JP2002338763A - Automotive exterior part - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an automotive exterior part which is prepared by using a thermoplastic olefin elastomer which has mechanical properties equal or superior to those of a halogenated polymer composition and is highly reliable since it has such durability and weather resistance as to enable the excellent mechanical properties to be retained for a long time. SOLUTION: This automotive exterior part has a surface layer formed from a thermoplastic olefin elastomer having a Shore A hardness (specified by JIS K 6253) of 50-100. The thermoplastic olefin elastomer comprises hard segments consisting mainly of a thermoplastic polymer and soft segments consisting of an ethylene/α-olefin/diene copolymer cross-linked with an organohydrogenpolysiloxane. The ethylene/α-olefin/diene copolymer essentially contains vinylnorbornene-derived units as diene units. The thermoplastic olefin elastomer is prepared from 1-1,000 pts.wt. thermoplastic polymer, 100 pts.wt. ethylene/α-olefin/diene copolymer, and 0.1-15 pts.wt. organohydrogenpolysiloxane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a belt molding, a weather strip, a modular wind molding having a skin layer made of an olefin-based thermoplastic elastomer,
Side molding, side molding packing, window surrounding molding,
The present invention relates to automotive exterior parts such as a bumper molding—a flash mount molding and a roof molding.

[0002]

2. Description of the Related Art When each part constituting an exterior part for an automobile is functionally classified, a skin layer and a glass window which constitute an outer shell of the automobile together with a glass window and a body can be smoothly opened and closed, and the elasticity can provide waterproofness and sealing. It consists of a functional part that exerts its properties, a main body or a core material fixed to the skin layer or the functional part. For example, in the modular window molding illustrated in FIG. 1, a main body 2 made of glass is fixed to a skin layer 1 made of a polymer constituting a glass window. In an automobile, as shown in FIG. 4
Attached to. The side molding illustrated in FIG.
A main body 2 made of iron or polyacetal (POM) is fixed to a skin layer 1, and is mounted on a body steel plate 4 in an automobile as illustrated in FIG.

Hitherto, as a polymer material constituting an exterior part for an automobile, a thermoplastic polymer containing a halogen or an aromatic atomic group or a crosslinked rubber which cannot be recycled has been used. In some automotive exterior parts,
There has been a demand for polymer-based materials to replace them. As such a polymer-based material, a thermoplastic elastomer composed of a simple elemental composition has been spotlighted, and its spread is urgent. Among thermoplastic elastomers, olefin-based thermoplastic elastomers, in particular, have mechanical properties and elastic properties showing physical properties close to crosslinked rubbers, and are also thermoplastic, so their advantages such as being recyclable have been evaluated. .

The olefin-based thermoplastic elastomer has a structure in which a crosslinked product of an ethylene-α-olefin-diene copolymer is dispersed as particles (domains) in a thermoplastic polymer such as polypropylene, that is, a so-called sea-island structure. . The domains exhibit the elastic properties of a crosslinked rubber and are dispersed in a thermoplastic polymer as a binder. Therefore, the olefin-based thermoplastic elastomer exhibits properties as an elastic matrix having fluidity, that is, a thermoplastic elastomer.

As the thermoplastic polymer constituting the olefin-based thermoplastic elastomer, polypropylene is generally used, but block type polypropylene is widely used for the purpose of exhibiting low hardness and excellent physical properties. On the other hand, the ethylene-α-olefin-diene copolymer constituting the olefin-based thermoplastic elastomer uses an atomic group of a hydrocarbon having about 3 to 10 carbon atoms as an α-olefin, and generally uses propylene having 3 carbon atoms. A typical example is an ethylene-propylene-diene copolymer (EPDM). In addition, as a diene component serving as a crosslinking point of EPDM, ethyl norbornene is evaluated to be suitable for dynamic crosslinking. Therefore, as the ethylene-α-olefin-diene copolymer constituting the olefin-based thermoplastic elastomer, ethylnorbornene-based EPDM is generally used.

[0006]

A halogen-based polymer composition is used in a current exterior molding of an automobile. However, as a condition of an alternative polymer material, the mechanical strength of the halogen-based polymer composition is low. It is required that the composition is not inferior to the polymer composition. In the halogen-based polymer composition, there is a correlation between the surface hardness and the breaking strength, and an approximate expression thereof is as shown in the following Expression 4. The standard value of the automotive exterior component substantially follows this approximate expression. Therefore, in order to use the olefin-based thermoplastic elastomer as a substitute material for the halogen-based polymer composition, the breaking strength of the olefin-based thermoplastic elastomer should be at least equal to or greater than the breaking strength obtained from the correlation formula of Expression 4. However, in practice, the breaking strength is smaller than the breaking strength obtained from Equation 4 and is only an approximate value obtained from Equation 5. Formula 4: Ts ≒ A ÷ 2-20 (50 <A <100) Formula 5: Ts ≒ A ÷ 2-25 (50 <A <100) Ts: Breaking strength specified in JIS K 6251 (measurement temperature is 23 ±
Unit: MPa A: Shore A surface hardness specified in JIS K 6253 (after 10 seconds)

[0007] The design part constituting the exterior molding is
Since it constitutes the outer shell of an automobile, it is required to have excellent weather resistance. However, the olefin-based thermoplastic elastomer has a disadvantage that it is inferior in weather resistance as compared with the current halogen-based polymer composition. In other words, olefin-based thermoplastic elastomers having a simple composition are demanded as materials for automotive exterior parts, but they have mechanical properties equal to or higher than those of halogen-based polymer compositions. The challenge is to provide durability and weather resistance that can maintain mechanical properties for a long period of time.

In view of the above circumstances, the present invention has mechanical properties equivalent to or higher than those of a halogen-based polymer composition,
Moreover, it is an object of the present invention to provide an automotive exterior component made of an olefin-based thermoplastic elastomer having durability and weather resistance capable of maintaining the mechanical properties for a long period of time.

[0009]

Means for Solving the Problems The causes of the low mechanical strength and weather resistance of the current olefin-based thermoplastic elastomers are individually explained below, and the olefin-based thermoplastic elastomers obtained by improving these physical properties are used. The present invention will be described sequentially. First, the mechanical strength of the current olefin-based thermoplastic elastomer is low because the ethylene-α-olefin-diene copolymer is crosslinked using peroxide in order to obtain an olefin-based thermoplastic elastomer. . In general, mechanical properties such as breaking strength and elongation of an olefin-based thermoplastic elastomer depend on the average molecular weight of the thermoplastic polymer that functions as a binder, and the higher the average molecular weight of the thermoplastic polymer, the better the mechanical properties. ing. However, when the ethylene-α-olefin-diene copolymer is cross-linked using peroxide,
Radicals such as oxygen generated by decomposition of the peroxide attack, for example, tertiary carbon present in a propylene portion or a long-chain branched portion in a polypropylene molecule to cut a thermoplastic polymer chain. For this reason, the average molecular weight of the thermoplastic polymer decreases, and as a result, mechanical properties such as breaking strength and elongation decrease.

In order to obtain a mechanical strength equal to or higher than that of the halogen-based polymer composition, the present inventors cross-link a thermoplastic polymer such as polypropylene by a cross-linking method that does not cut the thermoplastic polymer. We believe that the olefin-based thermoplastic elastomer obtained by this method should be used as the polymer material for the skin layer (design part) of automotive exterior parts, and the selection of the polymer material obtained by such a crosslinking method was considered. went. As a result of intensive studies, the present inventors have adopted an olefin-based thermoplastic elastomer dynamically crosslinked by a hydrosilylation reaction as a polymer material for an automotive exterior component according to the present invention. This hydrosilylation reaction is a very selective reaction because it is initiated from the abstraction of hydrogen atoms by a catalyst as the first stage of the reaction, and it does not cleave thermoplastic polymers such as polypropylene at all. The average molecular weight of the polymer does not decrease. Therefore, the approximate correlation between the surface hardness and the breaking strength is comparable to that of the halogen-based polymer composition. In the dynamic crosslinking by the hydrosilylation reaction, an organohydrogenpolysiloxane is used as a crosslinking agent, and the crosslinking agent is crosslinked by an addition reaction with a diene of an ethylene-α-olefin-diene copolymer. The thermoplastic elastomer obtained by the hydrosilylation reaction has a structure in which a crosslinked product of an ethylene-α-olefin-diene copolymer and an organohydrogenpolysiloxane is formed in an olefin-based thermoplastic polymer.

Next, the reason why the current olefin-based thermoplastic elastomer has low weather resistance is explained by the fact that the diene, which is a crosslinking point of the ethylene-propylene-diene copolymer, remains unreacted. is there. Ethylene-α-olefin-diene copolymers in which the diene component is ethylnorbornene have been used in conventional olefin-based thermoplastic elastomers, but this copolymer contains 40 to 70% of diene even when crosslinked. It remains as an unstable unsaturated part. Then, the residual diene is deteriorated due to exposure to a humid environment or under ultraviolet light or a long-term heat history, and as a result, the olefin-based thermoplastic elastomer is discolored and mechanical properties such as breaking strength are deteriorated. As a countermeasure, the present inventors thought that an olefin-based thermoplastic elastomer composed of an ethylene-α-olefin-diene copolymer having a diene component rich in reactivity may be selected. If the double bond of the diene, which is a cross-linking point, is in a portion that is hardly sterically hindered in terms of molecular structure, the reactivity will be high. As such a diene component, vinyl norbornene is most suitable, so in the present invention, vinyl norbornene was selected as the diene component.

This vinyl norbornene exhibits a much higher crosslinking efficiency than ethyl norbornene used in a general-purpose ethylene-α-olefin-diene copolymer. For example, comparing an ethylene-α-olefin-diene copolymer containing 4.5 wt% of vinyl norbornene and an ethylene-α-olefin-diene copolymer containing the same amount of ethyl norbornene, peroxides performed under the same conditions The effective network density in the crosslinking is 17 × 10 ¹⁹ / cm ³ for the former, but 8 × 10 ¹⁹ / cm ³ for the latter, and the former has overwhelmingly high crosslinking efficiency. Is shown. In addition,
In both cases, the number of dienes is 23 × 10 ¹⁹ / cm ³ , so that ethyl norbornene has 60% or more of residual diene, while vinyl norbornene has less than 30%. If you make a crosslinking hydrosilylation reactions, effective network density, the former is 21 × 10 ¹⁹ atoms / cm ³ (residual diene less than 10%), whereas it is the latter 10 × 10 ¹⁹ pieces / cm ³ (the residual diene is about 50%), and the difference further widens.

That is, the present invention is provided with a skin layer made of an olefin-based thermoplastic elastomer having a Shore A hardness in the range of 50 to 100 specified in JIS K 6253. A hard segment mainly composed of a plastic polymer, and a soft segment comprising a crosslinked product of an ethylene-α-olefin-diene copolymer and an organohydrogenpolysiloxane, and the ethylene-α-olefin-diene copolymer Requires vinyl norbornene as a diene component, and the olefin-based thermoplastic elastomer is:
An automotive exterior component comprising 1 to 1,000 parts by weight of a thermoplastic polymer, 100 parts by weight of an ethylene-α-olefin-diene copolymer, and 0.1 to 15 parts by weight of an organohydrogenpolysiloxane.

However, when an olefin-based thermoplastic elastomer is obtained by dynamic crosslinking using an ethylene-α-olefin-diene copolymer containing vinylnorbornene as a diene component, a domain (crosslinked product) constituting a sea-island structure is formed. After the formation, the reaction continues, and the domains bond with each other with the progress of the reaction, and the domains are enlarged, resulting in a problem that the appearance and physical properties of the olefin-based thermoplastic elastomer are impaired. 4. A method for controlling the reaction rate by supplementing a diene other than vinyl norbornene to an ethylene-α-olefin-diene copolymer as a countermeasure method, and (a-1), (a-2), and (a) according to claim 3. The method of terminating the reaction simultaneously with the formation of a domain by supplementing the diene compound shown in -3), (b-1), (b-2),
It is preferable to adopt a method of supplementing the copolymer or polymer composition shown in (b-3) or (b-4) to isolate the domains and inhibit the binding. Accordingly, as a preferred embodiment, the automotive exterior component of the present invention is an invention in which the olefin thermoplastic elastomer obtained by the above method is selected (claim 2), and the olefin thermoplastic elastomer obtained by the above method. (Invention 3) and the invention (invention 4) in which an olefin-based thermoplastic elastomer obtained by the above method is selected. And, they exhibit the mechanical strength shown in Formula 3 of claim 5, which is comparable to the halogen-based polymer composition.

[0015] In the preceding section, the cause of the inferior mechanical strength and weather resistance of the conventional olefin-based thermoplastic elastomer was pointed out. In addition to these, the conventional olefin-based thermoplastic elastomer does not exhibit gloss, There was a drawback that it was easy to stick. However, the olefin-based thermoplastic elastomer used in the present invention, as described below,
These disadvantages can also be ameliorated. First, regarding the former manifestation of gloss, blending the copolymer or polymer composition of claim 4 can solve the problem that gloss is not manifested. Further, as described in claim 6, glossiness (gloss) of 25 or more is exhibited, and it is possible to synchronize with glossiness of the body of the automobile.

With respect to the latter scratching property, there is a known method for improving the slidability, in which a slidability is imparted. However, the olefin-based thermoplastic elastomer used in the present invention has an effect comparable to that of the halogen-based polymer composition. Since it has excellent physical properties, if the slidability is 0.30 or less, the scratch resistance can be remarkably improved. Therefore, by mounting the vehicle exterior component of the present invention according to claim 7 on a vehicle, the durability value can be improved.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The automotive exterior parts of the present invention are composed of an olefin-based thermoplastic elastomer, which contains a hard segment of a thermoplastic polymer and a soft segment of an ethylene-α-olefin-diene copolymer. It has a structure in which a crosslinked product of the union and the organohydrogenpolysiloxane is formed. Hereinafter, individual materials such as a thermoplastic polymer, an ethylene-α-olefin-diene copolymer, and an organohydrogenpolysiloxane constituting the olefin-based thermoplastic elastomer will be described in detail.

First, the thermoplastic polymer constituting the olefin-based thermoplastic elastomer will be described. The thermoplastic polymer is selected from olefin polymers. Here, the olefin-based polymer means a hydrocarbon-based polymer that does not contain elements such as halogen, nitrogen, and phosphorus, and aromatic atomic groups. That is, as the thermoplastic polymer, polyethylene, polypropylene, ethylene-propylene copolymer (block copolymer, random copolymer),
Ethylene-propylene-α-olefin copolymer (block copolymer, random copolymer and so-called polypropylene-based reactor olefin-based thermoplastic elastomer), ethylene-α-olefin copolymer (so-called L-LD
PE or soft olefin), propylene-α olefin copolymer (block copolymer, random copolymer and so-called polypropylene-based reactor olefin-based thermoplastic elastomer), ethylene-polypropylene-based elastomer / ethylene-propylene / polyethylene
(A type of block polypropylene), ethylene-
Acrylic copolymer (so-called EEA etc.), ethylene-vinyl alcohol copolymer (so-called EVOH), copolymer containing propylene other than the above, copolymer containing α-olefin other than the above, including cyclic olefin other than the above Copolymer,
α-olefin polymer, cyclic olefin polymer, copolymer containing ethylene other than the above, maleic acid-modified product,
Examples include polymers selected from the above-mentioned hydroxyl group adducts and the above-mentioned silane-modified products. Among these, in the present invention, a thermoplastic polymer having propylene as a main component,
This is preferable because reliability can be obtained for various physical properties of the olefin-based thermoplastic elastomer. Note that the thermoplastic polymer may be a mixture of several types.

Next, the ethylene-α-olefin-diene copolymer constituting the olefin-based thermoplastic elastomer will be described. As the α-olefin which is a component of the copolymer, propylene having 3 carbon atoms is generally used, and in the present invention, it is preferable to use propylene.

The constitutional ratio of ethylene in the ethylene-α-olefin-diene copolymer is not particularly limited.
10 to 40% low ethylene type or 50 to 70%
Although the high ethylene type may be used, the latter high ethylene type is preferable in consideration of obtaining more excellent physical properties. The composition ratio of α-olefin in the ethylene-α-olefin-diene copolymer is usually in the range of 30 to 70%, but is not particularly limited and is optional. Ethylene-α
The constituent ratio of the diene component in the olefin-diene copolymer is usually in the range of 1 to 8%, but is not particularly limited and is optional.

The ethylene-α-olefin-diene copolymer essentially contains vinyl norbornene as a diene component. As already mentioned, vinylnorbornene has the advantage of high cross-linking efficiency, but the reaction is too fast, which makes it difficult to produce an olefin-based thermoplastic elastomer. Therefore, as a countermeasure, a diene other than vinylnorbornene can be supplemented as a diene component of the ethylene-α-olefin-diene copolymer (claim 2).

That is, the present invention according to claim 2 uses an ethylene-α-olefin-diene copolymer in which the diene component is composed of a multicomponent having vinylnorbornene as an essential component. As the diene component other than vinyl norbornene, an atomic group having a non-conjugated double bond other than vinyl norbornene is selected. Representative examples of the atomic group having a non-conjugated double bond include dicyclonorbornene and ethylnorbornene. Ethylene-
Of the diene total weight in the α-olefin-diene copolymer, the effect of the reaction efficiency is small at the mole fraction of vinyl norbornene of 0.50 or less, and the effect of the reaction control is weak at the mole fraction of 0.95 or more. The ethylene-α-olefin-diene copolymer used has a mole fraction of vinyl norbornene of 0.50% of the total amount of the diene component.
The range is preferably from 0.95 to 0.95, more preferably from 0.70 to 0.90, and even more preferably from 0.75 to 0.90. Therefore, the total amount of the diene component is Xmol equivalent, the total amount of vinylnorbornene is Ymol equivalent, and the total amount of atomic groups having non-conjugated double bonds other than vinylnorbornene is Zmol.
X, Y, and Z are expressed as {Equation 1: Z ≦ Y ≦ 19
Z, Expression 2: Z + Y = X}.

Further, in the present invention, the ethylene-α-olefin-diene copolymer may be a mixture of two or more kinds so as to satisfy the above-mentioned formulas (1) and (2). For example, with respect to 100 parts by weight of a vinylnorbornene-based ethylene-α-olefin-diene copolymer having a diene component content of 5.0% by weight, an ethylnorbornene-based ethylene-α-olefin having the same amount of the diene component is used. Diene copolymer or dicyclopentadiene-based ethylene-α-olefin-diene copolymer is 10 to 1,900
Parts by weight, or a diene component content of 0.5 to 100 parts by weight of a vinyl norbornene-based ethylene-α-olefin-diene copolymer having a diene component content of 5.0% by weight.
19.0% by weight (but usually 1 to 8% by weight) of ethyl norbornene-based ethylene-α-olefin-diene copolymer or dicyclopentadiene-based ethylene-α-olefin-diene copolymer can be mixed, Further, the mixing ratio can be arbitrarily selected. In addition, the method of blending the diene compound described in (a-1), (a-2), and (a-3) described in claim 3 and the method of blending the diene compound described in claim 4 with (b-1), ( b-2), (b-3), (b
-4) Combined use with a copolymer or a polymer composition selected from the above, eliminates the problem that domains are bonded to each other and become huge due to the reactivity of the ethylene-α-olefin-diene copolymer. In the method, ethylene-α
The olefin-diene copolymer is limited to those whose diene component is composed of only vinyl norbornene.

As a guide of the molecule of the ethylene-α-olefin-diene copolymer, Mooney viscosity (for example, ML _{1 + 4} 12
0 ° C.) is generally used, but this is not limited in the present invention. It should be noted that excellent physical properties can be expected with a high Mooney type of 50 or more, and even better with 75 to 120. This viscosity range applies to all the claimed ethylene-α-olefin-diene copolymers in the present invention. Ethylene-α-olefin-diene copolymer is not limited in its properties such as branching and molecular weight distribution,
The fluidity may be modified by the addition of paraffin oil, or it may be reinforced by another polymer or filler.

In the present invention, besides vinyl norbornene, ethyl norbornene and dicyclopentadiene can be used as the diene component of the ethylene-α-olefin-diene copolymer. However, when the residual diene exceeds 30%, Since the durability of the physical properties of the olefin-based thermoplastic elastomer is adversely affected, it is necessary to make the reaction less than 30%, preferably 10% or less at the stage of the dynamic crosslinking at the time of producing the elastomer. Unless the organohydrogenpolysiloxane and catalyst are deactivated by moisture or heat, etc.
As a diene component, vinyl norbornene is superior in durability of physical properties of the olefin-based thermoplastic elastomer. In addition, if the diene component is limited to vinyl norbornene, the residual diene can be reduced to 30% or less at the stage of the dynamic crosslinking during the production of the elastomer, and there is no need to worry about the inactivation of the organohydrogenpolysiloxane and the catalyst. .

In the olefin-based thermoplastic elastomer constituting the skin layer of the automotive exterior component according to the present invention, the constituent ratio of the thermoplastic polymer to the ethylene-α-olefin-diene copolymer is as follows. If the amount of the thermoplastic polymer is less than 1 part by weight with respect to 100 parts by weight of the copolymer, the physical properties of the olefin-based thermoplastic elastomer may be deteriorated or may not exhibit fluidity. Since the soft properties of the olefinic thermoplastic elastomer are lost, the amount is preferably 1 to 1,000 parts by weight, particularly preferably 7 to 500 parts by weight.

The organohydrogenpolysiloxane that dynamically crosslinks the ethylene-α-olefin-diene copolymer includes those having two or more hydrogen atoms directly bonded to silicon atoms in the main chain or at the terminal, cyclic ones, There are various types depending on the length of the siloxane main chain and the form of branching, and a hydrogen atom directly bonded to a silicon atom has two or more at the main chain or at the terminal. There is no limitation in the present invention as long as it is more than one, and it is optional. Further, several kinds of organohydrogenpolysiloxanes may be used in combination. When the amount of the organohydrogenpolysiloxane used is less than 0.1 part by weight, the dynamic crosslinking becomes insufficient, and the amount is more than 15 parts by weight,
In the present invention, the amount is preferably 0.1 to 15 parts by weight, particularly preferably 1 to 8 parts by weight.

Preparation of an olefin-based thermoplastic elastomer requires a hydrosilylation catalyst such as chloroplatinic acid.
Examples of the hydrosilylation catalyst include chelate compounds having a platinum group element, rhodium, titanium or tin as a nucleus. In particular, industrially, platinum chlorides such as chloroplatinic acid, chloroplatinic acid hexahydrate, platinum chelates coordinated with siloxane or polysiloxane containing a vinyl group, non-conjugated double bond hydrocarbons Although a platinum chelate of the compound is used, the type of the hydrosilylation catalyst is not particularly limited in the present invention, and two or more types may be used. The amount of the hydrosilylation catalyst used is less than 0.005 ppm with respect to the ethylene-α-olefin-diene copolymer.If the weight of the metal atom is less than 0.005 ppm, the crosslinking is insufficient, and there is no particular upper limit. 30ppm
Is an appropriate amount, desirably 0.01 to 25 ppm.

According to the present invention, in the dynamic cross-linking of an ethylene-α-olefin-diene copolymer in which the diene component is limited to vinyl norbornene, the formation of a gel due to the bonding of domains is described. To control
At least one diene compound selected from (a-1), (a-2) and (a-3) can be added. (a-
1) The component contains at least 5 acryloyl groups per molecule.
It is a compound having no structural unit of Chemical Formula 1. When the number of acryloyl groups is less than 5, (a-2) described below,
Except for the component (a-3), there is no effect of preventing the formation of crosslinked particles (gel). The number of acryloyl groups is preferably from 10 to 50, and more preferably from 10 to 30. If it is more than 50, cured product particles of the component (a-1) itself may be formed. In addition, the flexibility of the olefin-based thermoplastic elastomer may be reduced. The molecular weight of the component (a-1) is 300
1010,000, preferably 400-5,000. Within this range, it is easy to handle in the production of the olefin-based thermoplastic elastomer composition. (a-1) The addition amount of the component is preferably 0.05 to 50 parts by weight, more preferably 0.1 part by weight, based on 100 parts by weight of the ethylene-α-olefin-diene copolymer.
3 to 15 parts by weight. Within this range, the formation of crosslinked particles (gel) is excellently prevented, and it is economical.

Examples of the component (a-1) include acrylic acid, alcohol, polyol acrylate, polyester acrylate, urethane acrylate and acrylic polymer having at least 5 acryloyl groups in one molecule. To 9 can be exemplified.

[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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Compounds having the structural units of formulas (2) and (3) are also included in the component (a-1) under the condition of 5 or more acryloyl groups, and are preferred compounds. Chemical formulas 10 to 12 are exemplified. Although those having the structural unit of Chemical Formula 1 are also effective in preventing the formation of crosslinked particles under the condition of 5 or more acryloyl groups, the preferable number of acryloyl groups, the molecular weight range, and the addition amount range are remarkably wide. Due to additional properties such as excellent slidability, scratch resistance and cold resistance, (a
-1) Not included in component.

[0038]

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[0039]

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[0040]

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The component (a-2) has 2 to 5 acryloyl groups in the molecule and has a structural unit represented by the following formula (2) or (3), and the number of acryloyl groups is 2 to 5 in one molecule. The feature is that there is a structure forming effect at least.
As the component (a-2), 1,9-nonanediol acrylate, 1,8-nonanediol acrylate, tricyclodecane dimethanol diacrylate, 2-ethyl-
2-propyl-propanediol acrylate,
To 21 and the like.

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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The molecular weight of the component (a-2) is in the range of 200 to 10,000, preferably 235 to 5,000. If it exceeds 10,000, the effect of preventing the formation of crosslinked particles (gel) becomes poor, and if it is less than 200, the compound cannot be constituted by an acryloyl group, chemical formula 2, or chemical formula 3. The addition amount of the component (a-2) is preferably 0.05 to 50 parts by weight, more preferably 0.3 to 20 parts by weight, based on 100 parts by weight of the ethylene-α-olefin-diene copolymer. If it is less than 0.05 parts by weight, there is no effect on the structure formation, and 50
An amount in excess of parts by weight is economically disadvantageous. The component (a-2) has good compatibility with an ethylene-α-olefin non-conjugated diene copolymer rubber composed of vinylnobornene.

The components (a-1) and (a-2) are a highly efficient crosslinking of an ethylene-α-olefin-diene copolymer utilizing an acryloyl group hydrosilylating agent and high-speed reactivity in a short time. It is presumed that the formation of the gel is suppressed by completing the reaction without binding the domains formed by the method (1). Among them, the structure of the portion other than the acryloyl group in the component (a-2),
It is presumed that Chemical Formula 3 provides some advantage, and expresses high-speed reactivity even if the dependence on the number of acryloyl groups is small. The superiority of Chemical formulas 2 and 3 is good compatibility with ethylene-α-olefin-non-conjugated diene copolymer rubber composed of vinylnobornene.

The crosslinked particle (gel) formation inhibitor of the component (a-3) has a structural unit represented by the following chemical formula 1, and is an acryloyl group, a methacryloyl group, a vinyl group, a propenyl group,
It has two or more unsaturated groups selected from a butenyl group and an allyl group in one molecule. The unsaturated group is preferably an acryloyl group, a vinyl group, or an allyl group. Two or more unsaturated groups are required in one molecule, preferably 2 to 5,
000, more preferably 2 to 2,000. If the number of unsaturated groups is less than 2, there is no effect of preventing the formation of crosslinked particles, and the mechanical strength may be reduced and the thermoplastic elastomer may have a sticky feeling. On the other hand, excessive insertion of the unsaturated group promotes an increase in the amount of the crosslinking agent. In Chemical Formula 1, R ² represents the same or different C1 to C3 alkyl group, phenyl group, and xylyl group, and a is a number satisfying 1 ≦ a ≦ 2.4. Although this organopolysiloxane is linear, R ² Si
It may be branched containing O _3/2 or R ² SiO _4/2 units. R ² is preferably a highly versatile methyl group or phenyl group. The molecular weight of the component (a-3) is 500 to 1,000,000.
, Preferably 1,000 to 700,000. 1,000,00
If it exceeds 0, uniform dispersion with the components (A) and (B) may be difficult. The addition amount of the component (a-3) is based on 100 parts by weight of the ethylene-α-olefin-diene copolymer.
0.05 to 600 parts by weight, preferably 0.5 to 400 parts by weight, more preferably 1 to 400 parts by weight. If the amount is less than 0.05 part by weight, the effect of preventing the formation of crosslinked particles (gel) is poor. If the amount exceeds 600 parts by weight, the mechanical strength is reduced, and the content of the phenyl group and the unsaturated group is high (a-3). Decrease. The component (a-3) is not only an acryloyl group that exhibits high-speed reactivity with a hydrosilylation agent or an organic peroxide, but also has many unsaturated groups. It is presumed that the olefin-diene copolymer also has a splitting and dispersing action (action) of the crosslinked product. Specific examples of the component (a-3) include:
3 is exemplified.

[0054]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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The above (a-1), (a-2) and (a-3)
These components may be used in combination in the same component, or in combination between these components. When used together in the same component, it is preferable that the total amount is a preferable addition amount of each component. In the case of combined use between components, (a-1)
When (a-2) is used in combination, it is preferable to adjust the total thereof to be 0.05 to 50 parts by weight based on 100 parts by weight of the ethylene-α-olefin-diene copolymer. In the case of the combination containing (a-3), the sum of (a-1) and (a-2) does not exceed 50 parts by weight, and (a-1),
The total of (a-2) and (a-3) is 0.05 to 600 parts by weight, preferably 0.5 to 450 parts by weight, and more preferably 1 to 400 parts by weight.
Adjust so that it becomes parts by weight.

The olefin-based thermoplastic elastomer used in the present invention includes the above (a-1), (a-2), (a-
(B-1), (b-2), (b-)
It is preferable to add at least one polymer selected from the components (3) and (b-4). By adding the above polymer, the prevention of the formation of crosslinked particles (gel) is not hindered, and a product having improved mechanical strength, rubber elasticity, and cold resistance can be obtained. Also,
Effects such as imparting gloss and improving moldability (deformable extrusion, high-speed extrusion, high fluidity, etc.) are exhibited.

The component (b-1) has a density of 0.85 to 0.91 g /
cm ^{3 is} an ethylene-α-olefin copolymer, and ethylene and at least one kind of C3 to C8 are preferable.
As the component (b-1), 1) a uniform linear ethylene copolymer having a molecular weight distribution Mw / Mn of about 2: “TA” manufactured by Mitsui Chemicals, Inc.
FMERP ”(trade name),“ Exa ”manufactured by Exson Chemical Company
ct ”(trade name), 2) Heterogeneous linear ethylene copolymer:
"Excellen VL" (trade name) manufactured by Sumitomo Chemical Co., "LUMITAC" (trade name) manufactured by Tosoh Corporation, "Attane" (trade name) manufactured by Dow Chemical Company, 3) Substantially linear with long chain branching Ethylene copolymer: Dow Chemical Company
Co., Ltd. ethylene 1-octene copolymer POE "Engage.
EG ”(trade name), POP“ AFF ”manufactured by Dow Chemical Company
INITY "(trade name), 4) Ethylene copolymer having strong random (amorphous rubber-like) properties: ethylene-propylene copolymer and ethylene-butene-1 copolymer. Alternatively, a composition obtained by dispersing the ethylene copolymer having strong randomness in 4) in propylene at a content of 50% by weight or more may be used. Specifically, "C" manufactured by Montell-JP
Reactor-made olefin-based thermoplastic elastomers such as "atalloy" (trade name), "Adsyl" (trade name) manufactured by Montell-JP, and "PER" (trade name) manufactured by Tokuyama Corporation are suitable. Others 5) CESR “DYNARON6200P” (trade name) manufactured by JSR, which is a product of living anion polymerization.

Non-crystalline propylene-α of component (b-2)
The olefin copolymer is preferably 30 to 45% by weight of FPO having an atactic ratio of more than 5% by weight in propylene. For example, there is "REXflex" (trade name) manufactured by Huntsman Corporation in which 2 to 15% by weight of ethylene is copolymerized.

The hydrogen-styrene random copolymer (b-3) is obtained by hydrogenating a random styrene-conjugated diene copolymer. Styrene-butadiene copolymer hydrogenated product Examples include HSBR “DYNARON1320P” (trade name) and “DYNARON1321P” (trade name) manufactured by JSR Corporation, and styrene-isoprene copolymer hydrogenated product.

The hydrogenated styrene block copolymer of the component (b-4) is obtained by hydrogenating a copolymer comprising a styrene polymer block and a conjugated diene polymer block. As the conjugated diene, butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-3,4
-Butadiene and the like. Asahi Kasei Corporation's SEBS "Tuftec" as a hydrogenated styrene-based block copolymer
(Trade name), Asahi Kasei Corp. SBBS "ToughTech P Series" (trade name), Shell-JP SEBS "Clayton"
(Trade name), Kuraray SEPS “Septon” (trade name), and JSR SEBC “DYNARON4600P” (trade name).

The above (b-1), (b-2), (b-
The components 3) and (b-4) are used alone or in combination. (b-1), (b-2), (b-3), (b-4)
Each component of the above, during dynamic crosslinking, promotes the formation of the structure and suppresses the formation of a gel, but this action is 1 part by weight or more based on 100 parts by weight of the ethylene-α-olefin-diene copolymer. The effect is exhibited by the blending amount. Also, among automotive exterior parts, flash mount moldings and roof moldings are desired to have a glossy design, but if they are blended in an amount of 30 parts by weight or more, the flow characteristics as a domain-containing polymer composition will be reduced. Even if it is extruded, the glossiness is expressed in the range of 15 to 40 as described in claim 6.
(Conventional olefin-based thermoplastic elastomers have a gloss of 1
0 or less). However, if the content exceeds 500 parts by weight, the absolute amount of the crosslinked product of the ethylene-α-olefin-diene copolymer that is a soft segment is reduced, so that the significance as an olefin-based thermoplastic elastomer is weakened. The nature will deteriorate. Therefore, in the present invention, the amount of each of the components (b-1), (b-2), (b-3) and (b-4) is 100 parts by weight of the ethylene-α-olefin-diene copolymer. Is preferably 1 to 500 parts by weight, particularly
A range of 50 to 300 parts by weight is preferred.

It is desired that parts such as weather strips among the exterior parts for automobiles have slidability. According to claim 7 of the present invention, silicone-based excellent physical properties and silicone-modified parts are used. A method of imparting slidability to the material itself by blending a slidable substance such as a thermoplastic polymer or a silicone-modified elastomer, such as a crushed thermoplastic polymer or rubber or a spherical polymer of a polymer. By adopting a method of reducing the contact area on the surface of an automobile exterior component by mixing particles to roughen the surface, a dynamic friction coefficient of 0.3 or less is developed. In addition, the measurement of the dynamic friction coefficient is as follows.
The test was carried out under the conditions of a glass plate having a load of 100 g and a speed of the slider of 1 m / min.

In the present invention, the addition amount of the above-mentioned slidable substance and particles is not limited. In the case of the above-mentioned compounding recipe, the addition amount of the slidable substance is based on 100 parts by weight of the olefin-based thermoplastic elastomer. When the amount is less than 0.1 part by weight, the slidability cannot be exhibited, and
Parts by weight are excessive, and silicone-modified thermoplastic polymers and silicone-modified elastomers are excessive at 100 parts by weight.Therefore, 0.1 to 10 parts by weight of silicone oligomer is used, and silicone-modified thermoplastic polymers and silicone-modified The elastomer is suitably used in an amount of 0.1 to 100 parts by weight. In the case of the above formulation, the addition amount of the particles is not able to exhibit the slidability if it is 1.0 part by weight or less with respect to 100 parts by weight of the olefin-based thermoplastic elastomer, and if the amount exceeds 300 parts by weight, the retention of the particles is reduced. 1.0 to 300 parts by weight is appropriate because it becomes difficult. The average particle size of the particles is also not particularly limited, but if the particle size is 5 μm or less, the contact area on the surface of the component cannot be reduced because it does not protrude from the thermoplastic elastomer. , 5 to 3,000 μm is appropriate.

Further, the olefin-based thermoplastic elastomer used in the present invention may contain a paraffin-based oligomer, whereby flexibility can be imparted. In addition, the oligomer spreads throughout the olefin-based thermoplastic elastomer at the time of molding, and also has a secondary function of lowering the viscosity of the olefin-based thermoplastic elastomer itself. In the present invention, the timing of blending the oligomer is not limited, but it is preferable to perform the oligomer in the first step. In recent years, a so-called oil-extended elastomer obtained by blending the oligomer in a process stage 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 amount of the oligomer is ethylene-α-olefin-diene copolymer.
If it exceeds 150 parts by weight with respect to 100 parts by weight, it bleeds, and if it is not at least 5 parts by weight, the effect will not appear so much,
5 to 150 parts by weight, in particular, 10 to 120 parts by weight is desirable,
It is not limited.

The olefin-based thermoplastic elastomer used in the present invention may be blended with materials having the following modifying effects, and these materials may be added before molding into exterior parts for automobiles. . In the olefin-based thermoplastic elastomer used in the present invention, the olefin-based thermoplastic elastomer is used to improve fluidity, adjust mechanical properties and hardness, and impart adhesion to metals and different kinds of polymers. The other polymer can be supplemented to the olefin polymer constituting the above. The polymer is not limited to an olefin-based polymer, and may be a monomer, oligomer, or inorganic substance. For example, if a maleic acid-modified product or a hydroxyl group-added product is added, adhesion to a metal or a different kind of plastic can be imparted, and if a silane-modified product is added, slidability can be imparted. The olefinic thermoplastic elastomer may contain a paraffinic oligomer, which can impart flexibility. The oligomer spreads throughout the polymer composition during molding, and the viscosity of the composition itself is reduced. It also has the secondary function of lowering. further,
Depending on the application, powders exhibiting slidability, pigments and design effects, or polymers, fillers and oligomers for supplementing physical properties, and various stabilizers for supplementing durability can also be added. The olefin-based thermoplastic elastomer used in the present invention needs to have a Shore A hardness specified in JIS K 6253 in the range of 50 to 100. The reason is that if the hardness is less than 50, the material is impossible, and if it exceeds 100, elastic characteristics such as dispersing the stress even when an external force is applied are not exhibited.

The thermoplastic elastomer constituting the skin layer of the automotive exterior part of the present invention is manufactured through the following manufacturing steps. The production stage comprises, as a first step, a process for obtaining a mixture as a material preparation, and as a second step, a process for dynamically cross-linking the mixture. The details of each step are described below. The first step is the preparation of the material, using a kneader such as a pressure kneader, a Banbury mixer, a two-roll, single-screw or twin-screw extruder, a thermoplastic polymer, an ethylene-α-olefin-diene copolymer, Mixing of an organohydrogenpolysiloxane or the like is performed. Since the temperature condition at that time needs to be a temperature condition equal to or higher than the flow start temperature of the thermoplastic polymer, a kneading history at a minimum of 80 ° C. is required, and the upper limit is at most considering the durability of the material. Since the temperature is 300 ° C. or lower, the temperature is preferably in the range of 80 to 300 ° C., particularly, 180 to 250 ° C.

The second step is a process of dynamically cross-linking the mixture, which is performed by providing a heat history (product of temperature and time) necessary for the cross-linking reaction and a high shear dynamic environment.
The particle size of the generated domain depends on the shearing as a dynamic condition.If the maximum shear rate is less than 50 sec ⁻¹ , domain formation is poor, and if it exceeds 2,000 sec ⁻¹ , it exceeds the durability of the device. Therefore, the temperature condition is preferably in the range of 80 to 300 ° C. as in the first step at the maximum shear rate of 50 to 2,000 sec ⁻¹ . The kneading equipment used in this step is optimally a twin-screw extruder capable of providing a higher maximum shear rate. At that time, it is preferable that the filling rate is more than 30 to 40%.

The olefin-based thermoplastic elastomer used in the present invention requires a hydrosilylation catalyst. The step of applying the catalyst 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. However, if charging is performed in the second step, there is no need to pay attention to this, so it is more reasonable to charge in the second step. Examples of the method for adding the hydrosilylation catalyst include a method in which the catalyst is dispersed or dissolved in a solvent, or a method in which the catalyst is incorporated in an inorganic or organic powder and charged.

The olefin-based thermoplastic elastomer used in the present invention is preferably formulated as (a-1) to (a-3)
Although the components and the effect of accelerating the reaction by the components (b-1) to (b-4) are used, the step of throwing these components is also used.
As in the case of the hydrosilylation catalyst, charging in the second step is desirable. The method for adding the above components may be the same as that for the hydrosilylation catalyst.

In the above-mentioned method for producing an olefin-based thermoplastic elastomer, the above two steps may be carried out separately, or may be carried out collectively by one apparatus. For example, by changing the shaft segment (shaft shape) and temperature conditions in each zone of the twin-screw extruder, the materials may be sequentially charged, and the first step is performed by a kneader, a Banbury mixer, or a twin-screw extruder. Thereafter, the second step may be performed in another twin-screw extruder, which is optional. In addition, antioxidants taking into account the dynamic thermal history during the production and molding of olefinic thermoplastic elastomers, stabilizers to improve weather resistance and durability, conductivity, flame retardancy and sliding If it is necessary to add a filler or additive for imparting properties, or a coloring agent, it is better to mix in the first step or the second step,
There is also a method in which a third step is provided and then input. Further, the reaction rate can be adjusted by using a compound having a triple bond carbon or a cyclic polysiloxane in combination with a hydrosilylation reaction retarder.

The olefin-based thermoplastic elastomer obtained by the above-mentioned production method is prepared into a bulk, a pail, a sheet, a pellet, a powder, and the like. Exterior parts are obtained. Hereinafter, the method for forming the automotive exterior part of the present invention will be described in detail. The olefin-based thermoplastic elastomer used in the automotive exterior component of the present invention is produced by a hydrosilylation reaction. Unless the organohydrogenpolysiloxane and the hydrosilylation catalyst are deactivated, the olefin-based thermoplastic elastomer is produced. Since the residual diene is reduced even after the completion of the dynamic crosslinking at the time, weather resistance is excellent.

As described above, the exterior parts for automobiles are composed of a skin layer, a functional part and a main body, and the exterior parts for automobiles according to the present invention comprise a polymer composition constituting the skin layer. These are specified for the thermoplastic elastomers described in Nos. 7 to 7. Therefore, the materials constituting the functional part and the main body are not limited and can be arbitrarily selected. For example, various materials such as a crosslinked rubber, a thermoplastic elastomer composed of an α-olefin-ethylene-diene copolymer containing ethyl norbornene as a diene component, a thermoplastic elastomer crosslinked with a peroxide, and a thermoplastic elastomer crosslinked by a hydrosilylation reaction. Can be selected.

The exterior parts for automobiles of the present invention can be formed by extrusion molding,
Utilizing the thermoplastic properties of materials such as injection molding, rotational molding, press molding, calendar molding, blow molding, etc.
Although it can be obtained by molding into an arbitrary shape, it is desirable to produce it by extrusion molding.

Among the exterior parts for automobiles, parts provided with a design by gloss, color, and unevenness, and parts having a function relating to surface characteristics such as slidability required for a portion in contact with glass are skins having these functions. It may be a composite of a layer and a main body constituting the interior, or may be composed of a polymer composition having several different characteristics. In such a case, in the present invention, for example, addition of a coloring pigment, addition of a material for improving gloss such as an amorphous polymer, addition of a material for reducing gloss such as particles, silicone-based oligomer and other silicone-based Addition of materials such as compounds and particles imparting slidability can be appropriately performed. It is preferable that not only the skin layer but also the main body constituting the interior of the automotive exterior component of the present invention is made of the olefin-based thermoplastic elastomer.

[0086] For exterior parts for automobiles such as weather strips, metal can be used as a core material, and the skin layer can be implanted with nylon fibers or the like. In this case, since a composite with a different material is used, a member such as a primer may be used, or the above-mentioned olefin-based thermoplastic elastomer may be provided with adhesiveness.

The following is a partial example of a method for producing an automotive exterior part of the present invention. The modular wind mall (Figure 1)
A main body 2 made of glass is fixed to a polymer (skin layer) 1 constituting a glass window, and the automobile is attached to a body steel plate 4 with an adhesive 3 as shown in FIG. The olefin-based thermoplastic elastomer used in this part is manufactured by an insert method using an injection molding machine.

In the side molding (FIG. 2), the skin layer 1 is made of iron or P.
It is integrated with the core material 2 made of OM.
As shown in FIG. 7, the body steel plate 4 is mounted by fitting. The olefin-based thermoplastic elastomer used in this part is produced by an extruder. The skin layer 1 of the current side molding may be coated in order to synchronize with the gloss of the body, but the olefin-based thermoplastic elastomer according to claim 4 used in the present invention has a gloss characteristic. You don't need it because it's good.

The flash mount molding (FIG. 3) has a skin layer 1 formed on a main body 2 made of a steel wire and a polymer, and as shown in FIG. Parts. The glass plate 5 is prevented from falling off by the adhesive 3. The above-mentioned olefin-based thermoplastic elastomer used in the present component is indispensable to be used as a polymer composition constituting the skin layer 1, but can also be used for the main body 2. This part is produced by an extruder in the same manner as the side molding. In addition, since it is desired to exhibit gloss similarly to the side molding, the use of the olefin-based thermoplastic elastomer described in claim 4 which has excellent gloss characteristics is optimal.

Roof molding (FIG. 4) and wind molding
In FIG. 5, the skin layer 1 is integrated with a core material 2 made of stainless steel, the roof molding is fixed by welding as shown in FIG. 9, and the wind molding is a body steel plate as shown in FIG. 4 is attached by fitting.
This part is produced by an extruder in the same manner as the side molding. In addition, since it is desired to exhibit gloss similarly to the side molding, the use of the olefin-based thermoplastic elastomer described in claim 4 which has excellent gloss characteristics is optimal.

[0091]

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 composition obtained by the Example and the comparative example is as follows. Hardness is JIS K 6253 (Shore A), elongation,
The breaking strength was in accordance with JIS K 6251, the compression set was in accordance with JIS K 6262, and the rebound resilience was in accordance with the method described in JIS K 6255 for tensile breaking strength.

(Example 1 and Comparative Example 1) 10 parts by weight of polypropylene (2000C, trade name, manufactured by Idemitsu Petrochemical Co., Ltd.) and polyethylene (Hizex, manufactured by Mitsui Chemicals, Inc.) 6800, trade name) 10 parts by weight, paraffinic process oil (Mitsui Chemicals, Lucant 2
00, trade name) 10 parts by weight, wet silica (Nippon Silica Industry Co., Nipsil LP, trade name) 15 parts by weight, antioxidant (Asahi Denka Kogyo Co., Ltd., AO-60, trade name) 1 part by weight, organo Hydrogen polysiloxane (KE, manufactured by Shin-Etsu Chemical Co., Ltd.)
-1950A, 10 parts by weight) was charged into a pressure kneader adjusted to a temperature of 150 ° C., and kneaded at 30 rpm for 10 minutes.
Polypropylene (2000C, trade name, manufactured by Idemitsu Petrochemical Co., Ltd.) 30
Parts by weight and 2 parts by weight of a black pigment, and kneaded for 10 minutes.
Various types of kneaded materials 1-1, 1-2, and 1-3 were obtained. And
When these kneaded materials were introduced into a twin-screw extruder (temperature: 200 ° C., 300 rpm, shear rate: about 1,200 sec ⁻¹ , chloroplatinic acid having a platinum amount of 200 ppm was dropped from the vent hole) and dynamically crosslinked,
Three types of thermoplastic elastomers were obtained from the kneaded materials 1-1, 1-2, and 1-3. Then, each moldability and physical properties were evaluated, and the results are as shown in Table 2. Then, the hardness A obtained by the above test was substituted into the following equation 6 to calculate X, and the result was compared with the breaking strength (Ts). According to the table, Comparative Example 1-1 composed of ENB (ethyl norbornene) EPDM was
> Ts, which was not very good in physical properties. On the other hand, in Example 1-1 in which the diene was composed of EPDM containing VNB (vinyl norbornene) as a constituent component, since Ts ≒ X, it could be evaluated to be equivalent to the chlorine-based polymer composition,
Since Example 1-2 had Ts> X, it was confirmed that it had physical properties superior to those of the chlorine-based polymer composition. Formula 6: X = A ÷ 2-20 Further, a sheet having a thickness of 1.0 mm and a size of 50 × 100 mm is prepared from the above three kinds of thermoplastic elastomers, and these sheets are exposed to carbon arc light at 80 ° C. After exposure for 1,500 hours, the results shown in Table 4 were obtained. From Tables 2 and 4, the thermoplastic elastomer obtained from the ENB-based EPDM (Comparative Example 1-1) was significantly deteriorated by the above exposure. On the other hand, the thermoplastic elastomer obtained from EPDM containing VNB as a component (Examples 1-1 and 1-2) hardly deteriorated and maintained physical properties before exposure.

[0093]

[Table 1]

[0094]

[Table 2]

[0095]

[Table 3]

[0096]

[Table 4]

(Example 2) In a production line in which two extruders (extruder A and extruder B) are connected by one die, the extruder A is provided with the thermoplastic elastomer of Example 1-1. Of the thermoplastic elastomer of Example 1-2 into the extruder B to produce a flash mount molding shown in the sectional view of FIG. In the obtained flash mount molding, the skin layer 1 was the same as that of Example 1.
-1, the main body 2 is the same as that of Example 1-2.
Of a thermoplastic elastomer. Cut the above flush mount molding into a length of about 50mm,
Exposure to carbon arc light for 1,500 hours under the following conditions. Then, when the skin layer 1 of the exposed flash mount molding was visually observed, almost no change in appearance was observed with respect to the unexposed flash mount molding. Therefore, it was confirmed that the exterior component according to the present invention was excellent in weather resistance.

Comparative Example 2 In the production line of Example 2, the extruder A contains the thermoplastic elastomer pellets of Comparative Example 1-1, and the extruder B contains the thermoplastic elastomer pellets of Example 1-2. And a flash mount molding shown in the sectional view of FIG. 3 was produced. In the obtained flash mount molding, the skin layer 1 was composed of the thermoplastic elastomer of Comparative Example 1-1, and the main body 2 was composed of the thermoplastic elastomer of Example 1-2. The flash mount molding was cut into a length of about 50 mm, and exposed to a carbon arc light for 1,500 hours in an environment of 80 ° C. When the exposed skin layer 1 of the flash mount molding was visually observed, countless fine cracks were present and whitened.

(Example 3, Comparative Example 3) ENB type E shown in Table 1
EPDM-1 which is a PDM and EPDM which is a VNB-based EPDM shown in Table 5
-4, and kneaded in the same manner as in Example 1 and Comparative Example 1 to obtain seven types of kneaded products 3-1 to 3-7 shown in Table 6.
And a twin screw extruder (temperature 200 ° C, 300rpm, shear rate is about
The chloroplatinic acid having a platinum amount of 1,200 sec ^-1 and 20 ppm was dynamically crosslinked with a vent hole) to obtain seven kinds of thermoplastic elastomers. Table 7 shows the evaluation results of the moldability and physical properties. As a result, Comparative Example 3-1 obtained from the kneaded product 3-1 had physical properties indicating that crosslinking was not sufficiently performed because the amount of the catalyst was insufficient. Kneaded material 3-
Comparative Example 3-2 obtained from Example No. 7 had low mechanical properties such as breaking strength and elongation, poor moldability, and had gel-like bumps and poor appearance. This inconvenience can be considered to be due to the fact that the reaction is too fast and the structure formation has not been developed, and that the thermoplastic component does not function and the mechanical properties are inferior. On the other hand, the thermoplastic elastomer according to the formulation of the present invention (Examples 3-1 and 3
-2, 3-3, 3-4, 3-5, and 3-6) had excellent elastic and mechanical properties, and also had good moldability and appearance. Therefore, according to the formulation of the present invention, even when a VNB-based EPDM is used, no adverse effect on the structure formation occurs, and excellent physical properties can be obtained. Then, the hardness A obtained by the above test is substituted into Equation 6 to calculate X, and the breaking strength is calculated.
Comparison with (Ts) was as shown in Table 8.
According to the table, Comparative Examples 3-1 and 3-2 had X> Ts and were not excellent in physical properties. On the other hand, Example 3-1
Since 3-5 was Ts ≒ X, it could be evaluated to be equivalent to the chlorine-based polymer composition. Examples 3-2 and 3
Since Ts> X, -3 and 3-4 were confirmed to have physical properties superior to those of the chlorine-based polymer composition.

[0100]

[Table 5]

[0101]

[Table 6]

[0102]

[Table 7]

[0103]

[Table 8]

(Example 4, Comparative Example 4) The materials having the contents shown in Table 9 were put into a pressurized kneading apparatus (Laboplast Mill, trade name, manufactured by Toyo Seiki Co., Ltd., capacity: 50 cc) whose temperature was adjusted to 180 ° C. Then, after kneading for 15 minutes, 10 kinds of compounds shown in Table 10 are added in parts by weight shown in the same table, and after 30 seconds, chloroplatinic acid having a platinum amount of 20 ppm is added, and then kneading is performed for 7 minutes. hand,
10 kinds of kneaded materials were obtained. Table 11 shows the evaluation results of the moldability and the physical properties. Table 10
In the table, the classification of components indicates which of a-1, a-2, and a-3 described in claim 2 is applicable. As the compound used in Comparative Example 4-1, a compound not corresponding to the content of Claim 2 was selected.
As a result of the above test, Examples 4-1, 4-2, 4-3, 4-
In 4, 4-5, 4-6, 4-7, 4-8, and 4-9, the torque starts increasing immediately after the catalyst is charged, and
After ~ 3 minutes, the maximum value (1.5-1.8 times the torque at the time of catalyst input) was exhibited, and after 4-5 minutes, it decreased to the level before the input, and the torque value hardly changed thereafter. On the other hand, Comparative Example 4-
In No. 1, the maximum value of the increase in torque (1.4 times the torque at the time of catalyst input) was observed during 0.5 to 1 minute, but the level decreased to the level before the input and the torque value hardly changed thereafter. As a result, Examples 4-1, 4-2, 4-3, 4-4, 4-
5, 4-6, 4-7, 4-8, and 4-9 had excellent elastic and mechanical properties, and also had good moldability and appearance.
Therefore, according to the formulation of the present invention, even when a VNB-based EPDM is used, no adverse effect on the structure formation occurs, and excellent physical properties can be obtained. It should be noted that the process of forming the structure can be seen from the transition of the increase in torque after the catalyst has been charged.
On the other hand, in Comparative Example 4-1, the mechanical properties such as breaking strength and elongation were low, the moldability was not good, and the appearance was poor due to gel-like bumps. This inconvenience can be considered to be caused by the fact that the reaction is too fast and the structure formation has not been developed, and the thermoplastic component does not function and the mechanical properties are inferior. It should be noted that the process of forming the structure can be seen from the transition of the increase in torque after the catalyst has been charged. Then, the hardness A obtained by the above test is substituted into Equation 6 to calculate X, and the breaking strength (T
Table 12 shows a comparison with s). From the table, Examples 4-1, 4-2, 4-3, 4-4, 4-
5, 4-6, 4-7, 4-8, and 4-9 satisfied Ts> X and were confirmed to have physical properties superior to chlorine-based polymer compositions. On the other hand, Comparative Example 4-1 had X> Ts and was not so excellent in physical properties.

[0105]

[Table 9]

[0106]

[Table 10]

[0107]

[Table 11]

[0108]

[Table 12]

Example 5 and Comparative Example 5 The materials shown in Tables 13 and 14 were kneaded for 10 minutes to obtain 11 kinds of kneaded materials. And these kneaded materials are twin-screw extruder (temperature 200 ° C, 300 rp
m, a shear rate of about 1,200 sec ^-1 , and chloroplatinic acid having a platinum amount of 200 ppm was dropped into the vent hole) to dynamically crosslink. As a result, 11 types of thermoplastic elastomers were obtained. When the moldability and physical properties were evaluated,
As shown in FIG. Then, the hardness A obtained by the above test was substituted into Equation 6 to calculate X and compared with the breaking strength (Ts). Comparative Example 5-1 had X> Ts and was not so excellent in physical properties. In addition, mechanical properties such as breaking strength and elongation were low, moldability was not good, and gel-like bumps were present and appearance was poor. This inconvenience can be considered to be due to the fact that the reaction is too fast and the structure formation has not been developed, and that the thermoplastic component does not function and the mechanical properties are inferior. Example 5-1,
5-2, 5-3, 5-4, 5-5, 5-6, 5-7, 5
-8 is Ts> X, and according to the formulation of the present invention, VNB EPDM
No adverse effect on the formation of structure was observed even when the compound was used, and excellent physical properties could be obtained, and it was confirmed that they had physical properties superior to those of the chlorine-based polymer composition. In Comparative Example 5-2, too much polymer was added, and the moldability was not good. In addition, the physical properties were not so good due to the trouble of the moldability. In Comparative Example 5-3, it was found that the selection of the polymer was inappropriate and the moldability and physical properties were adversely affected.

[0110]

[Table 13]

[0111]

[Table 14]

[0112]

[Table 15]

[0113]

[Table 16]

Example 6 Examples 5-1 and 5-2 and 5-
The thermoplastic elastomer (TPV) pellets of 3, 5-4, 5-6, 5-7, and 5-8 were charged into an extruder to produce a side molding shown in FIG. In the obtained side molding, the skin layer 1 is constituted by the above-mentioned thermoplastic elastomer. The glossiness of the obtained eight side moldings was measured, and the results were as shown in Table 17. Although the glossiness of the conventional olefin-based thermoplastic elastomer is about 10, all of the eight side moldings described above exceeded the conventional olefin-based thermoplastic elastomer. In particular, the side moldings produced from Examples 5-3, 5-4, 5-6, 5-7, and 5-8 had high gloss and excellent design. The above side molding was cut into a length of about 50 mm, and exposed to a carbon arc light for 1,500 hours in an environment of 80 ° C. Then, when the skin layer 1 of the exposed side molding was observed visually, almost no change in the appearance was observed with respect to the unexposed side molding. Therefore, it was confirmed that the exterior component according to the present invention was excellent in weather resistance.

[0115]

[Table 17]

Example 7 100 parts by weight of the thermoplastic elastomer pellets of Example 5-4 were mixed with additives for imparting slidability shown in Table 18, and then charged into an extruder. The roof molding shown in FIG. 6 was produced. In the obtained roof molding, the skin layer 1 is constituted by the above-mentioned thermoplastic elastomer. Then, the dynamic friction coefficient and glossiness of the obtained four points of the roof molding were measured, and the results are as shown in Table 19. The roof molding made of an olefin-based thermoplastic elastomer not containing the above additives is
Although the dynamic friction coefficient was 1.26, Examples 7-1 and 7-
2, 7-3 and 7-4 all had modified slidability. In addition, in all cases, the gloss exceeds 30,
The design was also excellent. Cut the above side molding into a length of about 50 mm, and apply carbon
Exposure to black light for 1,500 hours. Then, when the skin layer 1 of the exposed side molding was observed visually, almost no change in the appearance was observed with respect to the unexposed side molding. Therefore, the exterior parts according to the present invention are:
It was confirmed that the material had excellent weather resistance.

[0117]

[Table 18]

[0118]

[Table 19]

[0119]

According to the present invention, the present invention has mechanical properties equal to or higher than those of the halogen-based polymer composition, and
It is possible to provide an automotive exterior component made of a highly reliable olefin-based thermoplastic elastomer having durability and weather resistance capable of maintaining the mechanical properties for a long period of time.

[Brief description of the drawings]

FIG. 1 is a sectional view of a modular window molding.

FIG. 2 is a sectional view of a side molding.

FIG. 3 is a sectional view of a flash mount molding.

FIG. 4 is a sectional view of a roof molding.

FIG. 5 is a sectional view of a wind molding.

FIG. 6 is a diagram showing a state in which a modular window molding is mounted on an automobile.

FIG. 7 is a diagram showing a state where the side molding is mounted on an automobile.

FIG. 8 is a view showing a state in which the flash mount molding is mounted on an automobile.

FIG. 9 is a view showing a state where a roof molding is mounted on an automobile.

FIG. 10 is a view showing a state in which a wind molding is mounted on an automobile.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Skin layer 4 ... Body steel plate 2 ... Main body (core material) 5 ... Glass plate 3 ... Adhesive material 6 ... Door steel plate

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08L 83/05 C08L 83/05 83/06 83/06 83/07 83/07 101/00 101/00 (72) Invention Person Nakajiro Yoshida 1-406-1, Yoshino-cho, Saitama-shi, Saitama, Japan Shin-Etsu Polymer Co., Ltd., Tokyo plant (72) Inventor Shuyasu Noda 1-1406-1, Yoshino-cho, Saitama-shi, Saitama, Japan F-term in Shin-Etsu Polymer Co., Ltd., Tokyo plant ( reference) 3D023 AA01 AB01 AC01 AD05 AD22 4F100 AA20 AB03B AG00B AK01A AK02A AK03A AK04 AK07 AK13A AK25A AK52A AK62A AK66A AK75 AK75A AL02A AL05A AL09A AT00B BA02 CA06 EH17 EJ05A GB32 JB16A JK01 JK02 JK03 JK07 JK08 JK12A JL00 JL01 JL09 YY00A 4J002 BB01W BB03W BB05W BB07W BB12W BB14W BB15W BB15X BB175 BB20W BB21W BB22W BG055 BP02W CP04Y CP144 CP164 EH076 ET006 EU196 FD146 GN00 4J100 AA01Q AA02P AA03Q AS15R CA05 HA53 HC34 HC63 JA28

Claims (7)

[Claims] 1. The Shore A hardness specified in JIS K 6253 is
A skin layer made of an olefin-based thermoplastic elastomer in the range of 50 to 100 is provided, and the olefin-based thermoplastic elastomer includes a hard segment mainly containing a thermoplastic polymer and an ethylene-α-olefin-diene copolymer. The ethylene-α-olefin-diene copolymer is composed of a soft segment composed of a crosslinked polymer and an organohydrogenpolysiloxane, and the ethylene-α-olefin-diene copolymer includes vinylnorbornene as a diene component.The olefin-based thermoplastic elastomer includes: Thermoplastic polymer 1-1,
000 parts by weight, ethylene-α-olefin-diene copolymer 1
00 parts by weight, organohydrogenpolysiloxane 0.1
Automotive exterior parts characterized by comprising up to 15 parts by weight. 2. When the total amount of the diene component is Xmol equivalent, the total amount of vinylnorbornene is Ymol equivalent, and the total amount of atomic groups other than vinylnorbornene having a non-conjugated double bond is Zmol equivalent, ethylene-α-olefin-diene is obtained. The automotive exterior component according to claim 1, wherein the copolymer satisfies the following formulas (1) and (2). Formula 1: Z ≦ Y ≦ 19Z Formula 2: Z + Y = X 3. The diene component of the ethylene-α-olefin-diene copolymer is composed of only vinyl norbornene, and the ethylene-α-olefin-diene copolymer is composed of an organohydrogenpolysiloxane and the following (a)
The automotive exterior component according to claim 1, wherein the exterior component is cross-linked with at least one diene compound selected from (1), (a-2) and (a-3). (a-1) a compound having at least 5 acryloyl groups in the molecule and having no structural unit of formula 1 (a-2) having 2 to 5 acryloyl groups in the molecule and having a structure of formula 2 or 3 Compound having a unit (a-3) A compound having at least two unsaturated groups selected from an acryloyl group, a methacryloyl group, a vinyl group, a propenyl group, a butenyl group, and an allyl group, and having a structural unit of the formula 1) Embedded image Embedded image 4. The following (b-1), (b-2) and (b) with respect to 100 parts by weight of the ethylene-α-olefin-diene copolymer.
The automotive exterior part according to claim 3, wherein 1.0 to 510 parts by weight of at least one copolymer or polymer composition selected from (3) and (b-4) is blended. (b-1) ethylene-α having a density of 0.86 to 0.91 g / cm ³
Olefin copolymer (b-2) Non-crystalline propylene-α olefin copolymer (b-3) Polymer composition in which ethylene-α olefin copolymer is dispersed in propylene (b-4) Hydrogenated system Block copolymer 5. The breaking strength of the olefinic thermoplastic elastomer satisfies the relationship shown in the following formula 3, and the breaking strength satisfying this relationship is an evaluation method (measurement specified in JIS K 6266 irradiating with a sunshine weather meter for 1,000 hours). The automotive exterior part according to any one of claims 1 to 4, wherein the environment is maintained at 80% or more at 83 ± 2 ° C. Formula 3: Ts> A ÷ 2-20 (50 <A <100) Ts: breaking strength specified in JIS K 6251 (measurement temperature is 23 ±
Unit: MPa A: Surface Shore A hardness specified in JIS K 6253 (after 10 seconds) 6. The automotive exterior component according to claim 4, wherein the glossiness of the skin layer obtained by the evaluation method specified in JIS K 7015 is 15 to 40. 7. The slider is a 5.0 × 5.0 mm glass plate and the load is 1
The dynamic friction coefficient of the skin layer obtained under the conditions of 00 g and a slider speed of 1 m / min is 0.30 or less.
The automotive exterior component according to any one of the preceding claims.