JPS60108448A - Rubber compound composition - Google Patents

Abstract

PURPOSE:A composition, obtained by using a sulfur (compound) as a crosslinking agent and a sulfenamide based compound as a vulcanization accelerator in a rubber component consisting of a hologenated ethylene-alpha-olefin-nonconjugated diene copolymer rubber and a diene based rubber, and having improved mechanical strength. CONSTITUTION:A rubber compound composition obtained by incorporating (A) 5-95wt%, preferably 20-95wt% copolymer rubber of a halogenated ethylene, an alpha-olefin, preferably propylene, and a nonconjugated diene, preferably ethylidenenorbornene, with 0.2-10wt%, preferably 0.5-7wt% halogen content with (B) 95-5wt%, preferably 80-5wt%, diene based rubber, e.g. natural rubber, isoprene or SBR, and (C) a sulfur or sulfur-containing compound, e.g. 4,4'-dithio-bis-dimorpholine, as a crosslinking agent and (D) a sulfenamide based compound, e.g. N,N'-diisopropyl-2-benzothiazole sulfenamide as a vulcanization accelerator. The amounts of the components (C) and (D) based on 100pts.wt. total of the components (A) and (B) are as follows; 0.1-10pts.wt. component (C) and 0.1-5pts.wt. component (D).

Description

[Detailed description of the invention]

The present invention relates to quick-curing armpit gauze and rubber compositions with excellent mechanical strength, and more specifically to halogenated ethylene-α
- An olefin-nonconjugated diene copolymer rubber (hereinafter sometimes abbreviated as halogenated EPDM) and a diene thread rubber. Conventionally, blend compositions of HPDM and diene thread rubber have not been suitable due to the difference in vulcanization rate between diene thread rubber and WPDM, or poor compatibility, etc., so that crosslinking has not progressed to a certain extent and mechanical strength is not defined; A rubber composition having C is not obtained. In addition, in a blend composition of halogenated 1flPDM and diene thread rubber, the effective crosslinking agents for crosslinking the diene thread rubber and halogenated EPDM are completely different, so a rubber composition with satisfactory mechanical strength cannot be obtained. No. The object of the present invention is to provide a composition having a superior vulcanization rate and a very poor mechanical strength compared to the prior art. Unexploded vA and others conducted intensive studies and found that the use of a specific vulcanization accelerator can significantly improve the co-crosslinking properties and achieve the above objectives. Tetrahalogen content is 02~1Ow 11q
k halogenated EPDM5-9511

[當饅 and (b) fire-heat rubber, isoprene rubber, styrene-butadiene rubber, and tumediene rubber. A rubber component consisting of acrylonitrile butadiene rubber and 95 to 5 layers of diene thread rubber has 0 sulfur as a crosslinking agent. A rubber compounding composition containing a phenamide vulcanization accelerator is provided. The present invention will be explained in detail below. Halogen content of the halogenated nPDM of the component (5) of the present invention ij O, 2 to 1G East ii Preferably 1 or 0.5
~ If yxts is good and less than 0.2 weight, halogenated B
There is no ff# number as a PDM, and there is no difference between l'l'DM and the housing, so there is no effect on co-crosslinking properties. If it exceeds 1% by 10%, the elongation and ozone resistance will become too rapid, and it will not be possible to obtain a good 710% speed. Generally, Ni'DM, which is the base of the constituent components of the present invention, is trene, propylene is a-onfin, l-butene is used, and propylene is preferably used. An engineered resin containing at least 2 or more non-conjugated dienes such as ethylidenenorbornene, cyclopentadiene, flobenylnorbornene, 1,4-h+sadiene, and 4,7,8,9-tetrahydroindene as the third component. An α-olefin-nonconjugated diene copolymer rubber is used. The halogen citrus used is preferably chlorine or halogen. The diene thread rubber used as the constituent component of the present invention is commercially available natural rubber (NH) or Inglene rubber (IR). Styrene-butadiene rubber (BBR), butadiene rubber (
BR), acrylonitrile purdiencom (NHM), etc. are used. Constituent component of the invention C) Sulfur °C is powdered sulfur. Various types of sulfur such as precipitated sulfur and insoluble sulfur can be used, and sulfur-containing compounds such as 4,4'-dithiopisu dimorpholine, diventamedelene detrasulfide, and dipentastyrene hexasulfide can be used. Examples of the sulfenamide vulcanization accelerators of the present invention include he-N'N diisopropyl-2-benzothiazolesulfenamide (1) PH1), N-cyclohexyl-2-benzothiazylsulfenamide ((,! 88
), N-othousandiethylene-2-benzothiazolesulfenamide (Ous). Beta-shaributyl-2-penzothiol-zolylsulfenamide (BR8), N,N'-diV-chlorohexyl-2-benzothiazolylsulfenamide, etc. are used.
Ru. In the composition of the present invention, the ratio of (5) halogenated BPDM and (c) diene rubber is tetrahalogenated nPDM5 to 951I[
The weight range is preferably 20 to 95 yen, (b) diene rubber 95 to 5 yen, and preferably 80 to 5 yen. If the proportion of halogenated MPDM exceeds 95% by weight, the vulcanization rate will slow down, which is undesirable, and if it is less than -5% by weight, the properties of the halogenated HPDM/diene thread rubber will be very similar to that of diene thread rubber. More featureless. Further, m in the sulfur or base sulfur compound 0 sulfenamide vulcanization accelerator (C) of the present invention is a rubber component (N+
(b)) o, l as 0 sulfur for loOJt wrinkles
-t Ox11g, good t L<ldO,s ~3JI
ItM. 0 sulfenamide yarn 7JO (i1E accelerator 0.1-5
It is preferably in the range of 03 to 3 iri parts. If the rubber components of 0 and 0 are not combined within the above range, the vulcanization will not be balanced.5- Good physical properties cannot be obtained, which is not preferable, and the feature of the present invention is such 0, (2) The halogen content of PDM, which is a constituent tetrahalogenated PDM of the present invention, is measured by using an elemental minute needle or the like. In addition, for the production of component 4, it is possible to use known halogenation methods such as the gPDM solvent dissolution method, aqueous suspension method, and solid phase method. In preparing the rubber compound composition of the present invention, a conventional rubber kneading machine such as a panburi mixer, a two-der blender roll machine, etc. is used, and the color and texture are adjusted as necessary using carbon black, carbonated calcium V cum, etc. . Fillers such as silica and clay, process oils, plasticizers,
Stabilizers, etc. can be used in various combinations. The rubber compound composition #I of the present invention has excellent vulcanization speed 2 and very good mechanical strength, and also has the weather resistance and ozone resistance of nPDM, and can be used in a wide range of applications. It is. For example, the sidewalls and treads of automobile tires, bicycle tires, and M-frames. This invention is useful for hoses, etc. 6- The present invention will be described below based on Examples, but unless otherwise specified, the numerical values herein indicate weight percentages or weight %. In the examples, the vulcanization rate was measured using a JI9RIIB model Curalastometer (manufactured by Japan Synthetic Rubber @4). The time required to obtain an increase in value of 10% of the difference between the maximum torque value and the minimum torque value on the culastometer curve is t'c (10), and the increase in value of 90 capsules is obtained n. The time required for this is expressed as it'c(90). Note that a press machine was used for vulcanization. The method of tensile test is 72:6 according to JIB K6301 (1).
It was dissolved in hexitine and blown with chlorine gas at 55 to 60°C to obtain chlorinated EPDM containing 1114-chlorine. This chlorinated WPDMao part and natural rubber R198”a (M
70 parts of Ll+4 (100tl:)" 82 masticated with a roll) were kneaded with a roll M according to the formulation shown in 115i-1 to give a blend. Vulcanization of this blend The speed t-^ was determined, and the physical properties were measured after press vulcanization at 150°C. F carbon black 50 Z n 0 3 stearin a! 2 anti-aging crack 8roNA4) 1 vulcanization accelerator OB8'' 2 1 sulfur 2 tatami l...inai-fko ■sakana 2...small-cyclohexyl- 2-benzotheazilsulfenamide Table 2 Test results Vulcanization speed f (150°C) t'c (10) 2'54't' C (90) 7'18" Vulcanized physical properties Tensile strength i"B (#f/cd) 242 elongation gn(
%) 43゜Hardness Hs JIS-A 711 Comparative Example - 30 parts of 5filP65 (manufactured by Japan Synthetic Rubber ■) and Example-1
The test was carried out in the same manner as in Example 1 using 37 parts of natural rubber R88 used in Example 1. The results are shown in Table 3. Tn is extremely low compared to Example-1. Table-3 Test results Vulcanization speed (150°C) t' C(10) 2'54"t' c(so) 7'12' Vulcanized physical properties Hs JI19-A 73 9- Example-2 Example-5 Chlorinated BPDE3 and natural rubber R88 used in
It was carried out in the same manner as in Example 1 except for using the formulation shown in Table 4 for af use. The results are shown in Table-5. Example-
Similar to 1, it shows good TB. OB1/a shows good 7J:TBt-. Table-4 Combination recipe poly'? -100 to 4AF; J-honbu 5'F7 50Z port 03 Stearic acid 2 Anti-aging drug 81oNA 1 Vulcanization accelerator OB8''3 □ Sulfur 2 Well 3...N-,txyethylene-2-penzothiazole Fuenade lO- Table 5 Test results Vulcanization rate (150℃) t'e (10) 3'26"t'c (90) 9'jQ" Vulcanized physical properties i" B (# f /cyf) 230 Ris (rice cake) 430 1-4s JIS-A 71 Example-3 Chlorination used in Shoshii 1-1 E )' D ? , 131
J part and 8BR (blk3Rh500 Japanese synthetic rubber (41
030 parts, machined natural rubber R88”a (MLx+4(t
Vulcanization time t"tsocxao using 40 parts of strands rolled at 82°C) using the formulation of Cloth-1.
It was carried out in the same manner as in Example-1, except for using a minute. The results are shown in Table-7. Table-7 Test results Vulcanized AMIK, (5 aoC) t' c (10) 4'00"t' C (9G) 52'3B' Vulcanized physical properties TB (#f/c+J) 233 hiB (*) 380 HsJ18-A74 Example-4 Chlorinated IPDM and natural rubber i<ss used in Example-1
Chlorination using trimetallic metal 1) i'DM 70 parts, natural rubber 30M
The process was carried out in the same manner as in Example 1, except that the formulation in Table 1 was used and the vulcanization time was 40 minutes at taO°C [7 liters]. The results are shown in Table 8. This example also shows an excellent TB. -Low Table-8 Test Results Vulcanization Speed (150C) t' c(sO) 4'12"t' c(90) +s'oo" Vulcanization Physical Properties TB (#f/m) 240 EB(S) 41G HsJI8 -A72 Comparative Example-2 The kJPes used in Comparative Example-1, 70 parts of natural rubber R88"a warehoused hPas, and 30 parts of natural rubber were used with the compounding recipe in Table-1 except that the vulcanization time was kt50cx2G minutes. It was carried out in the same manner as Example - ■. The results are shown in Table 9. Example - 4 Kvibe Tn is smaller - Otori 3 - 12 - Table 9 Test results Vulcanization rate (150°C) t' C (1G ) a'24#t'c (90) 9'aO' Force-loss-sounding TB (#f/cj) 206 H8 (96) 500 HsJIS-A72 Example-5 mas5 (Japanese synthetic rubber C rumor @B PDM) was dissolved in hexane and chlorine gas was blown in at 55-60°C to obtain chlorinated mPobi containing 2.8-m of chlorinated fiPDM in the same manner as natural rubber R883 and 30 parts of this chlorinated fiPDM. The results are shown in Table 1O. This example also shows a very good TB. 14- Table io Test results Vulcanization speed Mouth 50°C) t'c (10) 2'54"Electric' C(90) 7'1ll" Vulcanized physical properties 'I'B (#f/cd) 252 B8 (%) 530 HsJIM-Aq3 Comparative example-3 Chlorinated j!lPDMao moiety used in Example-1 and natural rubber 1 (88 φ 370 parts Table for use in the meeting - Examples except using the formulation in 11 - n results conducted in the same manner as in summer)
It is shown in Table 12. With other vulcanization accelerators, the acceleration is very fast and slow.
B is not produced and the mechanical strength is not good. Table-11 Compounding recipe Polymer 100) 1AF carbon black 50 Zn0 3 Stearic acid 2 Old vj Tsukukutsuku JIIONA Penta-vulcanized t11-adalizer 'l'MTM +5 1.5MBT Sulfur 1.5 4#5... Tetrame T Lutewalam Seven Sulfide Well 6
...Mercagtobenzodeazole Table-12 Test results Vulcanization rate (150°C) t'c (10) 1'36"t' C (90) 6'12" Vulcanization physical properties 'I'B (#f /cd) taa EB (%)'350 HsJI8-A76 Patent applicant Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] (1) (A) Halogen-containing @ 0.2 to 1O*m% halogenated ethylene-α-olefin-nonconjugated diene copolymer rubber 5 to 95 weight 1 t (96) and (b) diene rubber 95 to A machine whose characteristic is to mix 0 sulfur and/or a sulfur compound as a crosslinking agent and a 0 sulfuramide vulcanization accelerator as a vulcanization accelerator into a rubber component consisting of 5 layers and 2 layers. Rubber compound composition capable of increasing physical strength by 4A