KR20200137991A - Thermoplastic elastomer composition and method of producing same - Google Patents

Abstract

The present invention provides a thermoplastic elastomer composition capable of producing a molded article having a desirable appearance for non-painting applications. The thermoplastic elastomer composition containing at least two olefin polymers has a content of a component insoluble in orthodichlorobenzene at 140°C of 20 to 50 wt%, and the isothermal crystallization time of 300 seconds or more measured at 130°C.

Description

Thermoplastic elastomer composition and its manufacturing method TECHNICAL FIELD

The present invention relates to a thermoplastic elastomer composition and a method for producing the same.

A molded article molded from a thermoplastic elastomer composition containing an olefin polymer has high tensile strength and tear strength, and has excellent low-temperature impact resistance so that it can withstand use in cold regions, for example, automobile-related members. It is used as a molding material for molding.

For example, Patent Document 1 describes a resin composition used for automobile parts including a matrix made of a propylene homopolymer or the like having a specific molecular weight distribution and crystallinity and a dispersed phase made of an ethylene-propylene copolymer. In Patent Document 1, the resin composition is produced by reacting a monomer, a crosslinking agent, an antioxidant, and a nucleating agent in one or two reactors.

In addition, in Patent Document 2, a resin composition containing a propylene homopolymer and an ethylene-α-olefin copolymer, a propylene-ethylene copolymer, and two types of ethylene-α-olefin copolymers having a specific density and MFR are essential. Thermoplastic elastomer compositions containing as components are described.

Japanese Patent Publication No. 2013-528247 Japanese Unexamined Patent Publication No. 2015-193710

In recent years, resin compositions used in automobile parts and the like have been studied for non-painting of a molded article molded from the thermoplastic elastomer composition, including an airbag cover attached to a visible portion. The molded article of the thermoplastic elastomer composition is required to have a good appearance regardless of its shape.

However, when a flat molded article having a groove-like thin portion formed on its surface is injection-molded with the resin composition described in Patent Document 1, gloss unevenness is likely to occur on the surface in the vicinity of the thin portion, and coating Good appearance to the extent that the process can be omitted is not obtained.

In addition, there is a demand for a thermoplastic elastomer composition that provides a better appearance regardless of the shape of a molded article than the thermoplastic elastomer composition described in Patent Document 2.

In view of the above problems, one aspect of the present invention provides a thermoplastic elastomer composition capable of producing a molded article having a desirable appearance for non-painting applications, even if injection molding into a shape having portions having different thicknesses, and a manufacturing method thereof. It is aimed at.

The inventors of the present invention found out that the content of the insoluble component in orthodichlorobenzene of the thermoplastic elastomer composition and the isothermal crystallization time are related to the appearance of a molded article made of the composition.

More specifically, it was found that a molded article formed of a thermoplastic elastomer composition that satisfies specific conditions with respect to the content of the insoluble component in orthodichlorobenzene and the isothermal crystallization time exhibits a stable and good appearance, and the present invention Came to complete. That is, the present invention includes the following inventions.

<1> As a thermoplastic elastomer composition containing at least two olefin polymers, the following requirement (I) and the following requirement (II):

(I) The content of the insoluble component in orthodichlorobenzene at 140°C of the thermoplastic elastomer composition measured using gel permeation chromatography is 20 parts by weight to 50 parts by weight based on 100 parts by weight of the thermoplastic elastomer composition. Wealth;

(II) Isothermal crystallization time measured at 130° C. using a heat flux type differential scanning calorimeter is 300 seconds or more;

Satisfying the, thermoplastic elastomer composition.

<2> The thermoplastic elastomer composition according to <1>, wherein the content of the insoluble component is from 20 parts by weight to 35 parts by weight.

<3> The thermoplastic elastomer composition according to <1> or <2>, wherein the content of the insoluble component is from 24 parts by weight to 30 parts by weight.

<4> The thermoplastic elastomer composition according to any one of <1> to <3>, in which the isothermal crystallization time is from 1500 seconds to 2000 seconds.

<5> The thermoplastic elastomer composition is a composition obtained by melt-kneading a heterophasic propylene polymerized material in the presence of a crosslinking agent and a crosslinking aid,

The heterophasic propylene polymerization material contains a propylene copolymer (A) and a propylene copolymer (B),

The content of the propylene copolymer (A) is 45 to 65 parts by weight with respect to 100% by weight of the total amount of the propylene copolymer (A) and the propylene copolymer (B), and the propylene copolymer (B) The content is from 35 parts by weight to 55 parts by weight,

The propylene copolymer (A),

A monomer unit derived from propylene (A1), and

A monomer unit (A2) derived from at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 12 carbon atoms,

With respect to 100 parts by weight of the monomer unit (A1) and the monomer unit (A2), the content of the monomer unit (A1) is 95 parts by weight-99.9 parts by weight, and the content of the monomer unit (A2) is 0.1 parts by weight- 5 parts by weight,

The propylene copolymer (B),

A monomer unit (B1) derived from propylene, and

And a monomer unit (B2) derived from at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 12 carbon atoms,

With respect to 100 parts by weight of the monomer unit (B1) and the monomer unit (B2), the content of the monomer unit (B1) is from 20 parts by weight to 78 parts by weight, and the content of the monomer unit (B2) is from 22 parts by weight. 80 parts by weight,

The thermoplastic elastomer composition in any one of <1>-<4>.

<6> The weight average molecular weight of the propylene copolymer (A) is 1.0 × 10 ⁵ to 7.0 × 10 ⁵ , and the weight average molecular weight of the propylene copolymer (B) is 4.0 × 10 ⁴ to 1.3 × 10 ⁶ And the thermoplastic elastomer composition according to <5>.

The thermoplastic elastomer composition according to <5> or <6>, wherein the weight average molecular weight of the <7> propylene copolymer (B) is 2.0 × 10 ⁵ to 1.1 × 10 ⁶ .

<8> The thermoplastic elastomer composition according to any one of <5> to <7>, in which the crosslinking agent is an organic peroxide.

<9> The thermoplastic elastomer composition according to any one of <5> to <8>, wherein the crosslinking aid is at least one compound selected from the group consisting of a maleimide compound, a polyfunctional vinyl compound, and a polyfunctional acrylate compound. .

<10> The thermoplastic elastomer composition according to any one of <5> to <9>, wherein the temperature at which the melt-kneading is performed is from 170°C to 270°C.

<11> The thermoplastic elastomer composition according to any one of <5> to <10>, in which the heterophasic propylene polymerization material is a polymerization material obtained by multistage polymerization.

As a method for producing a thermoplastic elastomer composition comprising a step of melt-kneading a <12> heterophasic propylene polymerization material in the presence of a crosslinking agent and a crosslinking aid,

The heterophasic propylene polymerization material contains a propylene copolymer (A) and a propylene copolymer (B),

The content of the propylene copolymer (A) is 45 to 65 parts by weight with respect to 100% by weight of the total amount of the propylene copolymer (A) and the propylene copolymer (B), and the propylene copolymer (B) The content is from 35 parts by weight to 55 parts by weight,

The propylene copolymer (A),

A monomer unit derived from propylene (A1), and

A monomer unit (A2) derived from at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 12 carbon atoms,

With respect to 100 weights of the monomer unit (A1) and the monomer unit (A2), the content of the monomer unit (A1) is from 95 parts by weight to 99.9 parts by weight, and the content of the monomer unit (A2) is from 0.1 parts by weight to 5 parts by weight,

The propylene copolymer (B),

A monomer unit (B1) derived from propylene, and

And a monomer unit (B2) derived from at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 12 carbon atoms,

With respect to 100 parts by weight of the total amount of the monomer unit (B1) and the monomer unit (B2), the content of the monomer unit (B1) is from 20 parts by weight to 78 parts by weight, and the content of the monomer unit (B2) is 22 parts by weight. It is from parts to 80 parts by weight,

The thermoplastic elastomer composition, the following requirement (I) and the following requirement (II):

(I) The content of the insoluble component in orthodichlorobenzene at 140°C of the thermoplastic elastomer composition measured using gel permeation chromatography is 20 parts by weight to 50 parts by weight based on 100 parts by weight of the thermoplastic elastomer composition. Wealth;

(II) Isothermal crystallization time measured at 130° C. using a heat flux type differential scanning calorimeter is 300 seconds or more;

Satisfying, the method for producing a thermoplastic elastomer composition.

A molded article containing the thermoplastic elastomer composition in any one of <13> said <1>-<11>.

An airbag cover containing the thermoplastic elastomer composition in any one of <14> said <1>-<11>.

According to one aspect of the present invention, it is possible to provide a thermoplastic elastomer composition capable of producing a molded article having an appearance suitable for non-painting applications, and related technologies thereof.

One embodiment of the present invention will be described below, but the present invention is not limited thereto. The present invention is not limited to each configuration described below, and various modifications are possible within the scope shown in the claims, and embodiments or implementations obtained by appropriately combining the technical means disclosed in different embodiments or examples. Examples are also included in the technical scope of the present invention. In addition, in this specification, "A to B" indicating a numerical range intends "A or more and B or less" unless otherwise specified.

<Thermoplastic elastomer composition>

The thermoplastic elastomer composition according to an aspect of the present invention is a thermoplastic elastomer composition containing at least two olefin polymers, and satisfies the requirements of the requirements (I) and (II). In addition, the thermoplastic elastomer composition according to one aspect of the present invention contains a crosslinking agent and a crosslinking aid, and by the crosslinking agent and the crosslinking aid, one olefin polymer or at least two olefin polymers are It has a crosslinking structure.

By satisfying the requirements (I) and (II), even if the thermoplastic elastomer composition according to an aspect of the present invention is injection-molded into a shape having a portion having a different thickness (thin portion), gloss unevenness is prevented in the portion. It is possible, and thus a molded article having an appearance suitable for non-painting applications can be produced. For this reason, for example, it can be suitably used for molded articles such as airbag covers and automotive exterior parts such as moldings, home appliances, building materials, furniture, etc. in airbags installed in automobile interior parts such as instrument panels and fillers. have.

[Solubility in orthodichlorobenzene at 140°C]

In the thermoplastic elastomer composition, the content of the insoluble component in orthodichlorobenzene at 140° C. measured using gel permeation chromatography as the requirement (I) is 20 parts by weight to 50 parts by weight based on 100 parts by weight of the thermoplastic elastomer composition. It is parts by weight.

The thermoplastic elastomer composition contains at least two types of olefin polymers, a non-crosslinked product of an olefin polymer and a crosslinked product of an olefin polymer. The non-crosslinked product in the olefin polymer contained in the thermoplastic elastomer composition is dissolved in orthodichlorobenzene at 140°C. On the other hand, the crosslinked product in the olefin polymer does not dissolve in 140°C orthodichlorobenzene, but elutes as an insoluble component. That is, the requirement (I) may be a three-dimensional degree of crosslinking of the olefin polymer contained in the thermoplastic elastomer composition, which can be analyzed using a difference in solubility in orthodichlorobenzene at 140°C.

In the thermoplastic elastomer composition according to an aspect of the present invention, the content of the insoluble component in orthodichlorobenzene at 140° C. is 20 to 50 parts by weight, preferably 20 parts by weight, based on 100 parts by weight of the thermoplastic elastomer composition. They are -45 parts by weight, more preferably 20 parts by weight to 35 parts by weight, and still more preferably 24 parts by weight to 30 parts by weight. When the content of the insoluble component in the 140°C orthodichlorobenzene is 20 to 50 parts by weight, the appearance of the molded article can be improved.

The content of the insoluble component to orthodichlorobenzene at 140°C may be adjusted to the type and amount of the crosslinking agent and crosslinking aid to be described later, the temperature and time for melt-kneading, and the like contained in the thermoplastic elastomer composition.

In addition, a method for measuring the solubility of the thermoplastic elastomer composition in orthodichlorobenzene at 140°C is described in detail in Examples.

[Solubility in orthodichlorobenzene at 50°C]

It is preferable that the thermoplastic elastomer composition contains two olefin polymers having different solubility in orthodichlorobenzene at 50°C. By using together two olefin polymers having different solubility in orthodichlorobenzene at 50°C, the isothermal crystallization time of the olefin polymer described later can be preferably adjusted.

In the thermoplastic elastomer composition according to an aspect of the present invention, the content of the insoluble component to orthodichlorobenzene at 50°C is preferably 45 to 65 parts by weight, more preferably based on 100 parts by weight of the thermoplastic elastomer composition. Specifically, it is from 47 parts by weight to 55 parts by weight.

When the content of the insoluble component to orthodichlorobenzene at 50° C. is within the above range, the appearance can be improved without impairing the low-temperature impact performance and material strength of the resulting molded article.

In the present invention, the content of the insoluble component and the soluble component to orthodichlorobenzene at 50°C, and the weight average molecular weight (Mw) and the amount of methyl group per 1000 carbon (CH ₃ /1000C) are as follows: It can be measured by cross fractionation chromatography (CFC), and the measurement method is described in detail in Examples.

[Isothermal crystallization time]

The thermoplastic elastomer composition according to an aspect of the present invention, as requirement (II), has an isothermal crystallization time measured at 130°C using a heat flux differential scanning calorimeter of 300 seconds or more, more preferably 300 seconds to 3000 Seconds, more preferably 500 seconds to 3000 seconds, still more preferably 1500 seconds to 2000 seconds.

If the isothermal crystallization time in the thermoplastic elastomer composition is 300 seconds or more in the above range, the appearance of the molded article can be improved, and if it is 2000 seconds or less, the rigidity of the molded article can be improved.

In addition, in this invention, the isothermal crystallization time is a value measured using the following method.

The thermoplastic elastomer composition is sandwiched between smooth plates, pressed at 230° C. and 1 MPa for 5 minutes, and cooled, and a press sheet (thickness 0.2 mm) obtained is used as a measurement sample.

Using a heat flux type differential scanning calorimeter, the measurement sample is held at 200°C for 5 minutes in a nitrogen atmosphere, and then cooled to 130°C at 320°C to 340°C/min and maintained. The relationship between the calorific value and time due to crystallization of the sample at this time is measured, and the time required to reach the calorific value of 1/2 of the total calorific value is taken as the isothermal crystallization time (second).

(Other properties)

Moreover, it is preferable that the resin composition further satisfies the following physical properties.

The melt flow rate of the thermoplastic elastomer composition at a temperature of 230° C. and a measurement load of 21.18 N measured in accordance with JIS K7210:1999 is preferably 1 g/10 min to 50 g/10 min from the viewpoint of the appearance of the obtained molded article. And more preferably 5 g/10 minutes to 30 g/10 minutes.

Further, the melting temperature of the thermoplastic elastomer composition is preferably 140°C or higher, and more preferably 145°C or higher, from the viewpoint of the rigidity of the obtained molded article. Moreover, this melting temperature is 175 degreeC or less normally. The melting temperature is the peak temperature of the endothermic peak with the largest peak temperature in the differential scanning calorific value curve at the time of the temperature increase operation measured by the differential scanning calorimeter. The measurement of the differential scanning calorific value curve by the differential scanning calorimeter is carried out under the following conditions, and the melting temperature may be determined from the differential scanning calorific value curve in the heating operation.

[Olefin polymer]

The thermoplastic elastomer composition contains, as an olefin polymer, a crosslinked product three-dimensionally crosslinked and a non-crosslinked product not three-dimensionally crosslinked, and in a preferred embodiment of the present invention, crosslinking of the olefin polymer The sieve and non-crosslinked may consist of at least two olefin polymers. In this case, at least two olefin polymers include an olefin polymer that is a soluble component to orthodichlorobenzene at 50°C, and an olefin polymer that is an insoluble component to orthodichlorobenzene at 50°C.

It is preferable that the thermoplastic elastomer composition according to one aspect contains an olefin polymer and contains an olefin polymer that is a soluble component for orthodichlorobenzene at 50°C. That is, so that the thermoplastic elastomer composition according to one aspect satisfies the above-described requirements (I) and (II), a crosslinked product of an olefin polymer is included, and an olefin polymer as a soluble component for orthodichlorobenzene at 50° C. Can include.

(Heterophasic propylene polymerization material)

The thermoplastic elastomer composition according to one aspect, preferably, as an olefin polymer, contains a heterophasic propylene polymerization material containing a propylene copolymer (A) and a propylene copolymer (B), and these heterophasic propylene polymerization materials, It may be a thermoplastic elastomer composition comprising a crosslinking agent and a crosslinked product three-dimensionally crosslinked by a crosslinking aid.

The heterophasic propylene polymerization material is usually obtained by multistage polymerization, contains a propylene copolymer (A) and a propylene copolymer (B), and is made of the other propylene copolymer in a matrix made of one propylene copolymer. It is a mixture having a structure in which the dispersed phase is uniformly dispersed.

The melting temperature of the heterophasic propylene polymerization material is preferably 140°C or higher, and more preferably 145°C or higher, from the viewpoint of the mold releasability during injection molding. Moreover, this melting temperature is 175 degreeC or less normally. The melting temperature is the peak temperature of the endothermic peak with the largest peak temperature in the differential scanning calorific value curve at the time of the temperature increase operation measured by the differential scanning calorimeter. The measurement of the differential scanning calorific value curve by the differential scanning calorimeter is carried out under the following conditions, and the melting temperature is determined from the differential scanning calorific value curve in the heating operation. For example, the melting temperature may be determined under the following measurement conditions.

Temperature-falling operation: The heterophasic propylene polymerization material is melted at 220°C, and then the temperature is lowered from 220°C to -90°C at a temperature cooling rate of 5°C/min.

Temperature raising operation: After the temperature reduction operation, immediately raise the temperature from -90 ℃ to 200 ℃ at 5 ℃ / min.

(Propylene copolymer (A))

The propylene copolymer (A) is a monomer unit (A1) derived from propylene, and a monomer unit derived from at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 12 carbon atoms (A2) Containing, with respect to the total amount of the monomer unit (A1) and the monomer unit (A2) 100% by weight, the content of the monomer unit (A1) is 95% by weight to 99.9% by weight, more preferably 97% by weight to 99% by weight. It is weight%, More preferably, it is 97 weight%-98.5 weight%, The content of a monomer unit (A2) is 0.1 weight%-5 weight%, More preferably, it is 1 weight%-3 weight%, Further Preferably it is 1.5% by weight to 3% by weight. When the content of the monomer unit (A1) and the monomer unit (A2) is within the range, it is easy to obtain a good appearance of the obtained molded article. The content of the monomer unit (A2) can be determined by infrared spectroscopy.

The weight average molecular weight of the propylene copolymer (A) is preferably 1.0 × 10 ⁵ to 7.0 × 10 ⁵ , and more preferably 1.0 × 10 ⁵ to 3.0 × 10 ⁵ .

As an α-olefin having 4 to 12 carbon atoms constituting the monomer unit (A2), 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1 -Undecene, 1-dodecene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, 2,2,4-trimethyl-1 -Pentene, etc. are mentioned.

The monomer constituting the monomer unit (A2) is preferably ethylene and an α-olefin having 4 to 10 carbon atoms, more preferably ethylene, 1-butene, 1-hexene, and 1-octene. These can be used alone or in combination of two or more.

The propylene copolymer (A) may be a random copolymer or a block copolymer.

(Propylene copolymer (B))

The propylene copolymer (B) is a monomer unit (B1) derived from propylene, and a monomer unit derived from at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 12 carbon atoms (B2) Including, with respect to 100% by weight of the total amount of the monomer unit (B1) and the monomer unit (B2), the content of the monomer unit (B1) is from 20% by weight to 78% by weight, more preferably from 30% by weight It is 70 weight%, More preferably, it is 40 weight%-65 weight%. Moreover, content of the monomer unit (B2) is 22 weight%-80 weight%, More preferably, it is 30 weight%-70 weight%, More preferably, it is 35 weight%-60 weight%. When the content of the monomer unit (B1) and the monomer unit (B2) is within the range, it is easy to obtain a good appearance of the obtained molded article. The content of the monomer unit (B2) can be determined by infrared spectroscopy.

The weight average molecular weight of the propylene copolymer (B) is preferably 4.0 × 10 ⁴ to 1.3 × 10 ⁶ , and more preferably 2.0 × 10 ⁵ to 1.1 × 10 ⁶ .

As an α-olefin having 4 to 12 carbon atoms constituting the monomer unit (B2), 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1 -Undecene, 1-dodecene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, 2,2,4-trimethyl-1 -Pentene, etc. are mentioned.

The monomer constituting the monomer unit (B2) is preferably ethylene and an α-olefin having 4 to 10 carbon atoms, more preferably ethylene, 1-butene, 1-hexene, and 1-octene. These can be used alone or in combination of two or more.

The propylene copolymer (B) may be a random copolymer or a block copolymer.

The propylene copolymer (B) specifically includes a propylene-ethylene copolymer, a propylene-ethylene-1-butene copolymer, a propylene-ethylene-1-hexene copolymer, and a propylene-ethylene-1-octene copolymer. However, it is more preferable to use a propylene-ethylene copolymer or a propylene-ethylene-1-butene copolymer.

(Mixing ratio of propylene copolymer (A) and propylene copolymer (B))

In the heterophasic propylene polymerization material, the mixing ratio of the propylene copolymer (A) and the propylene copolymer (B) is from the viewpoint of the appearance and low-temperature impact resistance of the obtained molded article, the propylene copolymer (A) and the propylene copolymer (B) With respect to the total amount of 100% by weight, the content of the propylene copolymer (A) is 45% by weight to 65% by weight, more preferably 47% by weight to 55% by weight, and the content of the propylene copolymer (B) is 35 It is weight%-55 weight%, More preferably, it is 45 weight%-53 weight%.

(Crosslinking agent)

It is preferable to use an organic peroxide as a crosslinking agent used in the said manufacturing method. As the organic peroxide, ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxy ketals, peroxydicarbonates, and peroxy esters can be exemplified.

As ketone peroxides, cyclohexane peroxide, methyl cyclohexanone peroxide, etc. are mentioned.

As diacyl peroxides, isobutyryl peroxide, benzoyl peroxide, etc. are mentioned.

Examples of hydroperoxides include 2,2,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzohydroperoxide, cumene hydroperoxide, and the like.

As dialkyl peroxides, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy) Hexine-3, t-butylcumyl peroxide, di-t-butyl peroxide, and the like.

As peroxyketals, 1,1-Bis(t-butylperoxy)cyclohexane, n-butyl-4,4-bis(t-butylperoxy) valerate, etc. are mentioned.

Examples of peroxydicarbonates include di-n-propylperoxydicarbonate, di-2-ethoxyethylperoxydicarbonate, and the like.

As peroxy esters, cumyl peroxy neodecanoate, t-butyl peroxy pivalate, t-hexyl peroxy benzoate, etc. are mentioned.

These can be used alone or in combination of two or more.

The amount of the crosslinking agent is preferably 0.05 parts by weight to 1.0 parts by weight, more preferably 0.10 parts by weight to 0.50 parts by weight, based on 100 parts by weight of the heterophasic propylene polymer material from the viewpoint of the appearance of the obtained molded article, More preferably, it is 0.20 weight part-0.40 weight part.

If the blending amount of the crosslinking agent is too small, the fluidity of the thermoplastic elastomer composition and the appearance of the resulting molded article may not be sufficient, and if it is excessive, the low-temperature impact performance and material strength of the resulting molded article may decrease.

(Crosslinking aid)

The crosslinking aid is for increasing the degree of crosslinking of the crosslinkable polymer and improving the mechanical properties of the thermoplastic elastomer composition, and a compound having a plurality of double bonds in the molecule is preferably used.

As such a crosslinking aid, it is preferable to use at least one compound selected from a maleimide compound, a polyfunctional vinyl compound, and a polyfunctional acrylate compound.

As a maleimide compound, N,N'-m-phenylene bismaleimide, toluylene bismaleimide, etc. are mentioned.

As a polyfunctional vinyl compound, divinylbenzene, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, etc. are mentioned.

The polyfunctional acrylate compound is an ester of polyhydric alcohol and (meth)acrylic acid, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, allyl(meth) Acrylate, etc. are mentioned. In addition, as a crosslinking aid, for example, a polyfunctional isocyanate compound such as hexamethylene diisocyanate (HDI), and a hydroxyl group such as hydroxyethyl (meth)acrylate (HEMA) ) You may use a polyfunctional urethane acrylate compound which is a reaction product of an acrylate.

These can be used alone or in combination of two or more.

The amount of the crosslinking aid is preferably 0.05 parts by weight to 1.0 parts by weight, more preferably 0.10 parts by weight to 0.70 parts by weight, based on 100 parts by weight of the heterophasic propylene polymer material from the viewpoint of the appearance of the obtained molded article. , More preferably, it is 0.20 weight part-0.60 weight part.

If the blending amount of the crosslinking aid is too small, the appearance of the obtained molded article may be insufficient, and if it is excessive, the fluidity of the thermoplastic elastomer composition may be insufficient.

(Other ingredients)

From the viewpoint of imparting releasability for the purpose of improving production stability in injection molding, the thermoplastic elastomer composition is a fatty acid having 5 or more carbon atoms, a metal salt of a fatty acid having 5 or more carbon atoms, an amide of a fatty acid having 5 or more carbon atoms, and And at least one releasing agent selected from the group of compounds consisting of esters of fatty acids having 5 or more carbon atoms.

Examples of the fatty acid having 5 or more carbon atoms include lauric acid, palmitic acid, stearic acid, behenic acid, oleic acid, erucic acid, linoleic acid, and ricinoleic acid.

Examples of the metal salts of fatty acids having 5 or more carbon atoms include salts of the above fatty acids and metals such as Li, Na, Mg, Al, K, Ca, Zn, Ba, and Pb, specifically lithium stearate, sodium stearate, Calcium stearate, zinc stearate, etc. can be illustrated.

As amides of fatty acids having 5 or more carbon atoms, lauric acid amide, palmitic acid amide, stearic acid amide, oleic acid amide, erucic acid amide, methylene bis stearic acid amide, ethylene bis stearic acid amide, ethylene bis oleic acid amide, Stearyl diethanolamide can be illustrated. Among them, erucic acid amide is preferable.

Examples of esters of fatty acids having 5 or more carbon atoms include the following alcohols and esters of the fatty acids.

Aliphatic alcohols such as myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, and 12 hydroxystearyl alcohol;

Aromatic alcohols such as benzyl alcohol, β-phenylethyl alcohol, and phthalyl alcohol;

Polyhydric alcohols such as glycerin, diglycerin, polyglycerin, sorbitan, sorbitol, propylene glycol, polypropylene glycol, polyethylene glycol, pentaerythritol, and trimethylolpropane;

Specifically, glycerin monooleate, glycerin dioleate, polyethylene glycol monostearate, citrate distearate, and the like may be mentioned.

The content of the release agent is preferably 0.01 parts by weight to 1.5 parts by weight, more preferably, based on 100 parts by weight of the heterophasic propylene polymer material, from the balance between the release property after injection molding and the appearance of the molded product surface. It is 0.05 part by weight-1.0 part by weight, More preferably, it is 0.10 part by weight-0.50 part by weight.

The thermoplastic elastomer composition is an inorganic filler such as talc, calcium carbonate, calcined kaolin, and hydrotalcite, organic fillers such as fiber, wood powder, cellulose powder, silicone oil, silicone gum, etc., as long as the effect of the present invention is not impaired. It may contain a lubricant, an antioxidant, a weather stabilizer, an ultraviolet absorber, a heat stabilizer, a light stabilizer, a pigment, a nucleating agent, an adsorbent, and the like.

<Method for producing thermoplastic elastomer composition>

A method for producing a thermoplastic elastomer composition according to an aspect of the present invention is a method for producing a thermoplastic elastomer composition including a step of melt-kneading a heterophasic propylene polymerized material in the presence of a crosslinking agent and a crosslinking aid.

Here, the process of producing the heterophasic propylene polymerization material and the process of producing the thermoplastic elastomer composition do not necessarily need to be carried out continuously, but are preferably carried out continuously. In other words, in the method for producing a thermoplastic elastomer composition according to an aspect of the present invention, a heterophasic propylene polymerized material obtained by the production method described below is obtained as a commercial product, and a heterophasic propylene polymerized material is used as a crosslinking agent and a crosslinking aid. Melt-kneading in the presence may be included.

(Production process of heterophasic propylene polymerization material)

As a manufacturing method of the heterophasic propylene polymerization material, the following manufacturing method 1 and manufacturing method 2 are mentioned.

<Manufacturing method 1> The manufacturing method of the heterophasic propylene polymerization material including a process (1-1) and a process (1-2)

Step (1-1): copolymerization of propylene with at least one olefin selected from the group consisting of ethylene and α-olefins having 4 to 12 carbon atoms by a multistage polymerization method in the presence of a propylene polymerization catalyst, The process of obtaining a propylene copolymer (A).

Step (1-2): At least one olefin selected from the group consisting of ethylene and α-olefins having 4 to 12 carbon atoms by a multistage polymerization method in the presence of the propylene copolymer (A) obtained in the above step And propylene are copolymerized to obtain a heterophasic propylene polymerization material containing a propylene copolymer (A) and a propylene copolymer (B).

<Manufacturing method 2> The manufacturing method of the heterophasic propylene polymerization material including the process (2-1) and the process (2-2)

Step (2-1): copolymerization of propylene with at least one olefin selected from the group consisting of ethylene and α-olefins having 4 to 12 carbon atoms by a multistage polymerization method in the presence of a propylene polymerization catalyst, The process of obtaining a propylene copolymer (B).

Step (2-2): At least one olefin selected from the group consisting of ethylene and α-olefins having 4 to 12 carbon atoms by a multistage polymerization method in the presence of the propylene copolymer (B) obtained in the above step And propylene are copolymerized to obtain a heterophasic propylene polymerization material containing a propylene copolymer (A) and a propylene copolymer (B).

In the present invention, the multistage polymerization method is a polymerization method in which a monomer is polymerized in the presence of a polymerization catalyst in a plurality of reaction regions connected in series, and is a polymerization method including the following steps a to c.

Step a: A step for obtaining a polymer by supplying a polymerization catalyst and a monomer to the uppermost first reaction region and polymerizing the monomer.

Step b: A step of transferring the polymer obtained in the first reaction zone to a second reaction zone connected to the first reaction zone.

Step c: A step of supplying a monomer to the second reaction region and polymerizing the monomer in the presence of the polymer obtained in the first reaction region to obtain a polymer.

When the number of reaction regions connected in series is 3 or more, steps corresponding to the steps b and c are performed also in the reaction regions after the third reaction region.

In the multi-stage polymerization, a reactor having one reaction zone in one reactor is carried out in a reaction apparatus connected in series in plural, a case where it is carried out in a reactor having a plurality of reaction zones in one reactor, and one The case of carrying out in a reaction apparatus in which a reactor having one reaction zone in the reactor and a reactor having a plurality of reaction zones in one reactor is connected may be mentioned.

As a reactor having a plurality of reaction zones in one reactor, a multistage split bed type reactor may be mentioned.

The number of reaction regions in the multistage polymerization method is not particularly limited. In the step (1-1) or the step (2-2), the number of reaction regions in the multistage polymerization method is preferably 6 to 10. In the step (1-2) or the step (2-1), the number of reaction regions in the multistage polymerization method is preferably 2 to 5.

It is preferable to perform the said process (1-2) or said process (2-1) in an atmosphere in which the hydrogen concentration is higher than 0.4 mol% and 10 mol% or less. The hydrogen concentration is more preferably 0.5 to 5.0 mol%.

In one embodiment of the present invention, in the first stage of the multistage polymerization, for example, a vessel type reactor can be used. The polymerization temperature can be, for example, 0 to 120°C. The polymerization pressure can be, for example, normal pressure to 10 MPaG.

Subsequently, in the second stage of the multistage polymerization, a gas phase reactor can be used, for example. It is preferable to set it as 40-80 degreeC, and, as for the polymerization temperature, it is more preferable to set it as 40-75 degreeC, for example. The polymerization pressure is preferably, for example, from normal pressure to 10 MPaG, and more preferably from normal pressure to 2.0 MPaG.

Subsequently, in the third stage of the multistage polymerization, for example, a gas phase reactor can be used. It is preferable to set the polymerization temperature to 0-120 degreeC, for example. The polymerization pressure is preferably, for example, from normal pressure to 10 MPaG, and more preferably from normal pressure to 2.0 MPaG. It is preferable that the hydrogen concentration is, for example, 0.4 to 10 vol%.

Subsequently, in the fourth stage of the multistage polymerization, a gas phase reactor can be used, for example. It is preferable to set the polymerization temperature to 0-120 degreeC, for example. The polymerization pressure is preferably, for example, from normal pressure to 10 MPaG, and more preferably from normal pressure to 2.0 MPaG. It is preferable that the hydrogen concentration is, for example, 0.4 to 10 vol%.

In one embodiment of the present invention, as a propylene polymerization catalyst preferably used in the method for producing a heterophasic propylene polymerization material, a propylene polymerization catalyst obtained by bringing a solid catalyst component into contact with an organoaluminum compound is exemplified.

In another embodiment of the present invention, as a propylene polymerization catalyst preferably used in a method for producing a heterophasic propylene polymerization material, a propylene polymerization catalyst obtained by contacting a solid catalyst component, an organoaluminum compound, and an external electron donor Can be mentioned.

As the solid catalyst component, at least one internal electron donor selected from the group consisting of a monoester compound, an aliphatic dicarboxylic acid ester compound, a diol diester compound, a β-alkoxy ester compound and a diether compound, and a titanium atom And, a solid catalyst component containing a magnesium atom and a halogen atom and satisfying the following requirements (i) to (iv) can be preferably used.

(i) According to the standard ISO15901-1: 2005, the total pore volume measured by the mercury intrusion method is 0.95 to 1.80 mL/g, and in accordance with the standard ISO15901-1: 2005, the ratio measured by the mercury intrusion method The surface area is 60 to 170 m 2 /g.

(ii) In accordance with the standard ISO13320:2009, in the volume-based particle diameter distribution measured by laser diffraction/scattering method, the cumulative percentage of the components 10 µm or less is 6.5% or less.

(iii) In accordance with the standard ISO15472: 2001, among the peak components obtained by separating the peak attributable to the 1 s orbit of an oxygen atom obtained by X-ray photoelectron spectroscopy (XPS), the binding energy is 532 eV or more, and 534 eV. The ratio of the area (G) of the peak component having the peak top in the range of 529 eV or more and less than 532 eV with respect to the area (F) of the peak component having a peak top in the following range (G/F ) Is 0.33 or less.

(iv) The content of titanium atoms is 1.50 to 3.40% by weight.

Such a solid catalyst component is, for example, a production method having a step of contacting a titanium halide compound solution containing a titanium halide compound and a solvent and a magnesium compound to obtain a slurry containing a solid product, in the step , The ratio (A/C) of A represented by the following formula (1) to C represented by the following formula (2) can be produced by a method for producing a solid catalyst component of 3 or less.

A = a/b ···(1)

C = a/c ···(2)

a: Volume of the titanium halide compound contained in the titanium halide compound solution (mL)

b: Volume of the solvent contained in the titanium halide compound solution (mL)

c: Volume of the solvent contained in the slurry containing the solid product (mL)

As the monoester compound used as an internal electron donor, an aromatic carboxylic acid ester compound and an aliphatic carboxylic acid ester compound are preferable. Examples of the aromatic carboxylic acid ester compound include methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, pentyl benzoate, hexyl benzoate, octyl benzoate, methyl toluate, ethyl toluate, propyl toluate, butyl toluate, pentyl toluate, Hexyl toluate, octyl toluate, and the like. As an aliphatic carboxylic acid ester compound, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, hexyl acetate, octyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, pentyl propionate, hexyl propionate, octyl propionate , Methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, pentyl butyrate, hexyl butyrate, octyl butyrate, methyl valerate, ethyl valerate, propyl valerate, butyl valerate, pentyl valerate, hexyl valerate, octyl valerate, Methyl caproate, ethyl caproate, propyl caproate, butyl caproate, pentyl caproate, hexyl caproate, octyl caproate, methyl enanthate, ethyl enanthate, propyl enanthate, butyl enanthate, pentyl enanthate, enanthate Hexyl, octyl enanthate, methyl caprylate, ethyl capryate, propyl caprylate, butyl caprylate, pentyl caprylate, hexyl caprylate, octyl caprylate, methyl pelargonate, ethyl pelargonate , Propyl pelargonate, butyl pelargonate, pentyl pelargonate, hexyl pelargonate, octyl pelargonate, methyl caprate, ethyl caprate, propyl caprate, butyl caprate, pentyl caprate , Hexyl caprate, octyl caprate, methyl laurate, ethyl laurate, propyl laurate, butyl laurate, pentyl laurate, hexyl laurate, octyl laurate, methyl myristic , Ethyl myristic acid, propyl myristic acid, butyl myristic acid, pentyl myristic acid, hexyl myristic acid, octyl myristic acid, methyl palmitate, ethyl palmitate, propyl palmitate, butyl palmitate , Pentyl palmitate, hexyl palmitate, octyl palmitate, methyl margarate, ethyl margarate, propyl margarate, butyl margarate, pentyl margarate, hexyl margarate, octyl margarate , Methyl stearate, ethyl stearate, propyl stearate, butyl stearate, pentyl stearate, hexyl stearate, octyl stearate, and the like.

As an aliphatic dicarboxylic acid ester compound used as an internal electron donor, ethane 2 acid dimethyl, ethane 2 acid diethyl, ethane 2 acid dipropyl, ethane 2 acid dibutyl, ethane 2 acid dipentyl, ethane 2 acid dihexyl, ethane 2 acid di Octyl, Propane 2 Dimethyl Acid, Propane 2 Diethyl, Propane 2 Dipropyl, Propane 2 Dibutyl, Propane 2 Dipentyl, Propane 2 Dihexyl, Propane 2 Dioctyl, Butane 2 Dimethyl San, Butane 2 Diethyl Diethyl, Butane 2 Sandipropyl, Butane 2 Sandibutyl, Butane 2 Sandipentyl, Butane 2 Sandihexyl, Butane 2 Sandioctyl, Pentane 2 Dimethyl, Pentane 2 Diethyl, Pentane 2 Sandipropyl, Pentane 2 Sandibutyl, Pentane 2 Sandipentyl, Dihexyl pentane, Dioctyl pentane 2, Diethyl hexane 2, Diethyl hexane 2 Diethyl hexane, Dipropyl hexane 2 Dibutyl hexane, Dipentyl hexane 2 Dihexyl hexane 2 Dioctyl hexane 2, (E) -Buta-2-ene 2 acid dimethyl, (E)-buta-2-ene 2 acid diethyl, (E)-buta-2-ene 2 acid dipropyl, (E)-buta-2-ene 2 acid dibutyl, ( E)-buta-2-ene 2 sandipentyl, (E)-buta-2-ene 2 sandihexyl, (E)-buta-2-ene 2 sandioctyl, (Z)-buta-2-ene 2 acid Dimethyl, (Z)-buta-2-ene 2 acid diethyl, (Z)-buta-2-ene 2 acid dipropyl, (Z)-buta-2-ene 2 acid dibutyl, (Z)-buta-2-ene 2 Sandipentyl, (Z)-buta-2-ene 2 Sandihexyl, (Z)-buta-2-ene 2 Sandioctyl, cyclohexane-1,2-dicarboxylic acid dimethyl, cyclohexane-1,2 -Diethyl dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid dipropyl, cyclohexane-1,2-dicarboxylic acid dibutyl, cyclohexane-1,2-dicarboxylic acid dipentyl, cyclohexane- 1,2-dicarboxylic acid dihexyl, cyclohexane-1,2-dicarboxylic acid dioctyl, 1,2-cyclohexene-1,2-dicarboxylic acid dimethyl, 1,2-cyclohexene-1,2 -Diethyl dicarboxylic acid, 1,2-cyclohexene-1,2-dicarboxylic acid dipropyl, 1,2-cyclohexene-1,2-dibutyl dicarboxylic acid, 1,2-cyclohexene-1, 2-dicarboxylic acid dipentyl, 1,2-cyclohexene-1,2-dicarboxylic acid di Hexyl, 1,2-cyclohexene-1,2-dicarboxylic acid dioctyl, 3-methylcyclohexane-1,2-dicarboxylic acid dimethyl, 3-methylcyclohexane-1,2-dicarboxylic acid diethyl , 3-methylcyclohexane-1,2-dicarboxylic acid dipropyl, 3-methylcyclohexane-1,2-dicarboxylic acid dibutyl, 3-methylcyclohexane-1,2-dicarboxylic acid dipentyl, 3-methylcyclohexane-1,2-dicarboxylic acid dihexyl, 3-methylcyclohexane-1,2-dicarboxylic acid dioctyl, 3,6-dimethylcyclohexane-1,2-dicarboxylic acid dimethyl, 3,6-dimethylcyclohexane-1,2-dicarboxylic acid diethyl, 3,6-dimethylcyclohexane-1,2-dicarboxylic acid dipropyl, 3,6-dimethylcyclohexane-1,2-dicar Dibutyl acid, 3,6-dimethylcyclohexane-1,2-dicarboxylic acid dipentyl, 3,6-dimethylcyclohexane-1,2-dicarboxylic acid dihexyl and 3,6-dimethylcyclohexane-1 And dioctyl, 2-dicarboxylic acid.

Examples of diol diester compounds used as internal electron donors include 1,2-dibenzoatepropane, 1,2-diacetyloxypropane, 1,2-dibenzoatebutane, 1,2-diacetyloxybutane, 1 ,2-dibenzoatecyclohexane, 1,2-diacetyloxycyclohexane, 1,3-dibenzoate propane, 1,3-diacetyloxypropane, 2,4-dibenzoatepentane, 2,4- Diacetyloxypentane, 1,2-dibenzoatecyclopentane, 1,2-diacetyloxycyclopentane, 1,2-dibenzoate-4-tert-butyl-6-methylbenzene, 1,2-diacetyl Oxy-4-tert-butyl-6-methylbenzene, 1,3-dibenzoate-4-tert-butyl-6-methylbenzene and 1,3-diacetyloxy-4-tert-butyl-6-methylbenzene And the like.

Examples of the β-alkoxy ester compound used as an internal electron donor include 2-methoxymethyl-3,3-dimethylbutanoate, 2-methoxymethyl-3,3-dimethylbutanoate, and 2-methoxymethyl- 3,3-dimethylbutanoate propyl, 2-methoxymethyl-3,3-dimethylbutanoate, 2-methoxymethyl-3,3-dimethylbutanoate pentyl, 2-methoxymethyl-3,3-dimethyl Hexyl butanoate, 2-methoxymethyl-3,3-dimethyl octyl butanoate, 3-methoxy-2-phenylpropionate methyl, 3-methoxy-2-phenylpropionate ethyl, 3-methoxy-2-phenylpropionic acid Propyl, 3-methoxy-2-phenylpropionate butyl, 3-methoxy-2-phenylpropionate pentyl, 3-methoxy-2-phenylpropionate hexyl, 3-methoxy-2-phenylpropionate octyl, 2-ethoxy Methyl-3,3-dimethylbutanoate methyl, 2-ethoxymethyl-3,3-dimethylbutanoate ethyl, 2-ethoxymethyl-3,3-dimethylbutanoate propyl, 2-ethoxymethyl-3,3 -Butyl dimethylbutanoate, 2-ethoxymethyl-3,3-dimethylbutanoate pentyl, 2-ethoxymethyl-3,3-dimethylbutanoate hexyl, 2-ethoxymethyl-3,3-dimethylbutanoate octyl , 3-ethoxy-2-phenylpropionate methyl, 3-ethoxy-2-phenylpropionate ethyl, 3-ethoxy-2-phenylpropionate propyl, 3-ethoxy-2-phenylpropionate butyl, 3-ethoxy- 2-phenylpropionate pentyl, 3-ethoxy-2-phenylpropionate hexyl, 3-ethoxy-2-phenylpropionate octyl, 2-propyloxymethyl-3,3-dimethylbutanoate methyl, 2-propyloxymethyl-3 ,3-dimethylbutanoate ethyl, 2-propyloxymethyl-3,3-dimethylbutanoate propyl, 2-propyloxymethyl-3,3-dimethylbutanoate, 2-propyloxymethyl-3,3-dimethyl moiety Pentyl carbonate, 2-propyloxymethyl-3,3-dimethyl hexyl butanoate, 2-propyloxymethyl-3,3-dimethylbutanoate octyl, 3-propyloxy-2-phenylpropionate methyl, 3-propyloxy-2 -Ethyl phenylpropionate, 3-propyloxy-2-phenylpropionate propyl, 3-propyloxy-2-phenylpropionate butyl, 3-propyloxy-2-phenylpropionate pentyl, 3-propyloxy-2-phenylpropionate hexyl, 3 -Propyloxy-2-phenylpropionate octyl, 2-methoxybenzene carboxylic acid methyl, 2-methoxybenzene carboxylic acid ethyl, 2-methoxybenzene carboxylic acid propyl, 2-methoxybenzene carboxylic acid butyl, 2-methoxyben Pentyl zencarboxylic acid, hexyl 2-methoxybenzenecarboxylic acid, octyl 2-methoxybenzenecarboxylic acid, methyl 2-ethoxybenzenecarboxylic acid, ethyl 2-ethoxybenzenecarboxylic acid, 2-ethoxy Benzenecarboxylic acid propyl, 2-ethoxybenzenecarboxylic acid butyl, 2-ethoxybenzenecarboxylic acid pentyl, 2-ethoxybenzenecarboxylic acid hexyl, 2-ethoxybenzenecarboxylic acid octyl, and the like. .

As a dieter compound used as an internal electron donor, 1,2-dimethoxypropane, 1,2-diethoxypropane, 1,2-dipropyloxypropane, 1,2-dibutoxypropane, 1,2-di -tert-butoxypropane, 1,2-diphenoxypropane, 1,2-dibenzyloxypropane, 1,2-dimethoxybutane, 1,2-diethoxybutane, 1,2-dipropyloxybutane, 1,2-dibutoxybutane, 1,2-di-tert-butoxybutane, 1,2-diphenoxybutane, 1,2-dibenzyloxybutane, 1,2-dimethoxycyclohexane, 1,2 -Diethoxycyclohexane, 1,2-dipropyloxycyclohexane, 1,2-dibutoxycyclohexane, 1,2-di-tert-butoxycyclohexane, 1,2-diphenoxycyclohexane, 1, 2-dibenzyloxycyclohexane, 1,3-dimethoxypropane, 1,3-diethoxypropane, 1,3-dipropyloxypropane, 1,3-dibutoxypropane, 1,3-di-tert-part Toxoxypropane, 1,3-diphenoxypropane, 1,3-dibenzyloxypropane, 2,4-dimethoxypentane, 2,4-diethoxypentane, 2,4-dipropyloxypentane, 2,4- Dibutoxypentane, 2,4-di-tert-butoxypentane, 2,4-diphenoxypentane, 2,4-dibenzyloxypentane, 1,2-dimethoxycyclopentane, 1,2-diethoxycyclo Pentane, 1,2-dipropyloxycyclopentane, 1,2-dibutoxycyclopentane, 1,2-di-tert-butoxycyclopentane, 1,2-diphenoxycyclopentane, 1,2-dibenzyl Oxycyclopentane, 9,9-bis(methoxymethyl)fluorene, 9,9-bis(ethoxymethyl)fluorene, 9,9-bis(propyloxymethyl)fluorene, 9,9-bis(part Oxymethyl)fluorene, 9,9-bis-tert-butoxymethylfluorene, 9,9-bis(phenoxymethyl)fluorene, 9,9-bis(benzyloxymethyl)fluorene, 1,2- Dimethoxybenzene, 1,2-diethoxybenzene, 1,2-dipropyloxybenzene, 1,2-dibutoxybenzene, 1,2-di-tert-butoxybenzene, 1,2-diphenoxybenzene and 1,2-dibenzyloxybenzene, etc. are mentioned.

Moreover, the internal electron donor described in Japanese Unexamined Patent Application Publication No. 2011-246699 can also be applied.

As internal electron donors, preferably, they are a dicarboxylic acid ester compound, a diol diester compound, and a β-alkoxy ester compound. Each of the internal electron donors may be used alone, or two or more types may be used in combination.

As an organoaluminum compound, the compound described in Unexamined-Japanese-Patent No. 10-212319 can be illustrated, for example. Among them, preferably, trialkyl aluminum, a mixture of trialkyl aluminum and dialkyl aluminum halide, or alkyl alumoxane, more preferably triethyl aluminum, tri iso-butyl aluminum, triethyl aluminum and diethyl aluminum A mixture of chlorides or tetraethyldialumoxane.

As the external electron donor, the compounds described in Japanese Patent Application Publication No. 2950168, Japanese Patent Application Publication No. 2006-96936, Japanese Patent Application Publication No. 2009-173870, and Japanese Patent Application Publication No. 2010-168545 can be exemplified. Among them, an oxygen-containing compound or a nitrogen-containing compound is preferred. As the oxygen-containing compound, alkoxy silicon, ether, ester, and ketone can be illustrated. Among them, preferably alkoxy silicon or ether, and cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, di iso-propyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butyl-n-propyldime Toxoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, dicyclobutyldimethoxysilane, dicyclopentyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, iso-butyltri Ethoxysilane, vinyl triethoxysilane, sec-butyl triethoxysilane, cyclohexyl triethoxysilane, and cyclopentyl triethoxysilane are mentioned.

The solvent used in the method for producing the solid catalyst component is preferably an inert hydrocarbon such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, and toluene.

The method for producing a heterophasic propylene polymerization material of the present invention further comprises a step of polymerizing a small amount of olefin in the presence of a solid catalyst component and an organoaluminum compound to produce a catalyst component covered with a polymer of the olefin (the The polymerization is usually referred to as prepolymerization, and therefore, the catalyst component may also include (usually referred to as a prepolymerization catalyst component). The olefin used in the prepolymerization is at least one of the olefins used as a raw material for the heterophasic propylene polymerization material in the polymerization. In the prepolymerization step, a chain transfer agent such as hydrogen may be used or an external electron donor may be used in order to control the molecular weight of the resulting olefin polymer.

In one aspect, in the prepolymerization, the organoaluminum compound is preferably 0.1 to 700 mol, and preferably 0.2 to 200 mol per 1 mol of transition metal atoms contained in the solid catalyst component. Further, the external electron donor is preferably 0.01 to 400 moles per mole of the transition metal atom contained in the solid catalyst component. It is preferable that the solid catalyst component contained per 1 L of the solvent is 1 to 500 g. The amount of olefin to be prepolymerized is usually 0.1 to 200 g per 1 g of the solid catalyst component.

[Melt and kneading process]

The thermoplastic elastomer composition according to an embodiment of the present invention can be produced by a production method including a melt-kneading step of melt-kneading the above-described heterophasic propylene polymerization material in the presence of a crosslinking agent and a crosslinking aid.

A monomer derived from at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 12 carbon atoms in a propylene copolymer by melt-kneading a heterophasic propylene polymer material in the presence of a crosslinking agent and a crosslinking aid The unit acts as a crosslinkable monomer unit and forms a crosslinked structure. Therefore, the thermoplastic elastomer composition contains at least a non-crosslinked product of the propylene copolymer (A) having a chain structure and a crosslinked product of the propylene copolymer (B) containing a large number of crosslinkable monomer units. The thermoplastic elastomer composition may further contain a crosslinked product of the propylene copolymer (A) and a non-crosslinked product of the propylene copolymer (B). It is preferable that the thermoplastic elastomer composition contains a non-crosslinked product of the propylene copolymer (A), a crosslinked product of the propylene copolymer (B), and a non-crosslinked product of the propylene copolymer (B).

The timing of adding the crosslinking agent and the crosslinking aid to the heterophasic propylene polymerization material may be simultaneously or separately, or may be added first. For example, a heterophasic propylene polymerization material may be supplied from the upstream side of an extruder, and a crosslinking agent and/or a crosslinking aid may be supplied at the same position as the supply position or at a downstream side thereof.

The temperature at which the melt-kneading is performed varies depending on the type of the crosslinking agent and the crosslinking aid to be added, but it is preferably a temperature such that each component after melt-kneading is sufficiently crosslinked, for example, 170°C to 270°C, and more Preferably it is 180-250 degreeC.

The time to perform melt-kneading varies depending on the type of crosslinking agent and crosslinking aid to be added, but it is preferably a time such that each component is sufficiently crosslinked after melt-kneading, and is, for example, 0.1 to 5.0 minutes, more preferably. It is 0.3 to 2.0 minutes.

[Injection molding process]

The molding temperature at the time of injection molding is generally 150°C to 300°C, preferably 180°C to 280°C, and more preferably 200°C to 250°C. The temperature of the mold is usually 0°C to 100°C, preferably 20°C to 90°C, more preferably 40°C to 80°C, and still more preferably 50°C to 75°C.

Example

[Reference Example 1] Preparation of solid catalyst component

Step (1-1): A 100 mL flask equipped with a stirrer, dropping funnel, and thermometer was replaced with nitrogen, and then 36.0 mL of toluene and 22.5 mL of titanium tetrachloride were added to the flask, followed by stirring. 4 A titanium chloride solution was obtained. After the temperature in the flask was set to 0°C, 1.88 g of magnesium diethoxide was divided into 4 times at 30 minute intervals at the same temperature, and stirred at 0°C for 1.5 hours. Subsequently, 0.60 mL of 2-ethoxymethyl-3,3-dimethylbutanoate ethyl was put into the flask, and the temperature in the flask was raised to 10°C. Then, it stirred at the same temperature for 2 hours, and 9.8 mL of toluene was added. Subsequently, the temperature in the flask was raised, and 3.15 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate was added into the flask at the time point at 60°C, and the temperature was raised to 110°C. The mixture in the flask was stirred for 3 hours at the same temperature.

The obtained mixture was solid-liquid separated to obtain a solid. The obtained solid was washed 3 times with 56.3 mL of toluene at 100°C.

Step (1-2): To the washed solid obtained in the step (1-1), 38.3 mL of toluene was added to prepare a slurry. 15.0 mL of titanium tetrachloride and 0.75 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate were added to the slurry to prepare a mixture, and the mixture was stirred at 110°C for 1 hour. Then, the stirred mixture was solid-liquid separation, and the obtained solid was washed three times with 56.3 mL of toluene at 60°C, and further washed three times with 56.3 mL of hexane at room temperature, and the washed solid was dried under reduced pressure to obtain a solid catalyst component. Got it.

With respect to this solid catalyst component, the titanium atom content was 2.53 weight%, the ethoxy group content was 0.44 weight%, and the internal electron donor content was 13.7 weight%.

Moreover, the central particle diameter measured by the laser diffraction/scattering method was 59.5 µm, and the cumulative percentage of the components 10 µm or less in the particle size distribution on a volume basis was 5.3%.

The amount of the peak component originating from the 1s orbital of the oxygen atom obtained by XPS and having a peak top in the range of 532 to 534 eV of binding energy is 85.0%, and the amount of peak components in the range of 529 eV or more and less than 532 eV of the binding energy The amount of the peak component having was 15.0%.

The total pore volume measured by the mercury intrusion method is 1.43 mL/g, the total volume of pores in the range of 5 to 30 nm is 0.160 mL/g, and the total volume of pores in the range of 30 to 700 nm Was 0.317 mL/g, and the specific surface area was 107.44 m2/g.

[Reference Example 2] Preparation of heterophasic propylene polymerization material-1

(2-1) prepolymerization

In an SUS autoclave with an inner volume of 3 L equipped with a stirrer, sufficiently dehydrated and degassed n-hexane 1.0 L, triethylaluminum (hereinafter sometimes referred to as "TEA") 20 mmol (mmol), 2.0 mmol of t-butyl-n-propyldimethoxysilane (electron donor component) was received. Among them, 6 g of the solid catalyst component prepared in Reference Example 1 was added, and 6 g of propylene was continuously supplied over about 30 minutes while maintaining the temperature in the autoclave at about 10°C to perform prepolymerization. Subsequently, the prepolymerization slurry was transferred to an SUS316L autoclave equipped with a stirrer having an inner volume of 150 L, and 100 L of liquid butane was added to obtain a slurry of the prepolymerization catalyst component.

(2-2) Main polymerization

In a reaction apparatus in which a slurry polymerization reactor and three gas phase reactors are arranged in series, in the following polymerization step (2-2-1) and the following polymerization step (2-2-2), a propylene copolymer (A-1) Produced and transferred to the rear stage without deactivating the produced propylene copolymer (A-1), and in the following polymerization step (2-2-3) and the following polymerization step (2-2-4), a propylene copolymer ( B-1) was prepared.

Polymerization process (2-2-1)

A vessel type reactor made of SUS304 equipped with a stirrer was used to perform copolymerization of propylene and ethylene. That is, propylene, ethylene, hydrogen, triethylaluminum, t-butyl-n-propyldimethoxysilane, and a slurry of the prepolymerization catalyst component prepared in (2-1) were continuously supplied to the reactor, and a polymerization reaction was carried out. . The reaction conditions were as follows.

Polymerization temperature: 50 ℃

Stirring speed: 150 rpm

Liquid level in reactor: 18 L

Propylene supply: 20.0 kg/hour

Ethylene supply: 0.03 kg/hour

Hydrogen supply: 24.0 NL/hour

Triethylaluminum supply amount: 37.2 mmol/hour

Supply amount of t-butyl-n-propyldimethoxysilane: 7.90 mmol/hour

Supply amount of slurry of prepolymerization catalyst component (in terms of polymerization catalyst component): 0.42 g/hour

Polymerization pressure: 3.50 MPa (gauge pressure).

Polymerization process (2-2-2)

A multistage gas phase polymerization reactor having 6 stages of reaction zones in the vertical direction, of which the uppermost stage is a fluidized bed, and the remaining 5 stages, is a fractional layer, was prepared.

From the vessel type reactor of the polymerization step (2-2-1), the slurry containing the polypropylene copolymer particles and the liquid propylene copolymer was continuously supplied to the fluidized bed, which is the uppermost stage of the multistage gas phase polymerization reactor, without deactivating.

The interstage transfer of the polypropylene particles in the multistage gas phase polymerization reactor was performed by a double valve system. This transfer means connects the upper reaction region and the lower reaction region with a 1-inch-sized pipe, installs two on-off valves in the pipe, and opens the upper valve with the lower valve closed. The powder is collected between the valves from the reaction zone of, and then the upper valve is closed and the lower valve is opened to transfer the polypropylene particles to the lower reaction zone.

From the bottom of the multistage gas phase polymerization reactor of the above configuration, propylene, ethylene and hydrogen were continuously supplied. Thereby, a fluidized bed or a fractionation bed is formed in each reaction zone, and the amounts of propylene, ethylene and hydrogen are controlled to keep the gas composition and pressure constant, and the propylene and ethylene are further copolymerized while purging the excess gas , To prepare a propylene copolymer (A-1). The reaction conditions were as follows.

Polymerization temperature: 65 ℃

Polymerization pressure: 1.70 MPa (gauge pressure).

In the multistage gas phase polymerization reactor, the concentration ratio of gas in the reactor was 1.40 mol% in ethylene/(propylene+ethylene) and 5.60 mol% in hydrogen/(hydrogen+propylene+ethylene).

Polymerization process (2-2-3)

The particles of the propylene copolymer (A-1) discharged from the multistage gas phase polymerization reactor of the polymerization step (2-2-2) were continuously supplied to the fluidized bed reactor. The fluidized bed reactor was equipped with a gas dispersion plate, and means for transferring the particles of the propylene copolymer (A-1) from the multistage gas phase polymerization reactor in the front end to the fluidized bed reactor was carried out by the double valve method. .

Propylene, ethylene and hydrogen are continuously supplied to the fluidized bed reactor of the above configuration, and the gas supply amount is adjusted and the excess gas is purged so that the gas composition and pressure are kept constant, while the propylene copolymer (A-1) In the presence of particles of, propylene and ethylene were copolymerized. The reaction conditions were as follows.

Polymerization temperature: 70 ℃

Polymerization pressure: 1.60 MPa (gauge pressure).

In the fluidized bed reactor, the concentration ratio of gas in the reactor was 45.9 mol% in ethylene/(propylene+ethylene) and 3.10 mol% in hydrogen/(hydrogen+propylene+ethylene).

Polymerization process (2-2-4)

Particles of the polypropylene copolymer discharged from the fluidized bed reactor of the polymerization step (2-2-3) were further continuously supplied to the fluidized bed reactor at the rear stage. The fluidized-bed reactor of the polymerization step (2-2-4) is provided with a gas distribution plate similarly to the fluidized-bed reactor of the polymerization step (2-2-3), and the polymerization step (2-2-3) The means for transferring the particles of the polypropylene copolymer from the fluidized-bed reactor to the fluidized-bed reactor of the polymerization step (2-2-4) was performed by a double valve system.

Except for the following conditions, propylene and ethylene are copolymerized in the same manner as in the polymerization step (2-2-3), and a heterogeneous propylene copolymer (A-1) and a propylene copolymer (B-1) are contained. Fragile propylene polymerization material-1 was obtained.

Polymerization temperature: 70 ℃

Polymerization pressure: 1.40 MPa (gauge pressure).

In the fluidized bed reactor, the concentration ratio of the gas in the reactor was 46.0 mol% in ethylene/(propylene+ethylene) and 3.20 mol% in hydrogen/(hydrogen+propylene+ethylene).

(2-3) Content of propylene copolymer (A-1) and propylene copolymer (B-1)

The content rate (X _A-1 ) of the propylene copolymer ( _A-1 ) and the content rate (X _B-1 ) of the propylene copolymer (B-1) in the obtained heterophasic propylene polymerization material _-1 are the propylene copolymer (A- 1) and the amount of heat of fusion of crystals of the entire heterophasic propylene polymerization material-1 were measured, respectively, and calculated using the following equation. The amount of crystal fusion was measured by differential scanning thermal analysis (DSC).

The conditions of differential scanning thermal analysis (DSC) were, first, as a 1st run (first scan), the temperature was raised from 50°C to 220°C at 200°C/min, and maintained at 220°C for 5 minutes. Then, the temperature was lowered from 220°C to 180°C at 70°C/min, and maintained at 180°C for 1 minute. Then, the temperature was lowered from 180°C to 50°C at 150°C/min, and maintained at 50°C for 2 minutes (temperature lowering process). Next, in the 2nd run (second scan), the temperature was raised from 50°C to 185°C at 16°C/min. The endothermic peak of the heterophasic propylene polymerization material-1 or the propylene copolymer (A-1) at the time of the 2nd run was measured, and from the obtained peak area, (ΔHf) _T and (ΔHf) _A-1 shown below Obtained. In addition, the amount of the sample per one used for differential scanning thermal analysis (DSC) is about 5 mg.

X _A-1 = (ΔHf) _T /(ΔHf) _A-1

X _B-1 = 1-(ΔHf) _T /(ΔHf) _A-1

(ΔHf) _T : Heat of fusion (J/g) of the propylene copolymer (A-1) contained in the entire heterophasic propylene polymerization material-1

(ΔHf) _A-1 : Heat of fusion of the propylene copolymer (A-1) (J/g)

In differential scanning thermal analysis (DSC) under the above conditions, the propylene copolymer (B-1) does not substantially exhibit an endothermic peak. For this reason, the peak area for calculating (ΔHf) _T corresponds to the peak area derived from the propylene copolymer (A-1) contained in the whole heterophasic propylene polymerization material-1. Therefore, (ΔHf) _T corresponds to the heat of fusion of the propylene copolymer (A-1) contained in the whole heterophasic propylene polymerized material-1, which is obtained by measuring the heat of fusion of the entire heterofarsic propylene polymerized material-1 .

Propylene copolymer (A-1) and propylene copolymer, determined based on the content rate (X _A-1 ) of the propylene copolymer ( _A-1 ) and the content rate (X _B-1 ) of the propylene copolymer (B-1) The content of the propylene copolymer (A-1) with respect to 100% by weight of the total amount of the polymer (B-1) was 50.4% by weight, and the content of the propylene copolymer (B-1) was 49.6% by weight.

(2-4) Content of the monomer unit derived from ethylene in the propylene copolymer (A-1) (Y _A-1 )

From the infrared absorption spectrum of the propylene copolymer (A-1) obtained in the polymerization step (2-2-1) and the polymerization step (2-2-2) by FT-IR5200 type (manufactured by Nippon Spectroscopy), the propylene copolymer ( Content (Y _A-1 ) of the monomer unit derived from ethylene in A-1) was calculated|required using the following formula.

Y _A-1 was quantified according to the method described in the Polymer Analysis Handbook (Author: Japan Analytical Chemical Society Polymer Analysis Research Conference Publication: Kinokuniya Bookstore).

1) Infrared absorption spectrum measurement data density: ρ (g/cm3) and thickness: t (cm), absorbance A'at wave number 732 cm ^-1 and absorbance _A'at wave number 718 cm ^-1 by the following formula from _718, yielding a surface of the absorption coefficient (K _{'732) a} frequency and appearance of the absorption coefficient at a _{^{718 cm -1 (K' 718)}} a of the wave number 732 cm ^-1. In addition, the density of the measurement sample of the infrared absorption spectrum was 0.9 g/cm 3. In addition, the thickness of the measurement sample of the infrared absorption spectrum was measured with a commercially available digital thickness meter (contact type thickness meter, brand name: ultra-high precision Digital Micro Head MH-15M, manufactured by Nippon Optical Co., Ltd.), and was 0.02 cm.

(K' ₇₃₂ ) _a = _A'732 /(ρt)

(K' ₇₁₈ ) _a = _A'718 /(ρt)

2) The extinction coefficient (K' ₇₃₂ ) _c after correction at wave number 732 cm ^-1 and the absorption coefficient (K′ ₇₁₈ ) _c after correction at wave number 718 cm ^-1 were calculated by the following equation.

(K' ₇₃₂ ) _c = 1/0.96((K' ₇₃₂ ) _a -0.268(K' ₇₁₈ ) _a ｝

(K' ₇₁₈ ) _c = 1/0.96((K' ₇₁₈ ) _a -0.150(K' ₇₁₈ ) _a ｝

3) Y _A-1 (weight%) was calculated by the following formula.

Y _A-1 = 0.575{(K' ₇₂₂ ) _c + (K' ₇₃₆ ) _c ｝

The content (Y _A-1 ) of the monomer unit derived from ethylene was 1.8% by weight with respect to 100% by weight of the total amount of the monomer unit derived from propylene and the monomer unit derived from ethylene.

(2-5) Content of the monomer unit derived from ethylene in the propylene copolymer (B-1) (Y _B-1 )

The content (Y _B-1 ) of the monomer unit derived from ethylene in the propylene copolymer (B-1) is determined by the infrared absorption spectrum (FT-IR5200 manufactured by Nippon Spectroscopy) of the obtained heterophasic propylene polymerization material. The content of the monomer unit derived from ethylene in Material-1 (T-C2') was measured and calculated using the following equation.

Y _B-1 = (T-C2'-(Y _A-1 × X _A-1 ))/X _B-1 (wt%)

T-C2' was quantified according to the method described in the Polymer Analysis Handbook (Author: Japan Analytical Chemistry Society Polymer Analysis Research Conference Publication: Kinokuniya Bookstore).

The density of measurement data of the infrared absorption spectrum: from t (cm) and the wave number 736 cm ^-1 'absorbance A of the wave number ₇₃₆ and 722 cm ^-1' absorbance A at the _722: ρ (g / ㎤) and thickness It was calculated to the apparent extinction coefficient of the expression by the wave number _{^{736 cm -1 (K '736)}} a frequency and appearance of the absorption coefficient at a _{^{722 cm -1 (K' 722)}} a. In addition, the density of the measurement sample of the infrared absorption spectrum was 0.9 g/cm 3. In addition, the thickness of the measurement sample of the infrared absorption spectrum was measured with a commercially available digital thickness meter (contact type thickness meter, brand name: ultra-high precision Digital Micro Head MH-15M, manufactured by Nippon Optical Co., Ltd.), and was 0.02 cm.

(K' ₇₃₆ ) _a = _A'736 /(ρt)

(K' ₇₂₂ ) _a = _A'722 /(ρt)

2) The extinction coefficient (K' ₇₃₆ ) _c after correction at wave number 736 cm ^-1 and the absorption coefficient (K′ ₇₂₂ ) _c after correction at wave number 722 cm ^-1 were calculated by the following equation.

(K' ₇₃₆ ) _c = 1/0.96((K' ₇₃₆ ) _a -0.268(K' ₇₂₂ ) _a ｝

(K' ₇₂₂ ) _c = 1/0.96((K' ₇₂₂ ) _a -0.150(K' ₇₃₆ ) _a ｝

3) T-C2' (mass%) was computed by the following formula.

T-C2' = 0.575{(K' ₇₂₂ ) _c + (K' ₇₃₆ ) _c ｝

The content (Y _B-1 ) of the monomer unit derived from ethylene was 42.1% by weight with respect to 100% by weight of the total amount of the monomer unit derived from propylene and the monomer unit derived from ethylene.

(2-6) Weight average molecular weight of propylene copolymer (A-1) and propylene copolymer (B-1)

The weight average molecular weight of the propylene copolymer (A-1) and the propylene copolymer (B-1) was calculated|required according to the conditions of the measurement using CFC mentioned later and the measurement procedure.

The weight average molecular weight of the propylene copolymer (A-1) was 5.1×10 ^5, and the weight average molecular weight of the propylene copolymer (B-1) was 8.7×10 ⁵ .

[Reference Example 3] Preparation of heterophasic propylene polymerization material-2

Except for the values shown in Table 1, in the same manner as in the heterocyclic propylene polymerization material-1, a propylene polymer (A-2) and a propylene copolymer (B-2) containing a heterocyclic propylene polymerization material-2 were prepared.

In the heterophasic propylene polymerization material-2, the content (X _A-2 ) of the propylene polymer (A-2) with respect to 100% by weight of the total amount of the propylene polymer (A-2) and the propylene copolymer (B _-2 ) is , and 47.1% by weight, the content (X _B-2) of propylene copolymer (B-2), was 52.9% by weight.

In addition, in the propylene polymer (A-2), the content (Y _A-2 ) of the monomer unit derived from ethylene with respect to 100% by weight of the total amount of the monomer unit derived from propylene and the monomer unit derived from ethylene is 0.0 It was weight%.

In addition, in the propylene copolymer (B-2), the content (Y _B-2 ) of the monomer unit derived from ethylene with respect to 100% by weight of the total amount of the monomer unit derived from propylene and the monomer unit derived from ethylene is, It was 47.0% by weight.

Moreover, the weight average molecular weight of the propylene polymer (A-2) was 4.6 X 10 ^5, and the weight average molecular weight of the propylene copolymer (B-2) was 9.2 X 10 ⁵ .

〔Material used〕

In Examples and Comparative Examples, the following materials were used.

(1) Heterophasic propylene polymerization material-1

Content of propylene copolymer (A-1): 50.4% by weight

Content of propylene copolymer (B-1): 49.6% by weight

Content of monomer unit derived from ethylene in propylene copolymer (A-1): 1.8% by weight

Content of monomer units derived from ethylene in propylene copolymer (B-1): 42.1% by weight

(2) Heterophasic propylene polymerization material-2

Content of propylene polymer (A-2): 47.1% by weight

Content of propylene copolymer (B-2): 52.9% by weight

Content of monomer unit derived from ethylene in propylene polymer (A-2): 0.0% by weight

Content of monomer unit derived from ethylene in propylene copolymer (B-2): 47.0% by weight

(3) Heterophasic propylene polymerization material-3 (Noble AZ564 manufactured by Sumitomo Chemical Co., Ltd.)

Content of propylene copolymer (A-3): 87% by weight

Content of propylene copolymer (B-3): 13% by weight

Content of monomer units derived from ethylene in propylene copolymer (A-3): 0% by weight

Content of monomer units derived from ethylene in propylene copolymer (B-3): 46% by weight

(4) Propylene-ethylene copolymer-1 (Noblen Z144CE4 manufactured by Sumitomo Chemical Co., Ltd.)

MFR = 27 g/10 min; Melting temperature = 141°C; Content of monomer derived from propylene = 96% by weight; Content of ethylene-derived monomer = 4% by weight)

(5) Ethylene-1-octene copolymer-1

Manufactured by Dow Chemical, Engage 8842

(Density = 0.857 g/cm 3)

(6) Ethylene-1-butene copolymer-1

Manufactured by Dow Chemical, Engage 7487

(Density = 0.860 g/cm 3)

(7) crosslinking agent-1

As a crosslinking agent-1, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (Kayahexa Ad-40C manufactured by Explosives Akuzo Co., Ltd., calcium carbonate and hydrated amorphous silicon dioxide) at a concentration of 40% by weight Diluted) was used.

(8) crosslinking agent-2

As the crosslinking agent-2, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (Kayahexa APO-10DL manufactured by Explosives Akuzo Co., Ltd., diluted to 10% concentration with paraffinic oil) was used. I did.

(9) crosslinking aid

As a crosslinking aid, trimethylolpropane trimethacrylate (Hycross MS-50 manufactured by Seiko Chemical Co., Ltd., diluted with an inorganic filler (amorphous silica) to a concentration of 50% by weight) was used.

(10) Other materials

Mold release agent: Erucsanamide (Nutron S manufactured by Nippon Purification)

Antioxidant 1: Irganox 1010 manufactured by BASF Japan Co., Ltd.

Antioxidant 2: Irgafoss 168 manufactured by BASF Japan Co., Ltd.

Antioxidant 3: Sumitomo Chemical Co., Ltd. Milker GA80

Light stabilizer 1: Sumitomo Chemical Co., Ltd. Sumisorb 300

Light stabilizer 2: Tinuvin 622SF manufactured by BASF Japan Co., Ltd.

Light stabilizer 3: Tinuvin XT850FF manufactured by BASF Japan Co., Ltd.

Light stabilizer 4: Tinuvin 123 manufactured by BASF Japan Co., Ltd.

Preservative (inorganic filler): Hydrotalcite (Kyowa Chemical Industries, Ltd., DHT-4A)

Inorganic filler: Calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., Vigot10)

[Example 1]

Crosslinking agent-1 is 0.7 parts by weight (0.28 parts by weight as added amount of 2,5-dimethyl-2,5-di(t-butylperoxy)hexane), crosslinking 0.8 parts by weight of an auxiliary agent (0.4 parts by weight as an added amount of trimethylolpropane trimethacrylate), 0.15 parts by weight of a release agent, 0.2 parts by weight of an antioxidant 1, 0.1 parts by weight of an antioxidant 2, 0.2 parts by weight of a light stabilizer 1 , 0.1 parts by weight of light stabilizer 2, 0.1 parts by weight of light stabilizer 3, and 0.2 parts by weight of preservative were added, and melt-kneaded by a twin-screw extruder at a cylinder temperature of 200°C for about 1 minute to obtain a thermoplastic elastomer composition. Got it.

[Examples 2 to 3]

Except having used the material shown in Table 2, it carried out similarly to Example 1, and produced the thermoplastic elastomer composition of Examples 2-3.

[Example 4]

A thermoplastic elastomer composition of Example 4 was prepared in the same manner as in Example 1, except that no preservative was added.

[Example 5]

75 parts by weight of heterophasic propylene polymerization material-1, 25 parts by weight of heterophasic propylene polymerization material-2 (100 parts by weight of the total amount of heterophasic propylene polymerization material-1 and heterophasic propylene polymerization material-2), crosslinking agent -1 0.5 parts by weight (0.20 parts by weight as the addition amount of 2,5-dimethyl-2,5-di(t-butylperoxy) hexane), 0.8 parts by weight of the crosslinking aid (addition of trimethylolpropane trimethacrylate) As 0.4 parts by weight), release agent 0.15 parts by weight, antioxidant 1 0.2 parts by weight, antioxidant 2 0.1 parts by weight, light stabilizer 1 0.2 parts by weight, light stabilizer 2 0.1 parts by weight, light stabilizer 3 0.1 parts by weight Part and 0.2 parts by weight of a preservative were added, and melt-kneading was performed for about 1 minute at a cylinder temperature of 200°C by a twin screw extruder to obtain a thermoplastic elastomer composition.

[Comparative Examples 1 to 5 and 8]

Except having used the material shown in Table 3, it carried out similarly to Example 1, and produced the thermoplastic elastomer compositions of Comparative Examples 1-5 and 8.

[Comparative Example 6]

35 parts by weight of heterophasic propylene polymerization material-3, 20 parts by weight of propylene-ethylene copolymer-1, 20 parts by weight of ethylene-1-octene copolymer-1, 25 parts by weight of ethylene-1-butene copolymer-1 Based on parts (100 parts by weight of the total amount of heterophasic propylene polymerization material-3, propylene-ethylene copolymer-1, ethylene-1-octene copolymer-1, and ethylene-1-butene copolymer-1), crosslinking agent-2 2.0 parts by weight (0.2 parts by weight as an added amount of 2,5-dimethyl-2,5-di(t-butylperoxy)hexane), 0.5 parts by weight as a crosslinking aid (0.25 parts by weight as an added amount of trimethylolpropane trimethacrylate) Parts), release agent 0.05 parts by weight, antioxidant 2 0.1 parts by weight, antioxidant 3 0.2 parts by weight, light stabilizer 1 0.2 parts by weight, light stabilizer 2 0.1 parts by weight, light stabilizer 4 0.1 parts by weight, preservative 0.2 parts by weight and 0.6 parts by weight of an inorganic filler were added, and melt-kneading was performed by a twin screw extruder at a cylinder temperature of 200°C for about 1 minute to obtain a thermoplastic elastomer composition.

[Comparative Example 7]

Except having used the material shown in Table 3, it carried out similarly to Example 5, and produced the thermoplastic elastomer composition of Comparative Example 7.

[Production of injection molded article]

To 100 parts by weight of the thermoplastic elastomer compositions of Examples 1 to 5 and Comparative Examples 1 to 8, 1 part by weight of a black pigment master batch (trade name SPEC824 manufactured by Sumika Color Co., Ltd.) was added, and an injection molding machine (trade name SE180D manufactured by Sumitomo Heavy Machinery Industries, Ltd.) was added. Using, injection molding was performed under conditions of a cylinder temperature of 220°C and a mold temperature of 25°C.

As the mold, a 400 × 100 × 3 mm flat plate mold was used, a 64 × 12.7 × 2 mm resin flat plate was installed on the core side (moving side) of the flat plate mold, and embossed on the cavity side of the plate mold. The processed insert was installed. Further, a thin portion (tear line portion) having a thickness of 1.0 mm was formed at the position where the resin flat plate was installed.

[Evaluation of physical properties]

About the thermoplastic elastomer compositions and injection molded articles of Examples 1-5 and Comparative Examples 1-8, various physical properties were evaluated by the following method.

(1) Melt flow rate (MFR)

According to JIS K7210:1999, it measured at 230 degreeC and load 21.18N.

(2) melting temperature

Using a heat flux type differential scanning calorimeter (DS CQ100 manufactured by TA Instruments), the differential scanning calorific value curve was measured under the following measurement conditions, and the melting temperature (°C) was determined from the differential scanning calorific value curve in the temperature raising operation.

<Measurement conditions>

Temperature-falling operation: It melt|dissolved at 220 degreeC, and then, the temperature was lowered from 220 degreeC to -90 degreeC at a temperature lowering rate of 5 degreeC/min.

Temperature raising operation: After the operation of lowering the temperature, the temperature was immediately raised from -90°C to 200°C at 5°C/min.

(3) Isothermal crystallization time

Using a heat flux type differential scanning calorimeter (DSC8500 manufactured by PerkinElmer), the sample was held at 200°C for 5 minutes in a nitrogen atmosphere, and then cooled to 130°C at about 320°C to 340°C/min and maintained. The relationship between the calorific value and time due to crystallization of the sample at this time was measured, and the time required to reach the calorific value of 1/2 of the total calorific value was taken as the isothermal crystallization time (second).

In addition, as a measurement sample, a press sheet (thickness 0.2 mm) obtained by sandwiching the thermoplastic elastomer compositions of Examples and Comparative Examples between smooth plates, pressing at 230° C. and 1 MPa for 5 minutes, and cooling, is used.

(4) Content of insoluble components in orthodichlorobenzene at 140°C

The content of the insoluble component to orthodichlorobenzene at 140°C was determined according to the conditions of measurement using the following GPC and the method of calculating the content of the insoluble component to orthodichlorobenzene at 140°C.

(Measurement conditions using GPC)

GPC device: HLC-8121GPC/HT (manufactured by Tosoh Corporation)

GPC column: TSKgel GMH6-HT 7.8 mm I.D. × 300 mm (manufactured by Tosoh Corporation) 3 pieces

Mobile phase: 2,6-di-t-butyl-4-methylphenol (BHT) as an antioxidant that inhibits polymer decomposition in orthodichlorobenzene (manufactured by Fujifilm Wako Junyaku Co., Ltd., Limited) (Fujifilm Wako Junyaku Corporation) Co., Ltd. make, limited express, purity 98%) was added and used at 0.1 w/V%.

Flow rate: 1 ml/min

Column oven temperature: 140 ℃ ㅇ

Auto sampler temperature: 140 ℃

System oven temperature: 40 ℃

Detection: differential refractive index detector (RID)

RID cell temperature: 140 ℃

Sample solution injection volume: 300 μl

Dissolving solvent: same as mobile phase

Automatic shaker for melting: DF-8020 (manufactured by Tosoh Corporation)

Procedure for preparing the sample solution: 20.0 mg of the thermoplastic elastomer composition and 20.0 ml of the dissolving solvent were put in a 30 ml screw vial, and then tightly sealed, and this was set in an automatic shaker for dissolution, followed by stirring at 140°C for 120 minutes. Subsequently, the obtained solution was filtered through a filter having a pore diameter of 0.8 µm or more. Here, filtration was performed at 140°C or higher, and within 20 minutes in order to avoid a change in concentration due to evaporation of the solvent. By these operations, a sample solution for GPC measurement was prepared.

(Calculation method of content of insoluble component to orthodichlorobenzene at 140°C)

Content of an insoluble component in 140 degreeC orthodichlorobenzene was computed by the following formula (3).

Content of insoluble components in orthodichlorobenzene at 140°C (% by weight) = (1-B/A) × 100 ... (3)

In Formula (3), A is a peak area obtained by passing a polyethylene standard substance NIST1475a to the measurement using the GPC, and drawing a base line to the peak for the obtained chromatogram. In addition, B is a peak area obtained by passing a sample solution to the measurement using the GPC and drawing a baseline on the peak for the obtained chromatogram. The baseline regulation was implemented based on the description of ISO16014-1.

(5) Content of Soluble Components and Insoluble Components in Orthodichlorobenzene at 50°C

According to the calculation method based on the conditions of measurement using the following CFC, the content of a soluble component and an insoluble component to orthodichlorobenzene at 50 degreeC was calculated|required.

(Measurement conditions using CFC)

CFC device: Automated 3D analyzer CFC-2 manufactured by Polymer ChAR

TREF column: Stainless steel microball packed column manufactured by Polymer ChAR

(3/8"o.d x 150mm)

Solvent and GPC mobile phase: 2,6-di-t-butyl-4-methylphenol (BHT) as an antioxidant that inhibits polymer decomposition in orthodichlorobenzene (manufactured by Fujifilm Wako Junyaku Co., Ltd., Limited) (Fujifilm Wako Junyaku Co., Ltd. product, limited express, purity 98%) added 0.05 w/V% and used

Sample solution concentration: 20 ml of solvent is added to 20 mg of sample

Dissolution of sample: heating and stirring at 145°C for 60 minutes

Injection volume into TREF column: 0.5 ml

GPC column: TSKgel GMHHR-H(S)HT2 7.8 mm I.D. × 300 mm (Tosoh) 3 pieces

Flow rate of GPC mobile phase: 1.0 ml/min

Detector: Infrared spectrophotometer IR5 manufactured by Polymer ChAR (built into CFC device)

Calibration of GPC column: Tosoh Corporation standard polystyrene (F-1, F-2, F-4, F-10, F-40, F-80, F-288, F-850, A-500, A-1000) , A-2500) Each 5 mg, each weighed in the combination shown in Table 4, was dissolved for 1 hour at 145° C. by adding 20 ml of a solvent, and the obtained solutions were analyzed by GPC, respectively, and the molecular weight and peak of each standard polystyrene Calibration was performed by creating a calibration curve from the relationship of the tower elution time.

Infrared spectrophotometer calibration: Polyethylene standard NIST1475a and Merck's isotactic polypropylene sample (product number 182389) Each 10 mg of 20 ml of solvent was added and dissolved at 145° C. for 1 hour, and the obtained solutions were each GPC After analysis, a calibration curve was prepared using the former CH ₃ /1000C as 0.1 and the latter CH ₃ /1000C as 333.3, and used to determine the CH ₃ /1000 _C of the sample.

Measurement procedure: 20 ml of a solvent is added to 20 mg of a sample, and heated and stirred at 145°C for 60 minutes to prepare a sample solution. 0.5 ml of the obtained sample solution was injected into a temperature-raised elution fractionation (TREF) column maintained at 145°C in a CFC device, and held for 20 minutes. Then, the temperature of the TREF column was lowered to 100° C. at a rate of 20° C./min, and maintained at 100° C. for 20 minutes. Then, the temperature of the TREF column was lowered to 30° C. at a rate of 0.5° C./min, and maintained at 30° C. for 30 minutes. Then, the temperature of the TREF column was raised to 50° C. at a rate of 20° C./min, and maintained at 50° C. for about 19 minutes. Then, the elution amount, Mw and CH ₃ /1000C at 50°C were measured by GPC (built into CFC) equipped with an infrared spectrophotometer. Subsequently, the temperature of the TREF column was raised to 140° C. at a rate of 20° C./min, and after holding for about 19 minutes, the elution amount at 140° C., Mw and CH ₃ /1000 C were determined by GPC with an infrared spectrophotometer (CFC Built in). From the ratio (wt%) of the elution amount at 50° C. to the total elution amount and the elution amount at 140° C., among the soluble components to orthodichlorobenzene at 140° C. in the thermoplastic elastomer composition, the soluble component to orthodichlorobenzene at 50° C. And the respective amounts (% by weight) of the insoluble component to orthodichlorobenzene at 50°C.

(6) Manufacturing method of injection molded article for physical property evaluation

Apart from the injection molded body, a side gate plate mold was used with an injection molding machine manufactured by Toshiba Machinery Co., Ltd., under conditions of a cylinder temperature of 220°C and a mold temperature of 50°C, the thermoplastic elastomer compositions of Examples and Comparative Examples were 90 mm long and horizontally. An injection molded article having a thickness of 150 mm and a thickness of 2 mm was obtained.

(6-1) Tensile breaking strength (TB), tensile breaking elongation (EB)

According to JIS K6251: 1993, the tensile breaking strength and tensile breaking elongation of the injection molded article manufactured in (7) were measured. In addition, it was set as a JIS No. 3 dumbbell and a tensile speed of 200 mm/min.

(6-2) Low temperature impact resistance (IZOD)

According to JIS K7110:1984, the impact resistance of the injection molded article manufactured in (7) was measured.

In addition, the measurement temperature is -40°C.

NB = not destroyed

B = destroyed

(7) Molded appearance

With respect to the injection molded article, the gloss unevenness occurring on the embossed surface was visually observed, and judgment was made based on the following criteria. When visual observation was carried out, a stand light was used, and the gloss uneven part was illuminated so that the gloss unevenness became prominent and observed.

○: The uneven gloss of the tear line is not visible.

×: The gloss unevenness of the tear line portion is conspicuous.

The results are shown in Tables 5 and 6.

The thermoplastic elastomer composition according to an aspect of the present invention is a known molding processing method, preferably an injection molding method, for automobile interior parts such as airbag covers, instrument panels and fillers, automobile exterior parts such as molding, home appliance members, and building materials. It is processed into molded objects such as furniture, miscellaneous goods, etc.

Claims (14)

As a thermoplastic elastomer composition containing at least two olefin polymers, the following requirement (I) and the following requirement (II):
(I) The content of the insoluble component to orthodichlorobenzene at 140°C as measured using gel permeation chromatography is 20 parts by weight to 50 parts by weight, making the total amount of the thermoplastic elastomer composition 100 parts by weight;
(II) Isothermal crystallization time measured at 130° C. using a heat flux type differential scanning calorimeter is 300 seconds or more;
Satisfying the, thermoplastic elastomer composition. The method of claim 1,
The thermoplastic elastomer composition, wherein the content of the insoluble component is from 20 parts by weight to 35 parts by weight. The method according to claim 1 or 2,
The thermoplastic elastomer composition, wherein the content of the insoluble component is from 24 parts by weight to 30 parts by weight. The method according to any one of claims 1 to 3,
The thermoplastic elastomer composition, wherein the isothermal crystallization time is from 1500 seconds to 2000 seconds. The method according to any one of claims 1 to 4,
The thermoplastic elastomer composition is a composition obtained by melt-kneading a heterophasic propylene polymer material in the presence of a crosslinking agent and a crosslinking aid,
The heterophasic propylene polymerization material contains a propylene copolymer (A) and a propylene copolymer (B),
The content of the propylene copolymer (A) is 45 parts by weight to 65 parts by weight based on 100 parts by weight of the total amount of the propylene copolymer (A) and the propylene copolymer (B), and the propylene copolymer (B) The content is from 35 parts by weight to 55 parts by weight,
The propylene copolymer (A),
A monomer unit derived from propylene (A1), and
A monomer unit (A2) derived from at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 12 carbon atoms,
With respect to 100 parts by weight of the total amount of the monomer unit (A1) and the monomer unit (A2), the content of the monomer unit (A1) is 95 parts by weight to 99.9 parts by weight, and the content of the monomer unit (A2) is 0.1 parts by weight. It is from parts to 5 parts by weight,
The propylene copolymer (B),
A monomer unit (B1) derived from propylene, and
And a monomer unit (B2) derived from at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 12 carbon atoms,
With respect to 100 parts by weight of the total amount of the monomer unit (B1) and the monomer unit (B2), the content of the monomer unit (B1) is from 20 parts by weight to 78 parts by weight, and the content of the monomer unit (B2) is 22 parts by weight. Parts-80 parts by weight,
Thermoplastic elastomer composition. The method of claim 5,
The weight average molecular weight of the propylene copolymer (A) is 1.0 × 10 ⁵ to 7.0 × 10 ⁵ , and the weight average molecular weight of the propylene copolymer (B) is 4.0 × 10 ⁴ to 1.3 × 10 ⁶ , thermoplastic elastomer Composition. The method according to claim 5 or 6,
The thermoplastic elastomer composition, wherein the propylene copolymer (B) has a weight average molecular weight of 2.0 × 10 ⁵ to 1.1 × 10 ⁶ . The method according to any one of claims 5 to 7,
The thermoplastic elastomer composition, wherein the crosslinking agent is an organic peroxide. The method according to any one of claims 5 to 8,
The thermoplastic elastomer composition, wherein the crosslinking aid is at least one compound selected from the group consisting of a maleimide compound, a polyfunctional vinyl compound, and a polyfunctional acrylate compound. The method according to any one of claims 5 to 9,
The temperature at which the melt-kneading is performed is from 170°C to 270°C. The method according to any one of claims 5 to 10,
The thermoplastic elastomer composition, wherein the heterophasic propylene polymerization material is a polymerization material obtained by multistage polymerization. A method for producing a thermoplastic elastomer composition comprising a step of melt-kneading a heterophasic propylene polymer material in the presence of a crosslinking agent and a crosslinking aid,
The heterophasic propylene polymerization material contains a propylene copolymer (A) and a propylene copolymer (B),
The content of the propylene copolymer (A) is 45 to 65 parts by weight with respect to 100% by weight of the total amount of the propylene copolymer (A) and the propylene copolymer (B), and the propylene copolymer (B) The content is from 35 parts by weight to 55 parts by weight,
The propylene copolymer (A),
A monomer unit derived from propylene (A1), and
And a monomer unit (A2) derived from at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 12 carbon atoms,
With respect to 100 parts by weight of the total amount of the monomer unit (A1) and the monomer unit (A2), the content of the monomer unit (A1) is 95 parts by weight to 99.9 parts by weight, and the content of the monomer unit (A2) is 0.1 parts by weight. It is from parts to 5 parts by weight,
The propylene copolymer (B),
A monomer unit (B1) derived from propylene, and
And a monomer unit (B2) derived from at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 12 carbon atoms,
With respect to 100 parts by weight of the total amount of the monomer unit (B1) and the monomer unit (B2), the content of the monomer unit (B1) is from 20 parts by weight to 78 parts by weight, and the content of the monomer unit (B2) is 22 parts by weight. It is from parts to 80 parts by weight,
The thermoplastic elastomer composition, the following requirement (I) and the following requirement (II):
(I) The content of the insoluble component to orthodichlorobenzene at 140°C as measured using gel permeation chromatography is 20 parts by weight to 50 parts by weight, making the total amount of the thermoplastic elastomer composition 100 parts by weight;
(II) Isothermal crystallization time measured at 130°C using a heat flux type differential scanning calorimeter is 300 seconds or more;
Satisfying, the method for producing a thermoplastic elastomer composition. A molded article containing the thermoplastic elastomer composition according to any one of claims 1 to 11. An airbag cover containing the thermoplastic elastomer composition according to any one of claims 1 to 11.