JP5290653B2 - Sliding composition and sliding product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To secure a low bending elastic modulus (flexibility) and sliding durability in addition to sliding properties to a glass member in a sliding composition used for a pressure contact part of a sliding product such as a glass run and a weather strip for improving various characteristics (glass seal characteristics and the like) of the sliding product. <P>SOLUTION: The sliding composition is produced by crystallizing a composite material, which is prepared by mixing 5-30 wt.% (10-30 wt.% preferably) of carbon black, 10-30 wt.% of an inorganic filler, and 5-20 wt.% of a silicone compound to an olefine resin material consisting of at least a crystalline olefine resin. For example, the sliding composition is formed on the contact face side with at least glass 5 in a pressure contact part 2 of the sliding product 10. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a slidable composition comprising a composite material containing a polymer component such as a resin and having slidability with respect to a glass member, and for example, an automobile using the slidable composition. It relates to sliding products such as glass run and weather strip.

  A slidable composition made of a composite material containing a polymer component such as a resin and having slidability with respect to a glass member is used for, for example, a pressure contact portion (a lip portion) in a sliding product such as a glass run of an automobile or a weather strip As the polymer material, rubber components such as ethylene-propylene-diene copolymer (hereinafter referred to as EPDM), olefin resin, and the like can be given.

The sliding product is made of, for example, a thermoplastic elastomer composition or the like, and is attached to an application target (a door panel or the like in the case of a glass run) and a glass member (window glass or the like) provided on the base. And a pressure contact portion that has pressure (elasticity) and retains the glass sealing property, and the slidable composition is applied to the contact surface of the pressure contact portion (for example, heat (Applied in a structure in which a plastic elastomer composition and a slidable composition are laminated). Further, a weather strip is known in which a rough surface portion including small convex portions (convex portions due to solid particles in the slidable composition) is formed on the surface of the slidable composition (surface on the sliding side). ing. According to such a sliding product, it is said that it has sufficient slidability with respect to the window glass of an automobile, and the increase in sliding resistance can be suppressed and elasticity can be obtained (for example, Patent Document 1). ).
JP 2004-48007 A (see, for example, paragraphs [0007], [0008], [0036], etc.).

  However, in the slidable composition applied to general sliding products, those having slidability have high flexural modulus (for example, extremely high flexural modulus compared to a base such as a general glass run). When applied to the pressure contact portion, the flexibility is greatly impaired because the pressure elastic modulus of the pressure contact portion is high. As described above, when the bending elastic modulus of the sliding composition is very high compared to the bending elastic modulus of the press contact portion (when the flexibility is low), for example, when a sliding product is assembled, the three-dimensional of the car panel Since it cannot follow a proper structure, it is easy to cause a waving phenomenon in the pressure contact portion, and as a result, there is a possibility that various characteristics (such as glass sealability) of the sliding product may be impaired. This is because the flexibility of the base material in the pressure contact portion is deprived by the laminated slidable composition and cannot follow.

  Further, since the small convex portion formed as described above has low sliding durability (wear resistance), a thick slidable composition is formed on the press contact portion in order to maintain the sliding property for a long period of time. There is a need. In this case, as the slidable composition itself becomes thicker, the flexural modulus further increases, so that various characteristics of the slidable product are further deteriorated.

  Therefore, in the slidable composition, not only the slidability to the glass member as described above is provided, but also a low bending elastic modulus (flexibility) and sliding durability are ensured, and various sliding products are provided. It is required to improve characteristics (glass sealability and the like).

The present invention has been made on the basis of the above problems, and the invention according to claim 1 is a polyolefin resin material containing at least a crystalline polyolefin resin, carbon black of 5 wt% to 30 wt%, at least silica or / and / or. A composition formed by molding a composite material containing 10 wt% to 30 wt% of an inorganic filler containing a binding compound of silica and a layered crystalline filler, and 5 wt% to 20 wt% of a silicone compound, It is characterized in that it has elasticity with respect to a member and imparts glass sealing properties.

  According to a second aspect of the present invention, in the first aspect of the invention, the polyolefin-based resin material includes an amorphous polyolefin resin.

  According to a third aspect of the present invention, in the first or second aspect of the present invention, the inorganic filler includes a layered crystalline filler.

According to a fourth aspect of the present invention, in the first to third aspects of the invention, the silica is 10 wt% or more.

According to a fifth aspect of the present invention, in the first to fourth aspects of the invention, the carbon black has an average particle size of 40 nm or more.

According to a sixth aspect of the present invention, there is provided a sliding product made of a thermoplastic elastomer composition, comprising: a base part assembled to a vehicle body panel; and a pressure contact part provided on the base part and elastically pressed against a glass member. And the slidable composition in any one of Claims 1-5 was formed in the surface which contact | connects at least a glass member among the said press-contact parts.

The invention according to claim 7 is the invention according to claim 6 , wherein the slidable composition has a flexural modulus of 350 MPa or less.

The invention according to claim 8 is the invention according to claim 6 or 7 , wherein the slidable composition has a hardness (D) according to JIS K 6253 within a range of 40-60. To do.

The composite material in which a relatively large amount of carbon black is blended with the polyolefin resin material as in the inventions of claims 1 to 8 is crystallized according to the blending amount of the carbon black (crystal of the olefin resin material). ) Is suppressed. When crystallization is suppressed in this way, mechanical strength is suppressed and bending elastic modulus is reduced (softened) as compared with the case where carbon black is blended according to the standard of the sliding product field. Silica in the inorganic filler has a structure covered with silanol groups, so it retains the silicone oil component and contributes to improving sliding durability, and also promotes crystallization of polyolefin resin materials. It is what has.

According to invention of Claims 1-8 , it becomes a slidable composition in which the area | region where the crystallization by carbon black was inhibited and the area | region where the crystallization by the silica was accelerated | stimulated coexisted. Thereby, low bending elastic modulus (flexibility) and sliding durability can be ensured together with sliding properties, and various properties (such as glass sealing properties) can be imparted as sliding products.

  This embodiment is a slidability formed by crystallizing a composite material containing at least an olefin resin material composed of a crystalline olefin resin, carbon black, an inorganic filler composed of at least silica, and a silicone compound. It relates to a composition. The carbon black in the composite material has a relatively large blending amount according to the standard in the sliding product field. More specifically, carbon black 5 wt% to 30 wt% (preferably 10 wt% to 30 wt%), inorganic filler 10 wt% to 30 wt%, and silicone compound 5 wt% to 20 wt% are added to the olefin resin material. It is a blend.

  Thus, when a composite material intentionally compounded with a relatively large amount of carbon black and silica is crystallized (crystallization of an olefin-based resin material), the composite material is inhibited from crystallization by carbon black. The crystallization is promoted by silica. The slidable composition thus obtained has slidability and a low flexural modulus (flexibility). In addition, the sliding durability is sufficiently good, and when applied to sliding products such as glass run and weatherstrip, the glass sealing property by the pressure contact part such as the lip part is good.

  In the slidable composition of the present embodiment, a composite material obtained by appropriately blending the following olefin resin material, carbon black, inorganic filler, silicone compound, etc. is used, and the composite material is used. It is obtained by kneading and crystallizing into a desired shape.

[Olefin resin materials]
Examples of the crystalline olefin resin contained in the olefin resin material include generally known ethylene homopolymers, propylene homopolymers, and crystalline copolymers mainly composed of ethylene, propylene, and the like. What is currently available (commercially available products etc.) 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 set the workability and elasticity of the slidable composition as compared with the case where only the crystalline olefin resin is included. Examples of the amorphous olefin resin include α-olefin homopolymers 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 is a copolymer of atactic polypropylene (propylene content of 50 mol% or more) and ethylene, or a copolymer of propylene and 1-butene.

  A preferable blending amount of the olefin-based resin material as described above includes, for example, a range of about 30 wt% to about 70 wt% (preferably 40 wt% to 60 wt%). As long as the characteristics are not significantly impaired, they can be used as appropriate.

[Carbon black]
As carbon black, generally known ones (commercially available products) can be appropriately applied, and examples thereof include those produced by an oil furnace method. Further, preferably, those having an average particle size of about 40 nm or more (41 nm in the examples described later) are used, or the blending amount with respect to the olefin-based resin material is about 5 wt% to about 30% (more preferably about 10 wt% to About 30 wt%), but can be appropriately modified and used as long as the properties of the intended slidable composition are not significantly impaired. In addition, when the average particle diameter is too small (for example, smaller than the average particle diameter of about 26 nm) or when the blending amount is too small (for example, when the blending amount is less than 5 wt%), crystals of the olefin resin material are used. Since the inhibitory action is weakened and the flexural modulus is increased, the flexibility is deteriorated. In addition, when the blending amount is too large (for example, when the blending amount is 35 wt% or more), not only the dispersibility in the composite material deteriorates (dispersion failure) but also the crystallization inhibitory action is too strong and fragile. Therefore, the various properties (sliding durability, etc.) of the slidable composition may be affected.

[Inorganic filler]
As the inorganic filler, at least one containing silica that functions as a nucleating agent that contributes to crystallization of the olefin resin material is used.

  For silica, generally known ones (commercially available products) can be applied as appropriate, for example, wet silica (for example, Tokuyama manufactured by Tokuyama), spherical silica (for example, Excelica manufactured by Tokuyama), Examples thereof include porous silica (for example, Sunfair manufactured by Asahi Glass Co., Ltd., God Ball manufactured by Suzuki Oil & Fat Co., Ltd., Microid manufactured by Tokai Chemical Industry Co., Ltd.), and the like.

  Since silica has an outer surface and an inner surface covered with silanol groups (Si—OH), a silicone compound or the like is easily held inside. For this reason, for example, a so-called “spotting phenomenon” (spotting generated at the die edge of the extrusion molding machine) during extrusion is suppressed, and sliding durability is enhanced.

  A preferable blending amount of silica with respect to the olefin-based resin material includes a range of about 10 wt% to about 30 wt%, and can be appropriately used as long as the characteristics of the target slidable composition are not significantly impaired. . For example, if the amount of silica is too large, the above-mentioned phenomenon (white-based phenomenon) is likely to occur and the appearance of the sliding product may be deteriorated, and the flexural modulus may be increased and the flexibility may be deteriorated. There is. Moreover, when there is too little said compounding quantity, it will become difficult to hold | maintain a silicone compound, and the above-mentioned phenomenon (liquid liquid etc.) will also occur easily.

  As a preferable particle diameter of silica, in addition to the function as a nucleating agent that contributes to crystallization as described above, the range of about 1 μm to about 100 μm can be mentioned in consideration of handleability. Any composition can be used as long as it does not significantly impair the properties of the composition.

  Moreover, the inorganic filler which combined suitably the plate-like and scale-like layered crystalline fillers, such as a kaolin, a talc, a mica, and a smectite, with silica may be sufficient. In this case, since the layered crystalline filler forms a fine rough surface on the surface of the slidable composition, the contact area between the pressed portion and the object to be slid (glass, etc.) is reduced, and sliding durability May improve. Further, since the appearance is matte black, there is an effect that the creases become inconspicuous.

  When silica is contained in the inorganic filler in the range of about 10 wt% to about 30 wt%, the preferred compounding amount of the layered crystalline filler includes a range of about 0 wt% to about 20 wt%. As long as it does not significantly impair the properties of the slidable composition. For example, when the amount of the layered crystalline filler is too large, the above-mentioned phenomenon is likely to occur, and the surface of the sliding product becomes rough and fragile, so that the sliding durability may be lowered. .

  Further, from a binding compound of silica and a layered crystalline filler, for example, a binding compound of spherical silica and plate-like kaolin (for example, Siritine manufactured by HOFFMAN MINALAL; silica 68 wt% to 84 wt%, kaolin 15 wt% to 25 wt%) The inorganic filler has the effect of retaining the silicone compound in the slidable composition with silica, and has the effect of reducing the contact area with an appropriate surface roughness, ensuring long-term sliding durability. The The compounding amount of the binding compound with respect to the olefin-based resin material includes a range of about 10 wt% to about 30 wt%, and can be appropriately used as long as the characteristics of the target slidable composition are not significantly impaired. . For example, if the blending amount is too large, the above-mentioned phenomenon (white-based phenomenon) is likely to occur, and the appearance of the sliding product is deteriorated, and the flexural modulus is increased and the flexibility may be deteriorated. There is. Moreover, when there is too little said compounding quantity, it will become difficult to hold | maintain a silicone compound, and the above-mentioned phenomenon (liquid liquid etc.) will also occur easily.

[Silicone compound]
As the silicone compound, generally known ones (commercially available products) can be appropriately applied. For example, silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, silicone gel (so-called gum silicone), and the like can be used. (As specific examples, KF96, KF50, KE72BS manufactured by Shin-Etsu Chemical Co., Ltd., TSF451, TSF456, TSF3051 manufactured by GE Toshiba Silicone, etc.), any one type or a combination of a plurality of types may be used. good. Preferably, the viscosity is about 100 cps to 100000 cps, or the blending amount with respect to the olefin resin material is about 5 wt% to about 20 wt%. If it is a grade which does not impair, it can change suitably and can be used. In addition, when there are too few compounding quantities of a silicone compound, sliding durability will become low. Further, when the blending amount is too large, the above-mentioned phenomenon (liquid liquid, etc.) is likely to occur, and this may adhere to the sliding product surface and deteriorate the appearance.

[Others]
In addition to the various components shown above, liquid polymers (liquid rubber), antioxidants, anti-aging agents, dehydrating agents, heat stabilizers, light stabilizers, UV absorbers, slidable powders (eg, PMMA, fluorine) Resin (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 retardants, antistatic agents, conductivity-imparting agents, tackifiers, crosslinking aids, colorants (such as titanium oxide), metal powders (such as ferrite), glass fibers, carbon fibers, organic fibers (such as aramid fibers), Composite fiber, glass balloon, glass flake, graphite, carbon nanotube, fullerene, black powder, various rubbers, organic foaming agent, thermal expansion Capsule, waxes, regenerated rubber, and the like, combining those of any one or more types, can be used as appropriate as long as that does not significantly impair the properties of the sliding product of interest.

[Production method]
In the slidable composition of the present embodiment, an olefin resin material, carbon black, an inorganic filler, a silicone compound, etc. are blended and kneaded to obtain a composite material, which is molded into a desired shape and slidable product As long as the method is obtained, a technique used in the field of sliding products (a technique using a kneader, a twin screw extruder, or the like) can be applied as appropriate. Various mixers can be applied to the kneading relating to the composite material, for example, a batch type mixer such as a lab plast mill, a twin-screw extrusion type molding machine (for example, one that can be extruded while kneading), etc. Can be mentioned.

  By these manufacturing methods, sliding products such as automotive glass runs, weather strips, etc., comprising a pressure contact portion formed by extruding the slidable composition and a base portion formed by crosslinking a thermoplastic elastomer composition are obtained. be able to.

[Sliding products]
The slidable composition of the present embodiment can be appropriately applied to a sliding product having a pressure contact portion such as an automotive glass run or weather strip, for example, as shown in the schematic diagram of FIG. An example of the glass run 10 is a cross-sectional shape. In FIG. 1, a long base portion 1 having a substantially U-shaped cross section and a plurality of (four in the figure) lip-shaped press contact portions 2 protruding from the inner wall of the base portion 1 are provided. Yes. Reference numeral 3 denotes a locking claw protruding from the outer wall of the base 1, and is for preventing the glass run 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 pressure contact portion 2 is formed of the slidable composition 6. According to such a structure, the press-contact part 2 (slidable composition 6) has elasticity with respect to the glass 5, and is slidably press-contacted, and glass sealing property is hold | maintained.

  In the slidable composition applied to such a sliding product, for example, the bending elastic modulus is 350 MPa or less and the hardness (hardness (D) according to JIS K 6253) is in the range of 40 to 65. However, it may be set as appropriate as long as the characteristics of the intended sliding product are not significantly impaired.

  Next, various composite materials were obtained based on this embodiment, and the characteristics of each slidable composition comprising the composite materials were examined.

[Verification]
First, a crystalline polypropylene resin (E-200GP manufactured by Prime Polymer Co., Ltd.) as the crystalline polyolefin resin, a propylene / 1-butene copolymer (UBETAC APAO UT2780 manufactured by Ube Industries), carbon black ( Asahi # 50 manufactured by Asahi Carbon Co., Ltd. (average particle diameter 85 nm); hereinafter referred to as carbon A) was blended and kneaded as shown in Table 1 below to obtain various composite materials M1 to M11. Next, using a D20-10 type lab blast mill single screw extruder (Toyo Seiki Seisakusho, 20Φ) (extrusion processing conditions: temperature at the front stage of the cylinder 180 ° C, temperature at the middle stage of the cylinder 190 ° C, temperature at the rear stage of the cylinder 200 ° C, A head temperature of 200 ° C., a die shape of 2 mm × 10 mm, a rotation speed of 50 rpm), and various composite materials M1 to M11 were extruded to produce various slidable progenies S1 to S11. Then, the hardness (D) (JIS K 6253) and the flexural modulus (JIS K 7171) of the slidable compositions S1 to S11 were examined, and the results are shown in Table 2 below.

  As shown in Table 2 above, the slidable compositions S1 to S3 using the composite materials M1 to M3 containing no carbon A are applied to the pressure contact portion of the sliding product (for example, a lip portion of a weather strip). Assuming the case where it is applied, it has been found that even if it has moderate hardness (hardness (D) of about 40 to 60), the flexural modulus becomes too high. On the other hand, in the case of the slidable compositions S4 to S11 using the composite materials M4 to M11 in which a relatively large amount of carbon A is blended, the flexural modulus is kept low as the blending amount of carbon A increases. Sufficiently suitable hardness was obtained. The reason why the flexural modulus decreases as the carbon A content increases is considered to be that the crystallization of the polyolefin resin material is suppressed by the carbon A. Moreover, it has sufficient elasticity and it can read that it is suitable for the press-contact part of a sliding product.

[Example]
First, the crystalline polypropylene resin as the crystalline polyolefin resin, the propylene / 1-butene copolymer as the amorphous polyolefin resin, carbon A as the carbon black, and other two types (Asahi # 60H (Asahi Carbon Co., Ltd.) Average particle size 41 nm), Asahi # 70 (average particle size 26 nm); hereinafter referred to as carbon B and C), silica (nip seal ER manufactured by Nippon Silica Kogyo Co., Ltd.), kaolin (manufactured by Tsuchiya Kaolin) Kaolin), talc (Crown talc PP manufactured by Matsumura Sangyo Co., Ltd.), mica (MK-300 manufactured by Corp Chemical Co.), smectite (Lucentite SWN manufactured by Corp Chemical Co., Ltd.), binding compound of silica and layered crystalline filler (Silicin manufactured by HOFFMAN MINEAL), silicone compound (Shin-Etsu Chemical Co., Ltd.) KF96-1000cs and KE76BS manufactured in a ratio of 1: 1) are used in the composition shown in Table 3 below, and kneaded in a laboratory blast mill (closed mixer 13600 manufactured by Toyo Seiki Seisakusho) Kneading conditions: chamber temperature 200 ° C., rotor rotation speed 100 rpm) and discharging the kneaded product when it reached 215 ° C., thereby obtaining composite materials M12 to M35.

  Also, instead of the polyolefin resin material, thermoplastic elastomer, silicone resin particles (momentive performance materials Japan Tospearl (average particle size 12 μm) 5 wt%, Shin-Etsu Chemical acrylic silicone resin powder X-22-8171 (5 wt%), the carbon A, the silica, and the silicone compound (KF96-1000cs manufactured by Shin-Etsu Chemical Co., Ltd.) were used in the formulations shown in Table 3 below, respectively, and the composite materials M12 to M35 The composite materials M36 and M37 were obtained by kneading by the same manufacturing method.

  In addition to the various materials shown in Table 3 below, each of the slidable compositions M12 to M37 includes, as additives, stearic acid (stearic acid manufactured by Nippon Oil & Fats Co., Ltd.) 1 wt%, calcium oxide (manufactured by Inoue Lime Co., Ltd.). Vesta # 20) 3 wt% and antioxidant (Irganox 1010 manufactured by Ciba Specialty Chemicals) 1 wt%.

  In the thermoplastic elastomer, the crystalline polypropylene resin 60 wt%, EPDM (Nodel IP-4760P manufactured by Dow Chemical Co., Ltd.) 20 wt%, the alkylphenol-based resin (Tactrol manufactured by Taoka Chemical Co., Ltd.) 2 wt%, the cross-linking agent Tin chloride (Nihon Kagaku Sangyo Co., Ltd.) 0.5wt% as an auxiliary agent, zinc oxide (Zinc oxide manufactured by Mitsui Kinzoku Kogyo Co., Ltd.) 1wt%, the above stearic acid 1wt%, the above oxidation An inhibitor 0.5 wt% and process oil (P300 manufactured by JOMO) were used. First, various components other than the cross-linking agent are put in a lab plast mill (closed mixer B600 manufactured by Toyo Seiki Co., Ltd.) and kneaded for 15 minutes (chamber setting temperature 160 ° C., rotor rotation speed 80 rpm), and then the cross-linking agent is put in. Further, the mixture was heated and dynamically crosslinked while kneading (chamber setting temperature 220 ° C., rotor rotation speed 100 rpm). When the crosslinked product reached 230 ° C., it was taken out from the Laboplast Mill.

  Next, using each of the composite materials M12 to M37, the samples S12 to S37 of the slidable composition were produced by extrusion using the same manufacturing method as in the above-described verification. (D), bending elastic modulus (flexibility), sliding durability, sliding property (presence of abnormal noise during sliding) were examined, and the results are shown in Table 4 below.

<Extrudability (existence of “Meani”)>
First, based on the same manufacturing method as the above-described verification, each of the composite materials M1 to M37 is extruded to continuously produce samples S12 to S37 each having a length of 300 mm for 5 hours. The presence or absence was observed. In addition, in the column of extrudability in Table 4 to be described later, the symbol “◎” indicates that “Meani” was not observed at all, and the symbol “◯” indicates that “Meani” was slightly observed but adhered to the molded body. Is not seen, symbol “△” is “Meani”, and when adhesion is observed in the molded product after 2 to 5 hours, symbol “X” is “Meani” and 0-2 hours It is assumed that adhesion was observed in the molded body at the time.

<Hardness>
In accordance with JIS K 6253, the hardness of each sample S12 to S37 was measured with a type D durometer.

<Bending elastic modulus (flexibility)>
Based on JISK7171, the bending elastic modulus of each sample S12-S37 was measured.

<Sliding durability>
First, based on the same manufacturing method as the above-mentioned verification, samples S12 to S37 having a strip shape ((7.0 mm ± 0.5 mm) × (120 mm ± 0.5 mm) × (0.7 mm ± 0.5 mm)) are produced. did. Next, as shown in the schematic diagram of FIG. 2, the sample 20 (samples S12 to S37) is fixed on the support base (test stand) 21 and the end portion of the glass member 22 (automobile window glass conforming to JIS R 3211). The end portion having an R10 spherical surface 22a) 22a was brought into pressure contact with a load of 29.4N. In this state, while dropping muddy water (mixed liquid of dust: water = 1: 3) on the surface of the sample 20 (surface on which the glass member 22 slides), the glass member 22 is placed in the horizontal direction (longitudinal direction of the sample 20; Sliding (stroke: 100 ± 0.5 mm, cycle: 60 times / minute, temperature atmosphere: 25 ° C.) with respect to the direction of the arrow 23 in the figure, and the state of wear of the sample 20 due to the sliding was observed. In this observation, the number of strokes of the glass member 22 was measured when the wear of the sample 20 due to the sliding reached 400 μm.

<Slidability (presence / absence of low-level sound)>
First, each sample S12 to S37 prepared as in the sliding durability test was strip-shaped ((3.0 mm ± 0.5 mm) × (10 mm ± 0.5 mm) × (0.7 mm ± 0.5 mm)). )) To obtain a sample piece. Next, as shown in the schematic views of FIGS. 3A (front view) and B (side view), the sample piece 30 is fixed to a jig 31, and the sample piece 30 is a glass member (automotive window according to JIS R 3211). A member corresponding to glass) 32 is pressed with a load of 9.8 N. In this state, while dropping muddy water (volcanic ash (JIS standard powder, Kanto Loam): water = 1: 3 mixed solution) onto the surface of the glass member 32 on which the surface of the sample piece 30 slides, Sliding (stroke; 100 ± 0.5 mm, cycle: 60 times / min, temperature atmosphere; 25 ° C.) with respect to the horizontal direction (longitudinal direction of the sample piece 30; the direction of the arrow in the figure) The presence or absence of occurrence was observed. In the column of presence / absence of abnormal sound generation in Table 4 to be described later, it is assumed that “present” indicates that no lower sound was generated, and “not present” indicates that a lower sound was not generated.

  From the results of Table 4, the following can be read.

[When thermoplastic elastomer is blended (comparative example)]
Samples S36 and S37, in which a relatively large amount of carbon black is blended with a thermoplastic elastomer, are sufficiently moderate in hardness when applied to the pressure contact portion of a sliding product, and have good flexibility and sliding properties. However, it was confirmed that the sliding durability would be extremely low even if the silicone resin particles, carbon black and the like were blended. Moreover, in sample S37 which mix | blended the silicone resin particle, it can be read that the extrudability is extremely low.

[When blending polyolefin resin materials, etc. (comparative example)]
Of the samples in which a relatively large amount of carbon black is blended with the polyolefin resin material, the sample S35 in which the polyolefin resin material does not contain a crystalline polyolefin resin has low sliding durability and slidability. I was able to confirm that.

  Samples S27 to S34 in which the polyolefin-based resin material includes a crystalline polyolefin resin has a tendency that good sliding durability is obtained as compared with samples S36 and S37. However, from the viewpoint of the sliding product, the samples S27 and S29 having a small amount of the inorganic filler have a low sliding durability, and the samples S28 and S30 having a large amount of the compound have a low sliding property. It could be confirmed. It can also be seen that the flexibility tends to decrease as the amount of the inorganic filler is increased.

  It was confirmed that even when the blending amount of the inorganic filler was an appropriate amount, the samples S31 and S32 in which the blending amount of the silicone compound was too small or not blended had low sliding durability and slidability. In addition, it was confirmed that Sample S33 having an excessive amount of the silicone compound had good flexibility, sliding durability, and sliding property, but had extremely low extrudability.

[When blending polyolefin resin materials, etc. (Example)]
On the other hand, samples S12 to S26 containing 5 wt% to 30 wt% of carbon black, 10 wt% to 30 wt% of inorganic filler, and 5 wt% to 20 wt% of silicone compound have an appropriate hardness in terms of sliding products and are good Extrudability, flexibility, sliding durability, and slidability were obtained.

  In addition, the inorganic filler may be composed only of silica as in samples S12 and S13. For example, the inorganic filler may be composed of silica and other layered crystalline fillers such as samples S14 to S20, or a binding compound. It can be seen that it may be composed. Further, it can be seen that the polyolefin resin material may be simply made of a crystalline polyolefin resin as in the sample S21.

  When attention is paid to the samples S12 to S26, the samples S12 to S24 having a carbon black content of 10 wt% to 30 wt% and an average particle diameter of 40 nm or more give relatively good results. For example, the sample S25 has a carbon black content. The sample S26 is relatively small and slightly inferior, and the average particle size of the carbon black is relatively small, and the flexibility and extrudability are slightly inferior, but these samples S25 and S26 can be sufficiently applied as sliding products. there is a possibility. For example, it can be said that the inferior point can be improved by appropriately setting the conditions during the extrusion process.

  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 samples S12 to S26 and the like have been verified and described. However, based on the common technical knowledge in the field of sliding products such as weather strips and glass runs, polyolefin resin materials, carbon black, inorganic fillers, silicones It is clear that the same effects as in the examples can be obtained even if the blending amount and type of various additives other than the compound are appropriately changed.

Schematic for demonstrating an example of the sliding product which can apply the slidable composition of this embodiment. Schematic for demonstrating the observation method of the sliding durability of a present Example. Schematic for demonstrating the observation method of the slidability of a present Example.

Explanation of symbols

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

Claims (8)

A polyolefin-based resin material containing at least a crystalline polyolefin resin, carbon black 5 wt% to 30 wt% , and inorganic filler 10 wt% to 30 wt% containing at least silica or / and a binding compound of silica and a layered crystalline filler , A composition formed by molding a composite material containing 5 wt% to 20 wt% of a silicone compound,
A slidable composition characterized by being elastically pressed against a glass member and imparting glass sealing properties.   The slidable composition according to claim 1, wherein the polyolefin-based resin material contains an amorphous polyolefin resin.   The slidable composition according to claim 1, wherein the inorganic filler contains a layered crystalline filler. The slidable composition according to any one of claims 1 to 3 , wherein the silica is 10 wt% or more. The slidable composition according to any one of claims 1 to 4 , wherein an average particle diameter of the carbon black is 40 nm or more. A sliding part made of a thermoplastic elastomer composition, comprising a base part assembled to a vehicle body panel, and a pressure contact part provided at the base part and having elasticity with respect to a glass member,
A sliding product comprising the slidable composition according to any one of claims 1 to 5 formed on at least a surface in contact with the glass member in the press contact portion. The sliding product according to claim 6, wherein the sliding composition has a flexural modulus of 350 MPa or less. The sliding product according to claim 6 or 7, wherein the slidable composition has a hardness (D) in accordance with JIS K 6253 within a range of 40-60.

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