JP2016098336A - Coated body material and weather strip - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coated body material make maintenance of desired slidability easy and capable of suppressing generation of abnormal tone during sliding in a coated body formed on a surface of a substrate and a weather strip using the coated body material.SOLUTION: There is provided a coated body material consisting of a thermoplastic elastomer for coated body by blending at least a rubber component, an olefin resin material, a crosslinker and a lubricant, where the lubricant consist of a solid lubricant consisting of graphite of 5 to 50 wt.% and a liquid lubricant consisting of a lipophilic lubricant and a hydrophilic lubricant of 3 to 15 wt.%, lipophilic lubricant/hydrophilic lubricant ratio which is a ratio of the lipophilic lubricant and the hydrophilic lubricant of the liquid lubricant is in a range of 50/50 to 90/10 and viscosity of the hydrophilic lubricant is smaller than that of the lipophilic lubricant.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a covering material and a weather strip, and relates to a molded body that requires slidability such as a weather strip for automobiles.

  For example, in a molded body that requires slidability, such as a weather strip for automobiles, a multilayer structure in which a slidable covering is formed on the surface of a substrate (for example, a portion that requires slidability) constituting the molded body. Things are known.

  As a specific example, a support part for attaching to a vehicle body (a door panel or the like in the case of a glass run) and a sliding object such as a glass member or the like (window glass or the like) provided on the support part are elastically pressed. In a molded body having a base made of an elastic contact portion (such as a lip portion), a configuration in which a covering is formed on the surface of the elastic contact portion of the base (the sliding target side) can be mentioned.

  In addition, as a technique for improving the slidability of the covering, for example, the surface of the covering may be obtained by roughening the surface of the covering or by applying a covering material made of a thermoplastic elastomer containing a lubricant. In other words, the friction coefficient is set to a low state (hereinafter appropriately referred to as a low friction state) so that desired slidability can be obtained. As a specific example, a gas reservoir is formed between the base body and the covering body of the molded body, and the surface of the covering body is roughened to be in a low friction state, or solid lubrication with a solid lubricant such as powdered silicone resin particles or the like. And liquid lubrication with a liquid lubricant such as silicone oil to make the surface of the coated body in a low friction state (for example, Patent Documents 1 to 3).

  The coated body is roughly divided into three sliding environments, dry environment, wet environment, and semi-wet environment (environment where both dry and wet environments are mixed). It is desirable to maintain a low friction state.

Japanese Patent No. 4408559 JP 2004-306937 A JP 2003-213141 A

  However, as described above, the covering body simply roughing the surface of the covering body by forming a gas reservoir or applying a covering material blended with a powdery solid lubricant or liquid lubricant is low in each sliding environment. It was difficult to make a frictional state. For example, even if the surface of the cover can be brought into a low friction state, the friction coefficient of each sliding environment increases as the sliding between the cover and the object to be slid is repeated. Since the difference tends to increase, it is difficult to maintain the low friction state.

  For this reason, it is difficult to maintain a desired slidability in each sliding environment, and abnormal sounds such as judder noise (so-called chatter noise) and squeal noise (so-called squeal) when sliding between the covering and the object to be slid. (For example, a stick-slip phenomenon occurs in a semi-wet environment).

  The present invention is based on the above-described problem, and uses a covering material that can easily maintain desired slidability in the covering and can suppress the generation of abnormal noise during sliding, and the covering material. Was to provide a weatherstrip that was.

  The covering material and the weather strip according to the present invention are technical ideas created to solve the above-mentioned problems. Specifically, one aspect of the covering material of the present invention is a surface of a substrate formed by extrusion molding. The coating material is formed of a thermoplastic elastomer for a coating material containing at least a rubber component, an olefin resin material, a crosslinking agent, and a lubricant, and the lubricant is 5 to 50 wt% of a solid lubricant made of graphite. And 3 to 15 wt% of a liquid lubricant comprising a lipophilic lubricant and a hydrophilic lubricant, wherein the ratio of the lipophilic lubricant to the hydrophilic lubricant of the liquid lubricant is a lipophilic lubricant / hydrophilic lubrication. The agent ratio is in the range of 50/50 to 90/10, and the viscosity of the hydrophilic lubricant is smaller than the viscosity of the lipophilic lubricant.

  The substrate may be made of a thermoplastic elastomer for a substrate containing at least a rubber component, an olefin resin material, a crosslinking agent, and a thermally expandable microcapsule, and the surface roughness may be 50 μm or less. Further, the thermoplastic elastomer for a covering is obtained by blending the other ingredients except the lubricant among the components blended in the thermoplastic elastomer for the covering, kneading and crosslinking, and then blending the lubricant. There may be.

  One aspect of the weather strip according to the present invention is a weather strip in which a covering is formed on the surface of a substrate by extrusion molding, and the covering is pressed against a sliding target. The covering includes the covering described above. It is made of a material, and the object to be slid is a glass member.

  As described above, according to the present invention, desired slidability can be easily obtained, and generation of abnormal noise during sliding can be suppressed.

BRIEF DESCRIPTION OF THE DRAWINGS Schematic explanatory drawing which shows an example of the weather strip using the multilayer structure elastomer molded object by this Embodiment. BRIEF DESCRIPTION OF THE DRAWINGS Schematic explanatory drawing of the apparatus used in order to observe the dynamic friction coefficient of this Example, abnormal noise, and durability. The schematic explanatory drawing which shows the observation method of the dynamic friction coefficient of a present Example.

  The covering material of the present embodiment and the weather strip using the covering material are not simply applied with a covering material made of a thermoplastic elastomer compounded with a lubricant or the like or roughened on the covering surface. As a lubricant compounded in the plastic elastomer, a lubricant containing 5 to 50 wt% of a solid lubricant made of graphite and 3 to 15 wt% of a liquid lubricant made of a lipophilic lubricant and a hydrophilic lubricant is applied, and lipophilic lubrication is applied. The agent / hydrophilic lubricant ratio (hereinafter appropriately referred to as the lipophilic hydrophilic ratio) is in the range of 50/50 to 90/10.

  For example, as in the prior art, a coated body simply roughened on the surface of the coated body has low durability and is likely to wear out, so that it is difficult to maintain a low friction state. In addition, a coated body simply applied with a powdery solid lubricant is easily removed from the coated body (thermoplastic elastomer as a binder) during sliding, and it is difficult to maintain a low friction state.

  Furthermore, when either one of a lipophilic lubricant or a hydrophilic lubricant is used as the liquid lubricant, a low friction state is maintained in a sliding environment of a dry environment, a wet environment, or a semi-wet environment. (For example, liquid lubrication with a lipophilic lubricant is hindered in a wet environment), and when both of them are used in combination, the dispersibility of the thermoplastic elastomer is lowered and a desired coating is formed. Will become difficult.

  On the other hand, as in this embodiment, graphite in which each layer is bonded to each other by van der Waals force with a fine layered substance (an irregular shape), and a lipophilic lubricant and a hydrophilic lubricant are within a predetermined range, respectively. According to the covering material composed of the blended thermoplastic elastomer, the graphite easily stays in the covering (thermoplastic elastomer) due to the anchor effect, and during sliding, the falling off from the covering is suppressed, Gradual peeling from the surface layer of the graphite results in solid lubrication. In addition, graphite is easily compatible with the lipophilic lubricant and has improved surface wettability. For example, liquid lubrication can be realized together with solid lubrication in a dry environment. Furthermore, since the surface of the coated body is slightly roughened by graphite (for example, the surface is finer than that in the case of forming a gas reservoir as in Patent Document 1), It can contribute to the reduction of the coefficient of friction in the sliding environment, and sufficient durability (sufficient than in the case of Patent Document 1) can also be obtained.

  In addition, hydrophilic lubricants are easily compatible with lipophilic lubricants through graphite (graphite functions like a coupling agent), and are compatible with coated elastomers. For example, in a wet environment, it hydrates with surface water on the surface of the coated body. Further, since the viscosity of the hydrophilic lubricant is smaller than the viscosity of the oleophilic lubricant, liquid lubrication is easily realized.

  As described above, according to the present embodiment, the friction coefficient can be reduced in each sliding environment of the covering body to be in a low friction state, and even if sliding between the covering body and the object to be slid is repeated, Since it can be controlled so that the friction coefficient of the sliding environment does not increase and the difference between the friction coefficients does not increase, it becomes easier to maintain the desired slidability in each sliding environment, and the generation of abnormal noise during sliding is suppressed. It is also possible to do.

  As described above, the covering material and the weather strip of the present embodiment have a configuration in which a thermoplastic elastomer in which graphite, a lipophilic lubricant, and a hydrophilic lubricant are blended in a predetermined range is applied. As long as the desired effect is achieved, for example, it is possible to appropriately change by applying techniques generally known in various fields such as the automotive parts field and the extrusion field. Specific examples shown in each item are given.

[Rubber component]
An ethylene-propylene-diene copolymer (hereinafter referred to as EPDM) can be applied as a rubber component blended in each thermoplastic elastomer of the covering material and the base material. Examples of the α-olefin of EPDM include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, and a preferred example is propylene. . A plurality of these α-olefin groups may be selected and used in combination such as propylene and 1-butene. In addition, the polyene copolymer is a cyclic non-conjugated polyene such as 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, norbornadiene, methyltetrahydroindene, 1,4 hexadiene, 7 -Methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4-ethylidene-1,7undecadiene, 4,8-dimethyl-1,4,8-decatriene, etc. Those that are non-conjugated polyenes. Each of these non-conjugated polyenes may be used alone or in combination of two or more, and the structural unit (content ratio of non-conjugated polyene in the ethylene-α-olefin / non-conjugated polyene copolymer) is, for example, from about 1 wt% to about 20 wt%, preferably about 1 wt% to about 15 wt%, more preferably about 5 wt% to about 11 wt%.

[Olefin resin materials]
The crystalline olefin resin contained in the olefin resin material blended in each thermoplastic elastomer of the covering material and the base material is mainly composed of, for example, ethylene homopolymer, propylene homopolymer, ethylene, propylene, etc. Generally known ones (such as commercially available products) such as crystalline copolymers can be applied as appropriate. Specific examples include high-density polyethylene, low-density polyethylene, crystalline ethylene copolymer of ethylene / butene-1 copolymer, isotactic polypropylene, propylene-ethylene copolymer, propylene / butene-1 copolymer, Examples include propylene / ethylene / butene-1 terpolymers, and polypropylene polymers are preferred. In addition, any one of the above crystalline olefin resins may be used alone, or two or more kinds may be used in appropriate combination.

  In addition to the crystalline olefin resin, an amorphous olefin resin may be included. In this case, it becomes easier to adjust the workability and elasticity of the molded body as compared with the case where only the crystalline olefin resin is included. However, if the amount is too large, it may affect the wear resistance, so it is preferable to pay attention to the amount. Examples of the amorphous olefin resin include an α-olefin homopolymer and two or more types of copolymers. However, in the case of a copolymer, an α-olefin unit which is a main component (propylene / 1-butene in the case of the amorphous olefin copolymer of the example) is bonded in an atactic structure. use.

  Specific examples include homopolymers such as atactic poly-1-butene, polypropylene (containing 50 mol% or more) and other α-olefins (ethylene, 1-butene, 1-pentene, 1-hexene, 4- Copolymers with methyl-1-pentene, 1-octene, 1-decene, etc.) and 1-butene (containing 50 mol% or more) and other α-olefins (ethylene, propylene, 1-pentene, 1-hexene) , 4-methyl-1-pentene, 1-octene, 1-decene, etc.). Moreover, each said copolymer may be used individually, respectively, and may be used in combination of 2 or more types as appropriate. Particularly preferred are atactic polypropylene (amorphous polypropylene), a copolymer of polypropylene and ethylene, and a copolymer of polypropylene and 1-butene.

[Crosslinking agent]
As a crosslinking agent to be blended in each thermoplastic elastomer of the covering material and the base material, a generally known crosslinking agent can be applied. It is easy to crosslink the rubber component. In the case of this phenol resin-based crosslinking agent, for example, alkylphenol formaldehyde resin, methylolated alkylphenol resin and the like can be mentioned. Further, a brominated phenolic resin having a terminal hydroxyl group brominated, for example, a halogenated phenolic resin such as a brominated alkylphenol resin can be used, and an alkylphenol formaldehyde resin is preferable. A preferred blending amount of the phenolic resin-based crosslinking agent is in the range of about 3 phr to about 20 phr, and a more preferred blending amount is in the range of about 4 phr to about 15 phr. However, it does not significantly impair the properties of the target coating or substrate. Any of them can be used as appropriate.

  In addition, when there are too few compounding quantities, a crosslinking reaction will not occur easily and the mechanical physical property of a molded object may fall. In particular, durability at high temperatures can be greatly deteriorated. Moreover, when there are too many compounding quantities, cross-linking reaction occurs excessively and cross-linking is locally biased, there is a possibility that workability (extrusion processability etc.) is lowered.

  Moreover, a crosslinking catalyst can be used, for example, a halogen compound can be applied. This halogen compound indicates a metal halide or an organic halide. Examples of the metal halide include stannous chloride, ferric chloride, cupric chloride, and the like. Examples thereof include halogenated resins such as chlorinated polypropylene, chlorinated polyethylene, butyl bromide rubber, and chloroprene rubber.

  Further, the preferred blending amount of the halide is in the range of about 0.1 phr to about 20 phr, and the more preferred blending amount is in the range of about 1 phr to about 15 phr, but the extent of not significantly impairing the properties of the target coating or substrate. Any of them can be used as appropriate. In addition, when there are too few compounding quantities, a crosslinking reaction will not occur easily and the mechanical physical property of an elastomer molded object may fall. Moreover, when there are too many compounding quantities, workability (extrusion workability etc.) may fall, or crosslinking reaction may become excess.

  In addition, various components, such as a crosslinking accelerator and a crosslinking assistant, may be blended. For example, as the crosslinking accelerator, those known in the field of thermoplastic elastomer materials can be applied, and examples thereof include zinc oxide, fatty acid, fatty acid metal salt and the like, stearic acid, calcium stearate, zinc stearate and the like. A commercially available product can also be suitably applied. A preferable blending amount of the crosslinking accelerator is in the range of about 0.5 phr to about 7 phr, and can be appropriately used as long as it does not significantly impair the properties of the target covering or substrate.

[Lubricant (solid lubricant)]
Among the lubricants contained in the thermoplastic elastomer of the covering material, as the solid lubricant, generally known ones can be applied, but at least graphite is applied, and in addition to the graphite, for example, molybdenum dioxide, dioxide Tungsten, PTFE (polytetrafluoroethylene) or the like may be used in combination as appropriate. In graphite, for example, the surface wettability is improved because it is easily compatible with a lipophilic lubricant described later. Further, the graphite contained in the covering is peeled off from the surface layer of the graphite during sliding, and the peeled material solidly lubricates the covering surface in a dry environment, for example. When used in combination (when the graphite and lipophilic lubricant are familiar), the peeling phenomenon of each layer of the graphite gradually proceeds, so it is possible to maintain a low friction state while maintaining durability. It becomes. Moreover, although it is also considered that the object to be slid is contaminated by the above-described exfoliated material, the exfoliated material familiar with the lipophilic lubricant as described above suppresses the contamination.

  As the particle diameter of the solid lubricant, for example, a medium having a median diameter of about 0.1 to 100 μm, preferably a range of about 5 to 30 μm, applied by laser analysis / scattering particle size distribution measurement may be used. If the particle diameter is too small or too large (for example, in the case of a particle diameter exceeding the above numerical range), it may be difficult to obtain desired solid lubrication and durability.

  Considering the dispersibility in the thermoplastic elastomer, the blending amount of the solid lubricant may be set within a range of 5 to 50 wt%, for example. If the blending amount is less than 5 wt%, it will be insufficient to make the coated body in a low friction state. If the blending amount exceeds 50 wt%, it may be difficult to obtain desired durability.

  Specific examples of graphite include natural graphite and artificial graphite, and particle shapes include scales, earths, lumps, etc., preferably scale-like graphite (for example, J-CAB, ACP made by Nippon Graphite). -1000 etc.).

[Lubricant (liquid lubricant)]
Of the lubricants contained in the thermoplastic elastomer of the covering material, as the liquid lubricant, a lipophilic lubricant and a hydrophilic lubricant can be used in combination, and generally known ones can be applied.

  Examples of lipophilic lubricants include silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, and silicone gel (so-called gum silicone) (specific examples include KF96, KF50, KE72BS manufactured by Shin-Etsu Chemical Co., Ltd., GE Toshiba). Silicone TSF451, TSF456, TSF3051, etc.), preferably applying dimethyl silicone oil.

  In the hydrophilic lubricant, for example, polyether-modified polydimethylsiloxane (specific examples include TSF4440, TSF4441 and TSF4452 from Momentive Performance Materials) can be used. The polyether chain is composed of ethylene oxide and polypropylene oxide, and polyethylene oxide is highly hydrophilic (high polarity), and thus exhibits water-soluble characteristics. Therefore, in a hydrophilic lubricant, it can be said that the more polyethylene oxide and the lower the molecular weight (lower viscosity), the stronger the water solubility.

  The lipophilic lubricant applied to this embodiment has the purpose of compatibilizing the thermoplastic elastomer as a binder to maintain a low friction state in a dry environment for a long time, and is a high viscosity type (high molecular weight and bleed speed) It is preferable to apply a lipophilic lubricant capable of suppressing On the other hand, in the hydrophilic lubricant applied to this embodiment, it is dissolved in the surface water on the surface of the covering in the wet environment and interposed between the object to be slid (glass member or the like). The purpose is to keep the low friction state for a long time, and it is preferable to apply a material having a relatively low viscosity (low molecular weight).

  Therefore, by setting the viscosity of the hydrophilic lubricant to be smaller than the viscosity of the lipophilic lubricant, and making the difference between the viscosity of the lipophilic lubricant and the viscosity of the hydrophilic lubricant, Can be easily placed around the lipophilic graphite, and a low friction state in a dry environment or the like can be expressed. On the other hand, a hydrophilic lubricant is dissolved in the surface water of the coated body to be slid ( Between the glass member and the like, and a low friction state in the wet environment can be exhibited.

[Thermal expansion microcapsule]
The thermoplastic elastomer as the base material may be blended with thermally expandable microcapsules (hereinafter, thermally expanded capsules). In this thermal expansion capsule, what can be expanded in the extrusion process, for example, a liquid that can generate gas by heating (heat of the extrusion process) (volatile expansion agent; for example, low boiling point hydrocarbon, chlorination) (Hydrocarbon) filled in a thermoplastic resin shell wall (for example, spherical shell wall) (thermally expandable thermoplastic resin particles), true specific gravity 0.1 or less, particle size (median diameter) 1 μm to 70 μm, and the liquid expands by heating (for example, heating at the extrusion temperature) at a temperature higher than the expansion start temperature (for example, 150 ° C. to 250 ° C.) to form a thermal expansion cell in the target substrate. Liquid encapsulated thermoplastic resin particles.

  The thermal expansion cell is formed in a size corresponding to the target substrate. For example, in the case of a weather strip product substrate for automobiles, the thermal expansion cell has an average cell diameter of 30 μm to 200 μm. An expansion cell may be mentioned. Moreover, 150 degreeC-250 degreeC is mentioned as a preferable range in the highest expansion | swelling temperature of a thermal expansion capsule, More preferably, 180 degreeC-230 degreeC is mentioned.

  As the component of the thermoplastic resin constituting the shell wall of the thermally expandable capsule, preferably, a (meth) acrylonitrile polymer and a polymer containing a large amount of (meth) acrylonitrile are mentioned, and monomers for these polymers (so-called Examples of the other monomer (comonomer) include vinyl halides, vinylidene halides, styrene monomers, (meth) acrylate monomers, vinyl acetate, butadiene, vinyl pyridine, chloroprene, and other monomers.

  The shell wall of the thermally expandable capsule is preferably uncrosslinked, but may be crosslinked with a general crosslinking agent such as divinylbenzene or ethylene glycol di (meth) acrylate. Moreover, it is preferable that the softening temperature of a shell wall is 250 degrees C or less, for example.

  Examples of the liquid (volatile expansion agent) filled in the thermally expanded capsule include hydrocarbons such as n-pentane, isopentane, neopentane, butane, isobutane, hexane, petroleum ether, methyl chloride, dichloroethylene, and trichloroethane. And chlorinated hydrocarbons such as trichloroethylene.

  As a further specific example of the thermal expansion capsule, it is possible to apply a fine cellular MS series (MS420, MS430, MS440, MS450, etc.) manufactured by Dainichi Seika Kogyo Co., Ltd., and Matsumoto Microsphere F100 manufactured by Matsumoto Yushi Co., Ltd. And EXPANCEL 930-120 manufactured by EXPANSEL, Sweden.

  The blending amount of the thermally expanded capsule can be appropriately set in consideration of, for example, the specific gravity of the target substrate. When such a thermally expanded capsule is added to a polymer component such as EPDM, in order to prevent scattering of the thermally expanded capsule and to improve dispersibility, other materials (for example, polymer elastic body, heat Any one or a plurality of plastic resins, softeners, inorganic fillers, etc. may be used after mixing. As specific examples, oil content products, pellet products previously contained in EVA, PE, and the like are commercially available.

  When the thermal expansion capsule is used after being mixed with other materials in advance, for example, the mixing ratio of the thermal expansion capsule is adjusted to about 10 wt% to 99 wt% (preferably 10 wt% to 50 wt%). . Moreover, any one kind of the above-mentioned thermal expansion capsules may be used, or a plurality of kinds may be used in combination. Furthermore, you may use in combination with the below-mentioned non-expandable capsule (for example, the type which does not include a volatile swelling agent) etc.

[Others]
In addition to the various components shown above, carbon black, processing aids, liquid polymers (liquid rubbers), antioxidants, anti-aging agents, dehydrating agents, heat stabilizers, light stabilizers are also included in the coating materials and substrate materials. , UV absorber, slidable powder (eg PMMA, fluororesin (Teflon (registered trademark) etc.) powder, acrylic powder, silicone rubber powder, silicone resin powder, polycarbonate powder, ultra high molecular weight polyethylene powder, etc. ), Anti-clouding agent, anti-blocking agent, slip agent, dispersant, flame retardant, antistatic agent, conductivity-imparting agent, tackifier, crosslinking aid, colorant (such as titanium oxide), metal powder (such as ferrite) , Glass fiber, carbon fiber, organic fiber (aramid fiber, etc.), composite fiber, glass balloon, glass flake, graphite, carbon nano Tubes, fullerenes, black powders, various rubbers, organic foaming agents, thermally expandable capsules, waxes, recycled rubbers, etc., any one or a combination of several types, and the characteristics of the target coating or substrate If it is a grade which does not impair large, it can use suitably.

[Weather Strip]
The covering material and the base material of the present embodiment can be applied to a weather strip such as an automotive glass run, and a specific example is a glass run as shown in FIG. The glass run in FIG. 1 includes a long support portion 1 having a substantially U-shaped cross section, and a plurality of (four in the figure) lip-shaped elastic contact portions 2 protruding from the inner wall of the support portion 1. The substrate 10 is configured. Reference numeral 3 denotes a locking claw portion protruding from the outer wall of the support portion 1, and is for preventing the base body 10 assembled to the vehicle body panel 4 from coming off the vehicle body panel 4. At least the contact surface side with the glass 5 in the elastic contact portion 2 and the bottom side inner wall (portion requiring sliding property) of the support portion 1 are formed by a covering 6. As described above, according to the multilayer structure in which the covering body 6 is formed on the base body 10, the elastic contact portion 2 (covering body 6) has elasticity with respect to the glass 5, and is slidably elastically held, so that the glass sealing property is maintained. Is done.

  Next, it is a sample created based on this embodiment, and as shown in Table 1, various covering materials S1 to S10 (Examples) and P1 to P9 (Comparative Examples) in which each lubricant is blended are used. , And multilayer extrusions GS1 to GS10 (Examples) and GP1 to GP9 (Comparative Examples) by co-extrusion molding with the base material K, and the surface roughness, dynamic friction coefficient, Abnormal noise, durability, and comprehensive evaluation were examined, and the results are shown in Table 2 below.

<Coating materials S1 to S10, P1 to P9>
First, 100 phr of ethylene / propylene / diene copolymer (Nodel IP 4760P manufactured by Dow Chemical Co.), which is one of EPDMs, is 200 phr of polypropylene resin (E-200GP manufactured by Prime Polymer Co., Ltd.) as an olefin resin material. 50 phr of paraffinic oil (P300, manufactured by JOMO) as an agent, 7 phr of an alkylphenol resin compound (Tacchiol 201, manufactured by Taoka Chemical Co., Ltd.) as a crosslinking agent, and a halogen-based crosslinking catalyst (stannous chloride, manufactured by Nippon Chemical Industry Co., Ltd.) as a crosslinking aid ) 1 phr, 1 phr of antioxidant (Irganox 1010 manufactured by Ciba Specialty Chemical Co., Ltd.) and 1 phr of zinc oxide (Zinc Oxide manufactured by Mitsui Mining & Smelting Co., Ltd.) are added to the Labo Plast Mill B600 (sealed Banbury type kneader) manufactured by Toyo Seiki Co., Ltd. I put it all together. Then, each of the materials charged in a lump (hereinafter referred to as “material before crosslinking”) was kneaded under conditions of a chamber temperature of 200 ° C. and a rotor rotation speed of 100 rpm to perform dynamic crosslinking, and the temperature of the kneaded product reached 220 ° C. At that time, the kneaded product was taken out.

  Next, in the kneaded product taken out, as a lubricant, an arbitrary amount of solid lubricant graphite (J-CPS made by Nippon Graphite), liquid lubricant and oleophilic dimethyl silicone (KF96 made by Shin-Etsu Chemical Co., Ltd., viscosity 1000 cps) , Or KF96—viscosity 100 cps), liquid lubricant and hydrophilic lubricant polyether modified silicone (Momentive Performance Materials TSF4452 viscosity 1000 cps, or TSF4441 viscosity 160 cps) any amount are shown in Table 1, respectively. After blending in such a manner (each weighed and blended), it was put into the Laboplast Mill B600 and kneaded under the conditions of a chamber temperature of 200 ° C. and a rotor rotation speed of 100 rpm, and the temperature of the kneaded product reached 200 ° C. At that time, the kneaded product is taken out, and various coating material S1 S9, to obtain a P1~P9.

  The materials before solidification, the solid lubricant, and the liquid lubricant are all added to the Laboplast Mill B600, kneaded under the conditions of a chamber temperature of 200 ° C. and a rotor rotation speed of 100 rpm, and dynamically crosslinked. When the temperature reached 220 ° C., the kneaded product was taken out and applied as the covering material S10.

<Substrate material K>
First, 100 phr of ethylene / propylene / diene copolymer (Nodel IP 4760P manufactured by Dow Chemical Co.), which is one of EPDM, is 83 phr of polypropylene resin (E-200GP manufactured by Prime Polymer Co., Ltd.) as an olefin resin material. 117 phr of paraffinic oil (P300, manufactured by JOMO) as the agent, 7 phr of alkylphenol resin compound (Tacchiol 201, manufactured by Taoka Chemical Co., Ltd.) as the crosslinking agent, and halogen-based crosslinking catalyst (stannous chloride, manufactured by Nippon Chemical Industry Co., Ltd.) as the crosslinking aid 1 phr, 1 phr of antioxidant (Irganox 1010 manufactured by Ciba Specialty Chemical Co.), 1 phr of zinc oxide (zinc oxide manufactured by Mitsui Kinzoku Mining Co., Ltd.), 23 phr of carbon black (Asahi # 60H manufactured by Asahi Carbon Co., Ltd.) B600 And the mixture is kneaded under the conditions of a chamber temperature of 200 ° C. and a rotor rotation speed of 100 rpm to perform dynamic crosslinking. When the temperature of the kneaded product reaches 220 ° C., the kneaded product is taken out to obtain a base material K. It was.

<Molded bodies GS1 to GS10, GP1 to GP9>
The molding machine includes a die for extruding the base material K (hereinafter referred to as a base extruder) and molding for extruding one selected from the covering materials S1 to S10 and P1 to P9 shown in Table 1. A coextrusion molding machine in which the head outlet of a machine (hereinafter referred to as a coated body extruder) was connected with a heat-resistant tube was applied. Then, one of the covering materials S1 to S10 and P1 to P9, which is appropriately selected, is co-extruded together with the base material K, so that a cross section is formed on the one end side surface of the plate-like base having a cross section of 2 mm × 30 mm. Formed a multilayer structure G (GS1 to GS10, GP1 to GP9) in which a 0.04 mm × 30 mm covering was formed.

  In addition, in the base material K that is co-extruded with the covering materials S8, S9, P8, and P9, before the co-extrusion molding, a thermal expansion capsule (Fine Cellular MS405 manufactured by Dainichi Seika Co., Ltd.) or silicone resin beads (Charlene R170 manufactured by Nissin Chemical Industry Co., Ltd.) was arbitrarily blended and dry blended as shown in Table 1 above. In the coextrusion molding, the temperature at the front stage of the cylinder of the substrate extruder is set to 180 ° C., the temperature at the middle stage of the cylinder is set to 190 ° C., the temperature at the rear stage of the cylinder is set to 200 ° C., and the head temperature is set to 200 ° C. The temperature was set to 180 ° C., the temperature in the middle stage of the cylinder was 200 ° C., the temperature in the rear stage of the cylinder was 210 ° C., and the temperature of the head was 220 ° C.

<Surface roughness, dynamic friction coefficient, abnormal noise, durability>
First, as shown in FIG. 2, in the molded bodies GS1 to GS10 and GP1 to GP9, strips ((7.0 mm ± 0.5 mm) × (120 mm ± 0.5 mm) × (0.7 mm ± 0.5 mm)), respectively. Each test piece 20 is made by punching into a rectangular strip shape, and the surface of the coated body of the test piece 20 is wiped with alcohol, and then a surface roughness meter (Surfcoder SE30D manufactured by Kosaka Laboratories) is used. The surface roughness (ten-point average roughness; Rz (μm)) of the surface of the coated body was measured by a ten-point average method (method based on JIS-B0601). In addition, the stylus tip radius of 2 μm was used as the stylus of the surface roughness meter.

  Next, the test piece 20 is fixed on the support base (test base) 21 (the base is fixed so that the covering body is positioned on the lower side in the drawing) and the end portion of the glass member 22 (according to JIS R 3211). The end part 22a having an R10 spherical surface corresponding to an automobile window glass) 22a was pressure-contacted (pressure-contacted to the covering) with a load of 29.4N. In this state, muddy water (mixed liquid of dust: water = 1: 3) is dropped on the surface of the test piece 20 (surface on which the glass member 22 slides) to simulate a wet environment, and the glass member 22 is Repeated sliding (stroke: 100 ± 0.5 mm, cycle: 60 times / minute, temperature atmosphere: normal temperature) in the horizontal direction (longitudinal direction of the test piece 20; the direction of the indicated arrow 23), the sliding is predetermined. The dynamic friction coefficient Fw (μd) in the wet environment of the covering of the test piece 20 was observed by the method shown in FIG. 3 to be described later every time the number of times reached (the first sliding, the 10,000th sliding, the 20000th sliding).

  In addition, the occurrence of abnormal noise was observed every time the sliding reached a predetermined number of times. Further, the durability was examined by measuring the number of sliding times of the glass member 22 when the wear of the covering of the test piece 20 by the sliding reached 400 μm.

  In the method shown in FIG. 2, muddy water is not dripped, that is, the dry environment is simulated, and the dynamic friction coefficient Fd (μd) in the dry environment of the covering of the test piece 20 is determined by the method shown in FIG. Observed. Then, a difference between the dynamic friction coefficients Fw and Fd (that is, Fw−Fd; hereinafter referred to as difference w / d) was calculated.

  FIG. 3 is a view for explaining the method for observing the dynamic friction coefficient. In the method shown in FIG. 3, first, the dirt on the surface of the test piece 20 is wiped off with alcohol, and then placed on a support base (test stand) 31 of a friction coefficient measuring machine (HEIDON-14D manufactured by Shinto Kagaku). (The substrate is placed so that the base is located in the lower part of the figure and the covering is located in the upper part of the figure). Thereafter, the weight member 32 which is composed of R50 spherical glass and applied with a load of 0.98 N is placed on the covering of the test piece 20 (the R50 spherical side is placed), and the weight member 32 is horizontally placed. The dynamic friction coefficient (Fw, Fd) is measured by sliding at a speed of 1000 mm / min (sliding while contacting the coating of the test piece 20) with respect to the direction (longitudinal direction of the test piece 20; the arrow direction in the figure). Then, the difference w / d is calculated.

<Comprehensive evaluation>
The surface roughness, dynamic friction coefficient, noise, and durability verification results shown above were compared and judged comprehensively. In addition, in the column of “Comprehensive evaluation” in Table 2 to be described later, the symbol “◎” indicates that a favorable result was obtained assuming that it is applied to a sliding product having a multilayer structure such as an automobile glass run or weather strip. The symbol “x” indicates an unacceptable result, the symbol “○” indicates a good result (inferior to “◎”, but better than “x”), “Δ” is a case where a sufficient result is obtained (when it is inferior to “◯” but at least better than “×” and may be sufficiently applicable as a sliding product).

<Molded bodies GP1 to GP9>
As shown in the results of Table 2, in the compacts GP1 to GP9, the overall evaluation resulted in x. First, the molded products GP1 and GP3 using the covering materials P1 and P3 in which the blending amount of the solid lubricant or the liquid lubricant is too small have relatively large dynamic friction coefficients Fw and Fd and a difference w / d from the beginning of sliding. Abnormal noise was generated and durability was low.

  The molded product GP2 using the coating material P2 having too much solid lubricant had extremely poor durability although the dynamic friction coefficients Fw and Fd and the difference w / d at the initial stage of sliding were smaller than the molded products GP1 and GP3.

  The molded product GP4 using the coating material P4 having too much liquid lubricant has poor processability and cannot form a desired molded product, and various observations cannot be performed.

  The molded products GP5 and GP6 using the covering materials P5 and P6 in which the lipophilic hydrophilic ratio of the liquid lubricant is out of the range of 50/50 to 90/10 have durability, but as the number of sliding increases. As a result, the difference w / d increased and an abnormal noise was generated.

  The molded product GP7 using the covering material P7 in which the viscosity of the hydrophilic lubricant of the liquid lubricant is larger than the viscosity of the oleophilic lubricant has a relatively large difference w / d from the beginning of sliding, and noise is generated. The durability was also low.

  In the molded body GP8 in which the thermal expansion capsule is blended in the base material K and the surface roughness of the coating body is too large, the dynamic friction coefficients Fw and Fd and the difference w / d increase as the number of sliding increases. Sound was generated and durability was low.

  The molded product GP9 in which the silicone resin beads were blended in the base material K already had a relatively large dynamic friction coefficient Fw and a difference w / d from the beginning of sliding, and the durability was extremely poor.

<Molded bodies GS1 to GS10>
On the other hand, a molded body using a covering material in which the blending amount of the solid lubricant and the liquid lubricant and the lipophilic hydrophilic ratio are within the range of this embodiment, respectively, and the viscosity of the hydrophilic lubricant is smaller than the viscosity of the lipophilic lubricant. GS1 to GS10 are smaller in dynamic friction coefficients Fw and Fd and difference w / d from the initial stage of sliding than the molded bodies GP1 to GP9, respectively, and hardly change even when the number of sliding times increases, and noise is generated. There was also no.

  In addition, the molded bodies GS1 to GS6 and GS8 were extremely excellent in durability, and excellent results of ま た は or ◯ were obtained in the comprehensive evaluation. In the compacts GS7, GS9, and GS10, a coating material S7 with a large amount of liquid lubricant, a coating material S9 with a large surface roughness, and a coating material S10 with a lubricant blended before crosslinking are used. Although the durability was lower than that of the molded bodies GS1 to GS6 and GS8, the durability was substantially the same as that of the molded bodies GP5 and GP6, and the overall evaluation was a sufficiently good result of Δ.

  Although the present invention has been described in detail only for the specific examples described above, it is obvious to those skilled in the art that various changes and modifications are possible within the scope of the technical idea of the present invention. Such variations and modifications are naturally within the scope of the claims.

  For example, in the examples, the comparative examples were described using specific examples of the covering materials S1 to S10, the molded bodies GS1 to GS10, etc., but the automotive parts field (sliding product field such as weather strips and glass runs), extrusion Based on the common general technical knowledge of various fields such as processing fields, the amount and type of rubber components, olefin resin materials, lubricants, thermal expansion capsules, crosslinking agents, and other various materials in base materials and coating materials are appropriately selected. Even if it changes, it is thought that the same operation effect as an example can be obtained.

DESCRIPTION OF SYMBOLS 1 ... Support part 2 ... Press-contact part 3 ... Locking claw part 4 ... Body panel 5 ... Glass member 6 ... Sliding composition 10 ... Base | substrate

Claims (4)

A covering material formed on the surface of a substrate by extrusion molding,
It consists of a thermoplastic elastomer for coatings containing at least a rubber component, an olefin resin material, a crosslinking agent, and a lubricant.
The lubricant includes 5 to 50 wt% of a solid lubricant composed of graphite, and 3 to 15 wt% of a liquid lubricant composed of a lipophilic lubricant and a hydrophilic lubricant,
The ratio of lipophilic lubricant / hydrophilic lubricant, which is the ratio of the lipophilic lubricant to the hydrophilic lubricant of the liquid lubricant, is in the range of 50/50 to 90/10, and the viscosity of the hydrophilic lubricant is A covering material characterized by being smaller than the viscosity of a lipophilic lubricant.   The said base | substrate consists of the thermoplastic elastomer for base | substrates which mix | blended at least the rubber component, the olefin resin material, the crosslinking agent, and the heat | fever expansible microcapsule, and the surface roughness is 50 micrometers or less. Cover material.   The thermoplastic elastomer for a coated body is characterized in that, after blending and kneading and cross-linking other components excluding a lubricant among the components blended in the thermoplastic elastomer for a coated body, the lubricant is blended. The covering material according to claim 1 or 2. A weather strip in which a covering is formed on the surface of the substrate by extrusion molding, and the covering is pressed against the object to be slid,
A weather strip, wherein the covering is made of the covering material according to any one of claims 1 to 3, and the object to be slid is a glass member.

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