JP5998475B2 - Rubber material composition and rolling device sealing member - Google Patents

Description

  The present invention relates to a seal member of a rolling device such as a rolling bearing, an automobile hub unit, a linear guide device, and a ball screw device, and a rubber composition suitable for the seal member.

Usually, a rolling bearing is provided with a seal in order to prevent leakage of encapsulated grease and entry of foreign matter from the outside. For example, in the rolling bearing 20 with seal shown in FIG. 1, a plurality of rolling elements 24 are held between an inner ring 21 and an outer ring 22 via a cage 23 so as to be freely rotatable. The seal 30 is fixed to the provided stop groove 25 and is schematically configured. The seal 30 is formed by integrally forming a ring-shaped cored bar 31 having a flange part on the outer periphery and an elastic member 32 on the outer side thereof. An annular main portion 33 made of an elastic member, a crimping portion 34 made of a collar portion of the core metal 31 and an elastic member on the outer side thereof, and locked in a retaining groove of the outer ring 22, and an inner periphery of the core metal 31 And a lip portion 35 that is in contact with a receiving groove 26 provided on the outer peripheral surface of the inner ring 21. 2 is an enlarged view of the receiving groove 26 of the inner ring 21 and the lip portion 35 of the seal 30. FIG.
In addition, a rolling bearing for a wheel that supports an axle of an automobile or a railway vehicle is usually used outdoors while being exposed to rainwater, wind and snow, dust, or the like. In extreme cases, it may be used immersed in water. Therefore, a rolling structure for wheels employs a sealing structure as shown in FIG. 3, for example. In the illustrated rolling bearing O, an outer ring equivalent member 1 which is a fixed ring is supported and fixed to a suspension device (not shown) by a mounting portion 2 formed on the outer peripheral surface thereof. Therefore, the outer ring equivalent member 1 does not rotate during use. An inner ring equivalent member 3 that is a rotating ring is provided concentrically with the outer ring equivalent member 1 inside the outer ring equivalent member 1, and the inner ring equivalent member 3 rotates during use. The inner ring equivalent member 3 includes a hub 4 and an inner ring 5. Of these, the spline groove 6 is formed on the inner peripheral surface of the hub 4, and the mounting flange 7 is provided on the outer peripheral surface of the outer end (the end that becomes the outer side in the width direction when assembled to the vehicle, the left end in FIG. 3). Is formed. When assembled to the vehicle, a drive shaft that is rotationally driven via a constant velocity joint is inserted into the spline groove 6, and the axle is fixed to the mounting flange 7.

Double-row outer ring raceways 8 and 8 are formed on the inner peripheral surface of the outer ring equivalent member 1, and inner ring raceways 9 and 9 are formed on the outer peripheral surface of the intermediate portion of the hub 4 and the outer peripheral surface of the inner ring 5, respectively. Yes. Then, rolling elements 10 and 10 are provided between the outer ring raceways 8 and 8 and the inner ring raceways 9 and 9 so that the inner ring equivalent member 3 can freely rotate inside the outer ring equivalent member 1. Moreover, in order to hold | maintain the rolling elements 10 and 10 so that rolling is possible, the holder | retainers 11 and 11 are provided. In the illustrated example, balls are used as the rolling elements 10 and 10, but in the case of a heavy vehicle hub unit, tapered rollers may be used as the rolling elements. Further, seal devices 12a and 12b are provided between the outer end portion of the outer ring equivalent member 1 and the intermediate portion outer peripheral surface of the hub 4, and the inner peripheral surface of the outer ring equivalent member 1 and the inner ring equivalent member are provided. The outer end opening of the space 13 where the rolling elements 10 and 10 are installed is closed between the outer peripheral surface 3 and the outer peripheral surface 3.
As shown in an enlarged view in FIG. 4, the sealing device 12 a includes a metal core 105, a slinger 106, and an elastic member 107. Of these, the cored bar 105 is integrally formed by subjecting a metal plate such as a low carbon steel plate to punching processing such as press processing and plastic processing. Such a metal core 105 is composed of an outer diameter side cylindrical portion 109 that can be fitted and fixed to the inner peripheral surface of the end portion of the outer ring equivalent member 1 constituting the rolling bearing O, and an inner edge in the axial direction of the outer diameter side cylindrical portion 109. It is formed in an annular shape with a substantially L-shaped cross section including an inner ring portion 110 that is bent inward in the diameter direction from (the left end edge in FIG. 4). The slinger 106 is integrally formed by performing punching and plastic working such as press working on a metal plate having excellent corrosion resistance such as a stainless steel plate. Such a slinger 106 has an inner diameter side cylindrical portion 112 that can be fitted and fixed to the outer peripheral surface of the outer end portion of the inner ring 5 constituting the rolling bearing O, and an outer edge in the axial direction of the inner diameter side cylindrical portion 112 (FIG. 4). And an outer annular portion 113 that is bent outward in the diameter direction from the right end edge), and is formed in an annular shape with a substantially L-shaped cross section.
The elastic member 107 is made of an elastic member, and includes three seal lips 114, 115, and 116 on the outer side, the middle side, and the inner side, and the base end portion is coupled and fixed to the core bar 105. Then, the tip end edge of the outer seal lip 114 located on the outermost side is brought into sliding contact with the inner surface of the outer ring portion 113 constituting the slinger 106, and the intermediate seal lip 115 and the inner seal lip which are the remaining two seal lips. The tip edge of 116 is brought into sliding contact with the outer peripheral surface of the inner diameter side cylindrical portion 112 constituting the slinger 106, thereby preventing leakage of the encapsulated grease and introducing dust, water, muddy water, etc. from the outside into the bearing. Prevent intrusion.
As shown in an enlarged view in FIG. 5, the sealing device 12 b includes a cored bar 216 and an elastic member 217 each formed in an annular shape. Of these, the cored bar 216 is made of a metal plate and is fitted and fixed to the outer end of the outer ring equivalent member 1. The elastic member 217 is made of an elastic material, is formed on the cored bar 216, and is bonded and fixed by adhesion or the like. The elastic member 217 includes an outer diameter side, an inner diameter side, two side seal lips 218 and 219, and one radial seal lip 220. Then, the two side seal lips 218 and 219 are inclined toward the outer side in the diametrical direction (upward in FIG. 5) toward the tip edge (the left end edge in FIG. 3), thereby entering the space 13. The foreign matter entry prevention function is secured. Further, the radial seal lip 220 is inclined in a direction toward the inner side (right side in FIG. 5) of the space 13 toward the tip edge (lower right edge in FIG. 5), thereby ensuring a grease leakage prevention function. ing.
More specifically, the sealing device 12b includes a cored bar 216 and an elastic member 217, each of which is formed in an annular shape. The cored bar 216 of the sealing device 12b is integrally formed by subjecting a metal plate such as a low carbon steel plate to a punching process such as a press process and a plastic process. The metal core 216 includes an outer diameter side cylindrical portion 222 that can be fitted and fixed to the inner peripheral surface of the end portion of the outer ring equivalent member 1 that constitutes the rolling bearing O, and an outer edge of the outer diameter side cylindrical portion 222 (see FIG. 5). And a support plate part 223 bent inward in the diameter direction from the left end edge). Among these, the outer diameter side cylindrical portion 222 is composed of a large diameter portion 224 and an elastic member 217 closer to the inner end (rightward in FIG. 5) and the outer side surface (left side in FIG. 5) of the support plate portion 223 constituting the core metal 216. Surface) and is sandwiched between the outer peripheral surface of the elastic member 217 and the inner peripheral surface of the opening end portion of the outer ring equivalent member 1. And by this structure, the fitting part of the said metal core 216 and the outer ring equivalent member 1 is sealed. The outer diameter of the large-diameter portion 224 in a free state is set to be slightly larger than the inner diameter of the outer end opening of the outer ring equivalent member 1, and the large diameter portion 224 is the outer end of the outer ring equivalent member 1. An internal fit can be fixed to the opening by an interference fit. Further, the support plate portion 223 has a substantially S-shaped cross-sectional shape, and approaches the rolling elements 10 and 10 installed in the space 13 as it goes inward in the diameter direction (downward in FIG. 5) (in FIG. 5). Inclined to the right.

On the other hand, the elastic member 217 constituting the sealing device 12b together with the cored bar 216 is insert-molded to the cored bar 216 and bonded and fixed by adhesion or the like. The outer peripheral edge portion of such an elastic member 217 covers the outer peripheral surface of the inclined portion 227. Also, the outer diameter of the portion of the elastic member 217 that covers the outer peripheral surface of the inclined portion 227 in a free state is set slightly larger than the inner diameter of the outer end opening of the outer ring equivalent member 1. In the state where the large-diameter portion 224 is fitted and fixed to the outer end opening, the portion of the elastic member 217 covering the outer peripheral surface of the inclined portion 227 is the outer peripheral surface of the inclined portion 227. And the inner peripheral surface of the outer end opening are elastically pressed to ensure the sealing performance of the portion.
Further, the base portion 226 of the elastic member 217 completely covers the outer surface (the left side surface in FIG. 5) of the support plate portion 223 over the entire circumference. Further, an outer diameter side, an inner diameter side, two side seal lips 218 and 219, and one radial seal lip 220 are formed on the outer surface and inner peripheral edge of the base portion 226, and two side seal lips 220 are formed. By tilting the seal lips 218 and 219 toward the outer edge in the diametrical direction (upward in FIG. 5) toward the tip edge (the left edge in FIG. 5), a function of preventing foreign matter from entering the space 13 is secured. ing. Further, the radial seal lip 220 is inclined in the direction toward the inner side (right side in FIG. 5) of the space 13 toward the tip edge (lower right edge in FIG. 3), thereby ensuring the grease leakage prevention function. ing. Conventionally, synthetic rubber such as NBR has been used as one of the materials of the elastic member.

  By the way, the sealing performance of the rolling bearing greatly depends on the material of the elastic member used for the seal 30 and the sealing devices 12a and 12b mentioned above. In recent years, there has been a demand for a seal that does not lose its sealing performance even in a cryogenic environment where the minimum temperature is -40 ° C. or lower, particularly in automobile bearings.

Patent Document 1 discloses that as a means for improving the cold resistance of a sealing material, NBR having an acrylonitrile amount (AN amount) of 25% or less is used for the seal to improve the cold resistance.
Patent Document 2 discloses that cold resistance is achieved by blending a plasticizer with a low AN amount of NBR.
Patent Document 3 discloses that NBR contains microcrystalline wax and paraffin wax to improve ozone resistance.

JP 2006-200616 A JP 2005-188556 A JP 2006-257327 A

  However, Patent Document 1 has a problem that ozone resistance is lowered while cold resistance is improved by lowering the AN amount. Patent Documents 2 and 3 describe that waxes are added to improve ozone resistance. However, in an extremely low temperature environment, the added wax hardly appears as a protective film on the seal surface, and is resistant to ozone. May decrease.

  Then, this invention makes it a subject to provide the rubber material composition excellent in both low temperature property and ozone resistance, and the sealing member for rolling devices.

In order to solve the above problems, the rubber material composition of the present invention is a rubber material composition in which a plasticizer, a wax, and an additive are blended with acrylonitrile butadiene rubber, and the wax is a microcrystalline wax and A wax mixture of paraffin wax, the acrylonitrile butadiene rubber has an acrylonitrile amount of 22-28%, the microcrystalline wax has a melting point of 50-90 ° C, and the paraffin wax has a melting point of 40-70 ° C, The wax mixture has a mixing ratio of microcrystalline wax and paraffin wax of 20:80 to 80:20, and the additive includes an anti-aging agent, a coupling agent, a pigment, a dye, a mold release agent, a processing aid, Selected from the group consisting of wear improvers, friction improvers and conductivity enhancers It is characterized in that the amount of the wax mixture is 3 to 8 phr.
In the rubber material composition of the present invention, the amount of the wax mixture is 8 phr when the amount of acrylonitrile butadiene rubber is 22%, and the amount of acrylonitrile of the acrylonitrile butadiene rubber is 26%. In the case, it is 4 phr, and when the amount of acrylonitrile of the acrylonitrile butadiene rubber is 28%, it is preferably 3 phr.
Further, the rolling device seal member of the present invention is a rolling device seal member mounted on a rolling device sealing device, the elastic member comprising an elastic material containing the rubber material composition, and the elastic member. A core bar fixed to the member is provided.

  According to the present invention, it is possible to obtain a rubber material composition having excellent ozone resistance while having extreme cold resistance. Further, there is an effect that a durable and long-life rolling device seal member can be obtained using the rubber material composition as a material.

  Embodiments of the present invention will be described below with reference to the drawings.

In the present invention, first, to improve the cold resistance of the rubber material, a low AN amount of NBR and a plasticizer excellent in cold resistance were selected and blended. Here, the plasticizer excellent in cold resistance indicates not only a low freezing point but also a high compatibility with NBR as the plasticizer itself. (By blending a plasticizer highly compatible with rubber, curing of the rubber can be suppressed even at temperatures below the freezing point of the plasticizer). However, as described above, when NBR with a low AN amount is used, ozone resistance is lowered. Since the bloom of wax on the rubber surface is effective for ozone resistance, as a result of intensive studies on the improvement of ozone resistance by wax, paraffin wax having a melting point of 40 ° C. to 70 ° C. and melting point of 50 ° C. to 90 ° C. By blending microcrystalline wax with paraffin wax: microcrystalline wax = 20: 80 to 80:20 in a proportion of 3 to 8 phr, better ozone resistance can be obtained than when the above two types of wax are blended individually. I found out.
The mechanism of ozone resistance obtained by the combined use of two waxes is not clearly understood, but is inferred as follows. In general, paraffin wax tends to bloom against diene rubbers such as NBR, but the durability of the membrane is poor, while microcrystalline wax takes time to bloom, but the formed membrane is relatively stable It is said. Inferring from these, first, paraffin wax quickly blooms to show excellent ozone resistance in the initial stage, and after a certain period of time, excellent ozone resistance is achieved by a durable film formed by microcrystalline wax. It is considered that the ozone resistance is excellent for a long period from the beginning. In addition, the reason why a paraffin wax having a melting point of 40 ° C. to 70 ° C. and a microcrystalline wax having a melting point of 50 ° C. to 90 ° C. can obtain a good result is that the wax having the above-mentioned characteristics has an optimal bloom resistance on the rubber surface. This is probably because the compatibility between the wax and rubber is optimal for ozone resistance. The degree of bloom (amount) of the wax on the rubber surface varies depending on the compatibility of the rubber and the wax. When the compatibility with rubber is good, the amount of bloom is small, and when it is bad, the amount of bloom is large. When the amount of bloom is small, the effect on the ozone resistance is low, and when it is large, the wax is deposited so as to sag and the appearance is deteriorated.
Acrylonitrile butadiene rubber (NBR), which is the base rubber of the rubber composition of the present invention, is obtained by copolymerizing butadiene and acrylonitrile, and the amount of acrylonitrile (AN amount) is preferably 22 to 28%. If the AN amount is less than 22%, the cold resistance is good, but the performances such as ozone resistance, heat resistance, and oil resistance are lowered. If the AN amount exceeds 28%, the required cold resistance cannot be obtained.

  As the plasticizer, a plasticizer having a low freezing point and good compatibility with NBR is used. In order to obtain sufficient cold resistance, the freezing point is preferably 0 ° C. or lower, more preferably −10 ° C. or lower. The compatibility with NBR is preferably such that the plasticizer solubility parameter (SP value) is 8.3 to 9.3, more preferably 8.5 to 9.0. Specific plasticizers having the above characteristics include dioctyl adipate (DOA), diisononyl adipate (DINA), dioctyl azelate (DOZ), and dioctyl sebacate (DOS) which are aliphatic dibasic ester plasticizers. In addition, phosphate ester plasticizers, ether ester plasticizers, and polyester plasticizers are preferably used. Moreover, as a compounding quantity of a plasticizer, 8-15phr is preferable. If the blending amount is less than 8 phr, the required cold resistance cannot be obtained. If the blending amount exceeds 15 phr, the hardness of the resulting rubber material may be insufficient.

  Two types of wax, paraffin wax and microcrystalline wax, are used in combination. In order to obtain an optimal amount of bloom on the rubber surface required for ozone resistance, the paraffin wax preferably has a melting point of 40 ° C. to 70 ° C., the microcrystalline wax preferably has a range of 50 ° C. to 90 ° C., and the paraffin wax has 45 More preferably, the microcrystalline wax is from 60 ° C to 80 ° C. In addition, the blending amount of the wax is preferably 3 to 8 phr in the range of the AN amount described above (22 to 28%), and if it is less than 3 phr, sufficient ozone resistance cannot be obtained, and more than 8 phr. When it mix | blends, there is too much precipitation amount of a wax and an external appearance will worsen. Further, since there is a correlation between the AN amount and ozone resistance, it is necessary to increase the amount of wax blended when the AN amount is low, and to reduce the blended amount of wax when the AN amount is high (for example, AN 8 phr when the amount is 22%, 3 phr when the amount is 28%). In addition, the blending ratio of paraffin wax and microcrystalline wax is preferably paraffin wax: microcrystalline wax = 20: 80 to 80:20, and more preferably 35:65 to 65:35.

In the acrylonitrile butadiene rubber composition, a silicate may be blended as a reinforcing material. Suitable silicates include kaolin clay (Al2O3 · 2SiO2 · 2H2O), calcined clay (Al2O3 · 2SiO2), rholite (Al2O3 · 4SiO2 · 2H2O), sericite (K2O · 3Al2O3 · 6SiO2 ·) for aluminum silicates. 2H2O), mica (K2O · 3Al2O3 · 6SiO2 · 2H2O), nepheline cinnite (Na2OK2O · Al2O3 · 2SiO2), hydrous aluminum silicate (Al2O3 · mSiO2 · nH2O) and the like, and silicates (3MgO · 4SiO2 · H2O) and the like, and calcium silicates include wollastonite (CaO.SiO2) and the like.
Of these, aluminum silicates are preferred. The kaolin clay is a fine particle size generally called hard clay (particle size 2 μm), considering the crystallinity of the particles and the activity of hydroxyl groups on the crystal surface.
The following are preferred) because they are more excellent in reinforcement. These silicates may be used alone or in combination.

Moreover, it is preferable to use carbon black as a reinforcing material in order to enhance the reinforcing effect. Carbon black is not particularly limited. For example, SAF (Super
Abrasion Furnace Black), ISAF (Intermediate Super Abbreviation Black), HAF (High)
Abrasion Furnace Black), MAF (Medium Abrasion Furnace Black), FEF (Fast Extracting Furnace)
black), GPF (General Purpose Furnace black), SRF (Simi-Reinforcing)
Examples include Furnace black, FT (Fine Thermal Furnace black), and MT (Medium Thermal Furnace black). Among these, HAF, MAF, FEF, GPF and SRF, which are excellent in balance between reinforcement and molding processability, are preferable, and FEF, GPF and SRF are particularly preferable.
When carbon black is used in combination with silicate, the amount of each acrylonitrile butadiene rubber composition is acrylonitrile butadiene rubber 100
It is preferable that the silicate is 10 to 150 parts by weight, the carbon black is 10 to 90 parts by weight, and the total amount is 20 to 240 parts by weight with respect to parts by weight. If the total blending amount is less than 20 parts by weight, a sufficient reinforcing effect cannot be obtained, and satisfactory results in wear resistance cannot be obtained. On the other hand, when the total blending amount exceeds 240 parts by weight, not only further improvement of the reinforcing property and wear resistance is not recognized, but also the molding processability is extremely lowered and the manufacturing becomes substantially difficult. Further, the hardness becomes too high, the elongation becomes low, and the original rubber elasticity is lowered.

  The acrylonitrile butadiene rubber composition is blended with a vulcanizing agent (crosslinking agent), a vulcanization aid, and a vulcanization acceleration aid for molding. Examples of the vulcanizing agent include powdered sulfur, sulfur white, precipitated sulfur, highly dispersible sulfur, morpholine disulfide, alkylphenol disulfide, N, N-dithio-bis (hexahydro-2H-azepinone-2), thiuram polysulfide, etc. Sulfur compounds capable of discharging sulfur, dicumyl peroxide, peroxides such as di (t-butylperoxy) diisopropylbenzene, 2,5-dimethylhexane, and benzoyl peroxide. Among them, it is preferable to use powdered sulfur, highly dispersible sulfur or morpholine disulfide from the viewpoints of dispersibility, ease of handling, and heat resistance. Examples of the vulcanization acceleration aid include metal oxides such as zinc oxide, metal carbonates, metal hydroxides, organic acids such as stearic acid and derivatives thereof, and amines. These vulcanization aids and activators may be used in combination of two or more, and are usually blended in an amount of 0.1 to 10 weights per 100 parts by weight of acrylonitrile butadiene rubber.

  Furthermore, an anti-aging agent, a coupling agent, a pigment, a dye, a mold release agent, a processing aid, a wear improver, a friction improver, a conductivity imparting agent, and the like can be added as necessary. Any of these may be known ones, but preferred examples are shown below. Examples of the antioxidant include amine / ketone condensation products, aromatic secondary amines, monophenol derivatives, bis or polyphenol derivatives, hydroquinone derivatives, sulfur-based antioxidants and phosphorus-based antioxidants. Among these, amine-ketone condensation product-based 2,2,4-trimethyl-1,2-dihydroquinoline polymer, condensation reaction product of diphenylamine and acetone, aromatic secondary amine-based N, N'- Di-β-naphthyl-p-phenylenediamine, 4,4′-bis- (α, α-dimethylbenzyl) diphenylamine, N-phenyl-N ′-(3-methacryloyloxy-2-hydroxypropyl), p-phenylene A diamine etc. can be mentioned.

In order to prevent thermal decomposition and improve heat resistance, it is more preferable to use a secondary anti-aging agent together with the anti-aging agent. Examples of the secondary antiaging agent include sulfur-based 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, and zinc salts thereof.
When it is necessary to improve the moldability, a higher fatty acid ester or a metal salt thereof can be appropriately added as a processing aid in order to improve the fluidity and releasability of the uncrosslinked rubber.
When referring to the physical properties, the hardness of the rubber composition is affected by the addition amount of the various additives listed above. However, from the viewpoint of hermeticity and followability when applied to seals and sealing devices, the hardness described in JISK6253 is described. The range of 50 to 90 is preferable on the spring hardness A scale. When the hardness is less than 50, the frictional resistance of the seal or the sealing device increases and the wear resistance decreases. Further, if the hardness exceeds 90, the rubber elasticity is lowered as described above, so that the sealing performance and followability of the lip portion of the seal and the sealing device are lowered, in a dusty environment or in a situation exposed to muddy water. If used, the life of the rolling bearing may be reduced.

  A method for obtaining a rubber composition using each of the above components is not particularly limited, but an acrylonitrile butadiene rubber (NBR), a plasticizer, and various additives, a rubber kneading roll, a pressure kneader, and a banbury. It is possible to knead uniformly using a conventionally known rubber kneading apparatus such as a mixer. Although the kneading conditions are not particularly limited, sufficient dispersion of various additives can be achieved by kneading usually at a temperature of 30 to 80 ° C. for 5 to 60 minutes. The molding conditions are not limited, and the kneaded product can be applied with a known rubber molding method such as compression molding, transfer molding, injection molding, etc., and is usually pressurized at 120 to 200 ° C. for about 30 seconds to 30 minutes. Vulcanization and further secondary vulcanization at 120 to 200 ° C. for about 10 minutes to 10 hours as necessary.

Hereinafter, the present invention will be described with reference to examples and comparative examples.
As shown in Tables 1 and 2, a rubber component, a vulcanizing agent and other additives are blended, and sufficiently kneaded with a rubber kneading roll. A crosslinked sheet was obtained through a vulcanization step by hot pressing for 10 minutes. The following evaluation was performed about the obtained rubber material.
(1) Evaluation of cold resistance The cold resistance was evaluated based on the glass transition temperature. A 10 mg sample for measurement was cut from the vulcanized rubber sheet, and the midpoint glass transition temperature was measured based on JISK7121.
(2) Ozone resistance evaluation Ozone resistance was measured according to JISK6259. The sample was stretched by 20% and exposed to an air atmosphere with an ozone concentration of 50 pphm. After 72 hours, the state of the sample was visually determined. The case where there are no cracks on the surface is “NC”, the case where there are few cracks is “A”, the case where there are a few cracks is “B”, the case where there are many cracks is “C”, "1" when it can be confirmed when it is doubled, "2" when it can be confirmed with the naked eye, "3" when the crack length is less than 1 mm, "4" when it is less than 3 mm and less than 3 mm, and "5" when it is more than 3 mm Further, the case of further cutting was evaluated on the basis of “cutting”. For example, if the number of cracks that can be confirmed with the naked eye is slightly large, “B-2” is set.
(3) Evaluation of heat resistance According to JISK6257, the hardness after hot air deterioration was measured at 120 ° C. for 70 hours, and the heat resistance was evaluated by comparing with the initial hardness.
In addition, the compounding agent described in the table | surface is as follows.
・ Rubber A: “Nipol” manufactured by ZEON
DN407 "(22% acrylonitrile content)
-Raw rubber B: "N240S" manufactured by JSR (26% acrylonitrile content)
・ Rubber C: “Nipol” manufactured by Nippon Zeon
DN2850 "(acrylonitrile content 28%)
・ Raw material D: “Nipol” manufactured by Nippon Zeon
DN1042 "(acrylonitrile content 33%)
・ Raw material E: “Nipol” manufactured by ZEON
DN401 "(18% acrylonitrile content)
・ Plasticizer A: Aliphatic dibasic acid ester type “DOA” manufactured by Daihachi Chemical
・ Plasticizer B: Polyether ester ADEKA "RS-107"
・ Anti-aging agent: “NOCRACK CD” manufactured by Ouchi Shinsei Chemical
Paraffin wax A: “PW-125” manufactured by Nippon Seiki Co., Ltd. Melting point: 53 ° C.
Paraffin wax B: “PW-115” manufactured by Nippon Seiki Co., Ltd. Melting point: 48 ° C.
-Paraffin wax C: Nippon Seiki "HNP-9" Melting point: 75 ° C
・ Microcrystalline wax: Seiko Chemical's "Santite R" Melting point: 75 ° C
・ Vulcanization accelerator A: “Noxeller TET” manufactured by Ouchi Shinsei Chemical
・ Vulcanization accelerator B: “Accel CZ-R” manufactured by Kawaguchi Chemical
Vulcanization accelerator auxiliary agent A: manufactured by Kao stearate "Lunac S-35"
・ Vulcanization acceleration aid B: Zinc oxide “French Law No. 1” manufactured by Sakai Chemical
・ Vulcanizing agent: Sulfur Tsurumi Chemical "Sulfax PMC"
・ Processing aid: “TE80” manufactured by Sanyo Trading
・ Coupling agent: Toshiba Silicone's “TSL8380”
・ Scorch inhibitor: "Vulcalent E / C" manufactured by LANXESS

  In Examples 1 to 6, by blending the AN amount, the microcrystalline wax amount, and the paraffin wax amount within the scope of the present invention, both the cold resistance and the ozone resistance are incompatible with each other. In addition, the balance with cold resistance is good. On the other hand, for Comparative Examples 1 to 7 in which any of the AN amount, the microcrystalline wax amount, and the paraffin wax amount is out of the scope of the present invention, Comparative Examples 1 to 5 are more ozone resistant than the Examples. Inferior, Comparative Example 6 is inferior in cold resistance, and Comparative Example 7 is inferior in heat resistance.

  INDUSTRIAL APPLICABILITY The present invention has industrial applicability as a rolling bearing sealing device having good sealing performance even in a low temperature environment of -40 ° C. or lower and having ozone resistance.

It is a figure which shows the cross section which shows an example of a rolling bearing with a seal. It is an enlarged view which shows the lip part periphery of FIG. The cross section which shows an example of the rolling bearing for wheels is shown. FIG. 4 is an enlarged view of one sealing device (12a) of the wheel rolling bearing shown in FIG. 3; FIG. 4 is an enlarged view of the other sealing device (12b) of the wheel rolling bearing shown in FIG. 3.

O Rolling bearing 1 Outer ring equivalent member 4 Inner ring equivalent member 10 Rolling element 11 Cage 12a
Sealing device 12b
Seal device 20 Rolling bearing with seal 21 Inner ring 22 Outer ring 30 Seal 31 Core metal 32 Elastic member 105
Core metal 106
Slinger 107
Elastic member 217
Elastic member

Claims (3)

A rubber material composition in which acrylonitrile butadiene rubber is blended with a plasticizer, a wax, and an additive ,
The wax is a wax mixture of microcrystalline wax and paraffin wax;
The acrylonitrile butadiene rubber has an acrylonitrile content of 22-28%,
The melting point of the microcrystalline wax is 50-90 ° C .;
The melting point of the paraffin wax is 40-70 ° C.,
The wax mixture has a blending ratio of microcrystalline wax and paraffin wax of 20:80 to 80:20,
The additive includes at least one selected from the group consisting of an anti-aging agent, a coupling agent, a pigment, a dye, a mold release agent, a processing aid, a wear improver, a friction improver, and a conductivity imparting agent,
A rubber material composition, wherein the amount of the wax mixture is 3 to 8 phr.   The rubber material composition according to claim 1, wherein the amount of the wax mixture is 8 phr when the acrylonitrile butadiene rubber has an acrylonitrile content of 22%, and the acrylonitrile butadiene rubber has an acrylonitrile content of 26 phr. %, It is 4 phr, and when the amount of acrylonitrile of the acrylonitrile butadiene rubber is 28%, the rubber material composition is 3 phr. A rolling device seal member mounted on a rolling device sealing device,
A rolling device seal member, comprising: an elastic member made of an elastic material containing the rubber material composition according to claim 1; and a core metal fixed to the elastic member.

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