KR960000745B1 - Thermoplastic elastomer laminates and glass run channels - Google Patents

Abstract

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Description

Thermoplastic Elastomer Laminates and Glass Run Channels Molded From Them

1 is a cross-sectional view of a glass run channel of the present invention.

2 is an enlarged cross-sectional view of a portion of the glass run channel shown in FIG. 1 in which a window glass is contacted.

3 shows an aspect in which the glass run channel is fitted to an automobile door.

4 is a cross-sectional view showing the state of the fitted glass run channel when the window glass is opened.

5 is a cross-sectional view showing the state of the fitted glass run channel when the window glass is closed.

FIELD OF THE INVENTION The present invention relates to thermoplastic elastomer laminates and glass run channels formed therefrom that are effectively used in the manufacture of automotive interior trims and seals, and more particularly to thermoplastics comprising a base layer of thermoplastic elastomer and a surface layer of lubricating resin. A glass run channel having an elastomer laminate and a window glass slide composed of the laminate.

Various laminates have been conventionally used for manufacturing automotive interior trims and sealing materials. For example, glass run channels are known as one of the important sealants used in automobiles. The glass run channel is a guide member provided between the window glass and the window frame to facilitate the up / down and opening / closing operation of the window glass and to enable a close (liquid hermetic) sealing operation between the window glass and the window frame.

Materials commonly used in the production of glass run channels include (1) vulcanized rubbers, adhesives and nylon fibers composed of ethylene / propylene / diene copolymer rubbers having excellent weather resistance and heat resistance, and (2) the vulcanization. Composites of rubber and adhesives, and (3) non-rigid PVC for contour extrusion.

Conventional glass run channels composed of such composites have a body having a groove-shaped cross section and a tongue drain extending from the end of the side wall of the groove toward the central side of the groove, respectively.

In a conventional glass run channel, a nylon film or the like is laminated on the surface of the window glass slide of each drain portion by an adhesive or the nylon film so that the window glass is well separated from the slide and the contamination is prevented. The surface of each slide portion of the drain portion before and after lamination and the like is embossed to reduce the contact area between the slide portion and the window glass.

However, in the method of manufacturing the glass run channel as described above, since there is no adhesiveness between the non-rigid synthetic resin or the surface material such as vulcanized rubber and nylon, the window of the main body of the glass run channel formed of the non-rigid synthetic resin or vulcanized rubber The process of laminating a nylon film on the surface of the window glass slide by coating the surface of the glass slide with an adhesive, and the process of embossing the surface of the slide before and after lamination of the nylon film, Therefore, there were inconveniences such as a large number of steps and a long time.

On the other hand, when the glass run channel is produced by contour extrusion of the composite material 3, that is, non-rigid polyvinyl chloride, the manufacturing method is simple. However, the composite strip is poor in heat resistance and dimensional stability, and is poor in actual performance than the composites (1) and (2).

When a conventional glass run channel is molded from the composite material (1) or (2), a nylon film or the like is laminated to the window glass sliding part of the drainage portion as an adhesive, which causes a problem of durability of the channel. Nylon membranes are likely to delaminate from the window glass slide over time and by outdoor exposure. Further, the embossed pattern formed on the surface of the window glass sliding part by the embossing process is insufficient in terms of harmony of fineness and uniformity, and the window glass sliding part and the window glass when closing the window glass. There are many improvements in terms of close contact between the windows and smooth sliding between the window glass sliding portion and the window glass when the window glass is opened.

Therefore, it is excellent in weather resistance, heat resistance, dimensional stability, etc., can be manufactured by a simple manufacturing method, and it implement | achieves the laminated body which can be used for the purpose of interior trim, sealing material, etc., and the window glass sliding part formed by the said laminated body is included. It was desired to provide a glass run channel.

The present invention is intended to solve the problems of the prior art as described above, and an object of the present invention is to provide a thermoplastic elastomer laminate which is excellent in heat resistance, weather resistance and dimensional stability, can be manufactured by a simple manufacturing process, and has excellent so-called economic efficiency. To provide.

Another object of the present invention is to provide a glass run channel which is excellent in economy and durability, excellent in close contact with the window glass when the window glass is closed, and excellent in sliding property with respect to the window glass when the window glass is opened.

The 1st thermoplastic elastomer laminated body of this invention consists of the layer which consists of thermoplastic elastomeric (A) which consists of crystalline polyolefin and rubber, and the layer which consists of ultra high molecular weight polyolefin (B).

The thermoplastic elastomer (A) is preferably 70 to 10 parts by weight of crystalline polypropylene (a) and 30 to 90 parts by weight of rubber (b) made of ethylene / propylene copolymer rubber or ethylene / propylene / diene copolymer rubber ( The mixture containing components (a) and (b) is 100 parts by weight) is subjected to a dynamic heat treatment in the presence of an organic peroxide, thereby partially crosslinking the rubber (b).

The ultrahigh molecular weight polyolefin (B) preferably has an intrinsic viscosity [η] of 10-40 dl / g measured in 135 ° C decalin.

The second thermoplastic elastomer laminate of the present invention comprises a layer composed of a thermoplastic elastomer (A) composed of crystalline polyolefin and rubber, and a layer composed of an ultrahigh molecular weight polyolefin composition (C), wherein the ultrahigh molecular weight polyolefin composition is 135 ° C. A polyolefin having an intrinsic viscosity [η] of 0.1 to 5 dl / g measured in decalin is an essential component, and the ultra high molecular weight polyolefin is in an amount of 15 to 40% by weight based on 100% by weight of the total of the ultra high molecular weight polyolefin and the polyolefin. It exists, It is characterized by the intrinsic viscosity [eta] of 3.5-8.3 dl / g measured in 135 degreeC decalin of the said ultra high molecular weight polyolefin composition (C).

The thermoplastic elastomer (A) is the same as that used in the first thermoplastic elastomer laminate of the present invention.

The ultrahigh molecular weight polyolecin composition (C) may contain 1 to 20% by weight of liquid or solid lubricant.

The third thermoplastic elastomer laminate of the present invention comprises a layer made of graft modified thermoplastic elastomer (GA) and a layer made of ultra high molecular weight polyolefin (B), wherein the graft modified thermoplastic elastomer (GA) is (i) peroxide. 95 to 10 parts by weight of crosslinked olefin copolymer rubber, (ii) 5 to 90 parts by weight of polyolefin (the sum of the components (iii) and (ii) is 100 parts by weight), (iii) α, β-unsaturated carboxylic acid Or a derivative thereof or a blend containing 0.01 to 10 parts by weight of an unsaturated epoxy monomer by dynamic heat treatment and partial crosslinking in the presence of an organic peroxide.

The graft modified thermoplastic elastomer (GA) is preferably 5 to 100 parts by weight of (iv) peroxide non-crosslinked rubbery material and / or (iii) to 100 parts by weight in total of the components (i) and (ii). It may further contain 3 to 100 parts by weight of mineral oil softener.

In the graft-modified thermoplastic elastomer (GA), the content of the peroxide crosslinked olefin copolymer rubber is 95 to 60 parts by weight, and the content of the polyolefin (ii) is 5 to 40 parts by weight (component) It is preferable that the sum total of (ii) is 100 weight part).

The ultrahigh molecular weight polyolefin (B) used here is the same as that used for the 1st thermoplastic elastomer laminated body of this invention.

The fourth thermoplastic elastomer laminate of the present invention comprises a layer made of a graft modified thermoplastic elastomer (GA) and a layer made of an ultra high molecular weight polyolefin composition (C), and the graft modified thermoplastic elastomer (GA) is a (x) peroxide. 95 to 10 parts by weight of crosslinked olefin copolymer rubber, (ii) 5 to 90 parts by weight of polyolefin (the sum of the components (iii) and (ii) is 100 parts by weight), and (iii) α, β-unsaturated carboxylic acid Or a derivative thereof, or a blend containing 0.01 to 10 parts by weight of an unsaturated epoxy monomer, by dynamic heat treatment and partial crosslinking in the presence of an organic peroxide, wherein the ultrahigh molecular weight polyolefin composition (C) has an extreme viscosity measured in 135 ° C decalin [ The ultrahigh molecular weight polyolefin having a η] of 10 to 40 dl / g and a polyolefin having an intrinsic viscosity [η] of 0.1 to 5 dl / g measured in 135 ° C decalin as essential components. Polyolefin exists in the ratio of 15-40 weight% with respect to a total of 100 weight% of ultra high molecular weight polyolefin and the said polyolefin, and the intrinsic viscosity [eta] measured in 135 degreeC decalin of the said ultra high molecular weight polyolefin composition (C) is 3.5- It is characterized in that the 8.3dl / g.

The graft modified thermoplastic elastomer (GA) is preferably the same as in the third thermoplastic elastomer laminate of the present invention.

In the graft modified thermoplastic elastomer (GA), the content of the peroxide crosslinked olefin copolymer rubber is 95 to 60 parts by weight, and the content of the polyolefin (ii) is 5 to 40 parts by weight (component) It is preferable that the sum total of (ii) is 100 weight part).

The ultrahigh molecular weight polyolefin composition (C) may contain 1 to 20% by weight of a liquid or solid lubricant based on the composition (C).

The first glass run channel of the present invention includes a body having a grooved cross section and tongue drainages extending from the end of the side wall of the groove toward the center of the groove, wherein portions of the glass run channel in contact with the window glass are determined. It is composed of a thermoplastic elastomer layer composed of a polymer polyolefin and rubber and an ultrahigh molecular weight polyolefin (B) layer, wherein the ultrahigh molecular weight polyolefin (B) layer is designed to be in contact with the window glass, and the ultrahigh molecular weight polyolefin (B) It is characterized by the intrinsic viscosity [η] measured in 135 degreeC decalin of 10-40 dl / g.

The thermoplastic elastomer (A) used above is preferably those defined in the first thermoplastic elastomer laminate of the present invention.

The second glass run channel of the present invention includes a body having a grooved cross section and tongue drainages extending from the end of the side wall of the groove toward the center of the groove, wherein portions of the glass run channel in contact with the window glass are determined. It is composed of a layer of thermoplastic elastomer (A) composed of a polyolefin and a rubber and an ultrahigh molecular weight polyolefin composition (C) layer, the ultrahigh molecular weight polyolefin composition (C) layer is designed to be in contact with the window glass, Ultrahigh molecular weight polyolefins having an intrinsic viscosity [η] of 10 to 40 dl / g measured in 135 ° C decalin of the ultrahigh molecular weight polyolefin composition (C) and intrinsic viscosity [η] measured in 135 ° C decalin being 0.1 to 5 dl / g The polyolefin is an essential component, and the ultra high molecular weight polyolefin is present in an amount of 15 to 40% by weight based on 100% by weight of the total of the ultra high molecular weight polyolefin and the polyolefin. It is characterized by the intrinsic viscosity [η] measured in 135 degreeC decalin of an ultrahigh molecular weight polyolefin composition (C) being 3.5-8.3 dl / g.

The thermoplastic elastomer (A) used above is preferably those defined in the first thermoplastic elastomer laminate of the present invention.

The ultrahigh molecular weight polyolefin composition (C) may contain 1 to 20% by weight of a liquid or solid lubricant.

The third glass run channel of the present invention includes a body having a grooved cross section and tongue drains extending from the end of the side wall of the groove toward the center of the groove, wherein portions of the grass run channel in contact with the window glass are grafted. It is composed of a layer of modified thermoplastic elastomer (GA) and a layer of ultra high molecular weight polyolefin (B), the layer of the ultra high molecular weight polyolefin (B) is designed to contact the window glass, the graft modified thermoplastic elastomer (GA) ), (I) 95 to 10 parts by weight of peroxide crosslinked olefin copolymer rubber, (ii) 5 to 90 parts by weight of polyolefin (the total of the components (iii) and (ii) is 100 parts by weight), ( V) dynamic heat treatment and partial crosslinking of α, β-unsaturated carboxylic acids or derivatives thereof or blends containing 0.01 to 10 parts by weight of unsaturated epoxy monomers in the presence of an organic peroxide Eojin will be characterized in that the ultra high molecular weight polyolefin (B), 135 ℃ an intrinsic viscosity [η] is 10~40dl / g measured in decalin.

The fourth glass run channel of the present invention includes a body having a grooved cross section and tongue drainage portions extending from the end of the side wall of the groove toward the center of the groove, wherein portions of the glass run channel in contact with the window glass are grafted. It is composed of a layer of modified thermoplastic elastomer (GA) and a layer of ultra high molecular weight polyolefin composition (C), the layer of the ultra high molecular weight polyolefin composition (C) is designed to be in contact with the window glass, The graft-modified thermoplastic elastomer (GA) comprises (i) 95 to 10 parts by weight of peroxide crosslinked olefin copolymer rubber, (ii) 5 to 90 parts by weight of polyolefin (the sum of the components (iii) and (ii) 100 parts by weight), (iii) a bled containing 0.01 to 10 parts by weight of an α, β-unsaturated carboxylic acid or a derivative thereof, or an unsaturated epoxy monomer is subjected to dynamic heat treatment and The ultrahigh molecular weight polyolefin composition (C) obtained by crosslinking has an ultrahigh molecular weight polyolefin having an intrinsic viscosity [η] of 10 to 40 dl / g measured in 135 ° C decalin, and an extreme viscosity [η] measured in 135 ° C decalin. The polyolefin having 0.1 to 5 dl / g is an essential component, and the ultra high molecular weight polyolefin is present in an amount of 15 to 40% by weight based on 100% by weight of the total amount of the ultra high molecular weight polyolefin and the polyolefin, and the ultrahigh molecular weight polyolefin composition (C It is characterized by the intrinsic viscosity [eta] measured in 135 degreeC decalin of 3.5-8.3 dl / g.

The thermoplastic elastomer laminate according to the present invention and the glass run channels formed from the laminate will be described in detail.

First, the thermoplastic elastomer laminate of the present invention will be described.

The thermoplastic elastomer laminate of the present invention is roughly classified into the following four types.

The first thermoplastic elastomer laminate of the present invention is composed of a specific thermoplastic elastomer (A) layer and an ultrahigh molecular weight polyolefin (B) layer.

The second thermoplastic elastomer laminate of the present invention comprises a specific thermoplastic elastomer (A) layer and a specific ultrahigh molecular weight polyolefin composition (B).

According to the present invention, the third thermoplastic elastomer laminate is composed of a specific graft-modified thermoplastic elastomer (GA) layer and a specific ultrahigh molecular weight polyolefin (B) layer.

The fourth thermoplastic elastomer laminate of the present invention is composed of a specific graft thermoplastic elastomer (GA) layer and an ultrahigh molecular weight polyolefin composition (C) layer.

[Thermoplastic Elastomer (A)]

The thermoplastic elastomer (A) used in the 1st and 2nd thermoplastic elastomer (A) laminated body of this invention is comprised from crystalline polyolefin and rubber | gum.

As a crystalline polyolefin used by this invention, the homopolymer or copolymer of C2-C20 alpha olefin is mentioned.

Specific examples of the crystalline polyolefins used herein include the following (co) polymers.

(1) ethylene homopolymer (low pressure polyethylene, high pressure polyethylene), (2) copolymer of ethylene and other monomers of 10 mol% or less or vinyl monomers such as vinyl acetate, ethyl acrylate, (3) propylene homopolymer, (4) random copolymers of propylene and other α-olefins up to 10 mol%, (3) propylene homopolymers, (4) propylene and random copolymers of up to 10 mol% other α-olefins, (5) propylene Block copolymers of up to 30 mole% of other α-olefins (6) 1-butene homopolymers, (7) 1-butenes and random copolymers of up to 10 mole% of other α-olefins, (8 \) 4-methyl -1-pentene homopolymer, (9) 4-methyl-1-pentene and other α-olefin random copolymers of up to 2-mol%.

Specific examples of other α-olefins used in the copolymer include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, and the like.

The rubber used in the present invention is not particularly limited, and preferably an olefin copolymer rubber is mentioned.

The olefin copolymer rubber is an amorphous random elastomeric copolymer derived from an alpha -olefin having 2 to 20 carbon atoms, an amorphous alpha -olefin copolymer derived from two or more alpha -olefins, an alpha -olefin and at least two conjugates. (Alpha) -olefin / nonconjugated diene derived from diene is mentioned.

The solid example of the said olefin copolymer rubber used here is as follows.

(1) Ethylene / α-olefin copolymer rubber [Ethylene / α-olefin (molar ratio) = about 90/10 to 50 to 50]

(2) Ethylene / α-olefin / non-conjugated diene copolymer rubber [ethylene / α-olefin (molar ratio) = about 90/10 to 50/50]

(3) Propylene / α-olefin copolymer rubber [propylene / α-olefin (molar ratio) = about 90/10 to 50/50]

(4) Butene / α-olefin copolymer rubber [butene / α-olefin (molar ratio) = about 90/10 to 50/50]

The α-olefins used in the copolymer rubber may be the same α-olefins as those used to form the crystalline polyolefin contained in the thermoplastic elastomer (A).

Specific non-conjugated dienes used in the copolymer include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbo and the like.

The copolymer rubbers exemplified above have a Mooney viscosity ML _{1 + 4} (100 ° C.) of 10 to 250, particularly 40 to 150, and have an iodide of 25 or less when copolymerized with the non-conjugated diene.

In the thermoplastic elastomer of the present invention, the olefin copolymer rubber may exist in a non-crosslinked state, a partially crosslinked state, or a total crosslinked state, but is preferably present in a partially crosslinked state.

In addition to the olefin copolymer rubbers, examples of rubbers useful in the present invention include dienes such as styrene-butadiene rubber (SBR), nitrile rubber (NBR), natural rubber (NR) butyl rubber (IIR), SEBS, and polystyrene. There are rubber.

In the thermoplastic elastomer used in the present invention, the crystalline polyolefin / rubber weight ratio is 90/10 to 10/90, preferably 70/30 to 10/90.

When using the combination of the said olefin copolymer rubber and another rubber as the rubber in this invention, the use ratio of the said other rubber is 40 weight part or less with respect to a total of 100 weight part of the said crystalline polyolefin and the said rubber. Preferably it is 5-20 weight part.

Thermoplastic elastomers preferably used in the present invention include crystalline polypropene and ethylene / α-olefin copolymer rubber or ethylene / α-olefin / nonconjugated diene copolymer rubber, and the crystalline polypropylene and copolymer rubber Is present in a partially crosslinked state, and the crystalline polypropylene / rubber weight ratio is 70/30 to 10/90.

A mineral oil softener, a heat stabilizer, an antistatic agent, a weathering stabilizer, an antiaging agent, a filler, a coloring agent, a lubricating agent, etc. can be mix | blended with the said thermoplastic elastomer as needed.

More specific examples of the thermoplastic elastomer preferably used in the present invention include rubber (b) 40 consisting of 60 to 10 parts by weight of crystalline polypropylene (a) and ethylene / propylene copolymer rubber or ethylene / propylene / diene copolymer rubber. A mixture containing ˜90 parts by weight (the sum of the parts (a) and (b) is 100 parts by weight) and rubber (b) other than rubber (c) and / or mineral oil softener (d) 5-100 parts by weight, There are those obtained by partial crosslinking of the rubber (b) by dynamic heat treatment in the presence of an organic peroxide.

Specific examples of the organic peroxides that can be used to prepare the thermoplastic elastomers of the present invention include dicumyl peroxide, di-t-butylperoxide, 2,5-dimethyl-2,5-di (t-butylperoxine ) Hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyn-3, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butyl Peroxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2, 4-dichlorobenzoyl Peroxide, t-butylperoxy benzoate, t-butylperbenzoate, t-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, t-butycumyl peroxide and the like.

Among them, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylper) in terms of aromaticity and scorch stability Oxy) hexine-3, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and n-butyl-4 , 4-bis (t-butylperoxy) valerate is preferred, with 1,3-bis (t-butylperoxyisopropyl) benzene being most preferred.

In the present invention, the amount of the organic peroxide used is usually 0.05 to 3% by weight, preferably 0.1 to 1% by weight based on 100% by weight of the total of the crystalline polyolefin and rubber.

In the present invention, in the partial crosslinking treatment using the organic peroxide, sulfur, P-quinone dioxime, P, P'-dibenzoyl quinone dioxime, N-methyl-N-4-dinitrosoaniline, Peroxy crosslinking bonding aids such as nitrosobenzene, diphenyl guanidine and trimethylol propane-N, N'-m-phenylene dimaleimide, divinylbenzene, triallyl cyanurate; Polyfunctional methacrylate monomers such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylol propane trimethacrylate and allyl methacrylate; Polyfunctional vinyl monomers, such as vinyl butyrate and vinyl stearate, can be used.

In the partial crosslinking treatment, by using the compounds exemplified above, a uniform and gentle crosslinking reaction can be expected.

Among the above compounds, divinyl benzene is most preferably used in the present invention because it is easy to handle and compatible with crystalline polyolefins and rubbers, which are the main components of the material to be treated, and has a dispersant action on organic peroxides, By maintaining the crosslinking effect by the heat treatment uniformly, a thermoplastic elastomer having a good balance between fluidity and physical properties can be obtained.

The amount of the crosslinking aid or polyfunctional vinyl monomer used is preferably 0.1 to 2% by weight, in particular 0.3 to 1% by weight. When the amount of the crosslinking aid or the polyfunctional vinyl monomer exceeds 2% by weight, when the amount of the organic peroxide used is large, the crosslinking reaction proceeds at an excessive speed, and the thermoplastic elastomer obtained is poor in fluidity, and on the other hand, the organic When the amount of peroxide is small, the obtained thermoplastic elastomer may cause a change in physical properties due to the thermal history during the processing. Therefore, the crosslinking aid and the polyfunctional vinyl monomer should not be used in excess.

In this specification, the term “dynamic heat treatment” means to knead the above components in a molten state.

The kneading apparatus used for the dynamic heat treatment may use conventional ones such as an open mixing roll, a closed Banburi mixer, an extruder, a kneader, and a continuous mixer.

Among these kneading apparatuses, closed ones are preferable, and kneading is preferably performed in an inert gas atmosphere such as nitrogen gas or carbon dioxide gas. In addition, the kneading is preferably performed at a temperature at which the half life of the organic peroxide used is less than 1 minute.

The kneading temperature is usually 150 to 280 ° C, preferably 170 to 240 ° C, and the kneading time is 1 to 20 minutes, preferably 3 to 10 minutes. Applying shear strength is a 10~10 ⁴ sec ^-1, preferably 10 ² ~ 10 ³ sec ^-1.

Thermoplastic elastomers preferably used in the present invention are those that are partially crosslinked. The term “partially crosslinked” herein means a case in which the gel content of the thermoplastic elastomer is 20 to 98% as measured by the following method, and in the present invention, preferred thermoplastic elastomers are those having a gel content of 45 to 98%. to be.

[Measurement of Gel Content]

As a sample, about 100 mg of pellets of the thermoplastic elastomer are weighed and soaked in a closed container in a sufficient amount of 30 ml of cyclohexane at 23 ° C. for 48 hours.

The sample is then taken out of the container, placed on filter paper and dried for at least 72 hours at room temperature until constant weight is reached.

The gel content of the sample is represented by the following formula.

Gel content% = (dry weight after cyclohexane immersion) / (weight before cyclohexane immersion) x 10,000

Since the thermoplastic elastomer (A) which comprises 1 layer of the 1st and 2nd thermoplastic elastomer laminated body of this invention consists of crystalline polyolefin and rubber | gum, it is excellent in fluidity | liquidity.

[Graft Modified Thermoplastic Elastomer (GA)]

The graft modified thermoplastic elastomers (GA) used in the third and fourth thermoplastic elastomer laminates of the present invention include (a) peroxide crosslinked olefin copolymer rubbers, (b) polyolefins, and (c) α, β-unsaturated. Carboxylic acids or derivatives thereof or blends containing unsaturated epoxy monomers are those obtained by dynamic heat treatment and partial crosslinking treatment in the presence of an organic peroxide.

The blend used in the present invention may contain (d) a peroxide non-crosslinked rubbery material and (e) a molten softener.

The peroxide crosslinked olefin copolymer rubber (a) used in the blend has a low fluidity or does not flow when crosslinked by mixing with an organic peroxide and kneading under heating, for example ethylene / propylene / ratio Amorphous elastomeric copolymers derived from olefins such as conjugated diene copolymer rubber or ethylene / butadiene copolymer rubber.

The non-conjugated dienes contained in the ethylene / propylene / non-conjugated diene copolymer rubber are specifically dicyclopentadiene, 1,4-hexadiene, dicyclooctadiene, methylene-norbornene, ethylidene-norbornene and the like. There is this.

Among the peroxide crosslinked olefin copolymer rubbers (a), those preferably used in the present invention include an ethylene component unit / propylene component unit molar ratio of 50/50 to 90/10, particularly 55/45 to 85/15, Ethylene / propylene copolymer rubber, or ethylene / propylene nonconjugated diene rubber.

Of these copolymer rubbers, ethylene / propylene / nonconjugated diene copolymer rubber, in particular ethylene / propylene / ethylene-norbornene copolymer rubber, can provide thermoplastic elastomers excellent in heat resistance, tensile strength properties and impact resistance, Particularly preferred.

Preferably, the peroxide crosslinked olefin copolymer rubber has a Mooney viscosity ML _{1 + 4} (100 ° C.) of 10 to 250, in particular 40 to 250.

When the said peroxide crosslinked olefin copolymer rubber whose pattern viscosity ML1 _{+ 4} (100 degreeC) is less than 10 is used, the tensile strength characteristic of the obtained thermoplastic elastomer composition will fall.

On the other hand, when a Mooney viscosity ML _{1 + 4} (100 degreeC) uses the peroxide crosslinked olefin copolymer rubber more than 250, the thermoplastic elastomer composition obtained tends to fall fluidity.

It is preferable that the said peroxide crosslinked olefin copolymer rubber has a iodine number of 25 or less. When the peroxide crosslinked olefin copolymer rubber having such an iodine value is used, the obtained thermoplastic elastomer has a good balance between fluidity and rubber properties.

The peroxide crosslinked olefin copolymer rubber (a) is 95 to 10 parts by weight, preferably 95 to 60 parts by weight based on 100 parts by weight in total of the peroxide crosslinked olefin copolymer rubber (a) and the polyolefin (b). It is commonly used in negative proportions.

When the peroxide crosslinked olefin copolymer rubber (a) is used in the above ratio, the obtained graft-modified thermoplastic elastomer (GA) is excellent in moldability and rubber properties such as rubber elasticity.

The polyolefin (b) used in the present invention is composed of a crystalline high molecular weight product obtained by high or low pressure polymerization of at least one monoolefin. Examples of such resins include isotactic or syndiotacitc monoolefin polymers.

Representatives of such resins are commercially available.

Specific examples of suitable raw material olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 1-octene, 1-decene and mixed olefins of two or more of these olefins. In the present invention, the raw olefins may be homopolymerized or copolymerized regardless of the polymerization technique, as long as a resinous product is obtained.

Peroxide degradable polyolefins are the most preferred polyolefins.

The peroxide decomposable polyol peffin refers to a polyolefin which is mixed with a peroxide and pyrolyzed during heat kneading to lower the molecular weight, thereby increasing the fluidity of the obtained resin. Examples of such polyolefins are copolymers of isotactic polypropylene propylene with small amounts of other α-olefins, such as propylene / ethylene copolymers, propylene / 1-butene copolymers, propylene / 1-hexene copolymers, propylene / 4-methyl-1-pentene copolymer, and the like.

The polyolefin used in the present invention preferably has a melt index (ASTM-D 1239-65T, 23 ° C.) of 0.1 to 50, in particular 5 to 20.

The use of the polyolefin is preferable for improving not only heat resistance but also fluidity of the thermoplastic elastomer composition.

The use amount of the polyolefin (b) is 5 to 90 parts by weight, preferably 5 to 40 parts by weight based on 100 parts by weight of the total amount of the peroxide crosslinked copolymer rubber (a) and the polyolefin (b).

When the said polyolefin (b) is used in the said ratio, since the obtained graft modified thermoplastic elastomer (GA) is excellent in rubber characteristics, such as rubber elasticity, and fluidity | liquidity, the said elastomer (GA) is excellent in moldability.

Said (alpha), (beta)-unsaturated carboxylic acid or its derivative (s), or unsaturated epoxy monomer (C) is used as a graft modifier.

Specific examples of the α, β-unsaturated carboxylic acid or derivatives thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid and bicyclo- [2,2,1] hept-2-ene. Unsaturated carboxylic acids such as -5,6-dicarboxylic acid; Anhydrides of unsaturated carboxylic acids such as maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic anhydride; Methyl acrylate, methyl methacrylate, dimethyl maleate, monomethyl maleate, diethyl fumarate, dimethyl itaconic acid, diethyl citraconate, dimethyl anhydrous tetrahydrophthalate, bicyclo [2,2,1] hept-2-ene- Esters of unsaturated carboxylic acids such as 5,6-dicarboxylic acid dimethyl and the like.

Of these, maleic acid, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid or anhydrides thereof and the like are more preferable.

Specific examples of the unsaturated epoxy monomers include glycidyl esters of unsaturated monocarboxylic acids such as glycidyl acrylate, glycidyl methacrylate, or glycidyl P-stearyl carboxylate; Maleic acid, itaconic acid, citraconic acid, butenetricarboxylic acid, endo-cis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid, or endo-cis-bicyclo [2, Monoglycidyl esters or polyglycidyl esters of unsaturated carboxylic acids such as 2,1] hept-ene-2-methyl-2,3-dicarboxylic acid; Allyl glycidyl ether, 2-methylallyl glycidyl ether, glycidyl ether of 0-allylphenol, glycidyl ether of m-allylphenol, glycidyl ether of p-allylphenol, isopropenylphenol Unsaturated glycidyl ethers such as glycidyl ether, glycidyl ether of m-biphenol, or glycidyl ether of P-biphenol; 2- (O-vinylphenyl) ethylene oxide, 2- (P-vinylphenyl) ethylene oxide, 2- (O-vinylphenyl) propylene oxide, 2- (P-vinylphenyl) propylene oxide, 2- (O-allylphenyl) ethylene oxide, 2- (P-allylphenyl) ethylene oxide, 2- (O-allylphenyl) ethylene oxide, 2- (P-allylphenyl) propylene oxide, P-glycid Dill styrene, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene , 5,6-epoxy-1-hexene, vinylcyclohexene monooxide or allyl-2,3-epoxycyclopentyl ether and the like can be exemplified.

The amount of the α, β-unsaturated carboxylic acid or derivative thereof or unsaturated epoxy monomer (c) is 0.01 to 100 based on 100 parts by weight of the total of the peroxy crosslinked olefin copolymer rubber (a) and polyolefin (b). Parts by weight, preferably 0.1 to 5 parts by weight.

As described above, when the α, β-unsaturated carboxylic acid or derivative thereof or unsaturated epoxy monomer (c) is used in the above amount, the obtained graft-modified thermoplastic elastomer (GA) is excellent in moldability and the ultra-high molecular weight polyolefin Excellent adhesion to layer (B) or to the ultrahigh molecular weight polyolefin composition layer (C).

The peroxide non-crosslinked rubbery material (d) used in the present invention is, for example, polyisobutylene, butyl rubber, propylene / ethylene copolymer rubber or isotactic polypropylene having a propylene content of 70 mol% or more. As described above, it refers to a hydrocarbon rubbery material which does not crosslink and does not reduce fluidity even when mixed with peroxide and kneaded under heating in the same manner as described above.

Among them, polyisobutylene is particularly preferable because polyisobutylene is excellent in physical properties and easy to handle.

The peroxide non-crosslinked rubber material (d) contributes to improving the fluidity of the elastomer composition, and particularly those having a Mooney viscosity ML _{1 + 4} (100 ° C.) of 60 or less are preferred.

In the present invention, the use ratio of the peroxide non-crosslinked rubbery material (d) is 5 to 100 parts by weight based on a total of 100 parts by weight of the peroxide crosslinked olefin copolymer rubber (a) and the polyolefin (b). Preferably it is 5-50 weight part.

The light softening agent (e) used in the present invention usually weakens the intermolecular attraction of the rubber to promote the rolling of the rubber, assists in dispersing fillers such as carbon black or white carbon, or lowers the hardness of the vulcanized rubber. It is used to increase the flexibility or elasticity of vulcanized rubber.

The mineral oil softener (e) is usually classified into paraffinic, naphthenic and aromatic softeners.

The usage-amount of the said mineral oil softener (e) is 3-100 weight part with respect to a total of 100 weight part of a peroxide crosslinked olefin copolymer rubber (a) and a polyolefin (b), Preferably it is 5-80 weight part.

The graft-modified thermoplastic elastomer (GA) used in the present invention includes the peroxy crosslinked olefin copolymer rubber (a), polyolefin (b) and α, β-unsaturated carboxylic acid or a derivative thereof or an unsaturated epoxy monomer (c), If necessary, the blend obtained by mixing the peroxide non-crosslinked rubbery material (d) and mineral oil softener (e) in the above ratio is prepared by a method of dynamic thermal treatment in the presence of an organic peroxide, followed by partial crosslinking.

It is preferable to use the peroxide non-crosslinked rubbery material (d) and mineral oil softener (e).

A filler and a coloring agent can be mix | blended with the graft modified thermoplastic elastomer (GA) used by this invention to the extent which does not impair the objective of this invention.

Specific examples of the fillers used in the present invention include calcium carbonate, calcium sulfate, clay, kaolin, talc, silica, diatomaceous earth, mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide , Graphite, glass fiber, glass beads, pumice ballon, carbon fiber and the like.

Specific examples of the coloring agent include carbon black, titanium oxide, zinc oxide, iron oxide red (i ron oxide red, ultramarine blue, Prussian blue, azo pigments, natroso pigments, lake pigments, phthalocyanine pigments, and the like. There is this.

The graft-modified thermoplastic elastomer (GA) includes known heat stabilizers such as phenol, sulfite, phenylalkane, phosphite and amine stabilizer; Anti-aging agent; Weather stabilizer; Antistatic agent; Slip slip agents, such as a metal soap and a wax, etc. can further be contained in the ratio normally employ | adopted for manufacture of polyolefin or an olefin copolymer rubber.

Partially crosslinked graft modified thermoplastic elastomers (GA) may be prepared by dynamic heat treatment of a blend comprising the components in the presence of an organic peroxide.

The "dynamic heat treatment" means to knead the components together in a molten state.

The goodness of the organic peroxide used in the preparation of the graft modified thermoplastic elastomer (GA) is the same as that used in the case of the thermoplastic elastomer (A) described above.

The use ratio of the organic peroxide is 100% by weight in total of the peroxide crosslinked olefin copolymer rubber (a), polyolefin (b) and α, β-unsaturated carboxylic acid or derivatives thereof, or unsaturated epoxy monomer (c). 0.05 to 3% by weight, preferably 0.1 to 1% by weight.

When the organic peroxide is used in the above ratio, the obtained graft modified thermoplastic elastomer (GA) is excellent in rubber properties such as heat resistance, tensile properties, elastic recovery and impact elasticity, strength properties, and excellent moldability.

The kneading conditions such as kneading temperature, kneading time, shear force, etc. of the kneading apparatus used in the manufacture of the graft modified thermoplastic elastomer (GA) are the same as those used in the case of the thermoplastic elastomer (A).

The polyfunctional methacrylate monomers and the polyfunctional vinyl monomers, which can be used in the partial crosslinking treatment with the organic peroxide, are the same as those used in the case of the thermoplastic elastomer (A).

The effect obtained by the crosslinking aid and the polyfunctional methacrylate monomer is the same as that expected in the case of the thermoplastic elastomer (A), and the amount of use thereof is also the same as in the case of the thermoplastic elastomer (A).

In this connection, the use of the crosslinking aid or the polyfunctional vinyl monomer, especially the amount of use of these compounds, is the same as in the case of the thermoplastic elastomer (A).

In addition, in order to accelerate the decomposition of the organic peroxide, tertiary amines such as triethylamine or 2,4,6-tris (dimethylamine) phenol, and naphthenates, that is, aluminum, cobalt vanadium, copper and calcium And decomposition accelerators such as zirconium, manganese, magnesium, naphthenate of lead or mercury.

The graft modified thermoplastic elastomers used in the present invention are partially crosslinked. By “partially crosslinked” it is meant that the gel content of the elastomer is 20-98%, preferably 45-98%.

The gel content of the elastomer is determined by the same method employed in the case of the thermoplastic elastomer (A).

The graft modified thermoplastic elastomer (GA), which constitutes one of the filaments of the third and fourth thermoplastic elastomer laminates of the present invention, consists of partially crosslinked olefin copolymer rubbers and polyolefins, in particular the peroxide degradable polyolefins. Therefore, fluidity is excellent.

[Ultra High Molecular Weight Polyolefin (B)]

Ultra high molecular weight polyolefins (B) used in the first and third thermoplastic elastomer laminates of the present invention are, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, Lubrication resins, such as a homopolymer or copolymer of alpha-olefins, such as 1-dodecene, 4-methyl-1- pentene, and 3-methyl-1- pentene. Among these polymers, ethylene homopolymers and copolymers of ethylene and other α-olefins as main components are preferred.

Ultrahigh molecular weight polyolefins having an ultimate viscosity [η] of 10 to 40 dl / g, especially 15 to 35 dl / g, measured in 135 ° C decalin are preferred.

In the ultrahigh molecular weight polyolefin (B), the same filler and colorant as those used in the graft-modified thermoplastic elastomer (GA) can be blended in the same manner.

In addition, in the ultrahigh molecular weight polyolefin (B) used in the present invention, the same additives used in the graft-modified thermoplastic elastomer (GA) may be blended in the proportions commonly used for preparing olefin plastics or olefin copolymer rubbers. .

[Ultra High Molecular Weight Polyolefin Composition (C)]

The ultrahigh molecular weight polyolefin composition (C) used in the second and fourth thermoplastic elastomer laminates of the present invention is an ultrahigh molecular weight polyolefin having an intrinsic viscosity [η] of 10 to 40 dl / g in 135 ° C decalin, and 135 ° C. A low molecular weight or high molecular weight polyolefin having an intrinsic viscosity [η] of 0.1 to 5 dl / g measured in decalin is an essential component, and the ultra high molecular weight polyolefin is based on 100% by weight of the total of the ultra high molecular weight polyolefin and the low molecular or high molecular weight polyolefin. It exists in the ratio of 15-40 weight%, and the intrinsic viscosity [eta] measured in 135 degreeC decalin of the said ultrahigh molecular weight polyolefin composition (C) is 3.5-8.3 dl / g.

The ultrahigh molecular weight polyolefin, which is a constituent material of the composition (C), is the ultrahigh molecular weight polyolefin (B) having an intrinsic viscosity [η] as described above.

The low molecular weight or high molecular weight polyolefin other than the ultra high molecular weight polyolefin in the composition (C) may be ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, Homopolymers or copolymers of α-olefins such as 4-methyl-1-pentene and 3-methyl-1-pentene.

In this invention, the ethylene homopolymer and the copolymer of ethylene and another alpha olefin are used suitably as said low molecular weight or high molecular weight polyolefin.

The ultrahigh molecular weight polyolefin composition (C) may contain 1 to 20% by weight of a liquid or solid lubricant based on the composition (C).

Liquid lubricants used in the composition (C) include petroleum lubricants and synthetic lubricants.

Specific examples of the petroleum lubricating oil used above include liquid paraffin, spindle oil, refrigerant oil, dynamo oil, turbine oil, machine oil, cylinder oil and the like.

Specific examples of the synthetic lubricating oil to be used include synthetic hydrocarbon oils, polyglycol oils, polyphenyl ether oils, ester oils, phosphate ester oils, polychlorotrifluorofluoroethylene oils, fururoester oils, chlorinated biphenyl oils, silicone oils, and the like. There is this.

Specific examples of the solid lubricant mainly used in the composition (C) include graphite and molybdenum disulfide. However, in addition, boron nitride, tungsten disulfide, lead oxide, glass powder, metal soap, etc. can be used. The solid lubricant can be used alone or in combination with a liquid lubricant and, for example, such combined lubricant can be added to the ultrahigh molecular weight polyolefin composition in the form of a sol, gel, or suspension.

In the ultrahigh molecular weight polyolefin composition (C), additives such as mineral oil softeners, heat stabilizers, antistatic agents, weather stabilizers, heat aging agents, fillers, colorants, slip agents, etc., as necessary, are not impaired within the scope of the present invention. Can be added.

In manufacturing the thermoplastic elastomer laminate of the present invention, the ultrahigh molecular weight polyolefin composition (C) can be coextruded with the thermoplastic elastomers ((A) and (GA)], and the thermoplastic elastomer layer and the ultrahigh molecular weight The polyolefin composition layers can be laminated directly with one another without a film (sheet) forming process, which is economical.

On the other hand, the ultrahigh molecular weight polyolefin (B) having an ultimate viscosity [η] of 10 to 40 dl / g measured in 135 ° C decalin is co-extruded with the thermoplastic elastomers ((A) and (GA)] as it is. It cannot be laminated directly by. Therefore, when laminating the thermoplastic elastomer layer and the ultra high molecular weight polyolefin layer, at least one of the layers must be molded into a film (or sheet) in advance, and thus, it is uneconomical compared with the ultra high molecular weight polyolefin composition (C). .

[Thermoplastic elastomer laminate]

The first thermoplastic elastomer laminate of the present invention is composed of the thermoplastic elastomer (a) layer and the ultrahigh molecular weight polyolefin (B) layer.

The first thermoplastic elastomer laminate of the present invention can be obtained by laminating the two layers together.

The thermoplastic elastomer (A) layer (hereinafter referred to as (A) layer), depending on the shape, size and required properties of the desired final product, together with the ultra-high molecular weight polyolefin (B) layer by the following method It can laminate | stack and it is not specifically limited to this method.

(1) A lamination method in which the manufactured (A) and (B) layers are melt-bonded to each other by a calender roll forming machine or a compression molding machine at a temperature higher than the melting point of at least one of these layers.

(2) A lamination method in which one of the layers (A) and (B) is previously formed as a sheet, and this is melt-compressed to another layer in an extrusion calender.

In the first thermoplastic elastomer laminate of the present invention as described above, since the layer made of the thermoplastic elastomer (A) is composed of crystalline polyolefin and rubber, it is excellent in heat resistance, heat aging resistance, and rubber elasticity.

In the first thermoplastic elastomer laminate of the present invention, the layer made of the ultra high molecular weight polyolefin (B) is excellent in wear resistance, scratch resistance, sliding resistance and chemical resistance.

The 2nd thermoplastic elastomer laminated body of this invention is comprised from the said thermoplastic elastomer (A) layer and the said ultrahigh molecular weight polyolefin composition (C) layer.

The second thermoplastic elastomer laminate of the present invention can be obtained by stacking the two layers with each other, and the method of obtaining them depends on the shape, size, and physical properties of the desired final product, but is not particularly limited.

The layer (A) may be laminated to the ultrahigh molecular weight polyolefin composition in a manner similar to that used in the case of the first thermoplastic elastomer laminate of the present invention.

In addition, in manufacturing the second thermoplastic elastomer laminate of the present invention, the following lamination method (3) can be used.

(3) A method of coextruding the (A) layer and the (C) layer with another extrusion molding machine to perform these melt bonding.

In this invention, the said method (3) is a favorable lamination method.

In the second thermoplastic elastomer laminate of the present invention, since the layer containing the thermoplastic elastomer (A) is composed of crystalline polyolefin and rubber, it is excellent in heat resistance, heat aging resistance and rubber elasticity.

In the second thermoplastic elastomer laminate of the present invention, the layer made of the ultrahigh molecular weight polyolefin composition (C) is excellent in wear resistance, scratch resistance, sliding resistance and chemical resistance.

The third thermoplastic elastomer laminate of the present invention is composed of a layer made of the graft-modified thermoplastic elastomer (GA) and a layer made of the ultrahigh molecular weight polyolefin (B).

The third thermoplastic elastomer laminate of the present invention can be obtained by laminating the two layers.

In this case, the same lamination method as in the case of the first thermoplastic elastomer laminate of the present invention can be adopted.

The layer composed of the graft modified thermoplastic elastomer (GA) in the third thermoplastic elastomer laminate of the present invention contains partially crosslinked copolymer rubber, polyolefin, preferably peroxide degradable polyolefin.

The fourth thermoplastic elastomer laminate of the present invention is composed of a layer made of the graft-modified thermoplastic elastomer (GA) and a layer made of the ultrahigh molecular weight polyolefin composition (C).

The 4th thermoplastic elastomer laminated body of this invention can be obtained by laminating | stacking said 2 layers mutually.

In this case, the same lamination method as in the second thermoplastic elastomer laminate of the present invention can be adopted, and the coextrusion method (3) is preferred.

In the fourth thermoplastic elastomer laminate of the present invention, the layer of the graft modified thermoplastic elastomer (GA) is composed of a partially crosslinked olefin copolymer rubber and a polyolefin, preferably a peroxide decomposed polyolefin, so that it is heat-resistant and heat-resistant furnace. Excellent chemical conversion and rubber elasticity.

In the first to fourth thermoplastic elastomer laminates of the present invention, the thickness of the thermoplastic elastomer (A) layer and the graft-modified thermoplastic elastomer (GA) layer is 0.1 to 50 mm, and the ultra high molecular weight polyolefin (B) layer and the ultra high molecular weight polyolefin composition. The thickness of (C) layer is 5 micrometers-10 mm.

An example of the glass run channel of the present invention will be described in detail with reference to the accompanying drawings.

In FIG. 1 showing an example of the glass run channel of the present invention in cross section, the glass run channel includes a main body 2 having a groove-shaped (U-shaped) cross section, and a groove side from the side wall end of the groove toward the center side of the groove. It includes an extended tongue drain 3.

The drain pairs 3 and 3 are inclined inside the grooves of the main body 2, and the outer surface of each drain portion becomes the window contact part 4, and the points 5 of the window glass contact part 4 are provided. 5) is in a positional relationship that can be opened and closed with each other on their own. The main body 3 has hooks on both side walls thereof for fitting the main body 2 to the window frame.

The main body 2 and the drainage portions 3, 3 are integrally molded from an elastomer. According to the present invention, at least the window glass contacts 4, 4 contain a base layer composed of the thermoplastic elastomer (A) or the graft modified thermoplastic elastomer (GA), and the ultra high molecular weight polyolefin (B) or ultra high molecular weight polyolefin composition. It is composed of a laminate made of one lubricant resin, that is, the laminate may be any one of the first to fourth thermoplastic elastomer laminates of the present invention.

As indicated in FIG. 2 showing an enlarged view of the window glass contact 4, it is preferred that the base layer 7 has a rough surface 8. On this shark skin surface 8, the lubricant resin layer 9 having a surface 10 similar to the two surfaces 8 is laminated by melt bonding.

In the third, fourth, and fifth degrees representing an aspect in which the glass run channel is fitted into the vehicle window, the vehicle door is provided with a window glass 12 which can be opened and closed by vertical operation, and in the window frame 13. The glass run channel 1 is tightened. As shown in FIG. 4 and FIG. 5, the window frame 13 is formed to have a U-shape as a whole, and the inward protrusion 15 is formed at the inlet of the recess 14 of the window frame 13. Is formed. The glass run channel 1 is inserted into the recess 14 of the window frame 13 and the width 6 of the channel 1 is coupled to the protrusion 15 so that the glass run channel ( 1) is fixed to the window frame 13.

As shown in FIG. 4, when the window glass 12 is in an inward state, the points 5, 5 of the glass sliding parts 4, 4 become close enough to face each other, as shown in FIG. As described above, when the window glass is in an ascending state, the points 5 and 5 are separated by the window glass 12 inserted between the points 5 and 5, while the points 5 and 5 are separated. The window glass 12 is in contact with the surface.

In the glass run channel 1 of the present invention, at least a part of the channel in contact with the window glass is composed of the substrate 7 composed of the thermoplastic elastomer A or the graft modified thermoplastic elastomer GA, and the substrate 7 It is provided with the lubrication resin layer 9 comprised from the said ultra high molecular weight polyolefin (B) or the ultra high molecular weight polyolefin composition (C) melt-bonded on the surface.

That is, the thermoplastic elastomer used in the present invention can be thermoformed into a thermoformed article of any shape and dimension, and at the same time, it is excellent in the characteristics required for the window glass sliding part of the glass run channel such as elasticity, flexibility, and compressibility. It has excellent properties such as durability, weather resistance and water resistance.

In addition, the main body 2 and the base layer 7 of the drainage portion 3 of the glass run channel composed of the thermoplastic elastomer have excellent rubber properties such as heat resistance, tensile properties, flexibility, impact elasticity, and the like. Particularly preferably used thermoplastic elastomers are graft modified thermoplastic elastomers partially crosslinked with the partially crosslinked thermoplastic elastomer.

The thermoplastic elastomer can be molded into a molded article by a conventional molding apparatus such as compression molding, transfer molding, injection molding and extrusion processing.

The thermoplastic elastomer (A) and the graft-modified thermoplastic elastomer (GA) exhibit strong adhesion to the lubrication resin layer 9 composed of the ultra high molecular weight polyolefin (B) or the ultra high molecular weight polyolefin composition (C), and the resin layer (9) constitutes the surface material layer of the base layer (7) and is a laminated structure excellent in interlaminar strength immediately after adhesion and after time elapsed by melt bonding with the lubricity resin layer (9) and excellent in interlaminar strength after weathering test. Can be formed. Moreover, in this invention, the thermoplastic elastomer used for manufacture of the said base layer 7 can be shape | molded by the molded article which has a sharkskin-like surface, This molding process, the said lubricating resin layer 9, and the said base layer 7 By using together the fusion | melting adhesion process of the liver, a sharkskin-like surface pattern can be reproduced favorably on the outer surface of the said lubricity resin layer 9.

However, according to the conventional coating treatment using the adhesive as described above, it is extremely difficult to reproduce the sharkskin pattern as described above on the outer surface of the lubricity resin layer. It can only be achieved by using a combination of processes.

As described above, according to the present invention, a glass run channel can be efficiently manufactured with a small number of processes and reduced time and effort, while conventionally such as adhesive coating, curing or firing of a coated adhesive, and embossing of a target pattern. All necessary processes can be omitted. In addition, by providing the lubricity resin layer 9 composed of the ultra-high molecular weight polyolefin (B) or the like as the surface material layer of the base layer 7, it is possible to reduce the friction coefficient between the window glass and the glass run channel. In addition, compared with the uneven | corrugated pattern obtained by the embossing process of a prior art, a sharkskin-like protrusion part can be formed in uniform spot shape on the outer surface of the said lubrication resin layer 9. Therefore, in the glass run channel of the present invention, the window glass may be in contact with the glass run channel (liquid hermetic) when the window glass is closed, and at the same time, the window may be reduced by the reduction of sliding friction when opening the window glass. The glass can be opened and closed smoothly and lightly.

In the glass run channel of the present invention, it is preferable that the material of the drains 3 and 3 is the same as the material of the body 2.

When the main body 2 is constituted with the thermoplastic elastomer as described above, the drainage parts 3.3 made of the same material of the main body 2 are not only durable, but also of the degree of adhesion to the lubricity resin layer 9. It is also practical.

Sharkskin (dry or scaly skin) phase patterns useful in the glass run channels of the present invention can be exhibited during molding by appropriately selecting the physical properties of the starting thermoplastic elastomer.

The appearance of the shark-skin obtained as described above is different from the melt fracture which may appear during compression molding of the resin or elastomer, and the molded article having such sharkskin on its surface is repeatedly coarse, Have

In addition, the surface of the lubricity resin layer 9 laminated on the surface of the sharkskin pattern has the same sharkskin pattern as shown on the surface, and therefore, the lubrication resin layer 9 is usually 3 to 50 µm. It is laminated on the sharked pattern surface with a thickness of. If necessary, the thickness of the lubricating resin layer 9 may be thicker or more than the defined value.

Since the place where the drainage parts 3 and 3 come into contact with the window glass 12 usually changes when the window glass enters and exits the place, the coating of the lubricating resin, and if necessary, shaping the pattern, It is desirable to cover the relatively large space of the drains 3, 3.

In the glass run channel shown in FIG. 1, an in-side portion 16 of the channel is indicated, the end of the window glass being aligned opposite this portion, and the surface of the portion 16 is It may be coated with a lubricating resin layer 9 composed of ultra high molecular weight polyolefin (B) or the like.

The first to fourth thermoplastic elastomer laminates of the present invention are between the thermoplastic elastomer (A) layer and the ultrahigh molecular weight polyolefin (B) layer, between the thermoplastic elastomer (A) layer and the ultrahigh molecular weight polyolefin composition (C) layer, and the graft-modified thermoplastic elastomer. The interlayer adhesion between the (GA) layer and the ultrahigh molecular weight polyolefin (B) layer and between the graft modified thermoplastic elastomer (GA) layer and the ultrahigh molecular weight polyolefin composition (C) layer is excellent, respectively.

The first to fourth thermoplastic elastomer laminates of the present invention are lighter than vulcanized rubber or a composite material composed of nylon fibers or non-rigid PVC, and do not have surface adhesion due to leakage of a plasticizer or the like, and have mechanical strength, heat resistance, and heat. It has excellent aging characteristics, weather resistance, abrasion resistance, scratch resistance, sliding property and dimensional stability.

The first to fourth thermoplastic elastomer laminates of the present invention can be produced by a simple process as compared with the conventional composite materials as described above, and thus are excellent in economy. In particular, the thermoplastic elastomer laminate having an ultra-high molecular weight polyolefin composition (C) layer, the coextrusion lamination of the thermoplastic elastomer (A) and the ultra-high molecular weight polyolefin composition (C), or the graft modified thermoplastic elastomer (GA) and the Since it can manufacture by the coextrusion layer of an ultrahigh molecular weight polyolefin composition (C), it is more economical than the thermoplastic elastomer which has the said ultrahigh molecular weight polyolefin (B) layer.

The first to fourth thermoplastic elastomers of the present invention have the same effect as described above, and include interior automotive trims or sealing materials (especially glass run channels or belt line moles for lubrication with glass, furniture, building materials). It can be used for appliance housing, bag clothing case, sports goods, office grabbing, miscellaneous goods.

The glass run channel of the present invention is excellent in durability, intimate contact with the window glass when it is closed, and light sliding performance during opening and closing operation, because the thermoplastic elastomeric laminate is used in contact with the window glass of the glass channel. .

The glass run channel of the present invention can omit all of the embossing before and after the coating of the adhesive, the curing or firing of the coated adhesive, and as a result, thus reducing the number of steps used and the required operation. It can save time.

The present invention will be signed with reference to the examples, but the present invention is not limited to the following examples.

Example 1

80 parts by weight of ethylene / propylene / ethylidene norbornene copolymer rubber (hereinafter referred to as “EPDM (1)”) having an ethylene content of 70 mol%, an iodine of 12, and a Mooney viscosity ML _{1 + 4} (100 ° C.) of 120; 20 parts by weight of polypropylene having a MFR (ASTM D138-65T, 230 ° C) of 13 and a density of 0.91 g / cm < 3 > was kneaded for 5 minutes in a Benburi mixer under a nitrogen atmosphere of 180 ° C.

The kneaded material was rolled to obtain a sheet-like product, which was formed into square pellets with a sheet cutter.

Next, 0.3 part by weight of 1,3-bis (t-butylperoxyisopyrophyll) benzene (hereinafter referred to as "peroxide (A)") and divinyl benzene (hereinafter, 0.5 parts by weight of DVB 'were mixed and mixed in a Henschel mixer.

The mixture obtained above was extruded by the single screw extruder of L / D = 30 and a screw diameter of 50mm in 220 degreeC nitrogen atmosphere, and the thermoplastic elastomer (a) was obtained.

The gel content of the copolymer rubber in the thermoplastic elastomer (a) was measured by the above method. The results are shown in Table 1. In addition, the thermoplastic elastomeric elastomer (a) was compression molded at 190 ° C. to prepare a test sheet, and the break point tensile stress (T *), flexibility, and moldability were tested by the following method.

[Test Methods]

(1) Breaking point tensile stress (T *)

According to JIS K 6301, the tensile stress at break (T _B : unit kgf / cm²) was measured at a stress rate of 200 mm / min.

(2) flexibility

Flexibility was evaluated by torsional stiffness (unit kgf / cm²) as measured according to ASTM D1043.

(3) forming

The moldability was evaluated by the melt flow rate (MFR: unit g / 10min, 230 degreeC, 2.16 kg) measured by ASTMD1238.

Using a 50mm diameter T-die extruder (manufactured by Toshiba Machine) with a full-flighted screw and coathanger type T die, L / D = 28, extrusion temperature 240 ° C., take-up The thermoplastic elastomer (a) was extruded in the form of a sheet under the condition of a speed of 2.5 m / min.

The sheet-like thermoplastic elastomer (a) extruded in the molten state was laminated on an ultrahigh molecular weight polyolefin film (trade name: Skived Film, thickness 0.1mm, manufactured by Kogyo Co., Ltd.). By passing this laminating agent through a pair of rolls, the said elastomer (a) and the ultrahigh molecular weight polyolefin membrane were made to contact with the 60 degreeC roll and room temperature roll, respectively.

Thus, a laminate composed of a 1.0 mm thick thermoplastic elastomer (a) layer and a 0.1 mm thick ultra high molecular weight polyolefin layer was obtained.

The interlaminar adhesion strength of the laminate was measured according to the following conditions.

Interlayer adhesion sugar test

Test Method: Peel to 180˚

Test piece: width 25mm, length 100mm

Stress Speed: 25mm / min

Interlayer Bonding Strength (kgf / cm):

Table 1 shows the results of the peeling bar / width of the test piece.

Example 2

A thermoplastic elastomer (b) was prepared in the same manner as in Example 1 except that the oxides (A) and DVB were not used. It manufactured by the method similar to Example 1 using this thermoplastic elastomer (b). The results are shown in Table 1.

Example 3

In addition to EPDM (1) and PP (1), 10 parts by weight of butyl rubber IIR-065 (unsaturation degree: 0.8 mol%, manufactured by Esso, hereinafter referred to as “IIR (1)”), and paraffinic process oil (Idemitsu The laminate was manufactured in the same manner as in Example 1, except that 30 parts by weight of Kosan Co., Ltd., trade name DIANA PROCESS OIL) was used, in the same manner as in Example (1). The results are shown in Table 1.

Example 4

Ethylene / propylene / ethylidene norbornene copolymer rubber having an ethylene content of 78 mol%, an iodine value of 13, and a paraffinic forces oil 40PHR, having a Mooney viscosity ML _{1 + 4} (100 ° C.) of 75 (hereinafter, 64 parts by weight of EPEM (2) ') and 14 parts by weight of polypropylene having a MFR (ASTM D1238-65T, 230 ° C) of 11 and a density of 0.91 g / cm ³ (hereinafter referred to as "PP (2)') 14 parts by weight of butyl rubber (hereinafter referred to as " IIRP (2) ") having a molar viscosity of ML _{1 + 4} (100 ° C) of 45 and an unsaturation of 1.0 mol%, and 8 parts by weight of paraffinic process oil The mixture was kneaded for 5 minutes in a mixer at 180 ° C order atmosphere.

The training material was rolled to obtain a sheet-like product, which was formed into square pellets with a sheet cutter.

Next, the square pellets obtained above were mixed with 0.4 parts by weight of the peroxide (A) in 0.4 parts by weight of DVB in a tumbler mixer, and the square pellets were coated with the suspension.

Next, the coated pellets were extruded using an extruder in a 210 ° C. nitrogen atmosphere to obtain a thermoplastic elastomer (d).

Next, the laminated body was manufactured by the method similar to Example 1 using the said thermoplastic elastomer (d). Physical properties were measured in the same manner as in Example 1.

The results are shown in Table 1.

TABLE 1

Note: "breaking" means breaking of the substrate.

Example 5

The thermoplastic elastomer (a) of Example 1 was extrusion-molded at 230 ° C, and at the same time, 23 parts by weight of ultrahigh molecular weight polyethylene having an ultimate viscosity [η] of 28 dl / g measured in 135 ° C decalin and an extreme measured in 135 ° C decalin An ultra high molecular weight polyethylene composition having an extreme viscosity [η] of 7.0 dl / g and a density of 0.965 g / m ³ measured in 135 ° C decalin composed of 77 parts by weight of a low molecular weight polyethylene having a viscosity [η] of 0.73 dl / g was used as the thermoplastic. Coextrusion was carried out on the surface of the elastomer (a).

In this way, a laminate composed of a 1.0 mm thick thermoplastic elastomer (a) layer and a 0.1 mm thick ultra high-volume polyethylene composition layer was obtained.

The interlayer adhesion strength of the laminate produced above was measured in the same manner as above.

The results are shown in Table 2.

Example 6

A laminate was prepared in the same manner as in Example 5 except that the thermoplastic elastomer (b) of Example 2 was used instead of the thermoplastic elastomer (a). The physical properties were measured in the same manner as above.

The results are shown in Table 2.

Example 7

A laminate was produced in the same manner as in Example 5 except that the thermoplastic elastomer (c) of Example 3 was used instead of the thermoplastic elastomer (a). The physical properties were measured in the same manner as above.

The results are shown in Table 2.

Example 8

A laminate was prepared in the same manner as in Example 5 except that the thermoplastic elastomer (d) of Example 4 was used instead of the thermoplastic elastomer (a).

The physical properties were measured in the same manner as above.

The results are shown in Table 2.

TABLE 2

Note: "breaking" means breaking of the substrate.

Example 9

80 parts by weight of EPDM (1) and 20 parts by weight of pp (1) were kneaded in a Benburi mixer for 5 minutes under a 180C nitrogen atmosphere. This kneaded material was rolled to obtain a sheet-like product, which was formed into a square pellet with a sheet cutter.

Next, 0.3 parts by weight of peroxide (A) and 0.5 parts by weight of maleic anhydride (hereinafter referred to as "AMH") were added to the square reel obtained above, and kneaded in a Henschel mixer.

The mixture obtained above was extruded with the single screw extruder of L / D = and a screw diameter of 50 mm in 220 degreeC and nitrogen atmosphere, and the graft modified thermoplastic elastomer (e) was obtained.

The gel content of the copolymer rubber in the thermoplastic elastomer (e) was measured by the above method. The results are shown in Table 3.

In addition, the graft modified thermoplastic elastomer (e) was compression molded at 190 ° C. to prepare a test sheet, and the break point tensile stress (T _a ), flexibility, and formability were tested in the above method. The results are shown in Table 3.

The graft was carried out under conditions of L / D = 28, extrusion temperature 240 ° C., take-up speed of 2.5 m / min, using a 50 mm diameter T-per-extruder (manufactured by Toshiba Machine Co., Ltd.) having an on-flying screw and a coater-type T die. The modified thermoplastic elastomer (e) was extruded in the form of a sheet. The sheet-like graft-modified thermoplastic elastomer (e) extruded in the melt state was laminated on an ultrahigh molecular weight polyolefin film having an intrinsic viscosity [η] of 15 dl / g measured in 135 ° C decalin. The laminate was passed through a pair of rolls so that the graft-modified thermoplastic elastomer (e) and the ultrahigh molecular weight polyolefin film were in contact with the roll at 60 ° C. and the roll at room temperature, respectively.

The interlayer adhesive strength of the laminate obtained above was measured in the same manner as above. The results are shown in Table 3. In addition, the coefficient of kinetic friction of the ultrahigh molecular weight polyethylene membrane surface was measured under the following conditions.

Measurement of the dynamic friction coefficient: It was measured stepwise using a Matsubara type wear tester.

Wear roll material: SUS 304 (roughness approx. 6S)

Circumferential speed: 12m / min

Load: 10kg

Contact area: 2cm ²

Example 10

A graft-modified thermoplastic elastomer (f) was produced in the same manner as in Example 9 except that 0.6 parts by weight and 2.0 parts by weight of peroxide (A) and MAH were used.

Next, the lamination agent was manufactured by the method similar to Example 9 using the said graft modified thermoplastic elastomer (f). The properties were specified as above. The results are shown in Table 3.

Example 11

A thermoplastic elastomer (g) was prepared in the same manner as in Example 9 except that 10 parts by weight of IIR (1) and 30 parts by weight of the paraffinic process oil were used in addition to EPDM (1) and PP (1). . Next, the lamination agent was manufactured by the method similar to Example 9 using the said graft modified thermoplastic elastomer (g). The properties were specified as above. The results are shown in Table 3.

Example 12

Graft-modified thermoplastic elastomer (h) was produced in the same manner as in Example 11 except that 0.5 parts by weight of glycidyl methacrylate was used instead of 0.5 parts by weight of MAH. Next, the laminated body was manufactured by the method similar to Example 11 using the said graft modified thermoplastic elastomer (h). The physical properties were measured as above. The results are shown in Table 3.

Example 13

EPDM (1), PP (1), IIR (1) and the paraffinic process oil were carried out in the same manner as in Example 11 except that 60 parts by weight, 40 parts by weight, 20 parts by weight and 40 parts by weight of each were used. . A graft modified thermoplastic elastomer (i) was prepared.

Next, the laminated body was manufactured by the method similar to Example 12 using the said graft modified thermoplastic elastomer (i). The physical properties were measured as above. The results are shown in Table 3.

Example 14

90 parts by weight, 10 parts by weight, 20 parts by weight and 40 parts by weight of EPDM (1), PP (1), IIR (1) and the paraffinic process oil, respectively, and glycidyl instead of 0.5 parts by weight of MAH. The graft-modified thermoplastic elastomer (i) was produced in the same manner as in Example 11 except that 3 parts by weight of glycidyl methacrylate was used instead of 3 parts by weight of methacrylate.

Next, the laminated body was manufactured by the method similar to Example 11 using the said graft modified thermoplastic elastomer (i).

The physical properties were measured as above. The results are shown in Table 3.

Example 15

Example 11 except that 70 parts by weight, 30 parts by weight, 40 parts by weight, 60 parts by weight and 40 parts by weight of EPDM (1), PP (1), IIR (1) and the paraffinic process oil and MAH were used, respectively. It carried out by the same method and manufactured the graft modified thermoplastic elastomer (k).

Next, the laminated body was manufactured by the method similar to Example 11 using the said graft modified thermoplastic elastomer (k). The physical properties were measured as above. The results are shown in Table 3.

Example 16

The extruded graft modified thermoplastic elastomer (e) was extruded at 230 ° C and simultaneously composed of 23% by weight of ultra high molecular weight polyethylene having an extreme viscosity [η] of 30 dl / g and 135% by weight of low molecular weight polyethylene measured in 135 ° C decalin, The ultrahigh molecular weight polyethylene composition having an ultimate viscosity [η] of 5.5 dl / g and a density of 0.95 g / m ³ measured in decalin at 135 ° C was coextruded on the surface of the graft-modified thermoplastic elastomer (e).

In this way, a laminate composed of a 1.0 mm thick thermoplastic elastomer (e) layer and a 0.1 mm thick ultra high molecular weight polyethylene composition layer was obtained. The coefficient of dynamic friction of the ultrahigh molecular weight polyethylene composition layer in the laminate was 0.15. The results are shown in Table 3.

Comparative Example 1

A 0.1 mm thick polyamide sheet (trade name: Nylon 6, manufactured by Toray Industries) was used in the same manner as in Example 9, except that the ultrahigh molecular weight polyolefin film was used, and a 1.0 mm graft-modified thermoplastic elastomer (e) layer was used. And a polyamide layer having a thickness of 0.1 mm were obtained. The coefficient of dynamic friction of the surface of the polyamide layer was 0.8. The results are shown in Table 3.

TABLE 3

Note: 'breaking' means breaking of a newsstand.

Example 17

75 parts by weight of ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber having an ethylene content of 70 mol%, an iodine value of 12, and a Mooney viscosity ML _{1 + 4} (100 ° C) of 120, and PP (1 25 parts by weight were kneaded for 5 minutes in a Banburi mixer under a nitrogen atmosphere of 180 ° C.

Next, the kneaded material was rolled to obtain a sheet-like product, which was formed into a square pellet by sheet gutter.

In the above-mentioned square pellet, 0.5 weight part of DVB and 0.3 weight part of peroxides (A) were added, and it stirred in the Henschel mixer.

Next, the mixture obtained above was extruded in 220 degreeC nitrogen atmosphere using the single screw extruder whose L / D = 30 and screw diameter is 50 mm, and obtained the thermoplastic elastomer (1). It was 97 weight%, when the gel content of the said thermoplastic elastomer (1) was measured by the said method.

The thermoplastic elastomer (l) was extruded at 230 ° C. to produce a glass run channel consisting of a body and a drain, and at the same time, 15 dl / g, measured in 135 ° C. decalin, preheated to 90 ° C., 0.1 mm thick, ultrahigh The molecular weight polyethylene membrane was laminated on the surface of the glass run channel by hot melt adhesion at the outlet of the mold to obtain the glass run channel of the present invention.

The cross sectional view of the glass run channel obtained above is shown in FIG.

This glass run channel was approximately trapezoidal in shape.

As shown in FIG. 3, the total length of the inclined portion and the horizontal portion of the glass run channel 1, fastened to the window oil frame 13, was 1500 mm, and the vertical portion thereof was 90 mm. As shown in FIG. 1, the outer width of the bottom of the main body 2 was 15 mm, the height of the outer side of the side was 20 mm, and the length of the drainage portions 3 was 10 mm. The ultrahigh molecular weight polyethylene composition layer had an average thickness of 30 μm.

The molding time of the glass run channel was 0.2 minutes / m shorter than that of the conventional method, that is, the molding time was reduced to 60% of the molding time of the conventional method.

The glass run channel obtained above was fastened to the window frame for a test, and the window glass of 3.2 mm thickness was installed in the inside.

The window oil glass was repeatedly opened and closed, and the durability test of the glass run channel was conducted. As a result, the glass run channel was found to be excellent in durability without impairing the function of the glass run channel after 5,000 opening and closing operations were repeated. On the other hand, in the conventional glass run channel having a laminate structure in which a window glass sliding part was manufactured by attaching a nylon film to a non-rigid polyvinyl chloride resin layer, the contact surface with the window oil glass was worn after 25,000 opening and closing operations. That is, the frictional resistance between the window glasses has been extremely increased, so that such conventional glass run channels cannot be used.

Example 18

75 parts by weight of the ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber of Example 17 and 25 parts by weight of PP (1) were trained in a Banburi mixer for 5 minutes in a 180 ° C. nitrogen atmosphere.

Next, the kneaded material was rolled to obtain a sheet-like product, which was formed into a square pellet with a sheet cutter.

0.5 weight part of DVB and 0.3 weight part of peroxides (A) were added to the square pellet obtained above, and it stirred in the Henschel mixer.

Next, the mixture obtained above was extruded in a branch atmosphere at 220 ° C. using a single screw extruder having a L / D = 30 and a screw diameter of 50 mm to obtain a graft-modified thermoplastic elastomer (m).

The gel content of the graft modified thermoplastic elastomer (m) was 96% by weight as measured by the above method.

The graft modified thermoplastic elastomer (m) was molded in the same manner as in Example 17 to obtain a glass run channel.

The molding time was shortened to 60% of the molding time of the conventional method. The durability test was done in the same manner as in Example 17. As a result, it was found that the glass run channel of the present invention has excellent durability even after 50,000 open-loop operations.

Example 19

The thermoplastic elastomer (l) of Example 17 was extruded at 230 ° C. to prepare a glass run channel having a body portion and a drainage portion, and at the same time, an ultrahigh molecular weight polyethylene having an ultimate viscosity [η] of 28 dl / g measured in 135 ° C. decalin. The density of extreme viscosity [η] measured in decalin at 135 ° C., composed of 23% by weight and 77% by weight of low molecular weight polyethylene having an ultimate viscosity [η] of 135 ° C. decalin at 0.73 dl / g, has a density of 7.0 dl / g. An ultrahigh molecular weight polyethylene composition of 0.965 g / cm ³ was coextruded laminated onto the surface of the glass run channel to obtain a glass run channel of the present invention.

The cross sectional view of the glass run channel obtained above is shown in FIG. This glass run channel was approximately trapezoidal in shape.

As shown in FIG. 3, the length of the inclined portion and the horizontal portion of the glass run channel 1, fastened to the window oil frame 13, was 1500 mm in length, and the vertical portion thereof was 90 mm in length.

As shown in FIG. 1, the outer width of the bottom of the main body 2 was 15 mm, the height of the outer side of the side was 20 mm, and the length of the drainage portions 3 was 10 mm. The ultrahigh molecular weight polyethylene composition layer had an average thickness of 30 μm.

The molding time of the glass run channel was 0.2 minutes / m shorter than that of the conventional method, that is, the molding time was reduced to 60% of the molding time of the conventional method.

The glass run channel obtained above was fastened to the window frame for a test, and the window glass of 3.2 mm thickness was installed in the inside. The window glass was repeatedly opened and closed, and the durability test of the glass run channel was conducted.

As a result, the glass run channel was found to be excellent in durability after repeating 50,000 opening and closing operations without compromising the function of the glass run channel. On the other hand, in the conventional glass run channel having a laminated structure in which a window glass sliding part was manufactured by attaching a nylon film to a non-rigid polyvinyl chloride resin layer, the contact surface with the window glass was worn after 25,000 opening and closing operations.

That is, the frictional resistance between the window glasses is extremely increased, such a conventional glass run channel can not be used.

Example 20

Instead of the ultrahigh molecular weight polyethylene composition of Example 19, 100 parts by weight of this ultrahigh molecular weight polyethylene composition and 2 parts by weight of an ethylene / propylene copolymer synthetic oil having a number average molecular weight of 1300 and a dynamic friction coefficient of 100 cSt at 100 ° C as a liquid lubricant. The same procedure as in Example 19 was carried out except that the mixture was stirred in a Henschel mixer and releted by a single screw extruder, to prepare an ultrahigh molecular weight polyethylene composition.

Next, using the ultra high molecular weight polyethylene composition, a glass run channel was prepared in the same manner as in Example 19.

The molding time of the glass run channel was reduced to 60% of the conventional method. This glass run channel showed excellent durability even after 50,000 switching operations, without impairing the function of the glass run channel.

Example 21

A glass run channel was produced in the same manner as in Example 9 except that the graft-modified thermoplastic elastomer (m) of Example 18 was used instead of the thermoplastic elastomer (1).

The molding time of the glass run channel was reduced to 60% of the conventional method. This glass run channel was excellent in durability as the function as a glass run channel was not impaired even after 50,000 times of opening and closing operations.

Claims (22)

A thermoplastic elastomer laminate comprising a layer of thermoplastic elastomer (A) composed of crystalline polyolefin and rubber and a layer of ultra high molecular weight polyolefin (B). 30 to 90 parts by weight of the rubber (b) according to claim 1, wherein the thermoplastic elastomer (A) is 7010 parts by weight of crystalline polyolefin (a) and ethylene / propylene copolymer rubber or ethylene / propylene / diene copolymer rubber. A thermoplastic elastomer laminate obtained by partially heat-crosslinking the rubber (b) by subjecting the mixture containing components (a) and (b) to 100 parts by weight) by dynamic heat treatment in the presence of an organic peroxide. The thermoplastic elastomer laminate according to claim 1, wherein the intrinsic viscosity [η] measured in 135 ° C decalin of the ultrahigh molecular weight polyolefin (B) is 10 to 40 dl / g. It is composed of a layer of thermoplastic elastomer (A) composed of crystalline polyolefin and rubber and a layer of ultra high molecular weight polyolefin composition (C), wherein the ultra high molecular weight polyolefin composition (C) has an intrinsic viscosity measured in decalin at 135 ° C. ] An ultra high molecular weight polyolefin having 10 to 40 dl / g and a polyolefin having an extreme viscosity [η] of 0.1 to 5 dl / g measured in 135 ° C decalin as essential components, and the ultra high molecular weight polyolefin is an ultra high molecular weight polyolefin and the polyolefin. It exists in the ratio of 15-40 weight% with respect to 100 weight% of the sum total, and the intrinsic viscosity [eta] measured in 135 degreeC decalin of the said ultrahigh molecular weight polyolefin composition (C) is 3.5-8.3 dl / g, It is characterized by the above-mentioned. Thermoplastic Elastomer Laminates. The rubber (b) 30 to 90 according to claim 4, wherein the thermoplastic elastomer (A) is 70 to 10 parts by weight of the crystalline polyolefin (a) and ethylene / propylene copolymer rubber or ethylene / propylene / diene copolymer rubber. A thermoplastic elastomer laminate obtained by dynamically heat-treating a weight part (the sum of the components (a) and (b) is 100 parts by weight) in the presence of an organic peroxide, and partially crosslinking the rubber (b). The thermoplastic elastomer laminate according to claim 4, wherein the ultrahigh molecular weight polyolefin composition (C) contains 1 to 20% by weight of a liquid or a solid lubricant with respect to the composition (C). Graft modified thermoplastic elastomer (GA) and a layer of ultra-high molecular weight polyolefin (B), the graft modified thermoplastic elastomer (GA), (i) peroxide crosslinked olefin copolymer rubber 95-10 Parts by weight, (ii) 5 to 90 parts by weight of polyolefin (the total of component (i) and (ii) is 100 parts by weight), (iii) α, β-unsaturated carboxylic acid or derivative thereof, or unsaturated epoxy monomer 0.01 A thermoplastic elastomer laminate, obtained by dynamic heat treatment and partial crosslinking of a blend containing ˜10 parts by weight in the presence of an organic peroxide. The method according to claim 7, wherein the graft modified thermoplastic elastomer (GA), based on 100 parts by weight of the total of the components (i) and (ii), (iv) 5 to 100 parts by weight of peroxide non-crosslinked rubbery material and And / or (v) 30 to 100 parts by weight of mineral oil-based softener. The content of the peroxide crosslinked olefin copolymer rubber (i) is 95 to 60 parts by weight, and the content of the polyolefin (ii) is 5 to 40 parts by weight (component (i). ) And (ii) the total is 100 parts by weight) thermoplastic elastomer laminate. 8. The thermoplastic elastomer laminate according to claim 7, wherein the ultrahigh molecular weight polyolefin (B) has an intrinsic viscosity [?] Measured in 135 ° C decalin of 10 to 40 dl / g. Graft-modified thermoplastic elastomer (GA) and a layer of ultra-high molecular weight polyolefin composition (C), the graft-modified thermoplastic elastomer (GA) is (i) peroxide crosslinked olefin copolymer rubber 95 ~ 10 parts by weight, (ii) 5 to 90 parts by weight of polyolefin (the sum of the above components (i) and (ii) is 100 parts by weight), (iii) an α, β-unsaturated carboxylic acid or a derivative thereof, or an unsaturated epoxy monomer Obtained by dynamic heat treatment and partial crosslinking of a blend containing 0.01 to 10 parts by weight in the presence of an organic peroxide, wherein the ultrahigh molecular weight polyolefin composition (C) has an intrinsic viscosity [η] of 10 to 40 dl / g in 135 ° C decalin. An ultra high molecular weight polyolefin and a polyolefin having an ultimate viscosity [η] of 0.1 to 5 dl / g measured in 135 ° C decalin are essential components, and the ultra high molecular weight polyolefin is the same as the ultra high molecular weight polyolefin. It exists in the ratio of 15-40 weight% with respect to 100 weight% of total polyolefins, and the intrinsic viscosity [(eta)] measured in 135 degreeC decalin of the said ultra high molecular weight polyolefin composition (C) is 3.5-8.3 dl / g, It is characterized by the above-mentioned. Thermoplastic elastomer laminate. The graft-modified polyolefin (GA) according to claim 11, wherein (iv) 5 to 100 parts by weight and / or (v) A thermoplastic elastomer laminate, further comprising 30 to 100 parts by weight of a mineral oil softener. The content of the peroxide crosslinked olefin copolymer rubber (i) is 95 to 60 parts by weight, and the content of the polyolefin (ii) is 5 to 40 parts by weight (components (i) and (ii). The total of 100) parts by weight) thermoplastic elastomer laminate. The thermoplastic elastomer laminate according to claim 11, wherein the ultra-high molecular weight polyolefin composition (C) contains 1 to 20% by weight of a liquid or solid lubricant based on the composition (C). Thermoplastic elastomer (A) comprising a body having a grooved cross section and tongue drainage portions extending from the end of the side wall of the groove toward the center of the groove, the portions of the glass run channel being in contact with the window glass comprising crystalline polyolefin and rubber Layer and an ultrahigh molecular weight polyolefin (B) layer, wherein the ultrahigh molecular weight polyolefin (B) layer is designed to be in contact with the window glass, and measured in 135 ° C decalin of the ultrahigh molecular weight polyolefin (B). A glass run channel, characterized by an extreme viscosity [η] of 10-40 dl / g. The rubber (b) 30 to 90 according to claim 15, wherein the thermoplastic elastomer (A) is 70 to 10 parts by weight of crystalline polypropylene (a) and ethylene / propylene copolymer rubber or ethylene / propylene / diene copolymer rubber. Glass run channel characterized in that the mixture consisting of parts by weight (the sum of the components (a) and (b) is 100 parts by weight) is obtained by crosslinking the rubber (b) by dynamic heat treatment in the presence of an organic peroxide. . Thermoplastic elastomer (A) comprising a body having a grooved cross section, and tongue drainage portions extending from the end of the side wall of the groove to the side of the groove, the portions of the glass run channel being in contact with the window glass, the crystalline polyolefin and rubber Layer and an ultrahigh molecular weight polyolefin composition (C) layer, wherein the ultrahigh molecular weight polyolefin composition (C) layer is designed to be in contact with the window glass, and the ultrahigh molecular weight polyolefin composition (C) is 135 ° C. The ultrahigh molecular weight polyolefin having an ultimate viscosity [η] of 10 to 40 dl / g measured in decalin and the polyolefin having an ultimate viscosity [η] of 0.1 to 5 dlg measured in 135 ° C of decalin are essential components. 15 to 40% by weight relative to the total 100% by weight of the ultrahigh molecular weight polyolefin and the polyolefin, and 135 ° C of the ultrahigh molecular weight polyolefin composition (C) Grass run channel according to one characterized in that the intrinsic viscosity [η] is 3.5 ~ 8.3dl / g as measured in Lin. 18. The rubber (b) according to claim 17, wherein the thermoplastic elastomer (A) is 70 to 10 parts by weight of crystalline lollipropylene (a) and ethylene / propylene copolymer rubber or ethylene / propylene / diene copolymer rubber. Glass run channel characterized in that the mixture consisting of parts by weight (the sum of the components (a) and (b) is 100 parts by weight) is obtained by crosslinking the rubber (b) by dynamic heat treatment in the presence of an organic peroxide. . 18. The glass run channel according to claim 17, wherein the ultra high molecular weight polyolefin composition (C) contains 1 to 20% by weight of liquid or solid lubricant. A body having a grooved cross section and portions of a glass run channel in contact with the window glass having tongue drainages extending from the end of the sidewall of the groove toward the center of the groove, the graft modified thermoplastic elastomer (A) layer and the ultrahigh molecular weight lolliolefin (B) layer, the ultra-high molecular weight polyolefin (B) layer is designed to be in contact with the window glass, and the graft modified thermoplastic elastomer (GA) is (i) peroxide crosslinked olefin copolymer rubber 95 to 10 parts by weight, (ii) 5 to 90 parts by weight of polyolefin (the sum of the components (i) and (ii) is 100 parts by weight), (iii) α, β-unsaturated carboxylic acid or a derivative thereof, or unsaturated A blend containing 0.01 to 10 parts by weight of an epoxy monomer was obtained by dynamic heat treatment and partial crosslinking in the presence of an organic peroxide, which was carried out at 135 ° C of the ultrahigh molecular weight polyolefin (B). Glass run channel, characterized in that the ultimate viscosity [η] measured in the calin is 10 ~ 49dl / g. A layer of graft modified thermoplastic elastomer (GA) having a body having a grooved cross section and tongue drainages extending from the end of the sidewall of the groove toward the center of the groove, the portions of the glass run channel being in contact with the window glass. And a layer made of an ultra high molecular weight polyolefin composition (C), the layer made of the ultra high molecular weight polyolefin composition (C) is designed to be in contact with the window glass, and the graft-modified thermoplastic elastomer (GA) is 95 to 10 parts by weight of (i) peroxide crosslinked olefin copolymer rubber, (ii) 5 to 90 parts by weight of polyolefin (the sum of the components (i) and (ii) is 100 parts by weight), (iii) α , β-unsaturated carboxylic acid or a derivative thereof or a blend containing 0.01 to 10 parts by weight of an unsaturated and epoxy monomer is obtained by dynamic heat treatment and partial crosslinking in the presence of an organic peroxide, The ultrahigh molecular weight polyolefin composition (C) is an ultrahigh molecular weight polyolefin having an ultimate viscosity [η] of 10-40 dl / g measured in 135 ° C decalin and a polyolefin having an extreme viscosity [η] of 0.1-5 dl / g measured in 135 ° C decalin. Wherein the ultra high molecular weight polyolefin is transcribed in an amount of 15 to 40 wt% based on 100 wt% of the total polyolefin, and is measured in 135 ° C decalin of the ultra high molecular weight polyolefin composition (C). A glass run channel characterized by an extreme viscosity [η] rk of 3.5 to 8.3 dl / g. 22. The glass run channel according to claim 21, wherein the ultra high molecular weight polyolefin composition (C) contains 1 to 20% by weight of liquid or solid lubricant based on the composition (C).