JP4470633B2 - NBR composition - Google Patents

Description

The present invention relates to NBR compositions. More particularly, to effectively NBR composition used as a vulcanization molding material for reciprocating sliding seal material.

Nitrile rubber (NBR) compositions are excellent in oil resistance and are used as sealing materials for oil seals, O-rings, packings and the like in a wide range of fields such as automobiles and industrial machinery industries. For example, Patent Document 1 proposes a wear-resistant rubber composition for reciprocating seals in which NBR contains carbon black and chromium oxide. However, a molded product obtained from such a molding material for sealing has problems such as accelerated degradation of the sealing material due to heat generation at the sliding portion of the seal and energy loss of the device due to sliding resistance due to large friction.
Japanese Examined Patent Publication No. 6-74352

The object of the present invention is to achieve reciprocation that achieves low friction, which can achieve longer life and energy saving of equipment when reciprocating sliding seal material is used for sliding parts without impairing wear resistance. An object of the present invention is to provide an NBR rubber composition that provides a dynamic sliding seal material .

The object of the present invention is to provide aluminum oxide, silicon carbide, tungsten carbide and zirconium oxide which are inorganic compounds having a white carbon of 20 to 150 parts by weight and an average particle size of 0.6 to 2 μm and a Mohs hardness of 6 or more with respect to 100 parts by weight of NBR. This is achieved by an NBR composition containing 3 to 50 parts by weight of at least one of the following .

Vulcanized moldings obtained from NBR compositions in which NBR is blended with white carbon and an inorganic compound with an average particle size of 0.6-2 μm and Mohs hardness of 6 or more are used for NBR's inherent mechanical strength (normal physical properties) and NBR. Low friction can be remarkably improved without substantially impairing the wear resistance as seen when carbon black is blended. This is because white carbon that enables low friction is selected as a filler, and wear resistance that is difficult to achieve with only white carbon that is inferior to conventional carbon black. In this respect, by adding a specific inorganic compound having no reinforcing effect, it is possible to suppress self-wear and wear of the sliding surface of the mating member without impairing wear resistance.

As described above, the NBR composition according to the present invention is suitably used as a vulcanization molding material for seal materials such as oil seals, packings, and O-rings that require wear resistance and friction resistance. Specifically, it is used as a vulcanization molding material for a reciprocating sliding seal material for a shock absorber, for example. Similar effects can be obtained with acrylic rubber or fluororubber instead of NBR.

As NBR, an acrylonitrile-butadiene rubber having a bound acrylonitrile content of 18 to 48%, preferably 20 to 35%, and a Mooney viscosity ML _{1 + 4} (100 ° C.) of 32 to 85, preferably 32 to 80, is used. Actually, commercially available products such as Nippon Zeon product DN302 can be used as they are. To this NBR, white carbon and an inorganic compound are added to prepare the NBR composition of the present invention.

White carbon (reinforcing silica) includes dry-type white carbon produced by the thermal decomposition method of halogenated silicic acid or organosilicon compounds and the method of heat-reducing silica sand and oxidizing the vaporized SiO into air. Wet process white carbon produced by pyrolysis of sodium acid, etc., and amorphous silica can be used. Commercially available products such as Nippon Aerosil product Aerosil 200 and Japan Silica Industrial product Nipsil LP are used as they are. It is done. Further, those having a specific surface area of about 30 to 200 m ² / g are generally used. Although white carbon is inferior in wear resistance as compared with carbon black generally used due to its price, handleability and good wear resistance, it is possible to reduce the friction coefficient.

These white carbons are used in a ratio of about 20 to 150 parts by weight per 100 parts by weight of NBR. If the blending ratio is less than this, the desired effect of reducing friction resistance is not achieved. On the other hand, if the blending ratio is more than this, the rubber hardness becomes very high and the rubber elasticity is lost.

As the inorganic compound, those having an average particle diameter (measured by a laser diffraction method) of 0.6 to 2 μm and a Mohs hardness of 6 or more are used. Specifically, aluminum oxide (alumina), silicon carbide, tungsten carbide and At least one of zirconium oxide , preferably aluminum oxide or silicon carbide is used. By using an inorganic compound with a Mohs hardness of 6 or more, it is possible to improve the wear resistance, and by using an average particle size of 2 μm or less, it is possible to significantly reduce the wear of the sliding counterpart. Become. Here, such an inorganic compound is used in a ratio of 3 to 50 parts by weight, preferably 3 to 30 parts by weight, and more preferably about 3 to 20 parts by weight per 100 parts by weight of NBR. If the usage ratio is less than this, the effect of improving the wear resistance which is the object of the present invention cannot be obtained, whereas if it is used in a higher ratio, the normal physical properties are deteriorated.

  The vulcanization of NBR blended with white carbon and an inorganic compound can be used alone or in combination with any vulcanization system such as sulfur vulcanization and peroxide vulcanization, but a sulfur vulcanization system is preferably used.

  In the composition, in addition to the above essential components, other reinforcing compounds such as polyfunctional unsaturated compounds such as triallyl (iso) cyanurate, trimethylolpropane tri (meth) acrylate, triallyl trimellitate, activated calcium carbonate, etc. Agent, filler such as talc, clay, graphite, calcium silicate, processing aid such as stearic acid, palmitic acid, paraffin wax, acid acceptor such as zinc oxide, magnesium oxide, hydrotalcite, anti-aging agent, dioctyl Various compounding agents generally used in the rubber industry such as plasticizers such as sebacate (DOS) are appropriately added and used.

  The composition is prepared by kneading using a kneader such as an intermix, kneader, Banbury mixer or an open roll. The vulcanization is performed using an injection molding machine, a compression molding machine, a vulcanizing press, or the like. In general, it is carried out by heating at about 160 to 200 ° C. for about 3 to 30 minutes, and if necessary, secondary vulcanization is also carried out by heating at about 140 to 160 ° C. for about 0.5 to 10 hours.

  Next, the present invention will be described with reference to examples.

Example 1
NBR (DN302) 100 parts by weight White carbon (Aerosil 200) 70 〃
Alumina (Nippon Light Metal Products A32: Average particle size 1μm, Mohs hardness 9) 5 〃
Zinc oxide 5 〃
Stearic acid 1.5 〃
DOS 20 〃
Anti-aging agent (Nocrac 224, a new chemical product from Ouchi) 2 〃
Sulfur 0.8 〃
Vulcanization accelerator (Ouchi Emerging Chemicals Noxeller TT) 2〃
Vulcanization accelerator (Ouchi Emerging Chemicals Noxeller CZ) 2 〃
The above components were kneaded with a kneader and an open roll, and the kneaded product was subjected to press vulcanization at 170 ° C. for 20 minutes and oven vulcanization at 150 ° C. for 4 hours to prepare a 250 × 120 × 2 mm test piece. Using the obtained test piece, the following items were measured.
Normal physical properties: JIS K-6301 compliant Dynamic friction coefficient: When using a surface property measuring machine ( manufactured by Shinto Chemical Co., Ltd. ), 4 mm diameter SUS steel ball friction, load 50 g, moving speed 5 mm / min. JIS lubricant No. 3 is applied to the surface of the vulcanizate to be measured, assuming actual usage conditions. Taber wear: Wear volume is measured according to JIS K6264
0.2 ~ 0.3cc ◎, 0.3 ~ 0.4cc ○, 0.4 ~ 0.5cc △, 0.5 ~ 0.6cc ×
Product friction force: Measure the friction force under conditions of pressure 2MPa and stroke ± 0.2mm
40N or less is evaluated as small, 40 to 50N as medium, and 50N or greater as large. Product wear: Wear area measured under conditions of pressure 2MPa, stroke ± 1mm, 100 hours
What wear area of 0.1 mm ² or less ◎, ○ those 0.1 to 0.2 mm ^2, evaluated axis wear those 0.2 to 0.3 mm ² △, as × a 0.3 mm ² or more of: pressure 2 MPa, stroke ± Measures the wear depth under the condition of 1 mm for 100 hours
Abrasion depth of 1 μm or less is evaluated as ◎, 1 to 2 μm is evaluated as ○, 2 to 3 μm is evaluated as △, and 3 μm or more is evaluated as ×.

Example 2
In Example 1, the amount of alumina was changed to 3 parts by weight.

Comparative Example 1
In Example 1, the amount of alumina was changed to 1 part by weight.

Example 3
In Example 1, the amount of alumina was changed to 10 parts by weight.

Example 4
In Example 1, the amount of white carbon was changed to 65 parts by weight, and the amount of alumina was changed to 30 parts by weight.

Example 5
In Example 1, the same amount of silicon carbide (Yakushima Electric Works OY-20; average particle size 0.6 μm, Mohs hardness 9) was used instead of alumina.

Example 6
In Example 1, the same amount of tungsten carbide (Japan New Metal Products WC-F; average particle size 0.6 μm, Mohs hardness 9) was used instead of alumina.

Example 7
In Example 1, the same amount of zirconium oxide (first rare element chemical industrial product UEP; average particle size of 0.25 μm, Mohs hardness 7.5) was used instead of alumina.

Comparative Example 2
In Example 1, the same amount of iron oxide (Bayer product Bayoxide E III; average particle size 0.2 μm, Mohs hardness 6) was used instead of alumina.

Comparative Example 3
In Example 1, the same amount of titanium oxide (Bayer's product R-KB-4; average particle size 0.2 μm, Mohs hardness 6) was used instead of alumina.

The measurement results obtained in each of the above examples are shown in Table 1 below.
Table 1
Measurement item Real-1 Real-2 Ratio-1 Real-3 Real-4 Real-5 Real-6 Real-7 Ratio-2 Ratio-3
Normal physical properties Hardness (JIS A) 80 80 80 81 80 80 80 80 80 80
Tensile strength (MPa) 23.8 24.2 24.0 23.5 22.9 24.0 23.7 23.8 23.6 23.5
Elongation (%) 340 340 350 330 300 340 320 320 310 310
Coefficient of dynamic friction (%) 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35
Taber wear (cc) ○ ○ △ ◎ ◎ ○ ○ ○ △ △
Product friction force Small Small Small Small Small Small Small Small Small Product wear ◎ ◎ △ ◎ ◎ ◎ ◎ ◎ ○ ○
Shaft wear ◎ ◎ ◎ ◎ ○ ◎ ◎ ◎ ◎ ◎

Comparative Example 4
In Example 1, the same amount of Nippon Light Metal Products A31 (average particle size 5 μm, Mohs hardness 9) was used as alumina.

Comparative Example 5
In Example 1, alumina was not used.

Comparative Example 6
In Example 1, white carbon and alumina were not used, and 90 parts by weight of FEF carbon black was used.

Comparative Example 7
In Example 1, the same amount of calcium silicate (NYCO product NYAD1250; average particle size 4.5 μm, Mohs hardness 4.5) was used instead of alumina.

The measurement results obtained in Comparative Examples 4 to 7 are shown in Table 2 below.
Table 2
Measurement item ratio -4 ratio -5 ratio -6 ratio -7
Vulcanization properties Hardness (JIS A) 80 80 80 81
Tensile strength (MPa) 23.1 24.1 19.4 23.0
Elongation (%) 310 330 250 320
Coefficient of dynamic friction (%) 0.35 0.35 0.5 0.35
Tapered wear (cc) ○ × ○ ×
Product friction force Small Small Large Small product wear ◎ × ○ ×
Shaft wear × ◎ ◎ ◎

Claims (3)

Relative NBR100 parts by weight white carbon 20 to 150 parts by weight of the average particle diameter of 0.6~2μm and aluminum oxide is a Mohs hardness of 6 or more inorganic compounds, silicon carbide, at least one 3-50 weight tungsten carbide and zirconium oxide An NBR composition used as a vulcanization molding material for a reciprocating sliding seal material . A reciprocating sliding seal material vulcanized and molded from the NBR composition according to claim 1. The reciprocating sliding seal material according to claim 2, which is used for a shock absorber.