JPH054308A - Glass running channel - Google Patents

Abstract

PURPOSE:To obtain a glass running channel excellent in economics, durability, tight contact with window glass and light sliding properties, by a method wherein a part contactable with windshield glass of the surface of a draining part is constituted by laminating a superpolymeric polyolefin layer having specific composition to a polyolefin thermoplastic elastomer layer. CONSTITUTION:A glass running channel 1 is constituted of a groovelike main body 2 and a tonque-piece-like draining part 3 overhanging toward a center side from the vicinity of the top part of a side wall of the same, in a cross section. Then a part which is the surface of the draining part and is contactable at least with windshield glass is constituted of a layer which is laminated to a polyolefin thermoplastic elastomer layer and comprised of a superpolymeric polyolefin and low-molecular-weight or polymeric polyolefin. Hereupon, the superpolymeric polyolefin is constituted of the superpolymeric polyolefin whose intrinsic viscosity measured within a decalin solvent having a temperature of 135 deg.C is within a range of 10-40dl/g and that within a range of 0.1-5dl/g.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass run channel, and more particularly, to a glass run provided with a window glass sliding portion composed of a laminate composed of a thermoplastic elastomer substrate layer and a slip resin surface layer. Regarding the channel.

[0002]

BACKGROUND OF THE INVENTION Generally, a window glass in a vehicle of an automobile requires an opening / closing operation by raising and lowering for ventilation ventilation or for communication with the outside of the vehicle. It is called a glass run channel between the window glass and the window frame in order to facilitate the lifting / opening / closing operation of the window glass and at the same time enable the tight (liquid-tight) sealing operation between the window glass and the window frame. A guide member is provided.

A conventional glass run channel is formed of a soft synthetic resin such as a soft vinyl chloride resin or a vulcanized rubber such as an ethylene-propylene-diene copolymer rubber, and a main body having a groove-shaped cross section, and its main body. It consists of a tongue-shaped drainer that extends from the top of the side wall toward the center.

In the conventional glass run channel, a nylon film or the like is formed on the surface of the window glass sliding portion in order to make the water draining portion well away from the sliding portion with the window glass and to prevent the window glass from being soiled. Glued together,
Further, in order to reduce the contact area with the window glass, embossing is applied before or after lamination of the nylon film or the like.

In the conventional glass run channel, since there is no adhesiveness between the soft synthetic resin or vulcanized rubber and the surface material of nylons, the body of the glass run channel is molded with the soft synthetic resin or vulcanized rubber. Then, a step of applying an adhesive to the obtained molded product and laminating a film such as nylon is necessary, and further, embossing must be performed before or after this adhesion,
There is an inconvenience that the number of steps is large and labor is required.

Further, in the conventional glass run channel,
Since there is a step of laminating with an adhesive, there is also a problem in durability, and there is also the drawback that peeling easily occurs between the surface film layer and the substrate due to time and outdoor exposure. Furthermore, the concavo-convex pattern that can be formed by embossing is not yet sufficiently satisfactory in the combination of fineness and uniformity, and the close contact between the window glass sliding part and the window glass at the time of closing, and the opening at the time of opening There is still room for improvement in the light sliding property between the window glass sliding portion and the window glass.

[0007] Therefore, the inventors of the present invention conducted extensive studies to solve the above problems of the glass run channel, and selected a polyolefin-based thermoplastic elastomer as the elastomer forming at least the window glass sliding portion of the glass run channel. Then, if the ultra high molecular weight polyolefin is heat-fused and laminated on the polyolefin-based thermoplastic elastomer layer, the manufacturing work is easy, and the durability,
The inventors have found that it is possible to obtain a glass run channel that is excellent in close contact with a window glass when closed and in a light sliding property with the window glass when opened, and completed the present invention.

[0008]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and is excellent in economy, durability, close contact with a window glass when closed, and It is an object of the present invention to provide a glass run channel excellent in light sliding property with respect to a window glass when opened.

[0009]

SUMMARY OF THE INVENTION A glass run channel according to the present invention comprises:
A glass run channel made of a thermoplastic polyolefin elastomer, which is composed of a groove-shaped main body in a cross section and a tongue-shaped drainer protruding from the vicinity of the top of the side wall toward the center side, which is At least a portion of the surface that can come into contact with the window glass is composed of an ultrahigh molecular weight polyolefin layer laminated on a polyolefin-based thermoplastic elastomer layer, and the ultrahigh molecular weight polyolefin layer is composed of the following ultrahigh molecular weight polyolefin composition: It is characterized by being.

An ultrahigh molecular weight polyolefin having an intrinsic viscosity [η] measured in a 135 ° C. decalin solvent in the range of 10 to 40 dl / g and an intrinsic viscosity [η] measured in a 135 ° C. decalin solvent are 0.1. A polyolefin composition consisting essentially of a low to high molecular weight polyolefin in the range of ~ 5 dl / g, wherein the ultra high molecular weight polyolefin is 100 total weight of ultra high molecular weight polyolefin and low to high molecular weight polyolefin. It exists in a ratio of 15 to 40% by weight with respect to the weight% and is 135 ° C.
Intrinsic viscosity [η] measured in decalin solvent is 3.5-
Ultra high molecular weight polyolefin composition in the range of 8.3 dl / g.

Examples of the polyolefin thermoplastic elastomer preferably used in the present invention include the following partially crosslinked polyolefin thermoplastic elastomers and modified polyolefin thermoplastic elastomers. (1) Rubber (b) comprising 70 to 10 parts by weight of crystalline polypropylene (a) and ethylene / propylene copolymer rubber or ethylene / propylene / diene copolymer rubber
30 to 90 parts by weight [the total amount of the components (a) and (b) is 100 parts by weight] is dynamically heat treated in the presence of an organic peroxide to obtain the rubber (b). ) Is a partially crosslinked polyolefin thermoplastic elastomer. (2) (i) Peroxide-crosslinking olefin-based copolymer rubber 95 to 10 parts by weight, and (ii) olefin-based plastic 5 to 90 parts by weight [the total amount of components (i) and (ii) is 100 parts by weight. And (iii) α, β-unsaturated carboxylic acid or a derivative thereof, or 0.01 to 10 parts by weight of an unsaturated epoxy monomer is added to a blend in the presence of an organic peroxide. Heat treated to
A partially crosslinked modified polyolefin thermoplastic elastomer.

In the present specification, the term "polyolefin-based thermoplastic elastomer" may refer not only to a non-grafted modified polyolefin-based thermoplastic elastomer but also to a graft-modified polyolefin-based thermoplastic elastomer. is there.

[0013]

DETAILED DESCRIPTION OF THE INVENTION An example of the glass run channel according to the present invention will be specifically described below with reference to the drawings.

In FIG. 1, which shows a cross-sectional structure of an example of a glass run channel of the present invention, the glass run channel 1 has a groove-shaped (U-shaped) main body 2 in a horizontal cross section, and a center from the vicinity of the top of the side wall portion thereof. It is composed of a tongue-shaped water draining portion 3 that projects toward the side. The pair of drainers 3 and 3 extend obliquely toward the inside of the groove of the main body 2, and the outer surface side of the pair of drainers 3 and 3 serves as a window glass contact portion 4, and the tips 5 and 5 thereof can be opened and closed with respect to each other. There is a positional relationship. The main body 2 is provided with a hook 6 for attaching to the window frame on the outer wall thereof.

Although the main body 2 and the draining portion 3 are integrally formed of an elastomer, according to the present invention, at least the window glass contacting portion 4 is provided with a base layer made of a thermoplastic polyolefin-based elastomer and an ultrahigh molecular weight polyolefin composition. And a slippery resin layer made of a material. As shown in FIG. 2 in which the window glass contact portion 4 is enlarged, the surface 8 of the base layer 7 made of a thermoplastic polyolefin-based elastomer is
It is preferable that a repeating pattern of fine irregularities is provided. On the surface 8 having such a sharkskin-like fine concavo-convex pattern, a slipping resin layer 9 made of an ultrahigh molecular weight polyolefin composition is laminated by heat fusion, and the outer surface 10 thereof has the same fine concavo-convex pattern. It is preferable that a repeating pattern of is applied.

In FIGS. 3, 4 and 5 for explaining the mounting of this glass run channel to an automobile,
A window glass 12 is provided on a door 11 of an automobile so that it can be opened and closed by raising and lowering it. That is, in FIGS. 4 and 5, the window frame 13 has a U-shaped cross section as a whole, and an inwardly projecting portion 15 is formed at the entrance of the recess 14. The glass run channel 1 is fixed to the window frame 13 by inserting the glass run channel 1 into the recess 14 and engaging the engaging hook 6 with the projection 15. As shown in FIG. 4, when the windowpane 12 is lowered, the tips 5 and 5 of the glass sliding parts face each other and are closed, and as shown in FIG. Then, the tips 5 and 5 of the window glass sliding portion are separated by the window glass 12 fitted between them, but are in contact with the window glass surface.

According to the invention, the glass run channel 1
Among these, at least a portion which comes into contact with the window glass is provided with a base layer 7 of a polyolefin-based thermoplastic elastomer, and a lubricous resin layer 9 made of an ultrahigh molecular weight polyolefin composition heat-fused to the surface of the base layer 7. .

That is, the thermoplastic polyolefin-based elastomer used in the present invention can be thermoformed into any shape and size, and the elasticity and flexibility required for the sliding portion of the window glass of the glass run channel. ,
It has excellent properties such as compressibility, and also has excellent properties such as durability, weather resistance, and water resistance. The thermoplastic polyolefin-based elastomer may be modified by graft copolymerization of a polar group-containing monomer such as maleic anhydride. The polyolefin-based thermoplastic elastomer exhibits strong adhesiveness to the slip resin layer 9 made of the ultra-high molecular weight polyolefin composition which becomes the surface material layer, and by heat fusion with the slip resin layer 9, immediately after adhesion and It is possible to form a laminated structure having excellent interlayer adhesive strength over time, and further, interlayer adhesive strength after a weather resistance test. Moreover, the thermoplastic polyolefin-based elastomer used as the base layer 7 in the present invention can also be molded so as to have a sharkskin-like molded appearance.
By combining the slip-bonding step of the slipping resin layer 9 made of an ultra-high molecular weight polyolefin composition as the surface material layer and the base layer 7, the sharkskin-like fine irregularities are formed on the outer surface of the slipping resin layer 9. You can also faithfully reproduce the pattern. It is extremely difficult to copy such a sharkskin-like surface with minute uneven patterns by the conventional adhesive coating method, and it has become possible only by combining the above-mentioned molding step and heat fusion step.

According to the present invention, by adopting the above-described structure, the adhesive applying step, the adhesive curing or baking step, and the embossing step before or after the adhesive step are all omitted, and the number of steps is small and the number is small. The glass run channel can be efficiently manufactured with time and effort. Further, by providing the slipping resin layer 9 made of the ultrahigh molecular weight polyolefin composition as the surface material layer, not only the coefficient of friction with the window glass can be reduced, but also in comparison with the conventional embossed uneven pattern. Thus, it becomes possible to form fine sharkskin-like irregularities on the surface with a uniform pitch. Therefore, in the glass run channel according to the present invention, when the window glass is closed, close contact (liquid tight) with the window glass is possible, and when the window glass is opened, its sliding resistance is reduced,
Smooth opening and closing operations are possible.

Polyolefin Thermoplastic Elastomer The polyolefin thermoplastic elastomer used in the present invention is composed of crystalline polyolefin and rubber.

Examples of the crystalline polyolefin used in the present invention include homopolymers or copolymers of α-olefins having 2 to 20 carbon atoms. Specific examples of the crystalline polyolefin include the following (co) polymers. (1) Ethylene homopolymer (manufacturing method may be either low pressure method or high pressure method) (2) Copolymerization of ethylene with 10 mol% or less of other α-olefin or vinyl monomer such as vinyl acetate or ethyl acrylate Polymer (3) Propylene homopolymer (4) Random copolymer of propylene and 10 mol% or less of other α-olefin (5) Block copolymerization of propylene and 30 mol% or less of other α-olefin Copolymer (6) 1-butene homopolymer (7) Random copolymer of 1-butene and 10 mol% or less of other α-olefin (8) 4-Methyl-1-pentene homopolymer (9) 4 -Methyl-1-pentene and other α up to 20 mol%
-Random copolymer with olefin As the above α-olefin, specifically, ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-
Examples include hexene and 1-octene.

The rubber used in the present invention is not particularly limited, but an olefin copolymer rubber is preferable. The above olefin-based copolymer rubber has 2 to 20 carbon atoms.
Amorphous random elastic copolymer containing α-olefin as a main component, which is an amorphous α-olefin copolymer composed of two or more α-olefins, and non-conjugated with two or more α-olefins Examples include α-olefin / non-conjugated diene copolymers composed of diene.

Specific examples of such an olefinic copolymer rubber include the following rubbers. (1) Ethylene / α-olefin copolymer rubber [ethylene / α-olefin (molar ratio) = about 90/10
50/50] (2) Ethylene / α-olefin / non-conjugated diene copolymer rubber [ethylene / α-olefin (molar ratio) = about 90/10
-50/50] (3) Propylene / α-olefin copolymer rubber [propylene / α-olefin (molar ratio) = about 90/1
0-50 / 50] (4) Butene / α-olefin copolymer rubber [butene / α-olefin (molar ratio) = about 90/10
50/50] Specific examples of the α-olefin include the same α-olefins as the specific examples of the α-olefin constituting the crystalline polyolefin component described above.

As the non-conjugated diene, specifically,
Examples thereof include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene and ethylidene norbornene.

Mooney viscosity ML of these copolymer rubbers
_{1 + 4} (100 ° C) is 10 to 250, especially 40 to 150
Is preferred. The iodine value when the non-conjugated diene is copolymerized is preferably 25 or less.

The above-mentioned olefin copolymer rubber can exist in all crosslinked states such as uncrosslinked, partially crosslinked and totally crosslinked in the polyolefin thermoplastic elastomer, but in the present invention, it is partially crosslinked. It is preferably present in a state.

The rubber used in the present invention includes:
In addition to the above olefin copolymer rubber, other rubber,
For example, styrene-butadiene rubber (SBR), nitrile rubber (NBR), natural rubber (NR), butyl rubber (I
IR) and other diene rubbers, SEBS, polyisobutylene, and the like.

In the thermoplastic polyolefin-based elastomer used in the present invention, the weight blending ratio of crystalline polyolefin and rubber (crystalline polyolefin / rubber) is
90/10 to 10/90, preferably 70/30 to 1
The range is 0/90.

When a combination of an olefin copolymer rubber and another rubber is used as the rubber, the other rubber is 1 in the total amount of the crystalline polyolefin and the rubber.
40 parts by weight or less, preferably 5 to 100 parts by weight
It is mixed in a ratio of 20 parts by weight.

The thermoplastic polyolefin-based elastomer preferably used in the present invention comprises crystalline polypropylene and ethylene / α-olefin copolymer rubber or ethylene / α-olefin / non-conjugated diene copolymer rubber A thermoplastic elastomer which is present in a partially crosslinked state in an elastomer and has a weight blending ratio of crystalline polypropylene and rubber (crystalline polypropylene / rubber) within the range of 70/30 to 10/90. is there.

In the thermoplastic polyolefin elastomers mentioned above and below, if necessary, mineral oil softeners, heat stabilizers, antistatic agents, weathering stabilizers, antiaging agents, fillers, coloring agents, lubricants, etc. The additive can be added within a range that does not impair the object of the present invention.

More specific examples of the polyolefin-based thermoplastic elastomer preferably used in the present invention include:
Rubber (b) 40 to 9 comprising 60 to 10 parts by weight of crystalline polypropylene (a) and ethylene / propylene copolymer rubber or ethylene / propylene / diene copolymer rubber
0 parts by weight [the total amount of the components (a) and (b) is 100
Parts by weight] and a rubber (c) other than the rubber (b) and / or 5 to 100 parts by weight of a mineral oil-based softening agent (d) are dynamically heat treated in the presence of an organic peroxide. The polyolefin-based thermoplastic elastomer obtained by partially crosslinking the rubber (b) is obtained.

Specific examples of the above organic peroxide include dicumyl peroxide, di-tert-butyl peroxide, and 2,5-dimethyl-2,5-di- (tert-butylperoxy).
Hexane, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy)- 3,3,5-Trimethylcyclohexane, n-butyl
-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperbenzoate, tert-butylperoxyisopropyl carbonate, Diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide and the like can be mentioned.

Among these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane and 2,5-dimethyl-2,5-di-from the viewpoint of odor and scorch stability. (Tert-Butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4 1,4-Bis (tert-butylperoxy) valerate is preferred, and among them, 1,3-bis (tert-butylperoxyisopropyl) benzene is most preferred.

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

In the present invention, sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N are used in the partial crosslinking treatment with the above organic peroxide.
-4- Dinitrosoaniline, nitrosobenzene, diphenylguanidine, peroxy crosslinking aids such as trimethylolpropane-N, N'-m-phenylenedimaleimide, or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, A polyfunctional methacrylate monomer such as diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate or allyl methacrylate, or a polyfunctional vinyl monomer such as vinyl butyrate or vinyl stearate can be blended.

By using the above compounds,
A uniform and mild crosslinking reaction can be expected. Particularly, divinylbenzene is most preferred in the present invention. Divinylbenzene is a dispersant for organic peroxide, which is easy to handle, has good compatibility with the crystalline polyolefin and the rubber which are the main components of the above-mentioned substance to be crosslinked, and has the action of solubilizing organic peroxide. As a result, a thermoplastic elastomer having a uniform cross-linking effect by heat treatment and a good balance of fluidity and physical properties can be obtained. In the present invention, the above-mentioned crosslinking aid or polyfunctional vinyl monomer is used in an amount of 0.1
It is preferably used in a proportion of from 2 to 2% by weight, particularly from 0.3 to 1% by weight. When the blending ratio of the cross-linking aid or the polyfunctional vinyl monomer exceeds 2% by weight, when the blending amount of the organic peroxide is large, the cross-linking reaction proceeds too fast. Inferiority, on the other hand, when the blending amount of the organic peroxide is small, the crosslinking aid and the polyfunctional vinyl monomer remain as unreacted monomers in the polyolefin-based thermoplastic elastomer, and the polyolefin-based thermoplastic elastomer is Changes in physical properties may occur due to heat history during processing and molding. Therefore, the cross-linking aid and the polyfunctional vinyl monomer should not be blended in excess.

The above-mentioned "dynamically heat-treating" means kneading each of the above components in a molten state. As the kneading device, a conventionally known kneading device, for example, an open type mixing roll, a non-open type Banbury mixer, an extruder, a kneader, a continuous mixer or the like is used. Of these, a non-open type kneading device is preferable, and kneading is preferably performed in an atmosphere of an inert gas such as nitrogen gas or carbon dioxide gas.

The kneading is preferably carried out 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 17
The temperature is 0 to 240 ° C., and the kneading time is 1 to 20 minutes, preferably 3 to 10 minutes. The applied shearing force is usually 10 to 10 ⁴ sec ⁻¹ , preferably 10 ² to 10 ³ sec ⁻¹ , as the shearing force.

The preferred thermoplastic polyolefin-based elastomer used in the present invention is partially crosslinked, but the term "partially crosslinked" means that the gel content measured by the following method is 20 to 98%. The gel content is preferably in the range of 45 to 98% in the present invention.

[Measurement method of gel content] As a sample, about 100 m of pellets of polyolefin thermoplastic elastomer are used.
g Weigh accurately and immerse in a closed vessel in 30 ml of cyclohexane, a sufficient amount for this pellet, at 23 ° C. for 48 hours.

Next, this sample is taken out on a filter paper and dried at room temperature for 72 hours or more until a constant weight is obtained. The gel content is represented by the following formula. Gel content [%] = (dry weight after immersion in cyclohexane)
÷ (Weight before immersion in cyclohexane) × 100 Further, in the present invention, the following modified polyolefin-based thermoplastic elastomer (MTPE) can be used as a preferable polyolefin-based thermoplastic elastomer constituting the base layer 7. . (I) Peroxide cross-linking olefin copolymer rubber 9
5 to 10 parts by weight, and (ii) olefin plastics 5 to 90 parts by weight [the total amount of components (i) and (ii) is 100 parts by weight]
And (iii) an α, β-unsaturated carboxylic acid or derivative thereof,
Alternatively, a modified polyolefin in which a blend containing 0.01 to 10 parts by weight of a polar group-containing monomer such as an unsaturated epoxy monomer is dynamically heat-treated in the presence of an organic peroxide to partially crosslink. It is a thermoplastic elastomer.

The peroxide-crosslinking olefin copolymer rubber (i) used in the present invention is, for example, ethylene.
Amorphous elastic copolymers containing olefin as the main component, such as propylene / non-conjugated diene copolymer rubber and ethylene / butadiene copolymer rubber, to be mixed with organic peroxide and kneaded under heating. Means a rubber that is crosslinked to reduce the fluidity or does not flow.

Specific examples of the non-conjugated diene include dicyclopentadiene, 1,4-hexadiene, dicyclooctadiene, methylene-norbornene, ethylidene-
Examples include norbornene.

In the present invention, among the above-mentioned peroxide-crosslinking olefin copolymer rubbers, the molar ratio of ethylene component unit to propylene component unit (ethylene component unit / propylene component unit) is 50/50 to 50. 90/1
Ethylene / propylene copolymer rubbers and ethylene / propylene / non-conjugated diene copolymer rubbers, which are 0, particularly in the range of 55/45 to 85/15, are preferably used. Among them, ethylene / propylene / non-conjugated diene copolymer rubber, particularly ethylene / propylene / ethylidene norbornene copolymer rubber is preferable because it can provide a thermoplastic elastomer excellent in heat resistance, tensile strength characteristics and impact resilience.

The peroxide cross-linking olefin copolymer rubber has a Mooney viscosity ML _{1 + 4} (100 ° C.) of 1
It is preferably in the range of 0 to 250, particularly 40 to 150. When a peroxide-crosslinking olefin copolymer rubber having a Mooney viscosity ML _{1 + 4} (100 ° C.) of less than 10 is used, the thermoplastic elastomer composition obtained tends to have reduced tensile strength properties. On the other hand, Mooney viscosity M
When a peroxide-crosslinking olefin-based copolymer rubber having L _{1 + 4} (100 ° C.) of more than 250 is used, the thermoplastic elastomer composition obtained tends to have low fluidity.

Further, the peroxide crosslinked olefinic copolymer rubber preferably has an iodine value of 25 or less. When the peroxide-crosslinking olefin copolymer rubber having an iodine value within the above range is used, a thermoplastic elastomer having a good balance of fluidity and rubber properties can be obtained.

In the present invention, the peroxide-crosslinkable olefin copolymer rubber (i) is used in an amount of 95 to 10 parts by weight,
It is preferably used in a proportion of 95 to 60 parts by weight. However, the total amount of the peroxide-crosslinked olefin copolymer rubber (i) and the olefin plastic (ii) is 100 parts by weight.

When the peroxide-crosslinking olefin-based copolymer rubber (i) is used in the above proportion, the resulting graft-modified polyolefin-based elastomer has excellent moldability and rubber properties such as rubber elasticity. ing.

The olefinic plastic (ii) used in the present invention can be produced by either the high pressure method or the low pressure method.
It consists of a crystalline, high molecular weight solid product obtained by polymerizing one or more mono-olefins. Examples of such resins include isotactic or syndiotactic monoolefin polymer resins. These representative 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-
Examples include octene, 1-decene and mixed olefins of two or more of these. In the present invention, any polymerization method may be adopted, whether it is homopolymerization or copolymerization, as long as a resinous product is obtained.

In the present invention, a particularly preferable olefin plastic is a peroxide decomposition type olefin plastic. In the present invention, the peroxide-decomposable olefin-based plastic refers to an olefin-based plastic in which the fluidity of the resin is increased by reducing the molecular weight by thermally decomposing by mixing with peroxide and kneading with heating. Tactic polypropylene; a copolymer of propylene and a small amount of other α-olefin, such as propylene-ethylene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-4-methyl -1-Pentene copolymer and the like can be mentioned.

The olefinic plastic used in the present invention has a melt index (ASTM-D-1238).
-65T, 230 ° C) is preferably in the range of 0.1 to 50, particularly 5 to 20.

In the present invention, the olefin plastic contributes to the improvement of the fluidity and the heat resistance of the elastomer composition. In the present invention, the olefin plastic (ii) is used in a proportion of 5 to 90 parts by weight, preferably 5 to 40 parts by weight. However, the total amount of the peroxide-crosslinked olefin copolymer rubber (i) and the olefin plastic (ii) is 100 parts by weight.

When the olefin-based plastic (ii) is used in the above proportion, the resulting graft-modified polyolefin-based elastomer has excellent rubber properties such as rubber elasticity and excellent fluidity, and as a result, is molded. It has excellent properties.

In the present invention, examples of the modifier (iii) used for graft-modifying the thermoplastic polyolefin-based elastomer include α, β-unsaturated fatty acids or derivatives thereof, unsaturated epoxy monomers and the like. To be

Specific examples of the α, β-unsaturated fatty acid or its derivative include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid and itaconic acid; maleic anhydride, itaconic anhydride, Acid anhydrides such as norbornene carboxylic anhydride and tetrahydrophthalic anhydride; hydroxyalkyl esters or hydroxyalkoxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate and hydroxyethoxymethacrylate. . In the present invention, maleic anhydride and hydroxyethyl acrylate are preferably used.

Specific examples of unsaturated epoxy monomers include glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, glycidyl itaconate and glycidyl crotonate. In the present invention, glycidyl methacrylate is preferably used.

The above "dynamic heat treatment", kneading device,
The kneading conditions and "partial cross-linking" are the same as in the case of the above-mentioned non-graft-modified polyolefin-based thermoplastic elastomer.

Since the thermoplastic polyolefin-based elastomer used in the present invention is composed of crystalline polyolefin and rubber, it has excellent fluidity. The body 2 and the substrate layer 7 of the draining portion 3 of the glass run channel made of the thermoplastic polyolefin-based elastomer described above are excellent in rubber properties such as heat resistance, tensile properties, flexibility and anti-elasticity. In the present invention, the partially crosslinked non-graft modified polyolefin-based thermoplastic elastomer and the partially crosslinked graft modified polyolefin-based thermoplastic elastomer as described above are preferable.

The thermoplastic polyolefin-based elastomer as described above can be molded using a conventionally used molding apparatus such as compression molding, transfer molding, injection molding, and extrusion molding.

Ultra High Molecular Weight Polyolefin Composition The ultra high molecular weight polyolefin composition used in the present invention includes the following compositions.

(1) An ultrahigh molecular weight polyolefin having an intrinsic viscosity [η] measured in a 135 ° C. decalin solvent in the range of 10 to 40 dl / g and an intrinsic viscosity [η] measured in a 135 ° C. decalin solvent. A polyolefin composition consisting essentially of a low to high molecular weight polyolefin within the range of 0.1 to 5 dl / g, wherein the ultra high molecular weight polyolefin comprises an ultra high molecular weight polyolefin and a low to high molecular weight polyolefin. It is present in a proportion of 15 to 40% by weight with respect to the total weight of 100%, and
The intrinsic viscosity [η] measured in a decalin solvent at 35 ° C is 3.
An ultra high molecular weight polyolefin composition in the range of 5 to 8.3 dl / g.

(2) An ultrahigh molecular weight polyolefin composition comprising the ultrahigh molecular weight polyolefin composition of (1) above and 1 to 20% by weight of a liquid or solid lubricant based on the ultrahigh molecular weight polyolefin composition.

Examples of the ultrahigh molecular weight polyolefin and the low molecular weight to high molecular weight polyolefin as described above include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4 -Methyl
It is composed of a homopolymer or copolymer of α-olefin such as -1-pentene and 3-methyl-1-pentene. In the present invention, ethylene homopolymer, and ethylene and other α
-A copolymer containing ethylene as a main component and composed of an olefin is desirable.

As the liquid lubricating oil used in the composition (2), petroleum-based lubricating oil, synthetic lubricating oil, etc. are used. Specific examples of the petroleum-based lubricating oil include liquid paraffin, spindle oil, refrigerating machine oil, dynamo oil, turbine oil, machine oil, and cylinder oil.

Specific examples of the synthetic lubricating oil include synthetic hydrocarbon oils, polyglycol oils, polyphenyl ether oils, ester oils, phosphate ester oils, polychlorotrifluoroethylene oils, fluoroester oils, chlorinated biphenyls. Oil, silicone oil, etc. are used.

As the solid lubricating oil used in the composition (2), graphite and molybdenum disulfide are mainly used, but boron nitride, tungsten disulfide and lead oxide are also used. Glass powder, metallic soap, etc. can also be used. The solid lubricating oil can be used alone or in combination with the liquid lubricating oil, and can be blended with the ultra high molecular weight polyolefin in the form of, for example, powder, sol, gel, suspense.

Further, the above-mentioned ultrahigh molecular weight polyolefin composition may contain, if necessary, a mineral oil softener, a heat stabilizer, an antistatic agent, a weather stabilizer, an antiaging agent, a filler, a coloring agent, a lubricant. Can be added within a range that does not impair the object of the present invention.

Since the ultrahigh molecular weight polyolefin composition of the above (1) and (2) can be subjected to coextrusion lamination processing with a thermoplastic polyolefin-based elastomer, a film (sheet) is produced in the production of the glass run channel of the present invention.
The polyolefin-based thermoplastic elastomer layer and the ultra-high molecular weight polyolefin layer can be directly laminated without undergoing a molding step, which is economical.

On the other hand, if the ultrahigh molecular weight polyolefin, for example, the ultrahigh molecular weight polyolefin having an intrinsic viscosity [η] measured in the solvent of decalin at 135 ° C. in the above (1) is in the range of 10 to 40 dl / g, the It is not possible to perform coextrusion lamination processing with a plastic elastomer, and therefore, at the time of laminating the polyolefin thermoplastic elastomer layer and the ultra high molecular weight polyolefin layer, at least one of them must be formed into a film (sheet) in advance, It is inferior in economy as compared with the case of the above ultrahigh molecular weight polyolefin composition.

In the glass run channel according to the present invention, the draining section 3 is preferably made of the same material as the main body 2. When the main body 2 is made of a thermoplastic polyolefin-based elastomer, if the draining portion 3 is also made of the same material, it is sufficiently practical for durability and bonding strength with the slip resin layer 9. .

Shark skin (shark skin) that can be used in the glass run channel according to the present invention can be developed at the time of molding by appropriately selecting the properties of the raw material polyolefin thermoplastic elastomer.

The appearance of the obtained sharkskin is different from the melt fracture which is sometimes observed during extrusion molding of resin or elastomer, and the skin of the molded product is periodically roughened to form fine irregularities.

Further, it is necessary that the sharkskin is exposed on the surface of the slippery resin layer 9 provided on the sharkskin, and the thickness of the slippery resin layer 9 is usually 3 to 50 μm.
It is laminated so that it becomes m. In addition, in the present invention, the thickness of the slipping resin layer 9 can be further increased or decreased according to need.

Since the portion where the water draining portion 3 comes into contact with the window glass 12 is generally different when the window glass 12 enters and when it leaves the window glass 12, coating with a slipping resin and formation of a sharkskin applied as necessary. Is preferably applied to a relatively wide area of the draining section 3.

Further, in the specific example shown in FIG. 1, there is a portion 16 in the inside of the main body 2 that comes into contact with the end of the window glass, and this portion 16 also has a surface on the surface of the main body 2 made of a thermoplastic polyolefin-based elastomer. A slipping resin layer 9 made of an ultrahigh molecular weight polyolefin composition can be provided.

[0078]

According to the present invention, it is possible to omit all the steps of applying the adhesive, hardening or baking the adhesive, and embossing steps before and after the step. As a result, the number of steps can be reduced. In addition, since the working time can be shortened, it is possible to manufacture a glass run channel with excellent economic efficiency, durability, close contact with the window glass when closed, and light sliding when opening and closing. A glass run channel having excellent properties can be provided.

The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

[0080]

Example 1 Ethylene / propylene / 5-ethylidene-2-
Norbornene copolymer rubber [ethylene content 70 mol%, iodine value 12, Mooney viscosity ML _{1 + 4} (100 ° C.)
120] 75 parts by weight and polypropylene [MFR 13 g
/ 10 minutes (ASTM D 1238-65T, 230
)) And a density of 0.91 g / cm ³ ] 25 parts by weight with a Banbury mixer in a nitrogen atmosphere at 180 ° C. for 5 minutes, and then the kneaded product is passed through a roll to form a sheet, which is then cut with a sheet cutter. It was cut into square pellets.

This square pellet was filled with divinylbenzene.
5 parts by weight and 0.3 parts by weight of 1,3-bis (t-butylperoxyisopropyl) benzene were added and mixed by stirring with a Henschel mixer.

Next, this mixture was extruded at a temperature of 220 ° C. in a nitrogen atmosphere using a uniaxial extruder having L / D = 30 and a screw diameter of 50 mm to obtain a thermoplastic polyolefin-based elastomer.

The gel content of the obtained thermoplastic polyolefin-based elastomer was 97% by weight as determined by the above-mentioned method. This thermoplastic polyolefin-based elastomer was extruded at a temperature of 230 ° C. to form a glass run channel body and a draining portion, and the surface thereof had an intrinsic viscosity [η] of 28 dl / g measured in a 135 ° C. decalin solvent. Ultrahigh molecular weight polyethylene composition consisting of 23% by weight of ultrahigh molecular weight polyethylene and 77% by weight of low molecular weight polyethylene having an intrinsic viscosity [η] of 0.73 dl / g measured in 135 ° C decalin solvent [135 ° C decalin solvent Viscosity [η] measured by
7.0 dl / g, density of 0.965 g / cm ³ ] is 25
The glass run channel of the present invention was obtained by coextrusion lamination at 0 ° C.

The obtained glass run channel has a substantially trapezoidal shape, and the total length of the inclined portion and the horizontal portion of the glass run channel 1 fixed to the window frame 13 in FIG. The length of the part is 90 mm,
At the bottom of the body 2, the outer width of the bottom is 15 mm, and the outer height of the side is 20 m.
The length of the drainage part 3 was 10 mm, the length was approximately equal to the cross-sectional shape shown in FIG. 1, and the thickness of the ultra high molecular weight polyethylene layer was 30 μm on average.

The time required for molding the glass run channel was 0.2 minutes per 1 m shorter than the time required by the conventional method, which was 60% of that of the conventional method. The obtained glass run channel was mounted on a test window frame, and a 3.2 mm-thick window glass was fitted and a durability test (upper and lower window glass repeated tests) was performed. As a result, this glass run channel has 5
It withstood a window glass up-and-down test repeated 10,000 times and maintained the function as a glass run channel. However, the conventional glass run channel (the sliding portion of the window glass has a laminated structure in which a nylon film is adhered to the soft vinyl chloride resin layer) causes breakage at the window glass contact surface after 25,000 times, As a result, the frictional resistance with the window glass was remarkably increased and the glass could not be used.

[0086]

Example 2 In Example 1, 100 parts by weight of an ultra-high molecular weight polyethylene composition was used instead of the ultra-high molecular weight polyethylene composition of Example 1, and a number average molecular weight of 1300 as a liquid lubricant, and a kinematic viscosity at 100 ° C. Is 100 cSt
Example 2 was repeated except that 2 parts by weight of the ethylene / propylene copolymer synthetic oil of was mixed with a Henschel mixer, and the ultrahigh molecular weight polyethylene composition pelletized with a single-screw extruder was used.

The molding time of the obtained glass run channel was 55% of that of the conventional method, and the window glass up-and-down repeated test withstood 50,000 times.

[0088]

[Example 3] Ethylene / propylene / 5-ethylidene-2-
Norbornene copolymer rubber [ethylene content 70 mol%, iodine value 12, Mooney viscosity ML _{1 + 4} (100 ° C.)
120] 75 parts by weight and polypropylene [MFR 13 g
/ 10 minutes (ASTM D 1238-65T, 230
)) And a density of 0.91 g / cm ³ ] 25 parts by weight with a Banbury mixer in a nitrogen atmosphere at 180 ° C. for 5 minutes, and then the kneaded product is passed through a roll to form a sheet, which is then cut with a sheet cutter. It was cut into square pellets.

This square pellet was filled with divinylbenzene.
5 parts by weight, 0.3 parts by weight of 1,3-bis (t-butylperoxyisopropyl) benzene, and 0.5 parts by weight of maleic anhydride were added and mixed by stirring with a Henschel mixer.

Next, this mixture was extruded at a temperature of 220 ° C. in a nitrogen atmosphere using a uniaxial extruder having L / D = 30 and a screw diameter of 50 mm to obtain a graft-modified polyolefin thermoplastic elastomer.

The gel content of the obtained thermoplastic polyolefin-based elastomer was 96% by weight as determined by the above method. This thermoplastic polyolefin-based elastomer was extruded at a temperature of 230 ° C. to form a glass run channel body and a draining portion, and the surface thereof had an intrinsic viscosity [η] of 28 dl / g measured in a 135 ° C. decalin solvent. Ultrahigh molecular weight polyethylene composition consisting of 23% by weight of ultrahigh molecular weight polyethylene and 77% by weight of low molecular weight polyethylene having an intrinsic viscosity [η] of 0.73 dl / g measured in 135 ° C decalin solvent [135 ° C decalin solvent Viscosity [η] measured by
7.0 dl / g, density of 0.965 g / cm ³ ] is 25
The same glass run channel as in Example 1 was obtained by coextrusion lamination at 0 ° C.

The molding time of the obtained glass run channel was 60% of that in the conventional method, and the window glass up-and-down repeated test withstood 50,000 times.

[Brief description of drawings]

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

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

FIG. 3 is a diagram for explaining how to attach a glass run channel to an automobile door.

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

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

[Explanation of symbols]

1 ・ ・ ・ Glass run channel 2 ・ ・ ・ Glass run channel main body 3 ・ ・ ・ Drainer 4 ・ ・ ・ Contact part with window glass 7 ・ ・ ・ Polyolefin thermoplastic elastomer A base layer 8 consisting of a base layer surface having a repeating pattern of fine irregularities (provided as needed) 9 a slipping resin layer 10 consisting of an ultra high molecular weight polyolefin composition .Surface of the slippery resin layer having a repeating pattern of fine irregularities (provided as necessary)

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Claims (4)

[Claims] 1. A glass run channel made of a thermoplastic polyolefin elastomer, comprising a groove-shaped main body in a cross section and a tongue-shaped drainer extending from the vicinity of the top of the side wall toward the center. , At least a portion of the surface of the drainage portion that can come into contact with the window glass is composed of an ultrahigh molecular weight polyolefin layer laminated on a polyolefin-based thermoplastic elastomer layer, and the ultrahigh molecular weight polyolefin layer has the following ultrahigh molecular weight polyolefin composition: Glass run channel characterized by being composed of a substance; ultra-high molecular weight polyolefin having an intrinsic viscosity [η] measured in a solvent of decalin at 135 ° C within the range of 10 to 40 dl / g, and a solvent of decalin at 135 ° C Low molecular weight or high molecular weight porosity having an intrinsic viscosity [η] measured in 0.1 to 5 dl / g. A polyolefin composition consisting essentially of an olefin, wherein the ultrahigh molecular weight polyolefin is present in a proportion of 15 to 40% by weight based on 100% by weight of the total weight of the ultrahigh molecular weight polyolefin and the low to high molecular weight polyolefin. And the intrinsic viscosity [η] measured in a 135 ° C. decalin solvent was 3.5 to 8.
An ultra high molecular weight polyolefin composition in the range of 3 dl / g. 2. A rubber (b) in which the thermoplastic polyolefin-based elastomer layer comprises 70 to 10 parts by weight of crystalline polypropylene (a) and ethylene / propylene copolymer rubber or ethylene / propylene / diene copolymer rubber. 30 to 90 parts by weight [the total amount of components (a) and (b) is 100 parts by weight], and is obtained by dynamically heat treating the mixture in the presence of an organic peroxide.
The glass run channel according to claim 1, wherein the rubber (b) is composed of a partially crosslinked polyolefin-based thermoplastic elastomer. 3. The thermoplastic polyolefin elastomer layer comprises: (i) 95 to 10 parts by weight of a peroxide-crosslinking olefin copolymer rubber; (ii) 5 to 90 parts by weight of an olefin plastic [component (i) and The total amount of (ii) is 100 parts by weight] and (iii) 0.01 to 10 parts by weight of an α, β-unsaturated carboxylic acid or derivative thereof, or an unsaturated epoxy monomer. The glass run channel according to claim 1, wherein the material is dynamically heat-treated in the presence of an organic peroxide to be composed of a partially cross-linked modified polyolefin-based thermoplastic elastomer. 4. The ultrahigh molecular weight polyolefin composition according to claim 1, wherein the ultrahigh molecular weight polyolefin composition contains 1 to 20% by weight of a liquid or solid lubricant based on the ultrahigh molecular weight polyolefin composition. The glass run channel according to any one.