Dihydrodicyclate Oral Pentenyl Oxetyl, Dihydrodicyclopenteyl Ochetyl Titaconate, Dihydrodicyclopentenyl Oxetyl Maleate, Dihydrodicyclopentenoloxychetyl Fumarate, Butyl Methacrylate (CAS No. 4245 — 38— 8), Atalinoleic acid butyl (CAS No. 2177—18—6), Methacrylic acid 1,1-dimethylprop Nyl, Acrylic acid 1,1-Dimethylpropenyl, Methacrylic acid 3,3-Dimethylbuteyl, Acrylic acid 3,3-Dimethylbuturyl, Itaconic acid dibule, Maleic acid dibule, Fumarate dibilene, Dicyclopentadiene, Methyl Noresicyclopentagen, ethylidene norbornene, 1,1_dimethylpropenyl methacrylate, 1,1-dimethylpropenyl acrylate, 3,3-dimethylbutyrmethacrylate, 3,3-dimethylbutyracrylate, bur 1 , 1-Dimethylpropenyl ether, Bulle 3, 3-Dimethylbutyrether, 1-acryloyloxy 1-phenyloxyl, 1-acryloyloxy 2-phenylenyl, 1-methacryloyloxy 1-1 monophenyloxyl, 1-methacryloyloxy 1-Phenylmethene, (meth) acrylic acid Unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, tetraconic acid, and cinnamate; non-polymerizable polycarboxylic acids such as phthalic acid, succinic acid, and adipic acid, and (meth) aryl alcohol, 2- Free carboxyl group-containing esters such as monoesters with hydroxyl-containing unsaturated compounds such as hydroxyethyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3 —Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) Hydroxyalkyl (meth) acrylates such as acrylate, 4-hydroxybutyl (meth) acrylate; monoalkylene glycols such as polyethylene glycol and polypropylene glycol mononole (number of alkylene glycol units is 2 to 23, for example) N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-bis (2-hydroxyethyl) (meth) acrylamide, etc. Hydroxyl group-containing unsaturated amides; o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxymono-a-methylstyrene, p-hydroxy α-methylstyrene, ρ—Bulbendyl alcohol, (meth) arinoreal alcohol, Methylaminomethyl (meth) acrylate, Jetylaminomethyl (meth) acrylate, 2-Dimethylaminoethynole (meth) acrylate, 2-Dethylaminoethyl (meth) atrelate, 2- (Di-η —Propynoleamino) ethyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 2-jetylaminopropynole (meth) acrylate, 2- (di-η—propyramino) propyl (meth) acrylate Dialkylaminoalkyl (meta) such as 3-dimethylaminopropyl (meth) acrylate, 3-jetylaminopropinole (meth) acrylate, 3- (di-11-propylamino) propino (meth) acrylate ) Atarylates; Ν-Dimethylaminomethyl (meth) acrylamide, Ν-Jetylaminomethyl ( ) Acrylamide,-(2-dimethylaminoethyl) (meth) acrylamide, Ν- (2-jetylaminoethyl) (meth) acrylamide, Ν- (2-dimethylaminopropyl) (meth) acrylamide,-( 2-Dialkylamino such as 2-jetinoleaminopropyl) (meth) acrylamide, Ν- (3-dimethylinoaminopropyl) (meth) atrylamide, Ν- (3-jetylaminopropyl) (meth) acrylamide In addition to alkyl group-containing unsaturated amides; Ν, ー -dimethyl-ρ-aminostyrene, ,, Ν-jetyl ρ-aminostyrene, dimethyl (ρ-butylbenzyl) amine, jetyl (ρ-vinylbenzyl) amine, Dimethyl (ρ-vininolephenethyl) amine, Jetyl (ρ-Bulfeneethyl) amine, Dimethyl (ρ-Bulbeniloxy) Til) amine, dimethyl [2- (ρ-bibenzylbenzyloxy) ethyl] amine, jetyl (ρ-vinylbenzyloxymethyl) amine, jetyl [2- (ρ-butylbenzyloxy) ethyl] amine, dimethyl (ρ —Vinolephenethyloxymethyl) amine, dimethyl [2- (ρ-vinylphenethyloxy) ethyl] amine, jetinole (ρ-butenephenyloxymethyl) amine, jeti Tertiary amino group-containing vinyl aromatic compounds such as ru [2- (p-vininolephenethyl) ethyl] amine, 2-burpyridine, 3-bulupyridine, 4-bulupyridine; (meth) aryl Examples thereof include glycidyl ether, glycidyl (meth) atalylate, and 3,4-oxycyclohexylenolate (meth) acrylate.

[0058] The content ratio of the structural unit derived from the component (C-4) in the component (C-4) is preferably 0.01 to 20% by mass. % Is more preferable. If this proportion is less than 0.01% by mass, the degree of cross-linking of the resulting thermoplastic elastomer composition will be insufficient, and the bow I tension strength will be too low to have suitable mechanical strength. May be 1 / ヽ. On the other hand, if this ratio exceeds 20% by mass, the hardness of the resulting thermoplastic elastomer composition tends to be excessively high.

[0059] The type of radical polymerization initiator used when copolymerizing the monomer mixture is not particularly limited. For example, peroxides such as potassium persulfate, p-menthane hydride peroxide and methyl isopropyl ketone peroxide; azo compounds such as azobisisobutyoxy-tolyl can be used. The amount of radical polymerization initiator used should be 0.001 to 1.0 parts by mass per 100 parts by mass of the monomer mixture! /.

[0060] The copolymerization reaction for obtaining the component (C-4) can be carried out by a usual polymerization method such as a suspension polymerization method, an emulsion polymerization method or a solution polymerization method. ? The emulsifier used in the W-polymerization method may be any substance that can emulsify and disperse the above monomer mixture. For example, alkyl sulfates, alkyl aryl sulfonates, salts of higher fatty acids can be used. The reaction temperature is usually 0 to 80 ° C., and the reaction time is usually about 0.01 to 30 hours. The acrylic rubber thus obtained has a Mooney viscosity (ML, 100 ° C) force of 10

1 + 4

~: 150 is preferred.

[0061] In the thermoplastic elastomer composition of the present embodiment, the particle diameter of the particulate crosslinked rubber (C) is preferably 20 m or less, and 0.1 to: L8 ii m More preferably, it is 0.5-15 / m. By setting the particle size of component (C) to 20 // m or less, both rubber elasticity and fluidity can be achieved. If the particle size of component (C) is more than 20 μm, the fluidity tends to deteriorate. In order to reduce the particle size of component (C) to 20 / m or less, for example, using a continuous extruder, a high shear force (shear rate of 10 to 2000) is used. 0 / sec) and obtained by dynamic heat treatment.

[0062] (Hydrogenated block copolymer (D))

The thermoplastic elastomer composition of the present embodiment has a two-end block consisting of a conjugated diene polymer block force having a 1,2-pillar amount of 25% or less, and a 1,2-bule. Hydrogenated block copolymer (D) (D) (D) (hydrogenated block copolymer (copolymer before hydrogenation) containing an intermediate block having a block content of more than 25% of an ethylene polymer block force) Hereinafter, it is preferable to further contain “(D) component” in order to easily form a three-dimensional network structure.

[0063] Both terminal blocks of the copolymer before hydrogenation are conjugated polymer block (hereinafter also referred to as "A block") having a 1,2-bule bond content of 25% or less. The intermediate block of the pre-hydrogenated copolymer is a conjugated diene polymer block (hereinafter also referred to as ΓΒ block) having a 1,2-Biel bond content of more than 25%. Preferably A and B blocks total 100 weight ° / ₀ and the case of, A blocks is 5 to 90 mass ⁰ I and B blocks are 10 to 95 weight ^_0/0, A Proc 10 to 80 mass ^_0/0,及Pi B block is further preferred that 20 to 90 wt% arbitrariness. If the A block is less than 5% by mass (B block is more than 95% by mass), it will be difficult to form a three-dimensional network structure, because it will be difficult to exhibit sufficient crystallinity relative to the component (A) that is the matrix There is a tendency. On the other hand, if the A block is more than 90% by mass (B block is less than 10% by mass), the hardness of the resulting thermoplastic elastomer composition tends to be excessively increased.

[0064] Component (D) is a hydrogenated copolymer (A—B—A type block copolymer) that has both terminal blocks and a B block between these two A blocks. It is a hydrogenated block copolymer obtained by adding. That is, A block and B block are copolymer blocks before hydrogenation. The A block is a 1,3-butadiene polymer block containing butadiene as a main component (90 mass% or more, preferably 95 mass% or more of the entire A block). Further, the 1,2-bule condensation amount of the A block is less than 25%, preferably 20% or less, and more preferably 15% or less. When the 1,2-bule bond content of the A block is 25% or more, the melting point of the crystal after hydrogenation is remarkably lowered, and the mechanical strength tends to be lowered. In addition, the number average molecular weight (Mn) of the A block is a force S that is 25000 to 630000, preferably a force S that is 100000 to 480000 S, and more preferably V. (D ) In the component, the A block is hydrogenated and shows a structure similar to low density polyethylene.

[0065] The B block is a conjugated diene polymer block containing a conjugated diene compound as a main component (50% by mass or more, preferably 60% by mass or more of the entire B block). Examples of the conjugated diene compounds include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentagen, 2-methyl-1,3-pentane, 1,3-hexagen. 4,5-jetyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene and the like. Of these, 1,3-butadiene, isoprene, and 1,3-pentadiene are preferred, and 1,3-butadiene is particularly preferred. The B block is made up of two or more of these compounds! /, Te! /, Even V.

[0066] The 1,2-bule bond content of the B block is more than 25%, preferably 30 to 95%, and more preferably 35 to 90%. When the 1,2-bule bond content of the B block is 25% or less, the hydrogenated block copolymer (D) tends to be resinous and tend to be less flexible. In addition, the 1,2-bule bond content of the B block exceeds the 1,2-bule bond content of the A block. B Block 1,2-Buule Bond Content Strength If the A block is less than the 1,2-Bell bond content, the flexibility of the resulting thermoplastic elastomer composition tends to decrease. The number average molecular weight (Mn) of the B block is preferably 5,000 to 650000, and is preferably 20000 to 540000.

[0067] The component (D) is preferably one in which 80% or more of all double bonds of the copolymer before hydrogenation are hydrogenated, and more preferably 90% or more. 95 ~: L00% is particularly preferable. When the hydrogenation rate is less than 80%, the thermal stability and durability of the resulting thermoplastic elastomer composition tend to be easily lowered. The number average molecular weight (Mn) of the component (D) is more preferably 50000-700000, more preferably 100000-600000. When the number average molecular weight (Mn) is less than 50000, the heat resistance, strength, fluidity, and processability of the resulting thermoplastic elastomer composition tend to be lowered. On the other hand, if the number average molecular weight (Mn) is more than 700,000, the fluidity, processability and flexibility of the resulting thermoplastic elastomer composition tend to be lowered.

[0068] The copolymer before hydrogenation is, for example, aliphatic carbon such as pentane, hexane, heptane, and octane. Hydrocarbon solvents; cycloaliphatic hydrocarbon solvents such as cyclopentane, methylcyclopentane, cyclohexane, and methinolenc hexane; or inert hydrocarbon solvents such as benzene, xylene, tonolene, and ethenolevenbenzene In the organic solvent, the bu aromatic compound and the gen compound, or the bu aromatic compound and the conjugated diene compound and other monomers copolymerizable therewith, and the organic alkali metal compound as a polymerization initiator for the living cation polymerization. It can be obtained by doing so. The component (D) can be easily obtained by hydrogenating the pre-hydrogenated polymer thus obtained.

[0069] Examples of the organic alkali metal compound used as the polymerization initiator include organic lithium compounds and organic sodium compounds. Of these, organolithium compounds such as n-butyllithium, sec-butyllithium, and tert-butyllithium are preferable. The amount of the organic alkali metal compound used is not particularly limited, and various amounts can be used as necessary. Usually, the amount is 0.02 to 15 parts by mass with respect to 100 parts by mass of the monomer, and 0.03 to 5 parts by mass is preferably used. The polymerization temperature is usually from 10 to 150 ° C, preferably from 0 to 120 ° C. Furthermore, it is desirable that the polymerization atmosphere is an inert gas atmosphere such as nitrogen gas. The polymerization pressure is not particularly limited as long as the polymerization pressure is within a range of pressure sufficient to maintain the monomer and solvent in the liquid phase.

[0070] Further, in the process of polymerizing and preparing the pre-hydrogenation copolymer, there is no particular limitation on the method of introducing each of the monomers into the polymerization system, and the batch, continuous, intermittent Or a combination of these. Furthermore, the addition amount of other copolymerization components, the addition amount of polar substances, the number and type of polymerization vessels, etc., and the charging method of each component are selected so that the physical properties of the obtained component (D) are favorable. Bayo V ヽ.

[0071] A copolymer obtained by introducing a coupling residue into a copolymer molecular chain using a coupling agent after polymerization by the above method may be used as a copolymer before hydrogenation. Coupling agents that can be used at this time include, for example, dibutenebenzene, 1,2,4trivinylbenzene, epoxidized 1,2-polybutadiene, epoxidized soybean oil, epoxidized diamine oil, benzene 1, 2, 4 1 Triisocyanate, Jetyl oxalate, Jetinole malonate, Jetyl adipate, Dioctyl adipate, Dimethyl phthalate, Jetyl phthalate, Jetyl terephthalate, Jetyl carbonate 1, 1, 2, 2-tetrachloroethane, 1,4-bi (Trichloromethyl) benzene, trichlorosilane, methyltrichlorosilane, butyl trichlorosilane, tetrachlorosilane, (dichloromethyl) trichlorosilane, hexachlorodisilane, tetraethoxysilane, tetrachlorotin, 1,3-dichloro-1,2 -You can list propanone. Of these, dibutenebenzene, epoxidized 1,2-polybutadiene, trichlorosilane, methyltrichlorosilane, and tetrachlorosilane are preferred.

[0072] Component (D) is obtained by partially or selectively hydrogenating the pre-hydrogenated copolymer obtained as described above. The hydrogenation method and reaction conditions are not particularly limited, and are usually 20 to: 150 ° C., 0.1 to: OMPa under hydrogen pressure and in the presence of a hydrogenation catalyst. The hydrogenation rate can be arbitrarily selected by changing the amount of the hydrogenation catalyst, the hydrogen pressure during the hydrogenation reaction, the reaction time, and the like. As a hydrogenation catalyst, a compound containing any one of Group Ib, IVb, Vb, VIb, VIIb, and Group VIII metals, such as Ti, V, Co, Ni, Zr, Ru, Rh, Pd, Hf, Re A compound containing a Pt atom can be used. Specifically, for example, meta-orthocene compounds such as Ti, Zr, Hf, Co, Ni, Pd, Pt, Ru, R and Re; metals such as Pd, Ni, Pt, R and Ru are carbon Supported heterogeneous catalyst supported on a carrier such as silica, alumina, diatomaceous earth, etc .; a homogeneous system combining organic salts of metal elements such as Ni and Co or acetylacetone salt and a reducing agent such as organic aluminum Ziegler type catalysts; organometallic compounds or complexes such as R _U and Rh, and fullerenes and carbon nanotubes occluded with hydrogen. Of these, meta-octene compounds such as Ti, Zr, Hf, Co, and Ni are preferable in that they can be hydrogenated in an inert organic solvent in a homogeneous system. Furthermore, a metaguchicene compound containing any of Ti, Zr, and Hf is preferable. In particular, a hydrogenation catalyst obtained by reacting a titanocene compound with alkyl lithium is preferred because it is inexpensive and particularly useful industrially. In addition, the said hydrogenation catalyst may be used individually by 1 type, and may use 2 or more types together. After hydrogenation, the catalyst residue is removed as necessary, or a phenol-based or amine-based antioxidant is added, and then component (D) is isolated from the hydrogenated reaction solution. Isolation of component (D) is carried out, for example, by adding acetone or alcohol to the hydrogenated reaction solution for precipitation, or by pouring the hydrogenated reaction solution into hot water with stirring and distilling off the solvent. Can do.

[0073] The copolymer before hydrogenation is coupled with a plurality of A-B-A-type block copolymers. It may have a structural part connected through an agent residue. That is, the pre-hydrogenated copolymer has a block structure represented by [A—B—A—X]-(ABA) (where n is an integer of 2 to 4, and X represents a coupling agent residue). It may be done. Furthermore, the pre-hydrogenated copolymer can be obtained in such a range that the molecular weight of the coupling agent residue is sufficiently smaller than the molecular weight of the A block and B block, and does not affect the crystallinity of the component (D). For example, the block structure is [A— B— X] ― (BA) (where n is an integer of 2 to 4, X is the remaining coupling agent)

n

It may be represented by a group). That is, the block structure may be represented by [A—B] —A after omitting a relatively small coupling agent residue.

[0074] The copolymer before hydrogenation may be a modified block copolymer modified by introducing a predetermined functional group. The predetermined functional group to be introduced is at least one selected from the group consisting of a carboxyl group, an acid anhydride group, a hydroxyl group, an epoxy group, a halogen atom, an amino group, an isocyanate group, a sulfonyl group, and a sulfonate group. Can be mentioned. A known method may be adopted as the modification method. The functional group content in the modified block copolymer is preferably from 0.01 to L0 mol% when the total of the structural units constituting the modified block copolymer is 10 Omol%. More preferably, it is 1 to 8 mol%, particularly preferably 0.15 to 5 m%. Examples of the monomer used for introducing the functional group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, glycidyl acrylate, glycidyl methacrylate, allylglycidino ether, and hydroxyethinore. Examples include methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, dimethylaminoethyl methacrylate, and the like.

[0075] The sea phase constituting the thermoplastic elastomer composition of this embodiment has (D) component ¾r ^, and the content ratio of (D) component in this sea phase is 1 to 30 parts by mass. It is particularly preferably 3 to 25 parts by mass, and even more preferably 5 to 20 parts by mass. When the content ratio of component (D) is less than 1 part by mass, the rubber elasticity of the resulting thermoplastic elastomer composition tends to decrease. On the other hand, when the content of component (D) is more than 30 parts by mass, the fluidity and heat resistance of the resulting thermoplastic elastomer composition tend to be lowered. [0076] (Foaming agent)

The thermoplastic elastomer composition of this embodiment may further contain a foaming agent (hereinafter also referred to as “component (E)”) as necessary. Examples of the component (E) include a thermal foaming agent, a volatile foaming agent, air, a supercritical fluid gas, and a hollow particle foaming agent. The component (E) can be appropriately selected depending on the production method. Moreover, (E) component can be used individually by 1 type or in combination of 2 or more types.

[0077] Heat: ^ Examples of foaming agents include nitroso-based foaming agents such as N, N, -dinitrosopentamethylenetetramine, N, N'-dimethyl-1-N, N'-dinitrosotephthalamide; Azo foaming agent of norium azodicarboxylate such as rubonamide, barium azodicarboxylate; P, p-oxybisbenzenesulfonyl hydrazide, 4, 4, oxybis (benzensulfonyl hydrazide), p-toluenesulfoni Sulfohydrazide-based blowing agents such as rilsemicarbazide; triazine-based blowing agents such as trihydrazinotriazine; tetrazole-based blowing agents such as 5-phenyltetrazole, azobistetrazoldiguanidine, azobistetrazolaminoguanidine, etc. An inorganic foaming agent such as sodium hydrogen carbonate. Two or more of these thermal foaming agents may be used in combination. The addition amount of these thermoplastic foaming agents may be selected according to the type of foaming agent, the target foaming ratio, etc., but 0.1 to L00 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer composition. It is preferable to do.

[0078] Examples of the volatile foaming agent include aliphatic hydrocarbons such as propane, butane, and pentane; alicyclic hydrocarbons such as cyclobutane, cyclopentane, and cyclohexane; chlorodifluoromethane, difluoromethane, and trifluoromethane. , Trichlorodichloromethane, dichloromethane, dichlorofluoromethane, dichlorodifluoromethane, trichlorofluoroleoromethane, chloromethane, black ethane, dichlorotrifluoroleoroethane, dichlorofluoroethane, chlorodifluoroethane, dichloropentafluoro Loetane, pentafluororeethane, trifluoroethane, dichlorotetrafluoroethane, trichlorodifluoroethane, tetrachlorodifreoethane, black pentafluoroethane, perfluoronorthobutane, etc. Gen hydrocarbons; water, and the like can be listed; carbon dioxide, nitrogen, air and inorganic gases. Two or more of these volatile foaming agents may be used in combination. The amount of these volatile foaming agents added may be selected according to the type of foaming agent and the target foaming ratio. One composition is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass.

[0079] As the supercritical fluid, it is preferable to use an inert gas such as carbon dioxide or nitrogen in a supercritical state. For example, in the case of carbon dioxide, the supercritical state can be obtained by setting the temperature to 31 ° C or higher and the pressure to 7.3 MPa or higher. Carbon dioxide is in a supercritical state at relatively low temperature and pressure, and it is suitable for foam molding using injection molding because of its large amount dissolved in molten resin (thermoplastic elastomer composition). .

[0080] The hollow particle type foaming agent refers to a thermally expandable microsphere composed of an outer shell having a thermoplastic resin strength and a component expanding agent contained in the outer shell. Examples of the component expansion agent to be encapsulated include those similar to the above volatile foaming agent. The proportion of the component expanding agent in the thermally expandable microspheres is preferably 5 to 30% by mass. On the other hand, the thermoplastic resin constituting the outer shell includes (meth) acrylonitrile, (meth) acrylate, vinyl halide, vinylidene halide, styrenic monomer, butyl acetate, butadiene, chloroprene, butyl pyridine, etc. A homopolymer or a copolymer consisting of This thermoplastic resin includes dibutenebenzene, ethylene glycol (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylol propane tri (meth) acrylate, 1,3-butylene glycol di (meth) ) It may be cross-linked or cross-linkable with a cross-linking agent such as acrylate, allyl (meth) acrylate, triacryl formal, triallyl isocyanurate. The mass average particle diameter of the hollow particle foaming agent (in an unexpanded microsphere state) is preferably 1 to 100 m.

[0081] In order to adjust the generated bubble diameter, a foaming nucleating agent (nucleating agent) may be added together with the component (E) as necessary. As the foam nucleating agent, powders of inorganic compounds such as calcium carbonate, talc, my strength, silica, and titania can be used. By containing these foam nucleating agents, the cell diameter can be easily adjusted, and a foamed molded article having appropriate flexibility and the like can be obtained. The particle size of the foam nucleating agent is not particularly limited, but is preferably 0.01 to 50 μm, and particularly preferably 0.05 to 20 μιη. When the particle size force is less than 01 μm ^, it is difficult to obtain an effect as a foam nucleating agent, and the cell diameter becomes large, which is not preferable. On the other hand, if the particle size exceeds 50 ^ m, the number of cells becomes coarse and the number becomes small, and the foamed molded article becomes too soft and is inferior in cushioning properties. [0082] The content of the foam nucleating agent is 0.01 to 20 parts by mass when the total amount of the polymer components contained in the thermoplastic elastomer composition used in the present invention is 100 parts by mass. Is more preferably 0.01 to 5 parts by mass, and particularly preferably 0.0 to 10 parts by mass. The foam nucleating agent is preferably added to the molding machine as a master batch using, for example, polypropylene resin.

[0083] (Softener (F))

The thermoplastic elastomer composition of the present embodiment may further contain a softener (hereinafter also referred to as “component (F)”) as necessary. By containing this component (F), flexibility can be further improved. Examples of the component (F) include aromatic oil, naphthenic oil, and oil. Mineral oil softeners such as raffin oil, white oil, petrolatum, gilsonite; vegetable oil softeners such as castor oil, cottonseed oil, rapeseed oil, palm oil, coconut oil, rosin; dimethyl phthalate, jetyl phthalate, dibutyl phthalate, diisopetite Phthanolates such as ruphthalate, dioctyl phthalate, ptyloctyl phthalate, di (2-ethylhexyl) phthalate, diisooctino phthalate, diisodecyl phthalate; dimethyl adipate, diisobutyl adipate, dione (2-Ethylhexyl) adipate, diisooctyladipate, diisodecyladipate, octyldecyladipate, di (2-ethylhexyl) azelate, disooctylazelate, diisobutinoreazelate, Dibutyl sebacate, G In addition to fatty acid esters such as (ruhexyl) sebacate and diisooctyl sebacate, di (2-ethylhexyl) fumarate, diethylene glycol monooleate, glycerinole monoricinoleate, trilauryl phosphate, tristearyl Mention may be made of plasticizers such as phosphate, tri (2-ethylhexyl) phosphate, tricresyl phosphate, epoxidized soybean oil, polyether ester, trimellitic acid.

[0084] Examples of the polyether ester-based plasticizer include those obtained by condensing an alkoxy dioxyethylene alcohol with an aliphatic dicarboxylic acid. Specifically, Ade force sizer RS-705 (trade name (manufactured by Asahi Denka Kogyo Co., Ltd.)), Monosizer 1 W-264 (trade name (manufactured by Dainippon Ink & Chemicals, Inc.)) and the like are applicable. The polyether ester plasticizer is not particularly limited with respect to its production method. It can be easily obtained by reacting ruhexylic acid and ethenoredalicol in a molar ratio of 2: 1. For example, it can be obtained by reacting 2-ethylhexylic acid with a mixed ether glycolol containing a predetermined amount of pentaethylene glycol, hexaethylene glycol, or heptaethylene glycol, etc. Using diesters obtained by reacting glycol, hexaethylene glycol, or heptaethylene glycol, etc. separately with 2-ethyl hexyl acid in a conventional manner, the average degree of polymerization of polyethylene glycol is 5 to: It can also be produced by mixing so as to be L0. Specifically, Ade force sizer RS-107, RS-1000, RS-735, RS-700, etc. (all trade names (Asahi Denki Kogyo Co., Ltd.)) are applicable.

[0085] Examples of trimellitic acid-based plasticizers include trimellitic acid esters obtained by condensing three carboxylic acids of trimellitic acid with alcohol. For example, trimethyl trimellitic acid, triethyl trimellitic acid, tripropyl trimellitic acid, tryptyl trimellitic acid, triamyl trimellitic acid, trihexyl trimellitic acid, triheptyl trimellitic acid, trimethyl trimellitic acid Octyl, trimellitic trimellitic acid 2-triethylhexyl, trinonyl trimellitic acid, tris trimellitic acid (decyl), tris trimellitic acid (dodecyl), tris trimellitic acid (tetradecyl), tris trimellitic acid (C8 ~ C12 mixed alkyl), trimellitic acid tris (C7 to C9 mixed alkyl), and trimellitic acid trilauryl. Specifically, Ade force sizer C-8, C-880, C-79, C-810, C-9N, C_10, etc. (all trade names (Asahi Denka Kogyo Co., Ltd.)).

[0086] The content ratio of the component (F) is preferably 0 to 200 parts by mass, more preferably 0 to 180 parts by mass with respect to 100 parts by mass of the crosslinked rubber (C). It is particularly preferably 0 to 150 parts by mass. By setting the content ratio of the component (F) within this numerical range, the flexibility and fluidity of the obtained thermoplastic elastomer composition can be further improved. (F

) When the content of the component is more than 200 parts by mass with respect to 100 parts by mass of the crosslinked rubber (C), it tends to bleed out.

[0087] In the case where the component (A) or the component (C) is an ethylene 'a-olefin copolymer rubber, the component (F) is a mineral oil softener (F-1) (hereinafter referred to as " (F-1) component ”is preferable from the viewpoint of compatibility. Mineral oil-based softeners are generally aromatic rings, naphthe A mixture of the three rings and the paraffin chain, in which the carbon number of the paraffin chain occupies 50% or more of the total carbon number is paraffinic oil, and the carbon number of the naphthenic ring is 30 to 30 45% oils are classified as naphthenic oils, and aromatic oils with 30% or more of the total number of carbon atoms in the aromatic ring are classified as aromatic oils. The component (F-1) blended in the thermoplastic elastomer composition of this embodiment is preferably paraffinic, more preferably hydrogenated paraffinic U /.

[0088] The weight average molecular weight (Mw) of the component (F-1) is 300 to 2000, preferably S, and preferably 500 to 1500. Further, the kinematic viscosity at 40 ° C of the component (F-1) is preferably 20 to 800 cSt, and preferably 50 to 600 cSt. The pour point of the (F-1) component is preferably 1-40 to 0 ° C, and preferably 30 to 0 ° C.

[0089] Commercially available products of such component (F-1) include, for example, Diana process oil PW90, PW100, PW380, PS32, PS90 (all trade names (manufactured by Idemitsu Kosan Co., Ltd.). )). Examples of naphthenic mineral oil softeners include FUCKOL FLEX # 1060N, # 1150N, # 1400N, # 2040N, # 2050N (all trade names (manufactured by Fuji Kosan Co., Ltd.)). Furthermore, examples of the aromatic mineral oil softener include Fukkor AROMA # 1, # 3, and # 5 (all trade names (manufactured by Fuji Kosan Co., Ltd.)). Of these, Diana process oils PW90, PW100, and PW380 (V, trade names (made by Idemitsu Kosan Co., Ltd.)), which are paraffinic mineral oil softeners, are preferably used.

[0090] The content ratio of the component (F-1) is preferably 0 to 200 parts by mass, more preferably 0 to 180 parts by mass with respect to 100 parts by mass of the component (A). It is particularly preferably 0 to 150 parts by mass. By setting the content ratio of the mineral oil softener (F-1) within this numerical range, the flexibility and fluidity of the resulting thermoplastic elastomer composition can be further improved. If the content ratio of the component (F-1) exceeds 200 parts by mass with respect to 100 parts by mass of the component (A), there is a tendency to bleed out.

[0091] The method for adding the component (F-1) is not particularly limited. Component (A), component (C), and oil-extended rubber (X) may be added to EAO copolymer (A) or oil-extended rubber (X) during kneading, (A) component, (B) component, and (C) component or oil-extended rubber (X), (B) component, and (C) component dynamic dissolution (A) component, (B) component, and (C) component or oil-extended rubber (X), (B) component, and (C) component, which may be added during melt kneading, are dynamically melt kneaded. Later, it may be further melt-kneaded and added.

[0092] (Various additives)

Various additives can be blended in the thermoplastic elastomer composition of the present embodiment. Additives that can be blended include, for example, antioxidants, antistatic agents, blocking agents, sealability improvers, lubricants, anti-aging agents, heat stabilizers, weathering agents, metal deactivators, and UV absorbers. Stabilizer, light stabilizer, copper damage preventive agent, etc .; antibacterial 'fungal agent, dispersant, plasticizer, crystal nucleating agent, flame retardant, tackifier, foaming aid, titanium oxide, carbon black, etc. Colorant; Metal powder such as pigment and ferrite; Inorganic fiber such as glass fiber and metal fiber; Organic fiber such as carbon fiber and aramid fiber; Composite fiber, Inorganic whisker such as potassium titanate whisker, Glass beads, Glass balloon , Glass flakes, asbestos, my strength, calcium carbonate, talc, wet silica, dry silica, alumina, alumina silica, calcium silicate, hydrated talcite, kaolin, diatomaceous earth, graph Fillers such as Ito, pumice, epo powder, cotton flock, cork powder, barium sulfate, fluororesin, polymer beads, or mixtures thereof, polyolefin wax, cellulose powder, rubber powder, wood powder, etc .; water Examples thereof include a hydrogenated styrene / butadiene block copolymer and a hydrogenated styrene / isoprene block copolymer.

[0093] 2. Method for producing thermoplastic elastomer composition

The thermoplastic elastomer composition of this embodiment can be produced by using a predetermined first composition and a predetermined second composition and dynamically heat-treating them. The first composition has a component (A) and a component (B) ¾r, and the component (Β) has a three-dimensional network structure in a matrix composed of the component (Α) (thermoplastic elastomer Composition). The second composition comprises a mixture containing rubber (G) (hereinafter also referred to as “(G) component”) and thermoplastic resin (H) (hereinafter also referred to as “(H) component”). It is obtained by dynamically heat-treating in the presence of a crosslinking agent (thermoplastic elastomer composition). That is, in the thermoplastic elastomer composition of the present embodiment, first, two types of compositions having different compositions and the like (first composition and second composition) are prepared, and then each prepared composition is prepared. Can be produced by dynamically heat-treating the composition.

[0094] (Rubber (G))

The component (G) is rubber. Specific examples of the component (G) include those similar to the component (C) described above.

[0095] (Thermoplastic resin (H))

Component (H) is a thermoplastic resin. This component (H) is at least one selected from the group consisting of (H-1) polyolefin resin, (H-2) polyester resin, (H-3) polyamide resin, and (H-4) polyester elastomer. It is preferable that The component (H) includes the component (B) described above.

[0096] (H-1) Polyolefin resin

The polyolefin resin (hereinafter also referred to as Γ (Η_1) component) may be a homopolymer or a common polymer as long as the content of the structural unit derived from _α -olefin is more than 50 mol%. It may be a polymer. This copolymer may be a copolymer of ct-olefins, or a copolymer of a-olefin and other monomers copolymerizable with this CK-olefin. As the component (H-1), (H-la) crystalline polyolefin-based resin and / or (H-lb) amorphous polyolefin-based resin can be used.

[0097] As (H-1) component, (H-la) crystalline polyolefin resin (hereinafter also referred to as "(H-la) component") is used. The crystallinity is preferably 50% or more, more preferably 53% or more, and particularly preferably 55% or more. In addition, the crystallinity of the (H-la) component is closely related to the density. For example, in the case of polypropylene, the density of the monocrystal (monoclinic) is 0.936 gZcm ³ , and the smectic type microcrystal (pseudo The density of the hexagonal crystal is 0.886 gZcm ³ , and the density of the amorphous (atactic) component is 0.850 g / cm ³ . In addition, the density of the poly-1-butene and the isotactic crystal component is 0.91 gZcm ³ , and the density of the amorphous (atactic) component is 0.87 gZcm ³ .

Therefore, the density of the (H-la) component is preferably 0.98 g / cm ³ or more, and more preferably 0.90 to 0.94 g / cm ³ . By setting this range, the crystallinity of the (H-la) component can be 50% or more. When the crystallinity of the (H-la) component is less than 50% and the density is less than 0.89 g / cm ³ , the resulting thermoplastic elastomer is obtained. -The heat resistance and strength of the composition tend to decrease.

[0099] The α-olefin that constitutes the (H-la) component preferably has 2 or more carbon atoms, and more preferably has a carbon number power of 12 to 12. Specifically, propylene and 1-butene are preferable. (.Eta. la) in the component, the content of the structural unit (al) derived from a non-one Orefin is, (H- la) if the sum of the structural units that constitute the component was 100 m _O l%, or more 80 mol% It is more preferable that it is 90-100 mol%.

[0100] When the (H-la) component is a copolymer, this copolymer may be a block copolymer or a random copolymer. However, in order to obtain a block copolymer having the above-mentioned crystallinity, the content ratio of the structural units excluding the structural unit (al) derived from α-olefin is the total of the structural units constituting the block copolymer. Of 100 mol%; preferably 40 mol% or less, more preferably 20 mol% or less. This block copolymer can be obtained by living polymerization using a Ciderer's Natta catalyst!

[0101] In addition, in order to obtain a random copolymer having the above-described crystallinity, the content ratio of the structural unit excluding the structural unit (al) derived from α-olefin is a constituent of the random copolymer. When the total of the constituent units is 100 mol%, it is preferably 15 mol% or less, more preferably 10 mol% or less. This random copolymer requires, for example, α-olefin and hydrogen as a molecular weight regulator in the presence of a solvent-powered catalyst containing a Ziegler Natta catalyst, a soluble vanadium compound, and an organoaluminum compound. According to the method, it can be produced by a method of polymerizing while supplying (a polymerization method by a medium-low pressure method) or the like. This polymerization can be carried out by a gas phase method (fluidized bed or stirred bed) or a liquid phase method (slurry method or solution method).

[0102] The soluble vanadium compound includes VOC1 and / or VC1, alcohol, and

3 4

It is preferable to use the reaction product of Examples of the alcohol include methanol, ethanol, η-propanol, isopropanol, η-butanol, sec-butanol, t-butanol, n-hexanol, n-octanol and 2-ethynole. Hexanol, n-decanol, n-dodecanol and the like. Of these, alcohols having 3 to 8 carbon atoms are preferred.

[0103] Examples of the organoaluminum compound include triethylaluminum, triiyl, and the like. Soptylaluminum, tree n-hexylaluminum, cetylanonium monochloride, diisobutylaluminum monochloride, ethylanonium sesquichloride, butylanoleumium sesquichloride, ethylaluminum dichloride, butylaluminum dichloride, trimethylaluminum and water And methylaluminoxane which is a reaction product of Of these, ethylaluminum sesquichloride, butyl aluminum sesquichloride, ethylano 1/5; a mixture of yum sesquichloride and triisobutylaluminum, and a mixture of triisobutylaluminum and butylaluminum sesquichloride are preferably used. Further, hydrocarbons are preferably used as the solvent. Of these, n-pentane, 11-hexane, n-heptane, n-octane, isooctane, and cyclohexane are more preferably used. These hydrocarbons can be used singly or in combination of two or more.

[0104] The melting point of the (H-la) component, that is, the melting peak temperature of the crystal measured by a differential scanning calorimeter (DSC) is preferably 100 ° C or higher, more preferably 120 ° C or higher. I like it. When the melting point of the (H_la) component is less than 100 ° C, sufficient heat resistance and strength tend not to be exhibited. The melt flow rate (MFR) of the (H-la) component (temperature 230 ° C, load 2, 16 kg) is preferably 0.1 to 1000 gZl0inin, 0.5 to 500 g / l0 min. More preferred:! ~ LOOg / lOmin is particularly preferred. When the MFR is less than 0.1 lgZlOmin, the kneadability and extrusion processability of the raw material composition tend to be insufficient. On the other hand, if it exceeds lOOOOgZlOmin, the strength of the resulting thermoplastic elastomer composition tends to decrease.

Therefore, the (H-la) component has a crystallinity of 50% or more, a density of 0.89 gZcm ³ or more, an ethylene monomer unit content of 20 mol% or less, a melting point of 100 ° C. or more, In addition, it is particularly preferable to use a polypropylene having a melting point of 140 to 170 ° C. and / or a copolymer of propylene and ethylene, which preferably has an MFR of 0.1 to 100 g / lOmin. The (H-la) component can be used alone or in combination of two or more.

[0106] In addition, as the (H-la) component, polyethylene, propylene, butene-1, 1, 4-methyl-pentene-1, hexene-1, octene-1, etc., a-olefin having 3 to 6 carbon atoms, and Copolymers (ethylene content is 90 mol% or more) can also be used. Polye Tylene may be obtained by either the high pressure method or the low pressure method. Two or more of these may be mixed.

[0107] When (H— lb) amorphous polyolefin resin (hereinafter referred to as “(H— lb) component”) is used as component (H— 1), this (H— The crystallinity of the lb) component by soot diffraction is preferably less than 50%, more preferably 30% or less, and particularly preferably 20% or less. Further, (H- lb) is the density of the component, from 0.85 to 0. It is further preferred that 89gZcm is ³ is preferred instrument from 0.85 to 0. 88GZcm ^3.

[0108] The α-olefin that constitutes the (H—lb) component preferably has 3 or more carbon atoms, more preferably 3 or more carbon atoms. The content of the structural unit (a2) derived from a-olefin in the (H- lb) component is ^^, 60 mol% or more with the total of the structural units constituting the (H- lb) component being 100 mol%. I prefer to be there.

[0109] The (H—lb) component includes homopolymers such as atactic polypropylene and atactic poly 1-butene; more than 50 mol% of propylene and other c —olefin (ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-11-pentene, 1-octene, 1-decene, etc.); more than 50 mol% of 1-butene and other monoolefins (ethylene, propylene) 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, etc.) and the like. Atactic polypropylene and atactic poly-1-butene can be obtained by polymerization using a zirconocene compound and a methylaluminoxane catalyst. In addition, atactic polypropylene can be obtained as a by-product of the polypropylene exemplified as the aforementioned (Η-la) component.

[0110] When the (H-lb) component is a copolymer, the copolymer may be a block copolymer or a random copolymer. However, in the case of a block copolymer, the structural unit (a2) derived from —olefin, which is contained in a proportion exceeding 50 mol%, needs to be bonded with an atactic structure. This block copolymer can be obtained by living polymerization using a Ziegler Natta catalyst. Further, the random copolymer can be obtained by the same method as in the case of the aforementioned (H 1 la) component. When the (H-lb) component is a copolymer of a-olefin and ethylene having 3 or more carbon atoms, this (H-lb ) When the total of the structural units constituting the component is 100 mol%, the content ratio of the structural unit (a2) derived from _α -olefin is preferably 60 to: LOO mol%.

[0111] The component (H—lb) includes atactic polypropylene, a copolymer comprising a structural unit derived from propylene exceeding 50 mol% and a structural unit derived from ethylene, and a copolymer of propylene and 1-butene. U, especially preferred.

[0112] The polystyrene-reduced number average molecular weight Mn of the (H-lb) component by GPC is preferably 1000 to 20 000, and more preferably 1500 to 15000. The (H-lb) component can be used as a single worm or in combination of two or more. In addition, (H-1) component is a combination of (H-la) component and (H-lb) component used in worms, depending on the purpose and application. But let ’s do it.

[0113] (H-2) Polyester resin

Polyester resin (hereinafter also referred to as “(H-2) component”) generally means polycondensation reaction of saturated dicarboxylic acid and saturated dihydric alcohol, ring-opening reaction of rataton, hydroxyl group and force loxyl group in one molecule. A thermoplastic resin obtained by polycondensation reaction of a compound having For example, polyethylene terephthalate, polytrimethylene terephthalate (polypropylene terephthalate), polytetramethylene terephthalate (polybutylene terephthalate), polyhexamethylene terephthalate, polycyclohexane-1,4-dimethylene terephthalate, polyneopentyl terephthalate Polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate, polyproprolactone, p-hydroxybenzoic acid polyester, polyarylate, and the like. In the present embodiment, two or more kinds of polyester resins may be used in combination. Of these, polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate are preferable. In addition, the terephthalic acid moiety may be substituted with an alkyl group, a halogen group, or the like.

[0114] (H-3) Polyamide resin

As the polyamide resin (hereinafter also referred to as “component (H-3)”), various known ones can be used. Specific examples include nylon 6 (Ν6), nylon 66 (Ν66), nylon 11 (Ν11), nylon 12 (Ν12), aliphatic polyamide having an aromatic ring (nylon MXD6), and the like. A copolymer of the above polyamide resin can also be used. As a concrete example Nylon 6 and Nylon 66 copolymer (N6 N66), Nylon 6 and Nylon 10 alternating copolymer (Nylon 610: N610), Nylon 6 and Nylon 12 alternating copolymer (N Illon 612: N612) and the like.

These polyamide resins can be used alone or as a blend of two or more. Specific examples of blends include Nylon 6 and Nylon 66 blends (N6 / N66), Nylon 6 and Nylon 11 blends (N6 / N11), Nylon 6 and Nylon 12 blends (N6 / N12), blend of nylon 6 and nylon 610 (N6 / N610), blend of nylon 6 and nylon 612 (N6ZN612), blend of nylon 66 and nylon 11 (N66 / N11), nylon 66 With Nylon 12 (N66 / N12), Nylon 66 with Nylon 610 (N66 / N610), Nylon 66 with Nylon 612 (N66 / N612), Nylon 11 with Nylon 12 Blend (Nylon N12), blend of nylon 11 and nylon 610 (Ν11 / ΊΝΓ610), blend of nylon 11 and nylon 612 (NllZN612), blend of nylon 12 and nylon 610 ( N12 no N610), nylon 12 and nylon 612 blend Products (N12-N612), blends of nylon 610 and nylon 612 (N61C N612), etc., blends of nylon 6, nylon 11 and nylon 610 (N6 / N11ZN610), nylon 6 Blends of Nylon 11 and Nylon 612 (N6 / N11 / N612), Blends of Nylon 6 and Nylon 12 and Nylon 610 (N6 / N12 / N610), Blends of Nylon 6, Nylon 12 and Nylon 612 (N6 / N12 / N612), Nylon 6 and Nylon 610 and Nyguchi 612 blends (N6ZN610 / N612), Nylon 66, Nylon 11 and Nylon 610 blends (N66 Nll / N610), Blends of nylon 66, nylon 11 and nylon 612 (ΝδδΖΝΙΐΖΝΘΙ ^), blends of nylon 66, nylon 12 and nylon 610 (N66 / N12 / N610), blends of nylon 66, nylon 12 and nylon 612 (Ν66 ノ N12 Ν612), nylon 66 and Nairro Nylon 610 and Nylon 612 blends (N66 / N610ZN612), etc., Nylon 6 and Nylon 66 and Nylon 11 and Nylon 610 blends (Ν6 Ν66 N11ZN610), Nylon 6 and Ny Nylon 66, Nylon 11 and Nylon 612 (N6 N66 N11 N612), Nylon 6, Nylon 66, Nylon 12 and Nylon 610 (N6ZN66 / N12ZN6) 10), Nylon 6 / Nylon 66 / Nylon 12 / Nylon 612 blend (N6 / N66 / N12 / N612), Nylon 6 / Nylon 66 / Nylon 610 / Nylon 612 blend (N6 / N66 / N610 / N612), Nylon 6, Nylon 11, Nylon 12 and Nylon 61 0 blend (N6 ΝΙΙ / ΝΙ ^ ΖΝδΙθ Nylon 6, Nylon 11, Nylon 12 and Nylon 612 blend (N6 / ll / Nl 2 / N612 ), Nylon 6, Nylon 11, Nylon 610 and Nylon 612 blends (N6ZN11ZN610ZN612), Nylon 6, Nylon 12, Nylon 610 and Nylon 612 blends (N6ZN12-N610 / N612), etc. Blend, Nylon 6, Nylon 66, Nylon 11, Nylon 610, Nylon 62 (N6ZN66 NllZN610ZN612), Nylon 6, Nylon 66, Nylon 12, Nylon 610, Nylon 612 (N6 / N66 / N 12 ZN610ZN612) and other five-component blends, nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612 blend (Ν6 / Ν66 / Ν11 / N12 / Ν610 / Ν612), etc.6 Mention may be made of component blends.

[0116] (Η—4) Polyester elastomer

Polyester elastomer (hereinafter also referred to as “(Η_4) component”) is known as a multi-block copolymer having polyester and polyester as main repeating units. In this mode of implementation! The component (Η-4) used in the past consists of a high melting point crystalline polymer hard segment having a crystalline aromatic polyester, an aromatic containing an aliphatic polyether and a low melting point containing Ζ or an aliphatic polyester unit. Consists of polymer soft segments.

[0117] The high-melting crystalline polymer node segment constituting the component (IV-4) is mainly formed from an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol or an esteno-Hi-forming derivative thereof. Polyester. The aromatic dicarboxylic acids, terephthalic Le acid, isophthalic acid, phthalic acid, naphthalene one 2, 6-Jikarupon acid, naphthalene one ^2, 7 Jikarubon acid, anthracene dicarboxylic acid, diphenyl one 4, 4, one dicarboxylic acid, di-off Examples include enoxyethane dicarboxylic acid, 4,4, -diphenyl ether dicarboxylic acid, 5-sulfoisophthalic acid, and sodium 3-sulfoisophthalate. Power to use mainly aromatic dicarboxylic acids Depending on necessity, a part of aromatic dicarboxylic acids may be converted to 1,4-cyclohexanedicanoleponic acid, cyclopentanedicarboxylic acid, 4,4,1 dicyclohexane. An alicyclic dicarboxylic acid such as sildicarboxylic acid; an aliphatic dicarboxylic acid such as adipic acid, succinic acid, oxalic acid, sepacic acid, decanedicarboxylic acid, and dimer acid may be substituted. Of course, ester-forming derivatives of dicarboxylic acids, such as lower alkyl esters, arylenoesterols, carbonates, acid halides, etc. can be used equally.

[0118] Examples of the diol include diols having a molecular weight of 400 or less, for example, aliphatic diols such as 1,4-butanediol, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentinole glycol, decamethylene glycol and the like. Alicyclic diols such as 1,1-cyclohexanedimethanol, 1,4-dicyclohexanedimethanol, and tricyclodecane dimethanol; xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxypheny ^ /) Propane, 2, 2-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2-hydroxy) phenyl] sulfone, 1,1 bis [4 — (2-hydroxyethoxy) Phenylol] cyclohexane, 4,4,1 dihydroxy 1 p-terphenyl, 4, 4, 1 dihi Proxy one p- quarter full aromatic diol favored arbitrary enyl and the like. Powerful diols can also be used in the form of estenogenic derivatives such as acetyl, alkali metal salts and the like. Two or more of these dicarboxylic acids and their derivatives or diol components may be used in combination. An example of the most preferred high melting crystalline polymer segment is polybutylene terephthalate derived from terephthalic acid and Z or dimethyl terephthalate and 1,4-butanediol.

[0119] The low melting point polymer soft segment constituting the component (H-4) is an aliphatic polyether.

Containing aromatic and / or aliphatic polyester units. Aliphatic polyesters include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, ethylene oxide and propylene oxide. Examples thereof include an oxide copolymer; an ethylene oxide addition polymer of poly (propylene oxide) glycol; a copolymer of ethylene oxide and tetrahydrofuran, and the like. By containing such an aliphatic polyether, rubber elasticity can be imparted to the component (H-4), and flexibility can be improved without impairing the mechanical properties of the thermoplastic elastomer composition. Can do.

[0120] Further, as the aromatic polyester, the above-described high melting crystalline polymer node segment is used. The same thing as the crystalline aromatic polyester can be mentioned. Furthermore, examples of the aliphatic polyester include poly (ε-force prolactone), polyenantlactone, polycapri-latatotone, and polypropylene adipate. Among those containing aromatic polyether or aliphatic polyester units containing these aliphatic polyethers, poly (tetramethylene oxide) glycol, poly (propylene) are obtained from the elastic properties of the resulting polyester block copolymer. Oxide) Glycol ethylene oxide adduct, poly-polypropylene), polybutylene adipate, etc. are preferred.

[0121] (First composition)

The first composition can be prepared, for example, according to the method disclosed in Patent Document 1 described above. However, the method for preparing the first composition is not limited to the method disclosed in Patent Document 1.

[0122] (Second composition)

The second composition can be prepared by dynamically heat-treating the mixture having the component (G) and the component (ii) in the presence of a crosslinking agent (dynamic crosslinking). The cross-linking agent used for dynamic cross-linking is not particularly limited as long as it is a compound capable of cross-linking component (G). For example, organic peroxides, phenol cross-linking agents, sulfur, sulfur compounds, ρ It is preferable to use —quinone, ρ-quinonedioxime derivatives, bismaleimide compounds, epoxy compounds, silane compounds, amino resins, and the like. Of these, it is particularly preferable to use an organic peroxide or a phenolic crosslinking agent.

[0123] Among the crosslinking agents, organic peroxides are 1,3-bis (t-butylveroxyisopropyl) benzene, 2,5-dimethyl-1,2,5-di (t-butyloxy) Xin-1,3-2,5-dimethyl-1,2,5-di (t-butylperoxy) hexane, α, α, monobis (tert-butylepoxy) diisopropylbenzene, dicumyl peroxide, di-t-butylpero Toxide, t-Butyl peroxide, t-Butylcumyl peroxide, p-Mentanehydride Peroxide, 1,1-bis (t-Butyloxy) -1,3,3,5-Trimethylcyclohexane, Dilauroyl peroxide , Dicetyl peroxide, t-butylperoxybenzoate, 2,4-dichlorobenzoic peroxide, p-cyclobenzoylperoxide, benzoylperoxide, di (t-propyl Rubaokishi) Pabe Nzoeto, n- butyl —4,4-bis (t-petitenoleperoxy) valerate, t-butyl baroxyisopropyl carbonate and the like. 1,3-bis (t-butylperoxysopropyl) benzene, 2,5-dimethyl-1,2,5-di (t-butylperoxy) hexyne1,3,2,5-dimethyl-2,5 -Di (t-butylperoxy) hexane, α, α, monobis (t-butylperoxy) diisopropylbenzene, etc. ^ The temperature is relatively high. These organic peroxides can be used singly or in combination of two or more.

[0124] Further, when the organic peroxide is used in combination with the crosslinking aid, the crosslinking reaction can be gently carried out, and particularly uniform crosslinking can be formed. The crosslinking aids include sulfur or sulfur compounds (powdered sulfur, colloidal sulfur, precipitated sulfur, insoluble sulfur, surface-treated sulfur, dipentamethylene thiuram tetrasulfide, etc.), oxime compounds (p-quinone oxime, p, p, -dibenzoylquinone oxime, etc.), multifunctional monomers (ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol diol di (meth) acrylate) Rate, polyethylenglyconoresi (meth) acrylate, trimethylol propane tri (meth) acrylate, diallyl phthalate, tetraaryloxetane, triaryl cyanurate, N, N, 1 m-phenol Lenbismaleimide,, N'-toluylene bismaleimide, maleic anhydride , It may be mentioned Jibieruben Zen, di (meth) zinc acrylate). Among these, it is particularly preferable to use p, p′-dibenzoylquinone oxime, N, N, 1m-phenylene balemaleimide, and dibibenzene. These crosslinking aids can be used in combination of two or more. Of the crosslinking aids, N, N, 1m-phenylene bismaleimide can also be used as a crosslinking agent because it also acts as a crosslinking agent.

[0125] When an organic peroxide is used, the amount of the organic peroxide is preferably 0.05 to 1.5 parts by mass with respect to 100 parts by mass of component (G). More preferably, the content is 0.1 to 1.0 part by mass. If the amount of the organic peroxide is less than 0.05 parts by mass, the rubber elasticity tends to decrease. On the other hand, if the blending amount of the organic peroxide exceeds 1.5 parts by mass, the extrudability of the thermoplastic elastomer composition and the processability such as injection moldability tend to decrease. C0126] The crosslinking aid is preferably used in an amount of 4 parts by mass or less, more preferably 0.2 to 3 parts by mass with respect to 100 parts by mass of component (G). If the amount of the crosslinking aid used is more than 4 parts by mass, the degree of crosslinking becomes excessively high and the adhesiveness at the time of injection fusion tends to be lowered. Among the crosslinking agents, the phenolic crosslinking agents include p-substituted phenolic compounds represented by the following general formula (1), o-substituted phenol-aldehyde condensates, m-substituted phenol monoaldehyde condensates, bromine Alkyl-phenol-aldehyde condensates and the like, but p-substituted phenol compounds are particularly preferred.

[0127] [Chemical 1]

[0128] In the general formula (1), n is an integer of 0 to 10; X is at least one of a hydroxyl group, a halogenated alkyl group, and a halogen atom; and R is a carbon number:! 15 saturated charcoal hydrogen groups.

[0129] The p-substituted phenolic compound can be obtained by a condensation reaction of p-substituted phenol and an aldehyde (preferably formaldehyde) in the presence of an alkali catalyst. When using a phenol type crosslinking agent, it is preferable to use 0.2-10 mass parts with respect to 100 mass parts of (G) component, and it is still more preferable to use 0.5-5 mass parts. If the amount of the phenolic crosslinking agent used is less than 0.2 parts by mass, the rubber elasticity tends to decrease. On the other hand, if it exceeds 10 parts by mass, the extrusion processability and ejection processability of the thermoplastic elastomer composition tend to decrease. Phenolic crosslinking agents can be used alone, but a crosslinking accelerator can be used in combination to adjust the crosslinking rate. As the crosslinking accelerator, metal halides (such as stannous chloride and ferric chloride), organic halides (such as chlorine-polypropylene, odorous butyl rubber, and chloroprene rubber) can be used. In addition to the crosslinking accelerator, a metal oxide such as zinc oxide or a dispersing agent such as stearic acid is also used. It is more desirable to use.

[0130] (Production of thermoplastic elastomer composition)

The thermoplastic elastomer composition of this embodiment can be produced by further dynamically heat-treating the above-described first composition and the composition of the second composition. Examples of the apparatus that can be dynamically heat-treated include a continuous extruder and a closed kneader. More specifically, examples include an open-type mixing roll, a non-opened bread pallet mixer, a single screw extruder, a twin screw extruder, a twin screw kneader, and a pressure kneader. Among these, it is preferable to use a continuous extruder (single screw extruder, twin screw extruder, twin screw kneader) from the viewpoints of economy, processing efficiency, and the like. One of the first composition and the second composition is prepared in advance, and the other composition is prepared by dynamically heat-treating with a continuous extruder. At the same time, one of the previously prepared compositions may be supplied to the downstream portion of the continuous extruder, and both compositions may be dynamically heat-treated together.

[0131] —Spindle extruders and twin screw extruders preferably have an LZD (ratio of effective screw length (L) to outer diameter (D)) of 30 or more, and 36 to 60 Is more preferable. As a twin screw extruder, for example, the force that can use any one that two screws squeeze or one that does not squeeze can be used. A product that rubs together is more preferable. As the twin screw extruder, PCM (Ikegai), KTX (Shito Steel), TEX (Nippon Steel), TEM (Toshiba Machine), ZSK (Warner) (all And trademark).

[0132] Further, as the twin-screw kneader, L / D (ratio of effective screw length (L) and outer diameter (D)) is preferably 5 or more, more preferably 10 or more. . In addition, as a twin-screw kneader, for example, a force that can use an arbitrary one such as one in which two screws squeeze or one that does not squeeze is used. It is preferable to have strength. Examples of such a twin-screw kneader include Mixtron KTX'LCM'NCM (manufactured by Kobe Steel, Ltd.), CIM. CMP (manufactured by Nippon Steel, Ltd.) (V, deviation is also a trademark), and the like. Two or more continuous extruders may be connected and used.

[0133] The processing temperature of the dynamic heat treatment is preferably 120 to 350 ° C, and is preferably 150 to 290 ° C. More preferably. The treatment time is preferably 20 seconds to 320 minutes, more preferably 30 seconds to 25 minutes. The shearing force to be applied is preferably 10 to 20000 / sec in terms of shear rate, and more preferably 100 to 10,000 / sec.

[0134] The thermoplastic elastomer composition thus obtained preferably has a melt flow rate (MFR) of not less than 0.1 lgZlOmin measured at a temperature of 230 ° C and a load of 98 N. More preferably, it is at least 5 gZlOmin. Further, the durometer A hardness measured in accordance with JIS-K6253 is preferably 95 or less and 10 or more, more preferably 90 or less and 15 or more. If it exceeds 95, it tends to be inferior in flexibility. On the other hand, if it is less than 10, the wear resistance tends to be inferior. Furthermore, the compression set measured at 70 ° C. for 22 hours in accordance with JIS-K6262 is preferably 50 or less, and more preferably 40 or less.

[0135] 3. Molded products and foam molded products

One embodiment of the molded article of the present invention is obtained by molding a thermoplastic elastomer composition which is one embodiment of the present invention described so far. Moreover, one embodiment of the foam molded article of the present invention is obtained by foam molding the thermoplastic elastomer composition which is one embodiment of the present invention. Therefore, the molded product and the foamed molded product of this embodiment are excellent in flexibility and rubber elasticity (rebound resilience, compression set), and are used for automobile bumpers, exterior moldings, gaskets for windshields, Door seal gaskets, trunk seal gaskets, roof side rails, emblems, inner panels, door trims, console boxes, and other skin materials; weather strips, etc .; Laser sheets that require scratch resistance; Seal materials, interior / exterior skin materials, etc .; Civil engineering / architecture seal materials, interior / exterior skin materials, waterproof sheet materials, etc .; General machinery / equipment seal materials, etc .; Weak electrical components; Water packing, Seals in fuel cell stacks Materials, skin materials, housings, etc .; railroad track pads, rolls for information equipment, cleaning blades, films for electronic parts; semiconductor manufacturing processes, Protective films and seal materials used in flat panel display (FPD) manufacturing processes such as liquid crystal display devices; image protective films such as photographs, cosmetic films for building materials, medical equipment parts, electric wires, daily goods, sports It can be widely used for general processed products such as goods. [0136] The molding method for producing the molded article of the present embodiment may be performed according to a regular method that is not particularly limited. Further, the foam molding method for producing the foam molded article of the present embodiment is not particularly limited, but for example, it can be produced according to the following methods (1) to (7).

[0137] (1) A thermoplastic elastomer composition and a foaming agent are melt-kneaded in a melt extruder, and then extruded. (2) A foaming agent is added to the thermoplastic elastomer composition by dry blending, followed by extrusion using a melt extruder. (3) In a melt extruder, a foaming agent is press-fitted into the molten thermoplastic elastomer composition and then extruded. (4) The thermoplastic elastomer composition and the foaming agent are melt-kneaded in a melt extruder and then injection molded. (5) The foaming agent is added to the thermoplastic elastomer composition and then injection molded. (6) Thermoplastic elastomer composition and foaming agent are melt-kneaded with a melt extruder and then placed in a press mold and hot press molded. (7) After melt-kneading the thermoplastic elastomer composition and the foaming agent with a patch-type kneader, calendering is performed, followed by heating.

Example

[0138] Hereinafter, the present invention will be specifically described based on Examples, but the present invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified. The methods for measuring and evaluating various physical properties are shown below.

[0139] [Preparation of test piece]: 120 mm X 120 mm X 2 mm by injection-molding a thermoplastic elastomer composition using an injection molding machine (trade name “N-100”, manufactured by Nippon Steel) Test specimens of the dimensions were prepared. Using the prepared test piece, hardness (Du mouth A), tensile breaking strength, tensile breaking elongation, and compression set were measured.

[Hardness (Du mouth A)]: Measured according to JIS K6253 and used as an index of flexibility.

[0141] [Tensile breaking strength, tensile breaking elongation]: Measured according to JIS K6251.

[0142] [Compression set]: Measured at 70 ° C for 22 hours in accordance with JIS K6262, and used as an index of rubber elasticity.

[Menoleto flow rate (MFR)]: Measured under the conditions of 230 ° C and 98N load in accordance with JIS K7210 and used as an index of fluidity. [0144] [Foaming]: As a foaming agent, the obtained thermoplastic elastomer composition is made of a thermal ^^ type chemical foaming agent master batch (product name: Polyslen EE275J, manufactured by Eiwa Kasei Kogyo Co., Ltd.) A master patch was obtained by adding a part and stirring and mixing.This master patch was a single-screw extruder with a diameter of 40 mm (trade name “FS-40”, manufactured by Ikegai Co., Ltd., L / D = 28, screw rotation (30 rpm, full flight screw) and extrusion foamed at a foaming temperature of 180 ° C. The foamability was evaluated by observing an enlarged photograph of the cross section of the foam obtained by extrusion foaming, and evaluating according to the following criteria.

◯: The foam cross section is in the form of a closed cell.

X: The foam cross section has a non-foamed or crushed cell shape.

[Confirmation of Morphology]: A thin film slice was prepared by cutting a test piece of thermoplastic elastomer composition strength in the thickness direction using a microtome. The thin film section was stained with RuO and photographed with a transmission electron microscope.

Four

[0146] (Preparation of component (i))

Oil-extended rubber 80 parts, crystalline polyethylene 30 parts, hydrogenated block copolymer 30 parts, and anti-aging agent 0. 2 parts, pre-heated to 150 ° C (capacity 10 liter, Moriyama † ± S 4 Orpm (shear rate SOOZsec 15 minutes until kneaded for 15 minutes until the crystalline polyethylene is melted and each compounding component is uniformly dispersed, and a molten composition was obtained. Was pelletized at a temperature setting of 200 ° C. using a feeder-luder (manufactured by Moriyama Co., Ltd.) to obtain a thermoplastic elastomer composition (component (I)), and the formulation is shown in Table 1. The oil-extended rubber, crystalline polyethylene, hydrogenated block copolymer and anti-aging agent used are shown below.

[0147] (Oil-extended rubber)

Ethylene Z-propylene Z5-ethylidene-2-norbornene terpolymer (ethylene content: 66%, 5-ethylidene-2-norbornene content: 4.5%, intrinsic viscosity: 4.6) Content: 50%, norafine Softener content: 50%.

[0148] (Crystalline polyethylene)

Linear low density polyethylene (LLDPE) (trade name “NOPATEC LL UF423”, Nippon Polycheme ring, crystallinity: 40%, melting point by DSC: 124 ° C, melt flow rate (MFR) (190 ° C, 21Ν): 2 · Og / 10 min).

[0149] (Hydrogenated block copolymer)

In a reaction vessel with an internal volume of 50 liters purged with nitrogen, cyclohexane (24 kg), tetrahydrofuran (lg), 1,3-butadiene (1200 g), and n-butyllithium (3.3 g) were added, Adiabatic polymerization at 70 ° C force was performed. After completion of the polymerization reaction, adiabatic polymerization was carried out by adding tetrahydrofuran (340 g) and 1,3-butadiene (2800 g) at a temperature of 5 ° C. After 30 minutes, methyldichlorosilane (2.3 g) was added, and the reaction was further continued for 15 minutes. After completion of the reaction, the mixture was stirred for 20 minutes while supplying hydrogen gas at a pressure of 0.4 MPa-G and reacted with living polymer terminal lithium as a living pheon to obtain lithium hydride. Tetrachlorosilane (7.2 g) was added to the reaction solution at 90 ° C and stirred for about 20 minutes. Then, a hydrogenation catalyst mainly composed of titanocene compound was added, and hydrogen gas was supplied at a pressure of 0.8 MPa-G. Then, hydrogenation reaction was performed for 2 hours. After the absorption of hydrogen was completed, the reaction solution was returned to room temperature and normal pressure and extracted from the reaction vessel. The extracted reaction solution is stirred into water, and the solvent is removed by steam distillation. A—B—A structure (“A” is a polybutadiene block (A block) with a low 1,2-bule bond content). “B” is a hydrogenated block copolymer of a polybutadiene block (block) having a high 1,2-Biel bond content. The resulting hydrogenated block copolymer has a hydrogenation rate of 99%, a weight average molecular weight of 300,000, and the pre-hydrogenation copolymer has a bull bond content of 15% (per one end). The vinyl bond content of the B block of the polymer was 78%. The melt flow rate of the hydrogenated block copolymer measured at 230 ° C and 21.2N was 2.5 gZ10 min.

[0150] (Anti-aging agent)

Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (trade name: Irganox 1010, manufactured by Tipa Specialty Chemicals).

[0151] (Preparation of ingredient 1)

After mixing 77 parts of butadiene rubber, 23 parts of polypropylene, 35 parts of mineral oil and 15 parts of calcium carbonate with a Henschel mixer, it is put into a pressure-type aerator (capacity 10 liters, manufactured by Moriyama Co., Ltd.) heated to 150 ° C in advance. The melted kneaded product is kneaded at 40 rpm (shear rate 200 / sec) for 15 minutes until the polypropylene melts and each component is uniformly dispersed. Got. The obtained kneaded material in a molten state was subjected to pellets using a feeder-ruder (manufactured by Moriyama Co., Ltd.). To 150.2 parts of the pelletized kneaded product, 1.5 parts of a crosslinking agent and 1.5 parts of a crosslinking aid were charged into a Henschel mixer and mixed for 30 seconds. After that, the twin screw extruder (same direction fully meshed type screw, screw flight part length (L) and screw diameter (D) ratio ((0) = 33.5, product name `` PCM45 '', Extruded with dynamic heat treatment at 200 ° C, residence time 1 minute 30 seconds, 300 rpm, shear rate 400 Zsec, and formed into a pellet-shaped thermoplastic elastomer E component ((mouth) 1) Component 1) obtained) The formulation is shown in Table 1.

[0152] (Preparation of (Kuchiichi 2) ingredients)

50 parts of butadiene rubber, 60 parts of oil-extended rubber (in the oil-extended rubber, 30 parts of rubber and 30 parts of mineral oil), 20 parts of polypropylene and 0.2 part of anti-aging agent were mixed in a Henschel mixer. Then, it is put into a pressure type adader (capacity 10 liters, manufactured by Moriyama Co., Ltd.) that has been heated to 150 ° C in advance and melted with polypropylene for 15 minutes at 40 rpm (shearing speed 200 cm 3 ec) until each component is evenly dispersed. By kneading, a kneaded material in a molten state was obtained. The obtained kneaded material in a molten state was pelletized using a feeder-ruder (manufactured by Moriyama). 14.5 parts of the cross-linking agent and 1.5 parts of the cross-linking aid were added to the Henschel mixer for 2 parts of the pelletized kneaded material, and mixed for 30 seconds. Then, twin screw extruder (same direction fully meshed type screw, screw flight part length (L) to screw diameter (D) ratio (L) / (D) = 33.5, product name `` PCM45 ”(manufactured by Ikegai Co., Ltd.) is used for dynamic heat treatment at 200 ° C, residence time 1 minute 30 seconds, 300 rpm, shear rate 400 nosec. An elastomer composition (component (Mouth_2)) was obtained. Table 1 shows the formulation.

[0153] (Preparation of ingredient (Raw 3))

144 parts oil-extended rubber (72 parts in rubber and 72 parts in mineral oil), 14 parts in polypropylene, 14 parts in amorphous olefin resin, 48 parts in mineral oil, and anti-aging agent 0 2 parts were mixed with a Henschel mixer and put into a pressure type kneader (capacity 10 liters, manufactured by Moriyama Co., Ltd.) preheated to 150 degrees, and each component was melted with polypropylene and amorphous olefin resin strength S By kneading for 15 minutes at 40 rpm (shearing speed 200 / sec) until uniformly dispersed, a melted kneaded product was obtained. The obtained kneaded material in a molten state is fed into a feeder norader (moder). Pellets using Ryama). To 20.2 parts of the pelletized kneaded product, 2.0 parts of a crosslinking agent and 2.0 parts of a crosslinking aid were charged into a Henschel mixer and mixed for 30 seconds. After that, twin screw extruder (same direction fully meshed screw, screw flight part length (L) to screw diameter (D) ratio (L) (D) = 33.5, product name `` PCM45 ”, Manufactured by Ikegai Co., Ltd.), and heat-treated dynamically at a temperature of 200 ° C, residence time 1 minute 30 seconds, 300 rpm, shear rate 400 nosec! / Plastic thermoplastic elastomer One composition (component (Mouth-3)) was obtained. Table 1 shows the formulation. The butadiene rubber, oil-extended rubber, polypropylene, amorphous olefin resin, cross-linking agent, and cross-linking aid used in the preparation of the components (Raw 1) to (Mouth 3) are shown below.

[0154] (Butadiene rubber)

2-Ethenorehexanol (0.2 mmol) was added dropwise to a 100 ml three-necked flask containing salty oxa (0.1 mmol), and the mixture was heated to 100 ° C. for 2 hours. After completion of the reaction, toluene solution of toluene 50m was prepared and a toluene solution of 2-ethylhexanol complex of zinc chloride was prepared. Under an atmosphere of nitrogen, 2.4 kg of cyclohexane and 300 g of 1,3-butadiene were placed in an autoclave having an inner volume of 5 liters purged with nitrogen. In addition, this autoclave was mixed with a solution of neodymium parasitic acid (0.04 mmol) in cyclohexane, methylalumoxane (2.4 mmol) in toluene, diisoptinoleluminium hydride (4. Ommol), and chloride. A toluene solution of zinc 2-ethylhexanol complex (0.04 mmol) was added to 5 parts mol of neodymium 1,3-butadiene and a catalyst component pre-aged at 50 ° C for 30 minutes. Polymerization was carried out at C for 60 minutes. The polymerization conversion of 1,3-butadiene was almost 100%. In order to measure the viscosity, a part of the polymerization solution was extracted, solidified and dried. Mooney viscosity (ML., 100 ° C) is 25, 1,4-cis bond content is 97.0%, 1,2_vinyl bond content

1 + 4

Was 1.2% and Mw / Mn was 2.5.

[0155] Next, the temperature of the polymerization solution was maintained at 50 ° C, and dioctyltin bis-2-ethylhexyl malate (7.2 mmol) was added. Thereafter, the mixture was allowed to stand for 30 minutes, a methanol solution containing 1.5 g of 2,4-di-t-butyl-p-cresol was added, and after the polymerization was stopped, the solvent was removed by steam stripping. Butadiene rubber was obtained by drying with a roll at 110 ° C. The resulting butadiene rubber has a Mooney viscosity (ML, 100 ° C) of 39, 1, 4-cis bond included. The amount was 97.0%, 1,2-bule bond content was 1.2%, and MwZMn was 2.8.

[0156] (Oil-extended rubber)

Product name “EP98A” (ethylene Z propylene / 5-ethylidene-2-norbornene terpolymer (ethylene content: 66%, 5-ethylidene-2-norbornene content: 4.5%, degree of occupation 3.8) : 57% by mass, paraffin softener content: 43%, JSR: hS) ₀

[0157] (Polypropylene)

Propylene 'ethylene block copolymer (Density: 0.90 gZcm ³ , MFR (Temperature 230 ° C, Load 2.16 kg): 60 gZlO min., Trade name “Novatech BC06C”, manufactured by Nippon Polypro Co., Ltd.)

[0158] (Amorphous olefin resin)

Propylene / 1-ptene amorphous copolymer (Propylene content: 71 mol ⁰ Melt viscosity: 800 000 cps, Density: 0.89 gZcm ³ , Mn: 6500, trade name “APAO UT2780”, manufactured by Ube Industries, Ltd. )

[0159] (Mineral oil)

Hydrogenated paraffinic mineral oil (trade name “Diana Process Oil PW90”, pour point: 1 15 ° C, kinematic viscosity (40 ° C): 95. 54 cSt, Idemitsu Kosan Neringu).

[0160] (Canolenum carbonate)

Product name “Whiteon 101” (manufactured by Shiroishi Kanorenmu).

[0161] (Crosslinking agent)

5-Dimethyl _ 2,5-Di (t-butylperoxy) hexa (trade name “Perhexa 25 B-40”, manufactured by NOF Corporation).

[0162] (Crosslinking aid)

Dibutenebenzene (purity 81%, manufactured by Nippon Steel Chemical Co., Ltd.).

[0163] (Anti-aging agent)

Pentaerythritol tetrakis [3— (3,5-Di-tert-butyl-4-hydroxyphenyl) propionate (trade name “Ilganox 1010”, manufactured by Chipa Specialty Chemicals)

[0164] [Table 1]

(Example 1)

(Ii) 40 parts of the component and (part 1) 60 parts of the pellets are mixed into a twin-screw extruder (in the same direction, fully intertwined screw, screw flight length (L), screw diameter ( D) ratio LZD = 33.5, product name “PCM45” (manufactured by Ikegai Co., Ltd.), dynamic at 200 ° C, residence time 1 minute 30 seconds, 300 rpm, shear rate 400 / sec Extruding while performing heat treatment As a result, a pellet-shaped thermoplastic elastomer composition (Example 1) was obtained. The resulting thermoplastic elastomer composition (Example 1) had a menoleto flow rate (MFR) of llg / 10 min and an evaluation of foamability of “◯”. In addition, this thermoplastic elastomer composition (Example 1) force V was used for the test piece prepared, and the hardness (du mouth A) measured was 72, the bow I tension breaking strength was 7 MPa, and the tensile breaking elongation was 460. %, And compression set was 33%.

[0166] Further, an electron micrograph showing the microstructure of the thermoplastic elastomer composition of Example 1 is shown in Fig. 1 (low magnification) and Fig. 2 (high magnification). In FIGS. 1 and 2, the microstructure of the cross section cut along the surfaces orthogonal to each other is shown. In Fig. 1 and Fig. 2, it is confirmed that the sea phase is composed of white to gray shades of fine mesh and a number of slightly rounded island phases that are dispersed in this phase. can do. In other words, it can be seen that the net-like structure observed in the sea phase V constitutes a three-dimensional network structure that spreads three-dimensionally. Further, FIG. 4 shows an electron micrograph showing the microstructure of the foam produced using the thermoplastic elastomer composition of Example 1.

[Examples 2 to 9, Comparative Examples:! To 3]

A thermoplastic elastomer composition (Examples 2 to 9, Comparative Examples 1 to 3) was obtained in the same manner as in Example 1 except that the formulation shown in Table 2 was used. Table 2 shows the physical property values and foamability of the obtained thermoplastic elastomer compositions, and various physical property values measured using test pieces made from these thermoplastic elastomer compositions. Also, FIG. 3 shows an electron microscope true showing the microstructure of the thermoplastic elastomer composition of Comparative Example 2, and FIG. 5 shows the microstructure of the foam produced using the thermoplastic elastomer composition of Comparative Example 2. The electron micrographs shown are respectively shown.

[0168] [Table 2]

[0169] As shown in Table 2, the thermoplastic elastomer compositions of Examples 1 to 9 had better foamability and compression than the thermoplastic elastomer compositions of Comparative Examples 1 to 3. It is clear that the permanent set is small and the balance between the two is excellent. In addition, comparing Fig. 1 and Fig. 3, in Fig. 1, the network structure is observed in the sea phase, whereas in Fig. 3, the network structure cannot be observed in the sea phase. Furthermore, comparing Fig. 4 and Fig. 5, in Fig. 4, the network structure is observed in the sea phase, whereas in Fig. 5, it is in the sea phase! / I can't observe the network structure! /.

Industrial applicability

[0170] The thermoplastic elastomer composition of the present invention, its molded product, and its foamed molded product are excellent in flexibility and rubber elasticity (rebound resilience, compression set). Therefore, automotive bumpers, exterior moldings, wind seal gaskets, door seal gaskets, trunk seal gaskets, roof side rails: Inner and outer skin materials such as emblem, inner panel, door trim, console box Leather seats that require scratch resistance; Aircraft 'Ship seals, interior and exterior skin materials, etc .; Civil engineering and construction seal materials, interior and exterior skin materials, waterproof sheet materials, etc .; Equipment sealing materials, etc .; weak electrical parts' water-supply packings, sealing materials in fuel cell stacks, skin materials, housings, etc .; railroad track pads, rolls for information equipment, cleaning blades, films for electronic parts; semiconductor products Protective films and sealing materials used in manufacturing processes or flat panel display (FPD) manufacturing processes such as liquid crystal display devices; photographs, etc. It can be widely used in general processed products such as image protective films, building decorative films for medical use, medical β parts, electric wires, daily goods, sports goods and the like.

Claims

The scope of the claims

[1] (ii) a sea phase having a first polymer and a second polymer, wherein the second polymer is present in a matrix comprising the first polymer;

(Mouth) island phase consisting of particulate third polymer,

A thermoplastic elastomer composition having a sea-island structure consisting of ¾r ^.

[2] The thermoplastic elastomer composition according to [1], wherein the second polymer constitutes a three-dimensional network structure in a matrix composed of the first polymer.

[3] The first polymer is an ethylene ′ α-olefin copolymer (共),

The second polymer is a crystalline ethylene resin (樹脂),

The thermoplastic elastomer composition according to claim 1 or 2, wherein the third polymer is a crosslinked rubber (C).

[4] The sea phase

1, 2—Blocks at both ends with a conjugated diene polymer blocking force with a Biel bond content of 25% or less,

1, 2—Intermediate block with conjugated diene polymer block power of> 25% bulule content;

Hydrogenated block copolymer (D) obtained by hydrogenating ¾r ^ block copolymer,

The thermoplastic elastomer composition according to claim 3, further comprising:

[5] The thermoplastic elastomer composition according to claim 3 or 4, wherein the crosslinked rubber (C) has a particle size of 20 μm or less.

[6] The thermoplastic elastomer or toma composition according to any one of claims 3 to 5, further comprising a foaming agent (E).

[7] The crosslinked rubber (C) is at least one selected from the group consisting of (C) force S, ethylene'a-olefin copolymer rubber, unsaturated nitrile mono-copolymer rubber, butadiene rubber, and acrylic rubber. 7. The thermoplastic elastomer composition according to any one of claims 3 to 6.

[8] further containing a softening agent (F),

The thermoplastic elastomer composition according to any one of claims 3 to 7, wherein a content ratio of the softening agent (F) is 200 parts by mass or less with respect to 100 parts by mass of the crosslinked rubber (C). object

[9] The softener (F) is a mineral oil softener (F-1),

9. The heat according to claim 8, wherein a content ratio of the mineral oil softener (F-1) is 200 parts by mass or less with respect to 100 parts by mass of the ethylene ′ _a -olefin copolymer (A). Plasticity Elastomer composition.

[10] An ethylene 'a-olefin copolymer (A) and a crystalline ethylene resin (B), and the crystalline ethylene is contained in a matrix of the ethylene' a-olefin copolymer (A). A first composition in which a resin (B) is present;

A second composition obtained by dynamically heat-treating a mixture containing rubber (G) and thermoplastic resin (H) in the presence of a crosslinking agent;

By dynamically heat-treating

A thermoplastic elastomer comprising obtaining a thermoplastic elastomer composition having a sea-island structure comprising a sea phase comprising the first composition force and an island phase comprising particulate crosslinked rubber (C). A method for producing a composition.

[11] A molded article formed by molding the thermoplastic elastomer composition according to any one of claims 1 to 9.

[12] A foam-molded article obtained by foam-molding the thermoplastic elastomer composition according to any one of claims 1 to 9.