JP2001348464A - Polymer matrix and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer matrix obtained by crosslinking an EPDM comprising vinyl norbornene as a diene (a vinyl norbornene-based EPDM) by a hydrosilylation reaction, which has sufficiently developed structure formation and contains a polyolefinic resin functioning as a part exhibiting fluidity and as a binder, and to provide a manufacturing method therefor. SOLUTION: The polymer matrix comprises a polyolefinic thermoplastic elastomer, as a dispersant, obtained by forming a crosslinked rubber in a polyolefinic resin and, dispersed therein, a crosslinked vinyl norbornene-based EPDM obtained by crosslinking by a hydrosilylation reaction or one having replaced a part of the EPDM by an atomic group bearing a non-conjugated double bond other than vinyl norbornene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer matrix used for interior and exterior materials of vehicles, interior materials as building materials, electric and electronic resin parts, electric wires, miscellaneous goods and the like, and production thereof. It is about the method.

[0002]

2. Description of the Related Art Polyolefin resins are used in various applications because of their excellent moldability, mechanical properties, durability and the like. In recent years, there has been an increasing need for soft polyolefin-based resins, and in response to this, various polyolefin-based thermoplastic elastomers obtained by modifying polyolefin-based resins have been developed. Polyolefin-based thermoplastic elastomers are obtained by direct synthesis (hereinafter, referred to as reactor-type TPO), types obtained by blending a non-crosslinkable rubber component with a polyolefin-based resin (hereinafter, referred to as blend-type TPO), and It is classified into a type obtained by dynamically cross-linking a rubber component in a high-shear environment (hereinafter, referred to as a dynamically cross-linked TPO). This dynamically crosslinked TPO exhibits physical properties close to those of vulcanized rubber in terms of mechanical and elastic properties, and is thermoplastic and can be recycled. It is being used as an alternative material.

A dynamically crosslinked TPO has a structure in which a crosslinked product such as an ethylene-propylene-diene copolymer (hereinafter referred to as EPDM) is dispersed in a polyolefin resin such as polypropylene. Since this crosslinked product exhibits the elastic properties of rubber and is dispersed in a polyolefin resin having a role as a binder, the dynamically crosslinked TPO
Has the properties of a rubber elastic body plastically deformed by a rise in temperature, that is, a thermoplastic elastomer.

[0004] In the case of a dynamically crosslinked TPO, a material composed of a rubber component such as a polyolefin resin and EPDM is highly dispersed or compatible in advance, and then high shear is applied to mix and knead the rubber component simultaneously with kneading. Manufactured by the method. This method is called a dynamic crosslinking method because the crosslinking is performed dynamically under high shear. In order to obtain a dynamically crosslinked TPO having lower hardness and higher physical properties by using the dynamic crosslinking method, it is important to select a material and optimize production conditions. Regarding the selection of the material for the dynamically crosslinked TPO, polypropylene is generally used as the polyolefin resin, and block type polypropylene is particularly widely used for the purpose of exhibiting low hardness and high physical properties. On the other hand, as for the rubber component constituting the dynamically crosslinked TPO, a high molecular weight (high Mooney viscosity) exhibiting high physical properties, or ethylene of 5% is used.
EPDM of about 0 to 65% (high ethylene type) is selected. As a diene component of EPDM, ethyl norbornene is considered to be suitable for dynamic crosslinking, and therefore, an ethylene-propylene-ethylnorbornene copolymer is generally used.

[0005] Optimization of the production conditions of the dynamically crosslinked TPO is as follows.
The purpose is to optimize the conditions of the dynamic crosslinking of the rubber component and the crosslinking method. Technical elements in the condition of dynamic crosslinking of the rubber component include the degree of crosslinking of the rubber component, fine dispersion of the rubber component,
Formation of a sea-island structure.
This is a major factor in determining various physical properties of O. The degree of crosslinking of the rubber component contributes to elastic properties such as rebound resilience and compression set of the dynamically crosslinked TPO. Fine dispersion of the rubber component contributes to mechanical strength such as breaking strength, breaking elongation and 100% modulus of the dynamically crosslinked TPO depending on the degree. To obtain a dynamically crosslinked TPO having high physical properties, it is necessary that the rubber component is highly crosslinked and highly finely dispersed in the polyolefin-based resin.
A maximum shear rate of ⁰ to 2000 sec ^-1 is essential.
The formation of the above-mentioned sea-island structure refers to a polyolefin resin /
The process until the kneaded product of the rubber component becomes a structure in which a crosslinked rubber is dispersed in a polyolefin-based resin (hereinafter referred to as a sea-island structure) is as follows. In general,
The dynamically crosslinked TPO is dynamically crosslinked after kneading a polyolefin resin and a rubber component to obtain a compatible system. When this compatible system is dynamically cross-linked, the rubber component is localized as the cross-linking points of the rubber component react, and with this localization, the polyolefin-based resin is eliminated from the rubber component and the sea-island structure is developed ( Phase separation). If this sea-island structure is ideal, then the polyolefin-based resin may comprise: a. A portion exhibiting fluidity, b. Crosslinked rubber binder (dispersion medium),
As a function. Therefore, dynamically crosslinked TPO
The formation of the sea-island structure is an important factor that determines the viscosity characteristics (formability) and mechanical durability. The degree of development of the sea-island structure is affected by the speed of the crosslinking reaction of the rubber component, and the selection of the crosslinking method, the compounding composition, the presence of the third component, and the like are influential factors.

Next, regarding the method of crosslinking the rubber component, a rubber component such as an ethylene-propylene-ethylnorbornene copolymer, an ethylene-propylene-dicyclopentadiene copolymer or an ethylene-propylene copolymer is used.
A method of crosslinking using sulfur, a sulfur-based crosslinking agent, a phenol-based crosslinking agent, a peroxide, or the like has been used for a long time. However, according to these methods, a sulfur atom or the like is supplied to the polyolefin-based resin, and the simple composition of the polyolefin-based resin is impaired, or the polyolefin-based resin is cut by peroxide, and the physical properties of the polyolefin-based resin are reduced. Problems, such as a decrease in In recent years, in order to solve the above-mentioned problems, organohydrogenpolysiloxane is used as a crosslinking agent (crosslinker agent), and platinum or a platinum group metal-based catalyst is used.
A method of cross-linking a PDM diene by a hydrosilylation reaction (addition reaction) has been proposed. In the crosslinking method by the hydrosilylation reaction, a silicon atom is supplied to the polyolefin resin. However, since silicon does not become a volatile component during combustion, the characteristics of the polyolefin resin are not impaired. However, since the platinum or platinum group metal-based catalyst required for the above hydrosilylation reaction is expensive, it is required to reduce the amount of the catalyst used. For example,
When the ethylene-propylene-ethylnorbornene copolymer is crosslinked by a hydrosilylation reaction, the weight of metal atoms is 100 to 200,000 ppm based on the copolymer.
A catalytic amount is required, but a reaction is carried out by selecting an ethylene-propylene-vinylnorbornene copolymer in which the diene component of EPDM is vinylnorbornene and performing an addition reaction (PTC / US98 / 03645 (WO98)
/ 38226)) succeeded in reducing the catalyst amount to about 0.01 to 20 ppm. This method enables reduction of the amount of catalyst used by increasing the rate of the hydrosilylation reaction.Furthermore, when the hydrosilylation reaction is fast, the crosslink density increases and higher elastic properties can be obtained. .

[0007]

However, a method for obtaining a dynamically crosslinked TPO from an ethylene-propylene-vinylnorbornene copolymer by a hydrosilylation reaction is as follows.
Since the crosslinking reaction proceeds too quickly, the polyolefin-based resin and the crosslinked ethylene-propylene-vinylnorbornene copolymer do not undergo phase separation and have a disadvantage that the development of the sea-island structure is insufficient. That is, since the polyolefin resin present in the dynamically crosslinked TPO is restricted by the ethylene-propylene-vinylnorbornene copolymer, it does not exhibit a function as a portion exhibiting fluidity or a function as a binder. As a result, there was a problem that the viscosity properties (moldability) and mechanical durability of the dynamically crosslinked TPO were reduced. Therefore, the present invention provides a polymer matrix obtained by crosslinking an ethylene-propylene-vinylnorbornene copolymer by a hydrosilylation reaction, in which the formation of a sea-island structure is sufficiently developed, and the polyolefin-based resin has a fluidity. It is an object of the present invention to provide a polymer matrix excellent in viscous properties (moldability), mechanical durability, and the like as a result of exhibiting a function as a portion and a binder, and a method for producing the same.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, if a substance having an affinity for the ethylene-propylene-vinylnorbornene copolymer exists, the copolymer will Such substances include ethylene-propylene rubber (EPR), EPDM, styrene rubber, polyester rubber, acrylic rubber, butadiene rubber, isoprene rubber, natural rubber and the like. Elastomers or crosslinked products containing these as main components are suitable, and it was considered that the smaller the particle size of the crosslinked product, the better the physical properties. And
Since the most suitable for such conditions is a dynamically crosslinked TPO, the inventors have found that a dynamically crosslinked TPO which has already been dynamically crosslinked is used as a dispersion medium, and based on such knowledge, the present invention has been completed. Was. Further, as another means for solving the above problems, in an ethylene-propylene-vinylnorbornene copolymer, a part of vinylnorbornene which is a diene component having a fast hydrosilylation reaction has a non-conjugated double bond other than vinylnorbornene. They found that they would be replaced with atomic groups, and based on such findings, completed the present invention.

That is, the first polymer matrix of the present invention comprises a polyolefin-based thermoplastic elastomer obtained by forming a cross-linked rubber in a polyolefin-based resin as a dispersion medium, and a hydrosilylation reaction in the dispersion medium. The crosslinked product of the ethylene-propylene-vinylnorbornene copolymer crosslinked by the above is dispersed. In the polymer matrix, a crosslinked product of an ethylene-propylene-vinylnorbornene copolymer is, as a crosslinking agent, an organohydrogenpolysiloxane,

Embedded image It is preferable that the crosslinked product is crosslinked by a hydrosilylation reaction using a diene compound having one or more kinds of atomic groups or a polymer having a diene shown in (1). Further, the polymer matrix is a polyolefin-based thermoplastic elastomer in which a cross-linked rubber is formed in a polyolefin-based resin, ethylene-propylene-crosslinked by a hydrosilylation reaction, for the reasons described below.
It is preferable to be composed of a crosslinked product of a vinyl norbornene copolymer and a polyolefin resin. Further, in the polymer matrix, the crosslinked rubber formed in the polyolefin resin is preferably a crosslinked rubber crosslinked by a hydrosilylation reaction for the reasons described below.

[0010] The first method for producing a polymer matrix is as follows: 100 parts by weight of an uncrosslinked ethylene-propylene-vinylnorbornene copolymer, 0.1 to 15 parts by weight of an organohydrogenpolysiloxane, and a polyolefin-based thermoplastic elastomer. 50-8000 s in a temperature range of 80-300 ° C. to a mixture consisting of 1-2000 parts by weight
The ethylene-propylene-vinylnorbornene copolymer is dynamically crosslinked by giving a maximum shear rate of ec- ¹ . In the above production method, the mixture is an uncrosslinked ethylene-propylene-vinylnorbornene copolymer 100 parts by weight, an organohydrogenpolysiloxane 0.1 to 15 parts by weight, a polyolefin-based thermoplastic elastomer 1 to 2000 parts by weight, and

Embedded image It is preferable to use 0.05 to 50 parts by weight of a diene compound or a diene-containing polymer which must have one or more kinds of atomic groups shown in (1). Further, the above-mentioned production method comprises the steps of:
000 parts by weight can be further added. further,
In the above production method, it is preferable to form a crosslinked product obtained by crosslinking a crosslinked product of the rubber constituting the polyolefin-based thermoplastic elastomer in the mixture by a hydrosilylation reaction. Further, in the above production method, it is preferable to dynamically crosslink the ethylene-propylene-vinylnorbornene copolymer using a hydrosilylation catalyst having a metal atom weight of 0.001 ppm or more.

The second polymer matrix of the present invention comprises:
A polymer matrix in which a crosslinked product of EPDM crosslinked by a hydrosilylation reaction is dispersed in a polyolefin-based resin, wherein the diene component of the EPDM includes vinyl norbornene and a non-conjugated double bond other than vinyl norbornene. And an atomic group having the same. The above-mentioned polymer matrix is made of EPD for the reason described later.
When the total amount of the diene component of M is X mol equivalent, and among the diene components, the amount of vinylnorbornene is Ymol equivalent and the amount of the atomic group having a nonconjugated double bond other than vinylnorbornene is Zmol equivalent, 0.1X < Y <0.95
It is preferable to satisfy the relationship of X, Z + Y = X. Also,
In the polymer matrix described above, among the diene components of EPDM, the atomic group having a non-conjugated double bond other than vinyl norbornene is preferably ethyl norbornene and / or dicyclopentadiene for the reasons described below. Further, in the above-mentioned polymer matrix, EPDM may be used to form an ethylene-propylene-vinylnorbornene copolymer, an ethylene-propylene-ethylnorbornene copolymer and / or an ethylene-propylene-dicyclopentadiene copolymer for the reasons described below. It is preferable that

The second method for producing a polymer matrix is as follows: 100 parts by weight of an uncrosslinked EPDM in which a diene component comprises vinyl norbornene and an atomic group having a non-conjugated double bond other than vinyl norbornene, and an organohydrogenpolysiloxane. In a mixture consisting of 0.1 to 15 parts by weight and 1 to 1000 parts by weight of a polyolefin resin, the weight of metal atoms is 0.001 ppm with respect to the EPDM.
The above-mentioned hydrosilylation catalyst is supplied to perform dynamic crosslinking by giving a maximum shear rate of 50 to 8000 sec ^{-1 in} a temperature range of 80 to 300 ° C. In the above-mentioned production method, for the reasons described below, EPDM has a total amount of diene components of Xmol equivalents, and among the diene components, an amount of vinylnorbornene is Ymol equivalents, and an amount of atomic groups having non-conjugated double bonds other than vinylnorbornene. Is defined as Zmol equivalent, 0.1X <Y <0.95X, Z + Y = X
It is preferable to satisfy the following relationship. Further, in the above production method, among the diene components of EPDM, the atomic group having a non-conjugated double bond other than vinyl norbornene is preferably ethyl norbornene and / or dicyclopentadiene. Further, in the above manufacturing method, EP
DM can be an ethylene-propylene-vinylnorbornene copolymer, an ethylene-propylene-ethylnorbornene copolymer and / or an ethylene-propylene-dicyclopentadiene copolymer.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, the first polymer matrix of the present invention comprises, as a dispersion medium, a polyolefin-based thermoplastic elastomer obtained by forming a crosslinked rubber product in a polyolefin-based resin. It is characterized in that a crosslinked product of an ethylene-propylene-vinylnorbonene copolymer crosslinked by a hydrosilylation reaction is dispersed in a medium. By having such characteristics, the polyolefin-based resin can function as a portion exhibiting fluidity without being restricted by the ethylene-propylene-vinylnorbornene copolymer or can function as a binder of the copolymer. Therefore, the viscosity characteristics (moldability) and mechanical durability of the polymer matrix can be improved. Naturally, since the formation of the sea-island structure is not adversely affected by the restriction from the ethylene-propylene-vinylnorbornene copolymer, the formation of the sea-island structure can be accelerated, and as a result, the amount of catalyst used can be reduced and It is possible to pursue labor saving in manufacturing.

In the first polymer matrix of the present invention, the polyolefin-based thermoplastic elastomer serving as a dispersion medium is a composite in which a cross-linked rubber is formed in a polyolefin-based resin. As the polyolefin resin constituting the polyolefin thermoplastic elastomer,
Polyethylene, polypropylene, ethylene-propylene copolymer (block copolymer, random copolymer), ethylene-propylene-α-olefin copolymer (block copolymer, random copolymer, polypropylene-based reactor TPO), ethylene -Α-olefin copolymer (L-LDPE, soft olefin), propylene-α-
Olefin copolymer (block copolymer, random copolymer, polypropylene-based reactor TPO), ethylene-polypropylene-based elastomer / ethylene-propylene / polyethylene (a type of block polypropylene),
Ethylene-acrylic copolymer (EEA etc.), ethylene-
Vinyl alcohol copolymer (EVOH), copolymers containing propylene other than those described above, copolymers containing α-olefins other than the above, α-olefin polymers containing other cyclic olefins, cyclic olefin polymers, Other copolymers containing ethylene, the above-mentioned maleic acid-modified product, the above-mentioned hydroxyl group-added product, and the above-mentioned silane-modified product.

Examples of the rubber constituting the polyolefin thermoplastic elastomer include EPR, EPDM, styrene rubber, polyester rubber, acrylic rubber, butadiene rubber, isoprene rubber, and natural rubber.
Uncrosslinked products such as EPR, EPDM, acrylic rubber, butadiene rubber, isoprene rubber, and natural rubber that do not contain an aromatic group are desirable, and EPDM is particularly optimal. The ethylene composition ratio of EPDM is not particularly limited, and is a low ethylene type of about 10 to 40%,
A high ethylene type of 50 to 70% may be used, but a high ethylene type is desirable to obtain high mechanical properties. The content of the diene component in the EPDM is usually in the range of 1 to 8%, but is not particularly limited and is optional. There is no limitation on the type of the diene component of EPDM, and the diene component may be a general component such as dicyclopentadiene or ethyl norbornene, or a special component such as vinyl norbornene. In addition, EP
If the Mooney viscosity of DM (ML _{1 + 4} 100 ° C.) is 50 or more, high physical properties can be expected, and if it is 75 to 120, it is more preferable. In addition, there is no limitation on physical properties such as branching and molecular weight distribution in rubber molecules, and the fluidity has been modified by addition of paraffin oil, or a thermoplastic polymer composed of other ethylene-based or α-olefin or the like. It may be reinforced by a filler such as carbon or silica. Further, the rubber may be a single polymer selected from the above or a mixture of several types. The crosslinked product of the rubber is not limited in terms of the conditions and method of dynamic crosslinking, but in view of the simple composition of the polyolefin resin, peroxide crosslinking or crosslinking by a hydrosilylation reaction is desirable. When a crosslinked rubber product is obtained by the hydrosilylation reaction, if the used hydrosilylation catalyst has not expired, it can be used as a catalyst required to obtain the polymer matrix of the present invention, as described later. This is advantageous because it can be performed. The crosslink density of the rubber crosslinked product is such that the amount of extraction with decalin at 180 ° C. is 3 to 9
It is preferably 7% in terms of structure formation, more preferably 10 to 95%. The average particle size, particle size distribution and shape of the crosslinked rubber are not limited and are optional. However, the average particle size is preferably as small as possible, particularly preferably 5 μm or less. The composition ratio of the crosslinked product of the polyolefin-based resin and the rubber constituting the polyolefin-based thermoplastic elastomer is also not limited, and can be arbitrarily selected depending on the hardness of the intended polymer-based matrix.

Next, a crosslinked product of an ethylene-propylene-vinylnorbornene copolymer to be dispersed in a polyolefin-based thermoplastic elastomer as a dispersion medium will be described. In the present invention, the crosslinked product of the ethylene-propylene-vinylnorbornene copolymer is limited to one dynamically crosslinked by a hydrosilylation reaction in consideration of the simple composition of the polyolefin resin. Further, in the ethylene-propylene-vinyl norbornene copolymer, the structural ratio of ethylene, the content of diene components, Mooney viscosity, intramolecular branching, molecular weight distribution and other molecular structural characteristics are arbitrary, and paraffin oil The fluidity may be modified by the addition or reinforced by another polymer or filler. The composition ratio of ethylene is as low as about 10 to 40% or 5% or less.
A high ethylene type of 0 to 70% may be used, but a high ethylene type is desirable for obtaining high physical properties. The content of the diene component in the ethylene-propylene-vinylnorbornene copolymer is usually preferably in the range of 1 to 8%, but is not particularly limited and is optional. Mooney viscosity (ML
_{(1 + 4} 100 ° C.) can be expected to have high physical properties if it is a high Mooney type of 50 or more, and more preferably 75 to 120.

In the first polymer matrix of the present invention, the composition ratio of the polyolefin thermoplastic elastomer and the uncrosslinked ethylene-propylene-vinylnorbornene copolymer is 100 parts by weight of the ethylene-propylene-vinylnorbornene copolymer. On the other hand, 1 to 2000 parts by weight of a polyolefin-based thermoplastic elastomer is suitable, and particularly preferably 5 to 500 parts by weight. If the amount of the polyolefin-based thermoplastic elastomer is less than 1 part by weight, the amount of the polyolefin-based resin in the polyolefin-based thermoplastic elastomer is insufficient, so that the mechanical properties are deteriorated or no fluidity is exhibited. The effect of the invention cannot be sufficiently obtained.

In the first polymer matrix of the present invention, in addition to a polyolefin thermoplastic elastomer and an uncrosslinked ethylene-propylene-vinylnorbornene copolymer, polyethylene, polypropylene, ethylene-propylene copolymer (block copolymer) Polymer, random copolymer), ethylene-propylene-α-olefin copolymer (block copolymer, random copolymer, polypropylene-based reactor TPO), ethylene-α-olefin copolymer (L-LDPE, soft Olefin), propylene-α-olefin copolymer (block copolymer, random copolymer, polypropylene-based reactor TPO), ethylene-polypropylene-based elastomer / ethylene-propylene / polyethylene (one type of block polypropylene), ethylene-ac Copolymer (EEA, etc.), ethylene-vinyl alcohol copolymer (EVOH), copolymers containing propylene other than the above, copolymers containing α-olefins other than the above, copolymers containing other cyclic olefins other than the above Polymer, α-olefin polymer containing cyclic olefin other than the above, cyclic olefin polymer, copolymer containing ethylene other than the above, maleic acid-modified product, hydroxyl-added product, and silane-modified product And the like. By blending these polyolefin resins, the fluidity of the polymer matrix of the present invention can be improved, and the degree of freedom in mechanical properties and hardness can be increased. For example, if block type or random type polypropylene or polyethylene is blended, the mechanical properties are improved by increasing the hardness, and the polypropylene-based reactor TPO, α-olefin polymer, α-olefin-ethylene copolymer, cyclic olefin polymer When the coalescing is blended, mechanical properties can be improved without increasing the hardness so much. Also,
A maleic acid-modified product or a hydroxyl group-added product can impart adhesiveness to a metal or a different kind of plastics. The polyolefin resin to be added may be a single resin or a mixture of two or more resins. And
When the amount of addition is less than 1 part by weight with respect to 100 parts by weight of the uncrosslinked ethylene-propylene-vinylnorbornene copolymer, there is no effect of addition, and when it exceeds 1000 parts by weight, elastic properties and texture as an elastomer are obtained. Therefore, 1 to 1000 parts by weight is appropriate, especially 5 to 50 parts by weight.
0 parts by weight is desirable.

When the ethylene-propylene-vinylnorbornene copolymer is crosslinked by a hydrosilylation reaction, the organohydrogenpolysiloxane used as a crosslinking agent is shown in Chemical formulas 5 to 12 in which two or more SiHs are present in the main chain. Are exemplified.

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Embedded image Several kinds of organohydrogenpolysiloxanes may be used in combination. The amount of the organohydrogenpolysiloxane used is an uncrosslinked ethylene-propylene-
0.1 parts by weight based on 100 parts by weight of the vinyl norbornene copolymer.
The amount is preferably 1 to 15 parts by weight, particularly preferably 1 to 8 parts by weight. When the amount of the organohydrogenpolysiloxane used is 0.1 parts by weight or less, crosslinking becomes insufficient, and when the amount is 15 parts by weight or more, it becomes excessive and disadvantageous in cost.

When crosslinking the ethylene-propylene-vinylnorbornene copolymer by a hydrosilylation reaction, in addition to the organohydrogenpolysiloxane as a crosslinking agent,

Embedded image A diene compound having one or two or more atomic groups or a polymer having a diene can be used,
Thereby, the rate of the hydrosilylation reaction can be increased. Examples of the diene compound include an acryloy compound, a methacryloy compound, an unsaturated polyester alkyd, a virpolysiloxane, an isoprene polymer, and examples of a polymer having a diene include a butadiene polymer. The diene compound or the polymer having a diene is not particularly limited as long as it has the atomic group shown in Chemical formula 7, but if the atomic group is 10 wt%, the hydrosilylation reaction is improved. Content is 10wt
% Is desirable. The molecular weight of the diene compound or the polymer having a diene is not particularly limited, but if it is 150 or more, the effect is remarkably observed. When the amount of the diene compound or the polymer having a diene is less than 0.05 part by weight with respect to 100 parts by weight of the uncrosslinked ethylene-propylene-vinylnorbornene copolymer, there is no effect. Thus, the cost is disadvantageous, so 0.05 to 50 parts by weight is preferable, and particularly 0.5 to 5 parts by weight is preferable.

Next, the method for producing the first polymer matrix according to the present invention will be described. The first polymer matrix of the present invention is produced by a method in which an uncrosslinked ethylene-propylene-vinylnorbornene copolymer is blended with the above-mentioned polyolefin-based thermoplastic elastomer and dynamically crosslinked. Specifically, the first step includes a process of preparing a kneaded material, and the second step includes a process of dynamically crosslinking the kneaded material.

In the process of preparing the kneaded material in the first step, a polyolefin-based thermoplastic elastomer, an ethylene-propylene-vinylnorbornene copolymer, a kneader such as a pressure kneader, a Banbury mixer and a two-roll or extruder are used. And a mixture of a crosslinking agent such as organohydrogenpolysiloxane. When further blending the above-mentioned polyolefin-based resin, kneading may be performed in this step, but not only all the material components are blended and kneaded at the same time, but also an ethylene-propylene-vinylnorbornene copolymer, and an organohydrogen polystyrene. After the siloxane is mixed, a polyolefin-based thermoplastic elastomer may be added and kneaded. Regarding the selection of the kneading device in this first step,
Although it is not particularly limited and is optional, it is preferably carried out by a pressure kneader, a Banbury mixer, or a single-screw or twin-screw extruder. In addition, regarding the temperature conditions for kneading, since it is necessary that the temperature conditions be equal to or higher than the flow start temperature of the polyolefin-based thermoplastic elastomer or the polyolefin-based resin, a kneading history of at least 150 ° C or higher is required. Is at most 300 ° C considering the durability of the material
Because of the following, a history in the range of about 180 to 250 ° C. is required. Further, for example, from a low temperature of about 80 ° C. to 25 ° C.
Kneading may be performed while increasing the temperature to a high temperature of about 0 ° C. This first step requires a shearing force from the kneading device, but it is insufficient when the maximum shear rate is 10 sec ^-1 or less,
If it exceeds 2000 sec- ¹ , the durability of the kneading apparatus will be exceeded, so a maximum shear rate of 10 to 8000 sec- ¹ is preferable, and a higher shear rate within this range is better.

The second step of dynamically crosslinking the kneaded product obtained in the first step is performed in consideration of a heat history (product of temperature and time) required for the crosslinking reaction and a dynamic environment due to high shear. The particle size of the resulting crosslinked ethylene-propylene-vinylnorbornene copolymer depends on the shear rate as a dynamic condition. When the maximum shear rate is 50 sec ^-1 or less, the formation of the crosslinked product is poor, and 8000 sec ^-1. If it exceeds, the durability of the device will be exceeded. Therefore, in the present invention, a maximum shear rate of 50 to 2000 sec ^-1 is appropriate, and it is better to be higher within this range. Regarding temperature conditions, if the temperature is lower than 80 ° C., the temperature falls below the lower limit of the flow start temperature of the polyolefin-based thermoplastic elastomer or the polyolefin-based resin, and if it exceeds 300 ° C., the temperature exceeds the endurance temperature of the material. And particularly preferably 180 to 280 ° C. The choice of the kneading apparatus in this step is arbitrary and not particularly limited, but a twin-screw extruder capable of giving a higher maximum shear rate is optimal. At this time, it is preferable that the filling rate be in a condition exceeding 30 to 40%.

The production of the first polymer matrix of the present invention requires a hydrosilylation catalyst. The step of applying the catalyst is optional, and may be the first step or the second step. When charging in the first step, it is necessary to pay attention to the temperature of the mixture, but if charging in the second step, it is not necessary to do so, so it is preferable to charge in the second step. In producing the first polymer matrix of the present invention, a method of adding a hydrosilylation catalyst is optional, and the catalyst is dispersed or dissolved in a solvent, or after being contained in an inorganic or organic powder, You can put it in.
Further, if the polyolefin-based thermoplastic elastomer as the dispersion medium is obtained using a hydrosilylation catalyst, the hydrosilylation catalyst contained in the polyolefin-based thermoplastic elastomer acts, so the catalyst is intentionally charged. do not have to. As the hydrosilylation catalyst, a chelate compound having a platinum group element, rhodium, titanium or tin as a nucleus, particularly, industrially, platinum chloride such as chloroplatinic acid, chloroplatinic acid hexahydrate, or vinyl group And a chelate of platinum coordinated with a siloxane or polysiloxane containing the same, and a chelate of platinum of a non-conjugated double bond hydrocarbon compound. In the present invention, there is no particular limitation on the type of hydrosilylation catalyst, and any number of compounds may be used. The amount of the hydrosilylation catalyst used is such that the weight of the metal atom is 0.001 p with respect to the uncrosslinked ethylene-propylene-vinylnorbornene copolymer.
If it is less than pm, the crosslinking is insufficient, and there is no particular upper limit, but if it is excessive, it is disadvantageous in terms of cost.
Is an appropriate amount, preferably 0.01 to 25 ppm.

When the ethylene-propylene-vinylnorbornene copolymer is crosslinked by a hydrosilylation reaction, a polymer containing a predetermined diene compound or a diene is used as a crosslinking agent in addition to the aforementioned organohydrogenpolysiloxane. In this case, the step of adding the diene compound or the polymer containing the diene is optional, and may be the first step or the second step. When dosing in the first step, it is necessary to pay attention to the temperature of the mixture,
There is no need to do this in the second step,
It is desirable to feed in the second step. Further, the method of adding the diene compound or the polymer containing a diene is also optional, and may be dispersed and dissolved in a solvent or included in an inorganic or organic powder, and then added. It may be added as a mixture. About the addition amount of the diene compound or the polymer containing a diene, it is effective that the amount of the diene compound or the polymer containing the diene is less than 0.01 part by weight based on 100 parts by weight of the ethylene-propylene-vinylnorbornene copolymer. When the amount is more than 10 parts by weight, it is excessive and causes a decrease in light fastness due to unreacted diene.
0 parts by weight is suitable, and particularly preferably 0.5 to 5.0 parts by weight.

In the first method for producing a polymer matrix, the above two steps may be performed separately,
It can also be carried out collectively by one device. For example, the material may be sequentially charged in each zone of the twin-screw extruder by changing the shaft segment (shaft shape) and temperature conditions. Further, the first step may be performed by a kneader, a Banbury mixer or a twin-screw extruder, and then the second step may be performed by another twin-screw extruder, which is optional in the present invention.

In the first method for producing a polymer matrix, an antioxidant, a stable material for improving light resistance and durability are taken into consideration in consideration of the heat history during production and molding of the polyolefin thermoplastic elastomer. If it is necessary to add an agent, a colorant or the like, it can be blended in the first step. Further, the reaction rate may be adjusted by using a compound having a triple bond carbon or a hydrosilylation reaction retarder represented by a cyclic polysiloxane. Similarly, taking into account the thermal history during the production and molding of the polymer matrix,
Antioxidants, stabilizers to improve lightfastness and durability,
If addition of a coloring agent or the like is necessary, in addition to the first step and the second step, a third step can be provided and introduced,
The properties of the polymer matrix include conductivity, flame retardancy,
Fillers and additives for imparting slidability and the like can be blended. Moreover, a paraffin-based oligomer may be contained in the polymer-based matrix, whereby flexibility can be imparted. Further, the oligomer also has a secondary function of spreading throughout the polymer matrix at the time of molding and lowering the viscosity of the matrix itself. The timing of blending the oligomer is not limited, but it is desirable to perform it in the first step. In recent years, so-called oil-extended elastomers obtained by compounding the oligomer in the production stage of synthetic rubber have been commercialized, but these may be used. The oligomer is graded according to the residual amount of impurities and the average molecular weight, but is not limited in the present invention. Further, the oligomer bleeds when it exceeds 150 parts by weight based on 100 parts by weight of the ethylene-propylene-vinylnorbornene copolymer, and the effect is not sufficiently exhibited unless it is at least 5 parts by weight.
Although 0 parts by weight is desirable, there is no particular limitation.

Next, the second polymer matrix of the present invention will be described. As described above, the second polymer matrix of the present invention is, in a polyolefin resin,
A polymer matrix in which a crosslinked product of EPDM crosslinked by a hydrosilylation reaction is dispersed,
The diene component of M is a multicomponent composed of vinyl norbornene and an atomic group having a non-conjugated double bond other than vinyl norbornene. By having such characteristics, the polyolefin-based resin functions as a portion exhibiting fluidity without being restricted by EPDM,
Since it can function as a binder for EPDM, it is possible to improve the viscosity characteristics (moldability) and mechanical durability of the polymer matrix. Naturally, since the formation of the sea-island structure is not adversely affected by the constraint from the EPDM, the formation of the sea-island structure can be accelerated, and as a result, the amount of catalyst used and the labor saving in production are pursued. It becomes possible.

In the EPDM constituting the second polymer matrix of the present invention, the diene component is limited to an EPDM composed of a multicomponent component essentially including vinylnorbornene. That is, vinyl norbornene is essential, and the remaining diene components are selected from atomic groups having a non-conjugated double bond other than vinyl norbornene. Representative examples of the atomic group having a nonconjugated double bond include dicyclonorbornene and ethylnorbornene. EPDM above
If the molar fraction of vinylnorbornene is 0.10 or less of the total weight of diene in the above, there is no effect of improving the elastic properties, and if the molar fraction is 0.95 or more, the formation of the sea-island structure is hindered. In the EPDM used in the present invention, the molar fraction of vinylnorbornene in the total amount of the diene component is preferably in the range of 0.1 to 0.95, and more preferably in the range of 0.30 to 0.90. , More preferably 0.70 to 0.90. Therefore, if the total amount of the diene component in EPDM is X mol equivalent, the vinyl norbornene is Y mol equivalent, and the atomic group having a nonconjugated double bond other than vinyl norbornene is Z mol equivalent, X,
It is desirable that Y and Z satisfy {0.1X <Y <0.95X, Z + Y = X}.

Further, EPDM constituting the second polymer matrix of the present invention may be a mixture comprising various kinds of copolymers. For example, when the content of the diene component is 5.0
Ethylene-propylene-ethylnorbornene and / or ethylene-propylene-dicyclopentadiene having the same amount of diene are added to 10 parts by weight of ethylene-propylene-vinylnorbornene copolymer of 100 wt%.
1900 parts by weight or diene content of 5.0 wt%
The diene content is 0.5 to 19.0 based on 100 parts by weight of the ethylene-propylene-vinylnorbornene copolymer.
wt% (but usually 1 to 8 wt%) of ethylene-propylene-ethylnorbornene and / or ethylene-propylene-dicyclopentadiene can be mixed, and their mixing ratio can be arbitrarily selected.
In the second polymer matrix of the present invention, EPD
The content of the diene relative to M is not particularly limited and is arbitrary, but is usually in the range of 1 to 8 wt%. The ethylene composition ratio is not particularly limited, and may be a low ethylene type of about 10 to 40% or a high ethylene type of 50 to 70%. Is desirable. In addition, Mooney viscosity (ML _{1 + 4} 100 ° C.) is generally used as a standard of EPDM molecules, and this is not limited in the present invention. However, if the Mooney viscosity is 50 or more, high physical properties can be expected. More preferably, it is 120. In the present invention, physical properties such as intramolecular branching and molecular weight distribution,
The fluidity may be modified by the addition of paraffin oil, or it may be reinforced with another polymer or filler, and the type of diene is not limited.

When the ethylene-propylene-vinylnorbornene copolymer is crosslinked by a hydrosilylation reaction, the organohydrogenpolysiloxane used as a crosslinking agent is the same as that described in the first polymer matrix. Use The amount of the organohydrogenpolysiloxane used is an uncrosslinked EPDN100.
The amount is preferably 0.1 to 15 parts by weight, more preferably 1 to 8 parts by weight, based on parts by weight. When the amount of the organohydrogenpolysiloxane used is 0.1 parts by weight or less, crosslinking becomes insufficient, and when the amount is 15 parts by weight or more, it becomes excessive and disadvantageous in cost.

The polyolefin resin constituting the second polymer matrix of the present invention refers to a resin which does not contain an element such as halogen, nitrogen or phosphorus, or an aromatic carbon according to a general interpretation. Specifically, polyethylene, polypropylene, ethylene-propylene copolymer (block copolymer, random copolymer), ethylene-propylene-α-
Olefin copolymer (block copolymer, random copolymer, polypropylene-based reactor TPO), ethylene-α-olefin copolymer (L-LDPE, soft olefin), propylene-α-olefin copolymer (block copolymer Coalesce, random copolymer, polypropylene-based reactor TPO), ethylene-polypropylene-based elastomer / ethylene-propylene / polyethylene (one type of block polypropylene), ethylene-acrylic copolymer (EEA, etc.), ethylene-vinyl alcohol copolymer ( EVOH), a copolymer containing propylene other than the above,
Other than the above, a copolymer containing an α-olefin, an α-olefin polymer containing a cyclic olefin other than the above, a cyclic olefin polymer, a copolymer containing ethylene other than the above, the above-mentioned modified maleic acid, and the above-mentioned hydroxyl group An adduct, and the above-mentioned silane modification are mentioned. A maleic acid modified product or a hydroxyl group-added product can impart adhesiveness to a metal or a different kind of plastics, and a silane modified product can impart slidability. The polyolefin-based resin may be a single polymer selected from the above polymers, or may be a mixture of several types. The amount of polyolefin-based resin added is uncrosslinked EP
If the amount is less than 1 part by weight with respect to 100 parts by weight of DM, there is no effect, and if it exceeds 1000 parts by weight, elastic properties and texture as an elastomer cannot be obtained.
Preferably, the amount is 5 parts by weight, particularly preferably 5 to 500 parts by weight.

Next, a method for producing the second polymer matrix according to the present invention will be described. The first polymer matrix of the present invention is produced by a method in which uncrosslinked EPDM is blended with the above-mentioned polyolefin resin, and this is dynamically crosslinked. Specifically, the first step includes a process of preparing a kneaded material, and the second step includes a process of dynamically crosslinking the kneaded material.

In the process of preparing the kneaded product in the first step, a polyolefin resin, the EPDM, and a crosslinking agent, organohydrogenpolypropylene, are kneaded by a kneader such as a pressure kneader, a Banbury mixer and a two-roll or extruder. Mixing of siloxane and the like is performed. The selection of the kneading apparatus in the first step is not particularly limited and is optional, but is preferably performed using a pressure kneader, a Banbury mixer, a single-screw or twin-screw extruder. Also,
Regarding the temperature conditions for kneading, since it is necessary to be a temperature condition equal to or higher than the flow start temperature of the polyolefin resin, a history of kneading at a minimum of 150 ° C. or higher is required, and the upper limit is considered in consideration of the durability of the material At most 300 ° C
Because of the following, a history in the range of about 180 to 250 ° C. is required. Further, for example, from a low temperature of about 80 ° C. to 25 ° C.
Kneading may be performed while increasing the temperature to a high temperature of about 0 ° C. This first step requires a shearing force from the kneading device, but it is insufficient when the maximum shear rate is 10 sec ^-1 or less,
If it exceeds 2000 sec- ¹ , the durability of the kneading apparatus will be exceeded, so a maximum shear rate of 10 to 8000 sec- ¹ is preferable, and a higher shear rate within this range is better.

The second step of dynamically crosslinking the kneaded product obtained in the first step is performed in consideration of the heat history (product of temperature and time) necessary for the crosslinking reaction and the dynamic environment due to high shear. The particle size of the crosslinked EPDM product depends on the shear rate as a dynamic condition. When the maximum shear rate is 50 sec ^-1 or less, the formation of the crosslinked product is poor, and when the maximum shear rate exceeds 8000 sec ^-1 , the durability of the device is reduced. Will exceed. Therefore, in the present invention, a maximum shear rate of 50 to 2000 sec ^-1 is appropriate, and it is better to be higher within this range. Also,
Regarding the temperature condition, if it is lower than 80 ° C., it falls below the lower limit of the flow starting temperature of the polyolefin resin, and if it exceeds 300 ° C., it exceeds the durable temperature of the material, so the range of 80 to 300 ° C. is appropriate. C is desirable. The choice of the kneading apparatus in this step is arbitrary and not particularly limited, but a twin-screw extruder capable of giving a higher maximum shear rate is optimal. At that time, the charge rate is 30
It is preferable to set the condition to exceed 40%.

In order to produce the second polymer matrix of the present invention, a hydrosilylation catalyst is required. The step of applying the catalyst is optional, and may be the first step or the second step. When charging in the first step, it is necessary to pay attention to the temperature of the mixture, but if charging in the second step, it is not necessary to do so, so it is preferable to charge in the second step. In producing the second polymer matrix of the present invention, the method of adding a hydrosilylation catalyst is optional, and the catalyst is dispersed or dissolved in a solvent, or after being contained in an inorganic or organic powder, You can put it in.
As the hydrosilylation catalyst, a platinum group element, rhodium, a chelate compound having titanium or tin as a nucleus, in particular,
Industrially, platinum chloride such as chloroplatinic acid, chloroplatinic acid hexahydrate, a chelate of platinum coordinated with a siloxane or polysiloxane containing a vinyl group, a non-conjugated double bond hydrocarbon compound Are exemplified. In the present invention, there is no particular limitation on the type of hydrosilylation catalyst, and any number of compounds may be used. The amount of hydrosilylation catalyst used is the amount of uncrosslinked EPDM
If the weight of the metal atom is less than 0.0001 ppm, the crosslinking is insufficient, and there is no particular upper limit, but if it is excessive, it is disadvantageous in terms of cost. ２５25 ppm.

In the second method for producing a polymer matrix, the above two steps may be separately performed,
It can also be carried out collectively by one device. For example, the material may be sequentially charged in each zone of the twin-screw extruder by changing the shaft segment (shaft shape) and temperature conditions. Further, the first step may be performed by a kneader, a Banbury mixer or a twin-screw extruder, and then the second step may be performed by another twin-screw extruder, which is optional in the present invention.

In the second method for producing a polymer matrix, an antioxidant and a stable material for improving light resistance and durability are taken into consideration in consideration of the heat history at the time of production and molding of the polyolefin thermoplastic elastomer. If it is necessary to add an agent, a colorant or the like, it can be blended in the first step. Further, the reaction rate may be adjusted by using a compound having a triple bond carbon or a hydrosilylation reaction retarder represented by a cyclic polysiloxane. Similarly, taking into account the thermal history during the production and molding of the polymer matrix,
Antioxidants, stabilizers to improve lightfastness and durability,
If addition of a coloring agent or the like is necessary, in addition to the first step and the second step, a third step can be provided and introduced,
The properties of the polymer matrix include conductivity, flame retardancy,
Fillers and additives for imparting slidability and the like can be blended. Moreover, a paraffin-based oligomer may be contained in the polymer-based matrix, whereby flexibility can be imparted. Further, the oligomer also has a secondary function of spreading throughout the polymer matrix at the time of molding and lowering the viscosity of the matrix itself. The timing of blending the oligomer is not limited, but it is desirable to perform it in the first step. In recent years, a so-called oil-extended elastomer obtained by blending the oligomer in the production stage of a synthetic rubber has been commercialized, but this may be used. The oligomer is graded according to the residual amount of impurities and the average molecular weight, but is not limited in the present invention. In addition, the oligomer bleeds when the amount exceeds 150 parts by weight based on 100 parts by weight of EPDM, and the effect is not sufficiently exhibited unless the amount is at least 5 parts by weight.
Although 10 to 120 parts by weight is desirable, there is no particular limitation.

The first and second polymer matrices of the present invention may be in the form of bulk, bale, sheet, pellet,
It can be formed into a shape that requires final molding of powder or the like (a molding method utilizing plastic deformation such as extrusion molding, injection molding, rotational molding, press molding, calendar molding, or blow molding), or is directly processed into the products described below. Finally, by the above-mentioned molding method, the product is processed into miscellaneous goods such as automobile parts, home electric parts, electric wire covering materials, medical parts, packaging materials, toys, toy essential parts, footwear and the like. When processing into the above-mentioned products, powders, pigments, polymers or fillers or oligomers for supplementing physical properties, various stabilizers for supplementing durability properties, depending on the application, depending on the application. Etc. can also be added. Among the products listed above, especially automotive parts include door glass, weather strip, belt mold, door glass inner strip (inner strip), sunroof weather strip, molding under door,
Various malls around windows, outside mirror packing,
Specific examples include exterior parts such as a glass run channel and a trip mall, instrument panels, door trims, headrests, seat belt covers, airbag covers, armrests, various lit covers, and assist parts such as assist grips.

[0040]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In addition, the evaluation method of the polymer matrix obtained by the example and the comparative example is as follows. [Evaluation Method] Extrusion Formability The temperature of a single screw extruder with a die having a clearance of 1.0 mm and an L / D of 22 was adjusted to 200 ° C., and the appearance when extruded into a film was evaluated. (Evaluation criteria): な け れ ば if smooth and free of defects, △ if smooth and some defects, and × if poor and poor.・ Press formability A sheet formed by the above extrusion molding is 25 × 50 × 1.0 mm.
Were cut and superimposed, and press molded at 200 ° C. × 5 minutes in a cavity of 100 × 100 × 1.0 mm to evaluate the appearance. (Evaluation criteria): な け れ ば if smooth and free of defects, △ if smooth and some defects, and × if poor and poor. -Hardness According to the method described in JIS-A-6301 (Shore A). -Elongation, breaking strength, compression set, rebound resilience The method described in JIS-A-6301 for tensile breaking strength was used.

(Example 1, Comparative Example 1) 100 parts by weight of EPDM (EPDM-1, EPDM-2) having the contents shown in Table 1, polypropylene: 2000C (manufactured by Idemitsu Petrochemical Co., Ltd.)
Product name) 10 parts by weight, polyethylene: HIZEX 68
00 (manufactured by Mitsui Chemicals, Inc., 10 parts by weight), paraffin-based process oil: Lucant 200 (manufactured by Mitsui Chemicals, Inc.)
Product name) 10 parts by weight, wet silica: Nipsil LP (trade name, manufactured by Nippon Silica Industry Co., Ltd.) 15 parts by weight, antioxidant: A
1 part by weight of O-60 (manufactured by Asahi Denka Kogyo KK), organohydrogenpolysiloxane: KE-1950A
10 parts by weight (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) were put into a pressure kneader whose temperature was adjusted to 150 ° C.
Kneaded, and further added 30 parts by weight of polypropylene: 2000C (same as above), and kneaded for 10 minutes to obtain a kneaded product 1 from EPDM-1 which is an ethylene-propylene-ethylnorbornene (ENB) copolymer. E which is a propylene-vinyl norbornene (VNB) copolymer
A kneaded material 2 was obtained from PDM-2. Then, these kneaded materials were put into a twin-screw extruder (temperature: 200 ° C., 300 rpm, shear rate: about 1200 cm ⁻¹ ) and dynamically cross-linked. From the kneaded material 1, a polyolefin-based thermoplastic elastomer (TPO-1, From Comparative Example 1-1), a polyolefin-based thermoplastic elastomer (TPO-2, Comparative Example 1-2) was obtained from the kneaded material 2. In order to obtain TPO-1, EP
Chloroplatinic acid, which is 50 ppm of platinum based on DM,
To obtain TPO-2, chloroplatinic acid having a platinum amount of 20 ppm with respect to EPDM was dropped from a vent hole. Further, after mixing TPO-1 and kneaded material 2 at the compounding ratio shown in Table 2, a twin-screw extruder (temperature 200 ° C., 300 rpm)
m, the shear rate was about 1200 cm ⁻¹ , and chloroplatinic acid having a platinum amount of 20 ppm with respect to EPDM-1 was dropped into the vent hole) to dynamically crosslink the polymer matrix. Examples 1-1, 1-2, 1-3)
I got Table 2 shows the evaluation results of the moldability and physical properties. As a result, Comparative Example 1-2 obtained from the ethylene-propylene-vinyl norbornene copolymer exhibited a higher compression set and rebound resilience than Comparative Example 1-1 obtained from the ethylene-propylene-ethylnorbornene copolymer. However, mechanical properties such as breaking strength and elongation were low, press formability was poor, and gel-like bumps were observed and appearance was poor. This defect is due to the fact that the crosslinking reaction is too fast and the formation of the sea-island structure is underdeveloped,
Therefore, it can be considered that the polyolefin resin does not function as a binder and the mechanical properties are inferior. On the other hand, the polymer matrix of the present invention (Examples 1-1, 1-2,
1-3) was excellent in elastic physical property and mechanical physical property, and good in moldability and appearance as compared with Comparative Example 1-1. This shows that according to the present invention, even when the ethylene-propylene-vinylnorbornene copolymer is used, no adverse effect on the formation of the sea-island structure occurs, and a high-performance polymer matrix can be obtained.

[0042]

[Table 1]

[0043]

[Table 2]

(Example 2, Comparative Example 2) TPO-3: Mirastomer 7030N (trade name, manufactured by Mitsui Chemicals, Inc.) is shown in Table 3.
EPDM (EPDM-3, EPDM-4,
EPDM-5), polypropylene (PP): 2000C
(Same as above), polyethylene (PE): HIZEX 680
0 (same as above), antioxidant: 1 part by weight of AO-60 (same as above),
Organohydrogenpolysiloxane: KE-195
0A (same as above) was charged into a pressure kneader adjusted to a temperature of 150 ° C. at a mixing composition shown in Table 4, and kneaded at 30 rpm for 10 minutes to obtain a 9-point kneaded material (2-1 to 2-9). Obtained. And these kneaded materials are twin-screw extruder (temperature 200 ° C, 30 ° C).
0 rpm and a shear rate of about 1200 sec ^-1 ), and dynamically crosslinked to obtain the polymer matrix (Examples 2-1 to 2-7, Comparative Examples 2-8 and 2-9) shown in Table 5. When fabricated and evaluated for moldability and physical properties respectively,
Table 5 shows the results. As a result, the polymer matrix of the present invention (Examples 2-1 to 2-7) showed the physical properties of TPO-3 (hardness 62, elongation 476%) and breaking strength 6.9 MP.
a, Compression set 70 ° C 39%, Compression set 23 ° C 2
(8%, rebound resilience 53%). In Comparative Example 2-1, the moldability was poor and some samples could not be obtained. The physical properties of Comparative Example 2-2 were TPO-
It was not much different from 3. In addition, in the formulation of the present invention, addition of polypropylene or polyethylene (Example 2-
4 to 2-7) showed that the physical properties were improved.

[0045]

[Table 3]

[0046]

[Table 4]

[0047]

[Table 5]

Example 3, Comparative Example 3 After mixing 100 parts by weight of the kneaded material 2 used in Example 1 and Comparative Example 1 with 10 parts by weight of TPO-3: Mirastomer 7030N (the same as above), The polymer was dynamically cross-linked by a twin-screw extruder (temperature: 200 ° C., 300 rpm, shear rate: about 1200 sec ⁻¹ ) to obtain 16 kinds of polymer-based matrices (Examples 3-1-1 to 3).
-8-2) was produced. In addition, from the vent hole of the extruder,
A urethane acrylate or a polybutadiene having an atomic group shown in Chemical Formula 1 shown in the column of unsaturated compound in Table 6 with respect to 100 parts by weight of EPDM, and Table 6 with respect to EPDM
The amount of chloroplatinic acid shown in the following was added dropwise. Table 7 shows the evaluation results of the moldability and physical properties. as a result,
In particular, when the unsaturated compound is added in the range of 0.05 to 50 parts by weight (Example 3-3-1 to Example 3-7-2), good physical properties are obtained even when the addition amount of the platinum catalyst is 0.1 ppm. was gotten.

[0049]

[Table 6]

[0050]

[Table 7]

(Example 4) 100 parts by weight of the kneaded material 2 used in Example 1 and Comparative Example 1 and TPO-1 (containing chloroplatinic acid, which is 20 ppm of platinum relative to EPDM) 30
Parts by weight and then a twin-screw extruder (temperature 200 ° C,
The polymer was dynamically crosslinked at 300 rpm at a shear rate of about 1200 sec ^-1 ) to obtain a polymer matrix. Its physical properties are hardness 65, elongation 528%, breaking strength 12.9MP.
a, compression set 70 ° C 32%, compression set 23 ° C 21
%, And rebound resilience of 58%, which were physical properties comparable to those of Example 1-1 having the same composition as shown in Table 2.

Example 5, Comparative Example 5 100 parts by weight of EPDM (EPDM-6 to 9) having the contents shown in Table 8, 10 parts by weight of polypropylene: 2000 C (same as above), and 10 parts by weight of polyethylene: HIZEX 6800 (same as before) Parts by weight, paraffinic process oil: Lucant 200 (same as above) 10
Parts by weight, wet silica: 15 parts by weight of Nipsil LP (same as above), antioxidant: 1 part by weight of AO-60 (same as above), and 10 parts by weight of organohydrogenpolysiloxane: KE-1950A (same as before) at 150 ° C. And kneaded at 30 rpm for 10 minutes, further added 30 parts by weight of polypropylene: 2000C (same as above), and kneaded for 10 minutes to obtain an ethylene-propylene-ethylnorbornene copolymer. From a certain EPDM-6 to kneaded material 5-1
With EPDM-6, an EPDM of multi-dimensional diene, EP
A kneaded product 5-2, 5-3 was obtained from DM-7, and a kneaded product 5-4 was obtained from EPDM-9, which is an ethylene-propylene-vinylnorbornene copolymer. And these kneaded materials are twin-screw extruder (temperature 200 ° C, 300 rpm,
The shear rate was about 1200 cm ^-1 , and chloroplatinic acid having a platinum amount of 20 ppm relative to EPDM-6 to 9 was dropped into the vent hole to perform dynamic crosslinking.
The four types of polymer matrices (Comparative Example 5-1, Example 5-1, Example 5-2, Comparative Example 5 2) was obtained. Table 9 shows the evaluation results of the moldability and physical properties. As a result, a polymer matrix obtained from an ethylene-propylene-ethylnorbornene copolymer (Comparative Example 5-1)
Was a physical property indicating that crosslinking was not sufficient because the amount of platinum catalyst was insufficient. In addition, the kneaded material 5-1 is
Under the same conditions, crosslinking was performed by injecting a platinum amount of 200 ppm.
2, elongation 476%, breaking strength 6.9MPa, compression set 70 ° C 39%, compression set 23 ° C 28%, rebound resilience 53
%. Compared with Examples 5-1 and 5-2, the polymer matrix obtained from the ethylene-propylene-vinylnorbornene copolymer (Comparative Example 5-2) has elastic properties such as compression set and rebound resilience. Although excellent, mechanical properties such as breaking strength and elongation were low, press formability was poor, and gel-like bumps were observed, resulting in poor appearance. This inconvenience is attributed to the fact that the cross-linking reaction is too fast and the formation of the sea-island structure is undeveloped. Therefore, it can be considered that the polyolefin resin does not function as a binder and the mechanical properties are poor. On the other hand, the polymer matrix (Examples 5-1 and 5-2) of the present invention was excellent in elastic physical properties and mechanical physical properties, and also excellent in moldability and appearance. From this, it can be seen that according to the present invention, even when the ethylene-propylene-vinylnorbornene copolymer is used, no adverse effect on the structure formation occurs, and a polymer matrix having high physical properties can be obtained.

[0053]

[Table 8]

[0054]

[Table 9]

(Example 6, Comparative Example 6) EPDM-6 and EPDM-9 having the contents shown in Table 8 were prepared at the compounding ratio shown in Table 10, and kneaded in the same manner as in Example 5 and Comparative Example 5. Thus, seven types of kneaded products (6-1 to 6-7) shown in Table 10 were obtained.
And a twin-screw extruder (temperature 200 degreeC, 300 rpm, a shear rate is about 1200 sec < ^-1 >,
Chloroplatinic acid, which is the amount of platinum in ppm, is dropped from the vent hole)
To obtain seven types of polymer matrices.
Table 11 shows the evaluation results of the moldability and physical properties. As a result, Comparative Example 6-1 obtained from the kneaded material 6-1
Was a physical property indicating that crosslinking was not sufficient because the amount of platinum catalyst was insufficient. Comparative Example 6-2 obtained from the kneaded product 6-7 has excellent elastic properties such as compression set and rebound resilience, but has low mechanical properties such as breaking strength and elongation, poor moldability, and gel. The shape was bad and the appearance was bad. This defect is considered to be caused by the fact that the cross-linking reaction is too fast and the formation of the sea-island structure is incomplete, and the polyolefin resin does not function as a binder, resulting in poor mechanical properties. On the other hand, the polymer matrix of the present invention (Examples 6-1, 6-2, 6-3, 6-4, 6-
5) was excellent in elastic properties and mechanical properties, and also good in moldability and appearance. From this, it can be seen that according to the present invention, even when vinyl norbornene-based EPDM is used, no adverse effect on the structure formation occurs, and a polymer matrix having high physical properties can be obtained.

[0056]

[Table 10]

[0057]

[Table 11]

[0058]

According to the present invention, since the phase separation between the polyolefin resin and the rubber is surely developed, a polymer matrix having excellent viscosity characteristics and mechanical durability can be obtained. If the polymer matrix of the present invention is used in miscellaneous goods such as automobile parts, home electric parts, electric wire covering materials, medical parts, packaging materials, toys, toy parts, footwear and the like, quality can be improved.

Continued on the front page F-term (reference) 4F070 AA04 AA12 AA13 AA15 AA16 AC45 AC73 AC75 AC92 AE08 GA01 GC07 4J002 AC00X AC01X AC02X BB00W BB03W BB05W BB06W BB08W BB12W BB14W BB15W BB15X BB20X BB20X BB15X GN00 GQ00

Claims (10)

[Claims] 1. An ethylene-propylene-vinyl norbornene copolymer crosslinked by a hydrosilylation reaction in a dispersion medium of a polyolefin-based thermoplastic elastomer obtained by forming a crosslinked rubber product in a polyolefin-based resin. A polymer matrix, wherein a crosslinked product of the above is dispersed. 2. A crosslinked product of an ethylene-propylene-vinylnorbornene copolymer comprising: an organohydrogenpolysiloxane as a crosslinking agent; The polymer matrix according to claim 1, wherein the polymer matrix is a crosslinked product obtained by a hydrosilylation reaction using a diene compound having one or more kinds of atomic groups or a polymer having a diene shown in (1). 3. The polymer matrix according to claim 1, wherein the crosslinked rubber formed in the polyolefin resin is a crosslinked rubber crosslinked by a hydrosilylation reaction. 4. A polymer matrix in which a crosslinked product of an ethylene-propylene-diene copolymer crosslinked by a hydrosilylation reaction is dispersed in a polyolefin-based resin, wherein the ethylene-propylene-diene copolymer is Wherein the diene component comprises vinyl norbornene and an atomic group having a non-conjugated double bond other than vinyl norbornene. 5. The ethylene-propylene-diene copolymer in which the total amount of diene components is X mol equivalents, the amount of vinyl norbornene in the diene components is Y mol equivalents, and the atomic group having a non-conjugated double bond other than vinyl norbornene is When the amount is Zmol equivalent, 0.1X <Y <0.95X,
5. The polymer matrix according to claim 4, wherein a relationship of Z + Y = X is satisfied. 6. The diene component of the ethylene-propylene-diene copolymer, wherein the atomic group having a non-conjugated double bond other than vinyl norbornene is ethyl norbornene and / or dicyclopentadiene.
The polymer matrix according to the above. 7. An ethylene-propylene-diene copolymer comprising an ethylene-propylene-vinyl norbornene copolymer and an ethylene-propylene-ethylnorbornene copolymer and / or an ethylene-propylene-dicyclopentadiene copolymer. The polymer matrix according to any one of claims 4 to 6. 8. A mixture comprising 100 parts by weight of an uncrosslinked ethylene-propylene-vinylnorbornene copolymer, 0.1 to 15 parts by weight of an organohydrogenpolysiloxane, and 1 to 2000 parts by weight of a polyolefin thermoplastic elastomer, The ethylene-propylene-diene copolymer is supplied with a hydrosilylation catalyst having a metal atom weight of 0.001 ppm or more, and a maximum shear rate of 50 to 8000 sec ^{-1 in} a temperature range of 80 to 300 ° C. A method for producing a polymer matrix, comprising dynamically crosslinking the ethylene-propylene-vinylnorbornene copolymer. 9. An uncrosslinked ethylene-propylene-vinylnorbornene copolymer (100 parts by weight), an organohydrogenpolysiloxane (0.1 to 15 parts by weight), a polyolefin-based thermoplastic elastomer (1 to 2000 parts by weight), and A mixture of 0.05 to 50 parts by weight of a diene compound or a diene-containing polymer essentially having one or more atomic groups shown in
A hydrosilylation catalyst having a metal atom weight of 0.001 ppm or more is supplied to the propylene-diene copolymer, and a temperature of 80 to 300 ° C. and a temperature of 50 to 8000 sec.
^A method for producing a polymer matrix, wherein a maximum shear rate of ^-1 is given to dynamically crosslink the ethylene-propylene-vinylnorbornene copolymer. 10. A diene component comprising 100 parts by weight of an uncrosslinked ethylene-propylene-diene copolymer comprising vinyl norbornene and an atomic group having a non-conjugated double bond other than vinyl norbornene, and organohydrogenpolysiloxane 0.1 part by weight. 1 to 15 parts by weight, and a mixture of a polyolefin resin and 1 to 1000 parts by weight, based on the ethylene-propylene-diene copolymer, a metal atom weight of 0.001 ppm or more of a hydrosilylation catalyst is supplied, 50 to 8000 sec in a temperature range of 80 to 300 ° C
^A method for producing a polymer matrix, wherein the polymer is subjected to dynamic crosslinking by giving a maximum shear rate of ^-1 .