JP2022108825A - Method for manufacturing weather strip - Google Patents

Abstract

To provide a method for manufacturing a weather strip that has excellent adhesiveness between a linear member and a corner member, and also has excellent heat resistance at a welded portion in a method easier than a conventional one.SOLUTION: A method for manufacturing a weather strip comprises steps of: (a) melting and kneading at least an ethylene α-olefinic copolymer rubber (A), an α-olefinic crystalline thermoplastic resin (B), and a crosslinking agent to manufacture a thermoplastic elastomer intermediate; (b) blending the thermoplastic elastomer intermediate, an olefinic block copolymer (C) being a hydrogenated block copolymer having a conjugated diene polymer block (c1) with 25 mol% or less of 1,2-vinyl bond content at both terminals and having a conjugated diene polymer block (c2) with more than 25 mol% of 1,2-vinyl bond content at a middle position, and a crystalline ethylenic resin (D) to obtain a mixture; and (c) molding the mixture in an injection molding machine.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for manufacturing a weatherstrip.

Thermoplastic elastomers (TPEs) are used in various fields such as automobiles, home appliances, medicine, foods, electric wires and daily necessities. Particularly in the automotive field, thermoplastic elastomers are attracting attention as alternative materials to vulcanized rubber mainly from the viewpoints of productivity, low cost, freedom of design, weight reduction, and recyclability.

Among them, weatherstrips, which are one of automobile parts, tend to replace vulcanized rubber with thermoplastic elastomers. For example, Patent Document 1 discloses a weatherstrip made of a thermoplastic elastomer composition containing an olefinic rubber, a hydrogenated block copolymer, and a polyolefinic resin other than the olefinic rubber.

JP 2016-113614 A

In recent years, due to the diversification of automobile design, there is an increasing need for composite members in which a molded body made of a thermoplastic elastomer composition and a molded body made of a crystalline ethylene resin are melt-bonded together in the design of weatherstrips. there is For example, after inserting a pre-molded linear member made of a crystalline ethylene resin into a mold for molding corners, the thermoplastic elastomer composition is injection-molded so that the linear member and the corner member are made of the thermoplastic elastomer composition. A weatherstrip can be manufactured that is bonded by heat-sealing.

However, such a weatherstrip does not have sufficient adhesiveness between the linear member and the corner member. In particular, the heat resistance of the fused portion between the straight member and the corner member is insufficient, and there is a problem that the fused portion is easily destroyed by heating.

Some aspects of the present invention provide a method for manufacturing a weatherstrip that is superior in adhesiveness between a linear member and a corner member and that is superior in heat resistance at the fused portion by a simpler method than in the past. provide a way.

One aspect of the method for manufacturing a weatherstrip according to the present invention includes:
At least an ethylene/α-olefin copolymer rubber (A), an α-olefin crystalline thermoplastic resin (B), and a cross-linking agent are melt-kneaded to produce a first thermoplastic elastomer intermediate. a step (a) of
The first thermoplastic elastomer intermediate, and a conjugated diene polymer block (c1) having a 1,2-vinyl bond content of 25 mol% or less at both ends and a 1,2-vinyl bond content of 25 mol% in the middle. A mixture is obtained by blending an olefinic block copolymer (C) which is a hydrogenated block copolymer having a super conjugated diene polymer block (c2) with a crystalline ethylene resin (D). step (b);
Step (c) of molding the mixture with an injection molding machine;
including.

In one aspect of the method for manufacturing the weatherstrip,
Any of the first thermoplastic elastomer intermediate, the component (C), and the component (D) may be pellets or powder.

In any aspect of the weatherstrip manufacturing method,
In the step (b), 5 to 30 parts by mass of the component (C) and 10 to 50 parts by mass of the component (D) are blended with 100 parts by mass of the first thermoplastic elastomer intermediate. A mixture may be obtained.

One aspect of the method for manufacturing a weatherstrip according to the present invention includes:
At least an ethylene/α-olefin copolymer rubber (A), an α-olefin crystalline thermoplastic resin (B), and a cross-linking agent are melt-kneaded to produce a first thermoplastic elastomer intermediate. a step (a) of
The first thermoplastic elastomer intermediate, and a conjugated diene polymer block (c1) having a 1,2-vinyl bond content of 25 mol% or less at both ends and a 1,2-vinyl bond content of 25 mol% in the middle. A step of melt-kneading an olefinic block copolymer (C) which is a hydrogenated block copolymer having a super conjugated diene polymer block (c2) to produce a second thermoplastic elastomer intermediate. (b-1);
a step (b-2) of obtaining a mixture by blending the second thermoplastic elastomer intermediate and a crystalline ethylenic resin (D);
Step (c) of molding the mixture with an injection molding machine;
including.

In one aspect of the method for manufacturing the weatherstrip,
Both the second thermoplastic elastomer intermediate and the component (D) may be pellets or powder.

In any aspect of the weatherstrip manufacturing method,
The component (D) may contain polyethylene (D1) having a weight average molecular weight of 1,000 to 30,000.

One aspect of the method for manufacturing a weatherstrip according to the present invention includes:
At least an ethylene/α-olefin copolymer rubber (A), an α-olefin crystalline thermoplastic resin (B), and a cross-linking agent are melt-kneaded to produce a first thermoplastic elastomer intermediate. a step (a) of
The first thermoplastic elastomer intermediate, and a conjugated diene polymer block (c1) having a 1,2-vinyl bond content of 25 mol% or less at both ends and a 1,2-vinyl bond content of 25 mol% in the middle. An olefinic block copolymer (C) which is a hydrogenated product of a block copolymer having a super conjugated diene polymer block (c2), and a crystalline ethylene resin (D) (where the weight average molecular weight is 1 ,000 to 30,000 excluding polyethylene), to produce a third thermoplastic elastomer intermediate (b'-1);
a step (b'-2) of obtaining a mixture by blending the third thermoplastic elastomer intermediate and polyethylene (D1) having a weight average molecular weight of 1,000 to 30,000;
Step (c) of molding the mixture with an injection molding machine;
including.

In one aspect of the method for manufacturing the weatherstrip,
Both the third thermoplastic elastomer intermediate and the component (D1) may be pellets or powder.

In any aspect of the weatherstrip manufacturing method,
In the step (c),
L/D of the injection molding machine = 16 to 25, compression ratio = 1 to 3,
The molding conditions may be cylinder temperature = 200 to 280, screw rotation speed = 20 to 400 rpm, and back pressure = 1 to 20 MPa.

In any aspect of the weatherstrip manufacturing method,
The melting point of component (B) may be 135° C. or higher.

In any aspect of the weatherstrip manufacturing method,
Content ratio of the conjugated diene polymer block (c1) when the total of the conjugated diene polymer block (c1) and the conjugated diene polymer block (c2) contained in the component (C) is 100 parts by mass may be 5 to 90 parts by mass.

In any aspect of the weatherstrip manufacturing method,
In the step (a), 1 to 25 parts by mass of the component (B) may be mixed with 100 parts by mass of the component (A).

According to the method for manufacturing a weatherstrip according to the present invention, a weatherstrip having excellent adhesiveness between the linear member and the corner member and excellent heat resistance at the fused portion can be manufactured by a simpler method than conventional methods. can do.

It is the figure which showed typically the structure of the injection molding machine used by this embodiment.

Preferred embodiments of the present invention will be described in detail below. It should be understood that the present invention is not limited only to the embodiments described below, but includes various modifications implemented without departing from the gist of the present invention.

In this specification, a numerical range such as "X to Y" is interpreted as including the numerical value X as the lower limit and the numerical value Y as the upper limit.

In this specification, the ethylene/α-olefin copolymer rubber (A) is referred to as "component (A)" and the α-olefin crystalline thermoplastic resin (B) is referred to as "component (B)." and a conjugated diene polymer block (c1) having a 1,2-vinyl bond content of 25 mol% or less at both ends and a conjugated diene polymer block (c2) having a 1,2-vinyl bond content of more than 25 mol% in the middle. ) is abbreviated as “component (C)” for olefin block copolymer (C), which is a hydrogenated product, and “component (D)” for crystalline ethylene-based resin (D). is sometimes used.

1. Method for Manufacturing Weatherstrip A method for manufacturing a weatherstrip according to an embodiment of the present invention comprises:
A step of producing a thermoplastic elastomer intermediate by melt-kneading at least an ethylene/α-olefin copolymer rubber (A), an α-olefin crystalline thermoplastic resin (B), and a cross-linking agent ( a) and
The thermoplastic elastomer intermediate and a conjugated diene polymer block (c1) having a 1,2-vinyl bond content of 25 mol% or less at both ends and a 1,2-vinyl bond content of more than 25 mol% in the middle Step (b) of obtaining a mixture by blending an olefin block copolymer (C) which is a hydrogenated block copolymer having a diene polymer block (c2) and a crystalline ethylene resin (D) )When,
Step (c) of molding the mixture with an injection molding machine;
including.
Each step of the weatherstrip manufacturing method according to the present embodiment will be described below.

1.1. step (a)
In the step (a), at least an ethylene/α-olefin copolymer rubber (A), an α-olefin crystalline thermoplastic resin (B), and a cross-linking agent are melt-kneaded and subjected to a first heat treatment. It is a process for manufacturing a plastic elastomer intermediate. The first thermoplastic elastomer intermediate obtained in step (a) is also called a dynamically crosslinked thermoplastic elastomer (TPV). TPV is a multiphase polymer material characterized by a sea-island structure in which crosslinked rubber particles are finely dispersed as domain phases at high density in a thermoplastic resin matrix phase.

For the melt-kneading of the raw material components, a melt-kneading means using a common kneader such as a Banbury mixer, a single screw extruder, a twin screw extruder, a kneader, a multiscrew extruder, and rolls is used.

In the step (a), at least the ethylene/α-olefin copolymer rubber (A), the α-olefin crystalline thermoplastic resin (B), and the cross-linking agent may be put into a kneader and melt-kneaded. However, in addition to the above ingredients, additives such as cross-linking aids, anti-aging agents, weathering agents, fatty acid derivatives, silicone compounds, coloring agents (titanium oxide, carbon black, etc.), extender oils, etc. may These additives preferably have high compatibility with the components (A) and (B) in order to suppress bleeding out on the surface of the molded article. Each raw material used in step (a) will be described below.

<Ethylene/α-olefin copolymer rubber (A)>
Component (A) is a copolymer rubber containing repeating units derived from ethylene and repeating units derived from α-olefin. Component (A) may contain repeating units derived from monomers other than ethylene and α-olefins. Component (A) may be a random copolymer, an alternating copolymer, or a block copolymer, but is preferably a random copolymer.

As the α-olefin, an α-olefin having 3 to 10 carbon atoms is preferable, and an α-olefin having 3 to 8 carbon atoms is more preferable. Specific examples of α-olefins include propylene, 1-butene, 2-methylpropene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene. be done. In synthesizing component (A), these α-olefins may be used singly or in combination of two or more.

Examples of monomers other than ethylene and α-olefins include 1,3-butadiene, 2-methyl-1,3-butadiene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and the like. 4 to 8 conjugated diene compounds; dicyclopentadiene, 5-ethylidene-2-norbornene, 1,4-hexadiene, 1,5-dicyclooctadiene, 7-methyl-1,6-octadiene, 5-vinyl- Non-conjugated diene compounds having 5 to 15 carbon atoms such as 2-norbornene; carboxylic acid vinyl esters such as vinyl acetate; unsaturated carboxylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate and ethyl methacrylate acid esters; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; Among these, non-conjugated diene compounds having 5 to 15 carbon atoms are preferable, and 5-ethylidene-2-norbornene and dicyclopentadiene are more preferable. In synthesizing component (A), these monomers other than ethylene and α-olefin may be used singly or in combination of two or more.

When the total mass of component (A) is 100% by mass, the content of repeating units derived from ethylene in component (A) is preferably 40 to 85% by mass, more preferably 50 to 80% by mass. %, particularly preferably 55 to 70% by mass.

When the total mass of component (A) is 100% by mass, the content of repeating units derived from α-olefins in component (A) is preferably 10 to 50% by mass, more preferably 15 to 50% by mass. 45% by mass, particularly preferably 25 to 40% by mass.

When the total mass of component (A) is 100% by mass, the content of repeating units derived from monomers other than ethylene and α-olefin in component (A) is preferably 0 to 15% by mass. Yes, more preferably 0 to 8% by mass, particularly preferably 0 to 5% by mass.

The content of repeating units derived from each monomer in component (A) can be determined by infrared spectroscopy. Specifically, using an infrared spectrophotometer, the infrared absorption spectrum of the component (A) is measured, and "Characterization of polyethylene by infrared absorption spectrum (Takayama, Usami et al.)" or "Die Makromolekulare Chemie , 177, 461 (1976) (McRae, M.A., Madam S, WF, etc.)”, the content of repeating units derived from each monomer in component (A) A percentage can be calculated.

Specific examples of component (A) include ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-1-octene copolymers, ethylene-propylene-1- butene copolymer, ethylene-propylene-1-hexene copolymer, ethylene-propylene-1-octene copolymer, ethylene-propylene-5-ethylidene-2-norbornene copolymer, ethylene-propylene-dicyclopentadiene copolymer polymers, ethylene-propylene-1,4-hexadiene copolymers, ethylene-propylene-5-vinyl-2-norbornene copolymers, and the like. Among these, ethylene-propylene copolymers and ethylene-propylene-5-ethylidene-2-norbornene copolymers are preferred. These components (A) may be used singly or in combination of two or more.

As an example of producing component (A), in the presence of a Ziegler-Natta catalyst, a known complex catalyst such as a metallocene complex or a non-metallocene complex, ethylene, an α-olefin, and other than ethylene and α-olefin and a method of copolymerizing with a monomer. Polymerization methods include slurry polymerization, solution polymerization, bulk polymerization, gas phase polymerization, and the like.

<α-olefin-based crystalline thermoplastic resin (B)>
Component (B) is a crystalline thermoplastic resin containing repeating units derived from α-olefins. Component (B) may contain less than 50% ethylene-derived repeat units.

As the α-olefin, an α-olefin having 3 or more and 20 or less carbon atoms is preferable. Specific examples of α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, and 1-tridecene. , 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 2-methylpropene, 1
-pentene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, 2,2,4-trimethyl-1-pentene and the like. . In synthesizing component (B), these α-olefins may be used singly or in combination of two or more.

The content ratio of repeating units derived from each monomer in component (B) can be obtained by the same method as for the content ratio of each monomer unit in component (A).

Examples of component (B) include propylene homopolymers and propylene random copolymers.

Examples of propylene random copolymers include
(1) a propylene-ethylene random copolymer containing repeating units derived from propylene and repeating units derived from ethylene;
(2) A propylene-ethylene-α-olefin random copolymer containing repeating units derived from propylene, repeating units derived from ethylene, and repeating units derived from an α-olefin having 4 to 20 carbon atoms. ,
(3) A propylene-α-olefin random copolymer containing repeating units derived from propylene and repeating units derived from an α-olefin having 4 to 20 carbon atoms,
etc.

Methods for producing propylene homopolymers and propylene random copolymers include a method of polymerizing propylene or the like in the presence of known complex catalysts such as Ziegler-Natta catalysts, metallocene complexes and non-metallocene complexes. . Polymerization methods include slurry polymerization, solution polymerization, bulk polymerization, gas phase polymerization, and the like.

The melting point of component (B) is preferably 135° C. or higher, more preferably 145° C. or higher, and particularly preferably 150° C. or higher. When the melting point of the component (B) is 135° C. or higher, heat resistance can be imparted to the resulting molded article, and in particular, the heat resistance of the fused portion with another molded article can be improved.

The melt flow rate of component (B) measured under conditions of a temperature of 230°C and a load of 21.2 N in accordance with JIS K7210 is good for both thermoplastic elastomer adherends and crystalline ethylene resin adherends. From the viewpoint of obtaining good adhesion, it is preferably 0.1 to 50 g/10 minutes, more preferably 0.1 to 25 g/10 minutes, and particularly preferably 0.1 to 15 g/10 minutes.

The density of component (B) measured according to JIS K7112 is not particularly limited, but is preferably 0.85 g/cm ³ or more and 0.95 g/cm ³ or less, and more preferably 0.85 g/cm 3 or more and 0.95 g/cm 3 or less. It is 87 g/cm ³ or more and 0.93 g/cm ³ or less.

In step (a), the amount of component (B) added is preferably 1 to 25 parts by mass, more preferably 5 to 22 parts by mass, and particularly preferably 100 parts by mass of component (A). 10 to 20 parts by mass.

<Crosslinking agent>
Examples of cross-linking agents include organic peroxides, sulfur compounds, alkylphenol resins having a methylol group, and the like. Among these, organic peroxides are preferred. By adding a crosslinking agent, component (A) is crosslinked to form crosslinked rubber particles, and a thermoplastic elastomer intermediate having a sea-island structure in which the crosslinked rubber particles are finely dispersed in component (B) is formed. .

Examples of organic peroxides include ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, percarbonates, peroxydicarbonates, and peroxyesters. and the like. Specific examples of organic peroxides include dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butyl peroxy)hexyne, 1,3-bis(tert-butylperoxyisopropyl)benzene, tert-butylcumyl peroxide, di-tert-butyl peroxide, 2,2,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzohydroperoxide, cumene peroxide, tert-butyl peroxide, 1,1-di(tert-butylperoxy)3,5,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane, isobutyl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide and the like.

Sulfur compounds include sulfur monochloride, sulfur dichloride, and the like.

In step (a), the amount of the cross-linking agent added is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 100 parts by mass, with respect to the total of 100 parts by mass of component (A) and component (B). 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass.

1.2. step (b)
In step (b), the first thermoplastic elastomer intermediate obtained in step (a) and a conjugated diene polymer block (c1) having a 1,2-vinyl bond content of 25 mol % or less at both ends are , an olefin-based block copolymer (C) which is a hydrogenated block copolymer having a conjugated diene polymer block (c2) having a 1,2-vinyl bond content of more than 25 mol% in the middle, and a crystalline ethylene-based It is a step of blending the resin (D) and obtaining a mixture. Since each raw material is homogenized by blending each raw material in advance, the adhesion between the straight member (thermoplastic elastomer or crystalline ethylene resin) and the corner member (the molded product of the above mixture) is excellent, and , a weatherstrip having excellent heat resistance at the fused portion can be manufactured.

In step (b), both the first thermoplastic elastomer intermediate, component (C) and component (D) are preferably pellets or powder. That is, in step (b), it is preferable to obtain a mixture by dry-blending the thermoplastic elastomer intermediate, component (C), and component (D) using a mixer or the like. The mixer is not particularly limited as long as it can mix the powder, such as a tumbler mixer and a drum mixer.

"Pellets" in the present invention refer to those made into particles for easy processing. The average particle size of the pellets is preferably 1-20 mm, more preferably 1-10 mm, and particularly preferably 1-5 mm. On the other hand, "powder" in the present invention refers to an aggregate of particles having an average particle size of less than 1 mm.

In step (b), component (C) and component (D) may be blended at once as described above, or component (C) and component (D) may be blended in separate steps. Alternatively, part or all of component (D) may be blended in a separate step.

Specifically, in the step (b), the first thermoplastic elastomer intermediate and the component (C) are melt-kneaded to produce a second thermoplastic elastomer intermediate (b-1); second
and the step (b-2) of blending the thermoplastic elastomer intermediate and the component (D) to obtain a mixture. In step (b-2), both the second thermoplastic elastomer intermediate and component (D) are preferably pellets or powder.

In step (b), the first thermoplastic elastomer intermediate, component (C), and part of component (D) (excluding polyethylene having a weight average molecular weight of 1,000 to 30,000) are combined. A step (b'-1) of melt-kneading to produce a third thermoplastic elastomer intermediate, and the third thermoplastic elastomer intermediate and polyethylene (D1) having a weight average molecular weight of 1,000 to 30,000 and a step (b'-2) of blending to obtain a mixture. In step (b'-2), both the third thermoplastic elastomer intermediate and component (D1) are preferably pellets or powder.

Each raw material used in step (b) will be described below.

<First thermoplastic elastomer intermediate>
The first thermoplastic elastomer intermediate (dynamically crosslinked thermoplastic elastomer (TPV)) obtained in step (a) above. Details are given above.

The amount of the first thermoplastic elastomer intermediate to be added is preferably 45 to 85 parts by mass when the total mass of the first thermoplastic elastomer intermediate, component (C) and component (D) is 100 parts by mass. , more preferably 50 to 80 parts by mass, particularly preferably 55 to 75 parts by mass.

<Olefin Block Copolymer (C)>
Component (C) has a conjugated diene polymer block (c1) having a 1,2-vinyl bond content of 25 mol % or less (hereinafter also referred to as "block (c1)") at both ends and 1, An olefinic block copolymer obtained by hydrogenating a block copolymer having a conjugated diene polymer block (c2) (hereinafter also referred to as "block (c2)") having a 2-vinyl bond content of more than 25 mol% be. Here, block (c1) and block (c2) are blocks before hydrogenation. By using component (C) and component (D) in combination, a molded article (composite member) can be manufactured.

The term "1,2-vinyl bond content" used herein refers to cis-1,4-bonds, trans-1,4-bonds, and 1 Among ,2-vinyl bonds, it means the content of 1,2-vinyl bonds. Here, the 1,2-vinyl bond content means the 1,2-vinyl bond content of the polymer before hydrogenation.

Block (c1) is preferably a polymer block based on 1,3-butadiene. The phrase “mainly composed of 1,3-butadiene” means that 90% by mass or more, preferably 95% by mass or more of the total repeating units of the block (c1) are repeating units derived from 1,3-butadiene. Say things. From the viewpoint of suppressing the melting point of the crystal after hydrogenation and maintaining the mechanical strength, the 1,2-vinyl bond content of the block (c1) is 25 mol % or less, preferably 20 mol % or less. Yes, more preferably 15 mol % or less.

The number average molecular weight (Mn) of block (c1) is preferably from 25,000 to 650,000, more preferably from 50,000 to 450,000. When the number average molecular weight (Mn) is 25,000 or more, the mechanical properties tend to improve. When the number average molecular weight (Mn) is 650,000 or less, workability tends to improve. The component (C) has blocks (c1) at both ends, and the number average molecular weight (Mn) of the blocks (c1) means the sum of the number average molecular weights (Mn) of the blocks (c1) at both ends. do.

Block (c2) is a conjugated diene polymer block having repeating units derived from a conjugated diene compound. Conjugated diene compounds include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4, 5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene and the like. Among these, 1,3-butadiene, isoprene and 1,3-pentadiene are preferred, and 1,3-butadiene is more preferred. In addition, the block (c2) may be composed of two or more types of monomer units.

The 1,2-vinyl bond content of block (c2) is more than 25 mol %, preferably more than 25 mol % and less than or equal to 95 mol %, more preferably more than 25 mol % and less than or equal to 85 mol %. From the viewpoint of maintaining the flexibility of component (C), the 1,2-vinyl bond content of block (c2) preferably exceeds 25 mol %.

The number average molecular weight (Mn) of block (c2) is preferably from 5,000 to 650,000, more preferably from 20,000 to 550,000. When the number average molecular weight (Mn) is 5,000 or more, the mechanical properties tend to improve. When the number average molecular weight (Mn) is 650,000 or less, workability tends to improve.

Block (c2) in the molecular structure of component (C) may contain an aromatic vinyl polymer block. When the block (c2) contains an aromatic vinyl polymer block, the content of the aromatic vinyl polymer block is such that the total repeating units of the block (c2) is 100% by mass, and the low temperature properties and flexibility are From the viewpoint of maintaining properties, the content is preferably 35% by mass or less, more preferably 30% by mass or less, and particularly preferably 25% by mass or less.

Examples of the aromatic vinyl compound as the repeating unit of block (c2) in the molecular structure of component (C) include styrene, tert-butylstyrene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, divinylbenzene, 1,1-diphenylstyrene, vinylnaphthalene, vinylanthracene, N,N-diethyl-p-aminoethylstyrene, vinylpyridine and the like. Among these, styrene is preferred.

When the total of block (c1) and block (c2) contained in component (C) is 100 parts by mass, the content of block (c1) is preferably 5 to 90 parts by mass, more preferably 10 parts by mass. ~80 parts by mass. When the content of the block (c1) is 5 parts by mass or more, it becomes easy for the component (C) to exhibit sufficient crystallinity relative to the component (A). It tends to form a mesh structure easily. On the other hand, when the content of the block (c1) is 90 parts by mass or less, excessive increase in hardness can be avoided. As used herein, the term "three-dimensional network structure" refers to a structure in which a network structure is formed in a three-dimensional direction by bonding without chemical cross-linking.

The olefinic block copolymer before hydrogenation includes, for example, aliphatic hydrocarbon solvents such as pentane, hexane, heptane and octane; alicyclic hydrocarbon solvents such as cyclopentane, methylcyclopentane, cyclohexane and methylcyclohexane; An aromatic vinyl compound and a conjugated diene compound, or an aromatic vinyl compound and a conjugated diene compound, and other copolymerizable with them in an inert organic solvent such as an aromatic hydrocarbon solvent such as xylene, toluene, ethylbenzene, etc. A monomer can be obtained by living anionic polymerization using an organic alkali metal compound as a polymerization initiator. The component (C) can be easily obtained by hydrogenating the obtained olefinic block copolymer before hydrogenation.

Examples of organic alkali metal compounds used as polymerization initiators include organic lithium compounds and organic sodium compounds. Among these, organic lithium compounds such as n-butyllithium, sec-butyllithium and tert-butyllithium are preferred. Although the amount of the organic alkali metal compound used is not particularly limited, it is usually used in an amount of 0.02 to 5 parts by weight, preferably 0.03 to 1.5 parts by weight, per 100 parts by weight of the monomer.

The polymerization temperature is usually -10 to 150°C, preferably 0 to 120°C. The atmosphere of the polymerization system is preferably replaced with an inert gas such as nitrogen gas. The polymerization pressure is not particularly limited as long as it is within a pressure range sufficient to maintain the monomers and solvent in the liquid phase. The method of introducing the monomers into the polymerization system is not particularly limited, and examples thereof include batch, continuous, intermittent, or a combination thereof.

The olefinic block copolymer before hydrogenation may be a copolymer in which a plurality of copolymer molecular chains are bonded via coupling residues. Such copolymers can be prepared by using a coupling agent on the block copolymer obtained by the method described above.

Coupling agents that can be used include, for example, divinylbenzene, 1,2,4-trivinylbenzene, epoxidized 1,2-polybutadiene, epoxidized soybean oil, epoxidized linseed oil, benzene-1,2,4- triisocyanate, dimethyl oxalate, diethyl phthalate, diethyl terephthalate, diethyl carbonate, 1,1,2,2-tetrachloroethane, 1,4-bis(trichloromethyl)benzene, trichlorosilane, methyltrichlorosilane, methyldichlorosilane, chlorosilane, butyltrichlorosilane, tetrachlorosilane, dimethyldichlorosilane, (dichloromethyl)trichlorosilane, hexachlorodisilane, tetraethoxysilane, tetrachlorotin, 1,3-dichloro-2-propanone and the like.

Component (C) can be obtained by partially or selectively hydrogenating the olefinic block copolymer obtained as described above before hydrogenation. The hydrogenation method and reaction conditions are not particularly limited, and are usually carried out at 20 to 150° C. under a hydrogen pressure of 0.1 to 10 MPa in the presence of a hydrogenation catalyst.

The hydrogenation rate can be arbitrarily selected by changing the amount of the hydrogenation catalyst, the hydrogen pressure during the hydrogenation reaction, the reaction time, or the like. Hydrogenation catalysts are usually compounds containing any one of group metals of the periodic table Ib, IVb, Vb, VIb, VIIb, and VIII, such as Ti, V, Co, Ni, Zr, Ru, Rh, Pd, and Hf. , Re, Pt atoms can be used. Specifically, for example, metallocene compounds such as Ti, Zr, Hf, Co, Ni, Pd, Pt, Ru, Rh, Re; metals such as Pd, Ni, Pt, Rh, Ru, carbon, silica, alumina , Supported heterogeneous catalysts supported on simple substances such as diatomaceous earth; Homogeneous Ziegler catalysts in which organic salts or acetylacetone salts of metal elements such as Ni and Co are combined with reducing agents such as organic aluminum; Ru, Rh and a fullerene or carbon nanotube in which hydrogen is occluded. Among them, a metallocene compound containing any one of Ti, Zr, Hf, Co, and Ni is preferable because it can be hydrogenated homogeneously in an inert organic solvent. Furthermore, a metallocene compound containing any one of Ti, Zr, and Hf is preferred. In particular, a hydrogenation catalyst obtained by reacting a titanocene compound with an alkyllithium is preferable because it is inexpensive and industrially particularly useful. In addition, the said hydrogenation catalyst may be used individually by 1 type, and may be used in combination of 2 or more types. After hydrogenation, the residue of the catalyst is removed if necessary, or a phenolic or amine antioxidant is added, and then the component (C) is isolated. Component (C) can be obtained, for example, by adding acetone or alcohol to the hydrogenated diene copolymer solution to cause precipitation, or by pouring the hydrogenated diene copolymer solution into hot water with stirring and removing the solvent by distillation. It can be isolated by the method of

The hydrogenation rate of component (C) is preferably 80% or more, more preferably 90% or more, and particularly preferably 95 to 100%. When the hydrogenation rate is 80% or more, thermal stability and durability tend to improve.

The number average molecular weight (Mn) of component (C) is preferably from 50,000 to 700,000, more preferably from 100,000 to 600,000. When the number average molecular weight (Mn) is 50,000 or more, heat resistance, strength, fluidity and workability tend to improve. When the number average molecular weight (Mn) is 700,000 or less, fluidity, workability and flexibility tend to improve. Incidentally, the component (C) can be obtained, for example, by the method disclosed in JP-A-3-128957.

According to JIS K7210, the melt flow rate of component (C) measured under the conditions of a temperature of 230°C and a load of 21.2 N is good for both thermoplastic elastomer adherends and crystalline ethylene resin adherends. From the viewpoint of obtaining good adhesion, it is preferably 0.1 to 20 g/10 minutes, more preferably 0.5 to 10 g/10 minutes, and particularly preferably 1 to 5 g/10 minutes.

The density of component (C) measured according to JIS K7112 is not particularly limited, but is preferably 0.85 g/cm ³ or more and 0.95 g/cm ³ or less, more preferably 0.85 g/cm 3 or more and 0.95 g/cm 3 or less. It is 86 g/cm ³ or more and 0.92 g/cm ³ or less.

A plurality of hydrogenated olefinic block copolymers obtained as described above linked via coupling agent residues can also be used as the component (C). That is, component (C) may be [(c1)-(c2)-(c1)] _n -X (where n is an integer of 3 or more and X represents a coupling agent residue). . Furthermore, if the coupling agent residue has a sufficiently small molecular weight relative to the blocks (c1) and (c2) and does not affect the crystallinity of the component (C), the component (C) can be [( c1)-(c2)] _n -X (where n is an integer of 3 or more and X represents a coupling agent residue).

Component (C) may also be a modified hydrogenated olefinic block copolymer modified with a functional group. As this functional group, at least one selected from the group consisting of a carboxy group, an acid anhydride group, a hydroxy group, an epoxy group, a halogen atom, an amino group, an isocyanate group, a sulfonyl group, a sulfonate group, and an oxazoline group is used. can do. A known method can be used for the denaturation method. The content of the functional group in this modified hydrogenated olefin block copolymer is preferably 0.01 to 10 mol% when the total repeating units constituting the modified hydrogenated olefin block copolymer is 100 mol%. , more preferably 0.1 to 8 mol %, particularly preferably 0.15 to 5 mol %. Preferred monomers that can be used to introduce functional groups include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, hydroxyethyl methacrylate, hydroxypropyl Methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, dimethylaminoethyl methacrylate and the like can be mentioned.

The amount of component (C) added is preferably 4 to 20 parts by mass when the total amount of the first thermoplastic elastomer intermediate, component (C) and component (D) is 100 parts by mass, and more It is preferably 5 to 18 parts by mass, particularly preferably 6 to 16 parts by mass.

<Crystalline ethylene resin (D)>
Component (D) is a crystalline ethylene-based resin having ethylene as the main repeating unit. Component (D) may contain less than 50% repeat units derived from monomers other than ethylene. By using component (C) and component (D) in combination, a molded article (composite member) can be manufactured.

Examples of monomers other than ethylene include α-olefins having 3 to 10 carbon atoms; 1,3-butadiene, 2-methyl-1,3-butadiene, 1,3-pentadiene, 2,3-dimethyl-1, Conjugated diene compounds having 4 to 8 carbon atoms such as 3-butadiene; dicyclopentadiene, 5-ethylidene-2-norbornene, 1,4-hexadiene, 1,5-dicyclooctadiene, 7-methyl-1,6 - Non-conjugated diene compounds having 5 to 15 carbon atoms such as octadiene and 5-vinyl-2-norbornene; carboxylic acid vinyl esters such as vinyl acetate; methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, methacryl unsaturated carboxylic acid esters such as ethyl acetate; and unsaturated carboxylic acids such as acrylic acid and methacrylic acid.

Examples of component (D) include ethylene homopolymers and ethylene copolymers containing repeating units derived from ethylene and repeating units derived from a monomer other than ethylene. Among component (D), ethylene homopolymer, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-pentene copolymer, ethylene-4-methyl-1-pentene copolymer, Ethylene-1-hexene copolymer is preferred, and high density polyethylene is more preferred.

It is also preferable to use polyethylene (D1) having a weight average molecular weight of 1,000 to 30,000 as part or all of component (D). The proportion of component (D1) used in component (D) is preferably 20% by mass or more, more preferably 40% by mass or more, based on 100% by mass of component (D). On the other hand, although the total amount of component (D) may be component (D1), component (D1) in component (D) is preferably 80% by mass or less, more preferably 60% by mass or less.

The melt flow rate of the component (D) measured under conditions of a temperature of 190° C. and a load of 21.2 N in accordance with JIS K7210 is, from the viewpoint of obtaining good adhesion to a molded article made of a crystalline ethylene-based resin, It is preferably 0.01 to 200 g/10 minutes, more preferably 1 to 100 g/10 minutes, and particularly preferably 5 to 30 g/10 minutes. When component (D1) is used, the melt viscosity of component (D1) measured at a temperature of 140° C. is preferably It is 10 to 30,000 mPa·s, more preferably 30 to 25,000 mPa·s, and particularly preferably 100 to 10,000 mPa·s.

The density of component (D) measured according to JIS K7112 is not particularly limited, but is preferably 0.91 g/cm ³ or more and 0.97 g/cm ³ or less, and more preferably 0.97 g/cm 3 or more. It is 94 g/cm ³ or more and 0.97 g/cm ³ or less.

Component (D) can be produced by polymerizing ethylene and, if necessary, a monomer other than ethylene in the presence of a polymerization catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. Examples of the polymerization method include a solution polymerization method, a bulk polymerization method, a slurry polymerization method, a gas phase polymerization method, and the like, and two or more of these may be combined.

The amount of component (D) added is preferably 10 to 40 parts by mass, more preferably 15 parts by mass, when the total amount of the thermoplastic elastomer intermediate, component (C) and component (D) is 100 parts by mass. 35 parts by mass, particularly preferably 20 to 30 parts by mass.

1.3. step (c)
Step (c) is a step of molding the mixture obtained in step (b) with an injection molding machine.

As the cylinder system of the injection molding machine used in this embodiment, as shown in FIG. ) method. The injection molding machine 100 shown in FIG. 1 includes a hopper 10 as a raw material inlet, a cylinder 12, a screw 14 rotating inside the cylinder 12, a tip 16 for injecting the melted and kneaded raw material into a mold, A heater 18 provided outside the cylinder 12 and a mold 20 are provided.

The basic flow of injection molding is as follows.
(1) The mixture obtained in step (b) is put into the hopper 10, and the screw 14 is rotated to feed the mixture to the front of the cylinder 12 while being melted and kneaded. This mixture is melted by the heat transmitted from the heater 18 provided outside the cylinder 12 and the frictional heat (shear heat) generated by kneading.
(2) The molten mixture is sent to the tip portion 16 while being compressed and kneaded, and the screw 14 descends backward. Back pressure is then applied from the rear of the screw to densify the mixture collected at the tip.
(3) The mixture collected at the tip of the screw is metered to the set screw position.
(4) The weighed mixture is injected into the mold 20 by pushing the screw 14 forward.
(5) After the mold 20 is held under pressure, heat is radiated and cooled, and then the molded product is taken out from the mold 20 . The mold cooling temperature is preferably 30 to 60°C.

Here, the length/diameter ratio (L/D) of the screw 14 is preferably 16-25, more preferably 17-24, and particularly preferably 18-24. Also, the compression ratio of the screw 14 is preferably 1.0 to 3.0, more preferably 1.5 to 2.9, and particularly preferably 2.0 to 2.8. If the length/diameter ratio (L/D) and compression ratio are less than the above range, the mixture may be poorly dispersed, and if it exceeds the above range, frictional heat may increase and the material may deteriorate. The surface of the screw 14 may be coated with a known coating such as chromium-based, titanium-based, nitride-based, or carbon-based.

The injection molding machine 100 used in this embodiment may be provided with a mechanism for controlling screw rotation and back pressure in order to improve the stability of weighing and injection operations. The screw rotation speed is preferably 20 to 400 rpm, more preferably 50 to 350 rpm, particularly preferably 50 to 300 rpm. Also, the back pressure is preferably 1 to 20 MPa, more preferably 2 to 15 MPa, and particularly preferably 5 to 10 MPa. If the screw rotation speed and the back pressure are less than the above ranges, the mixture may be poorly dispersed.

The cylinder temperature of the injection molding machine 100 used in this embodiment is preferably 200 to 280.degree. C., more preferably 210 to 270.degree. C., and particularly preferably 220 to 260.degree. Also, the injection rate is preferably 10 to 100 cc/sec. If the cylinder temperature and the injection rate are outside the above ranges, the adhesion to the adherend may be poor.

The drive system, mold clamping system, and injection direction of the injection molding machine 100 used in this embodiment can be selected as appropriate. Drive systems include hydraulic, electric, and hybrid systems; Toggle type; Examples of injection direction include horizontal type and vertical type.

1.4. Effects According to the weatherstrip manufacturing method according to the present embodiment, in the step (b), the first thermoplastic elastomer intermediate, the component (C) and the component (D) are blended in advance to manufacture a mixture. Since each raw material is homogenized by placing the A weatherstrip with excellent heat resistance can be manufactured. When each of the first thermoplastic elastomer intermediate, the component (C) and the component (D) to be mixed is pellets or powder, it is easier to homogenize, and it is easier to put the raw material into the hopper of the injection molding machine. Therefore, it is preferable.

2. Examples Specific examples of the present invention will be described below, but the present invention is not limited to these examples. In addition, "%" in the following Production Examples, Examples and Comparative Examples is based on mass unless otherwise specified.

2.1. Examples 1-6, Comparative Examples 1-3
2.1.1. step (a)
Ethylene/α-olefin-based copolymer rubber (A), α-olefin-based crystalline thermoplastic resin (B), cross-linking agent, cross-linking aid, black pigment, anti-aging agent of the type and amount shown in Table 1 below , Weathering agent, higher fatty acid amide, polydimethylsiloxane A (kinematic viscosity 100 cSt), polydimethylsiloxane B (kinematic viscosity 1000 cSt) are put into a twin-screw extruder "KTX30" (model name) manufactured by Kobe Steel, Ltd. The mixture was melt-kneaded under conditions of a cylinder temperature of 210° C., a screw rotation speed of 300 rpm, and a discharge rate of 30 kg/h to produce cylindrical thermoplastic elastomer composition intermediate-1 pellets having a diameter of 2 mm and a length of 4 mm.

2.1.2. step (b)
Next, thermoplastic elastomer intermediate-1, olefinic block copolymer (C) or olefinic block copolymer (C'), and crystalline ethylene resin (D) of the types and amounts shown in Table 1 below. , crystalline ethylene-based resin (D1-1), and crystalline ethylene-based resin (D1-2) pellets are blended for 1 minute in a Henschel mixer, and used in Examples 1 to 6 and Comparative Examples 1 to 3. A mixture was prepared.

2.1.3. Evaluation method 2.1.3.1. Preparation of adherend (1) Preparation of thermoplastic elastomer adherend "Santoprene 121-73W175" manufactured by Exxon Mobil was used in an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., trade name "SE75EV-C250", L/D = 23, compression ratio = 2.6), a sheet having a size of 120 mm x 120 mm x 2 mm was produced. This sheet was punched out with a dumbbell cutter to a length of 60 mm and a width of 50 mm to obtain a thermoplastic elastomer adherend.

(2) Preparation of crystalline ethylene-based resin adherend "Novatec HD HJ590N" manufactured by Japan Polyethylene Co., Ltd. was used as an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., trade name "SE75EV-C250", L / D = 23, A sheet having a size of 120 mm x 120 mm x 2 mm was produced by compression ratio = 2.6). This sheet was punched out with a dumbbell cutter to a length of 60 mm and a width of 50 mm to obtain a crystalline ethylene-based resin adherend.

2.1.3.2. Production of conjugate (step (c))
(1) Fabrication of joined body with thermoplastic elastomer adherend The thermoplastic elastomer adherend prepared above was pasted in advance in the split mold. Next, any one of the mixtures produced above is put into a hopper and injection molded into the cutout (inside the split mold to which the thermoplastic elastomer adherend is attached) so that it fits in the cutout (cylinder temperature = 260 ℃, screw rotation speed = 150 rpm, back pressure = 10 MPa), a flat plate (120 mm × 120 mm × 2 mm (length × width × thickness)) obtained by injection-bonding the molded body of the above mixture and the above-mentioned thermoplastic elastomer adherend. Obtained. Then, this flat plate was punched out with a JIS-2 dumbbell cutter to obtain a test piece (dumbbell-shaped test piece).

(2) Preparation of a bonded body with a crystalline ethylene resin adherend First, an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., trade name "SE75EV-C250", L / D = 23, compression ratio = 2.6 ), the crystalline ethylene-based resin adherend prepared above was attached in advance to the split mold. Next, any of the mixtures produced above is put into a hopper and injection molded into the cutout (inside the split mold to which the crystalline ethylene resin adherend is attached) so that it fits in the cutout (cylinder temperature = 260 ° C., screw rotation speed = 150 rpm, back pressure = 10 MPa), a flat plate (120 mm × 120 mm × 2 mm (length × width × thickness )) was obtained. Then, this flat plate was punched out with a JIS-2 dumbbell cutter to obtain a test piece (dumbbell-shaped test piece).

2.2. Comparative example 4
2.2.1. step (a)
Ethylene/α-olefin copolymer rubber (A), α-olefin crystalline thermoplastic resin (B-1), cross-linking agent, cross-linking aid, black pigment, aging of the types and amounts shown in Table 1 below Inhibitor, weathering agent, higher fatty acid amide, polydimethylsiloxane A (kinematic viscosity 100cSt), and polydimethylsiloxane B (kinematic viscosity 1000cSt) are put into a twin-screw extruder "KTX30" (model name) manufactured by Kobe Steel, Ltd. The mixture was melt-kneaded under conditions of a cylinder temperature of 210° C., a screw rotation speed of 300 rpm, and a discharge rate of 30 kg/h to produce cylindrical thermoplastic elastomer composition intermediate-1 pellets having a diameter of 2 mm and a length of 4 mm.

2.2.2. step (c)
Next, without performing step (b), in step (c) above, thermoplastic elastomer intermediate-1, olefinic block copolymer (C), and crystalline ethylene in the types and amounts shown in Table 1 below. Each test piece was obtained in the same manner as in Example 1, except that the system resin (D) was directly charged into the hopper of the injection molding machine.

2.3. Examples 7-8
2.3.1. step (a)
Ethylene/α-olefin copolymer rubber (A), α-olefin crystalline thermoplastic resin (B-1), cross-linking agent, cross-linking aid, black pigment, aging of the types and amounts shown in Table 1 below Inhibitor, weathering agent, higher fatty acid amide, polydimethylsiloxane A (kinematic viscosity 100cSt) and polydimethylsiloxane B (kinematic viscosity 1000cSt) are put into a twin-screw extruder "KTX30" (model name) manufactured by Kobe Steel, Ltd. Then, the mixture was melt-kneaded under conditions of a cylinder temperature of 210° C., a screw rotation speed of 300 rpm, and a discharge rate of 30 kg/h to produce cylindrical thermoplastic elastomer composition intermediate-1 pellets having a diameter of 2 mm and a length of 4 mm.

2.3.2. Step (b-1)
Next, the first thermoplastic elastomer composition intermediate-1 obtained in step (a) and the olefin-based block copolymer (C) were extruded into a twin-screw extruder "KTX30" (model name) manufactured by Kobe Steel, Ltd. and melt-kneaded under the conditions of a cylinder temperature of 210° C., a screw rotation speed of 300 rpm, and a discharge rate of 30 kg/h to produce cylindrical thermoplastic elastomer composition intermediate-2 pellets having a diameter of 2 mm and a length of 4 mm. did.

2.3.3. Step (b-2)
Next, each pellet of the thermoplastic elastomer composition intermediate-2, the crystalline ethylene resin (D) and/or the crystalline ethylene resin (D1-1) obtained in the step (b-1) is placed in a Henschel mixer. and blended for 1 minute to produce the mixtures used in Examples 7-8.

2.4. Example 9
2.4.1. step (a)
Ethylene/α-olefin copolymer rubber (A), α-olefin crystalline thermoplastic resin (B-1), cross-linking agent, cross-linking aid, black pigment, aging of the types and amounts shown in Table 1 below Inhibitor, weathering agent, higher fatty acid amide, polydimethylsiloxane A (kinematic viscosity 100cSt) and polydimethylsiloxane B (kinematic viscosity 1000cSt) are put into a twin-screw extruder "KTX30" (model name) manufactured by Kobe Steel, Ltd. Then, the mixture was melt-kneaded under conditions of a cylinder temperature of 210° C., a screw rotation speed of 300 rpm, and a discharge rate of 30 kg/h to produce cylindrical thermoplastic elastomer composition intermediate-1 pellets having a diameter of 2 mm and a length of 4 mm.

2.4.2. Step (b'-1)
Next, the thermoplastic elastomer composition intermediate-1 obtained in step (a), the olefin block copolymer (C), and the crystalline ethylene resin (D) were extruded into a twin-screw extruder manufactured by Kobe Steel, Ltd. KTX30" (model name) and melt-kneaded under the conditions of a cylinder temperature of 210°C, a screw rotation speed of 300 rpm, and a discharge rate of 30 kg/h to obtain a cylindrical thermoplastic elastomer composition intermediate having a diameter of 2 mm and a length of 4 mm. -3 pellets were produced.

2.4.3. Step (b'-2)
Next, the thermoplastic elastomer composition intermediate-3 and the crystalline ethylene-based resin (D1-1) pellets obtained in step (b'-1) were blended for 1 minute in a Henschel mixer, and the prepared a mixture for use in

2.5. Evaluation Test Each test piece prepared above was evaluated by performing the following test. The results are shown in Table 1 below.

(1) Adhesiveness Each test piece prepared above was bent 10 times at 180 degrees starting from the injection-bonded portion, and evaluated according to the following criteria.
(Evaluation criteria)
A: There is no breakage of the fused portion, and the adhesion is good.
B: Destruction of the fused portion occurs, and the adhesion is poor.

(2) Heat resistance Into a constant temperature bath adjusted to 85 ° C., one end of the test piece obtained above was suspended with a weight of 200 gf, and left to stand for 2 hours, 24 hours, and 48 hours. evaluated.
(Evaluation criteria)
A: There is no breakage of the fused portion after standing for 48 hours, and the heat resistance is very good.
B: Good heat resistance without breakage of the fused portion after standing for 24 hours.
C: The fused portion breaks in less than 2 hours, and the heat resistance is poor.

2.6. Evaluation Results Table 1 below shows the compositions of the thermoplastic elastomer intermediates and mixtures produced in Examples and Comparative Examples, and the evaluation results.

For each component listed in Table 1, the following were used.
Ethylene/α-olefin copolymer rubber (A): ethylene/propylene/5-ethylidene-2-norbornene terpolymer (ethylene unit content: 66 mass%, 5-ethylidene-2-norbornene unit content: 4.5 % by mass, intrinsic viscosity 4.6) A mixture of 50% by mass and a paraffinic softener (Diana Process Oil PW90, manufactured by Idemitsu Kosan Co., Ltd.) ・α-olefin-based crystalline thermoplastic resin (B-1): Product name " Novatec PP MA2", manufactured by Japan Polypropylene Corporation, propylene homopolymer, melting point 159°C, density 0.90 g/cm ³ , melt flow rate (230°C, load 21.2 N) 16 g/10 minutes・α-olefin-based crystalline heat Plastic resin (B-2): Trade name "Novatec PP FL02A", manufactured by Japan Polypropylene Co., Ltd., propylene random copolymer, melting point 139°C, density 0.90 g/cm ³ , melt flow rate (230°C, load 21.2N ) 20 g/10 min α-olefin-based crystalline thermoplastic resin (B-3): trade name “Novatec PP FX4E” manufactured by Japan Polypropylene Co., Ltd., propylene random copolymer, melting point 132° C., density 0.90 g/cm ³ , melt flow rate (230° C., load 21.2 N) 5.3 g/10 minutes Olefin-based block copolymer (C): trade name “DYNARON 6200P” manufactured by JSR, density 0.88 g/cm ³ , Melt flow rate (230 ° C., load 21.2 N) 2.5 g / 10 minutes, having a conjugated diene polymer block with a 1,2-vinyl bond content of 25 mol% or less at both ends and 1,2-vinyl in the middle Hydrogenated block copolymer/olefin-based block copolymer (C′) obtained by hydrogenating a block copolymer having a conjugated diene polymer block with a bond content of more than 25 mol %: trade name “INFUSE 9007”; Dow Chemical Co., density 0.87 g/cm ³ , melt flow rate (230° C., load 21.2 N) 0.5 g/10 min, ethylene/octene-1 copolymer/crystalline ethylene resin (D) : Trade name "Novatec HD HJ490", manufactured by Nippon Polyethylene Co., Ltd., weight average molecular weight 120,000, melting point 131°C, density 0.96 g/cm ³ , melt flow rate (190°C, load 21.2 N) 20 g/10 minutes, Ethylene/propylene copolymer/crystalline ethylene resin (D1-1): trade name “LICOCENE PE 5301” manufactured by Clariant, weight average molecular weight 4,800, melting point 12 9° C., polyethylene/crystalline ethylene resin (D1-2): trade name “EXCEREX 40800T”, manufactured by Mitsui Chemicals, Inc., weight average molecular weight 6,900, melting point 128° C., polyethylene/crosslinking agent: trade name “Perhexa 25B-” 40", manufactured by NOF Corporation, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane/crosslinking aid: trade name "Balnok PM", manufactured by Ouchi Shinko Chemical Industry Co., Ltd., N, N '-m-phenylene bismaleimide/black pigment: mixture of crystalline propylene-based resin and carbon black (carbon black content 40%)
· Anti-aging agent: trade name "adekastab AO-60", manufactured by ADEKA, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
・Weather resistant agent: trade name “ADEKA STAB LA-52”, manufactured by ADEKA, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate・high grade Fatty acid amide: trade name "Neutron-S", manufactured by Nippon Fine Chemical Co., Ltd., erucamide polydimethylsiloxane A: trade name "DOWSIL SH200 Fluid 100 cSt", manufactured by Dow Toray Industries, kinematic viscosity: 100 cSt
· Polydimethylsiloxane B: trade name "DOWSIL SH200 Fluid 1000 cSt", manufactured by Dow Toray Industries, kinematic viscosity: 1000 cSt

From the evaluation results in Table 1 above, according to the production methods of Examples 1 to 9, the adhesiveness to both the thermoplastic elastomer adherend and the crystalline ethylene resin adherend is excellent, and the fused portion has excellent adhesion. It was found that a joined body having excellent heat resistance can be obtained.

In the production method of Comparative Example 1, since the olefin block copolymer (C') was used instead of the component (C), although the thermoplastic elastomer adherend and the crystalline ethylene resin adherend adhered, the heat The heat resistance was insufficient in both the fused portion with the plastic elastomer adherend and the fused portion with the crystalline ethylene resin adherend.

In the manufacturing method of Comparative Example 2, since the component (C) was not used, the adhesiveness and heat resistance of the joined body to the thermoplastic elastomer adherend were insufficient.

In the manufacturing method of Comparative Example 3, since the component (C) and the component (D) were not used, the bonded product to the crystalline ethylene-based resin adherend had insufficient adhesiveness and heat resistance.

In the production method of Comparative Example 4, since the raw materials were directly added without going through the step (b), the adhesion strength to the thermoplastic elastomer adherend or the crystalline ethylene resin adherend was low, and the thermoplastic elastomer The heat resistance was insufficient in both the fused portion with the adherend and the fused portion with the crystalline ethylene-based resin adherend.

The present invention is not limited to the above embodiments, and various modifications are possible. The present invention includes configurations that are substantially the same as the configurations described in the embodiments (for example, configurations that have the same function, method, and result, or configurations that have the same purpose and effect). The present invention also includes configurations in which non-essential portions of the configurations described in the above embodiments are replaced with other configurations. Furthermore, the present invention also includes a configuration that achieves the same effects or achieves the same purpose as the configurations described in the above embodiments. Furthermore, the present invention also includes configurations obtained by adding known techniques to the configurations described in the above embodiments.

Claims (12)

At least an ethylene/α-olefin copolymer rubber (A), an α-olefin crystalline thermoplastic resin (B), and a cross-linking agent are melt-kneaded to produce a first thermoplastic elastomer intermediate. a step (a) of
The first thermoplastic elastomer intermediate, and a conjugated diene polymer block (c1) having a 1,2-vinyl bond content of 25 mol% or less at both ends and a 1,2-vinyl bond content of 25 mol% in the middle. A mixture is obtained by blending an olefinic block copolymer (C) which is a hydrogenated block copolymer having a super conjugated diene polymer block (c2) with a crystalline ethylene resin (D). step (b);
Step (c) of molding the mixture with an injection molding machine;
A method of manufacturing a weatherstrip, comprising: 2. The method of manufacturing a weatherstrip according to claim 1, wherein all of said first thermoplastic elastomer intermediate, said component (C), and said component (D) are pellets or powder. In the step (b), 5 to 30 parts by mass of the component (C) and 10 to 50 parts by mass of the component (D) are blended with 100 parts by mass of the first thermoplastic elastomer intermediate. 3. A method for producing a weatherstrip as claimed in claim 1 or claim 2, wherein a mixture is obtained. At least an ethylene/α-olefin copolymer rubber (A), an α-olefin crystalline thermoplastic resin (B), and a cross-linking agent are melt-kneaded to produce a first thermoplastic elastomer intermediate. a step (a) of
The first thermoplastic elastomer intermediate, and a conjugated diene polymer block (c1) having a 1,2-vinyl bond content of 25 mol% or less at both ends and a 1,2-vinyl bond content of 25 mol% in the middle. A step of melt-kneading an olefinic block copolymer (C) which is a hydrogenated block copolymer having a super conjugated diene polymer block (c2) to produce a second thermoplastic elastomer intermediate. (b-1);
a step (b-2) of obtaining a mixture by blending the second thermoplastic elastomer intermediate and a crystalline ethylenic resin (D);
Step (c) of molding the mixture with an injection molding machine;
A method of manufacturing a weatherstrip, comprising: 5. The method of manufacturing a weatherstrip according to claim 4, wherein both the second thermoplastic elastomer intermediate and the component (D) are pellets or powder. The method for producing a weatherstrip according to any one of claims 1 to 5, wherein the component (D) contains polyethylene (D1) having a weight average molecular weight of 1,000 to 30,000. At least an ethylene/α-olefin copolymer rubber (A), an α-olefin crystalline thermoplastic resin (B), and a cross-linking agent are melt-kneaded to produce a first thermoplastic elastomer intermediate. a step (a) of
The first thermoplastic elastomer intermediate, and a conjugated diene polymer block (c1) having a 1,2-vinyl bond content of 25 mol% or less at both ends and a 1,2-vinyl bond content of 25 mol% in the middle. An olefinic block copolymer (C) which is a hydrogenated product of a block copolymer having a super conjugated diene polymer block (c2), and a crystalline ethylene resin (D) (where the weight average molecular weight is 1 ,000 to 30,000 excluding polyethylene), to produce a third thermoplastic elastomer intermediate (b'-1);
the third thermoplastic elastomer intermediate and a weight average molecular weight of 1,000 to 30,00
0 polyethylene (D1) and a step (b'-2) of obtaining a mixture by blending;
Step (c) of molding the mixture with an injection molding machine;
A method of manufacturing a weatherstrip, comprising: 8. The method of manufacturing a weatherstrip according to claim 7, wherein both the third thermoplastic elastomer intermediate and the component (D1) are pellets or powder. In the step (c),
L/D of the injection molding machine = 16 to 25, compression ratio = 1 to 3,
The method for producing a weatherstrip according to any one of claims 1 to 8, wherein the molding conditions are cylinder temperature = 200 to 280, screw rotation speed = 20 to 400 rpm, and back pressure = 1 to 20 MPa. The method for producing a weatherstrip according to any one of claims 1 to 9, wherein the component (B) has a melting point of 135°C or higher. Content ratio of the conjugated diene polymer block (c1) when the total of the conjugated diene polymer block (c1) and the conjugated diene polymer block (c2) contained in the component (C) is 100 parts by mass is 5 to 90 parts by mass. The weatherstrip according to any one of claims 1 to 11, wherein in the step (a), 1 to 25 parts by mass of the component (B) is mixed with 100 parts by mass of the component (A). manufacturing method.

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