JP5885131B2 - Cold resistant rubber composition - Google Patents
Cold resistant rubber composition Download PDFInfo
- Publication number
- JP5885131B2 JP5885131B2 JP2013271623A JP2013271623A JP5885131B2 JP 5885131 B2 JP5885131 B2 JP 5885131B2 JP 2013271623 A JP2013271623 A JP 2013271623A JP 2013271623 A JP2013271623 A JP 2013271623A JP 5885131 B2 JP5885131 B2 JP 5885131B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- mass
- parts
- sbr
- cold
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001971 elastomer Polymers 0.000 title claims description 158
- 239000005060 rubber Substances 0.000 title claims description 158
- 239000000203 mixture Substances 0.000 title claims description 53
- 244000043261 Hevea brasiliensis Species 0.000 claims description 78
- 229920003052 natural elastomer Polymers 0.000 claims description 77
- 229920001194 natural rubber Polymers 0.000 claims description 77
- 229920002857 polybutadiene Polymers 0.000 claims description 69
- 239000005062 Polybutadiene Substances 0.000 claims description 68
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 60
- 229920000459 Nitrile rubber Polymers 0.000 claims description 58
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 45
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 42
- 238000002156 mixing Methods 0.000 description 40
- 239000002174 Styrene-butadiene Substances 0.000 description 38
- 239000000853 adhesive Substances 0.000 description 15
- 230000001070 adhesive effect Effects 0.000 description 15
- 238000004073 vulcanization Methods 0.000 description 13
- 238000013329 compounding Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000013441 quality evaluation Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229920004411 Skyprene® Polymers 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- -1 ester compound Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L11/00—Compositions of homopolymers or copolymers of chloroprene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Springs (AREA)
- Fluid-Damping Devices (AREA)
Description
本発明は、鉄道車両用の空気バネ、特にそのダイヤフラム部等に使用されるゴム組成物であって、寒冷地での使用に耐えられる優れた耐寒性や耐オゾン性と、ゴム／ゴム貼合部における粘着性や接着性に優れるゴム組成物に関するものである。 The present invention relates to a rubber composition used for an air spring for a railway vehicle, particularly a diaphragm portion thereof, and has excellent cold resistance and ozone resistance that can withstand use in a cold region, and rubber / rubber bonding. It is related with the rubber composition excellent in the adhesiveness and adhesiveness in a part.
鉄道等の車両において、車輪から車両に加わる振動等を軽減し車両の乗り心地を良くするために、空気バネが使用されている。鉄道車両用の空気バネは、例えば特許文献１の図１〜４に表されるような構造を有し、ゴム製の内筒（下面板）、外筒（上面板）、内外筒間を密封するダイヤフラム部、デフレート時の車両の乗り心地の悪化を低減するために設けられる積層ゴム（ストッパゴム）等からなる。ダイヤフラム部は、複数のゴムシート及び補強コード（繊維コードで補強されたゴムシート）を貼り合せて形成され、圧縮された空気を密封する。そして、空気バネでは、このダイヤフラム部が主に緩衝機能を発揮して車両に加わる振動を軽減する。 In a vehicle such as a railway, an air spring is used in order to reduce vibration applied to the vehicle from wheels and improve the riding comfort of the vehicle. An air spring for a railway vehicle has a structure as shown in FIGS. 1 to 4 of Patent Document 1, for example, and seals between a rubber inner cylinder (lower surface plate), outer cylinder (upper surface plate), and inner and outer cylinders. And a laminated rubber (stopper rubber) provided in order to reduce deterioration of the riding comfort of the vehicle during deflation. The diaphragm portion is formed by bonding a plurality of rubber sheets and reinforcing cords (rubber sheets reinforced with fiber cords), and seals compressed air. And in an air spring, this diaphragm part mainly exhibits a buffer function, and reduces the vibration added to a vehicle.
鉄道車両は寒冷地で使用される場合もある。この場合空気バネには寒冷地での使用に耐えられる優れた耐寒性、例えば低温下でもゴム弾性の低下が小さく亀裂等が発生しない性質が望まれる。 Railway vehicles are sometimes used in cold regions. In this case, the air spring is desired to have excellent cold resistance that can be used in a cold region, for example, the property that the rubber elasticity is hardly lowered and cracks are not generated even at low temperatures.
特許文献２には、低温下においても十分な機械的強度を有する耐寒性の型物ゴム（パッキング、ガスケット、シール等）として、スチレンブタジエンゴム（ＳＢＲ）１００重量部、ヨウ素吸着量が８０〜１３０ｍｇ／ｇのカーボンブラック３０〜５０重量部、ナフテン系プロセスオイル１０〜３０重量部、硫黄１〜２重量部及び加硫促進剤を原料とする耐寒性ゴム（請求項１）が開示されている。ＳＢＲのみでは、耐寒性と機械的強度の両立が難しいが、ヨウ素吸着量が前記範囲のカーボンブラックを使用することにより、又、加硫促進剤としてスルフェンアミド系促進剤等の遅効性促進剤を含有するものを用いることにより、機械的強度を低下させることなく耐寒性を向上できると述べられている。さらに、天然ゴム（ＮＲ）、ブタジエンゴム（ＢＲ）、クロロプレンゴム（ＣＲ）等を配合してもよいと述べられている。 In Patent Document 2, as a cold-resistant mold rubber (packing, gasket, seal, etc.) having sufficient mechanical strength even at low temperatures, 100 parts by weight of styrene butadiene rubber (SBR), and iodine adsorption amount is 80 to 130 mg. A cold-resistant rubber (Claim 1) using 30 to 50 parts by weight of carbon black / g, 10 to 30 parts by weight of naphthenic process oil, 1 to 2 parts by weight of sulfur and a vulcanization accelerator is disclosed. Although it is difficult to achieve both cold resistance and mechanical strength with SBR alone, by using carbon black having an iodine adsorption amount in the above range, a slow-acting accelerator such as a sulfenamide accelerator as a vulcanization accelerator It is stated that cold resistance can be improved without lowering the mechanical strength by using a material that contains. Furthermore, it is stated that natural rubber (NR), butadiene rubber (BR), chloroprene rubber (CR) and the like may be blended.
耐寒性に優れた空気バネ用ゴム組成物としては、ＮＲ／ポリブタジエンゴム（ＢＲ）混合ゴム（混合比はＮＲ≦ＢＲ）を挙げることができる。そして、特許文献３には、ＮＲ及びＢＲを主成分とするゴム成分を含有する空気バネ用ゴム組成物に、さらにエチレン・α−オレフィン・ジエン共重合体ゴム（ＥＰＤＭ）を所定量含有させたゴム組成物が開示されており、又、特許文献４には、ＮＲ及びＢＲを主成分とするゴム成分を含有する空気バネ用ゴム組成物に、さらにポリクロロプレンゴム（ＣＲ）を所定量含有するゴム組成物が開示されている。これらはいずれも、耐寒性に優れたＮＲ／ＢＲ混合ゴム（混合比はＮＲ≦ＢＲ）をベースとし、耐オゾン性を補うためにＥＰＤＭ又はＣＲを所定量配合したものである。その結果、耐寒性に優れかつ耐オゾン性にも優れた空気バネ用ゴム組成物が得られるとされている。 Examples of the air spring rubber composition having excellent cold resistance include NR / polybutadiene rubber (BR) mixed rubber (mixing ratio is NR ≦ BR). In Patent Document 3, a predetermined amount of ethylene / α-olefin / diene copolymer rubber (EPDM) is further added to a rubber composition for an air spring containing a rubber component mainly composed of NR and BR. A rubber composition is disclosed, and Patent Document 4 contains a predetermined amount of polychloroprene rubber (CR) in addition to a rubber composition for an air spring containing a rubber component mainly composed of NR and BR. A rubber composition is disclosed. These are all based on NR / BR mixed rubber (mixing ratio is NR ≦ BR) excellent in cold resistance and blended with a predetermined amount of EPDM or CR in order to supplement ozone resistance. As a result, it is said that a rubber composition for air springs having excellent cold resistance and ozone resistance can be obtained.
しかし、特許文献２〜４に開示されているゴム（組成物）は、動的オゾン劣化試験（ＪＩＳ Ｋ６２５９）による耐オゾン性は不十分であり、より耐オゾン性の向上が望まれていた。ここで、動的オゾン劣化試験とは、繰り返しひずみを与えながら一定濃度のオゾンを含む空気中に試験片を曝露した時のゴムの亀裂の発生状態を評価するものであり、実際の使用条件に近い環境での評価である（特許文献３、４における耐オゾン性試験は、実際の使用条件に必ずしも対応しない静的オゾン劣化試験と考えられる）。そこで、以下「耐オゾン性」とは、この動的耐オゾン性を言う。又、単に「耐寒性」と言うときは、低温下でもゴム弾性の低下が小さく亀裂等が発生しない性質、具体的にはＪＩＳ Ｋ６２６１で測定される脆化温度が−５５℃以下であることを言う。 However, the rubber (composition) disclosed in Patent Documents 2 to 4 has insufficient ozone resistance according to a dynamic ozone deterioration test (JIS K6259), and further improvement in ozone resistance has been desired. Here, the dynamic ozone degradation test evaluates the state of cracking of rubber when a test piece is exposed to air containing ozone at a constant concentration while repeatedly applying strain. This is an evaluation in a near environment (the ozone resistance test in Patent Documents 3 and 4 is considered to be a static ozone deterioration test that does not necessarily correspond to actual use conditions). Therefore, hereinafter, “ozone resistance” refers to this dynamic ozone resistance. Further, when simply saying “cold resistance”, it means that the rubber elasticity is small and cracks do not occur even at low temperatures, specifically, the embrittlement temperature measured by JIS K6261 is −55 ° C. or less. Say .
空気バネのダイヤフラム部は、複数のゴムシート及び補強コードを貼り合わせて形成された後、加硫して形成される。そこで、空気バネ使用時にゴムシート間の剥がれが生じないように、加硫後のゴムシート間の強い接着力（ゴム／ゴム接着力）が望まれている。特に、低温下ではダイヤフラムのゴム／ゴム貼合部に応力が集中し剥がれが生じ易いと考えられるため、ゴム／ゴム接着力の強化が望まれている。又、ダイヤフラム部の製造において、加硫工程の前すなわち未加硫ゴムシートを貼り合わせて所定の形状に整える工程で、ゴム／ゴム間が剥がれぬよう仮止めさせる必要があり、未加硫状態でのゴム／ゴム間の優れた「粘着性」（一時的な接着力）も望まれる。 The diaphragm portion of the air spring is formed by bonding a plurality of rubber sheets and reinforcing cords and then vulcanizing. Therefore, a strong adhesive force (rubber / rubber adhesive force) between the rubber sheets after vulcanization is desired so that peeling between the rubber sheets does not occur when using an air spring. In particular, it is considered that stress concentrates on the rubber / rubber bonding portion of the diaphragm at a low temperature, and peeling is likely to occur. Therefore, reinforcement of the rubber / rubber adhesion is desired. Also, in the manufacture of the diaphragm part, it is necessary to temporarily fix the rubber / rubber between the unvulcanized state before the vulcanization process, that is, in the process of pasting the unvulcanized rubber sheet and adjusting it to a predetermined shape. Excellent “tackiness” (temporary adhesion) between rubber / rubber is also desired.
本発明は、寒冷地で使用される車両用空気バネに好適に使用できるゴム組成物であって、（動的オゾン劣化試験で表される）耐オゾン性及び耐寒性が共に優れるとともに、さらにゴム／ゴム接着力及び粘着性にも優れるゴム組成物を提供することを課題とする。 The present invention relates to a rubber composition that can be suitably used for a vehicle air spring used in a cold region, and is excellent in both ozone resistance and cold resistance (expressed by a dynamic ozone deterioration test), and further rubber. It is an object to provide a rubber composition having excellent rubber adhesion and tackiness.
本発明の第１の態様は、ブタジエンゴム（ＢＲ）、天然ゴム（ＮＲ）及びクロロプレンゴム（ＣＲ）を含有し、前記ＢＲ、ＮＲ及びＣＲの合計１００質量部に対し、ＢＲが１０〜３５質量部、ＮＲが１０〜３５質量部及びＣＲが５０〜７５質量部含有されている耐寒性ゴム組成物である。 1st aspect of this invention contains a butadiene rubber (BR), natural rubber (NR), and chloroprene rubber (CR), and BR is 10-35 mass with respect to a total of 100 mass parts of said BR, NR, and CR. Part, NR is 10 to 35 parts by mass, and CR is 50 to 75 parts by mass.
本発明の第２の態様は、ＢＲ、ＮＲ及びＣＲ、並びに、スチレンブタジエンゴム（ＳＢＲ）及びニトリルゴム（アクリロニトリルブタジエンゴム：ＮＢＲ）からなる群より選ばれる少なくとも一つを含有し、前記ＢＲ、ＮＲ、ＣＲ、ＳＢＲ及びＮＢＲの合計１００質量部に対し、ＢＲの含有量が１０〜３５質量部、ＣＲの含有量が５０〜７５質量部、ＮＲ、ＳＢＲ及びＮＢＲの合計含有量が１０〜３５質量部であり、ＮＲ、ＳＢＲ及びＮＢＲの合計含有量に対し、ＳＢＲ及びＮＢＲの含有量が１０〜６０質量％である耐寒性ゴム組成物である。 A second aspect of the present invention contains BR, NR and CR, and at least one selected from the group consisting of styrene butadiene rubber (SBR) and nitrile rubber (acrylonitrile butadiene rubber: NBR). The content of BR is 10 to 35 parts by mass, the content of CR is 50 to 75 parts by mass, and the total content of NR, SBR and NBR is 10 to 35 parts by mass with respect to a total of 100 parts by mass of CR, SBR and NBR. Part, and is a cold resistant rubber composition in which the content of SBR and NBR is 10 to 60% by mass with respect to the total content of NR, SBR and NBR.
本発明の第１の態様によれば、耐オゾン性及び耐寒性に共に優れ、さらに空気バネの製造時におけるゴム／ゴム間の粘着性及びゴム／ゴム接着力にも優れ、寒冷地で使用される車両用空気バネの製造に好適に使用できるゴム組成物が提供される。 According to the first aspect of the present invention, both the ozone resistance and the cold resistance are excellent, and further, the rubber / rubber adhesiveness and the rubber / rubber adhesive force at the time of manufacturing the air spring are excellent, and it is used in a cold region. A rubber composition that can be suitably used for the manufacture of a vehicle air spring is provided.
本発明の第２の態様によれば、耐オゾン性、耐寒性及び粘着性が共に優れるとともに、ゴム／ゴム接着力が（前記第１の態様よりも）さらに優れるゴム組成物が提供される。従って、このゴム組成物を空気バネの形成に適用すると、耐オゾン性、耐寒性及びゴム／ゴム間の優れた粘着性とともに、加硫後のダイヤフラムのゴム間の剥がれを抑制するさらに強いゴム／ゴム接着力を与えることができるので、寒冷地で使用される車両用空気バネの製造により好適に適用できる。 According to the second aspect of the present invention, there is provided a rubber composition which is excellent in both ozone resistance, cold resistance and adhesiveness, and further excellent in rubber / rubber adhesion (as compared with the first aspect). Therefore, when this rubber composition is applied to the formation of an air spring, ozone / cold resistance and excellent adhesiveness between rubber / rubber, as well as stronger rubber / Since rubber adhesive force can be given, it can be suitably applied to the manufacture of a vehicle air spring used in cold regions.
以下、第１の態様、第２の態様について実施するための形態を、具体例等に基づき説明するが第１の態様、第２の態様の発明は、これらの形態や具体例に限定されるものではなく、特許請求の範囲によって示され、特許請求の範囲と均等の意味および範囲内でのすべての変更が含まれる。 Hereinafter, modes for carrying out the first mode and the second mode will be described based on specific examples and the like, but the inventions of the first mode and the second mode are limited to these modes and specific examples. It is intended to be defined by the following claims, and includes all modifications that are equivalent in meaning and within the scope of the claims.
本発明者は鋭意検討の結果、ＢＲ、ＮＲ及びＣＲを混合したゴム組成物であって、ＣＲを主体とし、それぞれの混合比を所定の範囲内とすることにより、耐オゾン性及び耐寒性に共に優れ、さらにゴム／ゴム接着力及びゴム／ゴム間の粘着性にも優れるゴムが得られることを見出し、第一の態様の本発明を完成した。 As a result of intensive studies, the inventor is a rubber composition in which BR, NR, and CR are mixed, and the main component is CR, and the mixing ratio is within a predetermined range, thereby improving ozone resistance and cold resistance. It was found that a rubber excellent in both, rubber / rubber adhesive strength and rubber / rubber adhesion was obtained, and the present invention of the first aspect was completed.
本発明者はさらに、前記のＢＲ、ＮＲ及びＣＲを、所定の範囲内の混合比で混合したゴム組成物において、ＮＲの一部をＳＢＲ又はＮＢＲで置き換えることにより、優れた耐オゾン性、耐寒性及びゴム／ゴム間の粘着性を保ちながら、ゴム／ゴム接着力がさらに向上することを見出し、第２の態様の本発明を完成した。 Furthermore, the present inventor further has excellent ozone resistance and cold resistance by replacing a part of NR with SBR or NBR in a rubber composition in which the above-mentioned BR, NR and CR are mixed at a mixing ratio within a predetermined range. The rubber / rubber adhesive strength was further improved while maintaining the rubber properties and the rubber / rubber adhesiveness, and the second aspect of the present invention was completed.
（１）第１の態様のゴム組成物について
本発明の第１の態様は、ＢＲ、ＮＲ及びＣＲを含有し、前記ＢＲ、ＮＲ及びＣＲの合計１００質量部に対し、ＢＲが１０〜３５質量部、ＮＲが１０〜３５質量部及びＣＲが５０〜７５質量部含有されている耐寒性ゴム組成物である。
(1) About rubber composition of 1st aspect 1st aspect of this invention contains BR, NR, and CR, and BR is 10-35 mass with respect to a total of 100 mass parts of said BR, NR, and CR. Part, NR is 10 to 35 parts by mass, and CR is 50 to 75 parts by mass.
本発明の第１の態様のゴム組成物は、ＢＲ、ＮＲ及びＣＲを上記の範囲の組成比で混合したことを特徴とする。この特徴により、優れた耐オゾン性及び耐寒性が得られる。また、粘着性に優れる。従って、ゴムを貼合わせる際に十分な粘着力で仮止めできるため、空気バネの製造等における成形性に優れる。 The rubber composition according to the first aspect of the present invention is characterized in that BR, NR, and CR are mixed at a composition ratio in the above range. Due to this feature, excellent ozone resistance and cold resistance can be obtained. Moreover, it is excellent in adhesiveness. Therefore, since it can be temporarily fixed with sufficient adhesive force when the rubber is bonded, it is excellent in moldability in the production of an air spring or the like.
ＢＲとは、ブタジエンの重合により得られる合成ゴムである。ＢＲには、シス−１，４結合の割合が大きい高シス型、シス−１，４結合の割合が比較的小さい低シス型、高シス型−シンジオタクチックポリブタジエン複合体等があり、いずれも好適に使用することができる。中でも、ガラス転移温度（Ｔｇ）が−９５〜−１１０℃と極めて低い高シス型ＢＲが好ましい。 BR is a synthetic rubber obtained by polymerization of butadiene. BR includes a high cis type having a large ratio of cis-1,4 bonds, a low cis type having a relatively small ratio of cis-1,4 bonds, and a high cis-syndiotactic polybutadiene complex. It can be preferably used. Among them, a high cis type BR having an extremely low glass transition temperature (Tg) of −95 to −110 ° C. is preferable.
高シス型のＢＲとしては、例えば、ＪＳＲ ＢＲ０１（ＪＳＲ社製）、ニポールＢＲ１２２０（日本ゼオン社製）、ウベポールＢＲ１５０（宇部興産社製）等、低シス型のＢＲとしては、ニポールＢＲ１２５０Ｈ（日本ゼオン社製）、ジエンＮＦ３５Ｒ（旭化成社製）等、高シス型−シンジオタクチックポリブタジエン複合体としては、ウベポールＶＣＲ４１２（宇部興産社製）等の商品名で販売しているものを用いることができる。 Examples of the high cis type BR include JSR BR01 (manufactured by JSR), Nipol BR1220 (manufactured by Nippon Zeon Co., Ltd.), Ubepol BR150 (manufactured by Ube Industries, Ltd.), and the like. As a high cis-syndiotactic polybutadiene complex such as diene NF35R (manufactured by Asahi Kasei Co., Ltd.), those sold under a trade name such as Ubepol VCR412 (manufactured by Ube Industries) can be used.
また、ＮＲとは、ゴムの木の樹液（ラテックス）によって作られ、シス−ポリイソプレンを主成分とするゴムである。ＮＲとしては、ＲＳＳ＃１、ＲＳＳ＃３等を用いることができ、素練りをして粘度を適宜調整したものを使用する。ＣＲとは、クロロプレンの重合によって得られ、ネオプレン（登録商標）等の商品名で販売されている合成ゴムである。ＣＲとしては、メルカプタン変性タイプ、キサントゲン変性タイプ、硫黄変性タイプがあり、いずれも用いることができる。特に、結晶化速度の遅いものが耐寒性に好適であり、例えばショウプレンＷＲＴ（昭和電工社製）、スカイプレンＢ−５Ａ（東ソー社製）、デンカクロロプレンＳ―４０Ｖ（電気化学工業社製）等の商品名で販売しているものを用いることができる。 NR is a rubber made of rubber tree sap (latex) and mainly composed of cis-polyisoprene. As NR, RSS # 1, RSS # 3, etc. can be used, and what kneaded and adjusted the viscosity suitably is used. CR is a synthetic rubber obtained by polymerization of chloroprene and sold under a trade name such as Neoprene (registered trademark). As CR, there are a mercaptan-modified type, a xanthogen-modified type, and a sulfur-modified type, and any of them can be used. In particular, those having a low crystallization rate are suitable for cold resistance. For example, Shopreen WRT (manufactured by Showa Denko KK), Skyprene B-5A (manufactured by Tosoh Corporation), Denka Chloroprene S-40V (manufactured by Denki Kagaku Kogyo Co., Ltd.), etc. Those sold under the trade name of can be used.
第１の態様のゴム組成物において、ＣＲの配合比はＢＲ、ＮＲ及びＣＲの合計１００質量部に対し５０〜７５質量部の範囲である。ＣＲの配合比が５０質量部未満の場合には、動的な耐オゾン性が低下し優れた耐オゾン性が得られにくくなる。一方、配合比が７５質量部を越える場合、ＢＲやＮＲを十分量配合できず、耐寒性が低下（脆化温度が上昇）し気温−４０〜−５０℃の極寒地でも使用可能なレベルの脆化温度（−６０℃以下）が得られにくくなる。 In the rubber composition of the first aspect, the compounding ratio of CR is in the range of 50 to 75 parts by mass with respect to 100 parts by mass of BR, NR and CR in total. When the blending ratio of CR is less than 50 parts by mass, dynamic ozone resistance is lowered and it becomes difficult to obtain excellent ozone resistance. On the other hand, when the blending ratio exceeds 75 parts by mass, a sufficient amount of BR or NR cannot be blended, the cold resistance is lowered (the embrittlement temperature is increased), and the level is such that it can be used even in extremely cold regions where the temperature is -40 to -50 ° C. It becomes difficult to obtain an embrittlement temperature (−60 ° C. or less).
第１の態様のゴム組成物において、ＢＲの配合比はＢＲ、ＮＲ及びＣＲの合計１００質量部に対し１５〜３０質量部の範囲である。ＢＲの配合比が１５質量部未満の場合には、（ＣＲの配合比が５０〜７５質量部の範囲の場合でも）耐寒性が低下（脆化温度が上昇）し、−６０℃以下の脆化温度が得られにくくなる。また、ゴム／ゴム接着力も低下する。一方、配合比が３０質量部を越える場合には、ＮＲの配合比を小さくする必要があり、粘着性が低下する。 In the rubber composition of the first aspect, the blending ratio of BR is in the range of 15 to 30 parts by mass with respect to 100 parts by mass in total of BR, NR and CR. When the blending ratio of BR is less than 15 parts by mass (even when the blending ratio of CR is in the range of 50 to 75 parts by mass), the cold resistance is lowered (the embrittlement temperature is increased), and the brittleness is −60 ° C. or less. It becomes difficult to obtain the crystallization temperature. Also, the rubber / rubber adhesion is reduced. On the other hand, when the blending ratio exceeds 30 parts by mass, it is necessary to reduce the blending ratio of NR, and the adhesiveness is lowered.
第１の態様のゴム組成物において、ＮＲの配合比はＢＲ、ＮＲ及びＣＲの合計１００質量部に対し１０〜３５質量部の範囲である。ＮＲの配合比が１０質量部未満の場合には粘着性が低下する。一方、配合比が３５質量部を越える場合は（ＣＲの配合比が５０〜７５質量部の範囲の場合では、ＢＲの配合比を小さくする必要があり）耐寒性が低下（脆化温度が上昇）し、−６０℃以下の脆化温度が得られにくくなる。 In the rubber composition of the first aspect, the compounding ratio of NR is in the range of 10 to 35 parts by mass with respect to 100 parts by mass in total of BR, NR and CR. When the blending ratio of NR is less than 10 parts by mass, the tackiness is lowered. On the other hand, when the compounding ratio exceeds 35 parts by mass (when the compounding ratio of CR is in the range of 50 to 75 parts by mass, it is necessary to reduce the compounding ratio of BR), cold resistance decreases (the embrittlement temperature increases). ) And an embrittlement temperature of −60 ° C. or less becomes difficult to obtain.
（２）第２の態様のゴム組成物について
本発明の第２の態様は、ＢＲ、ＮＲ及びＣＲ、並びに、ＳＢＲ及びＮＢＲからなる群より選ばれる少なくとも一つを含有し、前記ＢＲ、ＮＲ、ＣＲ、ＳＢＲ及びＮＢＲの合計１００質量部に対し、ＢＲの含有量が１０〜３５質量部、ＣＲの含有量が５０〜７５質量部、ＮＲ、ＳＢＲ及びＮＢＲの合計含有量が１０〜３５質量部であり、ＮＲ、ＳＢＲ及びＮＢＲの合計含有量に対し、ＳＢＲ及びＮＢＲの含有量が１０〜６０質量％である耐寒性ゴム組成物である。
(2) About the rubber composition of the second aspect The second aspect of the present invention contains at least one selected from the group consisting of BR, NR and CR, and SBR and NBR, and the BR, NR, For a total of 100 parts by mass of CR, SBR and NBR, the BR content is 10 to 35 parts by mass, the CR content is 50 to 75 parts by mass, and the total content of NR, SBR and NBR is 10 to 35 parts by mass. It is a cold resistant rubber composition in which the content of SBR and NBR is 10 to 60% by mass with respect to the total content of NR, SBR and NBR.
前記のように、空気バネのダイヤフラム部は、複数のゴムシート及び補強コードを貼り合わせて形成されるので空気バネ使用時にゴム間の剥がれが生じないようにゴムシート間の強い接着力（ゴム／ゴム接着力）が望まれている。鉄道車両の設計や種類によってはダイヤフラムへの負荷が大きいものもあることから、ゴム／ゴム接着力は高ければ高い程好ましい。 As described above, the diaphragm portion of the air spring is formed by laminating a plurality of rubber sheets and reinforcing cords, so that a strong adhesive force between the rubber sheets (rubber / Rubber adhesion) is desired. Depending on the design and type of the railway vehicle, there are cases where the load on the diaphragm is large. Therefore, the higher the rubber / rubber adhesion is, the better.
ゴム／ゴム接着力を上げる方法として、ベースのゴムを接着力の良い材料に変える方法が考えられる。しかし、公知の接着力の良い材料を用いると、優れた耐寒性、粘着性が得られない。又、ＢＲ／ＮＲ／ＣＲからなるゴム組成物において、ＮＲの比率を減らしＢＲの比率を増やすことにより、耐寒性等を保持しながら接着力を向上させることができるが、この場合は粘着性が弱く成形が困難になるとの問題があった。このように従来の耐寒性ゴムには、耐オゾン性、粘着性及びゴム／ゴム接着力の全てを満足させるものはなかった。 As a method of increasing the rubber / rubber adhesion, a method of changing the base rubber to a material having good adhesion can be considered. However, when a known material having a good adhesive strength is used, excellent cold resistance and tackiness cannot be obtained. Moreover, in the rubber composition composed of BR / NR / CR, by reducing the NR ratio and increasing the BR ratio, it is possible to improve the adhesive force while maintaining the cold resistance and the like. There was a problem that it was weak and difficult to mold. Thus, none of the conventional cold resistant rubbers satisfy all of ozone resistance, tackiness and rubber / rubber adhesion.
本発明者は、前記の第１の態様のゴム組成物、すなわち前記の耐寒性、耐オゾン性に優れるゴム配合におけるＮＲの一部をＳＢＲ又はＮＢＲに置き換えることで、「耐寒性」、「耐オゾン性」、「粘着性」を維持したまま「ゴム／ゴム接着力」をさらに向上できることを見出し、第２の態様の発明を完成したのである。 The present inventor replaces a part of NR in the rubber composition of the first aspect, that is, the rubber compound excellent in cold resistance and ozone resistance with SBR or NBR, thereby obtaining “cold resistance”, “resistance to resistance”. The inventors have found that “rubber / rubber adhesion” can be further improved while maintaining “ozone property” and “tackiness”, and have completed the invention of the second aspect.
ＳＢＲは、スチレンとブタジエンとの共重合体である。ＳＢＲには、乳化重合ＳＢＲ（Ｅ−ＳＢＲ）や溶液重合ＳＢＲ（Ｓ−ＳＢＲ）があり、いずれも好適に使用することができるが、ガラス転移温度（Ｔｇ）の低い、結合スチレン量が低めのものがより好ましい。ＳＢＲとしては、例えば、ニポール１５０２（日本ゼオン社製）、ニポールＮＳ６１２（日本ゼオン社製）、ＪＳＲ １５００（ＪＳＲ社製）等の商品名で販売されているものを用いることができる。 SBR is a copolymer of styrene and butadiene. SBR includes emulsion polymerization SBR (E-SBR) and solution polymerization SBR (S-SBR), both of which can be suitably used, but have a low glass transition temperature (Tg) and a low amount of bound styrene. Those are more preferred. As SBR, what is marketed by brand names, such as Nipol 1502 (made by Nippon Zeon), Nipol NS612 (made by Nippon Zeon), JSR 1500 (made by JSR), can be used, for example.
ＮＢＲは、アクリロニトリルとブタジエンとの共重合体であり、銘柄によらず好適に使用することができるが、ガラス転移温度（Ｔｇ）の低い、結合アクリロニトリル量が低めのものがより好ましい。ＮＢＲとしては、例えば、ニポール１０４３（日本ゼオン社製）、ニポールＤＮ４０１ＬＬ（日本ゼオン社製）、ＪＳＲ Ｎ２５０ＳＬ（ＪＳＲ社製）等の商品名で販売しているものを用いることができる。 NBR is a copolymer of acrylonitrile and butadiene, and can be suitably used regardless of the brand, but more preferably has a low glass transition temperature (Tg) and a low amount of bound acrylonitrile. As NBR, what is marketed with brand names, such as Nipol 1043 (made by Nippon Zeon), Nipole DN401LL (made by Nippon Zeon), JSR N250SL (made by JSR), can be used, for example.
前記の第１の態様のゴム組成物を構成するＮＲの一部をＳＢＲやＮＢＲに置き換えることにより「ゴム／ゴム接着力」を向上させることができる。ＳＢＲやＮＢＲは、ＮＲに比べると粘着性がやや劣るが、ＮＲをＳＢＲやＮＢＲで置き換える割合が所定の範囲内であれば、粘着性を維持したままゴム／ゴム接着力を向上させることができる。 “Rubber / rubber adhesion” can be improved by replacing part of NR constituting the rubber composition of the first aspect with SBR or NBR. SBR and NBR are slightly inferior in tack to NR, but if the ratio of replacing NR with SBR or NBR is within a predetermined range, the rubber / rubber adhesion can be improved while maintaining the tack. .
第２の態様のゴム組成物において、ＣＲの配合比は、ＢＲ、ＮＲ、ＣＲ、ＳＢＲ及びＮＢＲの合計１００質量部に対し、５０〜７５質量部の範囲である。ＣＲの配合比が５０質量部未満の場合には、動的な耐オゾン性が低下し優れた耐オゾン性が得られにくくなる。一方、配合比が７５質量部を越える場合、ＢＲやＮＲ等を十分量配合できず、耐寒性が低下（脆化温度が上昇）し、−６０℃以下の脆化温度が得られにくくなる。 In the rubber composition according to the second aspect, the compounding ratio of CR is in the range of 50 to 75 parts by mass with respect to 100 parts by mass in total of BR, NR, CR, SBR and NBR. When the blending ratio of CR is less than 50 parts by mass, dynamic ozone resistance is lowered and it becomes difficult to obtain excellent ozone resistance. On the other hand, when the blending ratio exceeds 75 parts by mass, a sufficient amount of BR, NR or the like cannot be blended, the cold resistance is lowered (the embrittlement temperature is increased), and an embrittlement temperature of −60 ° C. or less is hardly obtained.
第２の態様のゴム組成物において、ＢＲの配合比は、ＢＲ、ＮＲ、ＣＲ、ＳＢＲ及びＮＢＲの合計１００質量部に対し、１０〜３５質量部の範囲であり、好ましくは１５〜３０質量部の範囲である。ＢＲの配合比が１０質量部未満の場合には、（ＣＲの配合比が５０〜７５質量部の範囲の場合でも）耐寒性が低下（脆化温度が上昇）し、−６０℃以下の脆化温度が得られにくくなる。一方、配合比が３５質量部を越える場合には、ＮＲ、ＳＢＲ及びＮＢＲの合計の配合比を小さくする必要があり粘着性が低下する。 In the rubber composition of the second aspect, the blending ratio of BR is in the range of 10 to 35 parts by mass, preferably 15 to 30 parts by mass with respect to 100 parts by mass in total of BR, NR, CR, SBR and NBR. Range. When the blending ratio of BR is less than 10 parts by mass (even when the blending ratio of CR is in the range of 50 to 75 parts by mass), the cold resistance is lowered (the embrittlement temperature is increased), and the brittleness is −60 ° C. or less. It becomes difficult to obtain the crystallization temperature. On the other hand, when the blending ratio exceeds 35 parts by mass, it is necessary to reduce the total blending ratio of NR, SBR, and NBR, and the tackiness is lowered.
第２の態様のゴム組成物において、ＮＲ、ＳＢＲ及びＮＢＲの合計の配合比は、ＢＲ、ＮＲ、ＣＲ、ＳＢＲ及びＮＢＲの合計１００質量部に対し、１０〜３５質量部の範囲であり、好ましくは１５〜３０質量部の範囲である。ＮＲ、ＳＢＲ及びＮＢＲの合計の配合比が１０質量部未満の場合には粘着性が低下する。一方、合計の配合比が３５質量部を越える場合は（ＣＲの配合比が５０〜７５質量部の範囲の場合では、ＢＲの配合比を小さくする必要があり）耐寒性が低下（脆化温度が上昇）し、−６０℃以下の脆化温度が得られにくくなる。 In the rubber composition of the second aspect, the total compounding ratio of NR, SBR and NBR is in the range of 10 to 35 parts by mass with respect to 100 parts by mass of BR, NR, CR, SBR and NBR, preferably Is in the range of 15-30 parts by mass. When the total compounding ratio of NR, SBR and NBR is less than 10 parts by mass, the tackiness is lowered. On the other hand, when the total blending ratio exceeds 35 parts by mass (when the blending ratio of CR is in the range of 50 to 75 parts by mass, it is necessary to reduce the blending ratio of BR), cold resistance decreases (embrittlement temperature). Increases), and it becomes difficult to obtain an embrittlement temperature of -60 ° C or lower.
第２の態様のゴム組成物において、ＳＢＲ及びＮＢＲの合計の含有量は、ＮＲ、ＳＢＲ及びＮＢＲの合計含有量に対し１０〜６０質量％である。ＮＲの１０〜６０質量％をＳＢＲ、ＮＢＲ、又はＳＢＲ及びＮＢＲに置き換えることにより、「ゴム／ゴム接着力」をさらに高めることができる。 In the rubber composition of the second aspect, the total content of SBR and NBR is 10 to 60% by mass with respect to the total content of NR, SBR and NBR. By replacing 10 to 60% by mass of NR with SBR, NBR, or SBR and NBR, the “rubber / rubber adhesion” can be further increased.
ＳＢＲ及びＮＢＲの含有量が、ＮＲ、ＳＢＲ及びＮＢＲの合計含有量に対し１０質量％未満の場合は「ゴム／ゴム接着力」の向上効果が小さく、ＳＢＲ及びＮＢＲの含有量が、６０質量％を超える場合は、ゴムの粘着性が不十分となる場合がある。 When the content of SBR and NBR is less than 10% by mass relative to the total content of NR, SBR and NBR, the effect of improving “rubber / rubber adhesion” is small, and the content of SBR and NBR is 60% by mass. If it exceeds 1, the tackiness of the rubber may be insufficient.
（３）添加剤等について
第１の態様、第２の態様のいずれのゴム組成物についても、上記の必須の組成に加えて必要に応じ、発明の趣旨を損ねない範囲で、添加剤等の他の成分を配合することができる。この他の成分としては、カーボンやシリカ等の補強充填剤、加硫剤、加硫促進剤、加硫促進助剤、加硫遅延剤、老化防止剤、可塑剤、シランカップリング剤等を挙げることができる。なお、低温流動性に優れるエステル化合物（ＤＯＰ、ＤＯＡなど）を可塑剤として用いれば脆化温度をさらに低くすることができるが、可塑剤が継時的にブリードする、又は水や洗浄液等により抽出される結果、耐寒性向上効果が継時的に低減することが考えられる。従って、これらの可塑剤を使用しなくても十分な耐寒性を示すゴムを選定することが望ましい。
(3) Additives etc. For any of the rubber compositions of the first aspect and the second aspect, in addition to the above essential composition, the additives, etc., as long as they do not impair the spirit of the invention. Other ingredients can be blended. Other components include reinforcing fillers such as carbon and silica, vulcanizing agents, vulcanization accelerators, vulcanization acceleration aids, vulcanization retarders, anti-aging agents, plasticizers, silane coupling agents, and the like. be able to. In addition, if an ester compound (DOP, DOA, etc.) excellent in low-temperature fluidity is used as a plasticizer, the embrittlement temperature can be further lowered, but the plasticizer bleeds continuously or extracted with water or a cleaning solution. As a result, it can be considered that the effect of improving cold resistance is reduced over time. Therefore, it is desirable to select a rubber that exhibits sufficient cold resistance without using these plasticizers.
（４）第１の態様、第２の態様のゴム組成物の使用例
第１の態様の耐寒性ゴム組成物は、脆化温度が低く耐寒性に優れ、かつ耐オゾン性すなわち動的な耐オゾン性、及びゴム／ゴム接着性に優れる。さらに粘着性に優れているため、貼合わせに際して十分な粘着力で仮止めでき、空気バネ製造時における成形性が良い。従って、寒冷地で使用される鉄道車両の空気バネの構成材料として好適である。又、第２の態様の耐寒性ゴムは、耐寒性、耐オゾン性、粘着性に優れるとともに、「ゴム／ゴム接着力」が第１の態様に比べて一層優れているので、寒冷地で使用される鉄道車両の空気バネの構成材料としてさらに好適である。
(4) Example of use of rubber composition of first aspect and second aspect The cold-resistant rubber composition of the first aspect has a low embrittlement temperature and excellent cold resistance, and also has ozone resistance, ie, dynamic resistance. Excellent ozone and rubber / rubber adhesion. Furthermore, since it is excellent in adhesiveness, it can be temporarily fixed with sufficient adhesive force at the time of bonding, and the moldability at the time of manufacturing an air spring is good. Therefore, it is suitable as a constituent material of an air spring of a railway vehicle used in a cold region. In addition, the cold resistant rubber of the second aspect is excellent in cold resistance, ozone resistance and adhesiveness, and “rubber / rubber adhesion” is more excellent than the first aspect, so it is used in cold regions. It is further suitable as a constituent material of an air spring of a railway vehicle.
そこで、本発明の好ましい態様として、第１の態様のゴム組成物又は第２の態様のゴム組成物を使用して形成された鉄道車両用空気バネが提供される。 Therefore, as a preferred embodiment of the present invention, there is provided an air spring for a railway vehicle formed using the rubber composition of the first embodiment or the rubber composition of the second embodiment.
［１］実験１
１．ゴム組成物の調製
［ベースゴムとして使用したゴム］
ＮＲ ：ＲＳＳ＃３（素練り品）
ＢＲ ：ニポールＢＲ１２２０（日本ゼオン社製：高シスＢＲ）
ＣＲ ：ショウプレンＷＲＴ（昭和電工社製）
[1] Experiment 1
1. Preparation of rubber composition [rubber used as base rubber]
NR: RSS # 3 (paste)
BR: Nipol BR1220 (manufactured by Nippon Zeon Co., Ltd .: High cis BR)
CR: Showprene WRT (Showa Denko)
上記ゴムを表１〜３に示す比率（質量部）で配合したベースゴムに、各種添加剤（カーボン、硫黄、加硫促進剤、加硫促進助剤、老化防止剤、可塑剤等）を適量添加し混練して表１〜３に示すＡ〜Ｎの各ゴム組成物を調製した（添加剤の配合比は、ベースゴムの種類、比率に応じて適宜変更）。 Appropriate amounts of various additives (carbon, sulfur, vulcanization accelerator, vulcanization accelerator, anti-aging agent, plasticizer, etc.) are added to the base rubber in which the above rubber is blended in the ratios (parts by mass) shown in Tables 1 to 3. The rubber compositions A to N shown in Tables 1 to 3 were prepared by addition and kneading (the additive compounding ratio was appropriately changed according to the type and ratio of the base rubber).
２．ゴムの品質評価
調製した各ゴム組成物につき、未加硫状態における粘着性並びに、加硫後（製品）の耐寒性、耐オゾン性（動的耐オゾン性）及びゴム／ゴム接着性について、以下の［評価方法・基準］に示す方法、条件、基準にて測定、評価した。評価結果を表１〜３に示す。
2. Quality evaluation of rubber For each rubber composition prepared, the tackiness in the unvulcanized state, the cold resistance after vulcanization (product), the ozone resistance (dynamic ozone resistance) and the rubber / rubber adhesion are as follows: [Evaluation methods / standards] were measured and evaluated by the methods, conditions, and standards. The evaluation results are shown in Tables 1-3.
［評価方法・基準］
・耐寒性：ＪＩＳ Ｋ６２６１に基づき脆化温度を測定し、脆化温度≦−５５℃を合格、、≦−６０℃（極寒地でも使用可能なレベルの脆化温度）をより好ましい測定値として評価した。
・耐オゾン性（動的な耐オゾン性）：<規格> ＪＩＳ Ｋ６２５９に基づいて試験し、亀裂の有無を観察した。なお試験片にはＪＩＳ３号ダンベル試験片を用いた。
・粘着性：未加硫ゴムシートを貼り合せた後、１８０°ピール試験（ピール速度：５０ｍｍ／ｍｉｎ）によりピール強度を測定し、≧０．２０ｋｇｆ／２５ｍｍを合格、≧０．４０ｋｇｆ／２５ｍｍをより好ましい測定値として評価した。
・接着性：未加硫ゴムシートを貼り合せて加硫プレスした後、１８０°ピール試験（ピール速度：５０ｍｍ／ｍｉｎ）によりゴム／ゴムの接着力を測定し、≧１０ｋｇｆ／２５ｍｍを合格、≧１５ｋｇｆ／２５ｍｍをより好ましい測定値として評価した。
[Evaluation methods and standards]
-Cold resistance: Measures the embrittlement temperature based on JIS K6261, passes the embrittlement temperature ≤ -55 ° C, and evaluates ≤-60 ° C (the embrittlement temperature at a level that can be used even in extremely cold regions) as a more preferable measurement value. did.
Ozone resistance (dynamic ozone resistance): <Standard> Tested according to JIS K6259 and observed for cracks. A JIS No. 3 dumbbell test piece was used as the test piece.
・ Adhesiveness: After pasting the unvulcanized rubber sheet, the peel strength was measured by a 180 ° peel test (peel speed: 50 mm / min), and ≧ 0.20 kgf / 25 mm passed, ≧ 0.40 kgf / 25 mm It evaluated as a more preferable measured value.
-Adhesiveness: After vulcanizing and pressing an unvulcanized rubber sheet, the adhesive strength of rubber / rubber is measured by a 180 ° peel test (peel speed: 50 mm / min), and ≧ 10 kgf / 25 mm is passed, ≧ 15 kgf / 25 mm was evaluated as a more preferable measurement value.
［表１〜３に基づく考察］
ＣＲの配合比が（ＣＲ、ＮＲ及びＢＲの合計を基準として）４０質量％のＥ、Ｉでは耐オゾン性（動的な耐オゾン性）が低く、亀裂が発生している。この結果は、耐オゾン性（動的な耐オゾン性）を維持するためには、ＣＲの配合比を５０質量％以上にするべきことを示唆している。一方、ＣＲの配合比が１００質量％のＡ、８０質量％のＢ、Ｆでは耐寒性がない（脆化温度は−５５℃より高い）。ＢＲを１０質量％配合したＦでは耐寒性の向上が見られるものの、脆化温度≦−５５℃は達成されず合格基準を充たしていない。この結果より、耐寒性を合格とするためには、ＣＲの配合比を７５質量％以下にするべきことが示唆される。
[Discussion based on Tables 1-3]
When E and I have a CR compounding ratio of 40% by mass (based on the sum of CR, NR, and BR), ozone resistance (dynamic ozone resistance) is low, and cracks are generated. This result suggests that the blending ratio of CR should be 50% by mass or more in order to maintain ozone resistance (dynamic ozone resistance). On the other hand, when the CR compounding ratio is 100% by mass A, 80% by mass B, and F, there is no cold resistance (the embrittlement temperature is higher than −55 ° C.). In F containing 10% by mass of BR, although the cold resistance is improved, the embrittlement temperature ≦ −55 ° C. is not achieved and the acceptance criterion is not satisfied. This result suggests that the CR blending ratio should be 75% by mass or less in order to pass the cold resistance.
ＣＲにＮＲを配合したもののＢＲを配合しないＢ、Ｃ、Ｄ及びＥの場合では、ゴム／ゴムの接着力が低く合格基準に達する接着性は得られていない。又、ＢＲを配合しないＣの場合（すなわち、ＮＲの配合比が大きく３５質量％を超えている場合）では、ＣＲの配合比が５０〜７５質量％の範囲であるにも係らず、脆化温度≦−５５℃は達成されておらず、充分な耐寒性は得られていない。 In the case of B, C, D, and E, in which NR is blended with CR but BR is not blended, the adhesive strength of the rubber / rubber is low and the acceptable standard is not obtained. Further, in the case of C not containing BR (that is, when the mixing ratio of NR is large and exceeds 35% by mass), the embrittlement occurs even though the mixing ratio of CR is in the range of 50 to 75% by mass. The temperature ≦ −55 ° C. is not achieved, and sufficient cold resistance is not obtained.
一方、Ｊ、Ｋ、Ｌ、Ｍ、Ｎの結果が示すように、ＢＲを１０質量％以上配合することにより、合格基準に達する接着性、耐寒性が得られる。又、ＢＲの配合比を増す（すなわち、ＮＲの配合比を小さくする）ほど耐寒性がよくなる（脆化温度は低下する）が、一方粘着性は低下し、ＢＲの配合比が４０質量％でＮＲを配合していないＮでは合格基準に達する粘着性は得られていない。これらの結果は、合格基準に達する耐寒性、耐オゾン性、粘着性及び接着性を得るためには、（ＣＲの配合比を５０〜７５質量％とするとともに）ＢＲの配合比は１０〜３５質量％の範囲、ＮＲの配合比は１０〜３５質量％の範囲とするべきことを示唆している。なお、ＢＲの配合比が１０質量％のＪでは、好ましい耐寒性である脆化温度≦−６０℃は得られていない。又、ＮＲの配合比が１０質量％のＭでは、好ましい粘着性である≧０．４０ｋｇｆ／２５ｍｍは得られていない。この結果は、ＢＲの配合比は１５〜３０質量％が好ましく、ＮＲの配合比は１５〜３０質量％が好ましく、従ってＣＲの配合比は５０〜７０質量％が好ましいことを示唆している。 On the other hand, as indicated by the results of J, K, L, M, and N, the adhesiveness and cold resistance reaching the acceptance criteria can be obtained by blending BR in an amount of 10% by mass or more. In addition, as the blending ratio of BR is increased (that is, the blending ratio of NR is decreased), the cold resistance is improved (the embrittlement temperature is lowered), but the tackiness is decreased, and the blending ratio of BR is 40% by mass. In N which does not contain NR, the adhesiveness which reaches the acceptance standard is not obtained. From these results, in order to obtain cold resistance, ozone resistance, tackiness and adhesiveness that reach the acceptance standards, the blending ratio of BR is 10 to 35 (with the blending ratio of CR being 50 to 75% by mass). This suggests that the range of mass% and the blending ratio of NR should be in the range of 10 to 35 mass%. Note that with J having a BR blending ratio of 10% by mass, the embrittlement temperature ≦ −60 ° C., which is preferable cold resistance, is not obtained. Further, when the blending ratio of NR is 10% by mass, a preferable adhesiveness of ≧ 0.40 kgf / 25 mm is not obtained. This result suggests that the blending ratio of BR is preferably 15 to 30% by weight, the blending ratio of NR is preferably 15 to 30% by weight, and therefore the blending ratio of CR is preferably 50 to 70% by weight.
［２］実験２
１．ゴム組成物の調製
［ベースゴムとして使用したゴム］
ＮＲ ：ＲＳＳ＃３（素練り品）
Ｅ−ＳＢＲ：ニポール１５０２（日本ゼオン社製）
ＮＢＲ ：ニポールＤＮ４０１ＬＬ（日本ゼオン社製）
ＢＲ ：ニポールＢＲ１２２０（日本ゼオン社製：高シスＢＲ）
ＣＲ ：ショウプレンＷＲＴ（昭和電工社製）
[2] Experiment 2
1. Preparation of rubber composition [rubber used as base rubber]
NR: RSS # 3 (paste)
E-SBR: Nipol 1502 (manufactured by Nippon Zeon)
NBR: Nipol DN401LL (Nippon Zeon Corporation)
BR: Nipol BR1220 (manufactured by Nippon Zeon Co., Ltd .: High cis BR)
CR: Showprene WRT (Showa Denko)
上記ゴムを表４、５に示す比率（質量部）で配合したベースゴムに、各種添加剤（カーボン、硫黄、加硫促進剤、加硫促進助剤、老化防止剤、可塑剤）を適量添加し混練して表４、５に示す各ゴム組成物を調製した（添加剤の配合比はベースゴムの種類、比率に応じて適宜変更）。 Appropriate amounts of various additives (carbon, sulfur, vulcanization accelerator, vulcanization accelerator, anti-aging agent, plasticizer) are added to the base rubber compounded with the ratios (parts by mass) shown in Tables 4 and 5 above. Then, each rubber composition shown in Tables 4 and 5 was prepared by kneading (the mixing ratio of additives was appropriately changed according to the type and ratio of the base rubber).
２．ゴムの品質評価
調製した各ゴム組成物につき、未加硫状態における粘着性、並びに、加硫後（製品）の耐寒性、耐オゾン性（動的耐オゾン性）及び接着性を、実験１の［評価方法・基準］に示す方法、条件、基準により測定、評価した。評価結果を表４、５に示す。なお、表４及び５には、比較のため上記の実験１のＧについても示した。
2. Rubber Quality Evaluation For each rubber composition prepared, the tackiness in the unvulcanized state, the cold resistance after vulcanization (product), the ozone resistance (dynamic ozone resistance) and the adhesiveness of Experiment 1 Measurement and evaluation were performed according to the methods, conditions, and criteria shown in [Evaluation Methods / Standards]. The evaluation results are shown in Tables 4 and 5. Tables 4 and 5 also show G in Experiment 1 above for comparison.
［表４、５に基づく考察］
表４に記載のＯ、Ｐ、Ｑ及びＲは、ＣＲ及びＢＲの組成比については、第１の実施態様の一具体例であるＧと同じであるが、Ｇ中のＮＲの一部（２５％、５０％又は７５％）又は全部をＳＢＲで置換したものである。表５に記載のＳ、Ｔ、Ｕ及びＶは、ＣＲ及びＢＲの組成比については、第１の実施態様の一具体例であるＧと同じであるが、Ｇ中のＮＲの一部（２５％、５０％又は７５％）又は全部をＮＢＲで置換したものである。
[Discussion based on Tables 4 and 5]
O, P, Q and R described in Table 4 are the same as G, which is a specific example of the first embodiment, in the composition ratio of CR and BR, but a part of NR in G (25 %, 50% or 75%) or all of them are replaced with SBR. S, T, U and V described in Table 5 are the same as G, which is one specific example of the first embodiment, in the composition ratio of CR and BR, but a part of NR in G (25 %, 50% or 75%) or all of them are replaced with NBR.
表４、５より明らかなように、Ｏ、Ｐ、Ｑ及びＲ並びにＳ、Ｔ、Ｕ及びＶでは、Ｇの場合と同等の優れた耐寒性や耐オゾン性が得られている。さらに、接着性についてはＧより向上しており、ダイヤフラム用として好ましいゴム／ゴム接着力（１５ｋｇｆ／２５ｍｍ以上）が得られている（Ｇでは、１５ｋｇｆ／２５ｍｍ未満の接着性しか得られていない）。表４、５に示されている接着性に関する結果より、接着性の向上のために、第１の態様のゴム組成物において、ＮＲの一部、具体的には１０質量％以上をＳＢＲ又はＮＢＲで置換することが好ましいと示唆される。 As is clear from Tables 4 and 5, O, P, Q, and R, and S, T, U, and V have excellent cold resistance and ozone resistance equivalent to those of G. Furthermore, the adhesiveness is improved over G, and a rubber / rubber adhesive force (15 kgf / 25 mm or more) preferable for a diaphragm is obtained (G has an adhesiveness of less than 15 kgf / 25 mm). . From the results relating to adhesiveness shown in Tables 4 and 5, in order to improve the adhesiveness, in the rubber composition of the first aspect, a part of NR, specifically, 10% by mass or more is SBR or NBR. It is suggested that substitution with
一方、表４、５の粘着性の欄に示されているように、ＧのＮＲの７５％をＳＢＲで置き換えたＱ及び全部を置き換えたＲ、並びに、ＧのＮＲの７５％をＮＢＲで置き換えたＵ、全部を置き換えたＶでは粘着性が低下し、好ましい粘着性（０．４ｋｇｆ／２５ｍｍ以上）は得られていない。従って、好ましい粘着性を得るためには、ＳＢＲ又はＮＢＲによりＮＲを置換する割合は、ＮＲの６０質量％以下が好ましいと示唆される。 On the other hand, as shown in the adhesive column of Tables 4 and 5, Q in which 75% of NR of G was replaced with SBR and R in which all of G was replaced, and 75% of NR in G was replaced with NBR. In addition, in U and V in which all of them are replaced, the adhesiveness is lowered, and preferable adhesiveness (0.4 kgf / 25 mm or more) is not obtained. Therefore, in order to obtain preferable tackiness, it is suggested that the ratio of NR substitution by SBR or NBR is preferably 60% by mass or less of NR.
なお、ＮＲ、ＢＲを配合せずにＣＲにＳＢＲのみを２０質量％配合した基１のゴム組成物、ＮＢＲのみを２０質量％配合した基２のゴム組成物では、耐寒性が低く、脆化温度は−５０℃より高い。又、ＮＲの７５％をＮＢＲで置き換えたＵ、全部を置き換えたＶでは耐寒性も（規格は満たしているものの）低下傾向にある。 In addition, the rubber composition of group 1 in which only 20% by mass of SBR is blended with CR without blending NR and BR, and the rubber composition of group 2 in which only 20% by mass of NBR is blended have low cold resistance and become brittle. The temperature is higher than -50 ° C. In addition, in U where 75% of NR is replaced with NBR and V where all are replaced, cold resistance tends to decrease (although the standard is satisfied).
第１の態様、第２の態様の発明は、車両用空気バネ等、特に寒冷地で使用される鉄道車両用空気バネに好適に使用される。 The inventions of the first aspect and the second aspect are suitably used for air springs for railway vehicles used in cold regions, such as air springs for vehicles.
Claims (3)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013271623A JP5885131B2 (en) | 2013-12-27 | 2013-12-27 | Cold resistant rubber composition |
| CN201480003199.1A CN104837912A (en) | 2013-12-27 | 2014-12-18 | Cold-resistant rubber composition |
| CA2892484A CA2892484C (en) | 2013-12-27 | 2014-12-18 | Cold-resistant rubber composition |
| PCT/JP2014/083552 WO2015060466A1 (en) | 2013-12-27 | 2014-12-18 | Cold-resistant rubber composition |
| RU2015119965/05A RU2577363C1 (en) | 2013-12-27 | 2014-12-18 | Frost-resistant caoutchouc composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013271623A JP5885131B2 (en) | 2013-12-27 | 2013-12-27 | Cold resistant rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2015124354A JP2015124354A (en) | 2015-07-06 |
| JP5885131B2 true JP5885131B2 (en) | 2016-03-15 |
Family
ID=52993044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013271623A Active JP5885131B2 (en) | 2013-12-27 | 2013-12-27 | Cold resistant rubber composition |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5885131B2 (en) |
| CN (1) | CN104837912A (en) |
| CA (1) | CA2892484C (en) |
| RU (1) | RU2577363C1 (en) |
| WO (1) | WO2015060466A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106084786A (en) * | 2016-07-13 | 2016-11-09 | 安徽奥丰汽车配件有限公司 | A kind of high temperature resistant vehicle rubber tyre material |
| JP6312183B1 (en) * | 2017-03-31 | 2018-04-18 | 福岡県 | Rubber composition for use in high pressure gas seal member and high pressure gas seal member |
| CN107163330A (en) * | 2017-06-08 | 2017-09-15 | 合肥帧讯低温科技有限公司 | Low-temperature-resistant heat-insulating material and preparation method thereof |
| CN107141529A (en) * | 2017-06-14 | 2017-09-08 | 陈丽 | A kind of high intensity engineering tire glue |
| CN107118402A (en) * | 2017-06-14 | 2017-09-01 | 陈丽 | A kind of all-year tire tire glue |
| JP7132783B2 (en) | 2018-07-25 | 2022-09-07 | デンカ株式会社 | Rubber composition, vulcanized rubber and molded products thereof |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2326902C1 (en) * | 2006-08-16 | 2008-06-20 | Открытое акционерное общество "Ярославский шиноремонтный завод" (ОАО "ЯШРЗ") | Rubber mix for production of rail and sleeper pads for damping rail braces |
| CN101353453B (en) * | 2007-07-27 | 2012-10-10 | 中国铁道科学研究院金属及化学研究所 | Chloroprene rubber composition having improved cold tolerance |
| JP2010013504A (en) * | 2008-07-01 | 2010-01-21 | Toyo Tire & Rubber Co Ltd | Rubber composition for air spring, and air spring |
| RU2400497C2 (en) * | 2008-12-26 | 2010-09-27 | Открытое акционерное общество "Российские железные дороги" (ОАО "РЖД") | Rubber mix for making rail and sleeper pads for damping rail braces |
| CN101602866B (en) * | 2009-07-09 | 2011-09-14 | 四机赛瓦石油钻采设备有限公司 | Cold-resistant rubber material suitable for preparing air sac and preparation method thereof |
| JP5690120B2 (en) * | 2010-11-26 | 2015-03-25 | 電気化学工業株式会社 | Chloroprene rubber composition, vulcanized product thereof and molded article |
| JP5813480B2 (en) * | 2011-11-22 | 2015-11-17 | 株式会社ブリヂストン | Rubber composition for hose and hose |
| WO2013076989A1 (en) * | 2011-11-22 | 2013-05-30 | 株式会社ブリヂストン | Rubber composition for hoses, and hose |
| JP5998490B2 (en) * | 2012-01-27 | 2016-09-28 | 株式会社ブリヂストン | Rubber composition for air spring |
| JP5991855B2 (en) * | 2012-06-01 | 2016-09-14 | 東洋ゴム工業株式会社 | Rubber composition |
| CN103113641B (en) * | 2013-02-04 | 2014-12-31 | 无锡宝通带业股份有限公司 | Low-hardness high-fatigue-drawing-resistance flame-retardant steel wire rope core conveyer belt core rubber and preparation method thereof |
| CN103304863A (en) * | 2013-06-28 | 2013-09-18 | 青岛福凯橡塑新材料有限公司 | Rubber core adhesive and use thereof |
-
2013
- 2013-12-27 JP JP2013271623A patent/JP5885131B2/en active Active
-
2014
- 2014-12-18 RU RU2015119965/05A patent/RU2577363C1/en active
- 2014-12-18 WO PCT/JP2014/083552 patent/WO2015060466A1/en active Application Filing
- 2014-12-18 CN CN201480003199.1A patent/CN104837912A/en active Pending
- 2014-12-18 CA CA2892484A patent/CA2892484C/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015060466A1 (en) | 2015-04-30 |
| CA2892484C (en) | 2016-08-23 |
| CN104837912A (en) | 2015-08-12 |
| JP2015124354A (en) | 2015-07-06 |
| RU2577363C1 (en) | 2016-03-20 |
| CA2892484A1 (en) | 2015-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5885131B2 (en) | Cold resistant rubber composition | |
| JP4819410B2 (en) | Rubber composition for sidewall | |
| JP4672416B2 (en) | Pneumatic tire manufacturing method and pneumatic tire obtained by the manufacturing method | |
| JP2005213486A (en) | Rubber composition for under-tread and pneumatic tire using the same | |
| JPWO2012144200A1 (en) | Rubber composition for tire sidewall and pneumatic tire using the same | |
| JP5095093B2 (en) | Method for producing rubber composition and rubber composition obtained thereby | |
| JP2010174232A (en) | Rubber composition for tire | |
| JP5341298B2 (en) | Rubber composition for covering carcass cord and tire using the same | |
| JP5144032B2 (en) | Rubber composition for sidewall | |
| JP6473302B2 (en) | tire | |
| JP2013067676A (en) | Heavy-duty pneumatic tire | |
| JP4230859B2 (en) | Rubber composition for steel coating | |
| JP2007112846A (en) | Rubber composition for sidewall, method for producing the same and pneumatic tire using the rubber composition | |
| JP2017141326A (en) | Tire rubber composition and tire | |
| JP4424815B2 (en) | Oil resistant conveyor belt | |
| JP2011046819A (en) | Rubber composition for tire reinforcement layer | |
| JP2009029883A (en) | Method for producing unvulcanized rubber composition for tire | |
| JP2015189794A (en) | Rubber composition and pneumatic tire using the same | |
| JPH10219033A (en) | Rubber composition for high-attenuation support | |
| JP2012116909A (en) | Rubber composition for tire sidewall and pneumatic tire using the same | |
| JP2007269872A (en) | Rubber composition for sidewall, tire produced by using the same, rubber composition for clinch and tire produced by using the same | |
| JP2009091375A (en) | Rubber composition | |
| JP2009279763A (en) | Method for producing rubber vibration insulator and rubber vibration insulator | |
| JP2017019935A (en) | Production method of rubber composition for tire, rubber composition for tire and pneumatic tire | |
| JP2005171015A (en) | Rubber composition for coating steel cord |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20150402 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20151130 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20151216 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20160118 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5885131 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160131 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |