WO2009123228A1

WO2009123228A1 - Crosslinked thermoplastic elastomer composition and manufacturing method for said composition

Info

Publication number: WO2009123228A1
Application number: PCT/JP2009/056734
Authority: WO
Inventors: 毅岩; 圭司岡田; 智昭松木
Original assignee: 三井化学株式会社
Priority date: 2008-04-01
Filing date: 2009-03-31
Publication date: 2009-10-08
Also published as: JPWO2009123228A1

Abstract

Disclosed are a crosslinked thermoplastic elastomer composition, which possesses superior oil resistance and the hardness and mechanical properties of which are equal to conventional crosslinked thermoplastic elastomers, a compact thereof, and a manufacturing method for said composition. The crosslinked elastomer composition (D) comprises a crystalline polyolefin polymer (A) and a crosslinked ethylene copolymer (B). The crosslinking sites (C) in the aforementioned crosslinked ethylene copolymer (B) are at least one type of nitrogen-containing group selected from a group comprising amide groups and imide groups, and are an organic group (c1) that possesses an ester group.

Description

Cross-linked thermoplastic elastomer composition and method for producing the composition

The present invention relates to a crosslinked thermoplastic elastomer composition and a method for producing the composition, and more specifically, a crosslinked thermoplastic elastomer composition containing a crystalline olefin polymer and a specific crosslinked ethylene copolymer, and the composition. The present invention relates to a method for manufacturing a product.

Cross-linked thermoplastic elastomers are used in various fields such as automobile parts, electrical / electronic parts, and building parts, taking advantage of superior mechanical properties such as heat resistance and moldability.

Conventionally, as this cross-linkable thermoplastic elastomer, an extrusion vulcanized molded article composed of a rubber compound of ethylene / propylene / non-conjugated diene terpolymer (EPDM) is used in a part requiring low hardness and rubber elasticity. Has been used.

On the other hand, in place of vulcanized rubber using ethylene / propylene / non-conjugated diene terpolymer (EPDM) as a sealing material for various applications, it has been added from the viewpoint of productivity, environmental friendliness and weight reduction. Cross-linked thermoplastic elastomers (compositions) that do not require a sulfurization process are beginning to be used.

The crosslinked thermoplastic elastomer that does not require this vulcanization step is obtained by dynamically crosslinking a mixture of an ethylene / propylene (non-conjugated diene) copolymer and a crystalline polyolefin using a peroxide.

As a technique related to the composition of a crosslinked thermoplastic elastomer using a peroxide, a mixture of an ethylene / propylene (non-conjugated diene) copolymer and a crystalline polyolefin is dynamically crosslinked using a peroxide. Is a known technique, but polypropylene has been used as the crystalline polyolefin especially considering physical properties and moldability.

However, in this cross-linked thermoplastic elastomer, the addition of peroxide decomposes the crystalline polyolefin component and causes a decrease in molecular weight, resulting in sufficient fluidity. However, the mechanical properties ( There was a problem that the tensile strength, elongation, etc.) were reduced.

Accordingly, a crosslinked elastic polymer obtained by crosslinking an elastic polymer having a reactive substituent with a crosslinking agent having a reactive substituent and having a molecular weight of less than about 2000 in order to improve mechanical properties. In addition, a melt-processable thermoplastic composition containing the crosslinked elastic polymer and thermoplastic polymer has been proposed (see, for example, Patent Document 1).
JP 2000-515184 A

However, even the cross-linked elastic polymer and melt-processable thermoplastic composition described in Patent Document 1 are similar to other olefin elastomers including other cross-linked thermoplastic elastomers in terms of oil resistance. , Has the disadvantage of being inferior to urethane elastomers.

The present invention is a cross-linked thermoplastic elastomer composition having oil resistance superior to that of conventional cross-linked thermoplastic elastomers and having mechanical properties (tensile strength, elongation, etc.) equivalent to those of conventional cross-linked thermoplastic elastomers. It is an object to provide a product and a method for producing the composition.

As a result of intensive studies, the present inventors have found that a crosslinked thermoplastic elastomer composition containing a crosslinked ethylene copolymer crosslinked with the following specific organic group and a crystalline olefin polymer solves the above problems. The present invention has been completed.

That is, the cross-linked thermoplastic elastomer composition (D) of the present invention includes a crystalline olefin polymer (A) and a cross-linked ethylene copolymer (B), and the cross-linked ethylene copolymer (B) is cross-linked. The site (C) is an organic group (c1) having at least one nitrogen-containing group selected from the group consisting of an amide group and an imide group and an ester group.

The crosslinked ethylene copolymer (B) is an ethylene / α-olefin copolymer having a functional group capable of reacting with an isocyanate group, and an ethylene / α-olefin / nonconjugated polyene copolymer having a functional group capable of reacting with an isocyanate group. The polymer is preferably a polymer obtained by crosslinking at least one ethylene copolymer (E) selected from the group consisting of a polymer and an ethylene / unsaturated carboxylic acid copolymer.

The organic group (c1) preferably contains a divalent group represented by the following general formula R _2.

(In the above general formula R ₂ , each R ₃ is independently an alkylene group having 1 to 15 carbon atoms or an aromatic group having 6 to 15 carbon atoms which may have a branch, and each R ₄ is independently And an optionally substituted alkylene group having 1 to 15 carbon atoms.)
The organic group (c1) is preferably at least one organic group selected from the group consisting of the following general formula Ra and the following general formula Rb.

(In the above general formulas Ra and Rb, each Rc is independently a trivalent hydrocarbon group having 1 to 20 carbon atoms, and each Rd is independently a divalent hydrocarbon group having 1 to 20 carbon atoms. , R ₁ are each independently a diisocyanate residue, and R ₂ are each independently a divalent group represented by the following general formula.)

(In the above general formula R ₂ , each R ₃ is independently an alkylene group having 1 to 15 carbon atoms or an aromatic group having 6 to 15 carbon atoms which may have a branch, and each R ₄ is independently And an optionally substituted alkylene group having 1 to 15 carbon atoms.)
R ₁ is a divalent carbon atom having 6 to 20 carbon atoms having an optionally branched alkylene group having 2 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, and an alicyclic hydrocarbon group. It is preferably at least one group selected from the group consisting of hydrogen groups.

The weight ratio (A / B) between the crystalline olefin polymer (A) and the crosslinked ethylene copolymer (B) is preferably 10/90 to 50/50.

In the general formula Ra and the general formula Rb, n is preferably 0 to 3, and in the general formula R ₂ , m is preferably 7 to 20.

The crosslinked thermoplastic elastomer composition (D) forms a sea-island structure in which the sea phase is a crystalline olefin polymer (A) and at least a part of the island phase is a crosslinked ethylene copolymer (B). Such a crosslinked thermoplastic elastomer composition (D) is preferably composed of the crystalline olefin polymer (A), an ethylene / α-olefin copolymer having a functional group capable of reacting with an isocyanate group, and an isocyanate group. And at least one ethylene copolymer (E) selected from the group consisting of an ethylene / α-olefin / non-conjugated polyene copolymer and an ethylene / unsaturated carboxylic acid copolymer having a functional group capable of reacting with Into the mixture, an isocyanate group-containing oligomer (F) having an amide group, an ester group, and two or more isocyanate groups is introduced as a crosslinking agent. As crosslinking agent, introducing the polyester polycarboxylic acid (G) and the polyvalent isocyanate is preferably obtained by dynamically crosslinking the ethylene copolymer (E).

The number average molecular weight in terms of standard polyethylene glycol determined by gel permeation chromatography (GPC) of the isocyanate group-containing oligomer (F) is preferably more than 2000, and the isocyanate group-containing oligomer (F) is More preferably, it is represented by the general formula Rx.

(In the general formula Rx, each R ₁ is independently a diisocyanate residue, and each R ₂ is independently a divalent group represented by the following general formula.)

In the general formula Rx, n is preferably 0 to 3, and in the general formula R ₂ , m is preferably 7 to 20.

The isocyanate group-containing oligomer (F) is obtained by reacting a polyisocyanate with a polyester polycarboxylic acid (G) produced from a polyhydric alcohol and a polyvalent carboxylic acid. At least one of carboxylic acid and polyvalent isocyanate may contain a trivalent or higher monomer.

It is preferable that the polyvalent isocyanate contains a trivalent or higher polyvalent isocyanate.

In the ethylene copolymer (E), the functional group capable of reacting with an isocyanate group is preferably a carboxyl group or a carboxylic anhydride group.

The method for producing the cross-linked thermoplastic elastomer composition (D) comprises reacting with a crystalline olefin polymer (A), an ethylene / α-olefin copolymer having a functional group capable of reacting with an isocyanate group, and an isocyanate group. A mixture of at least one ethylene copolymer (E) selected from the group consisting of an ethylene / α-olefin / non-conjugated polyene copolymer having a functional group and an ethylene / unsaturated carboxylic acid copolymer; Introducing an isocyanate group-containing oligomer (F) having an amide group, an ester group, and two or more isocyanate groups as a crosslinking agent, or introducing a polyester polycarboxylic acid (G) and a polyvalent isocyanate as a crosslinking agent And the ethylene copolymer (E) is dynamically cross-linked.

The molded product of the present invention is composed of the cross-linked thermoplastic elastomer composition (D).

The molded article of the present invention is preferably an automotive part, and more preferably an automotive part selected from the group consisting of a boot, a wire harness cover, a seat adjuster cover, and a hose.

The crosslinkable thermoplastic elastomer composition (D) of the present invention has oil resistance superior to that of the conventional crosslinkable thermoplastic elastomer, and has the same mechanical properties (tensile strength, elongation as the conventional crosslinkable thermoplastic elastomer). Etc.). For this reason, the molded object formed from a bridge | crosslinking-type thermoplastic elastomer composition (D) can be used for various uses.

BEST MODE FOR CARRYING OUT THE INVENTION

Next, the present invention will be specifically described.

The cross-linked thermoplastic elastomer composition (D) of the present invention includes a crystalline olefin polymer (A) and a cross-linked ethylene copolymer (B), and a cross-linked site of the cross-linked ethylene copolymer (B) ( C) is an organic group (c1) having at least one nitrogen-containing group selected from the group consisting of an amide group and an imide group and an ester group.

The crosslinked thermoplastic elastomer composition (D) of the present invention is excellent in oil resistance because the organic group (c1) has a nitrogen-containing group and an ester group, which are hydrophilic groups. In addition, the crosslinked thermoplastic elastomer composition (D) comprises a crosslinked olefin polymer (A) and a crosslinked ethylene copolymer formed mainly from ethylene, if necessary, α-olefin and non-conjugated polyene, except for the crosslinking site. Since the polymer (B) is included, thermal deterioration during molding can be prevented. For this reason, the crosslinkable thermoplastic elastomer composition (D) has mechanical properties (tensile strength, elongation, etc.) equivalent to those of conventional crosslinkable thermoplastic elastomers.

[Crystalline Olefin Polymer (A)]
There is no limitation in particular as crystalline olefin polymer (A) used for this invention, A conventionally well-known crystalline olefin polymer can be used.

Crystallinity means that the melting point (Tm) is measured by differential scanning calorimetry (DSC).

Examples of the crystalline olefin polymer (A) include ethylene polymers and propylene polymers. As the ethylene-based polymer, an ethylene homopolymer, an ethylene / α-olefin copolymer (preferably a copolymer of ethylene and an α-olefin having 3 to 10 carbon atoms) and the like can be used. As the copolymer, a propylene homopolymer, a propylene / α-olefin copolymer or the like (preferably a copolymer of propylene and an α-olefin having 2 or 4 to 10 carbon atoms) can be used. .

Among these, as the crystalline olefin polymer (A), it is preferable to use a propylene polymer from the viewpoints of physical properties and moldability.

The propylene-based polymer is preferably a propylene-based polymer having an isotactic pentad fraction of the boiling heptane insoluble part of 0.955 or more and a content of the boiling heptane soluble part of 9% by weight or less, Specifically, a propylene homopolymer or a copolymer of propylene and a small amount of an α-sodium olefin having 2 or 4 to 10 carbon atoms is preferable.

Specific examples of such α- olefins having 2, 4 to 10 carbon atoms include ethylene, 1-butene, 1-pentene, 3-methyl-1- butene, 1-hexene, 3-methyl-1- Examples include pentene, 4-methyl-1- pentene, 1-octene, and 1-decene. Of these, ethylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1- pentene are preferable. The α-olefins may be used alone or in combination of two or more.

When the propylene-based polymer is a copolymer of propylene and a small amount of an α-sodium olefin having 2 or 4 to 10 carbon atoms, the α-olefin having 2 or 4 to 10 carbon atoms in the copolymer Is usually 10 mol% or less, preferably less than 5 mol%.

In the present invention, as the crystalline olefin polymer (A), the isotactic pentad fraction of the boiling heptane-insoluble part is 0.955 or more and the content of the boiling heptane-soluble part is 9% by weight or less. Use of a propylene-based polymer is preferable because a crosslinked thermoplastic elastomer resin composition (D) capable of forming a high-strength molded product can be obtained.

The isotactic pentad fraction in the boiling heptane-insoluble part and the content in the boiling heptane-soluble part are measured as follows.

After 5 g of the propylene polymer was completely dissolved in 500 ml of boiling xylene, the temperature was lowered to 20 ° C. and left for 4 hours. Thereafter, it is filtered and separated into a 20 ° C. xylene soluble part and an insoluble part. Next, the 20 ° C. xylene-insoluble part is further subjected to Soxhlet extraction with boiling n-heptane for 8 hours to separate into an extraction residue and an extract. This extraction residue is defined as a “boiling heptane insoluble part” of the propylene-based polymer. In the present specification, the “boiling heptane-soluble part” of the propylene-based polymer is the sum of the 20 ° C. xylene-soluble part and the previous boiling n-heptane extract. The weight percentage of the boiling heptane-soluble part is calculated from the weight of the boiling heptane-soluble part and the total propylene polymer weight used for the measurement.

The isotactic pentad fraction is the pentad unit in the propylene polymer molecular chain measured by the method published by A Zambelli et al. In Macromolecules 6 925 (1973), ie using ¹³ C-NMR. The isotactic fraction of In other words, the isotactic pentad fraction is the fraction of propylene monomer units at the center of a chain in which five propylene monomer units are continuously meso-bonded. However, regarding the attribution of the peak, since a corrected version of Macromolecules 6 , 925 (1973) is described in Macromolecules 8 , 678 (1975), it shall be performed based on this.

Specifically, the isotactic pentad fraction is measured as the area fraction of the mmmm peak in the total absorption peak in the methyl carbon region of the ¹³ C-NMR spectrum. The isotactic pentad fraction of NPL reference material CRM No. M19-14 Polypropylene PP / MWD / 2 from NATIONAL PHYSICAL LABORATORY, UK was measured to be 0.944.

The propylene polymer preferably used in the present invention can be prepared, for example, by the method described in JP-A-53-33289. A Lewis base can also be used during the polymerization. When a Lewis base is used, the content of the boiling heptane-soluble part is generally decreased, but the isotactic pentad fraction of the boiling heptane-insoluble part is not changed.

The melt flow rate (MFR; ASTM D 1238, 230 ° C., 2.16 kg load) of the propylene-based polymer as described above is preferably 0.1 to 100 g / 10 minutes, more preferably 0.5 to 80 g / 10. Min, more preferably 0.5 to 60 g / 10 min. When a propylene polymer having a melt flow rate within the above range is used, a cross-linked thermoplastic elastomer resin composition (D) having good processability (moldability) can be obtained, and mechanical strength characteristics and oil resistance can be obtained. A molded article having excellent physical properties such as the above can be obtained.

The crystalline olefin polymer (A) used in the present invention may be one produced by a known method or a commercially available product.

The crystalline olefin polymer (A) such as the propylene-based polymer as described above usually has a weight ratio (A / B) to the crosslinked ethylene copolymer (B) described later of 10/90 to 50/50. It is preferably 15/85 to 45/55, more preferably 20/80 to 40/60. When the crystalline olefin polymer (A) and the later-described crosslinked ethylene copolymer (B) are used in the above ratio, a crosslinked thermoplastic elastomer composition (D) having good fluidity and excellent moldability is obtained. From the composition, a molded article having excellent appearance can be obtained.

[Crosslinked ethylene copolymer (B)]
The crosslinked ethylene copolymer (B) used in the present invention comprises at least one nitrogen-containing group selected from the group consisting of an amide group and an imide group, an ester group, and a crosslinking site (C) of the copolymer. An organic group (c1) having

The crosslinked ethylene copolymer (B) is not particularly limited as long as it is an ethylene copolymer having an organic group (c1), but is obtained by crosslinking the ethylene copolymer (E) described later. It is preferable that it is a coalescence from the viewpoint of oil resistance of the cross-linked thermoplastic elastomer composition (D).

When the ethylene copolymer (E) is crosslinked, an isocyanate group-containing oligomer (F) having an amide group, an ester group, and two or more isocyanate groups is used as a crosslinking agent, or a polyester polycarboxylic acid. (G) and a polyvalent isocyanate are used as a crosslinking agent. The polyester polycarboxylic acid (G) and the polyvalent isocyanate are the two kinds of compounds and act as a crosslinking agent in the present invention. Moreover, as said polyvalent isocyanate, polyvalent isocyanate other than an isocyanate group containing oligomer (F) is used normally.

The organic group (c1) preferably contains a divalent group represented by the following general formula R ₂ from the viewpoint of oil resistance of the crosslinked thermoplastic elastomer composition (D), and the organic group (c1) is More preferably, it is at least one organic group selected from the group consisting of the following general formula Ra and the following general formula Rb.

(In the above general formula R ₂ , each R ₃ is independently an alkylene group having 1 to 15 carbon atoms or an aromatic group having 6 to 15 carbon atoms which may have a branch, and each R ₄ is independently And an optionally substituted alkylene group having 1 to 15 carbon atoms.)

(In the above general formulas Ra and Rb, each Rc is independently a trivalent hydrocarbon group having 1 to 20 carbon atoms, and each Rd is independently a divalent hydrocarbon group having 1 to 20 carbon atoms. , R ₁ each independently represents a diisocyanate residue, and R ₂ each independently represents a divalent group represented by the above general formula.)
In the above general formula Ra, each Rc independently represents a trivalent hydrocarbon group having 1 to 20 carbon atoms. Rc is a group present at the end of the crosslinking site, and usually Rc forms an imide ring together with two adjacent carbonyl groups and a nitrogen atom. A specific example of Rc is shown in the following general formula (1) together with two adjacent carbonyl groups and a nitrogen atom. In general formula Ra, there are two Rc, but they are independent of each other and may be the same or different from each other.

In the general formula Rb, each Rd is independently a divalent hydrocarbon group having 1 to 20 carbon atoms. Rd is a group present at the end of the crosslinking site, and specific examples of Rd include an optionally substituted alkylene group having 1 to 20 carbon atoms, preferably — (CH ₂ ) x—. Is an alkylene group (X is an integer of 1 to 20). In the general formula Rb, there are two Rd, but they are independent of each other and may be the same or different from each other.

In the above general formulas Ra and Rb, each R ₁ is independently a diisocyanate residue. The crosslinked ethylene copolymer (B) used in the present invention is usually obtained by dynamically crosslinking an ethylene copolymer (E) described later in the presence of a crosslinking agent described later. In this case, R ₁ is a diisocyanate residue (diisocyanate residue) used when the isocyanate group-containing oligomer (F) is produced, or a diisocyanate residue used during dynamic crosslinking. In general formulas Ra and Rb, there are a plurality of R _{1 s} , which are independent of each other and may be the same or different from each other.

The diisocyanate residue is a portion corresponding to -X- when the structure of the diisocyanate used is OCN-X-NCO.

As R ₁ , an optionally branched alkylene group having 2 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, and a divalent divalent hydrocarbon having 6 to 20 carbon atoms having an alicyclic hydrocarbon group. From the viewpoint of economy, it is preferably at least one group selected from the group consisting of hydrocarbon groups.

A preferred specific example of R ₁ is shown in the following general formula (2).

Each R ₂ is independently a divalent group represented by the above general formula. Since R ₂ has an ester group and an amide group, R ₂ is a divalent group having excellent hydrophilicity, and is a group contributing to the oil resistance of the crosslinked thermoplastic elastomer composition (D) of the present invention. In the general formulas Ra and Rb, when a plurality of R ₂ are present, they are independent of each other and may be the same or different from each other.

In the above general formula R ₂ , each R ₃ is independently an alkylene group having 1 to 15 carbon atoms or an aromatic group having 6 to 15 carbon atoms which may have a branch. As an embodiment of the crosslinked ethylene copolymer (B) used in the present invention, an ethylene copolymer (E) described later is used as an isocyanate group-containing oligomer (Fx) described later, or a polyester dicarboxylic acid and a diisocyanate. In this case, the R ₃ is a residue of a dicarboxylic acid used in producing an isocyanate group-containing oligomer (Fx) or a polyester dicarboxylic acid. In the general formula R ₂ , there are a plurality of R _{3 s} , which are independent of each other and may be the same or different from each other.

The dicarboxylic acid residue indicates a portion corresponding to -X- when the structure of the dicarboxylic acid used is HOOC-X-COOH.

R ₃ is an optionally substituted alkylene group having 1 to 15 carbon atoms or an aromatic group having 6 to 15 carbon atoms. As the alkylene group, an alkylene group represented by the following general formula (3) is preferable from the viewpoint of economy. Moreover, as an aromatic group, the aromatic group represented by the following general formula (3 ') is preferable from an economical viewpoint.

Among R ₃ represented by the above general formulas (3) and (3 ′), an alkylene group represented by — (CH ₂ ) s— (an integer of s = 2 to 6) is more preferable from the viewpoint of physical properties and moldability.

In the above general formula R ₂ , each R ₄ is independently an alkylene group having 1 to 15 carbon atoms which may have a branch. As an embodiment of the crosslinked ethylene copolymer (B) used in the present invention, an ethylene copolymer (E) described later is used as an isocyanate group-containing oligomer (Fx) described later, or a polyester dicarboxylic acid and a diisocyanate. In this case, R ₄ is a residue of a diol used for producing an isocyanate group-containing oligomer (Fx) or polyester dicarboxylic acid. In the general formula R ₂ , there are a plurality of R _{4 s} , which are independent of each other and may be the same or different from each other.

The diol residue indicates a portion corresponding to -X- when the structure of the diol used is HO-X-OH.

R ₄ is an alkylene group having 1 to 15 carbon atoms. Specifically, an alkylene group represented by the following general formula (4) is preferable from the viewpoint of economy.

In the above general formulas Ra and Rb, n is 0-5. The preferable range of n varies depending on Rc, Rd, R ₁ and R ₂ , but is 0 to 3, more preferably 0 to 2.

In the above general formula R ₂ , m is 1-20. A preferable range of m is 7 to 20, although it varies depending on R ₃ and R ₄ .

The crosslinked ethylene copolymer (B) used in the present invention is usually an ethylene / α-olefin copolymer having a functional group capable of reacting with an isocyanate group, and an ethylene / α-olefin having a functional group capable of reacting with an isocyanate group. A polymer obtained by crosslinking at least one ethylene copolymer (E) selected from the group consisting of non-conjugated polyene copolymers and ethylene / unsaturated carboxylic acid copolymers. In the crosslinking, a group such as a functional group capable of reacting with an isocyanate group that the ethylene copolymer (E) usually has, a carboxyl group derived from the unsaturated carboxylic acid, a carboxylic acid anhydride group derived from the unsaturated carboxylic acid, and the like The crosslinking agent (to be described later) reacts to form a crosslinking site (C).

That is, the structure of the portion other than the crosslinking site (C) in the crosslinked ethylene copolymer (B) is usually a structure derived from the ethylene copolymer (E) described later.

[Ethylene copolymer (E)]
The ethylene copolymer (E) in the present invention is an ethylene / α-olefin copolymer having a functional group capable of reacting with an isocyanate group, or an ethylene / α-olefin / non-conjugated polyene having a functional group capable of reacting with an isocyanate group. It is at least one copolymer selected from the group consisting of a copolymer and an ethylene / unsaturated carboxylic acid copolymer.

The functional group capable of reacting with the isocyanate group is usually a carboxyl group derivative such as a carboxyl group or a carboxylic anhydride group.

The ethylene / α-olefin copolymer having a functional group capable of reacting with an isocyanate group in the present invention, and the ethylene / α-olefin / nonconjugated polyene copolymer having a functional group capable of reacting with an isocyanate group are usually ethylene.・ Ethylene copolymers (E-1) obtained by graft-modifying α-olefin copolymers and ethylene / α-olefin / non-conjugated polyene copolymers with unsaturated carboxylic acids or unsaturated carboxylic acid derivatives Alternatively, ethylene, an α-olefin, a monomer having a functional group capable of reacting with an isocyanate group, and an ethylene copolymer (E-2) obtained by copolymerizing a non-conjugated polyene, if necessary, are used.

<Ethylene copolymer (E-1)>
There are no particular limitations on the ethylene / α-olefin copolymer before graft modification and the ethylene / α-olefin / non-conjugated polyene copolymer used to obtain the ethylene copolymer (E-1), and usually The density is 0.88 to 0.97 g / cm ³ , preferably 0.89 to 0.96 g / cm ³ .

As the α-olefin copolymerized with ethylene, an α-olefin having 3 to 10 carbon atoms is usually used. Specific examples of the α-olefin having 3 to 10 carbon atoms include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, and the like. -Hexene, 1-octene and 4-methyl-1-pentene are preferred. The α-olefins may be used alone or in combination of two or more.

Specific examples of the non-conjugated polyene that may be copolymerized with ethylene and α-olefin include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene. , 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 8-methyl-4-ethylidene-1,7-nonadiene, 4-ethylidene Linear unconjugated dienes such as -1,7-undecadiene;
Methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene Cyclic non-conjugated dienes such as 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclopentadiene, norbornadiene;
2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, 4-ethylidene-8-methyl-1,7-nanodiene, etc. And triene.

Of these, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, cyclopentadiene, and 4-ethylidene-8-methyl-1,7-nanodiene are preferable. In addition, a nonconjugated polyene may be used individually by 1 type, or may use 2 or more types.

As the ethylene / α-olefin copolymer before graft modification, the structural unit derived from ethylene is usually 40 to 99 mol%, preferably 50 to 90 mol%, more preferably 60 to 85 mol%, The structural unit derived from α-olefin is usually 60 to 1 mol%, preferably 50 to 10 mol%, more preferably 40 to 15 mol%. The amount of each structural unit can be determined by ¹³ C-NMR.

The ethylene / α-olefin copolymer before graft modification has an intrinsic viscosity [η] measured in decalin of 135 ° C. of 0.3 to 10 dl / g, preferably 0.5 to 10 dl / g.

The melt flow rate [MFR (190 ° C.)] at 190 ° C. and 2.16 kg load according to ASTM D1238 of the ethylene / α-olefin copolymer before graft modification is usually 0.001 to 100 g / 10 min, preferably Is 0.1 to 50 g / 10 min.

As the ethylene / α-olefin / non-conjugated polyene copolymer before graft modification, the structural unit derived from ethylene is 40 to 99 mol%, usually 50 to 90 mol%, preferably 60 to 85 mol%. The structural unit derived from α-olefin is 60 to 1 mol%, usually 50 to 10 mol%, preferably 40 to 15 mol% (provided that the total of ethylene content and α-olefin content is 100 mol%) And). The non-conjugated polyene content is usually 0.1 to 30, preferably 0.1 to 25 in terms of iodine value. The amount of structural units derived from ethylene and structural units derived from α-olefin can be determined by ¹³ C-NMR.

The method for preparing the ethylene / α-olefin copolymer or the ethylene / α-olefin / non-conjugated polyene copolymer before graft modification is not particularly limited. For example, a soluble vanadium compound and an alkylaluminum halide compound Prepared by random copolymerization of ethylene and α-olefin, and if necessary, non-conjugated polyene in the presence of a vanadium-based catalyst or a zirconium-based catalyst of a zirconium metallocene compound and an organoaluminum oxy compound. be able to.

Specific examples of the soluble vanadium compound used in the vanadium-based catalyst include vanadium tetrachloride, vanadium oxytrichloride, vanadium monoethoxydichloride, vanadium triacetylacetonate, oxyvanadium triacetylacetonate, and the like.

Specific examples of the alkylaluminum halide compound used in the vanadium catalyst include ethylaluminum dichloride, diethylaluminum monochloride, ethylaluminum sesquichloride, diethylaluminum monobromide, diisobutylaluminum monochloride, isobutylaluminum dichloride, isobutylaluminum. Examples include sesquichloride.

Specific examples of zirconium metallocene compounds used in zirconium-based catalysts include ethylene bis (indenyl) zirconium dibromide, dimethylsilylene bis (2-methylindenyl) zirconium dichloride, and bis (cyclopentadienyl) zirconium dibromide. And bis (dimethylcyclopentadienyl) zirconium dichloride.

Also, as the organoaluminum oxy compound used in the zirconium-based catalyst, there are aluminoxane or benzene insoluble organoaluminum oxy compound.

The zirconium-based catalyst may contain an organoaluminum compound together with a zirconium metallocene compound and an organoaluminum oxy compound. Specific examples of such organoaluminum compounds include triisobutylaluminum, dimethylaluminum chloride, methylaluminum sesquichloride, and the like.

The polymerization can be carried out in the form of a solution or suspension or in the middle region. In any case, it is preferable to use an inert solvent as a reaction medium.

Grafting ethylene / α-olefin copolymer or ethylene / α-olefin / non-conjugated polyene copolymer, which is one embodiment of ethylene copolymer (E), with unsaturated carboxylic acid or unsaturated carboxylic acid derivative The ethylene copolymer (E-1) obtained by modification is an unsaturated carboxylic acid or an unsaturated ethylene / α-olefin copolymer or ethylene / α-olefin / unconjugated polyene copolymer before graft modification. Graft-modified with a carboxylic acid derivative. That is, the ethylene copolymer (E-1) has a carboxyl group or a group derived from the carboxyl group as a functional group capable of reacting with an isocyanate group.

Examples of unsaturated carboxylic acids used here include acrylic acid, maleic acid, fumaric acid, 10-undecenoic acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid and nadic acid ^TM (endocis- Bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid). Examples of the unsaturated carboxylic acid derivatives include acid halide compounds, acid anhydrides, amide compounds, imide compounds, and ester compounds of the above unsaturated carboxylic acids. Specific examples include maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, and the like.

Among these, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid ^TM or acid anhydrides thereof, or 10-undecenoic acid is particularly preferable.

In the production of the ethylene copolymer (E-1), the number of functional groups capable of reacting with the isocyanate group contained in the ethylene copolymer (E-1) is such that the ethylene copolymer (E-1 The amount of unsaturated carboxylic acid or its derivative is adjusted so that it is usually 0.10 mmol / g or more, preferably 0.20 mmol / g or more, more preferably 0.30 mmol / g or more. To do. The upper limit of the number of functional groups is usually 2.0 mmol / g or less from the viewpoint of physical properties and moldability.

An ethylene copolymer (E-1) produced with a graft amount in which the number of functional groups falls within the above range is used by using an isocyanate group-containing oligomer (F) or a polyester polycarboxylic acid (G) described later and a polyvalent isocyanate. The crosslinked ethylene copolymer (B) obtained by crosslinking is excellent in dispersibility and thermal stability in the crosslinked thermoplastic elastomer composition (D) of the present invention, and the resin is colored when melted. It is also excellent in oil resistance. Further, by using the crosslinked ethylene copolymer (B), a crosslinked thermoplastic elastomer composition (D) capable of providing a molded article having excellent mechanical strength can be obtained.

The graft position of the unsaturated carboxylic acid or its derivative grafted to the ethylene / α-olefin copolymer or the ethylene / α-olefin / non-conjugated polyene copolymer before the graft modification is not particularly limited. If an unsaturated carboxylic acid or derivative thereof is bonded to any carbon atom in the polymer chain derived from the previous ethylene / α-olefin copolymer or ethylene / α-olefin / non-conjugated polyene copolymer Good.

The ethylene copolymer (E-1) can be prepared using various conventionally known methods, for example, the following methods.
(1) A method in which the ethylene / α-olefin copolymer or the ethylene / α-olefin / non-conjugated polyene copolymer before graft modification is melted and an unsaturated carboxylic acid or the like is added to perform graft copolymerization.
(2) A method in which the ethylene / α-olefin copolymer or the ethylene / α-olefin / non-conjugated polyene copolymer before graft modification is dissolved in a solvent and an unsaturated carboxylic acid or the like is added to perform graft copolymerization.

In any method, in order to efficiently graft copolymerize the graft monomer such as the unsaturated carboxylic acid, the graft reaction is preferably performed in the presence of a radical initiator.

As the radical initiator, organic peroxides, azo compounds and the like are used. Specific examples of such radical initiators include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxide benzoate) hexyne- 3,1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butylperacetate, 2,5-dimethyl-2,5-di- (tert-butylperoxide) hexyne-3, 2,5 -Dimethyl-2,5-di (tert-butylperoxide) hexane, tert-butylperbenzoate, tert-butylperphenylacetate, tert-butylperisobutyrate, tert-butylper-sec-octoate, tert-butylperpi Organic peroxides such as barate, cumyl perpivalate, tert-butyl perdiethyl acetate Azobisisobutyronitrile, azo compounds such as dimethyl azoisobutyrate, and the like. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (tert Dialkyl peroxides such as -butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferably used.

These radical initiators are usually 0.001 to 1 part by weight with respect to 100 parts by weight of the ethylene / α-olefin copolymer or ethylene / α-olefin / non-conjugated polyene copolymer before the graft modification, The amount is preferably 0.005 to 0.5 parts by weight, more preferably 0.01 to 0.3 parts by weight.

The reaction temperature in the grafting reaction using the radical initiator as described above or in the grafting reaction performed without using the radical initiator is usually set in the range of 60 to 350 ° C., preferably 150 to 300 ° C.

<Ethylene copolymer (E-2)>
The ethylene copolymer (E-2) can be obtained by copolymerizing ethylene, an α-olefin, a monomer having a functional group capable of reacting with an isocyanate group, and if necessary, a non-conjugated polyene.

As the α-olefin, an α-olefin having 3 to 20 carbon atoms is usually used. Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 2-butene, 1-pentene, 3- Methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1- Hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-hexadecene Examples include octadecene and 1-eicosene. Among these, ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene are exemplified. Among these, propylene, 1-butene, 4-methylpentene-1, 1-hexene and 1-octene are preferable, and propylene is more preferable. As the α-olefin, one kind may be used alone, or two or more kinds may be used.

Specific examples of the non-conjugated polyene copolymerized as needed include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1 , 4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 8-methyl-4-ethylidene-1,7-nonadiene, 4-ethylidene-1,7-undecadiene Chain non-conjugated dienes such as;
Methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene Cyclic non-conjugated dienes such as 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclopentadiene, norbornadiene;
2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, 4-ethylidene-8-methyl-1,7-nanodiene, etc. And triene.

The monomer having a functional group capable of reacting with an isocyanate group, which is used for obtaining the ethylene copolymer (E-2), usually has a carboxyl group or a group derived from the carboxyl group as a functional group capable of reacting with an isocyanate group. .

Examples of the monomer include polar group-containing monomers represented by the following general formula (Z).
CH ₂ = CH—R ⁵ —Z (Z)
In the above general formula (Z), R ⁵ is a hydrocarbon group such as a saturated or unsaturated aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, preferably a hydrocarbon having 1 to 20 carbon atoms. When the crosslinked ethylene copolymer (B) is obtained from the ethylene copolymer (E-2) and the isocyanate group-containing oligomer (Fx) described later, the Rc moiety of the general formula Ra or Corresponds to the Rd portion of the general formula Rb.

Examples of the saturated or unsaturated aliphatic hydrocarbon group include linear or branched hydrocarbon groups having 1 to 20 carbon atoms, and specifically include methylene, ethylene, trimethylene, methylethylene, tetramethylene. , Methyltrimethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptacamethylene, octadecamethylene, nonadeca Examples include methylene and icosamethylene.

As the alicyclic hydrocarbon group, a group having 3 to 20 carbon atoms having an alicyclic structure as a part of the structure is preferable, and specifically, cyclopropylene, cyclopentylene, cyclohexylene, cyclooctylene, and the like are included. Can be mentioned.

The aromatic hydrocarbon group is preferably a group having 6 to 20 carbon atoms having an aromatic ring in a part of its structure, specifically, —Ph—, —Ph—CH ₂ —, —Ph— (CH ₂ _{) 2 -, - Ph- (CH} 2) 3 -, - Ph- (CH 2) 6 -, - Ph- (CH 2) 10 -, - Ph- (CH 2) 11 -, - Ph- (CH 2 _{) 12 -, - Ph- (CH} 2) 14 - , and the like.

In the general formula (Z), Z represents a carboxyl group or a carboxylic anhydride group.

Specific examples of the polar group-containing monomer represented by the general formula (Z) include 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, 10 Ω-alkenylcarboxylic acids such as 2-undecenoic acid and 11-dodecenoic acid; 2-methyl-5-hexenoic acid, 2-methyl-6-heptenoic acid, 2-methyl-7-octenoic acid, 2-methyl-8-nonene Acid, 2-methyl-9-decenoic acid, 2-methyl-10-undecenoic acid, 2-methyl-11-dodecenoic acid, 2-ethyl-5-hexenoic acid, 2-ethyl-6-heptenoic acid, 2-ethyl -7-octenoic acid, 2-ethyl-8-nonenoic acid, 2-ethyl-9-decenoic acid, 2-ethyl-10-undecenoic acid, 2-propyl-5-hexenoic acid, 2-propyl-6-heptenoic acid 2-propyl-7-octenoic acid, 2-propyl-8-nonenoic acid, 2-propyl-9-decenoic acid, 2-propyl-10-undecenoic acid, 2-butyl-5-hexenoic acid, 2-butyl- 6-Heptenoic acid, 2-butyl-7-oct Alkenyl carboxylic acids in which the hydrocarbon moiety is linear, such as tennoic acid, 2-butyl-8-nonenoic acid, 2-butyl-9-decenoic acid, 2-butyl-10-undecenoic acid; 2-isopropyl-5- Hexenoic acid, 2-isopropyl-6-heptenoic acid, 2-isopropyl-7-octenoic acid, 2-isopropyl-8-nonenoic acid, 2-isopropyl-9-decenoic acid, 2-isopropyl-10-undecenoic acid, 2- Isobutyl-5-hexenoic acid, 2-t-butyl-6-heptenoic acid, 2-isopropyl-3-methyl-7-octenoic acid, 2-methyl-3-isopropyl-8-nonenoic acid, 3-isobutyl-3- General formulas such as alkenyl carboxylic acids having a branched hydrocarbon group such as methyl-9-decenoic acid, 2,2-dimethyl-10-undecenoic acid and 2,3,3-trimethyl-11-dodecenoic acid In the examples of the compound in which Z is a carboxyl group in (Z) and the compound in which Z is a carboxyl group, Such as the compounds obtained by replacing a cyclohexyl group to a carboxylic acid anhydride group, and Z is an acid anhydride group in the general formula (Z) and the like.

Examples of the monomer having a functional group capable of reacting with an isocyanate group other than the polar group-containing monomer represented by the general formula (Z) include a polar group represented by the following general formula (Z ′) and the general formula (W). Containing monomers can also be used.
CH ₂ = CH—R ⁶ —Z (Z ′)
_{^{CH 2 = CH-R 7 -}} (W) n ··· (W)
In the general formula (Z ′), R ⁶ is substituted with a carbonyl group such as a saturated or unsaturated aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group substituted with a carbonyl group. A hydrocarbon group, preferably a hydrocarbon group having 1 to 20 carbon atoms substituted with a carbonyl group, and Z represents a carboxyl group or a carboxylic anhydride group.

Specific examples of the polar group-containing monomer represented by the general formula (Z ′) include those represented by the following general formula (9).

In the general formula (W), R ⁷ is a carbonyl group such as a saturated or unsaturated aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, which may be substituted with a carbonyl group. An optionally substituted hydrocarbon group, preferably a hydrocarbon group having 1 to 20 carbon atoms, n represents 2 or 3, and W independently represents a carboxyl group or a carboxylic anhydride group.

Specific examples of the polar group-containing monomer represented by the general formula (W) include those represented by the following general formula (10).

The ethylene copolymer (E-2) can be obtained by copolymerizing a monomer having a functional group capable of reacting with ethylene, an α-olefin, and an isocyanate group, and if necessary, a non-conjugated polyene. Randomly combined. As the ethylene copolymer (E-2), the molar ratio ((α) :( β)) of the structural unit (α) derived from ethylene and the structural unit (β) derived from α-olefin is usually 40: 60 to 99: 1, preferably 50:50 to 90:10, more preferably 60:40 to 85:15.

Further, the molar ratio of the total amount of the structural unit derived from ethylene (α) and the structural unit derived from α-olefin (β) to the structural unit derived from a monomer having a functional group capable of reacting with an isocyanate group (γ) (( α) + (β) :( γ)) is usually 99.9: 0.1 to 50:50, preferably 99.5: 0.5 to 55:45.

When the ethylene copolymer (E-2) contains a structural unit derived from non-conjugated polyene, the iodine value is usually 0.1 to 30, preferably 0.1 to 25.

In the production of the ethylene copolymer (E-2), the α-olefin, the monomer having a functional group capable of reacting with an isocyanate group, and the non-conjugated polyene may be used alone or in combination of two or more. .

The ethylene copolymer (E-2) comprises (A) a transition metal compound selected from Groups 3 to 10 of the periodic table (Group 3 includes lanthanoids and actinoids), and (B) (B-1 Olefin polymerization catalyst comprising:) an organoaluminum oxy compound, (B-2) a compound that reacts with the compound (A) to form an ion pair, and (B-3) at least one compound selected from the organoaluminum compounds. In the presence of a monomer, the monomer having a functional group capable of reacting with ethylene, an α-olefin and an isocyanate group, and if necessary, a non-conjugated polyene is copolymerized.

In the production of the ethylene copolymer (E-2), the number of functional groups capable of reacting with the isocyanate group of the ethylene copolymer (E-2) is such that the ethylene copolymer (E-2) ) Of the monomer having a functional group capable of reacting with an isocyanate group so that it is usually 0.10 mmol / g or more, preferably 0.20 mmol / g or more, more preferably 0.30 mmol / g or more. Adjust usage. The upper limit of the number of functional groups is usually 2.0 mmol / g or less from the viewpoint of physical properties and moldability.

A cross-linked ethylene copolymer obtained by cross-linking the ethylene copolymer (E-2) produced under the conditions in which the number of functional groups falls within the above range using a cross-linking agent such as an isocyanate group-containing oligomer (F) described later. In the crosslinked thermoplastic elastomer composition (D) of the present invention, the coalesced (B) is excellent in dispersibility, excellent in thermal stability, and is excellent in oil resistance without coloring the resin when melted. Further, by using the crosslinked ethylene copolymer (B), a crosslinked thermoplastic elastomer composition (D) capable of providing a molded article having excellent mechanical strength can be obtained.

As the transition metal compound (A) used in the present invention, a known organometallic complex can be used in addition to the Ziegler-Natta catalyst and the metallocene catalyst. Preferred compounds as the transition metal compound (A) Examples include the following.

(In the formula, M ¹ represents a transition metal atom of Groups 3 to 10 of the periodic table, and R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ may be the same or different from each other. , Phosphorus-containing group, hydrocarbon group having 1 to 20 carbon atoms, halogenated hydrocarbon group having 1 to 20 carbon atoms, oxygen-containing group, sulfur-containing group, silicon-containing group, halogen atom, R ²⁵ , R Of the groups represented by ²⁶ , R ²⁷ and R ²⁸ , a part of the groups adjacent to each other may be linked to form a ring together with the carbon atom to which these groups are bonded, and X ¹ and X ² are May be the same as or different from each other, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a hydrogen atom or a halogen atom Y ¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms A divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, -O-, -CO-, -S-, _{-SO -, - SO 2 -,} - Ge -, - Sn -, - NR 21 -, - P (R 21) -, - P (O) (R 21) -, - BR 21 - or -AlR ²¹ - Wherein R ²¹ may be the same or different and is a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom or a halogen atom. .)

(Wherein, M ¹ is a transition metal atom selected from Group 3-10 of the periodic table, Cp represents a cyclopentadienyl group or its derivative bonded π to M ^1, Z ¹ is an oxygen atom, sulfur atom, a ligand containing a boron atom or a periodic table group 14 element, Y ¹ represents a ligand containing an atom selected from a nitrogen atom, phosphorus atom, oxygen atom and sulfur atom, X ¹ is May be the same as or different from each other, a hydrogen atom, a halogen atom, a hydrocarbon group containing up to 20 carbon atoms and optionally having one or more double bonds, up to 20 silicon atoms; A silyl group or a germanyl group containing a germanium atom is shown.)

(Wherein M ¹ represents a transition metal atom selected from Groups 3 to 10 of the periodic table, and R ¹¹ to R ¹⁴ , R ¹⁷ to R ²⁰ and R ⁴¹ may be the same or different from each other, and 1 to 40 hydrocarbon group, halogenated hydrocarbon group having 1 to 40 carbon atoms, oxygen-containing group, sulfur-containing group, silicon-containing group, halogen atom or hydrogen atom, R ¹¹ , R ¹² , R ¹³ , Of the groups represented by R ¹⁴ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ⁴¹ , a part of the groups adjacent to each other is linked to form a ring with the carbon atom to which these groups are bonded. X ¹ and X ² may be the same or different from each other, and are a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a hydrogen atom or a halogen atom, Y ¹ is TansoHara A divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, O -, - CO -, - S -, - SO -, - SO 2 -, - Ge -, - Sn -, - NR 21 -, - P (R 21) -, - P (O) (R 21) -, - BR ²¹ - or -AlR ²¹ - (provided that, R ²¹ may be the same or different from each other, a hydrocarbon group, halogenated hydrocarbon group of 1 to 20 carbon atoms having 1 to 20 carbon atoms, A hydrogen atom or a halogen atom.)

(Wherein M ¹ represents a transition metal atom selected from Groups 3 to 10 of the periodic table, and R ¹¹ , R ¹² , R ⁴¹ and R ⁴² may be the same as or different from each other and have 1 to 40 carbon atoms. Or a halogenated hydrocarbon group having 1 to 40 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom or a hydrogen atom, R ¹¹ , R ¹² , R ⁴¹ , R ⁴² Among the groups shown, a part of the groups adjacent to each other may be linked to form a ring together with the carbon atom to which these groups are bonded, and X ¹ and X ² may be the same or different from each other, A hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a hydrogen atom or a halogen atom, and Y ¹ represents the number of carbon atoms 1-20 divalent hydrocarbon groups (provided that R ¹¹ , R ^{1 2} , Y ¹ is not ethylene when R ⁴¹ and R ⁴² are all hydrogen atoms.), A divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, divalent Germanium-containing group, divalent tin-containing group, —O—, —CO—, —S—, —SO—, —SO ₂ —, —Ge—, —Sn—, —NR ²¹ —, —P (R ^{21) -, - P (O} ) (R 21) -, - BR 21 - and -AlR ²¹ - (However, R ²¹ may be the same or different from each other, a hydrocarbon group having 1 to 20 carbon atoms, A halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom or a halogen atom).

(Wherein M ¹ represents a transition metal atom selected from Groups 3 to 10 of the periodic table, R ⁴¹ and R ⁴² may be the same as or different from each other, and may be a hydrocarbon group having 1 to 40 carbon atoms, A halogenated hydrocarbon group having 1 to 40 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom or a hydrogen atom, and among the groups represented by R ⁴¹ and R ⁴² , A part thereof may be linked to form a ring together with the carbon atom to which these groups are bonded, and X ¹ and X ² may be the same as or different from each other, a hydrocarbon group having 1 to 20 carbon atoms, A halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a hydrogen atom or a halogen atom, Y ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, Divalent halogenation with 1 to 20 carbon atoms Hydrocarbon group, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, -O -, - CO -, - S -, - SO -, - SO 2 -, - Ge-, ^{-Sn -, - NR 21 -,} - P (R 21) -, - P (O) (R 21) -, - BR 21 - or -AlR ²¹ - (However, if R ²¹ is either the same or different from each other It is preferably a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom or a halogen atom.

The organoaluminum oxy compound (B-1) used in the present invention may be a conventionally known aluminoxane (also referred to as alumoxane), or a benzene-insoluble compound as exemplified in JP-A-2-78687. It may be an organoaluminum oxy compound. Furthermore, as an organoaluminum oxy compound, an organoaluminum oxy compound containing boron represented by the following general formula can be exemplified.

In the formula, R ⁸ represents a hydrocarbon group having 1 to 10 carbon atoms. R ⁹ may be the same as or different from each other, and represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.

As compound (B-2) (hereinafter sometimes referred to as “ionized ionic compound”) which forms an ion pair by reacting with the transition metal compound (A) used in the present invention, JP-A-1-501950 No. 1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP (US Patent) -5321106 Lewis acids, ionic compounds, borane compounds, and carborane compounds described in No. etc. Heteropoly compounds and isopoly compounds can also be mentioned.

Examples of the Lewis acid include magnesium-containing Lewis acid, aluminum-containing Lewis acid, and boron-containing Lewis acid. Among these, boron-containing Lewis acid is preferable. The ionic compound is a salt composed of a cationic compound and an anionic compound. The anion functions to cationize the transition metal compound by reacting with the transition metal compound and stabilize the transition metal cation species by forming an ion pair. Examples of such anions include organoboron compound anions, organoarsenic compound anions, organoaluminum compound anions, and the like, which are relatively bulky and stabilize the transition metal cation species. Such ionized ionic compounds can be used as a mixture of two or more.

The organoaluminum compound (B-3) used in the present invention is an aluminum compound substituted with a hydrocarbon group having 1 to 12 carbon atoms and / or a halogen atom, an alkoxy group, a siloxy group, an amide group or a hydrogen atom. is there. These organoaluminum compounds can be used in combination of two or more. The olefin polymerization catalyst used in the present invention is selected from the above transition metal compounds (A), organoaluminum oxy compounds (B-1), ionized ionic compounds (B-2), and organoaluminum compounds (B-3). When formed from at least one compound (B), for example, when the transition metal compound (A) is a transition metal compound containing a ligand having a cyclopentadienyl skeleton, the compound and an organoaluminum oxy compound ( B-1) and / or an ionized ionic compound (B-2) and, if necessary, an organoaluminum compound (B-3).

The olefin polymerization catalyst used in the present invention includes at least a transition metal compound (A), an organoaluminum oxy compound (B-1), an ionized ionic compound (B-2), and an organoaluminum compound (B-3). A solid catalyst in which one component is supported on a particulate carrier, a particulate carrier, a transition metal compound (A), an organoaluminum oxy compound (B-1) (or an ionized ionic compound (B-2) )) And an olefin polymer produced by prepolymerization and, if necessary, a prepolymerization catalyst comprising an organoaluminum compound (B-3).

The ethylene copolymer (E-2) is a monomer having a functional group capable of reacting with the ethylene, α-olefin and isocyanate group in the presence of the olefin polymerization catalyst as described above, and optionally a non-conjugated polyene. The polymerization conditions are usually as follows.

In the polymerization, the transition metal compound (A) is usually 0.00005 to 0.1 mmol, preferably 0.0001 to 0.05 mmol in terms of transition metal atoms per liter of polymerization volume. Used in quantity.

The organoaluminum oxy compound (B-1) is used in such an amount that the amount of aluminum atom is usually 1 to 10,000 mol, preferably 10 to 5,000 mol, per 1 mol of transition metal atom. The ionized ionic compound (B-2) is used in such an amount that the boron atom is usually 0.5 to 500 mol, preferably 1 to 100 mol, per 1 mol of the transition metal atom.

The organoaluminum compound (B-3) is used in an amount that is usually 0 to 200 mol, preferably 0 to 100 mol, based on 1 mol of aluminum atoms in the organoaluminum oxy compound (B-1). Used. The amount used is usually 0 to 1000 mol, preferably 0 to 500 mol, per 1 mol of boron in the ionized ionic compound (B-2).

When hydrogen is used, it is used in an amount of 10 ^-5 to 1 mol, preferably 10 ^-4 to 10 ^-1 mol, relative to 1 mol of the monomer to be polymerized. Copolymerization can be carried out by any of liquid phase polymerization methods such as suspension polymerization and solution polymerization, gas phase polymerization methods and high pressure methods. In the liquid phase polymerization method, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; benzene, toluene, Aromatic hydrocarbons such as xylene; inert hydrocarbon media such as halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane are used. Also, ethylene or α-olefin itself can be used as a solvent. These may be used in combination.

The polymerization temperature is usually in the range of −50 to 100 ° C., preferably 0 to 90 ° C. when the suspension polymerization method is performed, and is usually 0 to 300 when the solution polymerization method is performed. The temperature is preferably in the range of 20 ° C., preferably 20 to 250 ° C. When the gas phase polymerization method is carried out, the polymerization temperature is usually 0 to 120 ° C., preferably 20 to 100 ° C. In carrying out the high pressure method, the polymerization temperature is usually in the range of 50 to 1000 ° C., preferably 100 to 500 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 kg / cm ^{2. In} the case of the high pressure method, it is usually from 100 to 10,000 kg / cm ² , preferably from 500 to 5000 kg / cm 2. Condition ² The polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.

The molecular weight of the resulting ethylene copolymer (E-2) can be adjusted by adjusting the amount of hydrogen or changing the polymerization temperature and polymerization pressure.

<Ethylene / unsaturated carboxylic acid copolymer>
As the ethylene / unsaturated carboxylic acid copolymer, a copolymer obtained by copolymerizing at least ethylene and at least one unsaturated carboxylic acid is usually used. The copolymer has a carboxyl group or a carboxylic anhydride group derived from an unsaturated carboxylic acid. The ethylene / unsaturated carboxylic acid copolymer may be a copolymer obtained by copolymerizing ethylene, at least one unsaturated carboxylic acid and another monomer.

As the ethylene / unsaturated carboxylic acid copolymer, the constituent unit derived from the unsaturated carboxylic acid is preferably 1 to 30% by weight, more preferably 4 to 20% by weight with respect to 100% by weight of the copolymer. is there.

When the ethylene / unsaturated carboxylic acid copolymer has a constitutional unit derived from another monomer, the constitutional unit derived from the other monomer is usually based on 100% by weight of the copolymer. 30% by weight or less, preferably 10% by weight or less.

Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic anhydride, maleic acid monomethyl ester, maleic acid monoethyl ester, etc., and particularly acrylic acid or methacrylic acid. Acid is most preferred. The unsaturated carboxylic acid used for obtaining the ethylene / unsaturated carboxylic acid copolymer includes an acid anhydride of unsaturated carboxylic acid and an ester of unsaturated carboxylic acid.

Further, the above-mentioned other optional monomers include vinyl esters such as vinyl acetate and vinyl propionate, methyl acrylate, ethyl acrylate, isobutyl acrylate, nbutyl acrylate, 2-ethylhexyl acrylate, methacrylic acid. Examples thereof include unsaturated carboxylic acid esters such as methyl acid, isobutyl methacrylate and diethyl maleate, and carbon monoxide.

Ethylene / unsaturated carboxylic acid copolymer has a melt flow rate at 190 ° C. under a load of 2160 g according to ASTM D1238, usually 0.1 to 300 g / 10 min, preferably 0.5 to 100 g / 10 min. . Such an ethylene / unsaturated carboxylic acid copolymer is obtained by radical copolymerization of ethylene, an unsaturated carboxylic acid, and optionally other monomers under high temperature and high pressure, in the same manner as in the production of high-pressure polyethylene. Can be obtained by:

[Isocyanate group-containing oligomer (F)]
The isocyanate group-containing oligomer (F) has an amide group, an ester group, and two or more isocyanate groups, and an ethylene / α-olefin copolymer having a functional group capable of reacting with the isocyanate group, Functional groups capable of reacting with isocyanate groups of ethylene / α-olefin / non-conjugated polyene copolymers having functional groups capable of reacting with isocyanate groups, carboxyl groups and carboxylic acids possessed by ethylene / unsaturated carboxylic acid copolymers By reacting with the anhydride group, the crosslinked ethylene copolymer (B) is obtained. That is, the isocyanate group-containing oligomer (F) serves as a crosslinking agent for the ethylene copolymer (E).

The number average molecular weight calculated by gel permeation chromatography (GPC) of the isocyanate group-containing oligomer (F) is preferably more than 2000, more preferably 3000 or more, and particularly preferably 4000 or more. The number average molecular weight is usually 20000 or less and preferably 10,000 or less. When the number average molecular weight of the isocyanate group-containing oligomer (F) is within the above range, the cross-linked thermoplastic elastomer composition (D) is excellent in oil resistance and the production of the isocyanate group-containing oligomer (F) is easy. preferable.

The isocyanate group-containing oligomer (F) is particularly preferably represented by the following general formula Rx.

In the general formula Rx, n is preferably 0 to 3, and in the general formula R ₂ , m is more preferably 7 to 20.

(In the above general formula R ₂ , each R ₃ is independently an alkylene group having 1 to 15 carbon atoms or an aromatic group having 6 to 15 carbon atoms which may have a branch, and each R ₄ is independently And an optionally substituted alkylene group having 1 to 15 carbon atoms.)
In the general formula Rx, R ₁ and R ₂ are the same as R ₁ and R ₂ in the general formula Ra and Rb.

In the present invention, the isocyanate group-containing oligomer (F) represented by the general formula Rx, which is a preferred embodiment of the isocyanate group-containing oligomer (F), is also referred to as an isocyanate group-containing oligomer (Fx).

The isocyanate group-containing oligomer (F) is an isocyanate group-containing oligomer obtained by reacting a polyester polycarboxylic acid (G) produced from a polyhydric alcohol and a polyvalent carboxylic acid with a polyvalent isocyanate. And an isocyanate group-containing oligomer (hereinafter also referred to as an isocyanate group-containing oligomer (Fy)) characterized in that at least one of the polyhydric alcohol, polyvalent carboxylic acid and polyvalent isocyanate contains a trivalent or higher monomer. ) Is also preferred. The isocyanate group-containing oligomer (Fy) has at least three isocyanate groups at its terminals because at least one of polyhydric alcohol, polyvalent carboxylic acid and polyvalent isocyanate contains a trivalent or higher monomer as a raw material. Have. Therefore, the isocyanate group-containing oligomer (Fy) is excellent in crosslinking reactivity.

In the present invention, the isocyanate group-containing oligomer (F) can be obtained by reacting a terminal carboxyl group-containing oligomer with a polyvalent isocyanate such as diisocyanate.

The terminal carboxyl group-containing oligomer in the present invention is a polycarboxylic acid containing a carboxyl group at the molecular end and having a number average molecular weight of, for example, 200 to 20000, preferably 500 to 10,000. The number average molecular weight can be measured by gel permeation chromatography (GPC). In GPC measurement, the number average molecular weight of a peak including the molecular weight (retention time) of the maximum frequency of the measured chromatogram is calculated with reference to a calibration curve created using standard polyethylene glycol. Thereby, the number average molecular weight is calculated as a converted value of standard polyethylene glycol. In the terminal carboxyl group-containing oligomer, the viscosity at 80 ° C. measured with a cone plate viscometer is preferably 30000 mPa · s or less.

Examples of such terminal carboxyl group-containing oligomers include polyester polycarboxylic acid (G).

The polyester polycarboxylic acid (G) can be obtained, for example, by a reaction between a polyvalent carboxylic acid and a polyhydric alcohol. Examples of the polyvalent carboxylic acid include dicarboxylic acid.

Examples of dicarboxylic acids include oxalic acid, malonic acid, succinic acid, methyl succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and other aliphatic dicarboxylic acids (having 11 to 13 carbon atoms). , Hydrogenated dimer acid, maleic acid, fumaric acid, itaconic acid, orthophthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, dimer acid, dicarboxylic acid such as het acid, and alkyl esters of these dicarboxylic acids. In addition, since the alkyl ester of polycarboxylic acid such as dicarboxylic acid can react as a polyhydric alcohol in the same manner as polycarboxylic acid to obtain a polyester polycarboxylic acid (G), It is possible to use alkyl esters of divalent carboxylic acids.

Also, as the polyvalent carboxylic acid, a trivalent or higher polyvalent carboxylic acid having three or more carboxyl groups can be used.

These dicarboxylic acids and trivalent or higher polyvalent carboxylic acids can be used alone or in combination of two or more.

Examples of the polyhydric alcohol include diols having two hydroxyl groups.

Examples of the diol include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, and 3-methyl-1,5. -Pentanediol, 2,2-dimethyl-1,3-propanediol, neopentyl glycol, 1,6-hexanediol, 2,5-hexanediol, 2,2-diethyl-1,3-propanediol, 3, C2-22 alkanediols such as 3-dimethylolheptane, 2-ethyl-2-butyl-1,3-propanediol, 1,12-dodecanediol, 1,18-octadecanediol, such as 2-butene-1, 4-diol, 2,6-dimethyl-1-octene-3,8-diol, etc. Aliphatic diols such as alkene diol.

Examples of the diol include alicyclic diols such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A or its C2-4 alkylene oxide adduct.

Examples of the diol include aromatic diols such as resorcin, xylylene glycol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, bisphenol A, bisphenol S, bisphenol F, and C2-4 alkylene oxide adducts of these bisphenols. It is done.

Furthermore, examples of the diol include polyether diols such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polyethylene polypropylene block glycol, and polytetramethylene ether glycol.

Also, as the polyhydric alcohol, a trihydric or higher polyhydric alcohol having three or more hydroxyl groups can be used.

Examples of the trihydric or higher polyhydric alcohol include glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, Such as trimethylolethane, trimethylolpropane, 2,4-dihydroxy-3- (hydroxymethyl) pentane, 2,2-bis (hydroxymethyl) -3-butanol and other aliphatic triols (8 to 24 carbon atoms) Examples include triols such as polyols having four or more hydroxyl groups such as pentaerythritol, dipentaerythritol, D-sorbitol, xylitol, and D-mannitol.

These polyhydric alcohols can be used alone or in combination of two or more. As the polyhydric alcohol, a diol is preferable.

In addition, the polyester polycarboxylic acid obtained by reaction of dicarboxylic acid and diol is also described as polyester dicarboxylic acid.

The polyester polycarboxylic acid (G) is a mixture of polyvalent carboxylic acid and polyhydric alcohol, in which the acid group (carboxyl group, carboxylic acid ester) of the polyvalent carboxylic acid is in excess of the hydroxyl group of the polyhydric alcohol ( It can be obtained by blending at a ratio of COOH / OH exceeding 1.0 (preferably a ratio of 1.01 to 2.10) and subjecting them to an esterification reaction.

The esterification reaction is, for example, a condensation reaction or a transesterification reaction, and may be under known conditions. For example, an atmospheric pressure and an inert gas atmosphere are used, the reaction temperature is 100 to 250 ° C., and the reaction time is 1 to 50. It's time. In the esterification reaction, a catalyst (an organic tin catalyst, an organic titanium catalyst, an amine catalyst, an alkali metal salt or an alkaline earth metal salt described later), a solvent, or the like can be used as necessary.

The polyester polycarboxylic acid (G) thus obtained has a number average molecular weight of usually 200 to 20000, preferably 500 to 10,000. The acid value of the polyester polycarboxylic acid (G) is usually 5 to 500 mgKOH / g, preferably 10 to 250 mgKOH / g, and the hydroxyl value of the polyester polycarboxylic acid (G) is usually 5 mgKOH. / G or less, preferably 3 mgKOH / g or less.

As the terminal carboxyl group-containing oligomer, the polyester polycarboxylic acid (G) can be used alone or in combination of two or more.

In the present invention, the isocyanate group-containing oligomer (F) can be obtained by reacting the terminal carboxyl group-containing oligomer with a polyvalent isocyanate. Examples of the polyvalent isocyanate include diisocyanates and trivalent or higher polyvalent isocyanates. Polyvalent isocyanate can be used.

Examples of the diisocyanate to be reacted with the terminal carboxyl group-containing oligomer include aliphatic diisocyanate, alicyclic diisocyanate, araliphatic diisocyanate, and aromatic diisocyanate.

Examples of the aliphatic diisocyanate include hexamethylene diisocyanate (HDI), trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-, 2,3- or 1,3-butylene diisocyanate. And aliphatic diisocyanates such as 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate and 2,6-diisocyanatomethylcaproate.

Examples of alicyclic diisocyanates include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4,4'-, 2,4'- or 2,2'-dicyclohexylmethane. Diisocyanate or mixtures thereof (H ₁₂ MDI), 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or mixtures thereof (hydrogenated xylylene diisocyanate, H ₆ XDI), 2,5- or 2,6- Bis (isocyanatomethyl) norbornane or a mixture thereof (NBDI), 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2, And alicyclic diisocyanates such as 6-cyclohexane diisocyanate.

Examples of the araliphatic diisocyanate include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof (XDI), 1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof (TMXDI), ω , Ω'-diisocyanato-1,4-diethylbenzene, and the like.

Aromatic diisocyanates include, for example, 4,4′-, 2,4′- or 2,2′-diphenylmethane diisocyanate or mixtures thereof (MDI), 2,4- or 2,6-tolylene diisocyanate or mixtures thereof ( TDI), 3,3′-dimethoxybiphenyl-4,4′-diisocyanate, 1,5-naphthalene diisocyanate (NDI), m- or p-phenylene diisocyanate or mixtures thereof, 4,4′-diphenyl diisocyanate, 4,4 And aromatic diisocyanates such as' -diphenyl ether diisocyanate.

In addition, the diisocyanate includes the above-described diisocyanate multimers (for example, dimers, trimers, etc.), biuret-modified products produced by the reaction of the above diisocyanates or multimers with water, alcohols (one Allophanate-modified products produced by reaction with polyhydric alcohols or polyhydric alcohols), oxadiazine trione-modified products produced by reaction with carbon dioxide, or polyol-modified products produced by reaction with the above-mentioned polyhydric alcohols, etc. Is included. In addition, diisocyanates include sulfur-containing diisocyanates such as phenyl diisothiocyanate.

Further, as the polyvalent isocyanate, a trivalent or higher polyvalent isocyanate having three or more isocyanate groups can be used. As the trivalent or higher polyvalent isocyanate, polymeric MDI (polymethylene polyphenyl polyisocyanate) (for example, Cosmonate series manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.) containing a polynuclear body of three or more nuclei of MDI is suitable. Can be used for Polymeric MDI is a mixture containing trivalent or higher polyvalent isocyanate (polynuclear MDI trinuclear or higher) and usually also divalent isocyanate (MDI).

These polyisocyanates such as diisocyanates can be used alone or in combination of two or more. From the viewpoint of easy control of side reactions, the polyvalent isocyanate preferably contains at least a diisocyanate, and it is preferable to use an aliphatic diisocyanate, an alicyclic diisocyanate, or an araliphatic diisocyanate.

The isocyanate group-containing oligomer (F) comprises a terminal carboxyl group-containing oligomer and a polyisocyanate such as diisocyanate, and the isocyanate group of the polyvalent isocyanate such as diisocyanate is excessive with respect to the carboxyl group of the terminal carboxyl group-containing oligomer. (A ratio in which NCO / COOH exceeds 1.0, preferably a ratio of 1.05 to 2.50) and amidation reaction thereof.

When the equivalent ratio of NCO / COOH is in the above range, production can be stabilized. On the other hand, when the equivalent ratio of NCO / COOH is 1.00 or less, the isocyanate group content of the isocyanate group-containing oligomer (F) decreases, and the crystalline olefin polymer (A) can react with the isocyanate group. Selected from the group consisting of ethylene / α-olefin copolymers having functional groups, ethylene / α-olefin / nonconjugated polyene copolymers having functional groups capable of reacting with isocyanate groups, and ethylene / unsaturated carboxylic acid copolymers. It may take a long time to react with the mixture with at least one ethylene copolymer (E) or may not be able to react completely. On the other hand, if the equivalent ratio of NCO / COOH is too high, the residual amount of diisocyanate contained as an impurity in the isocyanate group-containing oligomer (F) increases, and this ethylene / α-olefin having a functional group capable of reacting with the isocyanate group At least one ethylene copolymer selected from the group consisting of copolymers, ethylene / α-olefin / non-conjugated polyene copolymers having functional groups capable of reacting with isocyanate groups, and ethylene / unsaturated carboxylic acid copolymers It may react with the union (E) and cause deterioration of physical properties and moldability.

The amidation reaction is not particularly limited. For example, in the presence of a catalyst, the reaction temperature is 120 ° C. or lower, preferably 40 to 120 ° C., more preferably 40 to 100 ° C., and the reaction time is 0.5 to 50 hours. The reaction is preferably carried out for 1 to 15 hours.

The catalyst is preferably an alkali metal salt or an alkaline earth metal salt. Examples of the alkali metal salt include lithium fluoride, lithium chloride, lithium hydroxide, sodium fluoride, sodium chloride, sodium hydroxide, potassium fluoride, potassium chloride, and potassium hydroxide. Examples of the alkaline earth metal salt include calcium stearate, calcium perchlorate, calcium chloride, calcium hydroxide, magnesium stearate, magnesium perchlorate, magnesium chloride, magnesium hydroxide and the like. A catalyst can be used individually or can use 2 or more types together. Preferably, from the viewpoint of amide selectivity in the amidation reaction, calcium stearate, calcium perchlorate, magnesium stearate, and magnesium perchlorate are preferable, and magnesium stearate is more preferable.

Further, the catalyst is added, for example, in a ratio of 0.001 to 10 mol parts, preferably 0.005 to 2 mol parts, relative to 100 mol parts of all carboxyl groups of the terminal carboxyl group-containing oligomer. If the addition ratio of the catalyst is less than this, the amidation reaction does not proceed sufficiently and the productivity may be lowered. On the other hand, at more than this, the amide selectivity of the amidation reaction does not change, which may be economically disadvantageous.

Also, when the reaction temperature is within the above range, production can be stabilized. On the other hand, when the reaction temperature exceeds 120 ° C., side reactions of isocyanate groups are promoted, and the isocyanate group content may be lower than the theoretical value, resulting in an increase in the viscosity of the resulting resin. Therefore, it is selected from the group consisting of an ethylene / α-olefin copolymer having a functional group capable of reacting with an isocyanate group and an ethylene / α-olefin / non-conjugated polyene copolymer having a functional group capable of reacting with an isocyanate group. The reactivity with at least one ethylene copolymer (E) may decrease. On the other hand, if the reaction temperature is too low, the reaction between the carboxyl group of the terminal carboxyl group-containing oligomer and the isocyanate group of a polyvalent isocyanate such as diisocyanate does not proceed sufficiently, and the productivity may decrease.

The amidation reaction can be preferably carried out under normal pressure, but it can also be carried out under reduced pressure while removing carbon dioxide generated during the reaction. Further, the amidation reaction can be carried out under pressure using carbon dioxide generated during the reaction. You can also

In the amidation reaction, the isocyanate group decomposes when it reacts with water (such as moisture in the air). Therefore, this reaction is preferably carried out in an inert gas atmosphere in order to avoid contact with moisture in the air. As an inert gas, nitrogen gas, helium gas, etc. are mentioned, for example, Preferably nitrogen gas is mentioned.

In the amidation reaction, a solvent can be used if necessary.

In the amidation reaction, a terminal carboxyl group-containing oligomer, a polyisocyanate such as diisocyanate, and a catalyst may be mixed at once, or a terminal carboxyl group-containing oligomer and a polyisocyanate such as diisocyanate are mixed in advance, A catalyst can also be mixed.

In the amidation reaction, a terminal carboxyl group-containing oligomer and a catalyst may be mixed in advance, and the mixture may be mixed with a polyvalent isocyanate such as diisocyanate, or a polyvalent isocyanate such as diisocyanate and a catalyst may be mixed in advance. The mixture and the terminal carboxyl group-containing oligomer can also be mixed.

In addition, when using hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide as a catalyst, mixing the terminal carboxyl group-containing oligomer and hydroxide, React to produce water. Therefore, in this case, after mixing, after removing moisture by dehydration, it is necessary to mix the mixture and a polyvalent isocyanate such as diisocyanate. Thereby, decomposition | disassembly of the isocyanate group by the produced | generated water can be suppressed.

The above reaction can also be carried out stepwise. For example, as the first stage, an isocyanate group-containing oligomer is synthesized by reacting a terminal carboxyl group-containing oligomer and a polyvalent isocyanate such as diisocyanate at an NCO / COOH equivalent ratio of less than 1.0. Next, as the second stage, the isocyanate group-containing oligomer obtained in the first stage and the polyvalent isocyanate of a type different from the polyvalent isocyanate used in the first stage are finally converted into an NCO / COOH equivalent ratio of 1.0. Is reacted so that the isocyanate group-containing oligomer (F) is obtained. By synthesizing the isocyanate group-containing oligomer (F) in this way, it is possible to obtain resins in which structural units derived from polyisocyanates such as diisocyanate are different at the molecular ends and in the molecules. In the two-stage reaction, the catalyst may be added to the first stage, may be added to the second stage, or may be added to both the first stage and the second stage.

The isocyanate group-containing oligomer (F) thus obtained has an isocyanate group content of 90 to 110%, preferably 95 to 105% of the calculated value from the blending ratio. When the isocyanate group content is within the above range, an ethylene / α-olefin copolymer having a functional group capable of reacting with an isocyanate group, and an ethylene / α-olefin / non-conjugated polyene copolymer having a functional group capable of reacting with an isocyanate group. Reactivity with at least one ethylene copolymer (E) selected from the group consisting of a polymer and an ethylene / unsaturated carboxylic acid copolymer is good. Therefore, the obtained cross-linked thermoplastic elastomer composition (D) of the present invention is excellent in physical properties and moldability. In addition, the carboxyl group amidation rate of the terminal carboxyl group-containing oligomer in producing the isocyanate group-containing oligomer (F) is usually 76 to 100%, preferably 86 to 100%. When the amidation rate is in the above range, excellent physical properties and moldability can be obtained.

As the isocyanate group-containing oligomer (F), it is preferable to use an isocyanate group-containing oligomer (Fx) or an isocyanate group-containing oligomer (Fy).

When an isocyanate group-containing oligomer (Fx) is used, an oligomer of a diol and a dicarboxylic acid represented by the following general formula Ry is used as the terminal carboxyl group-containing oligomer.

Incidentally, m, R ₃ and R ₄ are the same as m, and R ₃ and R ₄ in the above R _2. Wherein R ₃ is the residue of a carboxylic acid HOOC-R ₃ -COOH structure, represented by the following general formula (5) or (5 ') Specific examples of the carboxylic acid HOOC-R ₃ -COOH structure Is preferred. Also, the R ₄ is the residue of a diol HO-R ₄ -OH structure is preferably represented by the following general formula (6) Specific examples of diols HO-R ₄ -OH structure.

The isocyanate group-containing oligomer (Fx) can be obtained by reacting a diisocyanate with an oligomer of a diol represented by the Ry formula and a dicarboxylic acid. The structure of the diisocyanate is represented by OCN—R ₁ —. In the case of NCO, R ₁ may have a branched alkylene group having 2 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, and an alicyclic hydrocarbon group having 6 carbon atoms. From the viewpoint of economy, it is preferably at least one group selected from the group consisting of ˜20 divalent hydrocarbon groups. A specific example of the diisocyanate having an OCN—R ₁ —NCO structure is preferably represented by the following general formula (7).

The isocyanate group-containing oligomer (Fy) is obtained by reacting a polyisocyanate with a polyester polycarboxylic acid (G) produced from a polyhydric alcohol and a polyvalent carboxylic acid. When the isocyanate group-containing oligomer (Fy) is produced, as described above, at least one of the polyhydric alcohol, polyvalent carboxylic acid and polyvalent isocyanate contains a trivalent or higher monomer. That is, as the trivalent or higher monomer contained, any of the polyhydric alcohol, polyvalent carboxylic acid, and polyvalent isocyanate may contain a trivalent or higher monomer. Further, among the polyhydric alcohol, polyvalent carboxylic acid, and polyvalent isocyanate, a plurality of components may be trivalent or higher.

As the isocyanate group-containing oligomer (Fy), for example, an oligomer of a diol and a dicarboxylic acid represented by the general formula Ry is reacted with a polyvalent isocyanate containing a trivalent or higher polyvalent isocyanate such as polymeric MDI. What is obtained is mentioned.

[Polyester polycarboxylic acid (G) and polyvalent isocyanate]
There is no limitation in particular as polyester polycarboxylic acid (G), Polyester polycarboxylic acid (G) can be obtained by reaction of polyhydric carboxylic acid and polyhydric alcohol, for example. Examples of the polyvalent carboxylic acid include dicarboxylic acid.

Examples of the polyhydric alcohol include diols having two hydroxyl groups.

The polyester polycarboxylic acid (G) thus obtained has a number average molecular weight of usually 200 to 20000, preferably 500 to 10,000. The number average molecular weight can be measured by gel permeation chromatography (GPC). In GPC measurement, the number average molecular weight of a peak including the molecular weight (retention time) of the maximum frequency of the measured chromatogram is calculated with reference to a calibration curve created using standard polyethylene glycol. Thereby, the number average molecular weight is calculated as a converted value of standard polyethylene glycol. The acid value of the polyester polycarboxylic acid (G) is usually 5 to 500 mgKOH / g, preferably 10 to 250 mgKOH / g, and the hydroxyl value of the polyester polycarboxylic acid (G) is usually 5 mgKOH. / G or less, preferably 3 mgKOH / g or less. The polyester polycarboxylic acid (G) has a viscosity at 80 ° C. measured with a cone plate viscometer, preferably 30000 mPa · s or less.

Polyester polycarboxylic acid (G) can be used alone or in combination of two or more.

As the polyester polycarboxylic acid (G), an oligomer of a diol and a dicarboxylic acid represented by the following general formula Ry is preferably used.

The polyisocyanate is not particularly limited, and diisocyanate or trivalent or higher polyvalent isocyanate can be used.

Examples of the diisocyanate include aliphatic diisocyanate, alicyclic diisocyanate, araliphatic diisocyanate, and aromatic diisocyanate.

In addition, the diisocyanate includes the above-described diisocyanate multimers (for example, dimers, trimers, etc.), biuret-modified products produced by the reaction of the above diisocyanates or multimers with water, alcohols, or the above The allophanate modified body produced | generated by reaction with the produced polyhydric alcohol, the oxadiazine trione modified body produced | generated by reaction with a carbon dioxide gas, or the polyol modified body produced | generated by reaction with the above-mentioned polyhydric alcohol etc. are contained. In addition, diisocyanates include sulfur-containing diisocyanates such as phenyl diisothiocyanate.

These polyisocyanates such as diisocyanates can be used alone or in combination of two or more. From the viewpoint of easy control of the side reaction, at least diisocyanate is preferably used as the polyvalent isocyanate, and aliphatic diisocyanate, alicyclic diisocyanate, and araliphatic diisocyanate are preferably used.

When the structure of the diisocyanate is OCN—R ₁ —NCO, R ₁ may be an alkylene group having 2 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, and an aliphatic group. From the viewpoint of economy, it is preferably at least one group selected from the group consisting of a C 6-20 divalent hydrocarbon group having a cyclic hydrocarbon group. A specific example of the diisocyanate having an OCN—R ₁ —NCO structure is preferably represented by the following general formula (7).

In the case of obtaining the crosslinked ethylene copolymer (B) by crosslinking the ethylene copolymer (E) using the polyester polycarboxylic acid (G) and the polyvalent isocyanate as the crosslinking agent, the polyvalent isocyanate is used. However, it is preferable to contain a polyvalent isocyanate having three or more valences.

The crosslinked ethylene copolymer (B) used in the present invention is a polymer usually obtained by crosslinking the ethylene copolymer (E), preferably using the ethylene copolymer (E) as a crosslinking agent. Crosslinking is performed using an isocyanate group-containing oligomer (F) having an amide group, an ester group, and two or more isocyanate groups, or using a polyester polycarboxylic acid (G) and a polyvalent isocyanate as a crosslinking agent. Can be obtained.

That is, as an embodiment of the crosslinked ethylene copolymer (B) used in the present invention, it is obtained by crosslinking the ethylene copolymer (E) with the isocyanate group-containing oligomer (F). In this embodiment, the functional group capable of reacting with the isocyanate group of the ethylene copolymer (E) reacts with the isocyanate group of the isocyanate group-containing oligomer (F) to form a crosslinking site (C).

Moreover, as another aspect of the crosslinked ethylene copolymer (B) used for this invention, the functional group which can react with the isocyanate group which ethylene copolymer (E) has, and the carboxyl group which polyester polycarboxylic acid (G) has, The isocyanate group of the polyvalent isocyanate reacts to form a cross-linked site (C).

In the present invention, after producing the crosslinked ethylene copolymer (B), the crosslinked thermoplastic elastomer composition (D) may be obtained by mixing with the crystalline olefin polymer (A). From the viewpoint of dispersibility between the olefin polymer (A) and the crosslinked ethylene copolymer (B), the crosslinked thermoplastic elastomer composition (D) of the present invention comprises the crystalline olefin polymer (A) and the above-mentioned The isocyanate group-containing oligomer (F) is introduced into the mixture with the ethylene copolymer (E) as a crosslinking agent, or the polyester polycarboxylic acid (G) and the polyvalent isocyanate are introduced as a crosslinking agent. It is preferable to produce the union (E) by dynamic crosslinking.

[Crosslinked thermoplastic elastomer composition (D)]
The cross-linked thermoplastic elastomer composition (D) of the present invention contains the crystalline olefin polymer (A) and the cross-linked ethylene copolymer (B).

The crosslinkable thermoplastic elastomer composition (D) may contain a softener as a fluidity or hardness adjusting agent.

Specific examples of softeners include petroleum-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, polyethylene wax, polypropylene wax, petroleum asphalt, and petroleum jelly.
Coal tar softeners such as coal tar and coal tar pitch;
Fatty oil softeners such as castor oil, linseed oil, rapeseed oil, soybean oil, coconut oil;
Tall oil;
Sub, (Factis);
Waxes such as beeswax, carnauba wax, lanolin;
Fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate, zinc laurate;
Naphthenic acid;
Pine oil, rosin or derivatives thereof;
Synthetic polymer materials such as terpene resin, petroleum resin, coumarone indene resin, atactic polypropylene;
Ester softeners such as dioctyl phthalate, dioctyl adipate, dioctyl sebacate;
Examples thereof include microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, liquid polyisoprene, terminal-modified polyisoprene, hydrogenated terminal-modified polyisoprene, liquid thiocol, and hydrocarbon-based synthetic lubricating oil. Of these, petroleum softeners are preferable, and process oil is more preferably used.

The blending amount of the softener in the crosslinked thermoplastic elastomer composition (D) is usually 0 when the total of the crystalline olefin polymer (A) and the crosslinked ethylene copolymer (B) is 100 parts by weight. The range of ˜60 parts by weight, preferably 0 to 50 parts by weight is preferred.

When a softening agent is added to the crosslinked thermoplastic elastomer composition (D), a softening agent is added to the mixture of the crystalline olefin polymer (A) and the ethylene copolymer (E). Alternatively, a softener may be blended in the mixture of the crystalline olefin polymer (A) and the crosslinked ethylene copolymer (B). Moreover, you may mix | blend a softener with at least one of a crystalline olefin polymer (A) and an ethylene copolymer (E) previously.

In addition, the cross-linked thermoplastic elastomer composition (D) according to the present invention contains additives such as slip agents, fillers, antioxidants, weathering stabilizers, colorants, compatibilizers, and the like as necessary. You may mix | blend in the range which does not impair the objective of invention.

Such an additive may be blended in the production process of the cross-linked thermoplastic elastomer composition (D), and is added to the mixture of the crystalline olefin polymer (A) and the cross-linked ethylene copolymer (B). You may mix | blend.

Examples of the slip agent include fatty acid amide, silicone oil, glycerin, wax, and paraffinic oil.

Examples of the filler include conventionally known fillers, specifically, carbon black, clay, talc, calcium carbonate, kaolin, diatomaceous earth, silica, alumina, graphite, glass fiber, and the like.

Examples of the compatibilizing agent include ethylene / ethylene glycol copolymers and propylene / ethylene glycol copolymers.

In the crosslinked thermoplastic elastomer composition (D), the amount of the compatibilizing agent is usually 100 parts by weight when the total of the crystalline olefin polymer (A) and the crosslinked ethylene copolymer (B) is 100 parts by weight. The range of 0 to 30 parts by weight, preferably 0 to 20 parts by weight is preferred.

The cross-linked thermoplastic elastomer composition (D) is preferably a mixture of the crystalline olefin polymer (A) and the ethylene copolymer (E), an amide group, an ester group, Introducing an isocyanate group-containing oligomer (F) having one or more isocyanate groups or introducing a polyester polycarboxylic acid (G) and a polyvalent isocyanate as a crosslinking agent to dynamically crosslink an ethylene copolymer (E) Can be obtained. In the crosslinked thermoplastic elastomer composition (D) thus obtained, the sea phase is the crystalline olefin polymer (A), and at least a part of the island phase is the crosslinked ethylene copolymer (B). It is preferable to form a sea-island structure. A molded body formed from the cross-linked thermoplastic elastomer composition (D) that forms a sea-island structure is preferable because of its excellent physical properties and moldability.

As described above, the cross-linked thermoplastic elastomer composition (D) preferably forms a sea-island structure, but the island phase may be at least partly a cross-linked ethylene copolymer. You may have the island phase formed. Examples of the island phase formed from other components include an island phase formed from an isocyanate group-containing oligomer (F), an island phase formed from a polyester polycarboxylic acid (G) and a polyvalent isocyanate.

The weight ratio (A / B) between the crystalline olefin polymer (A) and the crosslinked ethylene copolymer (B) contained in the crosslinked thermoplastic elastomer composition (D) is usually 10 / It is 90 to 50/50, preferably 15/85 to 45/55, and more preferably 20/80 to 40/60. Within the above range, it is preferable because of excellent physical properties and moldability.

In addition, isocyanate group containing oligomer (F) was introduce | transduced into a mixture of a crystalline thermoplastic olefin polymer (A) and a copolymer of a crystalline olefin polymer (A) and an ethylene copolymer (E) as a crosslinking agent. When obtained by dynamically crosslinking the ethylene copolymer (E), the amount of the crosslinked ethylene copolymer (B) is determined from the amount of the ethylene copolymer (E) and the isocyanate group-containing oligomer (F). Is calculated. Further, when the polyester copolymer (G) and the polyvalent isocyanate are introduced as a crosslinking agent and the ethylene copolymer (E) is dynamically crosslinked, the ethylene copolymer (E), The amount of the crosslinked ethylene copolymer (B) is calculated from the amount of the polyester polycarboxylic acid (G) and the polyvalent isocyanate.

The cross-linked thermoplastic elastomer composition (D) of the present invention forms a sea-island structure in which the sea phase is a crystalline olefin polymer (A) and at least a part of the island phase is a cross-linked ethylene copolymer (B). It is preferable to do. The observation that the crosslinked thermoplastic elastomer composition (D) forms a sea-island structure can be performed by TEM observation of the obtained crosslinked thermoplastic elastomer composition (D). As a pretreatment for observing the sea-island structure of the crosslinked thermoplastic elastomer composition (D), the crosslinked thermoplastic elastomer composition (D) is subjected to trimming and used as a sample, and then the sample is stained with RuO ₄ . Then, an ultrathin section was prepared from the frozen sample, and carbon reinforcement was performed to obtain a measurement sample.

In general, it is known that crystalline polyolefin is difficult to be colored by dyeing with RuO ₄ , and when the sea phase is lighter than the island phase, the sea phase is a crystalline olefin polymer (A). It can be confirmed that at least a part of the island phase is the crosslinked ethylene copolymer (B).

In addition, when the island phase has an island phase formed from other components other than the crosslinked ethylene copolymer (B), two or more types of island phases having different color densities (shades) are present. Observed. In such a case, the degree of coloring varies depending on the structure, type and degree of crosslinking. Accordingly, at least one of the dark island phases is the crosslinked ethylene copolymer (B).

In the examples described later, all the TEM images obtained by TEM observation of the crosslinked thermoplastic elastomer composition (D) are less dyed than the island phase in the sea phase, and the sea phase is a crystalline olefin polymer. (A), and it was confirmed that at least a part of the island phase was a crosslinked ethylene copolymer (B).

Moreover, the mixture obtained by melt-kneading the crystalline olefin polymer (A) and the ethylene copolymer (E) in advance under a nitrogen stream is similar to the above-mentioned crosslinked thermoplastic elastomer composition (D). The sea-island structure can also be confirmed when performing TEM observation.

In Examples to be described later, in the TEM image obtained by TEM observation of the mixture of (A) and (E), the island phase was less stained than the sea phase. That is, as described above, since the crystalline polyolefin is difficult to be colored by dyeing with RuO ₄ , the island phase is crystalline olefin in the mixture of the crystalline olefin polymer (A) and the ethylene copolymer (E). It was a polymer (A) and the sea phase was judged to be an ethylene copolymer (E).

From the above, an isocyanate group-containing oligomer (F) is introduced as a crosslinking agent into a mixture of the crystalline olefin polymer (A) and the ethylene copolymer (E), or a polyester polycarboxylic acid as a crosslinking agent. It was found that the sea-island phase was reversed by introducing (G) and a polyvalent isocyanate and dynamically crosslinking the ethylene copolymer (E).

Further, the cross-linked thermoplastic elastomer composition (D) of the present invention preferably has a melt processing temperature of 200 ° C. or higher.

The cross-linked thermoplastic elastomer composition (D) of the present invention has excellent oil resistance because the cross-linked site (C) of the cross-linked ethylene copolymer (B) has hydrophilicity. In addition, since it has mechanical properties equivalent to those of conventional cross-linked thermoplastic elastomer compositions, it can be used as a modifier for engineering plastics used in various molded products and automobile parts.

For oil resistance, a test piece of 20 mm × 20 mm × 2 mm was prepared from a 2 mm thick sheet obtained by press-molding the crosslinked thermoplastic elastomer composition (D) at 200 ° C., and then applied to JIS No. 3 oil at 70 ° C. for 72 hours. The weight change rate ΔV can be calculated from the weight before and after the immersion according to the formula (I).
{(Tw−Td) / Td} × 100 = ΔV (I)
(In Formula (I), Tw is the weight of the test piece after immersion, and Td is the weight of the test piece before immersion.)
The weight change rate ΔV determined by the above formula (I) of the crosslinked thermoplastic elastomer composition (D) is usually 100 to 1%, preferably 50 to 1%.

The cross-linked thermoplastic elastomer composition (D) of the present invention is excellent in hardness. Specifically, the Shore A hardness measured according to JIS K6253 of the crosslinked thermoplastic elastomer composition (D) is usually 100 to 60, preferably 95 to 60.

Further, the crosslinked thermoplastic elastomer composition (D) of the present invention has mechanical properties equivalent to those of the conventional crosslinked thermoplastic elastomer composition. In accordance with JIS K6251 of the cross-linked thermoplastic elastomer composition (D), the tensile strength and elongation at break when the tensile test was performed under the following conditions are usually 8 MPa or more and 300% or more, Preferably, it is 10 MPa or more and 500% or more. The tensile test was performed by using the cross-linked thermoplastic elastomer composition (D) to produce a sheet with a press molding machine, punching out a JIS No. 3 test piece, and using the test piece under a tensile speed of 500 mm / min. Do.

[Method for Producing Crosslinked Thermoplastic Elastomer Composition (D)]
Hereinafter, a typical method for producing the crosslinked thermoplastic elastomer composition (D) will be described. A typical production method of the crosslinked thermoplastic elastomer composition (D) is that an isocyanate group-containing oligomer (as a crosslinking agent) is added to the mixture of the crystalline olefin polymer (A) and the ethylene copolymer (E). It is characterized in that F) is introduced or a polyester polycarboxylic acid (G) and a polyvalent isocyanate are introduced as a crosslinking agent to dynamically crosslink the ethylene copolymer (E).

When the crystalline olefin polymer (A) and the ethylene copolymer (E) are mixed to obtain a mixture, it is preferable to knead in a non-open type apparatus. Moreover, when obtaining a mixture, it is preferable to carry out in inert gas atmosphere, such as nitrogen and a carbon dioxide gas.

The kneading temperature at the time of kneading is equal to or higher than the temperature at which the crystalline olefin polymer (A) can be sufficiently melted, and when the ethylene copolymer (E) has a carboxyl group, the adjacent carboxyl group is dehydrated, The temperature is usually 170 to 280 ° C., preferably 190 to 240 ° C., in order to completely close the ring to form a carboxylic acid anhydride group. The kneading time for kneading is usually 1 to 20 minutes, preferably 1 to 10 minutes. Moreover, the shear forces exerted in performing kneading, 10 ~ 100,000sec ^-1 as the shear rate is preferably 100 ~ 50,000sec ^-1.

As the kneading apparatus, a mixing roll, an intensive mixer (for example, a Banbury mixer, a kneader), a single-screw or twin-screw extruder can be used, and a non-open type apparatus is preferable. Experimentally, it may be a lab plast mill.

In the method for producing a crosslinked thermoplastic elastomer composition (D), the crystalline olefin polymer (A) obtained by mixing the crystalline olefin polymer (A) and the ethylene copolymer (E). ) And an ethylene copolymer (E), an isocyanate group-containing oligomer (F) is introduced as a crosslinking agent, or a polyester polycarboxylic acid (G) and a polyvalent isocyanate are introduced as a crosslinking agent. The copolymer (E) is dynamically cross-linked, and dynamic cross-linking means cross-linking by kneading in a molten state (hereinafter also referred to as melt kneading).

A polyester polycarboxylic acid (G) and a polyvalent isocyanate are introduced as a crosslinking agent into a mixture of the crystalline olefin polymer (A) and the ethylene copolymer (E), and the ethylene copolymer (E) is moved. In the case of mechanical crosslinking, the polyester polycarboxylic acid (G) is preferably introduced into the mixture of the crystalline olefin polymer (A) and the ethylene copolymer (E) prior to the polyvalent isocyanate. Specifically, a mixture of a crystalline olefin polymer (A) and an ethylene copolymer (E) and a polyester polycarboxylic acid (G) are kneaded to obtain a kneaded product, It is preferable to knead with a polyvalent isocyanate.

The kneading temperature when kneading the mixture of the crystalline olefin polymer (A) and the ethylene copolymer (E) with the polyester polycarboxylic acid (G) is usually 100 to 240 ° C., preferably 120 to 210 ° C. The kneading time for kneading is usually 1 to 20 minutes, preferably 1 to 10 minutes. Further, the shear force applied at the time of kneading, 10 ~ 100,000sec ^-1 as the shear rate is preferably 100 ~ 50,000sec ^-1.

In the method for producing the crosslinked thermoplastic elastomer composition (D), when the isocyanate group-containing oligomer (F) is introduced into the mixture of the crystalline olefin polymer (A) and the ethylene copolymer (E) or Immediately before that, it is preferable to add an amidation catalyst to the mixture of the crystalline olefin polymer (A) and the ethylene copolymer (E).

In addition, when polyvalent isocyanate is introduced into a kneaded product obtained by kneading a mixture of a crystalline olefin polymer (A) and an ethylene copolymer (E) and a polyester polycarboxylic acid (G). Or immediately before that, it is preferable to add an amidation catalyst to the kneaded product.

As the amidation catalyst, an alkali metal salt or an alkaline earth metal salt is preferably used. Examples of the alkali metal salt include lithium fluoride, lithium chloride, lithium hydroxide, sodium fluoride, sodium chloride, sodium hydroxide, potassium fluoride, potassium chloride, and potassium hydroxide. Examples of the alkaline earth metal salt include calcium stearate, calcium perchlorate, calcium chloride, calcium hydroxide, magnesium stearate, magnesium perchlorate, magnesium chloride, magnesium hydroxide and the like.

The amidation catalyst can be used alone or in combination of two or more. As the amidation catalyst, calcium stearate, calcium perchlorate, magnesium stearate, and magnesium perchlorate are preferable from the viewpoint of amide selectivity in the amidation reaction, and magnesium stearate is more preferable.

As the amidation catalyst, a conventionally known catalyst can be used for the production of polyurethane foam (see, for example, Nobutaka Matsudaira and Tetsuro Maeda, “Polyurethane” No. 8 127-129, Tsuji Shoten (1964)). ).

Specific examples of catalysts used in the production of polyurethane foam include fats such as triethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, bis (N, N-dimethylaminoethyl ether), and morpholines. Group amines, organotin compounds such as tin octoate and dibutyltin dilaurate, alkali metal salts of carboxylic acids such as potassium acetate and sodium acetate, triethylamine, triethylenediamine, 1,3,5-tris (dimethylaminopropyl) ) -S-hexahydrotriazine, 2,4,6-tris (dimethylaminomethyl) phenol, tertiary amine catalyst such as 1,8-diazabicyclo [5,4,0] undecene-7, carboxylic acid and tertiary A quaternary ammonium salt composed of an amine is used. These catalysts can be used alone or in combination of two or more.

Furthermore, as the amidation catalyst, a phosphazenium compound represented by the following chemical formula (X), a phosphazenium salt of an active hydrogen compound represented by the following chemical formula (Y), or a phosphazenium hydroxide represented by the following chemical formula (Z) may be used. Good. When these amidation catalysts are used, the reactivity between an isocyanate group and a carboxyl group becomes extremely high, and amidation can be efficiently performed. Amidation catalysts can be used alone or in combination of two or more.

(In the formula, each R ¹ is independently a hydrocarbon group having 1 to 10 carbon atoms, and two R ¹ on the same nitrogen atom may be bonded to each other to form a ring structure. X is included. (The amount of water molecules is expressed in molar ratio and is 0 to 5.0.)

(In the formula, n is an integer of 1 to 8 and represents the number of phosphazenium cations, and Z ⁿ⁻ is the elimination of n protons from an active hydrogen compound having an active hydrogen atom on an oxygen or nitrogen atom. An anion of an n-valent active hydrogen compound derived as follows: a, b, c and d are each independently a positive integer of 3 or less or 0, but all are not 0 at the same time, R ² is each Independently, it is a hydrocarbon group having 1 to 10 carbon atoms, and two R ² on the same nitrogen atom may be bonded to each other to form a ring structure.)

(In the formula, Me represents a methyl group. A ′, b ′, c ′ and d ′ are 0 or 1, and all are not 0 at the same time.)
Examples of the phosphine oxide compound represented by the chemical formula (X) include tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide, tris (tripyrrolidinophosphoranylideneamino) phosphine oxide, tris (tripiperidinophospho). Ranylideneamino) phosphine oxide and the like, and tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide is preferable.

Examples of the phosphazenium salt of the active hydrogen compound represented by the chemical formula (Y) include dimethylaminotris [tris (dimethylamino) phosphoranylideneamino] phosphonium tetrafluoroborate, tetrakis [tri (pyrrolidin-1-yl) phosphoranylidene. Examples include amino] phosphonium tetrafluoroborate, tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium chloride, diethylaminotris [tris (diethylamino) phosphoranylideneamino] phosphonium tetrafluoroborate, and preferably tetrakis [tris ( Dimethylamino) phosphoranylideneamino] phosphonium chloride.

Examples of the phosphazenium hydroxide represented by the chemical formula (Z) include tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide, (dimethylamino) tris [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide. Of these, tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide is preferred.

The amount of these amidation catalysts used is such that when the isocyanate group-containing oligomer (F) is introduced into a mixture of the crystalline olefin polymer (A) and the ethylene copolymer (E), the ethylene copolymer It is 0.001 to 10 mol, preferably 0.005 to 2 mol, per 100 mol of the functional group that can react with an isocyanate group such as a carboxyl group in (E).

The amount of the amidation catalyst used is the amount of kneaded material obtained by kneading the mixture of the crystalline olefin polymer (A) and the ethylene copolymer (E) and the polyester polycarboxylic acid (G). In the case of introducing a polyvalent isocyanate, the amount of the functional group that the ethylene copolymer (E) can react with an isocyanate group such as a carboxyl group and the carboxyl group of the polyester polycarboxylic acid (G) The amount is 0.001 to 10 mol, preferably 0.005 to 2 mol, per 100 mol of the total amount.

If the amount of the amidation catalyst used is less than this, the amidation reaction does not proceed sufficiently and the productivity may decrease. On the other hand, at more than this, the amide selectivity of the amidation reaction does not change, which may be economically disadvantageous.

In the present invention, dynamic crosslinking is preferably performed in a non-open type apparatus. The dynamic crosslinking is preferably performed in an inert gas atmosphere such as nitrogen or carbon dioxide.

The kneading temperature at the time of dynamic crosslinking is not less than the temperature at which the crystalline olefin polymer (A) can be sufficiently melted, and suppresses the self-reaction of the isocyanate group-containing oligomer (F) and the isocyanate group of the polyvalent isocyanate. The viscosity of the isocyanate group-containing oligomer (F) and the polyvalent isocyanate is desirably not suitable for melt kneading, and is preferably 170 to 240 ° C, more preferably 190 to 230 ° C. The kneading time at the time of dynamic crosslinking is usually 1 to 20 minutes, preferably 3 to 10 minutes. Further, the applied shearing force when performing the dynamic crosslinking, 10 ~ 100,000sec ^-1 as the shear rate is preferably 100 ~ 50,000sec ^-1.

As the kneading apparatus, a lab plast mill, a mixing roll, an intensive mixer (for example, a Banbury mixer, a kneader), a single screw extruder, a twin screw extruder, or the like can be used. Although it can be used, a non-open device is preferred.

According to the present invention, the ethylene copolymer (E) is crosslinked with the isocyanate group-containing oligomer (F) or the polyester polycarboxylic acid (G) and the polyvalent isocyanate by dynamic crosslinking, and the crosslinked ethylene copolymer ( B), and a crosslinked thermoplastic elastomer composition (D) can be produced.

The production of the cross-linked thermoplastic elastomer composition (D) is preferably carried out continuously using the single screw extruder, twin screw extruder or the like. As a specific example, a crystalline olefin polymer (A) and an ethylene copolymer (E) are supplied to a twin screw extruder and the like, mixed, and then an isocyanate group-containing oligomer (F) or a polyester polycarboxylic acid (G) and polyisocyanate are supplied using a side foot etc., and the method of carrying out dynamic crosslinking of the ethylene copolymer (E) is mentioned.

Furthermore, the production of the crosslinked thermoplastic elastomer composition (D) can be continuously performed including the production of the ethylene copolymer (E). Specific examples include an ethylene / α-olefin copolymer, an ethylene / α-olefin / non-conjugated polyene copolymer, and an unsaturated carboxylic acid before graft modification described in the ethylene copolymer (E-1). Is supplied to a twin-screw extruder or the like to perform modification, and after obtaining an ethylene copolymer (E), the crystalline olefin polymer (A) is supplied using a side foot or the like and mixed. Then, a method of dynamically crosslinking the ethylene copolymer (E) by supplying using side feet or the like can be mentioned.

Other examples include an ethylene / α-olefin copolymer, an ethylene / α-olefin / non-conjugated polyene copolymer before graft modification, and an unsaturated carboxylic acid described in the ethylene copolymer (E-1). Etc. are supplied to a twin-screw extruder or the like to perform modification, and after obtaining an ethylene copolymer (E), the crystalline olefin polymer (A) is supplied using a side foot or the like, and mixing is performed. Next, the polyester polycarboxylic acid (G) is supplied using a side foot or the like, and the polyvalent isocyanate is supplied using a side foot or the like to dynamically crosslink the ethylene copolymer (E). Can be mentioned.

The temperature at which the crystalline olefin polymer (A) and the ethylene copolymer (E) are mixed is equal to or higher than the temperature at which the crystalline olefin polymer (A) can be sufficiently melted, and the viscosity is melted. It is desirable that it is not unsuitable for kneading, preferably 170 to 240 ° C, more preferably 190 to 230 ° C.

Further, in the production of the crosslinked thermoplastic elastomer composition (D), the isocyanate group-containing oligomer (F) and the polyvalent isocyanate are highly reactive with water, so that moisture can be surely excluded. desirable. In order to eliminate moisture, an isocyanate group-containing oligomer (F) or a polyester polycarboxylic acid (G) and a polyvalent isocyanate are converted into a crystalline olefin polymer (A) under an inert gas atmosphere such as nitrogen or carbon dioxide. It is preferable to add to the mixture with the ethylene copolymer (E).

In the production of the cross-linked thermoplastic elastomer composition (D), raw materials with high hygroscopicity such as isocyanate group-containing oligomer (F), polyester polycarboxylic acid (G), and optionally used compatibilizer are used as raw materials. It is preferable to perform a dehumidification treatment before use. If water is present during the production of the cross-linked thermoplastic elastomer composition (D), the isocyanate group reacts with water to form a urea bond with poor heat resistance, an amino group, or CO2 generation. There is a case. For this reason, it is preferable that water is not present as much as possible when the crosslinked thermoplastic elastomer composition (D) is produced.

Any method known in the art may be used as the dehumidification treatment. From the viewpoint of suppressing the dehumidification efficiency and side reactions such as the condensation reaction, the highly hygroscopic raw material is treated at a temperature of 70. A method of holding for 8 to 24 hours under the conditions of up to 120 ° C. and pressure of 0.1 to 10 kPa is preferred.

Furthermore, in the production of the crosslinked thermoplastic elastomer composition (D), it is preferable to rapidly cool the product taken out from an extruder or the like after dynamic crosslinking. Any method may be used for the rapid cooling as long as it is a known method.

The amount of the ethylene copolymer (E) and the isocyanate group-containing oligomer (F) used for the production of the cross-linked thermoplastic elastomer composition (D) is the amount of the ethylene copolymer (E) used for the production. The ratio (isocyanate group / functional group capable of reacting with an isocyanate group) of the amount [mol] of the functional group capable of reacting with an isocyanate group and the amount [mol] of the isocyanate group contained in the isocyanate group-containing oligomer (F) is 0. .3 to 2.5, preferably 0.5 to 2.0, and more preferably 0.7 to 1.5. When the ratio (isocyanate group / functional group capable of reacting with isocyanate group) is 1, the number of isocyanate groups and the number of functional groups capable of reacting with isocyanate groups are equivalent, which is particularly preferable.

When the functional group capable of reacting with the isocyanate group is a functional group that easily dehydrates to form a carboxylic anhydride group, such as a carboxyl group derived from maleic acid, the ratio (isocyanate group / isocyanate group) The functional group capable of reacting with an isocyanate group in the functional group capable of reacting with carboxylic acid anhydride is an amount in terms of a carboxylic acid anhydride group. Further, it is desirable to confirm the ratio of ring opening (carboxyl group) and ring closing (carboxylic anhydride group) by IR or the like.

The amount of the isocyanate group-containing oligomer (F) used in the production of the crosslinked thermoplastic elastomer composition (D) is the weight ratio of the crystalline olefin polymer (A) and the crosslinked ethylene copolymer (B). , The molecular weight of the isocyanate group-containing oligomer (F), the amount of the functional group that can react with the isocyanate group of the ethylene copolymer (E), the molecular weight of the ethylene copolymer (E), and the functionality that can react with the isocyanate group The ratio is determined by the ratio of the amount of the group to the amount of the isocyanate group (isocyanate group / functional group capable of reacting with the isocyanate group). Preferably, the crystalline olefin polymer (A) and the ethylene copolymer (E) are used. And 10 to 80 wt%, preferably 15 to 60 wt%, more preferably 100 wt% of the total of the isocyanate group-containing oligomer (F) Ku is 30 ~ 50wt%.

The amount of the ethylene copolymer (E) and the polyester polycarboxylic acid (G) used for the production of the cross-linked thermoplastic elastomer composition (D) is the amount of the ethylene copolymer (E) used for the production. Ratio [mol] of functional group capable of reacting with isocyanate group and amount [mol] of carboxyl group of polyester polycarboxylic acid (G) (carboxyl group / ethylene copolymer of polyester polycarboxylic acid (G) The functional group capable of reacting with the isocyanate group of the compound (E)) is 1.0 to 6.0, preferably 1.0 to 4.0, more preferably 1.0 to 3.0. is there.

The amount of the ethylene copolymer (E), the polyester polycarboxylic acid (G), and the polyvalent isocyanate used for the production of the crosslinked thermoplastic elastomer composition (D) is the same as that of the ethylene copolymer ( E) the amount [mol] of the functional group capable of reacting with the isocyanate group possessed by the amount [mol] of the carboxyl group possessed by the polyester polycarboxylic acid (G), and the amount of the isocyanate group possessed by the polyvalent isocyanate [ mol] (the sum of the amount of the functional group capable of reacting with the isocyanate group of the isocyanate group / ethylene copolymer (E) and the amount of the carboxyl group of the polyester polycarboxylic acid (G)) is 1 0.0 to 5.0, preferably 1.05 to 3.0, and more preferably 1.1 to 2.5.

When the functional group capable of reacting with the isocyanate group is a functional group that easily dehydrates to form a carboxylic anhydride group, such as a carboxyl group derived from maleic acid, the ratio (isocyanate group / ethylene The functional group capable of reacting with the isocyanate group in the sum of the amount of the functional group capable of reacting with the isocyanate group of the polymer (E) and the amount of the carboxyl group of the polyester polycarboxylic acid (G) is carboxylic acid. It is the amount in terms of anhydride group. Further, it is desirable to confirm the ratio of ring opening (carboxyl group) and ring closing (carboxylic anhydride group) by IR or the like.

The amount of the polyester polycarboxylic acid (G) and the polyvalent isocyanate used for the production of the crosslinked thermoplastic elastomer composition (D) is the same as that of the crystalline olefin polymer (A) and the crosslinked ethylene copolymer (B). ), The molecular weight of the polyester polycarboxylic acid (G) and the polyvalent isocyanate group, the amount of the functional group capable of reacting with the isocyanate group of the ethylene copolymer (E), and the polyester polycarboxylic acid (G) The sum of the amount of carboxyl groups, the molecular weight of the ethylene copolymer (E), the amount of functional groups capable of reacting with the isocyanate group, and the amount of carboxyl groups of the polyester polycarboxylic acid (G), Ratio (the amount of the functional group capable of reacting with the isocyanate group of the isocyanate group / ethylene copolymer (E) and the polyester) Terpolycarboxylic acid (G) with the amount of carboxyl groups), preferably crystalline olefin polymer (A), ethylene copolymer (E) and polyester polycarboxylic acid (G) The amount of the polyester polycarboxylic acid (G) and the polyvalent isocyanate is 10 to 80 wt%, preferably 15 to 60 wt%, and more preferably 30 to 50 wt% per 100 wt% of the total amount of styrene and polyvalent isocyanate.

[Molded body]
The molded product of the present invention is formed from the crosslinked thermoplastic elastomer composition (D).

Since the crosslinkable thermoplastic elastomer composition (D) has mechanical properties (tensile strength, elongation, etc.) equivalent to those of conventional crosslinkable thermoplastic elastomers, it can be used for various applications. In addition, since the crosslinkable thermoplastic elastomer composition (D) has excellent oil resistance as compared with the conventional crosslinkable thermoplastic elastomer, it is difficult to use the conventional crosslinkable thermoplastic elastomer. Can also be used.

The crosslinked thermoplastic elastomer composition (D) is lightweight, heat resistant, flexible, rubber elastic, moldability, low temperature characteristics, weather resistance, amphiphilicity, compatibility, reformability, and easy adhesion. Excellent adhesion.

Since the crosslinked thermoplastic elastomer composition (D) is excellent in molding processability, it can be molded by various molding methods. Examples of the molding include extrusion molding, injection molding, compression molding, calendar molding, vacuum molding, press molding, stamping molding, and blow molding. Examples of blow molding include breath blow molding, direct blow molding, injection blow molding, and the like.

The molded product of the present invention can be obtained by molding the crosslinked thermoplastic elastomer composition (D). For example, it can be obtained by molding the crosslinked thermoplastic elastomer composition (D) by a conventional plastic molding method such as extrusion molding, injection molding or compression molding. In addition, scraps and burrs generated by such a molding method can be recovered and reused.

Examples of the molded body of the present invention include bumper parts, body panels, side shields, glass run channels, instrument panel skins, door skins, ceiling skins, weatherstrip materials, hoses, steering wheels, boots, wire harness covers, seat adjuster covers. Automotive parts such as electric wire coverings, connectors, cap plugs, etc .; footwear such as shoe soles and sandals; leisure items such as swimming fins, underwater glasses, golf club grips, baseball bat grips, gaskets, waterproof cloth, Belts, garden hoses; various civil engineering and architectural gaskets and sheets. The molded article of the present invention is particularly suitable for uses requiring oil resistance, and automotive parts such as hoses, boots, wire harness covers, and sheet adjuster covers are particularly preferred uses.

As described above, automobile parts are preferable as the molded body of the present invention, and more detailed examples of the automobile parts include a mechanism member, an interior member, an exterior member, and other members.

Mechanical members include CVJ boots, suspension boots, rack and pinion boots, steering rod covers, AT cushions, AT slide covers, leaf spring bushes, ball joint retainers, timing belts, V belts, engine room hoses, air ducts, air Examples include a bag cover and a propeller shaft cover material.

Interior materials include various skin materials (instrumental panel, door trim, ceiling, rear pillar), console box, armrest, airbag case lid, shift knob, assist grip, side step mat, reclining cover, trunk seat, seat belt buckle, Examples include lever slide plates, door latch strikers, seat belt parts, and switches.

As exterior members, various molding materials (inner / outer window moldings, roof moldings, belt moldings, side trim moldings), door seals, body seals, glass run channels, mudguards, kicking plates, step mats, number plate housings, silencer gears , Control cable covers and emblems.

Other members include air duct packing, air duct hose, air duct cover, air intake pipe, air dam skirt, timing belt cover seal, opening seal / trunk seal member, bonnet cushion, fuel tank band, cable and the like.

The molded article of the present invention may be miscellaneous goods, daily necessities, or these members. Miscellaneous goods, daily necessities or these components include grips (eg, ballpoint pens, mechanical pencils, toothbrushes, cups, disposable razors, handrails, cutters, power tools, screwdrivers, power cables, door grips), assist grips, shift knobs, toys , Notebook skins, gaskets (for example, gaskets for tableware, tappers, etc.), various rubber feet, sports equipment (for example, sheathed soles, ski boots, skis, ski bindings, ski soles, golf balls, goggles members, snowboard members, snowboard shoes) , Snowboard bindings, surfboard members, body boards, banana boats, kiteboards, snorkeling members, water skiing members, parasailing members, wakeboard members and other sports equipment), belts ( In example, belts and watches belt, fashion belt), hairbrush, bath panel button sheet, cap, shoes of the inner sole, and the like health equipment member.

The molded article of the present invention may be a home appliance / electronic information member. Home appliances / electronic information members include hoses (for example, hoses for washing machines, futon dryers, air conditioners, etc.), anti-vibration rubber for air conditioner outdoor units / AV devices, mobile phone members (for example, earphone covers, antenna covers, Mobile phone members such as connector covers), keypads of various remote controls, silencer gears, grips (for example, grips such as digital cameras and videos), and the like.

The molded product of the present invention may be an industrial material. Industrial materials include architectural gaskets, waterproof sheets, water shielding sheets, suspensions, protective sheets, waterproofing materials, hoses (for example, hoses such as hydraulic hoses, pneumatic hoses, fire hoses), conveyor belts, gaskets, etc. Can be mentioned.

Since the crosslinkable thermoplastic elastomer composition (D) is excellent in amphiphilicity, it is compatible with both nonpolar resins and polar resins, and can be used by mixing with various resins. That is, the cross-linked thermoplastic elastomer composition (D) can be used as a modifier.

As the composition using the cross-linked thermoplastic elastomer composition (D) as a modifier, the cross-linked thermoplastic elastomer composition (D) and any resin (for example, polypropylene, polyethylene, olefin elastomer, It is obtained by mixing styrene resin, ester resin, amide resin, acrylonitrile / butadiene / styrene (ABS) resin, polycarbonate, polyvinylidene chloride, and thermoplastic polyurethane (TPU)). The composition which can be mentioned is mentioned.

As the composition obtained by mixing the cross-linked thermoplastic elastomer composition (D) and an arbitrary resin, the arbitrary resin is at least one selected from nonpolar resins (for example, polypropylene, polyethylene, olefin elastomer). In the case of a resin of a kind, the composition is preferable because it is excellent in electrostatic (chargeability), water absorption, adhesiveness, and wettability (paintability and colorability) as compared with a nonpolar resin.

In addition, as a composition obtained by mixing the cross-linked thermoplastic elastomer composition (D) and an arbitrary resin, an arbitrary resin is a polar resin (for example, a styrene resin, an ester resin, an amide resin). , At least one resin selected from acrylonitrile / butadiene / styrene (ABS) resin, polycarbonate, polyvinylidene chloride, and thermoplastic polyurethane (TPU)), the composition is lighter than the polar resin. And is excellent in thermal stability, fluidity, flexibility and low temperature impact resistance.

In addition, as a composition obtained by mixing the crosslinked thermoplastic elastomer composition (D) and an arbitrary resin, when the arbitrary resin is a polar resin and a nonpolar resin, the composition Is preferable because the cross-linked thermoplastic elastomer composition (D) acts as a compatibilizing agent.

In addition, the composition obtained by mixing the cross-linked thermoplastic elastomer composition (D) and an arbitrary resin is excellent in adhesion to other resins and other materials.

The molded body of the present invention may be a laminate. As the laminate, even a laminate having a layer formed from the cross-linked thermoplastic elastomer composition (D) and a layer formed from another resin or other material may be a cross-linked thermoplastic elastomer composition (D ) And an arbitrary resin may be used, and a laminate having a layer formed from a composition obtained by mixing an arbitrary resin and a layer formed from another resin or another material may be used. Examples of the other materials include metals (for example, copper, aluminum, gold, silver, etc.) and inorganic substances (for example, silica, titanium oxide, etc.).

Moreover, as a molded object of this invention, the above-mentioned various molded object may be formed from the composition obtained by mixing the said bridge | crosslinking-type thermoplastic elastomer composition (D) and arbitrary resin. .

Next, the molded body of the present invention will be described from the viewpoint of the molding method.

Specific examples of the molded body of the present invention include known extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, calendar molding, foam molding, powder slush molding, and the like. And a molded body obtained by the thermoforming method. The molded body of the present invention will be described below by giving several examples.

When the molded body according to the present invention is, for example, an extrusion molded body, an injection molded body, or a blow molded body, the shape and product type of the molded body are not particularly limited. For example, a sheet, a molding, a pipe, a hose, an electric wire covering material, A filament, a bottle, a tube, etc. are mentioned. In addition, these molded products are used especially for seats, skin materials, automotive inner and outer layer materials, building materials, various automotive boots, automotive moldings, air ducts, automotive instrument panels, interior trim materials such as door trims, etc. It is preferable to be used.

When extruding the cross-linked thermoplastic elastomer composition (D), conventionally known extruding equipment and molding conditions can be employed. For example, a single screw extruder, a kneading extruder, a ram extruder, a gear can be used. The melted composition can be formed into a desired shape by extruding it from a specific die or the like using an extruder or the like.

Sheets, pipes, hoses, wire covering materials, and tubes formed from the crosslinked thermoplastic elastomer composition (D) have oil resistance, mechanical properties, light weight, flexibility, heat resistance, stretchability, and aging resistance. It is excellent and can be used widely.

The sheet may be a laminate formed from a plurality of layers. When the sheet is a laminate, the sheet has at least one layer formed from the crosslinked thermoplastic elastomer composition (D). It only has to be.

Examples of layers other than the layer formed from the crosslinked thermoplastic elastomer composition (D) of the laminate include polyolefins such as polyethylene, polypropylene, and TPO (thermoplastic polyolefin), polyamides, polyesters, polystyrenes, thermoplastic polyurethanes, and the like. And polar metals, metals such as aluminum, iron, copper, gold, silver, silica, and titanium oxide, and inorganic substances. Since the crosslinked thermoplastic elastomer composition (D) is amphiphilic, it can be laminated on nonpolar resins and polar resins. Furthermore, the crosslinked thermoplastic elastomer composition (D) is useful as an adhesive material that can be bonded to both nonpolar resins and polar resins regardless of the resin.

When the molded article of the present invention is an injection molded article, the crosslinked thermoplastic elastomer composition (D) is injected into various shapes by adopting known conditions using a conventionally known injection molding apparatus. It can be manufactured by molding. The injection-molded product is excellent in oil resistance, mechanical properties, lightness, flexibility, heat resistance, stretchability, and aging resistance, and can be widely used.

When the molded article of the present invention is a blow molded article, by adopting known conditions using a conventionally known blow molding apparatus, blow molding the crosslinked thermoplastic elastomer composition (D) Can be manufactured. In this case, the blow molded article made of the crosslinked thermoplastic elastomer composition (D) may be a molded article having a multilayer structure. The molded body having the multilayer structure has at least one layer formed from the crosslinked thermoplastic elastomer composition (D). The blow molded article is excellent in oil resistance, mechanical properties, lightness, flexibility, heat resistance, stretchability, and aging resistance, and can be widely used for automobile boots.

When the molded body of the present invention is a press molded body, examples of the press molded body include a mold stamping molded body. Examples of the mold stamping molded body include a molded body obtained by press-molding a base material and a skin material at the same time and performing composite integral molding (mold stamping molding) of both. As a mold stamping molded body, the skin material can be formed of the crosslinked thermoplastic elastomer composition (D). Specific examples of the mold stamping molded body include automotive interior materials such as door rims, rear package trims, seat back garnishes, and instrument panels. The press-molded body is excellent in oil resistance, mechanical properties, lightness, flexibility, heat resistance, stretchability, and aging resistance.

When the molded article of the present invention is a foam molded article, it can be obtained by foam molding of the crosslinked thermoplastic elastomer composition (D) using known conditions. When performing foam molding, the crosslinked thermoplastic elastomer composition (D) preferably contains a foaming agent as an additive, and may contain a foaming aid. In addition, there is no limitation in particular as a foaming agent and foaming adjuvant, A well-known foaming agent and foaming adjuvant can be used. The cross-linked thermoplastic elastomer composition (D) containing a foaming agent and, if necessary, a foaming aid has good foaming properties, and the resulting foamed molded product has oil resistance, mechanical properties, and light weight. Excellent in flexibility, flexibility, heat resistance, elasticity, and aging resistance.

When the molded body of the present invention is a vacuum molded body, it can be obtained by vacuum molding the cross-linked thermoplastic elastomer composition (D) using known conditions. Examples of the vacuum molded body include interior skin materials such as instrument panels and door trims for automobiles. The molded body is excellent in oil resistance, mechanical properties, lightness, flexibility, heat resistance, stretchability, and aging resistance.

When the molded body of the present invention is a powder slush molded body, it can be obtained by powder slush molding of the crosslinked thermoplastic elastomer composition (D) using known conditions. Examples of the powder slush molded body include automobile parts, home appliance parts, toys, sundries and the like. The molded body is excellent in oil resistance, mechanical properties, lightness, flexibility, heat resistance, stretchability, and aging resistance.

When the molded product of the present invention is a laminate, the laminate may have at least one layer formed from the crosslinked thermoplastic elastomer composition (D). The layer formed from the crosslinked thermoplastic elastomer composition (D) includes the crosslinked thermoplastic elastomer composition (D) and any resin (PP, PE, St resin, ester resin, A layer formed from an amide resin, vinyl chloride, or the like) may be used. The laminate having a layer formed from the cross-linked thermoplastic elastomer composition (D) and a nonpolar resin such as polyolefin is obtained by the cross-linkable thermoplastic elastomer composition (D) having excellent amphiphilic properties. Since the electrostatic controllability, antistatic property, water absorption, adhesiveness and wettability of the nonpolar resin can be improved, it can be used for various applications. A laminate having a layer formed from the cross-linked thermoplastic elastomer composition (D) and a polar resin such as nylon, engineering plastic, or thermoplastic polyurethane is a cross-linked thermoplastic elastomer composition having excellent amphiphilic properties. (D) can improve the lightness, thermal stability, fluidity, flexibility, and low-temperature impact properties of the polar resin, so that it can be used in various applications.

Further, as described above, it is useful that the molded article of the present invention is an automobile molding. Specific examples of automobile malls include the following i) to iii).
i) Side molding, bumper molding, roof molding, window molding, glass run channel, weather strip molding, belt molding, etc. obtained by extrusion molding of a single layer.
ii) Side moldings, bumper moldings, roof moldings, window moldings, glass run channels, weather strip moldings, belt moldings and the like obtained by multilayer lamination extrusion molding with other materials. At that time, the cross-linked thermoplastic elastomer composition (D) is used at least at a site where scratch resistance or abrasion resistance is required.
iii) Body, terminal, corner, etc. obtained by injection molding, such as side molding, bumper molding, roof molding, window molding, glass run channel, weather strip molding, belt molding.

Further, when the molded article of the present invention is an automobile interior skin member, the following I) to III) are specifically mentioned.
I) Instrument panel (instrument panel) processed by vacuum molding or stamping molding of a sheet-like molded body obtained by extrusion molding or calender molding of the cross-linked thermoplastic elastomer composition (D) ) Skin, door skin, ceiling skin, console skin, etc.
II) Instrument panel (instrument panel) skin, door skin, and ceiling skin processed by pulverizing the crosslinked thermoplastic elastomer composition (D) into a powder of 1.0 mm or less and powder slush molding , Console epidermis and so on.
III) A handle skin, a console skin, an armrest skin, a shift knob skin, a parking lever grip skin, an assist grip skin, a seat adjustment grip skin, etc., which are molded and processed by the injection molding of the crosslinked thermoplastic elastomer composition (D). Various epidermis. In this case, the base material formed from the olefin resin and the skin formed from the cross-linked thermoplastic elastomer composition (D) are integrally formed by sequential injection molding with an olefin resin such as polypropylene, and simultaneous injection molding. You can also

Further, when the molded article of the present invention is an automobile interior skin member, as the crosslinked thermoplastic elastomer composition (D), a conventionally known heat stabilizer, anti-aging agent, weather stabilizer, antistatic agent A composition containing an additive such as a crystal nucleating agent or a lubricant may be used. In particular, an automobile interior skin member formed using the cross-linked thermoplastic elastomer composition (D) containing a lubricant is preferable because it is particularly excellent in scratch resistance and wear resistance. Examples of the lubricant include higher fatty acid amides, metal soaps, waxes, silicone oils, fluorine polymers, etc. Among them, higher fatty acid amides, silicone oils, fluorine polymers have excellent scratch resistance and abrasion resistance. An automobile interior skin member can be obtained, which is preferable.

Examples of the higher fatty acid amides include saturated fatty acid amides such as lauric acid amide, palmitic acid amide, stearic acid amide, and behemic acid amide; unsaturated fatty acid amides such as erucic acid amide, oleic acid amide, brassic acid amide, and elaidic acid amide. Amides; bis fatty acid amides such as methylene bis stearic acid amide, methylene bis oleic acid amide, ethylene bis stearic acid amide, ethylene bis oleic acid amide;

Examples of the silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, alkyl silicone oil, fluorosilicone oil, tetramethyltetraphenyltrisiloxane, and modified silicone oil.

Examples of the fluorine polymer include polytetrafluoroethylene, polyvinylidene fluoride, and vinylidene fluoride copolymer.

Among the higher fatty acid amides, silicone oils and fluoropolymers, erucic acid amide, oleic acid amide, ethylene bis-oleic acid amide, dimethyl silicone oil, phenyl methyl silicone oil, alkyl silicone oil, polytetrafluoroethylene, polyvinylidene fluoride, A vinylidene fluoride copolymer is preferable, and erucic acid amide, oleic acid amide, dimethyl silicone oil, and vinylidene fluoride copolymer are particularly preferable.

Examples of the molded body of the present invention include bumper parts, body panels, moldings, side shields, glass run channels, instrument panel skins, door skins, ceiling skins, other interior skin materials, weatherstrip materials, hoses, steering wheels, boots, etc. Automotive parts; electrical parts such as wire coverings, connectors, cap plugs; footwear such as shoe soles and sandals; leisure items such as swimming fins, underwater glasses, golf club grips, baseball bat grips, gaskets, waterproof cloth, belts , Garden hoses; various gaskets and sheets for civil engineering and construction. In particular, the molded product of the present invention is suitable for applications such as hoses, steering wheels, and boots that require oil resistance, mechanical properties, lightness, flexibility, heat resistance, stretchability, and aging resistance. In addition, the molded body of the present invention includes a costume case, a laminate (including glass), a foam, an electric cable, a sound insulation material, a vibration damping material, a vibration insulation material, a sound absorbing material, a sound insulation material, a foam material, a building material, and a building material skin material. It can be widely used for non-woven fabrics, modifiers, bulletproof materials and the like. The crosslinked thermoplastic elastomer composition (D) can also be used for applications such as an adhesive, a compatibilizing agent, a chipping resistant agent, and a chipping resistance improving agent.

Hereinafter, the present invention will be described based on synthesis examples, examples, and comparative examples, but the present invention is not limited thereto. Moreover, the analysis and measurement of a synthesis example, an Example, and a comparative example were based on the following method.

(Melt flow rate (MFR))
The melt flow rate was measured at 230 ° C. and a 2.16 kg load in accordance with ASTM D1238.

(Acid value)
The acid value was measured according to “Partial acid value” in Section 5.3 “Acid value” of JIS K6901 “Test method for liquid unsaturated polyester resin”.

(Hydroxyl value)
The hydroxyl value was measured according to 6.4 “Hydroxyl value” of JIS K1557 “Polyether test method for polyurethane”.

(Isocyanate group content)
The isocyanate group content was measured according to Section 6.3 “Isocyanate group content” of JIS K7301 “Testing method for tolylene diisocyanate type prepolymer for thermosetting urethane elastomer”.

(Number average molecular weight)
The number average molecular weight was measured under the following conditions using a gel permeation chromatograph (GPC) after 0.03 g of a sample was dissolved in 10 ml of tetrahydrofuran at room temperature and then filtered through a filter having a pore size of 0.45 μm. For the number average molecular weight, the number average molecular weight of the peak including the maximum frequency molecular weight (retention time) of the measured chromatogram was calculated with reference to a calibration curve created using standard polyethylene glycol.
Apparatus: HLC-8020 (manufactured by Tosoh Corporation)
Column: TSKgel guardcolum HXL-L + G1000H XL + G2000H XL + G3000H XL manufactured by Tosoh Corporation
Eluent: Tetrahydrofuran Flow rate: 0.8 ml / min Column temperature: 40 ° C
Injection volume: 20 μl
Detector: RI
(viscosity)
The viscosity was measured using a cone plate type rotational viscometer (made by ICI) under the conditions of cone type: 100 P, rotation speed: 75 rpm, temperature: 100 ° C. or 80 ° C.

(Amidation rate)
The amidation rate was calculated from ¹ H-NMR under the following conditions.
Device: JNM-AL400 (manufactured by JEOL)
Frequency: 400MHz
Measurement temperature: Room temperature integration number: 128 times After dissolving 20 mg of a sample in 0.65 ml of dimethylsulfoxide-d6 (containing 0.05% TMS) at room temperature, 1H-NMR was measured under the above conditions. The amidation rate was calculated from the integral value of proton (H) of the isocyanate derivative and the integral value of proton (NH) in the amide.

(Mechanical properties: tensile strength, elongation)
In accordance with JIS K6251, a tensile test was performed under the following conditions, and the tensile strength and elongation at break were measured.

The test was performed by producing a sheet with a press molding machine, punching out a JIS No. 3 test piece, and using the test piece at a tensile speed of 500 mm / min.

(hardness)
Hardness measured Shore A hardness based on JISK6253.

Measured by preparing a sheet with a press molding machine and reading the scale immediately after contact with the pressing needle using an A-type measuring instrument.

(Intrinsic viscosity [η])
The intrinsic viscosity [η] of the copolymer rubber was measured in 135 ° C. decalin.

(Oil resistance test)
A test piece of 20 mm × 20 mm × 2 mm was prepared from a 2 mm thick sheet press-molded at 200 ° C., and the weight change rate ΔV was calculated from the weight before and after being immersed in JIS No. 3 oil at 70 ° C. for 72 hours according to the formula (I).
{(Tw−Td) / Td} × 100 = ΔV (I)
(In Formula (I), Tw is the weight of the test piece after immersion, and Td is the weight of the test piece before immersion.)
(TEM observation method)
Measuring instrument: Transmission electron microscope H-7650 (manufactured by Hitachi, Ltd.)
Pretreatment: Trimming the specimen to make a sample, then staining the sample with RuO ₄ , creating an ultrathin section from the frozen sample, carbon reinforcing, and using as a measurement sample.
Photo magnification: 3000 times, 10,000 times [Synthesis Example E-1 Production of an ethylene / α-olefin copolymer (E-1) having a functional group capable of reacting with an isocyanate group]
1700 mL of dehydrated toluene was placed in a 2 L glass polymerization vessel purged with nitrogen, and a mixed gas of ethylene (100 L / h) / propylene (50 L / h) was circulated. When the temperature was raised to 80 ° C., triethylaluminum (10.2 mL) and 10-undecenoic acid (6.0 mL) were added sequentially, and metallocene activated with methylalumoxane ([Al] = 1.26 M in toluene solution 10.26 mL) was added. The catalyst (formula (8)) (20.3 mg) was added to initiate polymerization. After polymerization for 90 minutes at a stirring speed of 600 rpm and 80 ° C. in the above mixed gas flow state, isobutyl alcohol (30 mL) was added to terminate the polymerization. The temperature of the polymerization solution was lowered to 50 ° C., and then poured into 3.0 L of methanol (including 10 mL of concentrated hydrochloric acid) to precipitate a polymer.

The polymer is collected by filtration and dried under reduced pressure at 80 ° C. for 10 hours to give an ethylene / propylene / 10-undecenoic acid terpolymer (an ethylene / α-olefin copolymer having a functional group capable of reacting with an isocyanate group). (E-1)) was obtained.

The composition ratio of the structural unit derived from the monomer constituting the ethylene / α-olefin copolymer (E-1) having a functional group capable of reacting with an isocyanate group from ¹ H-NMR measurement is the structural unit derived from ethylene / derived from propylene The structural unit derived from 10-undecenoic acid was estimated to be 75.1 / 23.7 / 1.23 (mol%). Therefore, there are 0.38 mmol / g carboxyl groups derived from 10-undecenoic acid per 1 g of the ethylene / α-olefin copolymer (E-1) having a functional group capable of reacting with an isocyanate group.

[Synthesis Example E-2 Production of ethylene / α-olefin copolymer (E-2) having a functional group capable of reacting with an isocyanate group]
In the polymerization vessel, vanadium oxytrichloride and ethylaluminum sesquichloride are used as a polymerization catalyst, and a mixed gas of ethylene and 1-butene and hydrogen gas are supplied into a polymerization solvent hexane, at 40 ° C., 5 kg / cm ² , residence time 1 Ethylene and 1-butene were polymerized continuously under time conditions. Next, the solvent was separated from the obtained reaction solution to obtain the target ethylene / 1-butene random copolymer. The copolymer thus obtained has a 1-butene content of 19 mol%, an intrinsic viscosity [η] measured in decalin at 135 ° C. of 2.2 dl / g, and a glass transition temperature of −65. ° C.

10 kg of the above ethylene / 1-butene random copolymer was blended in a Henschel mixer with a solution of 300 g of maleic anhydride and 18 g of di-tert-butyl peroxide in 300 g of acetone.

Next, the blend obtained as described above was introduced from a hopper of a single screw extruder having a screw diameter of 40 mm and L / D = 26, extruded into a strand at a resin temperature of 260 ° C. and an extrusion rate of 6 kg / hour, and then water-cooled. And then pelletized to obtain a maleic anhydride graft-modified ethylene / 1-butene random copolymer. Unreacted maleic anhydride is extracted from the obtained graft-modified ethylene / 1-butene random copolymer with acetone, and an ethylene / α-olefin copolymer having a functional group capable of reacting with an isocyanate group (E-2 ) The amount of maleic anhydride grafted from this graft-modified ethylene / 1-butene random copolymer (ethylene / α-olefin copolymer (E-2) having a functional group capable of reacting with an isocyanate group) was determined by ¹ H-NMR measurement. When measured, the graft amount was 2.60% by weight. Accordingly, the ethylene / α-olefin copolymer (E-2) having a functional group capable of reacting with an isocyanate group has 0.261 mmol / g of a carboxylic acid anhydride group derived from maleic anhydride per gram.

[Synthesis Example E-3 Production of ethylene / α-olefin copolymer (E-3) having a functional group capable of reacting with an isocyanate group]
10 kg of ethylene / propylene copolymer (trade name Toughmer P-0680, MFR = 0.8 g / 10 min (190 ° C., 2.16 kgf), manufactured by Mitsui Chemicals, Inc.), 120 g of maleic anhydride and organic peroxide (NOF) A solution obtained by dissolving 6 g of trade name Perhexin 25B, 2,5-Dimethyl-2,5-bis (t-butylperoxy) hexyne-3) in 120 g of acetone was blended in a Henschel mixer.

The blend obtained as described above was set at a set temperature of 250 ° C. using a plastic engineering company twin screw extruder BT-30 (30 mmφ, L / D = 46, rotating in the same direction, four knee zones). A pellet sample formed from a graft-modified ethylene / propylene copolymer was obtained by kneading at an extrusion rate of 3 kg / h and a rotational speed of 200 rpm. Unreacted maleic acid and organic peroxide were removed from the pellet sample using a vacuum pump from the vent port of the extruder.

The amount of maleic anhydride grafted in the obtained graft-modified ethylene / propylene copolymer (ethylene / α-olefin copolymer (E-3) having a functional group capable of reacting with an isocyanate group) was measured by ¹ H-NMR measurement. As a result, the amount of maleic anhydride grafted was 1.0% by weight.

The obtained pellets were extracted with acetone, and the amount of unreacted maleic anhydride was measured by ¹ H-NMR. As a result, it was not detected. Therefore, the ethylene / α-olefin copolymer (E-3) having a functional group capable of reacting with an isocyanate group has 0.102 mmol / g of carboxylic acid anhydride group derived from maleic anhydride per 1 g.

[Synthesis Example E-4 Production of Ethylene / α-Olefin Copolymer (E-4) Having Functional Group Reactive with Isocyanate Group]
10 kg of ethylene / butene copolymer (trade name Toughmer P-0550 (MFR = 1.0 g / 10 min (190 ° C., 2.16 kgf)), manufactured by Mitsui Chemicals, Inc.), 120 g of maleic anhydride and organic peroxide (NOF) A solution obtained by dissolving 6 g of trade name Perhexin 25B, 2,5-Dimethyl-2,5-bis (t-butylperoxy) hexyne-3) in 120 g of acetone was blended in a Henschel mixer.

The blend obtained as described above was set at a set temperature of 250 ° C. using a plastic engineering company twin screw extruder BT-30 (30 mmφ, L / D = 46, rotating in the same direction, four knee zones). A pellet sample formed from the graft-modified ethylene / butene copolymer was obtained by kneading at an extrusion rate of 3 kg / h and a rotational speed of 200 rpm. Unreacted maleic acid and organic peroxide were removed from the pellet sample using a vacuum pump from the vent port of the extruder.

The amount of maleic anhydride grafted in the obtained graft-modified ethylene / butene copolymer (ethylene / α-olefin copolymer (E-4) having a functional group capable of reacting with an isocyanate group) was measured by ¹ H-NMR measurement. As a result, the amount of maleic anhydride grafted was 1.0% by weight.

The obtained pellets were extracted with acetone, and the amount of unreacted maleic anhydride was measured by ¹ H-NMR. As a result, it was not detected. Therefore, the ethylene / α-olefin copolymer (E-4) having a functional group capable of reacting with an isocyanate group has 0.102 mmol / g of carboxylic anhydride group derived from maleic anhydride per 1 g.

[Synthesis Example F-1 Production of Isocyanate Group-Containing Esteramide Oligomer (F-1)]
In a 2 liter reaction flask equipped with a reflux condenser, a nitrogen gas inlet tube, a thermometer, and a stirrer, 834.1 parts by weight of the polyester polycarboxylic acid (G-1) obtained in Synthesis Example G-1 below was added. , 165.9 parts by weight of 1,3-bis (isocyanatomethyl) cyclohexane (trade name: Takenate 600, manufactured by Mitsui Chemicals Polyurethanes) (NCO / COOH equivalent ratio: 2.10), 0.253 parts by weight Magnesium stearate (0.053 mol part with respect to 100 mol parts of the carboxyl group of the polyester polycarboxylic acid) and 0.500 parts by weight of Florene AC-1190 (manufactured by Kyoeisha Chemical Co., Ltd., antifoaming agent) were charged.

Thereafter, the temperature was raised to 80 ° C. with a mantle heater while introducing nitrogen, and then the reaction was continued at a reaction temperature of 80 ° C. for 5 hours to obtain an isocyanate group-containing ester amide oligomer (F) that is an isocyanate group-containing oligomer (F). -1) was obtained.

The isocyanate group-containing ester amide oligomer (F-1) obtained has an isocyanate content of 3.7% by weight (theoretical value 3.7% by weight), a viscosity of 4800 mPa · s / 100 ° C., and a number average molecular weight of 4390. there were.

Further, ¹ H-NMR of the resulting isocyanate group-containing ester amide oligomer (F-1) was measured. From the NMR chart, the chemical shift when the integral value of the 0.7346H portion appearing at the chemical shift of 0.6 ppm out of 10H of the alicyclic portion of the 1,3-bis (isocyanatomethyl) cyclohexane derivative is 0.7346. When the amidation rate was calculated from the integral value of NH of amide appearing at 7.8 ppm, it was 90%.

[Synthesis Example F-2 Production of Isocyanate Group-Containing Esteramide Oligomer (F-2)]
166.3 parts by weight of 1,3-bis (isocyanatomethyl) cyclohexane (trade name: Takenate 600, Mitsui) was added to a 2 liter reaction flask equipped with a reflux condenser, a nitrogen gas inlet tube, a thermometer and a stirrer. (Manufactured by Chemical Polyurethane Co., Ltd.), 0.240 parts by weight of magnesium stearate (0.05 mol parts with respect to 100 mol parts of carboxyl groups of the polyester polycarboxylic acid (G-1) obtained in Synthesis Example G-1 below) And 0.500 parts by weight of Florene AC-1190 (manufactured by Kyoeisha Chemical Co., Ltd., antifoaming agent).

Thereafter, the temperature was raised to 60 ° C. with a mantle heater while introducing nitrogen.

Here, 75.9 parts by weight of polyester polycarboxylic acid (G-1) heated to 75 ° C. was added.

Immediately after the addition, it was confirmed that the foaming and the temperature rose to 65 ° C. About 10 minutes after the addition, the temperature was lowered to 60 ° C. and the foaming stopped.

After confirming that the temperature was lowered and foaming was stopped, 75.9 parts by weight of polyester polycarboxylic acid (G-1) heated to 75 ° C. was added. The same phenomenon was confirmed earlier.

In this manner, 75.9 parts by weight of polyester polycarboxylic acid (G-1) heated to 75 ° C. in about 110 minutes was added 10 times in total, and then 74.7 parts by weight heated to 75 ° C. Polyester polycarboxylic acid (G-1) was added once. Also at this time, it was confirmed that the foaming and the temperature was raised to about 65 ° C. As described above, 833.70 parts by weight of the total amount of the polyester polycarboxylic acid (G-1) was added (NCO / COOH equivalent ratio: 2.13).

Thereafter, the mixture was heated to 80 ° C. and aged for 7 hours to obtain an isocyanate group-containing ester amide oligomer (F-2) which is an isocyanate group-containing oligomer (F).

In the obtained isocyanate group-containing ester amide oligomer (F-2), the isocyanate group content was 4.05% by weight (theoretical value: 3.95% by weight), the viscosity was 4300 mPa · s / 100 ° C., and the number average molecular weight was 3750. Met.

Further, ¹ H-NMR of the obtained isocyanate group-containing ester amide oligomer (F-2) was measured. From the NMR chart, the chemical shift when the integral value of the 0.7346H portion appearing at the chemical shift of 0.6 ppm out of 10H of the alicyclic portion of the 1,3-bis (isocyanatomethyl) cyclohexane derivative is 0.7346. When the amidation rate was calculated from the integral value of NH of amide appearing at 7.8 ppm, it was 90%.

[Synthesis Example F-3 Production of Isocyanate Group-Containing Esteramide Oligomer (F-3)]
A 2 liter reaction flask equipped with a reflux condenser, a nitrogen gas inlet tube, a thermometer and a stirrer was charged with 217.75 parts by weight of polymethylene polyphenyl polyisocyanate (trade name: Cosmonate M-200, Mitsui Chemicals Polyurethane). Made by the company, isocyanate group content is 31.0% by weight), 0.220 parts by weight of magnesium stearate (100 mol parts of carboxyl groups of polyester polycarboxylic acid (G-1) obtained in Synthesis Example G-1 below) 0.05 mol part) and 0.500 parts by weight of Florene AC-1190 (manufactured by Kyoeisha Chemical Co., Ltd., antifoaming agent) were charged.

Thereafter, the temperature was raised to 55 ° C. with a mantle heater while introducing nitrogen.

Here, 71.20 parts by weight of polyester polycarboxylic acid (G-1) heated to 70 ° C. was added.

Immediately after addition, it was confirmed that foaming and the temperature was raised to 60 ° C. About 10 minutes after the addition, the temperature was lowered to 55 ° C. and the foaming stopped.

After confirming that the temperature was lowered and foaming stopped, 71.20 parts by weight of polyester polycarboxylic acid (G-1) heated to 70 ° C. was added. The same phenomenon was confirmed earlier.

In this manner, 71.20 parts by weight of polyester polycarboxylic acid (G-1) heated to 70 ° C. in about 110 minutes was added 10 times in total, and then 70.25 parts by weight heated to 70 ° C. Polyester polycarboxylic acid (G-1) was added once. Also at this time, it was confirmed that the foaming and the temperature was raised to about 65 ° C. Polyester polycarboxylic acid (G-1) was added in a total amount of 782.25 parts by weight (NCO / COOH equivalent ratio: 2.13).

Thereafter, the mixture was heated to 75 ° C. and aged for 7 hours to obtain an isocyanate group-containing ester amide oligomer (F-3) which was an isocyanate group-containing oligomer (F).

In the obtained isocyanate group-containing ester amide oligomer (F-3), the isocyanate group content was 3.82% by weight (theoretical value 3.70% by weight), the viscosity was 4300 mPa · s / 100 ° C., and the number average molecular weight was 3750. Met.

Further, ¹ H-NMR of the obtained isocyanate group-containing ester amide oligomer (F-3) was measured. From the NMR chart, the chemical shift of H in the benzene ring portion of the polymethylene polyphenyl polyisocyanate derivative is 7.2 ppm, while the chemical shift of H in the amide bond is 9.8 ppm. It was 89% when calculated.

[Synthesis Example G-1 Production of Polyester Polycarboxylic Acid (G-1)]
A 5-liter flask equipped with a reflux condenser, a water separator, a nitrogen gas inlet tube, a thermometer and a stirrer was charged with 2045.1 parts by weight of adipic acid and 1306.5 parts by weight of neopentyl glycol (COOH / OH equivalent ratio: 1.12), and the temperature was raised with a mantle heater while introducing nitrogen.

Distillation of water started when the temperature reached 150 ° C., the temperature was raised to 230 ° C. while distilling water, and dehydration condensation was continued at 230 ° C. When the acid value and hydroxyl value of the reaction product reached the following values, the reaction product was withdrawn from the flask and cooled to obtain polyester polycarboxylic acid (G-1). The obtained polyester polycarboxylic acid (G-1) had an acid value of 54.8 mgKOH / g and a hydroxyl value of 2.7 mgKOH / g. The viscosity of the polyester polycarboxylic acid (G-1) was 1000 mPa · s / 80 ° C., and the number average molecular weight was 3841.

The synthesis conditions and properties of polyester polycarboxylic acid (G-1) are shown in Table 1.

[Synthesis Examples G-2 to G-4 Production of Polyester Polycarboxylic Acids (G-2) to (G-4)]
Synthesis Examples G-2 to G-4 were carried out in the same manner as Synthesis Example G-1, except that the synthesis conditions were changed to those described in Table 1. Table 1 shows the synthesis conditions and characteristics of the polyester polycarboxylic acids (G-2) to (G-4).

In addition, m in Table 1 means m in the general formula Ry, and is a value calculated from the charged amount of each polyester polycarboxylic acid raw material and the number average molecular weight.

[Example 1]
A lab plast mill (Model 20R200, manufactured by Toyo Seiki Seisakusho) was preheated to 200 ° C., and nitrogen was circulated at 1 L / min. The rotation speed was 60 rpm.

Here, 12.5 g of homopolypropylene (MFR 13.7 g / 10 min (230 ° C., 2.16 kgf), melting point (Tm) 162 ° C.) was added. The mixture was kneaded for 1 minute after the homopolypropylene was charged. The torque after kneading for 1 minute was 2.0 kg · m. The temperature was 200 ° C. and the rotation speed was 60 rpm.

Here, 20.4 g of ethylene / α-olefin copolymer (E-1) having a functional group capable of reacting with an isocyanate group was added. The mixture was kneaded for 4 minutes after adding ethylene / α-olefin copolymer (E-1) having a functional group capable of reacting with an isocyanate group. The torque after kneading for 4 minutes was 13.8 kg · m. The temperature was 200 ° C. and the rotation speed was 60 rpm.

Here, the isocyanate group-containing ester amide oligomer (F-1) is a functional group value of an ethylene / α-olefin copolymer (E-1) having a functional group whose isocyanate functional group number can react with an isocyanate group. 8.8 g was added so as to be equivalent to the number. The torque immediately after charging was 1.2 kg · m. The temperature was 200 ° C. and the rotation speed was 60 rpm. The mixture was kneaded for 5 minutes after adding the isocyanate group-containing ester amide oligomer (F-1).

The torque after kneading for 5 minutes was 17.6 kg · m. The temperature was 200 ° C. and the rotation speed was 60 rpm. Since the increase in torque was no longer observed, the rotation of the lab plast mill was stopped, the sample was taken out, and cold-pressed at 15 ° C. and 100 kg / cm ² for 5 minutes to obtain a thermoplastic crosslinked elastomer composition (D -1) was obtained.

13.8 g of this thermoplastic cross-linked elastomer composition (D-1) was placed in a mold of 8 cm × 8 cm × thickness 2 mm. To this, preheating is carried out at 200 ° C. for 7 minutes, followed by hot pressing for 3 minutes at 200 ° C. and 100 kg / cm ² , and then cooling at 15 ° C. and 100 kg / cm ² . It was performed by cold pressing for 5 minutes to obtain a sample for oil resistance, hardness measurement and TEM observation.

Similarly, 6.8 g of this thermoplastic cross-linked elastomer composition (D-1) was placed in a mold of 8 cm × 8 cm × 1 mm thickness. To this, preheating is carried out at 200 ° C. for 7 minutes, followed by hot pressing for 3 minutes at 200 ° C. and 100 kg / cm ² , and then cooling at 15 ° C. and 100 kg / cm ² . This was performed by cold pressing for 5 minutes to obtain a sample for measuring mechanical properties.

As a result of TEM observation of the thermoplastic crosslinked elastomer composition (D-1), a sea-island structure could be confirmed. The sea phase was slightly stained and the island phase was observed with a deep staining. It is known that homopolypropylene is difficult to color by staining with RuO ₄ . Therefore, it could be judged that the sea phase is a homopolypropylene and the sea-island structure is an ethylene / α-olefin copolymer in which the island phase is crosslinked.

Manufacturing conditions, oil resistance, hardness, mechanical property measurement results and TEM observation results are shown in a separate table.

[Example 2]
A lab plast mill (Model 20R200, manufactured by Toyo Seiki Seisakusho) was preheated to 200 ° C., and nitrogen was circulated at 1 L / min. The rotation speed was 60 rpm.

Here, 12.35 g of homopolypropylene (MFR 13.7 g / 10 min (230 ° C., 2.16 kgf), melting point (Tm) 162 ° C.) was added. The mixture was kneaded for 1 minute after the homopolypropylene was charged. The torque after kneading for 1 minute was 2.0 kg · m. The temperature was 200 ° C. and the rotation speed was 60 rpm.

Here, 22.30 g of ethylene / α-olefin copolymer (E-2) having a functional group capable of reacting with an isocyanate group was added. The mixture was kneaded for 4 minutes after the ethylene / α-olefin copolymer (E-2) having a functional group capable of reacting with an isocyanate group was added. The torque after kneading for 4 minutes was 14.6 kg · m. The temperature was 200 ° C. and the rotation speed was 60 rpm.

Here, the isocyanate group-containing ester amide oligomer (F-1) is a functional group value of an ethylene / α-olefin copolymer (E-2) having a functional group whose isocyanate functional group number can react with an isocyanate group. 6.60 g was added so as to be equivalent to the number. The torque immediately after charging was 1.2 kg · m. The temperature was 200 ° C. and the rotation speed was 60 rpm. The mixture was kneaded for 5 minutes after adding the isocyanate group-containing ester amide oligomer (F-1). The torque after kneading for 5 minutes was 15.7 kg · m. The temperature was 200 ° C. and the rotation speed was 60 rpm. Since the increase in torque was no longer observed, the rotation of the lab plast mill was stopped, the sample was taken out, and cold-pressed at 15 ° C. and 100 kg / cm ² for 5 minutes to obtain a thermoplastic crosslinked elastomer composition (D -2) was obtained.

13.8 g of this thermoplastic cross-linked elastomer composition (D-2) was placed in a mold of 8 cm × 8 cm × 2 mm thickness. To this, preheating is carried out at 200 ° C. for 7 minutes, followed by hot pressing for 3 minutes at 200 ° C. and 100 kg / cm ² , and then cooling at 15 ° C. and 100 kg / cm ² . It was performed by cold pressing for 5 minutes to obtain a sample for oil resistance, hardness measurement and TEM observation.

Similarly, 6.8 g of this thermoplastic cross-linked elastomer composition (D-2) was put into a mold having a size of 8 cm × 8 cm × thickness 1 mm. To this, preheating is carried out at 200 ° C. for 7 minutes, followed by hot pressing for 3 minutes at 200 ° C. and 100 kg / cm ² , and then cooling at 15 ° C. and 100 kg / cm ² . This was performed by cold pressing for 5 minutes to obtain a sample for measuring mechanical properties.

As a result of TEM observation of the thermoplastic crosslinked elastomer composition (D-2), a sea-island structure could be confirmed. The sea phase was slightly stained and the island phase was observed with a deep staining. It is known that homopolypropylene is difficult to color by staining with RuO ₄ . Therefore, it could be judged that the sea phase is a homopolypropylene and the sea-island structure is an ethylene / α-olefin copolymer in which the island phase is crosslinked.

[Example 3]
A lab plast mill (Model 20R200, manufactured by Toyo Seiki Seisakusho) was preheated to 200 ° C., and nitrogen was circulated at 1 L / min. The rotation speed was 60 rpm.

Here, 12.45 g of homopolypropylene (MFR 13.7 g / 10 min (230 ° C., 2.16 kgf), melting point (Tm) 162 ° C.) was added. The mixture was kneaded for 1 minute after the homopolypropylene was charged. The torque after kneading for 1 minute was 2.0 kg · m. The temperature was 200 ° C. and the rotation speed was 60 rpm.

Here, 22.90 g of ethylene / α-olefin copolymer (E-2) having a functional group capable of reacting with an isocyanate group was charged. The mixture was kneaded for 4 minutes after the ethylene / α-olefin copolymer (E-2) having a functional group capable of reacting with an isocyanate group was added. The torque after 4 minutes of kneading was 14.9 kg · m. The temperature was 200 ° C. and the rotation speed was 60 rpm.

Here, the isocyanate group-containing ester amide oligomer (F-2) is a functional group value of an ethylene / α-olefin copolymer (E-2) having a functional group whose isocyanate functional group number can react with an isocyanate group. 6.20 g was added so as to be equivalent to the number. The torque immediately after charging was 1.2 kg · m. The temperature was 200 ° C. and the rotation speed was 60 rpm.

The mixture was kneaded for 5 minutes after adding the isocyanate group-containing ester amide oligomer (F-2). The torque after kneading for 5 minutes was 15.7 kg · m. The temperature was 200 ° C. and the rotation speed was 60 rpm. Since the increase in torque was not observed, the rotation of the lab plast mill was stopped, the sample was taken out, and cold-pressed at 15 ° C. and 100 kg / cm ² for 5 minutes to obtain a thermoplastic cross-linked elastomer composition ( D-3) was obtained.

13.8 g of this thermoplastic cross-linked elastomer composition (D-3) was placed in a mold of 8 cm × 8 cm × thickness 2 mm. To this, preheating is carried out at 200 ° C. for 7 minutes, followed by hot pressing for 3 minutes at 200 ° C. and 100 kg / cm ² , and then cooling at 15 ° C. and 100 kg / cm ² . It was performed by cold pressing for 5 minutes to obtain a sample for oil resistance, hardness measurement and TEM observation.

Similarly, 6.8 g of this thermoplastic cross-linked elastomer composition (D-3) was placed in a mold of 8 cm × 8 cm × thickness 1 mm. To this, preheating is carried out at 200 ° C. for 7 minutes, followed by hot pressing for 3 minutes at 200 ° C. and 100 kg / cm ² , and then cooling at 15 ° C. and 100 kg / cm ² . This was performed by cold pressing for 5 minutes to obtain a sample for measuring mechanical properties.

As a result of TEM observation of the thermoplastic cross-linked elastomer composition (D-3), a sea-island structure could be confirmed. The sea phase was slightly stained and the island phase was observed with a deep staining. It is known that homopolypropylene is difficult to color by staining with RuO ₄ . Therefore, it could be judged that the sea phase is a homopolypropylene and the sea-island structure is an ethylene / α-olefin copolymer in which the island phase is crosslinked.

[Example 4]
A lab plast mill (manufactured by Toyo Seiki Seisakusho, model 20R200) was preheated to 200 ° C. and 1 L / min of nitrogen was circulated. The rotation speed was 60 rpm.

Here, 12.70 g of homopolypropylene (MFR 13.7 g / 10 min (230 ° C., 2.16 kgf), melting point (Tm) 162 ° C.) was added. The mixture was kneaded for 1 minute after the homopolypropylene was charged. The torque after kneading for 1 minute was 2.1 kg · m. The temperature was 200 ° C. and the rotation speed was 60 rpm.

Here, 23.10 g of ethylene / α-olefin copolymer (E-2) having a functional group capable of reacting with an isocyanate group was added. The mixture was kneaded for 4 minutes after the ethylene / α-olefin copolymer (E-2) having a functional group capable of reacting with an isocyanate group was added. The torque after kneading for 4 minutes was 15.3 kg · m. The temperature was 200 ° C. and the rotation speed was 60 rpm.

Here, the isocyanate group-containing ester amide oligomer (F-3) is a functional group value of an ethylene / α-olefin copolymer (E-2) having a functional group whose isocyanate functional group number can react with an isocyanate group. 6.60 g was added so as to be equivalent to the number. The torque immediately after charging was 1.2 kg · m. The temperature was 200 ° C. and the rotation speed was 60 rpm. The mixture was kneaded for 5 minutes after adding the isocyanate group-containing ester amide oligomer (F-3). The torque after kneading for 5 minutes was 16.0 kg · m. The temperature was 200 ° C. and the rotation speed was 60 rpm. Since the increase in torque was no longer observed, the rotation of the lab plast mill was stopped, the sample was taken out, and cold-pressed at 15 ° C. and 100 kg / cm ² for 5 minutes to obtain a thermoplastic crosslinked elastomer composition (D -4) was obtained.

13.8 g of this thermoplastic cross-linked elastomer composition (D-4) was placed in a mold of 8 cm × 8 cm × thickness 2 mm. To this, preheating is carried out at 200 ° C. for 7 minutes, followed by hot pressing for 3 minutes at 200 ° C. and 100 kg / cm ² , and then cooling at 15 ° C. and 100 kg / cm ² . It was performed by cold pressing for 5 minutes to obtain a sample for oil resistance, hardness measurement and TEM observation.

Similarly, 6.8 g of this thermoplastic cross-linked elastomer composition (D-4) was put into a mold having a size of 8 cm × 8 cm × thickness 1 mm. To this, preheating is carried out at 200 ° C. for 7 minutes, followed by hot pressing for 3 minutes at 200 ° C. and 100 kg / cm ² , and then cooling at 15 ° C. and 100 kg / cm ² . This was performed by cold pressing for 5 minutes to obtain a sample for measuring mechanical properties.

As a result of TEM observation of the thermoplastic cross-linked elastomer composition (D-4), the sea-island structure could be confirmed. The sea phase was slightly stained and the island phase was observed with a deep staining. It is known that homopolypropylene is difficult to color by staining with RuO ₄ . Therefore, it could be judged that the sea phase is a homopolypropylene and the sea-island structure is an ethylene / α-olefin copolymer in which the island phase is crosslinked.

[Comparative Example 1]
A lab plast mill (Model 20R200, manufactured by Toyo Seiki Seisakusho) was preheated to 200 ° C., and nitrogen was circulated at 1 L / min. The rotation speed was 60 rpm.

Here, 28.5 g of an ethylene / α-olefin copolymer (E-2) having a functional group capable of reacting with an isocyanate group was added. The mixture was kneaded for 4 minutes after the ethylene / α-olefin copolymer (E-2) having a functional group capable of reacting with an isocyanate group was added. The torque after kneading for 4 minutes was 14.7 kg · m. The temperature was 200 ° C. and the rotation speed was 60 rpm.

Here, 1,3-bis (isocyanatomethyl) cyclohexane (trade name: Takenate 600, manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.) is reacted with an isocyanate group having a functional group whose isocyanate functional group valency can react with an isocyanate group. 0.72 g was added so as to be equivalent to the functional group valence of the ethylene / α-olefin copolymer (E-2) having a functional group capable of being converted. The torque immediately after charging was 20.1 kg · m. The temperature was 200 ° C. and the rotation speed was 60 rpm. The mixture was kneaded for 5 minutes after 1,3-bis (isocyanatomethyl) cyclohexane was added. The torque after kneading for 5 minutes was 17.5 kg · m. The temperature was 200 ° C. and the rotation speed was 60 rpm. Since no increase in torque was observed, the rotation of the lab plastmill was stopped, the sample was taken out, and cold-pressed at 15 ° C. and 100 kg / cm ² for 5 minutes to obtain a thermoplastic crosslinked elastomer composition (D- 5) Obtained.

13.8 g of this thermoplastic cross-linked elastomer composition (D-5) was placed in a mold having a size of 8 cm × 8 cm × thickness 2 mm. To this, preheating is carried out at 200 ° C. for 7 minutes, followed by hot pressing for 3 minutes at 200 ° C. and 100 kg / cm ² , and then cooling at 15 ° C. and 100 kg / cm ² . It was performed by cold pressing for 5 minutes to obtain a sample for oil resistance, hardness measurement and TEM observation.

Similarly, 6.8 g of this thermoplastic cross-linked elastomer composition (D-5) was placed in a mold of 8 cm × 8 cm × 1 mm thickness. To this, preheating is carried out at 200 ° C. for 7 minutes, followed by hot pressing for 3 minutes at 200 ° C. and 100 kg / cm ² , and then cooling at 15 ° C. and 100 kg / cm ² . This was performed by cold pressing for 5 minutes to obtain a sample for measuring mechanical properties.

As a result of TEM observation of the thermoplastic cross-linked elastomer composition (D-5), a sea-island structure could be confirmed. The sea phase was slightly stained and the island phase was observed with a deep staining. It is known that homopolypropylene is difficult to color by staining with RuO ₄ . Therefore, it was judged that the sea phase was a sea-island structure, which was an ethylene / α-olefin copolymer crosslinked with homopolypropylene and island phases with 1,3-bis (isocyanatomethyl) cyclohexane.

[Comparative Example 2]
A lab plast mill (Model 20R200, manufactured by Toyo Seiki Seisakusho) was preheated to 200 ° C., and nitrogen was circulated at 1 L / min. The rotation speed was 60 rpm.

12.3 g of homopolypropylene (MFR 13.7 g / 10 min (230 ° C., 2.16 kgf), melting point (Tm) 162 ° C.) was added thereto. The mixture was kneaded for 1 minute after the homopolypropylene was charged. The torque after kneading for 1 minute was 2.0 kg · m. The temperature was 200 ° C. and the rotation speed was 60 rpm.

Here, 28.7 g of an ethylene / α-olefin copolymer (E-2) having a functional group capable of reacting with an isocyanate group was added. The mixture was kneaded for 4 minutes after the ethylene / α-olefin copolymer (E-2) having a functional group capable of reacting with an isocyanate group was added. The torque after kneading for 4 minutes was 14.6 kg · m. The temperature was 200 ° C. and the rotation speed was 60 rpm.

Here, the rotation of the lab plast mill was stopped, the sample was taken out, and cold-pressed at 15 ° C. and 100 kg / cm ² for 5 minutes to obtain a thermoplastic elastomer composition (D-6).

13.8 g of this thermoplastic elastomer composition (D-6) was placed in a mold of 8 cm × 8 cm × 2 mm thickness. To this, preheating is carried out at 200 ° C. for 7 minutes, followed by hot pressing for 3 minutes at 200 ° C. and 100 kg / cm ² , and then cooling at 15 ° C. and 100 kg / cm ² . It was performed by cold pressing for 5 minutes to obtain a sample for oil resistance, hardness measurement and TEM observation.

Similarly, 6.8 g of this thermoplastic elastomer composition (D-6) was placed in a mold having a size of 8 cm × 8 cm × thickness 1 mm. To this, preheating is carried out at 200 ° C. for 7 minutes, followed by hot pressing for 3 minutes at 200 ° C. and 100 kg / cm ² , and then cooling at 15 ° C. and 100 kg / cm ² . This was performed by cold pressing for 5 minutes to obtain a sample for measuring mechanical properties.

Further, as a result of TEM observation of the thermoplastic elastomer composition (D-6), the sea-island structure could be confirmed. The island phase was slightly stained and the sea phase was densely stained. It is known that homopolypropylene is difficult to color by staining with RuO ₄ . Therefore, it could be judged that the island phase is a homopolypropylene and the sea phase is a sea-island structure which is an ethylene / α-olefin copolymer having a functional group capable of reacting with an isocyanate group.

[Example 5]
A lab plast mill (Model 20R200, manufactured by Toyo Seiki Seisakusho) was preheated to 200 ° C., and nitrogen was circulated at 1 L / min. The rotation speed was 50 rpm.

8.53 g of homopolypropylene (manufactured by Prime Polymer Co., Ltd., trade name J105G, MFR 9.0 g / 10 min (230 ° C., 2.16 kgf)), ethylene / α-olefin having a functional group capable of reacting with an isocyanate group 7.54 g of copolymer (E-3), 3.22 g of ethylene / methacrylic acid copolymer (trade name Nucrel N1108C, manufactured by Mitsui DuPont Polychemical Co., Ltd.) as an ethylene / unsaturated carboxylic acid copolymer, oxidized 0.05 g of pentaeryristyl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1010, manufactured by Ciba Japan Co., Ltd.) as a compatibilizer Propylene / ethylene glycol copolymer (Sanyo Chemical Industries, Ltd.) previously dehumidified by holding for 12 hours at 105 ° C. and 1 kPa pressure Ltd., was the product name PELESTAT 300) and 3.52g on. The mixture was kneaded for 4 minutes after the addition. The maximum torque during this period was 4.1 N · m (temperature 200 ° C., rotation speed 50 rpm). Thereafter, 6.94 g of process oil (petroleum hydrocarbon) (trade name Diana Process Oil PW100, manufactured by Idemitsu Kosan Co., Ltd.) was added as a softening agent while kneading for 6 minutes. After completion of the addition, the mixture was further kneaded for 5 minutes, the kneading was stopped, and the temperature was lowered to 140 ° C.

When the temperature was lowered to 140 ° C., the number of revolutions was 50 rpm, and the mixture was kneaded for 4 minutes.

Thereafter, 12.44 g of a polyester polycarboxylic acid (G-1) that had been dehumidified by holding it at 105 ° C. and a pressure of 1 kPa for 12 hours in advance was added while kneading for 14 minutes. After completion of the addition, the mixture was further kneaded for 5 minutes. The final torque was 5.8 N · m (temperature 140 ° C., rotation speed 50 rpm). Here, kneading was stopped and the temperature was raised to 200 ° C.

When the temperature was raised to 200 ° C., the rotation speed was set to 100 rpm, 0.44 g of triethylenediamine and 0.48 g of 1,8-diazabicyclo [5,4,0] undecene-7 were added as catalysts and kneaded for 4 minutes. . The torque after kneading for 4 minutes was 1.01 N · m (temperature 200 ° C., rotation speed 100 rpm).

Here, 3.49 g of polymethylene polyphenyl polyisocyanate (manufactured by Mitsui Chemicals Polyurethane Co., Ltd., trade name Cosmonate M-200) was added as a polyvalent isocyanate while kneading. After completion of the addition, the mixture was further kneaded for 12 minutes. The final torque was 12.1 N · m (temperature 200 ° C., rotation speed 100 rpm). Here, kneading was stopped, a sample was taken out, and cold pressing was performed at 15 ° C. and 100 kg / cm ² for 5 minutes to obtain a thermoplastic crosslinked elastomer composition (D-7).

13.8 g of this thermoplastic cross-linked elastomer composition (D-7) was placed in a mold of 8 cm × 8 cm × thickness 2 mm. To this, preheating is performed at 230 ° C. for 7 minutes, then pressurization is performed by hot pressing for 3 minutes at 230 ° C. and 100 kg / cm ² , and then cooling is performed at 15 ° C. and 100 kg / cm ² . It was performed by cold pressing for 5 minutes to obtain a sample for oil resistance, hardness measurement and TEM observation.

Similarly, 6.8 g of this thermoplastic cross-linked elastomer composition (D-7) was put into a mold having a size of 8 cm × 8 cm × thickness 1 mm. To this, preheating is performed at 230 ° C. for 7 minutes, then pressurization is performed by hot pressing for 3 minutes at 230 ° C. and 100 kg / cm ² , and then cooling is performed at 15 ° C. and 100 kg / cm ² . This was performed by cold pressing for 5 minutes to obtain a sample for measuring mechanical properties.

Further, as a result of TEM observation of the thermoplastic cross-linked elastomer composition (D-7), the sea-island structure could be confirmed. The sea phase was slightly stained and the island phase was observed with a deep staining. Dyeing with RuO4 is known to be difficult to color homopolypropylene. Therefore, it was judged that the sea phase was a homopolypropylene and the sea-island structure was an ethylene / α-olefin copolymer in which at least a part of the island phase was crosslinked.

[Examples 6 to 17]
Examples 6 to 17 were carried out in the same manner as Example 5 except that the raw materials and reaction conditions were changed to the raw materials and reaction conditions described in the attached tables (Tables 2 to 5).

In Tables 2 and 4, * 1 to * 13 indicate the following components.

In Tables 2 and 4, n in the item of the isocyanate group-containing oligomer means n in the general formulas Rx, Ra, and Rb, and is a value obtained from the amount of raw materials charged in Synthesis Examples F-1 to F-3. It is. In Tables 2 and 4, n in the item of polyester polycarboxylic acid is the cross-linked ethylene copolymer (B) formed from the polyester polycarboxylic acid, polyisocyanate, and ethylene copolymer (E). It means n in the general formulas Ra and Rb, and is a value obtained from the amount of raw material charged in the example.
* 1: Polypropylene * 2: Homopolypropylene, manufactured by Prime Polymer Co., Ltd., trade name J105G
* 3: Ethylene-methacrylic acid copolymer, manufactured by Mitsui DuPont Polychemical Co., Ltd., trade name Nukurel N1108C
* 4: 1,3-bis (isocyanatomethyl) cyclohexane, manufactured by Mitsui Chemicals Polyurethanes, Inc., trade name Takenate 600
* 5: Polymethylene polyphenyl polyisocyanate, manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., trade name Cosmonate M-200, isocyanate group content is 31.0% by weight
* 6: Polymethylene polyphenyl polyisocyanate, manufactured by Mitsui Chemicals Polyurethanes, trade name Cosmonate T-100, isocyanate group content is 48.3 wt%
* 7: Pentaerystyl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by Ciba Japan, trade name Irganox 1010
* 8: Propylene / ethylene glycol copolymer, manufactured by Sanyo Chemical Industries, trade name Pelestat 300
* 9: Process oil (petroleum hydrocarbon) manufactured by Idemitsu Kosan Co., Ltd., trade name Diana Process Oil PW100
* 10: Triethylenediamine * 11: Magnesium stearate * 12: Tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium chloride * 13: 1,8-diazabicyclo [5,4,0] undecene-7

Claims

Including a crystalline olefin polymer (A) and a crosslinked ethylene copolymer (B),
The crosslinking site (C) of the crosslinked ethylene copolymer (B) is an organic group (c1) having at least one nitrogen-containing group selected from the group consisting of an amide group and an imide group, and an ester group. A cross-linked thermoplastic elastomer composition (D) characterized by the above.
The crosslinked ethylene copolymer (B) is an ethylene / α-olefin copolymer having a functional group capable of reacting with an isocyanate group, and an ethylene / α-olefin / nonconjugated polyene copolymer having a functional group capable of reacting with an isocyanate group. 2. The polymer obtained by crosslinking at least one ethylene copolymer (E) selected from the group consisting of a polymer and an ethylene / unsaturated carboxylic acid copolymer. The cross-linked thermoplastic elastomer composition (D) described.
The organic group (c1) is, crosslinked thermoplastic elastomer according to claim 1 or 2 characterized in that it comprises a divalent group represented by general formula R 2 (D).

(In the above general formula R 2 , each R 3 is independently an alkylene group having 1 to 15 carbon atoms or an aromatic group having 6 to 15 carbon atoms which may have a branch, and each R 4 is independently And an optionally substituted alkylene group having 1 to 15 carbon atoms.)
The cross-linking according to any one of claims 1 to 3, wherein the organic group (c1) is at least one organic group selected from the group consisting of the following general formula Ra and the following general formula Rb. Type thermoplastic elastomer composition (D).

(In the above general formulas Ra and Rb, each Rc is independently a trivalent hydrocarbon group having 1 to 20 carbon atoms, and each Rd is independently a divalent hydrocarbon group having 1 to 20 carbon atoms. , R 1 are each independently a diisocyanate residue, and R 2 are each independently a divalent group represented by the following general formula.)

(In the above general formula R 2 , each R 3 is independently an alkylene group having 1 to 15 carbon atoms or an aromatic group having 6 to 15 carbon atoms which may have a branch, and each R 4 is independently And an optionally substituted alkylene group having 1 to 15 carbon atoms.)
R 1 is a divalent carbon atom having 6 to 20 carbon atoms having an optionally branched alkylene group having 2 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, and an alicyclic hydrocarbon group. The crosslinked thermoplastic elastomer composition (D) according to claim 4, which is at least one group selected from the group consisting of hydrogen groups.
6. The weight ratio (A / B) between the crystalline olefin polymer (A) and the crosslinked ethylene copolymer (B) is 10/90 to 50/50, The crosslinked thermoplastic elastomer composition (D) according to any one of the above.
7. The general formula Ra and the general formula Rb, wherein n is 0 to 3, and in the general formula R 2 , m is 7 to 20, according to any one of claims 4 to 6, Cross-linked thermoplastic elastomer composition (D).
The crystalline olefin polymer (A), an ethylene / α-olefin copolymer having a functional group capable of reacting with an isocyanate group, and an ethylene / α-olefin / nonconjugated polyene copolymer having a functional group capable of reacting with an isocyanate group. In a mixture with a polymer and at least one ethylene copolymer (E) selected from the group consisting of an ethylene / unsaturated carboxylic acid copolymer,
Introducing an isocyanate group-containing oligomer (F) having an amide group, an ester group, and two or more isocyanate groups as a crosslinking agent, or introducing a polyester polycarboxylic acid (G) and a polyvalent isocyanate as a crosslinking agent And obtained by dynamically crosslinking the ethylene copolymer (E).
The sea-island structure in which the sea phase is a crystalline olefin polymer (A) and at least a part of the island phase is a crosslinked ethylene copolymer (B) is formed. The crosslinked thermoplastic elastomer composition (D) according to Item.
The number average molecular weight of the said isocyanate group containing oligomer (F) calculated | required by gel permeation chromatography (GPC) in conversion of a standard polyethyleneglycol exceeds 2000, Crosslinked type thermoplasticity of Claim 8 characterized by the above-mentioned. Elastomer composition (D).
The cross-linked thermoplastic elastomer composition (D) according to claim 8 or 9, wherein the isocyanate group-containing oligomer (F) is represented by the following general formula Rx.

(In the general formula Rx, each R 1 is independently a diisocyanate residue, and each R 2 is independently a divalent group represented by the following general formula.)

(In the above general formula R 2 , each R 3 is independently an alkylene group having 1 to 15 carbon atoms or an aromatic group having 6 to 15 carbon atoms which may have a branch, and each R 4 is independently And an optionally substituted alkylene group having 1 to 15 carbon atoms.)
R 1 is a divalent carbon atom having 6 to 20 carbon atoms having an optionally branched alkylene group having 2 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, and an alicyclic hydrocarbon group. The crosslinked thermoplastic elastomer composition (D) according to claim 10, which is at least one group selected from the group consisting of hydrogen groups.
In the general formula Rx, n is 0 to 3, wherein in the general formula R 2, m is 7 to crosslinked thermoplastic elastomer composition according to claim 10 or 11, characterized in that it is 20 (D ).
The isocyanate group-containing oligomer (F) is obtained by reacting a polyisocyanate with a polyester polycarboxylic acid (G) produced from a polyhydric alcohol and a polycarboxylic acid,
The cross-linked thermoplastic elastomer composition (D) according to claim 8, wherein at least one of the polyhydric alcohol, polycarboxylic acid and polyisocyanate contains a trivalent or higher monomer.
The cross-linked thermoplastic elastomer composition (D) according to claim 8, wherein the polyvalent isocyanate contains a trivalent or higher polyvalent isocyanate.
The crosslinkable heat according to any one of claims 8 to 14, wherein the functional group capable of reacting with an isocyanate group in the ethylene copolymer (E) is a carboxyl group or a carboxylic anhydride group. Plastic elastomer composition (D).
Crystalline olefin polymer (A), ethylene / α-olefin copolymer having functional group capable of reacting with isocyanate group, ethylene / α-olefin / nonconjugated polyene copolymer having functional group capable of reacting with isocyanate group A mixture with at least one ethylene copolymer (E) selected from the group consisting of a copolymer and an ethylene / unsaturated carboxylic acid copolymer,
Introducing an isocyanate group-containing oligomer (F) having an amide group, an ester group, and two or more isocyanate groups as a crosslinking agent, or introducing a polyester polycarboxylic acid (G) and a polyvalent isocyanate as a crosslinking agent The method for producing a crosslinked thermoplastic elastomer composition (D) according to any one of claims 1 to 15, wherein the ethylene copolymer (E) is dynamically crosslinked.
A molded body comprising the crosslinked thermoplastic elastomer composition (D) according to any one of claims 1 to 15.
The molded article according to claim 17, wherein the molded article is an automotive part.
The molded article according to claim 17, wherein the molded article is an automotive part selected from the group consisting of a boot, a wire harness cover, a seat adjuster cover, and a hose.