JP5356055B2 - Rolling sliding member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rolling slide member for slide door or seat slide, which improves abradability against rolling and ensures excellent abradability against rolling even under a high load using a resin high in fatigue property against compression and abradability against scraping. <P>SOLUTION: The rolling slide member for the slide door or seat slide is equipped at a contact portion with an opposite member with a resin molded body consisting of a resin composition containing a resin with an intrinsic viscosity [&eta;] of 1.2-2.0 dl/g on the basis of the fact that there is a positive correlation between the intrinsic viscosity [&eta;] and abradability against rolling. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to rolling sliding members such as rollers and rails used for sliding doors and seat slides of automobiles and the like. In particular, the present invention relates to a rolling sliding member that can withstand long-term use under a high temperature and high surface pressure environment.

  In a van type vehicle or the like, a side entrance that is opened and closed by a sliding door is used for getting on and off the rear half of the vehicle. Normally, sliding doors can be opened and closed smoothly by rolling support rollers mounted on the upper and lower edges and intermediate position of the door body on the vehicle body steel plate or on the guide rail provided on the vehicle body side. It has become.

  This support roller is comprised from the ball bearing attached to the spindle provided in the slide door. In addition, the outer surface of the outer ring of the ball bearing in contact with the guide rail is integrally molded with a synthetic resin outer skin to reduce metal noise generated by the rolling of the support roller when opening and closing the door and vibration during travel. Has been.

  When the support roller provided on such a slide door rolls on the vehicle body steel plate or on the guide rail provided on the vehicle body side, the resin outer skin of the support roller gradually wears. Such wear causes deterioration of the standing of the sliding door due to a decrease in the roller diameter and deterioration of the opening / closing noise due to the rough surface of the resin outer skin. In addition, since the sliding door is normally held in a closed state, a load is applied to the resin outer skin portion of the support roller for a long period of time, and the roundness and dimensional change of the rolling sliding member due to creep deformation of the resin outer shell, due to this, The sliding door opening / closing sound is worsened.

  Furthermore, depending on the use environment, the temperature of the use site may be 50 ° C. or higher, and under such conditions, when a resin material having low heat resistance is used, it is considered that deformation of the resin outer skin is caused. . Various chemicals such as car shampoo, car wax, acid rain, snow melting agents such as calcium chloride, gasoline, etc. when used under conditions in contact with air outside the passenger compartment (hereinafter also referred to as “exterior conditions”) It is conceivable that adhesion occurs. In the resin-made outer skin having low resistance to these chemicals, a solvent crack due to the chemical is generated, and the resin outer skin is cracked.

  For this reason, in order to maintain the quietness when opening and closing the sliding door for a long period of time, the characteristics of the synthetic resin outer skin are wear resistance under the door load conditions, heat deformation resistance, resistance to long-term use. Creep is required as a mechanical property. Further, when such a support roller is used under exterior conditions, resistance to various chemicals such as car wax, car shampoo, acid, alkali, snow melting agent and gasoline as described above is required. .

  Various studies have been conducted to improve the durability of the synthetic resin outer skin. For example, an outer skin made of a synthetic resin material having a melting point of 200 ° C. or higher is formed integrally with the outer ring on the outer circumferential surface of the outer ring, thereby improving the heat resistance of the support roller and preventing deformation of the outer skin even at high temperatures. Has been proposed (see Patent Document 1). Examples of the synthetic resin shell disclosed in Patent Document 1 include PA46 (polyamide 4-6) and PPS (polyphenylene sulfide) (paragraph “0015”). It is described that these synthetic resins are excellent in mechanical properties at high temperature, and therefore, the creep resistance against the load of the support roller and the durability against wear, impact, etc. can be improved (paragraph “0018”).

JP 2003-239946 A

  However, the support roller for a sliding door described in Patent Document 1 has a problem that the abrasion resistance of the resin outer skin formed integrally with the outer peripheral surface of the outer ring is insufficient.

  The present invention has been made in view of the above-mentioned problems in rolling sliding members, and the object of the present invention is to provide a rolling sliding member having excellent rolling wear resistance under high loads. is there.

  In order to achieve the above-mentioned object, the present inventors have intensively studied the types of resin materials constituting the sliding surface of the rolling sliding member and the physical properties thereof. As a result, it has been found that a rolling sliding member using a resin having a specific intrinsic viscosity [η] has excellent rolling wear resistance, and has completed the present invention.

  The rolling sliding member for a sliding door or seat slide of the present invention can improve rolling wear resistance by using a resin having high resistance to compression fatigue and rubbing wear.

It is an axial sectional view showing the structure of a support roller for a sliding door as an embodiment of the rolling sliding member of the present invention. It is a perspective view which shows the external appearance of the sliding door system of the motor vehicle using the support roller shown in FIG.

  The present invention relates to a resin molded body comprising a resin composition containing a resin having an intrinsic viscosity [η] (hereinafter, also simply referred to as “intrinsic viscosity” or “η”) of 1.2 to 2.0 dl / g. It is related with the rolling sliding member prepared in the contact part.

  Conventionally, various studies have been made in order to improve the durability of the synthetic resin outer skin used for the sliding member. For example, the part of the predetermined width including the maximum diameter part of the guide roller outer diameter surface is made of resin, and the remaining part of the outer diameter surface is made of metal, thereby improving the quietness when the sliding door is opened and closed, and the guide There is a method for preventing deformation due to a load when the roller is stopped. The above method is described in, for example, Japanese Patent Application Laid-Open No. 2000-81038. However, in this guide roller, the rail surface is parallel to the roller shaft in the roller travel region, and is used with a rail inclined to the roller shaft in the roller stop region. There is a problem that the degree is low. As described above, in the conventional roller, the roller surface is roughened due to wear, or the roundness of the roller is lowered due to creep deformation, and the opening / closing sound of the sliding door is deteriorated (large and unpleasant sound). Get up. In addition to the cracking of the resin shell due to the adhesion of chemicals, there are disadvantages such as poor moldability, brittleness, heavyness, high manufacturing cost, and low design freedom.

  Moreover, in patent document 1 (Unexamined-Japanese-Patent No. 2003-239946), in order to prevent a deformation | transformation of an outer skin even in a high temperature state, the outer skin made of a synthetic resin material having a melting point of 200 ° C. or higher is defined as the outer ring By forming them integrally, the heat resistance of the support roller is improved. Here, as the synthetic resin material, various synthetic resins are described in the paragraph “0015”. However, the support roller for sliding doors has problems that the resin outer skin formed integrally with the outer peripheral surface of the outer ring, the creep resistance due to long-term load, and the thermal deformation under high temperature conditions are insufficient. It was. Further, when used under exterior conditions, chemical resistance or design freedom may be a problem. For example, 46PA (polyamide 4-6) and 66PA (polyamide 6-6) have a relatively large number of amide bonds in the unit weight. For this reason, it is weak to calcium chloride used as a snow melting agent. In addition, since PBT (polybutylene terephthalate) has a glass transition point near room temperature, it is in a rubber state at room temperature and has poor creep resistance. PPA (polyphthalamide) has a different formulation for each material manufacturer, melting point, glass transition point and crystallinity change, and the general crystallinity is about 20%. Wear resistance is poor, and in actual use, it is necessary to devise a technique for ensuring crystallinity. Furthermore, although PPS (polyphenylene sulfide) has a melting point of 200 ° C. or higher, the thermal deformation temperature is low when the reinforcing fiber is not filled, and therefore, it cannot be passed through the coating furnace in the vehicle body coating process. In addition, since PPS has a low glass transition point, the physical properties change rapidly under high-temperature atmospheric conditions, and creep deformation is likely to occur due to a long-term load. In addition, when a reinforcing fiber is filled in PPS, there is a problem that it becomes brittle at the same time as elongation is deteriorated and wear resistance is also deteriorated. PEEK (polyetheretherketone) has poor wear resistance due to insufficient crystallinity, and is expensive compared to general resins. In addition, PEEK has a high molding temperature and poor moldability, and since the specific gravity is high, the molded product is heavy, and the wear resistance is poor due to insufficient crystallinity. Moreover, since PI (polyimide) is a thermosetting resin, there is a problem that there is a limitation in molding equipment.

  Further, in JP-A-2006-138334, a resin molded body having a specific crystallinity composed of a polyamide resin composition containing a specific semi-aromatic polyamide is disposed on the sliding surface of a rolling sliding member. Proposals have been made. However, in the above-described support roller for the sliding door, the rolling wear resistance may be insufficient when the door weight is large. In general, fillers and lubricants are added to improve the strength and wear of resin materials. However, the detailed mechanism of rolling wear is insufficient and the above-mentioned treatment is not possible. It cannot be applied generally, and depending on the prescription, it may cause deterioration.

  The inventors of the present application have conducted further studies on the polyamide resin in view of the above points, and found that there is a positive correlation between the intrinsic viscosity [η] and the rolling wear resistance. Furthermore, when intensive investigation was performed on the optimum intrinsic viscosity for the rolling sliding member, the rolling sliding member produced using a resin having an intrinsic viscosity of 1.2 to 2.0 dl / g has a resistance to compression fatigue and It has been found for the first time that it has excellent abrasion resistance, particularly compression fatigue resistance. Thus, the resin excellent in compression fatigue resistance and rubbing wear resistance can be suitably used for rolling sliding members that require excellent rolling wear resistance, in particular, the outer skin and rails of rollers of sliding doors.

  Here, by using a resin having an intrinsic viscosity [η] of 1.2 to 2.0 dl / g for a rolling sliding member, a mechanism for improving compression fatigue resistance and rubbing wear resistance is unknown. It is considered as follows. The present invention is not limited by the following estimation. That is, a slide door of a vehicle such as a general van type car has a weight of about 50 kg per sheet, and since one door is supported by two rollers, a weight of about 25 kg is applied per roller. For this reason, the outer skin of the roller is always exposed to a load of 25 kg. In particular, while rotating on the guide rail, the roller is compressed under a load of 25 kg at a portion in contact with the guide rail, and released from this compressed state when it is separated from the guide rail, and this state repeatedly occurs. Since such compression / opening is repeated each time the door is slid, when the durability is not sufficient, the material on the roller surface is detached in a short period of time, and the surface is peeled off, so-called surface destruction occurs. For this reason, the rolling sliding member needs to be excellent in compression fatigue resistance. In addition to the above, since the roller always rotates in contact with the guide rail under a high load, the surface is rubbed with the rotation and wears due to repeated fatigue. For this reason, the rolling sliding member requires rubbing wear resistance in addition to excellent compression fatigue resistance. On the other hand, a resin having an intrinsic viscosity of 1.2 dl / g or more is excellent in viscoelasticity because of its long molecular chain. For this reason, the rolling sliding member using such a resin can absorb a load flexibly even when the roller is in contact with the guide rail and a load is applied. In addition, thanks to the high viscoelasticity unique to this resin, the roller surface does not easily peel off even after long-term use (surface destruction is unlikely to occur). Therefore, the rolling sliding member of the present invention is excellent in compression fatigue resistance and rubbing wear resistance. Therefore, the rolling sliding member of the present invention can improve rolling wear resistance, particularly rolling wear resistance under a high load. Furthermore, by reducing the spherulite structure of the resin, the rolling wear resistance under a high load can be further improved. Therefore, the rolling sliding member of the present invention can be suitably used as a rolling sliding member for a sliding door or a seat slide.

  Hereinafter, the rolling sliding member of the present invention will be described in more detail. In this specification, “weight” is treated as a synonym for “mass” unless otherwise specified. For example, “wt%” is treated as a synonym for “mass%”. “%” Means “mass percentage (mass%)” unless otherwise specified.

  In the present invention, the “rolling sliding member” means a member in which at least one of the sliding member itself and the mating member rotates and contacts and / or slidably contacts the other. Specifically, not only members that rotate themselves, such as support rollers and guide rollers, but members that do not rotate themselves, such as support rails and guide rails, that come into contact with rotating counterpart members. Is also included. The material constituting the mating member and the material of the sliding contact surface are not particularly limited, and a metal or resin material can be widely applied. The sliding contact surface is the same as the rolling sliding member of the present invention. It can also consist of a resin or a resin composition.

  The rolling sliding member of the present invention includes, for example, as described above, an inner ring attached to a spindle, an outer ring rotatably attached to the inner ring, and a synthetic resin outer skin attached to the outer peripheral side of the outer ring. It can apply to the roller provided with. In this case, the said synthetic resin outer skin shall consist of the resin composition mentioned later. Therefore, the present invention is a roller comprising an inner ring attached to a spindle, an outer ring rotatably attached to the inner ring, and a synthetic resin outer skin attached to the outer peripheral side of the outer ring, Provided is a rolling sliding member in which the synthetic resin shell is made of a resin composition described later. At this time, it is preferable that a rolling element such as a spherical shape, a cylindrical shape, or a pin shape is interposed between the inner ring and the outer ring as necessary. With such a structure, the friction characteristics between the inner and outer rings can be improved.

  Further, the rolling sliding member of the present invention can be applied to a rail for supporting or guiding a rolling counterpart member such as a roller as described above. In this case, the contact surface of the rail with the mating member that rolls is made of a resin composition described later. Therefore, the present invention provides a rolling sliding member having a contact surface with a rolling counterpart member, the contact surface comprising a resin composition to be described later. At this time, since a contact surface made of a resin composition to be described later is formed on the rail side, a resin molded body made of the above resin alone or the following resin composition is not necessarily placed on the side of a rolling member such as a roller. It is not necessary to provide a resin molded body made of a product.

  When such a roller or rail is applied to, for example, a support roller or a guide rail in a slide door of an automobile or the like, a high surface pressure and high pressure of 15 MPa or more, preferably 15 to 30 MPa, 50 ° C. or more, and further 70 ° C. or more. May be exposed to temperature environment. Nevertheless, by using the resin according to the present invention, wear and deformation of the sliding surface can be suppressed, and the smooth and quiet opening / closing operation of the sliding door can be maintained for a long time. Further, since the wear resistance is improved and high reliability can be secured even under use conditions of less than 15 MPa, it is desirable to use the rolling sliding member (roller, rail, etc.) of the present invention.

  FIG. 1 is a cross-sectional view showing an example in which the rolling sliding member is applied to a supporting roller for a sliding door as described above as an embodiment of the rolling sliding member of the present invention. In FIG. 1, the roller 1 includes a ball bearing 2 fixed to a support shaft 10 and a synthetic resin outer shell 3 formed integrally with the outer periphery of the ball bearing 2. FIG. 2 is a perspective view showing the appearance of an automobile sliding door system using the roller 1. In FIG. 2, a slide door 14 is slidably supported via a roller 1 on guide rails 11, 12, and 13 attached to an automobile body.

  In FIG. 1, the ball bearing 2 is disposed in an inner ring 4 fixed to a support shaft 10, a rotatable outer ring 5, and an annular space 6 formed between the inner ring 4 and the outer ring 5. It comprises a plurality of balls 7 and a cage 8 that holds these balls 7.

  On the outer peripheral surface of the outer ring 5, circumferential grooves 5b and 5c are formed in the substantially central portion in the axial direction, and the resin composition described later having specific components and physical properties is provided by embedding the grooves 5b and 5c. A synthetic resin outer skin 3 made of a product is integrally formed on the circumference.

  Further, in order to prevent dust and moisture from entering the both sides of the end portion of the annular space 6 and to prevent leakage of a lubricant (not shown) sealed in the annular space 6, a hermetic seal 9 is provided. Is installed.

  The roller 1 having the above structure is attached to a predetermined position of the slide door 14 via the support shaft 10 and is fitted into guide rails 11, 12, 13 provided on the vehicle body side to open and close the slide door 14. Along with this, it rolls on these rails.

  The present invention is characterized in that a resin having an intrinsic viscosity [η] of 1.2 to 2.0 dl / g is used for a contact portion with a counterpart member. As described above, due to the type and physical properties of the resin material that constitutes the sliding surface of the rolling sliding member, the intrinsic viscosity of the resin contained in the resin composition that constitutes the sliding surface and the rolling wear resistance under high loads This is because the relationship with gender was found. Further, as will be described in detail below, the rolling wear resistance under a high load can be further improved by controlling the spherulite structure of the resin.

  In this invention, the resin molding which consists of a resin composition is arrange | positioned in the contact site | part with the other party member in a rolling sliding member. Here, the resin contained in the resin composition constituting the resin molded body to be arranged is not particularly limited as long as the intrinsic viscosity [η] is 1.2 to 2.0 dl / g. When the intrinsic viscosity [η] is lower than the lower limit, sufficient rolling wear resistance, particularly compression fatigue resistance and rubbing wear resistance cannot be obtained. On the other hand, when the intrinsic viscosity [η] exceeds the upper limit, the moldability is deteriorated. A preferable range of the intrinsic viscosity [η] varies depending on desired characteristics. For example, considering the compression fatigue resistance and rubbing wear resistance, the intrinsic viscosity is preferably high, preferably 1.3 dl / g or more, and more preferably 1.4 dl / g or more. On the other hand, considering the moldability, the intrinsic viscosity is preferably lower, preferably 1.3 to 1.8 dl / g, and more preferably 1.4 to 1.6 dl / g. For this reason, what is necessary is just to select the preferable intrinsic viscosity in the said range suitably for the resin which concerns on this invention according to a desired characteristic. In this specification, the “intrinsic viscosity [η]” means a value measured at 30 ° C. in concentrated sulfuric acid. Specifically, the viscosity of the resin solution is obtained at several concentrations, and this is set to 0. It means the viscosity of the extrapolated zero point resin solution. More specifically, it is a value determined according to the method described in the examples below. “Concentrated sulfuric acid” generally refers to an aqueous sulfuric acid solution having a concentration of 90% by mass or more, and in this specification, an aqueous sulfuric acid solution having a concentration of 95 to 100% by mass is particularly meant.

  In the present invention, the resin is not particularly limited as long as the intrinsic viscosity [η] is 1.2 to 2.0 dl / g. Also, the method for producing such a resin having a specific intrinsic viscosity is not particularly limited, and for example, a known method such as the method described in JP-A No. 2000-212434 may be modified as it is or if necessary. Can be applied. Moreover, it is preferable that the peak top (Mp) of the molecular weight of the resin is 50,000 to 100,000. If the Mp of the resin molecular weight is within the above range, the intrinsic viscosity [η] of the resin can be easily adjusted to 1.2 to 2.0 dl / g. Moreover, Mp of molecular weight measured by GPC method of a more preferable resin changes with desired characteristics. For example, considering compression fatigue resistance and rubbing wear resistance, the Mp of the resin is more preferably 52,000 to 100,000, still more preferably 63,000 to 100,000, and 63,500 to 100,000. Is particularly preferred. In consideration of moldability, the Mp of the resin is more preferably 58,000 to 88,000, and particularly preferably 62,500 to 76,000.

  The method for adjusting the peak top (Mp) of the molecular weight of the resin to the above range is not particularly limited, and a known method can be used. Specifically, a monomer is polymerized to produce a resin. At this time, (a) the amount of the polymerization initiator is adjusted; (a) the polymerization temperature is adjusted; (c) the polarity of the solvent is adjusted. Adjusting. These methods may be used alone or in appropriate combination. However, since the above methods (a) to (c) are closely related to each other, the above methods (a) to (c) It is preferable to use at least two methods in combination, and it is more preferable to use the above methods (a) to (c) in combination.

  In the present specification, “peak top (Mp) of molecular weight” means a value measured by a gel permeation chromatography (GPC) method. In particular, the molecular weight of each polymer molecule constituting the resin is detected on the horizontal axis. This means the molecular weight of the resin when the detected intensity is maximum when the detected intensity of the vessel is taken on the vertical axis and the molecular weight of the resin is measured by the GPC method. In addition, Mp of resin when using 2 or more types of resin for a resin molding is made into the molecular weight of resin when detection intensity becomes the maximum when the molecular weight of a resin mixture is measured by GPC method. As the detector, for example, a UV detector or an RI detector can be used. Specifically, the peak top (Mp) of the molecular weight of the resin is a value determined according to the method described in the examples below.

  The resin constituting the resin molded body disposed on the rolling sliding member of the present invention is not particularly limited as long as the intrinsic viscosity [η] is 1.2 to 2.0 dl / g. Preferably, polyamide can be used. Polyamides include aliphatic polyamides such as polyamide 6, polyamide 9, polyamide 11, polyamide 12, polyamide 46, polyamide 49, and polyamide 69; semi-aromatics comprising units derived from isophthalic acid and terephthalic acid and units derived from aliphatic diamine. Examples thereof include polyamide. Of these, it is preferable to use a semi-aromatic polyamide. Specific examples of the semi-aromatic polyamide include a dicarboxylic acid unit containing 30 mol% or more of an aromatic dicarboxylic acid unit and a diamine unit containing 30 mol% or more of an aliphatic diamine unit having 4 to 14 carbon atoms. Is mentioned.

  The content of the aromatic dicarboxylic acid unit in the dicarboxylic acid unit of the semi-aromatic polyamide is preferably in the range of 60 to 100 mol%, more preferably in the range of 70 to 100 mol%, and in the range of 80 to 100 mol%. The inside is more preferable. The content of the aliphatic diamine unit having 4 to 14 carbon atoms in the diamine unit of the semiaromatic polyamide is preferably in the range of 60 to 100 mol%, more preferably in the range of 70 to 100 mol%, and 80 More preferably within the range of ˜100 mol%.

  Examples of the aromatic dicarboxylic acid unit include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and 1,4-phenylenedioxydi. Acetic acid, 1,3-phenylenedioxydiacetic acid, diphenic acid, dibenzoic acid, 4,4′-oxydibenzoic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid, 4 , 4′-biphenyldicarboxylic acid and the like, and one or more of these may be included.

  Of these, structural units derived from terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid are preferred from the viewpoint of economy and performance of the resulting semi-aromatic polyamide, and structural units derived from terephthalic acid Is more preferable.

  The semi-aromatic polyamide is optionally dicarboxylic acid units other than the aromatic dicarboxylic acid units described above, for example, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid. , Aliphatic dicarboxylic acids such as trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 2,2-diethylsuccinic acid, azelaic acid, sebacic acid, suberic acid; 1,3-cyclopentanedicarboxylic acid, 1, A structural unit derived from one or more of alicyclic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid may be included.

  The content of these other dicarboxylic acid units is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less of the total dicarboxylic acid units. Furthermore, the semi-aromatic polyamide can also contain structural units derived from polyfunctional compounds such as trimellitic acid, trimesic acid, and pyromellitic acid as long as melt molding is possible.

  Examples of the aliphatic diamine unit having 4 to 14 carbon atoms include 1,4-tetramethylenediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, and 1,9-. Linear aliphatic diamines such as nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine; 2-methyl-1,5-pentanediamine, 3-methyl-1,5- Pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2,4-dimethylhexanediamine, 2-methyl-1,8-octane And structural units derived from branched aliphatic diamines such as diamine and 5-methyl-1,9-nonanediamine. It may include one or two or more.

  Of these, 1,4-tetramethylenediamine, 1,6-hexanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1, from the viewpoints of economy and physical properties of the obtained semi-aromatic polyamide. Structural units derived from 12-dodecanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine are preferred, and 1,9- More preferred are structural units derived from nonanediamine and / or 2-methyl-1,8-octanediamine.

  The semi-aromatic polyamide is optionally prepared in addition to the above-described aliphatic diamine unit having 4 to 14 carbon atoms, for example, cyclohexanediamine, methylcyclohexanediamine, bis (p-cyclohexyl) methanediamine, bis. (Aminomethyl) norbornane, bis (aminomethyl) tricyclodecane, alicyclic diamines such as bis (aminomethyl) cyclohexane; p-phenylenediamine, m-phenylenediamine, xylenediamine, 4,4′-diaminodiphenylsulfone, A structural unit derived from one or more aromatic diamines such as 4,4′-diaminodiphenyl ether may be included. The content of these other diamine units is preferably 40 mol% or less of the total diamine units, more preferably 30 mol% or less, and even more preferably 20 mol% or less.

  The melting point of the semi-aromatic polyamide is preferably 250 ° C. or higher and more preferably in the range of 270 to 330 ° C. from the viewpoint of increasing the crystallinity and improving the mechanical properties.

  In the present invention, the above resins may be used alone or in the form of a mixture of two or more.

  Moreover, it is preferable that resin which comprises the resin molding arrange | positioned at the rolling sliding member of this invention is crystalline. Here, “crystalline” means that the resin has a property that the polymer chains are regularly arranged at a temperature below the melting point. Here, the crystallinity of the resin is not limited as long as it can achieve desired effects such as rolling wear resistance, particularly rolling wear resistance under high loads, creep resistance, and chemical resistance. Specifically, the crystallinity of the resin is preferably 10 to 75%, more preferably 30 to 75%, further preferably 40 to 70%, and particularly preferably 40 to 65%. Here, when the crystallinity of the resin is within such a range, the resin is excellent in wear resistance, creep resistance, chemical resistance, and toughness. In the present invention, the crystallinity means a value measured by an X-ray diffraction method. Specifically, using a resin molded body made of a resin composition, the diffraction intensity from the crystalline region and the diffraction intensity from the amorphous region are separated from the wide-angle X-ray diffraction profile by the transmission method, and the crystal with respect to the total diffraction intensity is obtained. Calculated from the ratio of diffraction intensities from the region. The crystallinity of this resin molded body can be regarded as the crystallinity of the resin constituting the resin molded body.

  In addition, the glass transition point of the resin used in the present invention is preferably high from the viewpoint of the heat-resistant safety factor, but if it is too high, the melting point also increases and the moldability deteriorates as a result. The range of is preferable. In addition, the more preferable range of the said glass transition point is 110-135 degreeC, and the range of a more preferable glass transition point is 120-130 degreeC. In the present invention, the glass transition point means a value measured by DSC (differential scanning calorimeter).

  The content of the resin (particularly semi-aromatic polyamide) in the resin composition used in the present invention is preferably 20% or more, more preferably 40% or more, and 80% or more in terms of mass ratio. More preferably, it is particularly preferably 95% or more.

Moreover, it is preferable that the said resin composition which comprises the said resin molding used for this invention has a spherulite structure. And by rolling down the spherulite structure, rolling wear resistance under a high load can be further improved. The refined spherulite structure preferably contains at least spherulites having a size of 10 μm or less, particularly 0.01 to 10 μm, and more preferably contains at least spherulites having a size of 0.01 to 1.4 μm. . Here, the content of spherulites having a size of 10 μm or less is not particularly limited. Specifically, the content of spherulites having a size of 10 μm or less, particularly 0.01 to 10 μm, is 5% or more and 95% or less in the volume ratio of the total spherulite structure in the resin composition constituting the resin molded body. It is preferable to contain by a ratio. More preferably, the spherulites of the above size are contained in the resin composition constituting the resin molded body in a ratio of 75 to 95%, particularly 85 to 95% by volume ratio of the total spherulite structure. In the present specification, “size of spherulite” refers to a value measured by observing a cross section of a resin molded body with a polarizing microscope. When the spherulite structure is not a true sphere, the “spherulite size” refers to the maximum distance among the distances between any two points on the outline of the spherulite. In the present specification, the “spherulite content” is measured by the following method. That is, image analysis is performed on an image obtained by observing a cross section (5 samples) of the resin molded body with a polarizing microscope. In this image, the area (S ₁ ) of the spherulite part having a spherulite size exceeding 10 μm and the area (S ₂ ) of the spherulite part having a spherulite size of 10 μm or less are measured. From these values, the ratio (%) (= [S ₂ / (S ₁ + S ₂ )] × 100) of the area of the spherulite part having a spherulite size of 10 μm or less in the area of the entire spherulite part, This average value is used. Note that the spherulites seem to exist almost uniformly in any cross section of the resin molded body. For this reason, in this specification, the said area ratio is made into the content rate of the spherulite represented by volume ratio.

  The spherulite control of the resin composition can be controlled by adjusting the molding conditions without using powder, but it may increase the amorphous region and cause internal distortion during molding. It is desirable to carry out by adding powder, especially fine powder. Therefore, the resin composition of the present invention preferably contains a fine powder. In addition, the range with preferable mass content to the said resin composition of the said powder is 60 mass% or less by mass ratio, More preferably, it is 20 mass% or less, More preferably, it is less than 10 mass%, Most preferably, it is 5 mass. % Or less. Here, the lower limit of the content of the powder in the resin composition is not particularly limited, but is preferably 0.1% by mass, more preferably 0.5% by mass.

  As said powder, the fine powder which can refine | miniaturize a spherulite can be used. As the particle diameter of the fine powder, the average particle diameter measured by a laser diffraction method is preferably 20 μm or less. The lower limit of the average particle size of the fine powder is not particularly limited, but is preferably 0.1 μm or more. A specific example of the fine powder for refining the spherulites is not particularly limited. Specific examples include silica, diatomaceous earth, diatomaceous earth, silica gel, calcium silicate, sericite, flint, feldspar, aragonite, attapulgite, talc, clay, mica, and the like. Of these, talc and clay are preferred, and talc is particularly preferred. The fine powder capable of refining the spherulites may be used alone or in the form of a mixture of two or more.

  The resin composition used in the rolling sliding member of the present invention can contain a filler in addition to or in place of the material (such as fine powder) that can refine the spherulites. Examples of the filler include fibrous fillers such as glass fiber, carbon fiber, boron fiber, aramid fiber, and liquid crystal polyester fiber; needle-like shapes such as potassium titanate whisker, aluminum borate whisker, zinc oxide whisker, and calcium carbonate whisker. Filler: Mica, kaolin, clay, calcium carbonate, silica, fumed silica, fine particle silica, silica alumina, alumina, titanium dioxide, graphite, molybdenum disulfide, kaolinite, montmorillonite, minnesite, pyrophyllite, polytetrafluoroethylene And powdery fillers such as high molecular weight polyethylene can be used, and one or more of these can be used. Among these, glass fiber, carbon fiber, potassium titanate whisker, and aluminum borate whisker are preferably used from the viewpoint of the reinforcing effect, and aramid fiber, carbon fiber, titanic acid are used from the viewpoint of slidability. It is preferable to use potassium whisker, calcium carbonate whisker, zinc oxide whisker, mica, molybdenum disulfide, graphite, polytetrafluoroethylene, and high molecular weight polyethylene. From the viewpoint of dimensional stability, silica, alumina, mica, boric acid It is preferable to use aluminum whiskers. These fillers may be surface-treated with, for example, a silane coupling agent or a titanium-based coupling agent. The above fillers may be used alone or in the form of a mixture of two or more.

  In addition, if there is little content of the said filler, sufficient effect as a filler cannot be exhibited, and if it is too much, it may cause generation of abnormal wear and a decrease in toughness. The amount is preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less, based on the mass of the entire resin composition. The lower limit of the content of the filler when using the filler is not particularly limited, but is preferably 10% by mass, more preferably 15% by mass with respect to the mass of the entire resin composition.

  Furthermore, the resin composition used in the present invention contains various additives in addition to or in place of the above-described materials (fine powder, etc.) and / or fillers that can refine the spherulites. Can do. Examples of such additives include brominated polymers, antimony oxides, metal oxides, metal hydroxides, phosphorus compounds, phosphorus containing polymers, silicone compounds, nitrogen containing compounds and other flame retardants; benzophenone compounds, UV absorbers such as benzotriazole compounds and benzoate compounds; antistatic agents; plasticizers; lubricants; processing aids; colorants such as pigments and dyes; impact modifiers; other types of thermoplastic polymers be able to. The above additives may be used alone or in the form of a mixture of two or more.

  If the content of these additives is too large, harmful effects such as a decrease in strength occur. Therefore, the content of the additives is preferably 60% by mass or less, more preferably 55% by mass with respect to the mass of the entire resin composition. % Or less, more preferably 20% by mass or less. The lower limit of the content of the additive when using the additive is not particularly limited, but is preferably 0.1% by mass, more preferably 0.5% by mass with respect to the total mass of the resin composition. is there.

  Furthermore, in addition to the fillers and additives described above, the resin composition used for the rolling sliding member of the present invention includes conventionally known copper stabilizers and hindered phenol antioxidants as necessary. An agent, a hindered amine antioxidant, a phosphorus antioxidant, a thio antioxidant, a light stabilizer and the like can also be added. These substances may be used alone or in the form of a mixture of two or more. The content of these substances is not particularly limited, but is preferably 0.1 to 20% by mass with respect to the mass of the entire resin composition.

  The method for preparing the resin composition used in the rolling sliding member of the present invention is not particularly limited as long as it is a method capable of uniformly mixing the resin and other components as necessary, and usually melt kneading. Is adopted. Melt kneading can be carried out using a kneader such as a single screw extruder, a twin screw extruder, a kneader, a Banbury mixer, etc., and the type of apparatus used and melt kneading conditions are not particularly limited, The resin composition used in the present invention can be obtained by kneading at a temperature in the range of approximately 300 to 350 ° C. for 1 to 30 minutes. In this case, the resin composition prepared by melt kneading may be used for molding as it is, or may be molded after being pelletized once.

  Since the rolling sliding member of the present invention is provided with the resin molded body made of the resin composition as described above at the contact portion with the counterpart member, it has resistance to various chemicals and wear resistance at the contact portion. It can withstand high surface pressure and high temperature environment, and can maintain a smooth and quiet operating state over a long period of time, but the surface pressure during rolling sliding can be 30 MPa or less, especially Applicable to parts used in parts that may have a high surface pressure of 4 to 30 MPa, or parts that may be in a high temperature environment such as 50 to 125 ° C., particularly 70 to 125 ° C. It is desirable to do. Needless to say, the use of the present invention at lower temperatures and surface pressures is not a problem, but by applying to such high surface pressure and high temperature environments, the rolling of the present invention can be compared with conventional members. The features of the sliding member can be maximized.

  In addition, as the surface roughness of the sliding surface of the rolling sliding member, that is, the contact surface in contact with the mating member in the contact portion provided with the resin molded body made of the resin composition, Ra (center line average roughness) It is desirable that it is 2.0 micrometers or less (0-2.0 micrometers). This is because, when the surface roughness Ra of the sliding surface exceeds 2.0 μm, the rolling sliding member is easily affected by stress concentration due to the unevenness of the sliding surface, resulting in abnormal wear or local wear. This is because fatigue fracture tends to occur more easily and rolling noise tends to increase. In addition, in this specification, "surface roughness (Ra)" was measured using the contact-type surface roughness meter based on the method as described in JIS B0601-2001. At this time, the number of samples was set to 10 and the average value was obtained.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples.

  In addition, PA9T used in the following Examples and Comparative Examples is derived from a dicarboxylic acid unit containing 100 mol% of a structural unit derived from terephthalic acid, 1,9-nonanediamine and 2-methyl-1,8-octanediamine. It is a semi-aromatic polyamide composed of diamine units containing 100 mol% of structural units (the former: the latter = 80: 20 (molar ratio)).

Example 1
To refine the spherulite in PA9T ([η]: 2.0 dl / g, Mp: 100,000 (detector: UV detector), glass transition point: 125 ° C.) manufactured by Kuraray Co., Ltd. The resin composition (1) is obtained by adding 1.0% by mass to the resin composition from which talc (the average particle diameter measured by laser diffraction method is 14 μm) can be obtained as a fine powder of It was.

  Next, using the resin composition (1) thus obtained, a roller 1 having a synthetic resin outer skin 3 as shown in FIG. 1 was produced according to the following method. In other words, when molding the synthetic resin outer skin 3, the ball bearing 2 comprising the inner ring 4 and the outer ring 5 as shown in FIG. The molten resin composition (1) is injected into the space formed between 5 and the mold, and after the molten resin composition (1) is cooled and solidified, the mold is opened to form a molded product. Was taken out to obtain a roller (1). At this time, the mold temperature during molding is 140 ° C., and the holding time is 60 seconds. The dimensions of the synthetic resin outer skin 3 were 6 mm thick, 20 mm wide, and 40 mm in diameter.

  The synthetic resin shell thus obtained contained 90% by volume of spherulites having a size of 10 μm or less. Further, the crystallinity of the resin-made outer skin measured by the X-ray diffraction method was 50%.

Example 2
To refine spherulites using PA9T ([η]: 1.4 dl / g, Mp: 63,500 (detector: UV detector), glass transition point: 125 ° C.) manufactured by Kuraray Co., Ltd. The resin composition (2) is obtained by adding 1.0% by mass to the resin composition from which talc (the average particle diameter measured by laser diffraction method is 14 μm) can be obtained as a fine powder of It was. In Example 1, a roller (2) provided with a synthetic resin outer shell was produced in the same manner as in Example 1 except that the resin composition (2) was used instead of the resin composition (1).

  The synthetic resin shell thus obtained contained 90% by volume of spherulites having a size of 10 μm or less. Further, the crystallinity of the resin-made outer skin measured by the X-ray diffraction method was 50%.

Example 3
In Example 1, instead of the resin composition (1), PA9T manufactured by Kuraray Co., Ltd. ([η]: 1.4 dl / g, Mp: 63,500 (detector: UV detector), glass transition point: 125) A roller (3) provided with a synthetic resin outer shell was produced in the same manner as in Example 1 except that (C) was used alone.

  The synthetic resin-made outer shell thus obtained contained 90% by volume of spherulites having a size of 25 μm or less. Here, the content of spherulites having a size of 10 μm or less was less than 5% by volume. Further, the crystallinity of the resin-made outer skin measured by the X-ray diffraction method was 50%.

Reference example 4
To refine spherulites using PA9T ([η]: 1.2 dl / g, Mp: 52,000 (detector: UV detector), glass transition point: 125 ° C.) manufactured by Kuraray Co., Ltd. The resin composition (3) is obtained by adding 1.0% by mass to the resin composition from which talc (the average particle diameter measured by laser diffraction method is 14 μm) can be obtained as a fine powder of It was. In Example 1, a roller (4) having a synthetic resin outer shell was produced in the same manner as in Example 1 except that the resin composition (3) was used instead of the resin composition (1).

  The synthetic resin shell thus obtained contained 90% by volume of spherulites having a size of 10 μm or less. Further, the crystallinity of the resin-made outer skin measured by the X-ray diffraction method was 50%.

Reference Example 5
In Example 1, instead of the resin composition (1), PA9T manufactured by Kuraray Co., Ltd. ([η]: 1.2 dl / g, Mp: 52,000 (detector: UV detector)), glass transition point: 125 A roller (5) provided with a synthetic resin outer shell was produced in the same manner as in Example 1 except that (C) was used alone.

  The synthetic resin-made outer shell thus obtained contained 90% by volume of spherulites having a size of 25 μm or less. Here, the content of spherulites having a size of 10 μm or less was less than 5% by volume. Further, the crystallinity of the resin-made outer skin measured by the X-ray diffraction method was 50%.

Comparative Example 1
To refine spherulites using PA9T ([η]: 1.1 dl / g, Mp: 46,000 (detector: UV detector), glass transition point: 125 ° C.) manufactured by Kuraray Co., Ltd. As a fine powder, a talc (having an average particle diameter measured by laser diffraction method of 14 μm) is added so that the mass ratio is 1.0%, and the comparative resin composition (1) is added. Obtained. In Example 1, instead of the resin composition (1), a comparative roller (1) provided with a synthetic resin outer shell was produced in the same manner as in Example 1 except that the comparative resin composition (1) was used. .

  The synthetic resin shell thus obtained contained 90% by volume of spherulites having a size of 10 μm or less. Further, the crystallinity of the resin-made outer skin measured by the X-ray diffraction method was 50%.

Comparative Example 2
JP, 2006-138334, A In the same manner as described in Example 1, a comparison roller (2) having a synthetic resin outer skin was produced. That is, in Example 1, instead of the resin composition (1), PA9T manufactured by Kuraray Co., Ltd. ([η]: 1.1 dl / g, Mp: 46,000 (detector: UV detector), glass transition point) A comparative roller (2) having a synthetic resin outer shell was produced in the same manner as in Example 1 except that: 125 ° C.) was used alone.

  The synthetic resin-made outer shell thus obtained contained 90% by volume of spherulites having a size of 25 μm or less. Here, the content of spherulites having a size of 10 μm or less was less than 5% by volume. Further, the crystallinity of the resin-made outer skin measured by the X-ray diffraction method was 50%.

Comparative Example 3
JP, 2006-138334, A In the same manner as described in Example 3, a comparison roller (3) having a synthetic resin outer skin was produced. That is, PA9T ([η]: 1.1 dl / g, Mp: 46,000 (detector: UV detector), glass transition point: 125 ° C.) manufactured by Kuraray Co., Ltd. was used as a reinforcing filler (filler). ) To obtain a glass fiber (GF) in a mass ratio of 30% to obtain a comparative resin composition (2). In Example 1, a comparative roller (3) provided with a synthetic resin outer shell was produced in the same manner as in Example 1 except that the comparative resin composition (2) was used instead of the resin composition (1). .

  The synthetic resin-made outer shell thus obtained contained 90% by volume of spherulites having a size of 25 μm or less. Here, the content of spherulites having a size of 10 μm or less was less than 5% by volume. Further, the crystallinity of the resin-made outer skin measured by the X-ray diffraction method was 50%.

Comparative Example 4
PA9T manufactured by Kuraray Co., Ltd. ([η]: 1.1 dl / g, Mp: 46,000 (detector: UV detector), glass transition point: 125 ° C.) is used as a reinforcing filler (filler). It added so that it might become 15% of mass ratio with respect to the resin composition which can obtain carbon fiber (CF), and the comparative resin composition (3) was obtained. In Example 1, a comparative roller (4) having a synthetic resin outer shell was produced in the same manner as in Example 1 except that the comparative resin composition (3) was used instead of the resin composition (1). .

  The synthetic resin-made outer shell thus obtained contained 90% by volume of spherulites having a size of 25 μm or less. Here, the content of spherulites having a size of 10 μm or less was less than 5% by volume. Further, the crystallinity of the resin-made outer skin measured by the X-ray diffraction method was 50%.

Rollers (1) to (3) obtained in Examples 1 to 3 , Rollers (4) to (5) obtained in Reference Examples 4 to 5 and Comparative roller (1) obtained in Comparative Examples 1 to 4 The following evaluation tests were conducted on (4).

<Evaluation test method>
(1) Wear test The atmospheric temperature was set to 23 ° C or 70 ° C, and the amount of wear after rolling on an iron plate with a pressure of 5 MPa, 15 MPa or 30 MPa applied to each roller and rolling for 10 km was measured by mass measurement. Asked. Abrasion amount of less than 0.9 mg was evaluated as “◯”, and 0.9 mg or more was evaluated as “Δ”. When the roller was damaged, it was evaluated as “x”. In Table 1 below, the amount of wear (mg) is described in the upper part of the rolling friction amount, and the evaluation result is shown in the lower part.

(2) Intrinsic Viscosity [η] Measurement Inherent viscosity (η _inh ) of sample solutions of 0.05, 0.1, 0.2, and 0.4 g / dl in concentrated sulfuric acid at 30 ° C. is shown below. The value obtained by extrapolating this to a concentration of 0 was defined as the intrinsic viscosity [η].

In the above formula, t ₀ represents the flow time (second) of the solvent, t ₁ represents the flow time (second) of the sample solution, and c represents the concentration (g / dl) of the sample solution.

(3) Measurement of peak top (Mp) The peak top (Mp) of the resin was measured by gel permeation chromatography (GPC) method under the following conditions.

Column: manufactured by SHODEX, HFIP-806M
Eluent: HFIP (hexafluoroisopropanol)
Sample: Each resin dissolved in the eluent so that the resin concentration is 0.05% by mass. Sample injection amount: 10 μl
Flow rate: 1 mL / min Measurement temperature: 40 ° C
Detector: UV detector (SPD-7AV manufactured by Shimadzu Corporation)
Standard material for preparing calibration curve: Polymethyl methacrylate resin (PMMA) [(Mp) = 1890, 7100, 20800, 52600, 139000, 451000, 949000]
In the obtained chromatogram, the molecular weight showing the maximum peak height is referred to as peak top molecular weight (Mp).

  These results are summarized in Table 1.

  Note that the test conditions of the evaluation test are based on the results of actual measurement of the temperature of the portion corresponding to each guide rail 11 to 13 and the contact pressure of the roller for an actual vehicle as shown in FIG.

  That is, as a result of attaching a thermocouple to each of the guide rails 11 to 13 of the actual vehicle and measuring the temperature for one year, the temperature of all the guide rails reached 50 ° C. or more from April to November of the year. It has been confirmed that Further, as a result of inserting a tactile sensor sheet manufactured by NITTA CORPORATION as a surface pressure measuring sensor between the guide rail 12 and the roller shown in FIG. 2 and measuring the contact pressure, the contact pressure is 5 MPa or more. found.

  From the results in Table 1 above, the following was confirmed.

(1) Influence of Intrinsic Viscosity [η] Both the results at 23 ° C. and 70 ° C. compared to the comparative example having an intrinsic viscosity [η] of 1.1 dl / g. It was confirmed that the property (compression fatigue resistance) was improved.

(2) Effect of spherulite size When the rolling wear amount at 23 ° C. and 70 ° C. indicates that the content of spherulites whose size is 10 μm or less is less than 5% (mainly including those whose size is 25 μm or less) It was confirmed that the durability of the roller of the present invention with respect to the sliding pressure is further improved as compared with. As a result, when the spherulite having a size of 10 μm or less is contained in the resin or the resin composition in an amount of 5 to 95% by volume, durability against the sliding pressure of the roll (rolling sliding member) (compression fatigue resistance) is improved. To be considered.

  From the above results, the rolling wear resistance under a high load can be improved by applying the rolling sliding member according to the present invention to a roller or a rail provided at least at a contact portion with the counterpart member. In addition, by reducing the size of the spherulite structure, the rolling wear resistance under a high load can be further improved. Therefore, the rolling sliding member of the present invention can be a roller capable of maintaining the silence of the sliding door opening / closing sound after a long period of use in the sliding door support roller with sufficient resistance to use under high load conditions. It is expected. Similarly, the rolling sliding member of the present invention is sufficiently resistant to use under high load conditions even in a slide door rail, and maintains the quietness of the sliding door opening / closing sound after long-term use. It is expected to be a rail that can be used.

1 ... Roller (rolling sliding member),
2 ... Ball bearings,
3 ... Synthetic resin outer shell (resin molded body provided in contact with the mating member),
4 ... Inner ring,
5 ... Outer ring,
10 ... support shaft.

Claims (8)

Ri intrinsic viscosity [eta] the name comprises a resin molded article comprising a resin composition containing a resin is 1.4 ~2.0dl / g to contact sites of the mating member,
The resin is composed of a structural unit derived from terephthalic acid and a structural unit derived from 1,9-nonanediamine,
The resin has a spherulite structure, the resin composition contains talc as a fine powder, and the content of the talc in the resin composition is 0.1 to 5% by mass, for a sliding door or for a seat slide Rolling sliding member. The rolling sliding member according to claim 1 whose peak top (Mp) of molecular weight of said resin is 63,000-100,000. Rolling sliding member according to claim 1 or 2 wherein the resin composition is characterized in that it contains at least the spherulite size is 10μm or less. The rolling sliding member according to claim 3 , wherein spherulites having a size of 10 μm or less are contained in the resin composition at a ratio of 5% to 95% by volume ratio of the total spherulite structure. Is the surface roughness of the sliding surface (Ra) is 2.0μm or less, the rolling sliding member as claimed in any one of claims 1-4. The rolling sliding member is a roller having an inner ring attached to a spindle, an outer ring rotatably attached to the inner ring, and a synthetic resin outer skin attached to the outer peripheral side of the outer ring,
The rolling sliding member according to any one of claims 1 to 5 , wherein the synthetic resin outer skin is made of the resin composition. The rolling sliding member according to claim 6 , wherein a rolling element is interposed between the inner ring and the outer ring. The rolling sliding member is a rail having a contact surface with a rolling counterpart member,
The rolling sliding member according to any one of claims 1 to 5 , wherein the contact surface is made of the resin composition.