JP2020122128A - Method for producing thermoplastic elastomer composition - Google Patents

Abstract

To provide a method for producing a thermoplastic elastomer composition having excellent characteristics such as moldability.SOLUTION: A method for producing a thermoplastic elastomer composition includes the steps of dynamically crosslinking a carbodiimide group-containing compound (A), an olefin polymer (B) having a group that reacts with a carbodiimide group, a polar rubber (C), an olefin polymer (D) and a crosslinker (E), using a batch kneader, while satisfying conditions (1)-(3): (1) Tmax.≥T1, (2) T2≤T3, (3) 2.0≤P1≤8.5 [Tmax.=resin maximum temperature (°C) from crosslinker (E) input to composition discharge, T1=ΔE/(8.314×(LnA-3))-273.15, ΔE=activation energy (J/mol), A=frequency factor (hr), T2=resin temperature (°C) at crosslinker (E) input, T3=ΔE/(8.314×(LnA-5))-273.15, P1=LnA-ΔE/(8.314×(Tave.+273.15)), Tave.=resin average temperature (°C) from crosslinker (E) input to composition discharge].SELECTED DRAWING: None

Description

The present invention relates to a method for producing a thermoplastic elastomer composition containing a crosslinkable rubber and an olefin polymer.

Conventionally, a method for producing a thermoplastic elastomer by dynamically heat-treating an ethylene/α-olefin/non-conjugated polyene copolymer and a polyolefin resin in the presence of a crosslinking agent using a batch mixer is known. (Patent Document 1). However, it has been difficult to apply the conventional method to oil-resistant rubbers whose crosslinking behavior is different from that of the ethylene/α-olefin/non-conjugated polyene copolymer. Further, it could not be applied to a system in which the activity of the reaction is significantly changed in the presence of a crosslinking agent whose parameters such as activation energy are unknown, or a crosslinking aid such as a crosslinking accelerator or a crosslinking retarder. On the other hand, as a method of knowing the cross-linking property of the cross-linked rubber, there is a method of measuring a cross-linking curve in accordance with JIS K6300-2, but the conventional method can only estimate the cross-linking behavior when the temperature is constant, and the kneading is sequentially performed by kneading It could not be applied to a system where the temperature changes.

International Publication No. 2016/158612

The present invention provides a method for producing a thermoplastic elastomer composition containing a crosslinked polar rubber and an olefin-based polymer, both of which are highly dispersed with each other and which is excellent in moldability and other properties. To aim.

The gist of the present invention relates to the following [1] to [12].

[1] Carbodiimide group-containing compound (A),
An olefin polymer (B) having a group that reacts with a carbodiimide group,
Polar rubber (C),
The olefin polymer (D) and the cross-linking agent (E) capable of cross-linking the polar rubber (C)
A method for producing a thermoplastic elastomer composition, which comprises a step of dynamically cross-linking using a batch-type kneader under conditions satisfying the following conditions (1) to (3).
(1) Tmax. ≧ T1
(“Tmax.” is the maximum value (° C.) of the resin temperature from when the cross-linking agent (E) was introduced into the batch-type kneader to when the thermoplastic elastomer composition was discharged to the outside of the batch-type kneader. Is the temperature (°C) defined by the following formula (i).)
T1=ΔE/(8.314×(LnA-3))-273.15 (i)
(“ΔE” is the activation energy (J/mol) calculated from the slope of the Arrhenius plot created from the cross-linking curves measured at multiple temperatures using polar rubber (C) and cross-linking agent (E); Is the frequency factor (hr ⁻¹ ) calculated from the intercept.)
(2) T2 ≤ T3
(“T2” is the resin temperature (° C.) in the kneader when the cross-linking agent (E) is introduced into the batch type kneader, and “T3” is the temperature (° C.) defined by the following formula (ii). .)
T3=ΔE/(8.314×(LnA-5))-273.15 (ii)
(3) 2.0 ≤ P1 ≤ 8.5
("P1" is a value defined by the following formula (iii).)
P1=LnA−ΔE/(8.314×(Tave.+273.15)) (iii)
(“Tave.” is the average value (° C.) of the resin temperature from the state where the cross-linking agent (E) is present and the olefin polymer (D) is melted to the time when the kneading is completed and discharged.)

[2] The composition in the step of dynamically crosslinking contains a reaction product (I) of a carbodiimide group-containing compound (A) and an olefin polymer (B) having a group that reacts with a carbodiimide group, [ [1] The method for producing the thermoplastic elastomer composition described in [1].

[3] The method for producing a thermoplastic elastomer composition according to [1] or [2], wherein the polar rubber (C) contains a polar rubber (C1) having a group that reacts with a carbodiimide group.

[4] The method for producing a thermoplastic elastomer composition according to [3], wherein the polar rubber (C1) having a group that reacts with a carbodiimide group is a polar rubber having a group having active hydrogen in its side chain.

[5] The thermoplastic elastomer composition according to [3] or [4], containing a reaction product (II) of a carbodiimide group-containing compound (A) and a polar rubber (C1) having a group that reacts with a carbodiimide group. Method of manufacturing things.

[6] The method for producing a thermoplastic elastomer composition according to any one of [1] to [5], wherein the carbodiimide group-containing compound (A) is a polycarbodiimide having a repeating unit represented by the following general formula.
^{-N = C = N-R 1} -
(In the formula, R ¹ represents a divalent organic group.)

[7] The olefin polymer (B) having a group that reacts with a carbodiimide group is an olefin polymer having a group having active hydrogen in a side chain thereof. Method for producing thermoplastic elastomer composition.

[8] The olefin polymer (B) having a group that reacts with a carbodiimide group is a graft copolymer of a polyolefin and a compound (b) having a group that reacts with a carbodiimide group, [1] to [7]. ] The manufacturing method of the thermoplastic elastomer composition in any one of these.

[9] The method for producing a thermoplastic elastomer composition according to any one of [1] to [8], wherein the olefin polymer (D) is a propylene polymer.

[10] The composition in the step of dynamically crosslinking is based on 100 parts by mass in total of the olefin polymer (B) having a group that reacts with a carbodiimide group, the polar rubber (C), and the olefin polymer (D). hand,
The method for producing the thermoplastic elastomer composition according to any one of [1] to [9], wherein the carbodiimide group-containing compound (A) is blended in the range of 0.01 to 30 parts by mass.

[11] The method for producing a thermoplastic elastomer composition according to any one of [1] to [10], wherein the batch-type kneader has a meshing rotor.

According to the present invention, it is possible to provide a method for producing a thermoplastic elastomer composition which has elasticity of a crosslinked polar rubber and is excellent in properties such as moldability and mechanical properties. The thermoplastic elastomer composition produced by the present invention contains a polar rubber having crosslinks and an olefin polymer, and both are highly dispersed in each other.

[Production method]
The production method of the present invention comprises a carbodiimide group-containing compound (A), an olefin polymer (B) having a group that reacts with a carbodiimide group, a polar rubber (C), an olefin polymer (D), and the polar rubber ( The method has a step of dynamically crosslinking the crosslinking agent (E) capable of crosslinking C) using a batch-type kneader under conditions satisfying the following conditions (1) to (3). The conditions (1) to (3) will be described below.

Condition (1): Tmax. ≧ T1
In the condition (1), “Tmax.” is the maximum value (° C.) of the resin temperature from when the cross-linking agent (E) was put into the batch type kneader to when the thermoplastic elastomer composition was discharged to the outside of the batch type kneader. And “T1” is the temperature (° C.) defined by the following formula (i).

T1=ΔE/(8.314×(LnA-3))-273.15 (i)
In the formula (i), “ΔE” is the activation energy (J/mol) calculated from the slope of the Arrhenius plot created from the cross-linking curves measured at multiple temperatures using the polar rubber (C) and the cross-linking agent (E). And “A” is the frequency factor (hr ⁻¹ ) calculated from the intercept.

The crosslinking curve under the condition (1) can be measured by using a rotorless vulcanization tester or the like. The cross-linking curve can be measured in accordance with JIS K6300-2 using a polar rubber (C) and a cross-linking agent (E) capable of cross-linking the polar rubber (C) and/or a cross-linking aid. When a plurality of polar rubbers (C) are used together, it is preferable to measure with the ratio of the rubber actually used, but it is also possible to use the numerical value measured with the component with the highest usage ratio among the polar rubbers (C). it can. Specifically, the difference between the minimum value ML and the maximum value MH of the torque obtained by measuring the crosslinking curve is obtained as ME, and t'c(90) at 90% ME is obtained to obtain the crosslinking speed. By making an Arrhenius plot of the crosslinking rate obtained from a plurality of measurement temperatures, the activation energy ΔE (J/mol) can be calculated from the slope of the straight line, and the frequency factor A (hr ⁻¹ ) can be calculated from the intercept. At this time, if it is difficult to find the maximum value MH of the torque because there is no maximum point in the cross-linking curve or the equilibrium state is not reached, "Rubber Technology Basics" (edited by Japan Rubber Association, p291- The numerical value obtained by the method described in 292) is preferably used as the maximum torque value MH. Specifically, select some cross-linking times, find the slope of the tangent line of the cross-linking curve at that cross-linking time, and plot the slope of the tangent line on the vertical axis against the horizontal axis torque and extrapolate on the horizontal axis. This value can be used as the maximum torque value MH.

Tmax. in condition (1). When (° C.) is lower than T1 (° C.), the reaction temperature becomes insufficient and mechanical properties deteriorate.

Under the condition (1), Tmax. It is sufficient that (C) is T1 (C) or more, and further, the difference (Tmax.-T1) between them is preferably 5C or more, and more preferably 10C or more.

Condition (2): T2 ≤ T3
In the condition (2), “T2” is the resin temperature (° C.) in the kneading machine when the cross-linking agent (E) is charged into the batch-type kneading machine, and “T3” is the temperature defined by the following formula (ii). (°C).

T3=ΔE/(8.314×(LnA-5))-273.15 (ii)
“ΔE” and “A” in formula (ii) have the same meanings as “ΔE” and “A” in formula (i) described above.

When T2 (° C.) in the condition (2) is higher than T3 (° C.), the crosslinking reaction locally proceeds, so that a uniform composition cannot be obtained and moldability deteriorates.

Under the condition (2), T2 may be T3 or less, and the difference (T3-T2) between the two is preferably 5° C. or more, more preferably 10° C. or more.

Condition (3): 2.0 ≤ P1 ≤ 8.5
In the condition (3), “P1” is a value defined by the following formula (iii).

P1=LnA−ΔE/(8.314×(Tave.+273.15)) (iii)
In the formula (iii), “Tave.” means the average value of the resin temperature (° C.) from the state where the cross-linking agent (E) is present and the olefin polymer (D) is melted to the time when the kneading is completed and discharged. ). Further, “ΔE” and “A” have the same meanings as “ΔE” and “A” in the above-described formula (i).

The "state in which the olefin polymer (D) is melted" in "Tave." of the formula (iii) is a state when the resin temperature is equal to or higher than the melting point. When the olefin polymer (D) is composed of a plurality of components, “Tave.” is discharged from the molten state of the component having the highest ratio in the olefin polymer (D). The average value of the resin temperature up to.

In the condition (3), when P1 is less than 2.0, the crosslinking reaction becomes insufficient and mechanical properties are deteriorated, and when P1 is more than 8.5, deterioration of the resin progresses and mechanical properties are increased. And heat aging resistance deteriorates.

Under the condition (3), it is preferable that 2.0 ≦ P1 ≦ 8.2 is further satisfied, and it is more preferable that 2.2 ≦ P1 ≦ 8.2 is satisfied.

The batch type kneader is not particularly limited, and any type of kneader may be used as long as it is a batch type.

The shape of the rotor of the batch type kneader is not particularly limited, but a meshing type rotor is preferable. An intermeshing rotor is a rotor that has a structure in which biaxial rotors mesh with each other and kneads not only between the rotor and the chamber wall surface, but also between the rotor and the rotor. Is possible. A kneader having an intermeshing rotor is generally called an intermeshing mixer. By using a batch-type kneader having an intermeshing rotor, it becomes possible to sufficiently disperse the island phase while controlling kneading and dynamic crosslinking, and by suppressing the generation of gel-like substances, A thermoplastic elastomer composition having a better appearance and more excellent mechanical properties can be produced. In the following description, a batch-type kneader having such a mesh-type rotor will be referred to as a “mesh-type kneader”.

The meshing type kneader is preferably a closed type kneading device. Specific examples thereof include an intermeshing kneader manufactured by Kobe Steel Ltd. and Harburg-Freudenberger Maschinenbau GmbH.

Hereinafter, each component as a raw material of the thermoplastic elastomer composition produced by the present invention will be described.

[Carbodiimide group-containing compound (A)]
The carbodiimide group-containing compound (A) used in the present invention is not particularly limited as long as it is a compound having a carbodiimide group represented by -N=C=N-, but is preferably the following general formula. It is a polycarbodiimide having the repeating unit shown.
^{-N = C = N-R 1} -
(In the formula, R ¹ represents a divalent organic group.)

The method for synthesizing polycarbodiimide is not particularly limited, but polycarbodiimide can be synthesized, for example, by reacting an organic polyisocyanate in the presence of a catalyst that promotes a carbodiimidization reaction of an isocyanate group.

When the carbodiimide group-containing compound (A) is polycarbodiimide, the polystyrene-equivalent number average molecular weight (Mn) determined by gel permeation chromatography (GPC) is usually 400 to 500,000, preferably 1,000 to 10 1,000, more preferably 2,000 to 4,000. When the number average molecular weight (Mn) is within this range, each component in the composition exhibits good compatibility, and the thermoplastic elastomer composition obtained has rubber elasticity and oil resistance, and is also excellent in moldability. It becomes a thing.

The carbodiimide group-containing compound (A) may be used alone or in combination of two or more. For example, polycarbodiimide alone may be used, polycarbodiimide and monocarbodiimide may be used in combination, or monocarbodiimide alone may be used. In the present invention, the carbodiimide group-containing compound (A) preferably contains polycarbodiimide.

As the carbodiimide group-containing compound (A), a commercially available carbodiimide group-containing compound can be used as it is. Examples of commercially available carbodiimide group-containing compounds include Carbodilite (registered trademark) HMV-8CA, HMV-15CA, and LA1 manufactured by Nisshinbo Chemical Inc.

The carbodiimide group content in the carbodiimide group-containing compound (A) and in the obtained reaction product or thermoplastic elastomer composition can be measured by ¹³ C-NMR, IR, titration method or the like, and is grasped as a carbodiimide equivalent. It is possible. It is possible to observe a peak at 130 to 142 ppm by ¹³ C-NMR and 2130 to 2140 cm ⁻¹ by IR.

[Olefin-based polymer (B) having a group that reacts with a carbodiimide group]
The olefin-based polymer (B) having a group that reacts with a carbodiimide group used in the present invention is not particularly limited, but a compound (b) having a group that reacts with a carbodiimide group can be used to produce a carbodiimide group. It can be obtained by introducing into the polyolefin a group that reacts with. Here, the “group having reactivity with a carbodiimide group” includes, for example, a group having active hydrogen, or a group easily converted to a group having active hydrogen by water or the like.

As a method for introducing a group that reacts with a carbodiimide group into a polyolefin, a known method can be adopted. For example, a compound (b) having a group that reacts with a carbodiimide group is graft-copolymerized on a polyolefin main chain. And a method of radically copolymerizing the compound (b) having a group that reacts with a carbodiimide group and an olefin. Of these, graft copolymerization is preferred.

The case where the olefin polymer (B) having a group that reacts with a carbodiimide group is obtained by graft copolymerization and the case where it is obtained by radical copolymerization will be specifically described below.

(Graft copolymerization)
The olefin polymer (B) having a group that reacts with a carbodiimide group in its side chain is a compound having a group that reacts with a carbodiimide group with respect to an unmodified polyolefin (hereinafter, also referred to as a polyolefin main chain) that becomes a main chain ( It can be obtained by graft-copolymerizing b).

<Unmodified polyolefin (polyolefin main chain)>
The unmodified polyolefin used as the polyolefin main chain is, for example, a polymer containing an aliphatic α-olefin having 2 to 20 carbon atoms, a cyclic olefin, or a non-conjugated diene as a main component, and preferably having 2 to 10 carbon atoms. It is a polymer containing α-olefin, more preferably 2 to 8 α-olefin as a main component. These olefins may be used alone or in combination of two or more. In the present invention, a homopolymer or copolymer of ethylene, propylene, 1-butene, 4-methyl-1-pentene, 3-methyl-1-butene, 1-hexene, 1-octene, tetracyclododecene, norbornene. Coalescence can be preferably used. Further, these can be used in both the isotactic structure and the syndiotactic structure, and there is no particular limitation in stereoregularity.

In the thermoplastic elastomer composition produced by the present invention, the carbodiimide group-containing compound (A) as a raw material has an olefin-based polymer (B) having a group that reacts with a carbodiimide group [and a polar rubber (C) described later. Contains a polar rubber (C1) having a group that reacts with a carbodiimide group, it reacts with the polar rubber (C1) by melt-kneading, and the resulting reaction product acts as a compatibilizer to give a polar rubber ( It is considered that the compatibility between C) and the olefin polymer (D) is improved. This thermoplastic elastomer composition preferably contains a reaction product (I) of a carbodiimide group-containing compound (A) and an olefin polymer (B) having a group that reacts with a carbodiimide group.

Here, the effect of improving the compatibility by the reaction product (I) becomes more remarkable when the reaction product (I) has a main chain similar to that of the olefin polymer (D). The main chain of the olefin polymer (B) having a group that reacts with a carbodiimide group, which is the main chain of (I), and the structure of the main chain of the olefin polymer (D) are similar to each other. More preferable.

For example, when the olefin-based polymer (D) described later is a propylene-based polymer, a propylene-based polymer such as a propylene homopolymer or a copolymer of propylene and another α-olefin is used as the polyolefin main chain. A polymer can be preferably selected and used.

The density of the polyolefin used for the graft copolymerization, that is, the density of the polyolefin main chain before introducing the group that reacts with carbodiimide is usually 0.8 to 1.2 g/cm ³ , preferably 0.90 to 1.1 g/cm. ³ and more preferably 0.925 to 1.0 g/cm ³ .

The melt flow rate (MFR) of the polyolefin main chain according to ASTM D1238 at 190° C. or 230° C. under a load of 2.16 kg is usually 0.01 to 500 g/10 minutes, preferably 0.05 to 200 g/10 minutes, and further preferably It is 0.1 to 100 g/10 minutes. When the density and MFR are within this range, the density and MFR of the graft copolymer after modification are also about the same, and therefore handling is easy.

The crystallinity of the polyolefin main chain is usually 2% or more, preferably 5% or more, more preferably 10% or more. When the crystallinity is within this range, the graft copolymer after modification is excellent in handleability.

The number average molecular weight (Mn) of the polyolefin main chain used for graft copolymerization measured by gel permeation chromatography (GPC) is preferably 5,000 to 500,000, more preferably 10,000 to 100,000. .. When the average molecular weight (Mn) is within this range, the handleability is excellent. The number average molecular weight of ethylene-based polyolefin can be calculated in terms of polyethylene when the amount of comonomer is 10 mol% or less and in terms of ethylene-propylene when the amount of comonomer is 10 mol% or more (based on ethylene content of 70 mol%). It is possible.

The above-mentioned polyolefin main chain can be produced by any conventionally known method, for example, polymerization can be performed using a titanium-based catalyst, a vanadium-based catalyst, a metallocene catalyst, or the like. The polyolefin used for the graft modification may be in the form of resin or elastomer, both isotactic structure and syndiotactic structure can be used, and stereoregularity is not particularly limited. It is also possible to use a commercially available resin as it is.

In the present invention, the unmodified polyolefin serving as the polyolefin main chain may have properties similar to those of the olefin polymer (D) described later, or may be of a completely different type, but with high compatibility. When it is required, it is preferable that the density, monomer constitution, stereoregularity, structural unit sequence such as random/block, etc. are similar to those of the olefin polymer (D). Is preferred. Further, the unmodified polyolefin serving as the polyolefin main chain is more preferably a polyolefin resin having thermoplasticity.

<Compound (b) Having Group Reactive with Carbodiimide Group>
Examples of the compound (b) having a group that reacts with a carbodiimide group include compounds having a group having active hydrogen that is reactive with a carbodiimide group, and specific examples include carboxylic acid, carboxylic anhydride, amine, Examples thereof include compounds having a group derived from alcohol, thiol and the like. That is, in the present invention, as an olefin polymer (B) having a group that reacts with a carbodiimide group, for example, as a group that reacts with a carbodiimide group, a carboxylic acid anhydride group, a carboxy group (-COOH), a hydroxy group (-OH). A polyolefin having a group such as a thiol group (-SH) is preferably used.

As the compound (b) having a group that reacts with a carbodiimide group, among the above, a compound having a group derived from an unsaturated carboxylic acid such as a carboxylic acid or a carboxylic acid anhydride is preferably used. / Or its derivative is used preferably. In addition to the compound having a group having active hydrogen, a compound having a group which can be easily converted into a group having active hydrogen by water or the like can be preferably used, and specifically, has an epoxy group or a glycidyl group. Compounds. In the present invention, the compound (b) having a group capable of reacting with a carbodiimide group may be used alone or in combination of two or more.

When an unsaturated carboxylic acid and/or a derivative thereof is used as the compound (b) having a group that reacts with a carbodiimide group, the compound (b) includes an unsaturated compound having one or more carboxy groups and one or more carboxylic acid anhydride groups. Examples of the unsaturated group include a vinyl group, a vinylene group, an unsaturated cyclic hydrocarbon group, and the like. Specific compounds (b) include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo[2,2,1]. Unsaturated carboxylic acids such as hept-2-ene-5,6-dicarboxylic acid, or their acid anhydrides or their derivatives (for example, acid halides, amides, imides, esters, etc.) can be mentioned. Specific examples of the acid anhydrides or derivatives include malenyl chloride, maleenyl imide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo[2,2,1]hept-2-ene- 5,6-dicarboxylic acid anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citracone, dimethyl tetrahydrophthalate, bicyclo[2,2,1]hept-2- Examples thereof include dimethyl ene-5,6-dicarboxylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, aminoethyl methacrylate and aminopropyl methacrylate.

When the unsaturated carboxylic acid and/or its derivative is used as the compound (b) having a group that reacts with a carbodiimide group, it can be used alone or in combination of two or more. it can. Among these, maleic anhydride, (meth)acrylic acid, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic anhydride , Hydroxyethyl (meth)acrylate, glycidyl methacrylate and aminopropyl methacrylate are preferred. Further, it is a dicarboxylic acid anhydride such as maleic anhydride, itaconic acid anhydride, citraconic acid anhydride, tetrahydrophthalic acid anhydride, or bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic acid anhydride. Is particularly preferable.

<Graft copolymerization method>
Examples of the method for obtaining the olefin polymer (B) having a group that reacts with a carbodiimide group used in the present invention by graft copolymerization (graft modification) include, for example, the above-mentioned polyolefin (polyolefin main chain) to be the main chain. In addition, a method of graft-copolymerizing the compound (b) having a group that reacts with a carbodiimide group in the presence of a radical initiator can be mentioned. Such graft copolymerization may be carried out together with the compound (b), if necessary, in the presence of other ethylenically unsaturated monomers and the like.

The method of graft-copolymerizing the compound (b) having a group that reacts with a carbodiimide group on the polyolefin main chain is not particularly limited, and a conventionally known graft polymerization method such as a solution method or a melt-kneading method can be adopted.

(Radical copolymerization)
In the case of radical copolymerization, it is possible to employ the same olefin as the above-mentioned olefin for forming the polyolefin main chain, and as the compound (b) having a group that reacts with a carbodiimide group, It is possible to employ the same one as described above in the section of graft copolymerization.

The method for copolymerizing the olefin and the compound (b) having a group that reacts with a carbodiimide group is not particularly limited, and a conventionally known radical copolymerization method can be adopted.

(Characteristics of Olefin Polymer (B) Having Group Reacting with Carbodiimide Group)
The olefin polymer (B) having a group that reacts with a carbodiimide group used in the present invention is usually at least partly carbodiimide in the thermoplastic elastomer composition obtained by being used together with the carbodiimide group-containing compound (A). Reacts with the group-containing compound (A) to form a reaction product (I). The thermoplastic elastomer composition exhibits a form in which the constituent components are highly dispersed and has excellent mechanical properties because the reaction product (I) is used as a compatibilizer in the thermoplastic elastomer composition. It is considered that this is partly due to the action.

The content of the compound (b) having a group reactive with a carbodiimide group (content of a portion derived from the compound (b)) in the olefin polymer (B) having a group reactive with a carbodiimide group is usually 0. 0.1 to 10% by mass, preferably 0.1 to 3.0% by mass, and more preferably 0.1 to 2.0% by mass. When the content of the compound (b) is within the above range, a reaction with the carbodiimide group-containing compound (A) is likely to occur, which is preferable.

Further, in the present invention, when the content of the compound (b) having a group reactive with a carbodiimide group in the olefin polymer (B) having a group reactive with a carbodiimide group is within the above range, a carbodiimide group-containing compound A binding portion of the reaction product (I) between the (A) and the olefin polymer (B) having a group that reacts with a carbodiimide group is formed, and acts as a compatibilizer in the resulting thermoplastic elastomer composition. Is preferable because

In order to prevent gelation due to cross-linking, the lower the number average molecular weight of the olefin polymer (B) having a group that reacts with a carbodiimide group is, It is preferable that the molar ratio of (the number of moles)/(the number of moles of the olefin polymer (B) having a group that reacts with a carbodiimide group) is small. That is, when the compound (b) is present in a state close to the singular number, instead of the plural number, on the main chain of the olefin polymer (B) having a group that reacts with the carbodiimide group, This means that when the carbodiimide group (N=C=N) of the compound (A) reacts with the compound (b) part, gelation due to crosslinking hardly occurs.

In the present invention, by controlling the number average molecular weight (Mn) of the olefin polymer (B) having a group reactive with a carbodiimide group and the content of the compound (b) having a group reactive with a carbodiimide group. Even when the reaction product (I) with the carbodiimide group-containing compound (A) is formed during the production of the thermoplastic elastomer composition, gelation due to cross-linking is unlikely to occur and the production stability can be maintained. In the obtained thermoplastic elastomer composition, the reaction product (I) can sufficiently exhibit the performance as a compatibilizer.

In the present invention, the olefin polymer (B) having a group that reacts with a carbodiimide group preferably satisfies the following formula (1).
0.1<Mn/[(100-M)*f/M]<6 (1)
(In formula (1),
f: Formula weight (g/mol) of the compound (b) having a group that reacts with a carbodiimide group
M: Content of compound (b) having a group that reacts with a carbodiimide group (content of a portion derived from compound (b)) (mass %)
Mn: The number average molecular weight of the olefin polymer (B) having a group that reacts with a carbodiimide group. )

Further, from the viewpoint of production stability that gelation due to cross-linking does not occur, it is more preferably in the range satisfying the following formula (2), and most preferably in the range satisfying formula (3).
0.3<Mn/[(100-M)*f/M]<4 (2)
0.5<Mn/[(100-M)*f/M]<2.8 (3)

When the relationship between the number average molecular weight (Mn) of the olefin polymer (B) having a group that reacts with a carbodiimide group and the compound (b) having a group that reacts with a carbodiimide group is within the above range, the carbodiimide group-containing compound (A ) And an olefin-based polymer (B) having a group that reacts with a carbodiimide group, a carbodiimide group-containing compound (A) is added when a reaction product (I) is produced or when a thermoplastic elastomer composition is produced. It is possible to suppress the gelation due to the cross-linking resulting from the stable production.

Further, in the present invention, when the olefin-based polymer (B) having a group that reacts with a carbodiimide group is obtained by graft polymerization, the polyolefin serving as the graft main chain has an ethylene content such as linear low density polyethylene. When the amount of the resin is large, it tends to be easily crosslinked as compared with a resin having a large amount of α-olefin copolymerization such as an ethylene/butene copolymer. Therefore, when a resin having a high ethylene content is used as the graft main chain, the compound (b) having a group that reacts with a carbodiimide group is present on the molecular chain of the polyolefin in a number close to a singular number, that is, The lower the number in the calculation formula, the more the gelation due to crosslinking can be suppressed.

The number average molecular weight can be determined by a general molecular weight measuring method for polymers such as GPC method, light scattering method, low angle light scattering photometric method, vapor pressure osmotic pressure method, and membrane osmotic pressure method.

The melt flow rate (MFR) at 190° C. or 230° C. of the olefin polymer (B) having a group which reacts with a carbodiimide group at a load of 2.16 kg according to ASTM D1238 at 190° C. or 230° C. is the polar rubber (C) constituting the thermoplastic elastomer composition. ) And the characteristics of the olefin polymer (D), but usually 0.01 to 500 g/10 min, preferably 0.05 to 300 g/10 min. Within the above range, the compatibility between the polar rubber (C) and the olefin polymer (D) in the resulting thermoplastic elastomer composition is more excellent, which is preferable.

The density of the olefin polymer (B) having a group reactive with a carbodiimide group is generally 0.8~1.2g / cm ^3, preferably 0.8~1.1g / cm ^3, more preferably 0.8 Is about 1.0 g/cm ³ .

Among the olefin-based polymers (B) having a group that reacts with a carbodiimide group in such a range, polyethylene, polypropylene, polybutene 1, poly-4-methylpentene-1, and the copolymerization of these with α-olefin A maleic anhydride graft copolymer of a crystalline polyolefin such as a coalesced product is preferable, and a maleic anhydride graft copolymer of polyethylene or polypropylene is more preferable, although it depends on an object of compatibilization, and a maleic anhydride graft copolymer of polypropylene is preferable. Coalescence is more preferred.

The density of the olefin-based polymer (B) having a group that reacts with a carbodiimide group is not particularly limited, but it is close to the density of the olefin-based polymer (D) that constitutes the thermoplastic elastomer composition, and has a polarity. A material having a density close to that of the rubber (C) or a density between the density of the polar rubber (C) and the density of the olefin polymer (D) is more preferable.

As the olefin-based polymer (B) having a group that reacts with such a carbodiimide group, one appropriately prepared by the above-mentioned graft copolymerization or radical copolymerization may be used, or a commercially available one may be used. .. Examples of the commercially available polyolefin having a group that reacts with a carbodiimide group include Admer (registered trademark) manufactured by Mitsui Chemicals, Inc., Orevac (registered trademark) manufactured by Arkema, and Polybond (registered trademark) manufactured by Additive.

[Polar rubber (C)]
As the polar rubber (C), rubbers having polarity can be used without particular limitation. In addition to carbon (C) and hydrogen (H), nitrogen (N) and oxygen (O) are included in the molecular structure. A rubber having a polar group containing atoms such as sulfur, sulfur (S), halogen (F, Cl, Br, etc.) and phosphorus (P) is preferable, and a rubber having a polar group in the side chain is more preferable. The polar rubber (C) has excellent properties such as oil resistance to non-polar oil.

Specific examples of the polar rubber (C) include carboxy group-containing nitrile rubber, hydrogenated product of carboxy group-containing nitrile rubber, nitrile rubber, hydrogenated product of nitrile rubber, carboxy group-containing acrylic rubber, epoxy group-containing Examples thereof include acrylic rubber, acrylic rubber, carboxy group-containing epichlorohydrin rubber, epichlorohydrin rubber, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, polysulfide rubber, fluororubber and hydrogenated ethylenically unsaturated nitrile-conjugated diene rubber. Various rubbers commercially available as polar rubbers can also be used in the present invention. Among these, nitrile rubber and carboxy group-containing nitrile rubber are preferable from the viewpoint of properties such as oil resistance to nonpolar oils such as gasoline and lubricating oil.

The polar rubber (C) preferably has a number average molecular weight of 5,000 to 2,000,000, more preferably 10,000 to 500,000. Depending on the use of the rubber composition, if the number average molecular weight is equal to or more than the lower limit, desired rubber strength physical properties are easily obtained, and if it is equal to or less than the upper limit, desired molding processability is obtained. It is preferable because it is easy.

Further, the Mooney viscosity (ML ₁₊₄ , 100° C.) of the polar rubber (C) is preferably 10 to 200, more preferably 20 to 150. When the Mooney viscosity is at least the lower limit value, the desired rubber strength physical properties are easily obtained, and when it is at most the upper limit value, the handleability in the uncrosslinked state is good and the desired processability and moldability are obtained. It is preferable because it is easy.

The solubility parameter (SP value) of the polar rubber (C) is usually 16.5 to 30 (MPa) ^0.5 , preferably 17 to 29 (MPa) ^0.5 , and more preferably 17.5 to 28 (MPa) ^0.5 . When the SP value is relatively high as described above, the oil resistance to non-polar oils such as gasoline and lubricating oil is improved.

The polar rubber (C) may be used alone or in combination of two or more.

The polar rubber (C) used in the present invention is not particularly limited, but at least a part thereof is preferably an amorphous elastic copolymer which can be crosslinked by using a crosslinking agent.

(Polar rubber (C1) having a group that reacts with a carbodiimide group)
In the thermoplastic elastomer composition produced by the present invention, it is also preferable that the polar rubber (C) contains a polar rubber (C1) having a group that reacts with a carbodiimide group. In the present invention, the entire polar rubber (C) may be a polar rubber (C1) having a group that reacts with a carbodiimide group, or a part of the polar rubber (C) has a group that reacts with a carbodiimide group. It may be a polar rubber (C1). Here, as the "group having reactivity with a carbodiimide group", as mentioned above, for example, a group having active hydrogen, or a group easily converted into a group having active hydrogen by water or the like can be mentioned.

The polar rubber (C1) having a group that reacts with a carbodiimide group reacts with a carbodiimide group such as a carboxylic acid anhydride group, a carboxy group (-COOH), a hydroxy group (-OH), and a thiol group (-SH). Examples thereof include polar rubbers having a group in the side chain and the like, and particularly polar rubbers containing a carboxy group.

Preferable examples of the polar rubber (C1) include a carboxy group-containing nitrile rubber, a hydrogenated product of a carboxy group-containing nitrile rubber, a carboxy group-containing acrylic rubber, an epoxy group-containing acrylic rubber, and a carboxy group-containing epichlorohydrin rubber.

The polar rubber (C1) having a group that reacts with a carbodiimide group may be used alone or in combination of two or more.

When the polar rubber (C) constituting the thermoplastic elastomer composition produced by the present invention contains a polar rubber (C1) having a group that reacts with a carbodiimide group, it depends on the production process such as the order of melt-kneading. However, the resulting thermoplastic elastomer composition contains the reaction product (II) of the carbodiimide group-containing compound (A) and the polar rubber (C1) having a group that reacts with the carbodiimide group. It is preferable that the thermoplastic elastomer composition contains the reaction product (II) because the compatibility of each component in the thermoplastic elastomer composition is further improved.

[Olefin-based polymer (D)]
The olefin polymer (D) constituting the thermoplastic elastomer composition produced by the present invention is a polymer or copolymer mainly having a structural unit derived from an olefin, and is a group having reactivity with a carbodiimide group. Practically no. “Substantially free of a group having reactivity with a carbodiimide group” means that it does not actually react with the carbodiimide group of the carbodiimide group-containing compound (A) in the state of being prepared as the thermoplastic elastomer composition of the present invention. It means that no contribution is made to the action and effect of the present invention even if the group is contained in a very small amount.

Examples of the olefin-based polymer (D) are the same as those described in the section of the polyolefin main chain, which is the main chain of the olefin-based polymer (B) having a group that reacts with the carbodiimide group. .. That is, the olefin polymer (D) used in the present invention is a polymer or copolymer containing an aliphatic α-olefin having 2 to 20 carbon atoms, a cyclic olefin, or a non-conjugated diene as a main component, and preferably It is a polymer or copolymer mainly composed of an α-olefin having 2 to 10 carbon atoms, and more preferably an α-olefin having 2 to 8 carbon atoms. These olefins as monomers may be used alone or in combination of two or more. The comonomer content is usually 50 mol% or less, preferably 40 mol% or less, and more preferably 30 mol% or less.

In the present invention, the olefin polymer (D) is usually a polyolefin resin having thermoplasticity.

In the present invention, as the olefin polymer (D), ethylene, propylene, 1-butene, 4-methyl-1-pentene, 3-methyl-1-butene, 1-hexene, 1-octene, tetracyclododecene. A homopolymer or copolymer of norbornene can be preferably used. Further, these can be used in both the isotactic structure and the syndiotactic structure, and there is no particular limitation in stereoregularity. The above-mentioned polyolefin can be produced by any conventionally known method, for example, polymerization can be performed using a titanium-based catalyst, a vanadium-based catalyst, a metallocene catalyst, or the like.

In the present invention, the olefin polymer (D) is preferably a polypropylene polymer, and as the polypropylene polymer, a homopolymer of propylene, a copolymer of propylene and another α-olefin, or the like. The propylene-based polymer can be preferably selected and used. When the olefin polymer (D) is a polypropylene polymer, the melt flow rate (MFR) measured at 2.16 kgf and 230° C. according to ASTM D1238 is 0.01 to 500 g/10 minutes, preferably 0. The range is from 0.05 to 200 g/10 minutes, and more preferably from 0.1 to 100 g/10 minutes.

[Crosslinking agent (E)]
The crosslinking agent (E) used in the present invention is a crosslinking agent capable of crosslinking the polar rubber (C) described above. As the cross-linking agent (E), various known cross-linking agents generally used in cross-linking rubber can be used. Specifically, for example, organic peroxides, phenol resins, sulfur compounds, hydrosilicone compounds, amino resins, quinones or their derivatives, amine compounds, azo compounds, epoxy compounds, thiourea compounds, thiazole compounds. Examples of the crosslinking agent include compounds, triazine compounds and isocyanates. Of these, crosslinking agents such as organic peroxides, phenolic resins and sulfur compounds are preferable.

Examples of organic peroxides include dicumyl peroxide, di-tert-butyl peroxide, 2,5-di-(tert-butylperoxy)hexane, and 2,5-dimethyl-2,5-di-(tert-butylperoxy). Hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3,1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)- 3,3,5-Trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert. -Butyl peroxy isopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide, etc. are mentioned.

Among these, 2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di- (Tert-Butylperoxy)hexyne-3,1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4 Bifunctional organic peroxides such as 4,4-bis(tert-butylperoxy)valerate are preferable, and above all, 2,5-di-(tert-butylperoxy)hexane and 2,5-dimethyl-2,5- Most preferred is di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3.

When an organic peroxide is used as the crosslinking agent (E), it is preferable to use a crosslinking auxiliary together. Examples of such a crosslinking aid include quinonedioxime-based crosslinking aids such as sulfur and p-quinonedioxime; acrylic-based crosslinking aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; diallyl phthalate and triallyl. Allyl-based cross-linking aids such as isocyanurate; Other maleimide-based cross-linking aids; divinylbenzene; zinc oxide (for example, ZnO#1 and 2 types of zinc oxide, manufactured by Hakusui Tech Co., Ltd.), and metal oxides such as magnesium oxide. To be The amount of the crosslinking aid compounded is usually 0.01 to 10 mol, preferably 0.1 to 7 mol, and more preferably 0.5 to 5 mol, based on 1 mol of the organic peroxide.

Examples of the phenol resin-based cross-linking agent include a resole resin obtained by condensing an alkyl-substituted or unsubstituted phenol with an aldehyde (preferably formaldehyde) in the presence of an alkali catalyst. The alkyl group of the alkyl-substituted phenol is preferably an alkyl group having 1 to about 10 carbon atoms. Further preferred are dimethylolphenols or phenolic resins substituted with alkyl groups having 1 to about 10 carbon atoms in the p-position. Crosslinking with a phenolic resin-based crosslinking agent is described in, for example, US Pat. No. 4,311,628, US Pat. No. 2,972,600, and US Pat. No. 3,287,440.

The phenol resin-based cross-linking agent is also available as a commercial product. Examples of commercially available products include Takki roll 201, Takki roll 250-I, Takki roll 250-III manufactured by Taoka Chemical Co., Ltd.; SP1045, SP1055, SP1056 manufactured by SI Group; Shonor CRM manufactured by Showa Denko KK; Arakawa Chemical Co., Ltd. Tamanor 531; Sumitomo Bakelite Co., Ltd. Sumilite Resin PR; Gunei Chemical Industry Co., Ltd. cash register top and the like (all the above are trade names). These can be used in combination of two or more. Among them, Takkiroll 250-III (brominated alkylphenol formaldehyde resin) manufactured by Taoka Chemical Co., Ltd. and SP1055 (brominated alkylphenol formaldehyde resin) manufactured by SI Group are preferable.

Moreover, when using a phenol resin type crosslinking agent as a crosslinking agent (E), it is preferable to use a crosslinking auxiliary together. Examples of such a crosslinking aid include metal halides such as stannous chloride and ferric chloride, halogen-containing polymers such as chloroprene rubber and halogenated butyl rubber, and zinc oxide (for example, ZnO#1 and zinc oxide 2 Seed, manufactured by Hakusui Tech Co., Ltd.), and metal oxides such as magnesium oxide.

Examples of the sulfur-based compound (vulcanizing agent) include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dithiocarbamate.

When a sulfur compound is used as the crosslinking agent (E), it is preferable to use a vulcanization accelerator together. Examples of such a vulcanization accelerator include N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazole sulfenamide, N,N′-diisopropyl-2-benzothiazole sulfenamide, 2-mercaptobenzothiazole (for example, Sunceller M (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), 2-(4-morpholinodithio) benzthiazole (for example, Nocceller MDB-P (trade name; Ouchi Shinko Kagaku) Industrial Co., Ltd.)), 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-diethyl-4-morpholinothio)benzothiazole and dibenzothiazyl disulfide (for example, Sancellar DM (commercial product). Name: Sanshin Chemical Industry Co., Ltd.)) and other thiazole vulcanization accelerators; guanidine vulcanization accelerators such as diphenylguanidine, triphenylguanidine and diorsotolylguanidine; acetaldehyde aniline condensate and butyraldehyde aniline. Aldehydeamine-based vulcanization accelerators such as condensates; 2-mercaptoimidazoline- and other imidazoline-based vulcanization accelerators; thiourea-based vulcanization accelerators such as diethylthiourea and dibutylthiourea; tetramethylthiuram monosulfide (for example, Sancellar TS ( (Trade name; Sanshin Chemical Industry Co., Ltd.)), tetramethylthiuram disulfide (for example, Sancella TT (trade name; Sanshin Chemical Industry Co., Ltd.)), tetraethylthiuram disulfide (for example, Sancella TET (trade name; Sanshin) Chemical Industry Co., Ltd.)), tetrabutyl thiuram disulfide (for example, Sancellar TBT (trade name; Sanshin Chemical Industry Co., Ltd.)) and dipentamethylene thiuram tetrasulfide (for example, Sancella TRA (trade name; Sanshin Chemical Industry Co., Ltd.) ) Etc.; zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate (for example, Sancella PZ, Sancella BZ and Sancella EZ (trade name; Sanshin Chemical Industry Co., Ltd.) )) and dithioate vulcanization accelerators such as tellurium diethyldithiocarbamate; ethylene thiourea (for example, Sancellar BUR (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.), Sanseller 22-C (trade name; Sanshin Chemical Industry) )) and thiourea-based vulcanization accelerators such as N,N'-diethylthiourea; Zanthate-based vulcanization accelerators such as zinc loxatate; and zinc white (for example, META-Z102 (trade name; zinc oxide manufactured by Inoue Lime Industry Co., Ltd.)) and the like.

When a sulfur compound is used as the crosslinking agent (E), it is also preferable to use a vulcanization aid. Examples of the vulcanization aid include zinc oxide (for example, ZnO#1/zinc oxide type 2, manufactured by Hakusui Tech Co., Ltd.), magnesium oxide and the like.

In the thermoplastic elastomer composition of the present invention produced by the present invention, as the crosslinking agent (E), an organic peroxide-based crosslinking agent or a phenol resin-based crosslinking agent is preferably used among these crosslinking agents.

The thermoplastic elastomer composition produced according to the present invention contains the above-mentioned polar rubber (C) and a cross-linking agent (E) capable of cross-linking the polar rubber (C) as a raw material, whereby the raw material is dynamically It is made by heat treatment. In the thermoplastic elastomer composition, at least a part of the polar rubber (C) usually forms a crosslinked structure. That is, this thermoplastic elastomer composition usually contains a crosslinked product of the polar rubber (C). Since this thermoplastic elastomer composition contains a crosslinked polar rubber which is a crosslinked product of polar rubber, it has suitable elasticity and excellent chemical resistance.

In the thermoplastic elastomer composition produced by the present invention, the above-mentioned polar rubber (C), reaction product (II), or olefin system having a group that reacts with the carbodiimide group-containing compound (A) and the carbodiimide group. Either of the three-component reaction product (III) of the polymer (B) and the polar rubber (C) may form a crosslink, and the reaction product (II) or the reaction product (III) may be formed. And the polar rubber (C) may have cross-links with each other. In the thermoplastic elastomer composition, it is preferable that two or more kinds of components have cross-links with each other, because the respective components of the thermoplastic elastomer composition have better compatibility and separation is less likely to occur.

[Other ingredients]
The thermoplastic elastomer composition produced by the present invention comprises the above-mentioned carbodiimide group-containing compound (A), an olefin polymer (B) having a group reactive with a carbodiimide group, a polar rubber (C), an olefin polymer ( Components other than D) and the cross-linking agent (E) may be contained as raw materials within a range that does not impair the object of the present invention.

That is, the thermoplastic elastomer composition produced by the present invention may be blended with other resins, elastomers, etc. within a range not impairing the object of the present invention. Further, in the thermoplastic elastomer composition, known plasticizers (F) and cross-linking aids (G), as well as plasticizers, softeners, tackifiers, and anti-aging agents are included in the thermoplastic elastomer composition. Agent, processing aid, adhesion promoter, inorganic filler, inorganic fiber such as glass fiber, acrylic fiber, PET fiber, PEN fiber, kenaf, organic fiber such as plant fiber, organic filler, heat stabilizer, weather stabilizer Further, additives (H) such as an antistatic agent, a colorant, a lubricant, a flame retardant, an anti-blooming agent, a reinforcing agent, an activator, a hygroscopic agent, a colorant, and a thickener may be added.

Of these, the thermoplastic elastomer composition produced by the present invention preferably contains a plasticizer (F) and/or a crosslinking aid (G). The plasticizer (F) is not particularly limited, and known plasticizers can be used. For example, phthalate ester plasticizers such as dibutyl phthalate and dioctyl phthalate; dioctyl adipate, dibutyl sebacate and the like. Aliphatic dibasic acid ester plasticizer; trimellitic acid ester plasticizer such as tridecyl trimellitate; Aliphatic dibasic acid ether ester plasticizer such as dibutoxyethoxyethyl adipate; Ether ester plasticizer; Polyester Plasticizers; phosphate ester plasticizers; epoxy plasticizers such as epoxidized soybean oil and epoxidized linseed oil; petroleum oils such as process oils, lubricating oils, aromatic oils, naphthene oils, paraffin oils, liquid paraffin, and vaseline Coal tars such as coal tar and coal tar pitch; fatty oils such as castor oil, linseed oil, rapeseed oil, soybean oil and coconut oil; waxes such as tall oil, beeswax and lanolin; ricinoleic acid, palmitin Acids, stearic acid, fatty acids such as calcium stearate or metal salts thereof; petroleum resins, chromanindene resins, synthetic polymeric substances such as atactic polypropylene; other microchlorin wax, sub (factice), liquid polybutadiene, modified liquid polybutadiene, liquid Thiocol and the like are listed, and among these, various ester types such as phthalate ester plasticizers, aliphatic dibasic acid ether ester plasticizers, ether ester plasticizers, etc. from the viewpoint of affinity with polar rubber (C). Plasticizers are preferred. The cross-linking aid (G) is not particularly limited, and examples thereof include the cross-linking aid described above in the section of the cross-linking agent (E).

These other components may be blended from the beginning as a raw material during the production of the thermoplastic elastomer composition, or may be added at the stage of dynamically heat treating the raw material, so that the thermoplastic elastomer composition is It may be added after it is obtained.

[Blending ratio of each component]
The thermoplastic elastomer composition produced by the present invention is not particularly limited, but the olefin polymer (B), the polar rubber (C), and the olefin polymer (having a group that reacts with a carbodiimide group, The total amount of the carbodiimide group-containing compound (A) is 0.01 to 30 parts by mass, preferably 0.01 to 20 parts by mass, and more preferably 0.01 to 15 parts by mass based on 100 parts by mass of D). It is desirable that it is obtained by using it in a range.

The thermoplastic elastomer composition produced according to the present invention includes a carbodiimide group-containing compound (A), an olefin polymer (B) having a group that reacts with the carbodiimide group, the polar rubber (C), and the olefin system. In a total of 100% by mass of the polymer (D), the carbodiimide group-containing compound (A) is reacted with the carbodiimide group in a proportion of usually 0.01 to 30% by mass, preferably 0.01 to 20% by mass. The olefin polymer (B) having a group is usually 0.05 to 70% by mass, preferably 0.1 to 60% by mass, and the polar rubber (C) is usually 10 to 95% by mass, preferably 20 to It is a preferred embodiment that the olefin polymer (D) is used as a raw material in a proportion of 90 mass%, preferably 2 to 85 mass%, more preferably 4 to 70 mass%.

Furthermore, the thermoplastic elastomer composition produced by the present invention contains a carbodiimide group based on 100 parts by mass of the total of the olefin polymer (B) having a group that reacts with a carbodiimide group and the olefin polymer (D). It is desirable that the compound (A) is usually added in an amount of 0.01 to 30 parts by mass, preferably 0.03 to 25 parts by mass.

The thermoplastic elastomer composition has a mass ratio (C) of the polar rubber (C) and the total of the olefin polymer (B) and the olefin polymer (D) having a group that reacts with a carbodiimide group: [( B)+(D)] is usually 1:99 to 99:1, preferably 5:95 to 95:5.

In the thermoplastic elastomer composition produced according to the present invention, the mixing ratio of the polar rubber (C) and the olefin polymer (D) is not particularly limited, but the mass ratio of the raw materials (C ):(D) is usually 1:99 to 99:1, preferably 5:95 to 95:5. In this thermoplastic elastomer composition, for example, polar rubber (C) and olefin polymer (D) are mixed in a mass ratio (C):(D) of raw materials of 51:49 to 99:1. It may be contained, or may be contained in a ratio satisfying 30:70 to 70:30.

In the thermoplastic elastomer composition produced by the present invention, although depending on the types of the polar rubber (C) and the cross-linking agent (E), the cross-linking agent (E) is added to 100 parts by mass of the polar rubber (C). Is usually contained in an amount of 0.01 to 15 parts by mass, preferably 0.05 to 10 parts by mass.

When the thermoplastic elastomer composition produced by the present invention further contains a plasticizer (F), the plasticizer (F) is usually added in an amount of 1 to 150 parts by mass, relative to 100 parts by mass of the polar rubber (C). It is desirable to contain 3 to 100 parts by mass.

[Thermoplastic Elastomer Composition]
The thermoplastic elastomer composition produced by the present invention comprises the above-mentioned carbodiimide group-containing compound (A), an olefin polymer (B) having a group reactive with a carbodiimide group, a polar rubber (C), an olefin polymer ( D) and a crosslinking agent (E) capable of crosslinking the polar rubber (C) are dynamically heat-treated. This thermoplastic elastomer composition may contain the above-mentioned other components, if necessary. The blending ratio of each component in this thermoplastic elastomer composition is not particularly limited and is preferably as described above.

Since the thermoplastic elastomer composition produced by the present invention contains the carbodiimide group-containing compound (A) as a raw material and the compound (B) containing a group that reacts with a carbodiimide group, the resulting thermoplastic composition In the above, the above-mentioned carbodiimide group-containing compound (A) and the "group which reacts with a carbodiimide group" contained in the olefin polymer (B) having a group which reacts with a carbodiimide group react at least partially by melt kneading. It is considered that a reaction product (I) may be formed between the carbodiimide group-containing compound (A) and the olefin polymer (B) having a group that reacts with the carbodiimide group. This reaction product (I) has a carbodiimide group as well as a polyolefin chain derived from the olefin polymer (B) having a group that reacts with a carbodiimide group. Since such a reaction product (I) has a carbodiimide group which is a polar group, it has excellent compatibility with the polar rubber (C), and since it has a polyolefin chain, it has an olefin polymer (D). It is also highly compatible. Therefore, in this thermoplastic elastomer composition, the polar rubber (C) and the olefin polymer (D) were highly mixed and well dispersed as compared with the case where the both were simply mixed. It becomes a state. Therefore, this thermoplastic elastomer composition preferably contains the reaction product (I) of the carbodiimide group-containing compound (A) and the olefin polymer (B) having a group that reacts with the carbodiimide group.

Further, since the thermoplastic elastomer composition produced by the present invention contains the polar rubber (C) and the crosslinking agent (E) capable of crosslinking the polar rubber (C) as raw materials, this thermoplastic elastomer composition In the product, at least part of the polar rubber (C) forms crosslinks. That is, this thermoplastic elastomer composition usually contains a crosslinked polar rubber which is a crosslinked product of the polar rubber (C). In this thermoplastic elastomer composition, the crosslinked polar rubber, which is a crosslinked product of the polar rubber (C), and the olefin polymer (D) are highly dispersed.

Further, in the thermoplastic elastomer composition produced by the present invention, either the polar rubber (C), the reaction product (II), or the reaction product (III) described above may form a crosslink, Further, the reaction product (II) or the reaction product (III) and the polar rubber (C) may have cross-links with each other. That is, the thermoplastic elastomer composition may contain a crosslinked product in which two or more kinds of these components are crosslinked with each other.

Such a thermoplastic elastomer composition has suitable elasticity by containing a crosslinked product and is also excellent in chemical resistance, and by containing an olefin polymer (D), has excellent moldability. Have. Further, this thermoplastic elastomer composition is preferable because each component constituting the composition is highly dispersed and separation is unlikely to occur. This means that the reaction product (I), the reaction product (II), etc. are produced in the thermoplastic elastomer composition part to act as a compatibilizer, or at least a part of the raw material forms a crosslink. It is thought that this is due to the fact that they are intertwined with each other.

In the thermoplastic elastomer composition produced by the present invention, the crosslinked polar rubber, which is a crosslinked product of the polar rubber (C), and the olefin polymer (D) are highly dispersed, and the thermoplastic elastomer composition is obtained. The product has excellent moldability, the molded product obtained from the thermoplastic elastomer has excellent elasticity, and also exhibits excellent wear resistance and oil resistance. The fact that the respective components, particularly the crosslinked polar rubber and the olefin polymer (D) are highly dispersed in this thermoplastic elastomer composition means, for example, that a molded article obtained from the thermoplastic elastomer composition is It can be easily confirmed by observing the surface or cross section with a microscope or the like, and the dispersed particle size being sufficiently small.

The thermoplastic elastomer composition produced according to the present invention has a sea-island structure observed in a scanning electron microscope (SEM) image of 200 times or more, for example, about 1000 times, and the average particle size of the island phase is preferably. It is desirable that the range is 0.01 to 20 μm, and more preferably 0.01 to 10 μm.

A molded article containing at least a part of the thermoplastic elastomer composition produced by the present invention can be easily produced due to good moldability, and is a machine having flexibility, elasticity, breaking strength, compression set resistance and the like. Excellent in chemical properties, oil resistance and chemical resistance. The molding method for producing a molded body is not particularly limited, and any conventionally known method can be adopted, for example, injection molding, press molding, extrusion molding, or the like. You can

Such a thermoplastic elastomer composition can be suitably used as a molded body material in various fields in which an elastic molded body has been conventionally used.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

<Measurement and evaluation method>
In the following examples and comparative examples, each property was measured or evaluated as follows.

[Number average molecular weight (Mn)]
The number average molecular weight (Mn) was measured by gel permeation chromatography (GPC). It was measured as follows using a gel permeation chromatograph Alliance GPC-2000 type manufactured by Waters. The separation column used two TSKgel GMH6-HT and two TSKgel GMH6-HTL, the column size was 7.5 mm in diameter and 300 mm in length, and the column temperature was 140° C. and the mobile phase was o. -Using dichlorobenzene (Wako Pure Chemical Industries, Ltd.) and BHT (Takeda Yakuhin) 0.025 mass% as an antioxidant, moving at 1.0 ml/min, the sample concentration is 15 mg/10 mL, and the sample injection amount is 500 micro The liter was used and a differential refractometer was used as a detector. As the standard polystyrene, those having a molecular weight of Mw<1000 and Mw>4×10 ⁶ were manufactured by Tosoh Corporation, and those having a molecular weight of 1000≦Mw≦4×10 ⁶ were manufactured by Pressure Chemical. In the case of maleic anhydride-modified polypropylene, it was calculated in terms of polypropylene.

[Activation energy ΔE (J/mol), frequency factor A (hr ⁻¹ )]
According to JIS K6300-2, a crosslinking curve was measured at a plurality of temperatures to calculate t'c(90) to obtain a crosslinking rate. Specifically, first, the cross-linking curve is measured at 180° C., the cross-linking curve at 180° C. is fast, the cross-linking curve is measured at the low temperature side, and the slow cross-linking curve is measured at the high temperature side, The crosslinking rate at each temperature was obtained. The measurement temperature was measured at intervals of 5 to 10° C. and three or more points were measured. The obtained numerical values were Arrhenius-plotted by an ordinary method to obtain an approximate straight line, the activation energy ΔE (J/mol) was calculated from the slope of the straight line, and the frequency factor A (hr ⁻¹ ) was calculated from the intercept.

[Shore A hardness]
In accordance with JIS K6253, it was measured by a Shore hardness meter (A hardness meter) using a press sheet having a thickness of 2 mm.

[Compression set (CS)]
A press-formed sheet produced from a thermoplastic elastomer composition by a press-forming machine is 25% compressed using a spacer according to JIS K6262, heat-treated at 70° C. for 24 hours, and after treatment, in a constant temperature chamber at 23° C. After standing for 30 minutes, the thickness was measured and the compression set (CS) was calculated from the following formula.
CS=[(t0-t1)/(t0-t2)]×100
CS: compression set (%)
t0: Original thickness of the press-formed sheet (mm)
t1: Thickness of the press-formed sheet after being left for 30 minutes (mm)
t2: Thickness of the press-formed sheet with a compressive strain applied (mm)

[Strand formability]
The thermoplastic elastomer composition was introduced into HYPER REX (manufactured by Kobe Steel, Ltd., with a die attached to the tip) set at 190° C., and extruded in a strand shape. At this time, those in which the strands were stably extruded were evaluated as “◯”, those in which the strands were frequently cut were evaluated as “Δ”, and those in which the strands were not extruded were evaluated as “x”.

[Production Example 1]
<Production of maleic anhydride modified polypropylene (B-1)>
100 parts by mass of polypropylene (Prime Polymer Co., Ltd., Prime Polypro (registered trademark) F327), 1 part by mass of maleic anhydride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 2,5-dimethyl-2,5-bis( tert-butylperoxy)hexyne-3 (manufactured by NOF CORPORATION, trade name Perhexin (registered trademark) 25B) in an amount of 0.25 parts by mass, and a twin-screw kneader (manufactured by Japan Steel Works, Ltd., TEX-30). L/D=40, using a vacuum vent), a cylinder temperature of 220° C., a screw rotation speed of 200 rpm, and a discharge rate of 80 g/min were extruded to obtain a maleic anhydride-modified polypropylene (B-1). The obtained maleic anhydride-modified polypropylene (B-1) was dissolved in xylene, and then the obtained xylene solution was poured into acetone for reprecipitation and purification, and the grafted amount of maleic anhydride was measured by IR. The result was 0.7% by mass. The number average molecular weight (Mn) was Mn 28,000 as measured by GPC.

[Example 1]
Polycarbodiimide (A-1) that is a carbodiimide group-containing compound (Nisshinbo Chemical Co., Ltd., Carbodilite (registered trademark) HMV-15CA, carbodiimide equivalent 262 g), maleic anhydride-modified polypropylene (B-1) obtained in Production Example 1 , A part of polypropylene (D-1) (homopolypropylene, manufactured by Prime Polymer Co., Ltd., Prime Polypro (registered trademark) F113G, MFR: 3.0 g/10 min) [4.22 parts by mass (D-1) ¹⁾ ]. Was introduced into an extruder (manufactured by Nippon Steel Works, Ltd., TEX44, L/D=70) with the compounding amount (parts by mass) shown in Table 1, and the cylinder temperature was 290° C., the screw rotation speed was 760 rpm, and the discharge amount was 1.33 kg. The mixture was melt-kneaded at a rate of 1/min to obtain a composition containing a reaction product (contact product) of polycarbodiimide (A-1) and maleic anhydride-modified polypropylene (B-1) and polypropylene (D-1) (No. One-step formulation).

Then, the balance [23.00 parts by mass (D-1) ^{2) of} polypropylene (D-1), nitrile rubber (C-1) which is a polar rubber (manufactured by Nippon Zeon Co., Ltd., Nipol (registered trademark) 1042, NBR, Mooney viscosity=77.5, bound acrylonitrile amount=33.5%, SP value=about 20 (MPa) ^0.5 ), polar rubber (C1-1) having a group that reacts with a carbodiimide group (manufactured by Zeon Corporation) , Nipol (registered trademark) NX775, carboxyl group-containing NBR, Mooney viscosity = 44.0, bound acrylonitrile amount = 26.7%, SP value = about 20 (MPa) ^0.5 ), plasticizer (F-1) (corp.) ADEKA, Adeka Sizer (registered trademark) RS-107), additive (H-1) (manufactured by BASF, Irganox (registered trademark) 1010, phenolic antioxidant) and the above composition, a meshing type kneader (BB-L3200IM, manufactured by Kobe Steel, Ltd., 3.6 liters) was introduced so that the compounding amount (parts by mass) shown in Table 1 would be obtained, and the mixture was melt-kneaded at 120 rpm (second-stage compounding). After that, when the resin temperature T2 in the kneader reaches about 145° C., a cross-linking agent (E-1) (manufactured by NOF CORPORATION, Perhexa (registered trademark) 25B, organic peroxide-based cross-linking agent) and a cross-linking aid ( G-1) (a divinylbenzene-based crosslinking assistant, manufactured by NS Styrene Monomer Co., Ltd., DVB-810) was put into an intermeshing type kneader to give Tmax. About 210° C., Tave. Was carried out while kneading so as to be about 190° C. (third stage compounding) to obtain a thermoplastic elastomer composition. The amount of the thermoplastic elastomer composition obtained was about 3 kg/batch.

The obtained thermoplastic elastomer composition was introduced into HYPER REX (manufactured by Kobe Steel, Ltd.) set at 190° C., and the strand formability was evaluated. Further, the obtained thermoplastic elastomer composition was press-molded at 210° C. to a thickness of 2 mm and punched into various test shapes as samples, and the physical properties were measured by the above-mentioned test methods. The results are shown in Table 1.

[Example 2]
In Example 1, in addition to the additive (H-1), the additive (H-2) (Ouchi Shinko Chemical Industry Co., Ltd., Nocrac (registered trademark) 224) was used, and each component is shown in Table 1. A thermoplastic elastomer composition was obtained in the same manner as in Example 1 except that the blending amount (parts by mass) was used. The obtained thermoplastic elastomer composition was about 3 kg/batch. The results are shown in Table 1.

[Example 3]
In Example 1, the additive (H-2) was used in addition to the additive (H-1), and the kneader was an intermeshing type kneader (manufactured by Kobe Steel, Ltd., BB-14IM, 14.4 liters). ) And Tmax. About 220° C., Tave. A thermoplastic elastomer composition was obtained in the same manner as in Example 1 except that the kneading was carried out at about 200°C. The obtained thermoplastic elastomer composition was about 12 kg/batch. The results are shown in Table 1.

[Example 4]
In Example 3, Tmax. About 250° C., Tave. Was about 215° C., and a thermoplastic elastomer composition was obtained in the same manner as in Example 3. The obtained thermoplastic elastomer composition was about 12 kg/batch. The results are shown in Table 1.

[Example 5]
In Example 1, instead of the cross-linking agent (E-1), a cross-linking agent (E-2) (manufactured by NOF CORPORATION, Perhexin 25B, organic peroxide-based cross-linking agent) was added in an amount shown in Table 1 ( A thermoplastic elastomer composition was obtained in the same manner as in Example 1 except that it was used in (parts by mass). The obtained thermoplastic elastomer composition was about 3 kg/batch. The results are shown in Table 1.

[Example 6]
In Example 1, instead of the cross-linking agent (E-1) and the cross-linking aid (G-1), a cross-linking agent (E-3) (SI Group, SP1055F, phenol-based cross-linking agent) and a cross-linking aid ( G-2) (manufactured by Hakusui Tech Co., Ltd., two kinds of zinc oxide) was used in a compounding amount (parts by mass) shown in Table 1, and Tmax. About 250° C., Tave. Was kneaded at about 210° C. to obtain a thermoplastic elastomer composition in the same manner as in Example 1. The obtained thermoplastic elastomer composition was about 3 kg/batch. The results are shown in Table 1.

[Example 7]
Example 6 was carried out except that polypropylene (D-2) (Prime Polymer Co., Ltd., Prime Polypro (registered trademark) F227D, random PP) was used in place of polypropylene (D-1) ²⁾ in Example 6. A thermoplastic elastomer composition was obtained in the same manner as in Example 6. The obtained thermoplastic elastomer composition was about 3 kg/batch. The results are shown in Table 1.

[Comparative Example 1]
In Example 7, Tmax. About 180° C., Tave. Was about 175° C., and a thermoplastic elastomer composition was obtained in the same manner as in Example 7. The obtained thermoplastic elastomer composition was about 3 kg/batch. The results are shown in Table 2.

[Comparative example 2]
In Example 4, Tmax. Was about 225° C. and T2 was about 205° C., but a thermoplastic elastomer composition was obtained in the same manner as in Example 4. The obtained thermoplastic elastomer composition was about 12 kg/batch. The results are shown in Table 2.

[Comparative Example 3]
In Example 1, Tmax. About 270° C., Tave. Was kneaded to about 250° C., and a thermoplastic elastomer composition was obtained in the same manner as in Example 1. The obtained thermoplastic elastomer composition was about 3 kg/batch. The results are shown in Table 2.

[Comparative Example 4]
A thermoplastic elastomer composition was obtained in the same manner as in Example 6, except that the crosslinking aid (G-2) was not used. The obtained thermoplastic elastomer composition was about 3 kg/batch. The results are shown in Table 2.

The thermoplastic elastomer compositions obtained in Examples 1 to 7 were excellent in mechanical properties (A hardness, compression set) and moldability. On the other hand, since the thermoplastic elastomer composition obtained in Comparative Example 1 did not satisfy the condition (1) (Tmax.(°C) was less than T1(°C)), the compression set resistance was poor. Since the thermoplastic elastomer composition obtained in Comparative Example 2 did not satisfy the condition (2) (T2 was higher than T3), the moldability was poor. Since the thermoplastic elastomer composition obtained in Comparative Example 3 did not satisfy the condition (3) (P1 was larger than 8.5), deterioration of the resin proceeded and the composition could not be formed into a strand shape. .. Since the thermoplastic elastomer composition obtained in Comparative Example 4 did not satisfy the condition (3) (P1 was less than 2.0), the crosslinking was insufficient and the compression set resistance was poor.

According to the production method of the present invention, a thermoplastic elastomer composition having elasticity, excellent oil resistance, chemical resistance, and the like, and also excellent in moldability is produced. This thermoplastic elastomer composition can be suitably used as a molded article material in various fields in which elastic molded bodies have been conventionally used. Specific examples include rubber for tires, O-rings, industrial rolls, boots for automobiles (for example, boots for rack and pinion, boots for constant velocity joints), packing (for example, capacitor packing), gaskets, belts (for example, heat insulation). Belt, copier belt), hose (eg water hose, brake reservoir hose, radiator hose), anti-vibration rubber, sponge (eg weather strip sponge, heat insulating sponge, protect sponge, fine foam sponge), cable (eg ignition cable) , Cabtire cables, high tension cables), wire coating materials (eg, high voltage wire coating materials, low voltage wire coating materials, marine wire coating materials), glass run channels, color skin materials, paper feed rolls, shoe soles, roofing sheets, etc. Is mentioned.

Claims (11)

Carbodiimide group-containing compound (A),
An olefin polymer (B) having a group that reacts with a carbodiimide group,
Polar rubber (C),
The olefin polymer (D) and the cross-linking agent (E) capable of cross-linking the polar rubber (C)
A method for producing a thermoplastic elastomer composition, which comprises a step of dynamically cross-linking using a batch-type kneader under conditions satisfying the following conditions (1) to (3).
(1) Tmax. ≧ T1
(“Tmax.” is the maximum value (° C.) of the resin temperature from when the cross-linking agent (E) was introduced into the batch-type kneader to when the thermoplastic elastomer composition was discharged to the outside of the batch-type kneader. Is the temperature (°C) defined by the following formula (i).)
T1=ΔE/(8.314×(LnA-3))-273.15 (i)
(“ΔE” is the activation energy (J/mol) calculated from the slope of the Arrhenius plot created from the cross-linking curves measured at multiple temperatures using polar rubber (C) and cross-linking agent (E); Is the frequency factor (hr ⁻¹ ) calculated from the intercept.)
(2) T2 ≤ T3
(“T2” is the resin temperature (° C.) in the kneader when the cross-linking agent (E) is introduced into the batch type kneader, and “T3” is the temperature (° C.) defined by the following formula (ii). .)
T3=ΔE/(8.314×(LnA-5))-273.15 (ii)
(3) 2.0 ≤ P1 ≤ 8.5
("P1" is a value defined by the following formula (iii).)
P1=LnA−ΔE/(8.314×(Tave.+273.15)) (iii)
(“Tave.” is the average value (° C.) of the resin temperature from the state where the cross-linking agent (E) is present and the olefin polymer (D) is melted to the time when the kneading is completed and discharged.) The composition in the step of dynamically crosslinking contains a reaction product (I) of a carbodiimide group-containing compound (A) and an olefin-based polymer (B) having a group that reacts with a carbodiimide group. A method for producing the thermoplastic elastomer composition described. The method for producing a thermoplastic elastomer composition according to claim 1, wherein the polar rubber (C) contains a polar rubber (C1) having a group that reacts with a carbodiimide group. The method for producing a thermoplastic elastomer composition according to claim 3, wherein the polar rubber (C1) having a group that reacts with a carbodiimide group is a polar rubber having a group having active hydrogen in a side chain. The method for producing a thermoplastic elastomer composition according to claim 3 or 4, which comprises a reaction product (II) of a carbodiimide group-containing compound (A) and a polar rubber (C1) having a group that reacts with a carbodiimide group. The method for producing a thermoplastic elastomer composition according to any one of claims 1 to 5, wherein the carbodiimide group-containing compound (A) is a polycarbodiimide having a repeating unit represented by the following general formula.
^{-N = C = N-R 1} -
(In the formula, R ¹ represents a divalent organic group.) The thermoplastic elastomer composition according to any one of claims 1 to 6, wherein the olefin polymer (B) having a group that reacts with a carbodiimide group is an olefin polymer having a group having active hydrogen in a side chain. Manufacturing method. The olefin polymer (B) having a group reactive with a carbodiimide group is a graft copolymer of a polyolefin and a compound (b) having a group reactive with a carbodiimide group. A method for producing the thermoplastic elastomer composition described. The method for producing a thermoplastic elastomer composition according to claim 1, wherein the olefin polymer (D) is a propylene polymer. The composition in the step of dynamically cross-linking has a group that reacts with a carbodiimide group (B), a polar rubber (C), and 100 parts by mass of the olefin polymer (D) in total,
The method for producing a thermoplastic elastomer composition according to claim 1, wherein the carbodiimide group-containing compound (A) is blended in the range of 0.01 to 30 parts by mass. The method for producing a thermoplastic elastomer composition according to claim 1, wherein the batch-type kneader has an intermeshing rotor.