Patent Application
20140191477
The present invention relates to a hydrogenated nitrile rubber composition. More particularly, the present invention relates to a hydrogenated nitrile rubber composition that can be suitably used as a vulcanization-molding material for cup gaskets or bellows of mechanical seals used in water pumps of radiators, etc., for automobiles and construction machinery.
Water pumps are pumps in which an aqueous solution comprising ethylene-glycol, etc., as active ingredients is used as LLC (long life coolant), which is an anti-freeze fluid. Water pump mechanical seals used to seal LLC are disclosed, for example, in Patent Document 1. Cup gaskets and bellows, which are used as members of the mechanical seals and which are static seals incapable of sliding, are made from rubber materials. Patent Document 1 refers to FKM (fluororubber), NBR, IIR, U (polyurethane rubber, such as AU and EU), Q (silicone rubber, such as VMQ and FVMQ), CR, and the like as usable examples of rubber materials for the cup gaskets.
These members are used to seal (secondary sealing) between sealing materials and members for fixing the sealing materials. For example, rubber materials itself used for lip seals are required to be hard because the rubber itself is a sliding body. Unlike such materials, rubber materials itself for the cup gaskets and bellows are required to be elastic enough to prevent the formation of gaps between the sealing members and the fixing members. More specifically, the rubber materials for these members are required elasticity having a hardness (Durometer A; according to JIS K6253 corresponding to ASTM D2240, Durometer Type A) of less than 70.
Since rubber materials generally used in mechanical seal members must have certain levels of hardness and elastic modulus so as to seal gaps between the members, the rubber materials are compounded with only small amounts of fillers, which have high reinforcing properties. Consequently, the volume fraction of the rubber polymer increases, and the desired resistance to LLC (long life coolant) is less likely to be ensured.
More specifically, the cup gaskets and bellows are required to have the following properties:
(1) Since mechanical seals are used under conditions in which they are always in contact with sealing liquid, such as LLC, in an atmosphere circumstances of high temperature (up to 160° C.) and high pressure (up to 0.4 MPa), the cup gaskets or bellows, which are used as members of the mechanical seals, are required to have durability under such conditions. An improvement in LLC resistance is needed to enable the cup gaskets or bellows to sufficiently exhibit their performance.
(2) Flexible elastomeric materials, such as nitrile rubber, are used as vulcanization-molding materials for the cup gaskets and bellows, which are members of water pump mechanical seals. In order to ensure certain levels of hardness and elastic modulus, it is necessary to lessen the amounts of various fillers. Consequently, the volume fraction of the rubber polymer increases, and the desired LLC resistance cannot be ensured.
(3) If the LLC resistance of the cup gaskets and bellows is insufficient, swelling and softening cause destruction (rupture), thereby resulting in the leakage of a large amount of LLC. In the worst-case scenario, a breakdown caused by overheating occurs.
(4) In order to solve these problems, for example, Patent Documents 2 and 3 disclose (hydrogenated) nitrile rubber compositions comprising nitrile rubber or hydrogenated nitrile rubber, and magnesium hydroxide, without containing a zinc compound or calcined clay. In Examples of these documents, FEF carbon black is used as a filler; however, the use of FEF carbon black (particle size: 45 nm) results in inferior roll processability, as shown in the results of Comparative Example 1 to 3, described later.
Patent Document 1: JP-A-2005-265075
Patent Document 2: JP-A-2001-354806
Patent Document 3: JP-B-3676338
Patent Document 4: JP-A-2006-131700
Patent Document 5: JP-A-2002-80639
An object of the present invention is to provide a hydrogenated nitrile rubber composition that has excellent roll processability and can be suitably used as a vulcanization-molding material for a cup gasket or bellows having excellent LLC resistance used in a water pump mechanical seal.
The above object of the present invention can be achieved by a hydrogenated nitrile rubber composition comprising 100 parts by weight of hydrogenated nitrile rubber having a bound acrylonitrile content of 31 to 50% and an iodine value of 30 mg/100 mg or less, 30 to 300 parts by weight of carbon black having a particle size of 61 nm or more and/or other filler, 1 to 30 parts by weight of a polyfunctional unsaturated compound cocrosslinking agent, and 1 to 10 parts by weight of an organic peroxide. This hydrogenated nitrile rubber composition is preferably free of a plasticizer.
The hydrogenated nitrile rubber composition of the present invention has excellent roll processability, and can be crosslinked with peroxide to form a cup gasket or bellows having excellent LLC resistance used for a water pump mechanical seal.
The hydrogenated nitrile rubber used in the present invention has a bound acrylonitrile [AN] content of 31 to 50%, preferably 35 to 50%, and an iodine value of 30 mg/100 mg or less. The use of hydrogenated nitrile rubber in which the bound AN content and iodine value are outside the above range results in inferior LLC resistance.
The hydrogenated nitrile rubber composition having such properties is compounded in an amount of 100 parts by weight with carbon black having a particle size of 61 nm or more and/or other filler in an amount of 30 to 300 parts by weight, preferably 40 to 160 parts by weight. When the proportion of carbon black and/or other filler is less than this range, LLC resistance is insufficient; whereas when the proportion is greater than this range, roll processability is inferior.
Examples of the carbon black include those having a particle size (according to ASTM D1765) of 61 nm or more, preferably 61 to 500 nm. The use of carbon black having a particle size less than this range results in inferior roll processability. Moreover, examples of the filler other than the carbon black include silica, graphite, clay, talc, coke, calcium carbonate, alumina, silicon carbide, titanium oxide, and the like; preferably, at least one of graphite, silica, clay, etc., is used. The particle size of the other filler is not particularly limited, but is generally about 0.5 to 250 μm.
Since the use of a specific amount of such a filler can produce a rubber material having certain levels of hardness and elastic modulus and can reduce the volume fraction of the rubber polymer, the resulting rubber material has excellent LLC resistance. In general, a plasticizer is compounded to control hardness; however, the plasticizer is extracted at the time of use, consequently leading to changes in physical properties, such as hardness increase. It is thus preferable that a plasticizer is not used in the hydrogenated nitrile rubber composition of the present invention.
When any of these various other fillers, particularly silica, is used, it is preferable to use it in combination with a coupling agent, such as a silane-, titanium-, zirconium-, or aluminum-based coupling agent, in an amount of 8 parts by weight or less, preferably 5 parts by weight or less, based on 100 parts by weight of the hydrogenated nitrile rubber.
Examples of silane-based coupling agents include vinyl group-, epoxy group-, and amino group-containing silane coupling agents, such as vinyltrichlorosilane, vinyltrimetoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimetoxysilane, 3-glycidoxypropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane.
Examples of titanium-based coupling agents include titanium diisopropoxy bis(triethanolaminato), titanium lactate ammonium salt, titanium lactate, titanium dioctyloxy bis(octyleneglycolate), and the like.
Examples of zirconium-based coupling agents include zirconium tetra-n-butoxide, zirconium tetraacetylacetonate, zirconium tributoxy monoacetylacetonate, zirconium monobutoxy acetylacetonate bis(ethylacetoacetate), zirconium butoxy bis(ethylacetoacetate), zirconium tetraacetylacetonate, zirconium tributoxy monostearate, and the like.
Moreover, examples of aluminum-based coupling agents include acetoalkoxy aluminum diisopropylate, and the like.
Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3,1,3-di(t-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxy benzoate, t-butylperoxy isopropyl carbonate, n-butyl-4,4′-di(t-butylperoxy) valerate, and the like. The proportion of organic peroxide is about 1 to 10 parts by weight, preferably about 2 to 8 parts by weight, based on 100 parts by weight of the hydrogenated nitrile rubber. When the amount of organic peroxide is less than this range, the resulting vulcanizate has an insufficient crosslinking density. In contrast, when the amount is greater than this range, foaming occurs, and vulcanization-molding cannot be performed; or, if vulcanization-molding can be performed, rubber elasticity and elongation decrease.
Furthermore, preferred examples of the polyfunctional unsaturated compound cocrosslinking agent include difunctional or trifunctional (meth)acrylates, such as ethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate, 1,4-butyleneglycol dimethacrylate, 1,6-hexanediol dimethacrylate, and trimethylolpropane trimethacrylate. Other usable examples are triallyl isocyanurate, triallyl cyanurate, triallyl trimellitate, diallyl isocyanurate, and other allyl-based cocrosslinking agents that are generally used in combination with organic peroxides. The term “(meth)acrylate” as used herein refers to acrylate or methacrylate.
The proportion of polyfunctional unsaturated compound cocrosslinking agent is 0.5 to 30 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the hydrogenated nitrile rubber. When the proportion is less than this range, the desired LLC resistance (degree of swelling and degree of softening) targeted by the present invention cannot be achieved. As a result, a cup gasket or bellows of a water pump mechanical seal having the desired properties cannot be obtained. In contrast, when the proportion is greater than this range, rubber elasticity and elongation decrease.
Patent Document 4, which discloses an invention made by the present applicant, discloses a hydrogenated nitrile rubber composition comprising 100 parts by weight of hydrogenated nitrile rubber having a Mooney viscosity ML1+4 (100° C.) of 100 or less, an acrylonitrile content of 30 to 50%, and an iodine value of 28 or less, 60 to 250 parts by weight of carbon fiber, and 12 to 70 parts by weight of a polyfunctional group-based cocrosslinking agent having a molecular weight of 150 to 500 and a viscosity (20° C.) of 3 to 120 mPa·s. A sealing material formed from the hydrogenated nitrile rubber composition by vulcanization-molding is described to be suitable for sealing liquid, such as an aqueous solution mainly comprising water (e.g., LLC).
In this case, according to Patent Document 4, since carbon fiber is used as one component of the composition, the use of less than 12 parts by weight of a polyfunctional group-based cocrosslinking agent does not result in improvements in kneading properties and molding processability, or improvements in reinforcing effect and extraction resistance to various fluids. Conversely, the present invention effectively improves LLC resistance and roll processability, even though the proportion of polyfunctional unsaturated compound is in the range of 1 to 10 parts by weight.
In addition, Patent Document 5, which has one common inventor of the present coinventors, discloses a hydrogenated nitrile rubber composition comprising 100 parts by weight of hydrogenated nitrile rubber having a bound acrylonitrile content of 38% or less, a degree of hydrogenation of 90% or more, and an iodine value (central value) of 28 or less, and 120 parts by weight or more in total of carbon black and other fillers. The hydrogenated nitrile rubber composition provides a crosslinking product having a thermal conductivity at 20° C. of 0.4 W/m·k or more and a 50% modulus of 14 MPa or more. Patent Document 5 also indicates that when an organic peroxide is used, a polyfunctional unsaturated compound is preferably used in combination.
Example 4 of Patent Document 5 uses a hydrogenated nitrile rubber composition comprising hydrogenated NBR (AN content: 36.2%, degree of hydrogenation: 96%, iodine value: 11), SRF carbon black, silica, graphite, PTFE powder, a silane coupling agent, an antioxidant, and an organic peroxide; however, no polyfunctional unsaturated compound is used. The same applies to other Examples.
The preparation of the composition is carried out by suitably compounding, in addition to the above essential components, processing aids, such as stearic acid, palmitic acid, and paraffin wax; acid acceptors, such as zinc oxide, magnesium oxide, and hydrotalcite; antioxidants; and various other fillers (except for plasticizers) generally used in the rubber industry, by using an open roll or a kneading machine such as intermix, kneader, or Banbury mixer. Vulcanization of the kneaded compound is generally carried out by heating at about 150 to 200° C. for about 3 to 60 minutes using an injection molding machine, compression molding machine, vulcanizing press, or the like, optionally followed by oven vulcanization (secondary vulcanization) by heating at about 120 to 200° C. for about 1 to 24 hours. Thus, the kneaded compound is vulcanization-molded into the desired product, i.e., a cup gasket or bellows for a water pump mechanical seal.
The following describes the present invention with reference to Examples.
The above components were kneaded by a 3L kneader and a 10-inch roll, and the knead compound was compression-molded at 180° C. for 10 minutes, thereby forming a rubber sheet (thickness: 2 mm).
The knead compound and rubber sheet were tested for the following items.
In Example 1, the amount of MT carbon black was changed to 30 parts by weight or 300 parts by weight.
In Example 1, the same amount of SRF carbon black (Asahi #55, produced by Asahi Carbon Co., Ltd.; particle size: 66 nm) was used in place of MT carbon black.
In Example 4, the amount of SRF carbon black was changed to 30 parts by weight or 300 parts by weight.
In Example 1, the same amount of silica (Silica 100F, produced by Chuo Silika Co., Ltd.; particle size: 8 μm) was used in place of MT carbon black.
In Example 7, the amount of silica (Silica 100F) was changed to 30 parts by weight or 300 parts by weight.
In Example 7, 5 parts by weight of a silane-based coupling agent (KBM-602, produced by Shin-Etsu Chemical Co., Ltd.; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane) was used in combination with silica (Silica 100F).
In Example 10, the amount of silica (Silica 100F) was changed to 30 parts by weight or 300 parts by weight.
In Example 1, the same amount of graphite (Graphite G-30, produced by Chuetsu Graphite Works Co., Ltd.; particle size: 210 μm) was used in place of MT carbon black.
In Example 1, the same amount of clay (Kaocal, produced by Shiraishi Calcium Kaisha, Ltd.; particle size: 0.9 μm) was used in place of MT carbon black.
In Example 1, the amount of MT carbon black was changed to 75 parts by weight, and 75 parts by weight of silica (Silica 100F) was further used.
In Example 1, the amount of MT carbon black was changed to 15 parts by weight, and 15 parts by weight of silica (Silica 100F) was further used.
In Example 1, the amount of MT carbon black was changed to 150 parts by weight, and 150 parts by weight of silica (Silica 100F) was further used.
In Example 15, the same amounts of MT carbon black and silica (Silica 100F) were used in combination with 5 parts by weight of a silane-based coupling agent (KBM-602).
In Example 16, the same amounts of MT carbon black and silica (Silica 100F) were used in combination with 5 parts by weight of a silane coupling agent (KBM-602).
In Example 17, the same amounts of MT carbon black and silica (Silica 100F) were used in combination with 5 parts by weight of a silane coupling agent (KBM-602).
In Example 1, the hydrogenated nitrile rubber was changed to the same amount of Zetpol 0020 (produced by Zeon Corporation; bound AN content: 49.2%, iodine value: 23 mg/100 mg) [HNBR-B].
In Example 1, the hydrogenated nitrile rubber was changed to the same amount of Zetpol 2020 (produced by Zeon Corporation; bound AN content: 36%, iodine value: 28 mg/100 mg) [HNBR-C].
In Example 1, the amount of cocrosslinking agent was changed to 1 part by weight.
In Example 1, the amount of cocrosslinking agent was changed to 30 parts by weight.
In Example 1, the same amount of FEF carbon black (#60, produced by Asahi Carbon Co., Ltd.; particle size: 45 nm) was used in place of MT carbon black.
In Comparative Example 1, the amount of FEF carbon black was changed to 30 parts by weight or 300 parts by weight.
In Example 1, the amount of MT carbon black was changed to 20 parts by weight or 310 parts by weight.
In Example 7, the amount of silica (Silica 100F) was changed to 20 parts by weight or 310 parts by weight.
In Example 15, the amount of MT carbon black was changed to 10 parts by weight, and the amount of silica (Silica 100F) was changed to 10 parts by weight.
In Example 15, the amount of MT carbon black was changed to 160 parts by weight, and the amount of silica (Silica 100F) was changed to 160 parts by weight.
In Example 1, no cocrosslinking agent was used.
In Example 1, the amount of cocrosslinking agent was changed to 35 parts by weight.
In Example 1, the hydrogenated nitrile rubber was changed to the same amount of Zetpol 3110 (produced by Zeon Corporation; bound AN content: 25%, iodine value: 15 mg/100 mg) [HNBR-D].
In Example 1, the hydrogenated nitrile rubber was changed to the same amount of Zetpol 2030L (produced by Zeon Corporation; bound AN content: 36%, iodine value: 57 mg/100 mg) [HNBR-E].
Tables 1 to 4 below show the results obtained in the above Examples and Comparative Examples, together with the amount of each composition component (unit: part by weight), other than the common components (i.e., antioxidant and organic peroxide).
The above results indicate the following:
(1) When 30 to 300 parts by weight of MT carbon or SRF carbon, and 1 to 30 parts by weight of a cocrosslinking agent are used based on 100 parts by weight of hydrogenated nitrile rubber having a bound AN content of 31 to 50% and an iodine value of 30 mg/100 mg or less, LLC resistance is excellent, and no problem is found in roll processability.
The same effects are also obtained when 30 to 300 parts by weight of silica and 0 to 5 parts by weight of a silane coupling agent are used, or when 30 to 300 parts by weight in total of MT carbon and silica, and 0 to 5 parts by weight of a silane coupling agent are used.
(2) When the hydrogenated nitrile rubber used has a bound AN content less than the specified value and an iodine value greater than the specified value, sufficient LLC resistance is not obtained.
(3) When the amount of MT carbon and/or silica is less than the specified value, sufficient LLC resistance is not obtained; whereas when the amount is greater than the specified value, kneading properties are problematic, and a rubber material is not obtained.
(4) When the amount of cocrosslinking agent was less than the specified value, LLC resistance and roll processability were both problematic.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2011-199558 | Sep 2011 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2012/069852 | 8/3/2012 | WO | 00 | 2/14/2014 |
