NBR COMPOSITION

Abstract

An NBR composition that includes, based on 100 parts by weight of NBR, 0.2 to 0.7 parts by weight, preferably 0.2 to 0.5 parts by weight, of stearic acid, and paraffin wax, which has the melting start temperature of 65° C., in an amount equal to 2 to 6 times the amount of said stearic acid, and preferably further zinc oxide and a UV resistant antioxidant. The NBR composition has improved ozone resistance using stearic acid and paraffin wax, which are generally compounded in NBR compositions, while neither affecting the material physical properties or product appearance, nor increasing the compounding amount of an ozone resistant antioxidant.

Claims

1. An NBR composition comprising, based on 100 parts by weight of NBR, 0.2 to 0.7 parts by weight of stearic acid, and paraffin wax, which has the melting start temperature of 65° C., in an amount equal to 2 to 6 times the amount of said stearic acid.

2. The NBR composition according to claim 1, wherein 0.2 to 0.5 parts by weight of stearic acid is added.

3. The NBR composition according to claim 1, wherein zinc oxide is further added.

4. The NBR composition according to claim 1, wherein a UV resistant antioxidant is further added.

5. The NBR composition according to claim 1, wherein a sulfur-based vulcanizing agent is further added.

6. The NBR composition according to claim 2, wherein zinc oxide is further added.

7. The NBR composition according to claim 2, wherein a UV resistant antioxidant is further added.

8. The NBR composition according to claim 2, wherein a sulfur-based vulcanizing agent is further added.

Description

EMBODIMENTS FOR CARRYING OUT THE INVENTION

[0013] NBR is not limited by the content of acrylonitrile [AN] bound thereto, and those with any AN content can be used.

[0014] The amount of stearic acid compounded in NBR is 0.2 to 0.7 parts by weight, preferably 0.2 to 0.5 parts by weight, based on 100 parts by weight of NBR. If the compounding ratio is less than the above range, not only the vulcanization speed is delayed and the compression set characteristics are deteriorated, but also the ozone resistance and product appearance may be deteriorated. In contrast, if the ratio of stearic acid is greater than the above range, the product appearance is impaired, for example, cloudiness occurring.

[0015] As the paraffin wax, one having a melting start temperature (according to JIS K2235, 5.3.2 corresponding to ISO 6244, the temperature at which when a molten sample is adhered to the mercury sphere part of a thermometer for measuring the melting point and is solidified and the sample is heated under specified conditions, the first drop falls from the thermometer) of 65° C. is selected and used. If paraffin wax having a melting start temperature other than the above is used, the improvement of ozone resistance cannot be achieved.

[0016] The amount of the paraffin wax, which has the melting start temperature of 65° C. (64.5 to 65.4° C.), is limited to an amount equal to 2 to 6 times the amount of stearic acid used. If the ratio is less than the above range, the ozone resistance becomes insufficient. In contrast, if the paraffin wax is used at a ratio greater than the above range, the product appearance is deteriorated.

[0017] Example 1 of Patent Document 1 shows an example in which 1 part by weight of stearic acid and 2 parts by weight of wax (melting start temperature: 65° C.) are used based on 100 parts by weight of NBR; however, as described in Comparative Example 14 provided later, the product appearance is impaired when the amount of stearic acid used is 1 part by weight.

[0018] In addition to the above essential components, it is preferable to compound an acid acceptor, a UV resistant antioxidant, a sulfur-based vulcanizing agent, and the like.

[0019] As the acid acceptor, an oxide or hydroxide of a divalent metal, a hydrotalcite compound, or the like is used, and zinc oxide is preferably used. The compounding ratio thereof is about 1 to 20 parts by weight, preferably about 3 to 10 parts by weight, based on 100 parts by weight of NBR.

[0020] Examples of the UV resistant antioxidant having ozone resistance include amine-ketone-based, aromatic secondary amine-based, dithiocarbamate-based and thiourea-based antioxidants, special wax, and the like. Commercially available products, such as Nocrac 6C, Nocrac 224, Nocrac AW, Nocrac 810-NA, Nocrac G-1, Nocrac NBC-P, Nocrac NS-10-N, Nocrac TBTU, Sunnoc and Ozonoc (all produced by Ouchi Shinko Chemical Industrial Co., Ltd.), are used as they are singly or in combination of any two or more.

[0021] One of these UV resistant antioxidants is used at a ratio of about 0.2 to 5 parts by weight, preferably about 0.5 to 3 parts by weight, based on 100 parts by weight of NBR. According to the present invention, excellent ultraviolet light resistance (ozone resistance) is exhibited, even without particularly increasing the use ratio thereof. When two or more UV resistant antioxidants are used, they are used in a total amount of about 0.2 to 5 parts by weight, preferably about 0.5 to 4.5 parts by weight, based on 100 parts by weight of NBR.

[0022] Further, as the sulfur-based vulcanizing agent, powder sulfur, sublimed sulfur, precipitated sulfur, colloidal sulfur, surface treated sulfur, insoluble sulfur, polymer sulfur, or the like is used at a ratio of about 0.3 to 5 parts by weight, preferably about 0.5 to 2 parts by weight, based on 100 parts by weight of NBR.

[0023] Together with sulfur, guanidine-based, aldehyde-amine-based, aldehyde-ammonia-based, thiazole-based, sulfenamide-based, thiourea-based, thiuram-based, dithiocarbamate-based, and xanthate-based sulfur-containing vulcanization accelerators are used singly or in combination of any two or more, and a thiazole-based or thiuram-based vulcanization accelerator is preferably used.

[0024] Preferably examples of the vulcanization accelerator include thiazole-based vulcanization accelerators, such as di-2-benzothiazyldisulfide, N-cyclohexyl-2-benzothiazylsulfenamide, 2-mercaptobenzothiazole, zinc salt or cyclohexylamine salt of 2-mercaptobenzothiazole, 2-(N,N′-diethylthiocarbamoylthio)benzothiazole, and 2-(4′-morpholinodithio)benzothiazole; and thiuram-based vulcanization accelerators, such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetrakis(2-ethylhexyl)thiuram disulfide, and dipentamethylenethiuram tetrasulfide. In general, N-cyclohexyl-2-benzothiazylsulfenamide and tetraalkylthiuram monosulfide are used.

[0025] One of these sulfur-containing vulcanization accelerators is used at a ratio of about 0.5 to 6 parts by weight, preferably about 1 to 3 parts by weight, based on 100 parts by weight of NBR. When two or more sulfur-containing vulcanization accelerators are used, they are used in a total amount of about 0.5 to 6 parts by weight, preferably about 1 to 5 parts by weight, based on 100 parts by weight of NBR.

[0026] The composition is prepared by adding, in addition to each of the above components, a filler or reinforcing agent such as carbon black or silica, a plasticizer, and other necessary components, and kneading the resulting mixture with a kneader and an open roll in sequence, followed by heating at about 170 to 190° C. for about 3 to 10 minutes, and further followed by, if necessary, oven vulcanization (secondary vulcanization) by heating at about 140 to 160° C. for about 0.5 to 10 hours.

EXAMPLES

[0027] The following describes the present invention with reference to Examples.

Example 1

[0028] NBR DN101L (produced by Zeon Corporation; 100 parts by weight [0029] bound AN content: 41.5 to 43.5%, [0030] Mooney viscosity ML.sub.1+.sub.4(100° C.): 53 to 67) [0031] Carbon black (HTC#SS, produced by Nippon Steel 35 parts by weight [0032] Chemical Carbon Co., Ltd., [0033] a turbostratic graphite structure) [0034] Zinc oxide (Zinc Oxide #1, produced by 5 parts by weight [0035] Seido Chemical Industry Co., Ltd.) [0036] Antioxidant (Nocrac 6C, produced by 3 parts by weight [0037] Ouchi Shinko Chemical Industrial Co., Ltd.; [0038] Antioxidant (Nocrac 224, produced by 1.5 parts by weight [0039] Ouchi Shinko Chemical Industrial Co., Ltd.; [0040] Plasticizer (ADK Cizer RS107, 15 parts by weight [0041] produced by Adeka Corporation) [0042] Sulfur (Colloidal Sulfur A, 1.2 parts by weight [0043] produced by Tsurumi Chemical Industry Co., Ltd.) [0044] Vulcanization accelerator 2.5 parts by weight [0045] (N-cyclohexyl-2-benzothiazylsulfenamide; [0046] Nocceler CZ-P, produced by Ouchi Shinko [0047] Chemical Industrial Co., Ltd.) [0048] Vulcanization accelerator (tetramethylthiuram disulfide; 2.0 parts by weight [0049] Sanceler TT-G, produced by [0050] Sanshin Chemical Industry Co., Ltd.) [0051] Stearic acid (produced by Miyoshi Oil & Fat Co., Ltd.) 0.2 part by weight [0052] Paraffin wax (Suntight R, 0.5 part by weight [0053] produced by Seiko Chemical Co., Ltd., [0054] melting start temperature: 65° C.)

[0055] Each of the above components was kneaded with a kneader and an open roll in sequence, and the kneaded product (composition) was subjected to primary vulcanization at 180° C. for 4 minutes and oven vulcanization (secondary vulcanization) at 150° C. for 1 hour.

[0056] The obtained vulcanizate was measured and evaluated for the following various items.

Hardness: According to JIS K6253 Corresponding to ISO 18517

[0057] Three rubber sheets with a thickness of 2 mm were stacked, and the durometer hardness A was measured.

Tensile Test: According to JIS K6251 Corresponding to ISO 37

[0058] A rubber sheet with a thickness of 2 mm was punched into the shape of a JIS 5 dumbbell specimen using a punching jig, and three of the resulting specimens were measured for tensile strength and elongation at break.

Compression Set Test: According to JIS K6262 Corresponding to ISO 815-1

[0059] Three block specimens with a diameter of 29.0 ± 0.5 mm and a thickness of 12.5 ± 0.5 mm were tested at 120° C. for 72 hours at a compression rate of 25%.

Ozone Degradation Test: According to JIS K6259 Corresponding to ISO 1431

[0060] Using a punching jig, a rubber sheet with a thickness of 2 mm was punched into a strip shape having a smooth surface with a length (between grippers) of 40 mm or more, a width of about 10 mm and a thickness of 2.0 ± 0.2 mm. Three of the resulting specimens were tested under conditions of 40° C., 72 hours, an ozone concentration of 50 pphm, and a rubber elongation rate of 20%, and evaluated by the method described in JIS K6259, Appendix JA.

Method Described in Appendix JA

[0061] A-2: a few cracks (visible to the naked eye) [0062] B-2: many cracks (visible to the naked eye) [0063] C-2: innumerable cracks (visible to the naked eye) [0064] C-3: innumerable cracks (deep cracks, relatively large, less than 1 mm) [0065] C-4: innumerable cracks (deep cracks, large, 1 mm or more and less than 3 mm)

None: No Cracks

[0066] Appearance at the time of molding: The surface condition of O-ring shaped specimens with a diameter of 3.1 mm was visually observed. Those with a good surface condition were evaluated as O, and those with appearance defects such as cloudiness and patterns were evaluated as X.

Example 2

[0067] In Example 1, the amount of paraffin wax was changed to 1.0 part by weight.

Example 3

[0068] In Example 1, the amount of stearic acid was changed to 0.3 parts by weight and the amount of paraffin wax was changed to 1.0 part by weight, respectively.

Example 4

[0069] In Example 1, the amount of stearic acid was changed to 0.5 parts by weight and the amount of paraffin wax was changed to 1.0 part by weight, respectively.

Example 5

[0070] In Example 3, the same amount (100 parts by weight) of NBR JSR N215SL (produced by JSR, bound AN content: 48%, Mooney viscosity ML.sub.1+.sub.4(100° C.): 45) was used in place of NBR DN101L.

Example 6

[0071] In Example 3, the same amount (100 parts by weight) of NBR JSR N230S (produced by JSR, bound AN content: 35%, Mooney viscosity ML.sub.1+.sub.4(100° C.): 56) was used in place of NBR DN101L.

Example 7

[0072] In Example 3, the same amount (100 parts by weight) of NBR JSR N240S (produced by JSR, bound AN content: 28%, Mooney viscosity ML.sub.1+.sub.4(100° C.): 56) was used in place of NBR DN101L.

Example 8

[0073] In Example 3, the same amount (100 parts by weight) of NBR JSR N250S (produced by JSR, bound AN content: 19.5%, Mooney viscosity ML.sub.1+.sub.4(100° C.): 63) was used in place of NBR DN101L.

Comparative Example 1

[0074] In Example 1, neither stearic acid nor paraffin wax was used.

Comparative Example 2

[0075] In Example 1, stearic acid was not used.

Comparative Example 3

[0076] In Example 2, stearic acid was not used.

Comparative Example 4

[0077] In Example 2, stearic acid was not used, and the amount of paraffin wax was changed to 2 parts by weight.

Comparative Example 5

[0078] In Example 1, paraffin wax was not used.

Comparative Example 6

[0079] In Example 3, paraffin wax was not used.

Comparative Example 7

[0080] In Example 3, the amount of paraffin wax was changed to 0.5 parts by weight.

Comparative Example 8

[0081] In Example 3, the amount of paraffin wax was changed to 2.0 parts by weight.

Comparative Example 9

[0082] In Example 4, paraffin wax was not used.

Comparative Example 10

[0083] In Example 4, the amount of paraffin wax was changed to 0.5 parts by weight.

Comparative Example 11

[0084] In Example 1, the amount of stearic acid was changed to 1.0 part by weight, and paraffin wax was not used.

Comparative Example 12

[0085] In Example 1, the amount of stearic acid was changed to 1.0 part by weight.

Comparative Example 13

[0086] In Example 2, the amount of stearic acid was changed to 1.0 part by weight.

Comparative Example 14

[0087] In Example 1, the amount of stearic acid was changed to 1.0 part by weight and the amount of paraffin wax was changed to 2.0 parts by weight, respectively.

Comparative Example 15

[0088] In Example 3, the same amount (1 part by weight) of Suntight produced by Seiko Chemical Co., Ltd., (melting start temperature : 75° C.) was used as the paraffin wax.

Comparative Example 16

[0089] In Example 3, the same amount (1 part by weight) of Suntight S produced by Seiko Chemical Co., Ltd., (melting start temperature : 60° C.) was used as the paraffin wax.

Comparative Example 17

[0090] In Example 3, the same amount (1 part by weight) of Suntight SW produced by Seiko Chemical Co., Ltd., (melting start temperature : 100° C.) was used as the paraffin wax.

[0091] The results obtained in the above Examples and Comparative Examples are shown in the following Table 2. Table 1 shows the compounding amounts of stearic acid and paraffin wax (Suntight R) used in Examples 1 to 4 and Comparative Examples 1 to 14, in which DN101L was used as NBR.

TABLE-US-00001 Example Stearic acid (part by weight) Paraffin wax Suntight R (part by weight) Example 1 0.2 0.5 Example 2 0.2 1.0 Example 3 0.3 1.0 Example 4 0.5 1.0 Comparative Example 1 - - Comparative Example 2 - 0.5 Comparative Example 3 - 1.0 Comparative Example 4 - 2.0 Comparative Example 5 0.2 - Comparative Example 6 0.3 - Comparative Example 7 0.3 0.5 Comparative Example 8 0.3 2.0 Comparative Example 9 0.5 - Comparative Example 10 0.5 0.5 Comparative Example 11 1.0 - Comparative Example 12 1.0 0.5 Comparative Example 13 1.0 1.0 Comparative Example 14 1.0 2.0

TABLE-US-00002 Example Hardness Tensile strength (MPa) Elongation at break (%) Compression set (%) Ozone degradation: Presence or absence of crack Appearance at the time of molding Example 1 59 11.9 390 25 None O Example 2 59 12.7 420 26 None O Example 3 60 13.4 420 27 None O Example 4 60 11.1 400 26 None O Example 5 67 12.5 420 28 None O Example 6 67 10.5 400 25 None O Example 7 62 7.1 240 23 None O Example 8 60 6.3 230 24 None O Comparative Example 1 60 14.5 430 35 C-3 O Comparative Example 2 60 14.4 430 35 None O Comparative Example 3 59 13.3 410 36 None O Comparative Example 4 59 13.3 410 36 None × Comparative Example 5 59 11.9 420 24 C-4 O Comparative Example 6 60 13.0 430 24 C-4 O Comparative Example 7 61 11.9 370 25 A-2 O Comparative Example 8 60 9.5 360 26 None × Comparative Example 9 61 12.6 420 24 C-4 O Comparative Example 10 60 12.0 410 26 B-2 O Comparative Example 11 60 14.2 410 27 C-4 O Comparative Example 12 61 10.8 360 25 C-2 O Comparative Example 13 61 10.2 360 25 C-2 O Comparative Example 14 61 11.4 340 25 None × Comparative Example 15 60 14.9 440 28 C-2 O Comparative Example 16 60 15.6 410 28 A-2 O Comparative Example 17 60 13.6 420 29 C-2 O

[0092] The above results demonstrate the following.

[0093] The product of each Example satisfies all of the moldability, vulcanizate physical properties, compression set characteristics, and ozone resistance, and is not affected by the AN content of NBR.

[0094] When stearic acid is not used, not only the vulcanization speed is delayed and the compression set characteristics are deteriorated, but also the ozone resistance and the appearance at the time of molding may be deteriorated. (Comparative Examples 1 to 4).

[0095] When paraffin wax having a melting start temperature other than 65° C. is used, the ozone resistance is insufficient (Comparative Examples 15 to 17).

[0096] When paraffin wax is not used, the ozone resistance is insufficient (Comparative Examples 5, 6, 9 and 11).

[0097] Even when paraffin wax having a melting start temperature of 65° C. is used, if the amount thereof is less than an amount equal to twice the amount of stearic acid, the ozone resistance is insufficient (Comparative Examples 7, 10, 12 and 13).

[0098] When paraffin wax is compounded in an amount exceeding 6 times the amount of stearic acid, the appearance at the time of molding is deteriorated (Comparative Example 8).

[0099] When the components are used at the ratio described in Patent Document 1, the appearance at the time of molding is impaired (Comparative Example 14).