JP3055113B2 - Glass run channel - Google Patents

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 channel provided with a window glass sliding portion composed of a laminate comprising a thermoplastic elastomer base layer and a lubricating resin surface layer. About the channel.

[0002]

2. Description of the Related Art In general, a window glass of a vehicle of an automobile needs to be opened and closed by raising and lowering for ventilation and ventilation or for communication with the outside of the vehicle. A glass run channel is provided between the window glass and the window frame in order to facilitate the operation of raising and lowering the window glass and to enable a tight (liquid-tight) sealing operation between the window glass and the window frame. A guide member is provided.

A conventional glass run channel has a groove-shaped main body in a cross section made of a soft synthetic resin such as a soft vinyl chloride resin or a vulcanized rubber such as an ethylene-propylene-diene copolymer rubber. It consists of a tongue-shaped draining part protruding from the vicinity of the side wall top toward the center.

In a conventional glass run channel, a nylon film or the like is used as a sliding portion of a window glass in order to improve the separation of a draining portion from the sliding portion with the window glass and prevent the window glass from being stained. Bonded together by bonding,
In order to reduce the contact area with the window glass, embossing is performed before or after lamination of the nylon film or the like.

In the conventional glass run channel, since there is no adhesiveness between the above-mentioned soft synthetic resin or vulcanized rubber and a surface material such as nylon, the main body of the glass run channel is formed of the soft synthetic resin or vulcanized rubber. Then, a step of applying an adhesive to the obtained molded article and bonding a film such as nylon is required, and furthermore, embossing must be performed before or after this bonding.
There is an inconvenience that the number of steps is large and that it requires time and effort.

In a conventional glass run channel,
Since there is a lamination step using an adhesive, there is also a problem in durability, and there is also a drawback that peeling tends to occur between the surface film layer and the substrate over time or exposure to the outdoors. Furthermore, the concavo-convex pattern that can be formed by embossing is not yet sufficiently satisfactory in combination with fineness and uniformity, and the close contact between the sliding part of the windowpane and the windowpane when closed, and when opened. There is still room for improvement in the light sliding property between the window glass sliding portion and the window glass.

Therefore, the present inventors have conducted intensive studies to solve the above-mentioned problems of the glass run channel, and selected a polyolefin-based thermoplastic elastomer as an elastomer constituting at least a sliding portion of the window glass of the glass run channel. Then, if the ultra-high molecular weight polyolefin is heat-sealed and laminated on the polyolefin-based thermoplastic elastomer layer, the manufacturing operation is easy, and the durability and
The present inventors have found that a glass run channel excellent in close contact with a window glass at the time of closing and light sliding property with the window glass at the time of opening can be obtained, thereby completing the present invention.

[0008]

An object of the present invention is 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 having excellent sliding properties with 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 polyolefin-based thermoplastic elastomer comprising a groove-shaped main body in a cross section and a tongue-shaped drainage portion protruding from the vicinity of the side wall top toward the center side, wherein a glass run channel of the drainage portion is provided. At least a portion that can be in contact with the window glass on the surface is made of an ultrahigh molecular weight polyolefin layer laminated on the polyolefin thermoplastic elastomer layer, and the ultrahigh molecular weight polyolefin layer is composed of the following ultrahigh molecular weight polyolefin composition. It is characterized by having.

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

The polyolefin-based thermoplastic elastomer preferably used in the present invention includes the following partially crosslinked polyolefin-based thermoplastic elastomers and modified polyolefin-based thermoplastic elastomers. (1) Rubber made of crystalline polypropylene (a) 70 to 10 parts by weight and ethylene / propylene copolymer rubber or ethylene / propylene / diene copolymer rubber (b)
The rubber (b) obtained by dynamically heat-treating a mixture consisting of 30 to 90 parts by weight (the total amount of the components (a) and (b) is 100 parts by weight) in the presence of an organic peroxide. ) Is a partially crosslinked polyolefin-based thermoplastic elastomer. (2) 95 to 10 parts by weight of (i) peroxide-crosslinked olefin copolymer rubber and 5 to 90 parts by weight of (ii) olefin plastic [The total amount of components (i) and (ii) is 100 parts by weight. And (iii) a blend 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 dynamically reacted in the presence of an organic peroxide. Heat treated to
Modified polyolefin-based thermoplastic elastomer that is partially crosslinked.

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

[0013]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, an example of a glass run channel according to the present invention will be specifically described 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 the cross section and a center from the vicinity of the side wall top. And a tongue-shaped drainer 3 protruding toward the side. The pair of drainers 3 and 3 extend inclining toward the inside of the groove of the main body 2, and the outer surface side is a window glass contact part 4, and the tips 5 and 5 can be opened and closed with each other. Is in a good positional relationship. The main body 2 is provided with a hook 6 for attachment to a window frame on an outer wall thereof.

Although the main body 2 and the draining section 3 are integrally formed of an elastomer, according to the present invention, at least the window glass contact section 4 is formed of a base layer made of a polyolefin-based thermoplastic elastomer and an ultrahigh molecular weight polyolefin composition. And a lubricating resin layer made of a material. As shown in FIG. 2 showing the window glass contact portion 4 in an enlarged manner, the surface 8 of the base layer 7 made of a polyolefin-based thermoplastic elastomer is
It is preferable that a repeating pattern of fine unevenness is provided. A lubricating resin layer 9 made of an ultrahigh molecular weight polyolefin composition is laminated on the surface 8 having such a sharkskin-like fine uneven pattern by heat fusion, and the outer surface 10 has the same fine unevenness. Is preferably applied.

Referring to FIGS. 3, 4 and 5 for explaining attachment of the glass run channel to an automobile, FIG.
The vehicle door 11 is provided with a window glass 12 that can be opened and closed by elevating and lowering, while the glass run channel 1 is fixed to a window frame 13. That is, in FIGS. 4 and 5, the window frame 13 has a U-shaped cross section as a whole, and an inward projection 15 is formed at the entrance of the concave portion 14. The glass run channel 1 is fixed to the window frame 13 by inserting the glass run channel 1 into the concave portion 14 and engaging the engaging hook 6 with the projection 15. As shown in FIG. 4, when the window glass 12 is lowered, the tips 5, 5 of the glass sliding parts face each other and are closed, and as shown in FIG. In the figure, the tips 5, 5 of the window glass sliding portions are separated by the window glass 12 inserted between them, but are in contact with the window glass surface.

According to the present invention, the glass run channel 1
Of these, a base layer 7 of a polyolefin-based thermoplastic elastomer is provided at least in a portion in contact with a window glass, and a slip resin layer 9 made of an ultra-high-molecular-weight polyolefin composition thermally fused to the surface of the base layer 7 is provided. .

That is, the polyolefin-based thermoplastic elastomer used in the present invention can be thermoformed into an arbitrary shape and size, and has elasticity and flexibility required for a sliding portion of a window glass of a glass run channel. ,
It has excellent properties such as compressibility, and also has excellent properties such as durability, weather resistance, and water resistance. The polyolefin-based thermoplastic 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 lubricating resin layer 9 made of an ultrahigh molecular weight polyolefin composition serving as a surface material layer. It is possible to form a laminated structure having excellent interlayer adhesion strength over time, and furthermore, excellent interlayer adhesion strength after a weather resistance test. Moreover, the polyolefin-based thermoplastic elastomer used as the base layer 7 in the present invention can be molded so as to exhibit a sharkskin-like molded appearance.
By combining the step of heat-sealing the lubricating resin layer 9 made of the ultrahigh molecular weight polyolefin composition as the surface material layer and the base layer 7, sharkskin-shaped fine irregularities are formed on the outer surface of the lubricating resin layer 9. The pattern can be faithfully reproduced. It is extremely difficult to project such a sharkskin-shaped surface with a microscopic unevenness by a conventional adhesive application method, and it has become possible only by combining the above-mentioned molding step and heat fusion step.

According to the present invention, by employing the above-described structure, the step of applying the adhesive, the step of curing or baking the adhesive, and the step of embossing before or after the step are all omitted, and the number of steps is small and the number of steps is small. A glass run channel can be efficiently manufactured with a lot of trouble. In addition, by providing the lubricating resin layer 9 made of the ultrahigh molecular weight polyolefin composition as a surface material layer, not only can the coefficient of friction with the window glass be reduced, but also it can be compared with the concavo-convex pattern by the conventional embossing. As a result, it is 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 (liquid-tight) contact with the window glass becomes possible, and when the window glass is opened, its sliding resistance is reduced.
Smooth and easy opening and closing operations become possible.

Polyolefin Thermoplastic Elastomer The polyolefin thermoplastic elastomer used in the present invention comprises a crystalline polyolefin and a rubber.

The crystalline polyolefin used in the present invention includes a homopolymer or copolymer of an α-olefin having 2 to 20 carbon atoms. Specific examples of the crystalline polyolefin include the following (co) polymers. (1) Ethylene homopolymer (The production method may be either a low-pressure method or a high-pressure method.) (2) Copolymerization of ethylene with 10 mol% or less of other α-olefins or vinyl monomers such as vinyl acetate and ethyl acrylate. Polymer (3) Propylene homopolymer (4) Random copolymer of propylene and 10% or less of other α-olefin (5) Block copolymer of propylene and 30% or less of other α-olefin (6) 1-butene homopolymer (7) Random copolymer of 1-butene and 10% by mole or less of other α-olefin (8) 4-methyl-1-pentene homopolymer (9) 4 -Methyl-1-pentene and less than 20 mol% of other α
-Random copolymer with olefin As the α-olefin, specifically, 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, but an olefin copolymer rubber is preferred. The 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 Α-olefin / non-conjugated diene copolymer comprising diene.

Specific examples of such an olefin 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
５０50/50] (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 from 10 to 250, especially from 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 be present in the polyolefin thermoplastic elastomer in any cross-linked state, such as uncross-linked, partially cross-linked or totally cross-linked. It preferably exists 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 the like, diene rubbers, SEBS, polyisobutylene and the like.

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

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

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

The above-mentioned and below-mentioned polyolefin-based thermoplastic elastomers may contain, if necessary, mineral oil-based softeners, heat stabilizers, antistatic agents, weathering stabilizers, antioxidants, fillers, coloring agents, lubricants, etc. Can be added in a range that does not impair the object of the present invention.

More specific examples of the polyolefin thermoplastic elastomer preferably used in the present invention include:
60 to 10 parts by weight of a crystalline polypropylene (a) and rubber (b) 40 to 9 composed of an ethylene / propylene copolymer rubber or an ethylene / propylene / diene copolymer rubber
0 parts by weight [the total amount of 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 softener (d) are dynamically heat-treated in the presence of an organic peroxide. And a polyolefin-based thermoplastic elastomer obtained by partially crosslinking the rubber (b).

As the above-mentioned organic peroxide, specifically, dicumyl peroxide, di-tert-butyl peroxide, 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-butylcumyl peroxide and the like.

Of these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane and 2,5-dimethyl-2,5-di-, in terms 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 1,3-bis (tert-butylperoxyisopropyl) benzene is most preferred.

In the present invention, the organic peroxide is
It is used in an amount 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 the rubber.

In the present invention, sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N
-4- dinitrosoaniline, nitrosobenzene, diphenylguanidine, peroxy crosslinking aids such as trimethylolpropane-N, N'-m-phenylenedimaleimide, or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, Polyfunctional methacrylate monomers such as diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate can be blended.

By using a compound as described above,
A uniform and mild crosslinking reaction can be expected. Particularly, in the present invention, divinylbenzene is most preferred. Divinylbenzene is easy to handle, has good compatibility with the crystalline polyolefin and rubber, which are the main components of the above-mentioned crosslinked product, and has an action of solubilizing the organic peroxide. Therefore, a thermoplastic elastomer having a uniform cross-linking effect by heat treatment and a good balance between fluidity and physical properties can be obtained. In the present invention, the crosslinking aid or the polyfunctional vinyl monomer as described above is used in an amount of 0.1 to 0.1% based on the whole to-be-crosslinked product.
It is preferably used at a ratio of from 2 to 2% by weight, especially from 0.3 to 1% by weight. If the compounding ratio of the crosslinking aid or the polyfunctional vinyl monomer exceeds 2% by weight, the crosslinking reaction proceeds too quickly if the compounding amount of the organic peroxide is large, so that the obtained polyolefin-based thermoplastic elastomer cannot be flowable. Poor, on the other hand, when the 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 At the time of processing and molding, physical properties may change due to heat history. Therefore, the co-agent and the polyfunctional vinyl monomer should not be compounded in excess.

The term "dynamically heat-treating" refers to kneading 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 apparatus 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 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 17 to 280 ° C.
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 determined in the range of 10 to 10 ⁴ sec ^-1 , preferably 10 ² to 10 ³ sec ^-1 .

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

[Measurement method of gel content] A pellet of a polyolefin-based thermoplastic elastomer was used as a sample for about 100 m.
g and immersed in a closed container of 30 ml of cyclohexane sufficient 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 the weight becomes constant. The gel content is represented by the following equation. Gel content [%] = (dry weight after cyclohexane immersion)
÷ (weight before immersion in cyclohexane) × 100 In the present invention, the following modified polyolefin-based thermoplastic elastomer (MTPE) can be used as a preferred polyolefin-based thermoplastic elastomer constituting the base layer 7. . (I) Peroxide-crosslinked olefin copolymer rubber 9
5 to 10 parts by weight, and (ii) 5 to 90 parts by weight of the olefin-based plastic [the total amount of the components (i) and (ii) is 100 parts by weight].
And (iii) an α, β-unsaturated carboxylic acid or a derivative thereof,
Or a modified polyolefin which is dynamically heat-treated in the presence of an organic peroxide to form a partially crosslinked polymer containing 0.01 to 10 parts by weight of a polar group-containing monomer such as an unsaturated epoxy monomer. It is a thermoplastic elastomer.

The peroxide crosslinked olefin copolymer rubber (i) used in the present invention is, for example, ethylene
Amorphous, elastic copolymers containing olefins as the main component, such as propylene / non-conjugated diene copolymer rubber and ethylene / butadiene copolymer rubber, which are mixed with an organic peroxide and kneaded under heating. Refers to a rubber whose flowability is reduced or becomes non-flowable due to crosslinking.

Examples of the non-conjugated diene include dicyclopentadiene, 1,4-hexadiene, dicyclooctadiene, methylene-norbornene, and ethylidene-diene.
Norbornene and the like can be mentioned.

In the present invention, among the above peroxide-crosslinked olefin copolymer rubbers, the molar ratio of ethylene component units to propylene component units (ethylene component units / propylene component units) is 50/50 to 50/50. 90/1
Ethylene / propylene copolymer rubber and ethylene / propylene / non-conjugated diene copolymer rubber in the range of 0, especially 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 having excellent heat resistance, tensile strength characteristics and rebound resilience.

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

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

In the present invention, the peroxide-crosslinked olefin copolymer rubber (i) contains 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-based copolymer rubber (i) and the olefin-based plastic (ii) is 100 parts by weight.

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

The olefin-based plastic (ii) used in the present invention can be prepared by a high-pressure method or a low-pressure method.
It consists of a crystalline high molecular weight solid product obtained by polymerizing one or more monoolefins. Examples of such resins include isotactic or syndiotactic monoolefin polymer resins. These representative resins are commercially available.

Specific examples of suitable starting olefins include ethylene, propylene, 1-butene, 1-pentene,
Hexene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 1-
Octene, 1-decene, and a mixed olefin of two or more of these are exemplified. In the present invention, any of these homopolymerization and copolymerization may be adopted as long as a resinous material can be obtained.

In the present invention, a particularly preferred olefin plastic is a peroxide decomposable olefin plastic. In the present invention, a peroxide-decomposable olefin-based plastic refers to an olefin-based plastic which is mixed with a peroxide and kneaded under heating to be thermally decomposed to reduce the molecular weight and increase the fluidity of the resin. Tactic polypropylene; copolymers of propylene with other small amounts of 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 olefin-based plastic used in the present invention has a melt index (ASTM-D-1238).
(−65 T, 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-based 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-based copolymer rubber (i) and the olefin-based plastic (ii) is 100 parts by weight.

When the olefin-based plastic (ii) is used at the above ratio, the obtained graft-modified polyolefin-based elastomer has excellent rubber-like properties such as rubber elasticity and excellent fluidity. Excellent in nature.

In the present invention, the modifier (iii) used for graft-modifying the polyolefin-based thermoplastic elastomer includes monomers such as α, β-unsaturated fatty acids or derivatives thereof, and unsaturated epoxy monomers. Can be

Specific examples of α, β-unsaturated fatty acids and derivatives thereof 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; and hydroxyalkyl esters or hydroxyalkoxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, and hydroxyethoxy methacrylate. . In the present invention, maleic anhydride and hydroxyethyl acrylate are preferably used.

Further, specific examples of the unsaturated epoxy monomer 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”, a kneading device,
The kneading conditions and "partial cross-linking" are the same as in the case of the non-graft-modified polyolefin-based thermoplastic elastomer described above.

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

The above-mentioned polyolefin-based thermoplastic elastomer 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] in a range of 10 to 40 dl / g measured in a decalin solvent at 135 ° C. and an intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. A polyolefin composition consisting essentially of a low molecular weight to high molecular weight polyolefin in the range of 0.1 to 5 dl / g, wherein the ultrahigh molecular weight polyolefin is composed of an ultrahigh molecular weight polyolefin and a low molecular weight to high molecular weight polyolefin. 15 to 40% by weight based on 100% by weight of the total weight, and 1
2. The intrinsic viscosity [η] measured in a decalin solvent at 35 ° C. is 3.
An ultrahigh molecular weight polyolefin composition in the range of 5-8.3 dl / g.

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

The ultrahigh molecular weight polyolefin and the low molecular weight to high molecular weight polyolefin as described above include, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, -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
-Ethylene-based copolymers composed of olefins are preferred.

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

Specific examples of the synthetic lubricating oil include synthetic hydrocarbon oil, polyglycol oil, polyphenyl ether oil, ester oil, phosphate ester oil, polychlorotrifluoroethylene oil, fluoroester oil, chlorinated biphenyl oil. Oil, silicone oil and the like are used.

As the solid lubricating oil used in the composition (2), graphite and molybdenum disulfide are mainly used, but in addition, boron nitride, tungsten disulfide, and lead oxide , Glass powder, metal soap, etc. can also be used. The solid lubricating oil can be used alone or in combination with a liquid lubricating oil. For example, the solid lubricating oil can be blended with the ultrahigh molecular weight polyolefin in the form of a powder, a sol, a gel, a suspensoid or the like.

The above ultrahigh molecular weight polyolefin composition may contain, as necessary, a mineral oil softener, a heat stabilizer, an antistatic agent, a weather stabilizer, an antioxidant, a filler, a colorant, a lubricant, and the like. Can be blended within a range that does not impair the object of the present invention.

The ultrahigh molecular weight polyolefin compositions of the above (1) and (2) can be co-extruded and laminated with a polyolefin-based thermoplastic elastomer. Therefore, when producing the glass run channel of the present invention, a film (sheet) is used.
The polyolefin-based thermoplastic elastomer layer and the ultra-high molecular weight polyolefin layer can be directly laminated without a molding step, which is economical.

On the other hand, an ultra-high molecular weight polyolefin, for example, an ultra-high molecular weight polyolefin alone having an intrinsic viscosity [η] in the range of 10 to 40 dl / g measured in a decalin solvent at 135 ° C. in the above (1), requires a polyolefin heat It is not possible to perform co-extrusion lamination with a thermoplastic elastomer, and therefore, when laminating a polyolefin-based thermoplastic elastomer layer and an ultra-high molecular weight polyolefin layer, at least one of them must be formed into a film (sheet) in advance, Compared with the case of the ultrahigh molecular weight polyolefin composition, the economic efficiency is inferior.

In the glass run channel according to the present invention, the drainer 3 is preferably made of the same material as the main body 2. When the main body 2 is made of a polyolefin-based thermoplastic elastomer, if the draining portion 3 is also formed of the same material, it can sufficiently withstand practical use in terms of both durability and bonding strength with the lubricating resin layer 9. .

Shark skin (shark skin) which 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-based thermoplastic elastomer.

The appearance of the obtained sharkskin is different from the melt fracture which may be seen at the time of extrusion molding of a resin or an elastomer, and the skin of the molded article is periodically roughened to produce fine irregularities.

Further, it is necessary that the sharkskin is exposed also on the surface of the lubricating resin layer 9 provided on the sharkskin, and the thickness of the lubricating resin layer 9 is usually 3 to 50 μm.
m. In the present invention, the thickness of the lubricating resin layer 9 can be further increased or reduced as necessary.

Since the portion where the drainer 3 comes into contact with the window glass 12 is generally different between when the window glass 12 enters and exits, the coating with a lubricating resin and the formation of a sharkskin applied as necessary Is preferably applied to a relatively wide area of the drainer 3.

In the specific example shown in FIG. 1, there is a portion 16 in contact with the end of the window glass inside the main body 2, and this portion 16 is also provided on the surface of the main body 2 made of a polyolefin thermoplastic elastomer. And a lubricating resin layer 9 made of an ultrahigh molecular weight polyolefin composition.

[0078]

According to the present invention, the step of applying the adhesive, the step of curing or baking the adhesive, and the steps of embossing before and after the step can be omitted. As a result, the number of steps can be reduced. In addition, since the working time can be shortened, a glass run channel having excellent economy can be manufactured, and durability, close contact with a window glass when closed, and light sliding during opening and closing operations can be achieved. A glass run channel having excellent properties can be provided.

Hereinafter, the present invention will be described 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 [MFR13g
/ 10 min (ASTM D 1238-65T, 230
C.) and a density of 0.91 g / cm ³ ] and 25 parts by weight in a nitrogen atmosphere at 180 ° C. for 5 minutes using a Banbury mixer. It was cut to produce square pellets.

To the square pellets, add divinylbenzene 0.1%.
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. under a nitrogen atmosphere using a single screw extruder having an L / D = 30 and a screw diameter of 50 mm to obtain a polyolefin-based thermoplastic elastomer.

The gel content of the obtained polyolefin-based thermoplastic elastomer was 97% by weight as determined by the above method. This polyolefin-based thermoplastic elastomer was extruded at a temperature of 230 ° C. to form a glass run channel main body and a drain portion, and the surface had an intrinsic viscosity [η] of 28 dl / g measured in a decalin solvent at 135 ° C. Ultrahigh molecular weight polyethylene composition comprising 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 a decalin solvent at 135 ° C. [in a decalin solvent at 135 ° C. Intrinsic viscosity [η] measured by
7.0 dl / g, density 0.965 g / cm ³ ]
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.
The outer width of the bottom of the main body 2 is 15 mm and the outer height of the side is 20 m
m, the length of the drainer 3 was 10 mm, almost equal to the cross-sectional shape shown in FIG. 1, and the thickness of the ultrahigh molecular weight polyethylene layer was 30 μm on average.

The time required for forming the glass run channel was 0.2 minutes shorter per m than the time required by the conventional method, and was 60% of the conventional method. The obtained glass run channel was mounted on a test window frame, a 3.2 mm-thick window glass was fitted, and a durability test (upper and lower window glass repeated test) was performed. As a result, this glass run channel is 5
It survived the 0000-time window glass vertical repetition test and maintained its function as a glass run channel. However, the conventional glass run channel (in which the sliding portion of the window glass has a laminated structure in which a nylon film is adhered to a soft vinyl chloride resin layer) breaks at the window glass contact surface in 25,000 times, As a result, the frictional resistance with the window glass increased remarkably, making it unusable for use.

[0086]

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

The time required for molding the obtained glass run channel was 55% of that of the conventional method, and the window glass vertical repetition 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 [MFR13g
/ 10 min (ASTM D 1238-65T, 230
C.) and a density of 0.91 g / cm ³ ] and 25 parts by weight in a nitrogen atmosphere at 180 ° C. for 5 minutes using a Banbury mixer. It was cut to produce square pellets.

To the square pellets, add divinylbenzene 0.1%.
5 parts by weight, 1,3-bis (t-butylperoxyisopropyl) benzene, 0.3 part by weight, 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. under a nitrogen atmosphere using a single screw extruder having an L / D = 30 and a screw diameter of 50 mm to obtain a graft-modified polyolefin-based thermoplastic elastomer.

The polyolefin-based thermoplastic elastomer obtained had a gel content of 96% by weight, as determined by the method described above. This polyolefin-based thermoplastic elastomer was extruded at a temperature of 230 ° C. to form a glass run channel main body and a drain portion, and the surface had an intrinsic viscosity [η] of 28 dl / g measured in a decalin solvent at 135 ° C. Ultra-high molecular weight polyethylene composition consisting of 23% by weight of ultra-high molecular weight polyethylene and 77% by weight of low molecular weight polyethylene having an intrinsic viscosity [η] of 0.73 dl / g measured in a decalin solvent at 135 ° C. [in a decalin solvent at 135 ° C. Intrinsic viscosity [η] measured by
7.0 dl / g, density 0.965 g / cm ³ ]
Coextrusion and lamination were performed at 0 ° C. to obtain a glass run channel similar to that of Example 1.

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

[Brief description of the drawings]

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

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

FIG. 3 is a diagram illustrating attachment of a glass run channel to an automobile door.

FIG. 4 is a 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]

DESCRIPTION OF SYMBOLS 1 ... Glass run channel 2 ... Glass run channel main body 3 ... Draining part 4 ... Contact part with window glass 7 ... Polyolefin thermoplastic elastomer A base layer surface having a repeating pattern of fine irregularities (applied as required) 9 a lubricating resin layer made of an ultra-high molecular weight polyolefin composition 10・ Smooth resin layer surface having a repeating pattern of fine irregularities (applied as necessary)

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-137018 (JP, A) JP-A-2-649 (JP, A) JP-A-1-272646 (JP, A) JP-A-63-137 241050 (JP, A) JP-A-2-60951 (JP, A) JP-A-3-100549 (JP, U) (58) Fields investigated (Int. Cl. ⁷ , DB name) B60J 1/00-1 / 20 B32B 1/00-35/00

Claims (4)

(57) [Claims] 1. A glass run channel made of a polyolefin-based thermoplastic elastomer, comprising a groove-shaped main body in a cross section and a tongue-shaped drainage portion protruding from the vicinity of the top of the side wall toward the center. At least a portion of the surface of the draining portion that can come into contact with the window glass is made of an ultrahigh molecular weight polyolefin layer laminated on a polyolefin thermoplastic elastomer layer, and the ultrahigh molecular weight polyolefin layer has the following ultrahigh molecular weight polyolefin composition. A glass run channel characterized by being comprised of an ultrahigh molecular weight polyolefin having an intrinsic viscosity [η] in the range of 10 to 40 dl / g measured in a decalin solvent at 135 ° C. and a decalin solvent at 135 ° C. Low molecular weight to high molecular weight polymer having intrinsic viscosity [η] measured in the range of 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 molecular weight to high molecular weight polyolefin. And the intrinsic viscosity [η] measured in a 135 ° C decalin solvent is 3.5 to 8.
An ultra-high molecular weight polyolefin composition in the range of 3 dl / g. 2. The rubber (b) wherein the polyolefin-based thermoplastic elastomer layer is composed of 70 to 10 parts by weight of a 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), which 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 polyolefin-based thermoplastic elastomer layer comprises: (i) 95 to 10 parts by weight of a peroxide-crosslinked olefin-based copolymer rubber; and (ii) 5-90 parts by weight of an olefin-based 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 a derivative thereof, or an unsaturated epoxy monomer. The glass run channel according to claim 1, wherein the material is composed of a partially crosslinked modified polyolefin-based thermoplastic elastomer which is dynamically heat-treated in the presence of an organic peroxide. 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. A glass run channel according to any of the above.