JPS59176338A - Rubber vibration insulator composition - Google Patents

Abstract

PURPOSE:To provide a rubber vibration insulator compsn. having excellent vibration insulation characteristics and adhesiveness, by incorporating a halogenated ethylene/alpha-olefin/non-conjugated diene copolymer rubber. CONSTITUTION:A halogenated ethylene/alpha-olefin/non-conjugated diene copolymer rubber (halogenated EPDM) having a halogen content of 1-40wt% obtd. by halogenating (pref. chlorinating or brominating) EPDM contg. ethylene, alpha-olefin (e.g. propylene or butene-1) and non-conjugated diene (e.g. ethylidene norbornene or dicyclopentadiene) components, is used. At least 30wt% said halogenated EPDM and not more than 70wt% other rubber (e.g. natural rubber or styrene/ butadiene rubber) are kneaded together to obtain a rubber vibration insulator compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an EPDM-based anti-vibration rubber composition having excellent vibration-absorbing properties and adhesive properties.

General-purpose anti-vibration rubber has conventionally been manufactured using natural rubber or diene-based synthetic rubber alone or as a blend.

With the recent development of the automobile industry, anti-vibration rubbers are required to have greater vibration-absorbing properties, and are also required to have excellent heat resistance in order to withstand exhaust gas emissions.

As for vibration absorption characteristics, for example, the static-dynamic ratio shown by E' 70 Hz/E' IHz in a viscoelastic spectrometer is reduced, and the loss tangent (tarl δ) is increased in a relatively low frequency range of around 20 Hz at room temperature. It is said to be promising. The methods of improving vibration absorption properties that have been carried out in this field have mainly relied on compounding agents such as fillers and extender oils, but there have been limits to the improvements made by these. Therefore, instead of thinking of improving conventional rubber compositions, EPDM-based rubber has been considered as an active method, but this also has the disadvantage of poor adhesion to metals, and is used in the automobile industry. The application as anti-vibration rubber is: X: Rare.

An object of the present invention is to provide an EPDM-based vibration isolating rubber that has excellent anti-vibration properties and improved adhesiveness.

The anti-vibration rubber composition of the present invention is characterized in that the rubber component contains a halogenated ethylene-α-olefin-nonconjugated diene copolymer rubber having a halogen content of 1 to 40% by weight or more. It is something.

The halogenated ethylene-a-olefin-nonconjugated diene copolymer rubber used in the present invention consists of ethylene, propylene, α-olefin such as butene-1, ethylide 7-norbornene, zinclopenotadiene/, propenylnorbornene, etc. , 4-hexadiene, 4,7,8.9-tetrahydroindene and other non-conjugated dienes in 1m-! It can be obtained by halogenating an ethylene-σ-olefin-nonconjugated die/copolymer rubber containing at least two or more types by a known method.

...The type of rogens is likely to be chlorine or bromine.

There are no particular restrictions on chlorination.1For example, a method of crushing a copolymer rubber into fine particles and contacting it with bimolecular chlorine gas, a method of making the fine particles into an aqueous suspension and contacting them with molecular chlorine, or n -Hexa/.

A method in which a copolymer rubber is dissolved in a hydrocarbon such as n-hebutane, a certain carbon tetrachloride, tetrachloroethylene, or a chlorobenzene/logenated hydrocarbon, and brought into contact with molecular chlorine in a uniform solution state. This can be done by, for example.

Similarly to the chlorination in a homogeneous solution, bromination is carried out by dissolving the copolymer rubber in a hydrocarbon or a no-generated hydrocarbon and bringing it into contact with molecular bromine.

In order to accelerate the reaction during these rogogenation reactions, ultraviolet light may be irradiated or peroxide may be added.

...After the rhodanization reaction, it is treated as follows.

That is, in the case of chlorination in the same phase, a chlorinated copolymer rubber is obtained by expelling excess chlorine by passing nitrogen gas after the completion of the two reactions.

In the case of chlorination in a suspended state, after the reaction, the reaction product is washed with water and then dried to obtain a chlorinated copolymer. In the case of chlorination or bromination in a solution state, after the reaction, for example, the reaction product is treated with an aqueous solution of caustic soda, washed with water, and then steam stripped to obtain a chlorinated or brominated copolymer rubber. .

If the rogen content of the non-logenated ethylene-σ-olefin-nonconjugated diene copolymer rubber used in the present invention is too low, the effects of the present invention cannot be obtained, and if it is too high, the various physical properties of the copolymer rubber balance is lost. Therefore, the usable range is 1 to 40% by weight, preferably 2 to 3% by weight.
0 weight.

Halogenated ethylene α-olefin in the present invention
The non-conjugated renin copolymer rubber can be used in combination with other rubbers, and examples of other rubbers include natural rubber and diene-based synthetic rubber. As the diene synthetic rubber, polyimprene rubber, styrene-butadiene rubber and polybutadiene rubber are preferred. When used in combination with other rubbers.

The proportion of the non-logenated ethylene-a-olefin-nonconjugated diene copolymer rubber relative to 100 parts by weight of the rubber component is required to be at least 30 parts by weight in order to obtain the desired effect.

In preparing the rubber composition of the present invention, a kneading machine generally used for rubber, such as a Banbury Mixer 1 two-roll mixer, can be used.

During kneading, additives commonly used for rubber compounding, such as fillers such as carbon platters, are added to the rubber.
10 to 120 parts by weight per 0 parts by weight, 0 to 80 parts by weight of extender oil such as aromatic oil and naphthenic oil per 100 parts by weight of rubber, and other additives such as plasticizers and anti-aging agents.

Furthermore, acid acceptors such as MgO and epoxy resin can be used as necessary.

There are no particular restrictions on the adhesion between the rubber composition of the present invention and metal, and commercially available one-component or two-component rubber-metal adhesives may be used.

For example, one-component products such as Firestone's Loxite 3040 and Hughson Che
Chemlok 2 by mical
A two-component product using 05 as a primer and Chemronoku 220 as an overcoat.

Bayer's Desmodur
modur ) R and ICI's Vulcabond (Vulc)
Examples include incyanate adhesives such as abond) TX.

The present invention will be specifically explained below using Examples and Comparative Examples. In addition, the amount of compounding agents to be used, .

The vibration damping properties in the Examples and Comparative Examples were evaluated using a viscoelastic spectrometer manufactured by Harumoto Seisakusho.
Loss tangent tanδ in Hz, 20? l; E' at 70 Hz El at 20 CI Hz was measured, and the static dynamic ratio (E170 Hz/E' lHz) was determined, and the results were calculated based on the static dynamic ratio and the magnitude of tan δ. Static/dynamic ratio is small and ta
The larger nδ indicates better vibration damping characteristics.

The adhesion to metal was evaluated using a test method in accordance with JIS K6301, in which a sample of two parallel metal plates bonded with rubber was peeled off. Note that Kemronok 205 (Heewson Chemical) was used as the primer, and Kemronok 236 (Heewson Chemical) was used as the cement.

In addition, the tensile test method was based on JIS K6301.

(Ml, 00 is 100 cm tensile stress, TB is tensile strength.

BB is elongation, I (S is hardness) Example-1) PI) M (Japan Synthetic Rubber EP570) 2505'
was bath-dissolved in n-hexane, and chlorine was blown in at 55 to 60C to obtain chlorinated ID PDM with a chlorine content of 22%. The thus obtained chlorinated EPDM was kneaded with a plastomill according to the formulation shown in Table 1, and then mixed with a vulcanizing agent using a roll.
A vulcanization accelerator was mixed, and the resulting mixture was press-vulcanized at 150C for 120 minutes, and its physical properties were measured. The results are shown in Table-2.

Table-1 Compounding recipe Polymer 100 HAF carbon 50 Naphthenic oil 10 Zinc white 5 Stearic acid 1 Vulcanization accelerator CB S 1.5//
MBT 0.5i
2 total
170 Table-2 Test results Mloo (K9f/crI) 37T
B (K9f/cnI) 300EB
(H) 380 I-1s JIS-A
72 Adhesion strength Kyf fake) 41 Viscoelastic spectrometer 20tZ'tan δ
15l-1z O,1001 furnace 7
01-12 (dyn/cnt)
1.20 X 108E' 11-1z (dyn
〆-) 1.03X108 static-dynamic ratio = 1.17 Comparative example-1 1ji I) D M (Japan Synthetic Rubber EP570) 25
0g was dissolved in carbon tetrachloride, and chlorine was blown into the solution at 55 to 60C to obtain chlorinated EPI) lvl with a chlorine content of 08%.

The thus obtained chlorinated EPDM was kneaded in a plastomill according to the formulation shown in Table 1 of Example 1, and then a vulcanizing agent and a vulcanization accelerator were mixed in a roll to form the resulting compound. 1
Physical properties were measured after press vulcanization at 50CX for 90 minutes. The results are shown in Table-3.

Table-3 Test results M100CK9f/en) 52 ・1・B (K9f/crI) 2
77EB (chi) 320 IIs JIS-A
76 Adhesive strength (immediate f shoulder) 35 Viscoelastic spectrometer 20Ctan δ1
5H2O,095]',' 70H2(dyn/,7) 1.4
5X108E' 1 f-12 (dyn〆wl)
1.26×108 Static dynamic ratio=115 Comparative example-2 EPDM (EP57C manufactured by Japan Synthetic Rubber) was prepared into a compound using the same method as in Comparative example-1, press-cured at 150C for 90 minutes, and the physical properties were measured. The results are shown in Table 4vE.

Table - 41 people's buttocks, M 100 (K9 enemy) 48 TB' (K9f/m) 242EB
(%) 310 H3JIS-A 78 Adhesive strength 30 Viscoelastic spectrometer 2'OCtan
δ 15Hz 0.09
01 70Hz (dyn/i) 1.96
X108EI IH2 (dyn7 reward) 16
3×108 quiet ratio=120 Example-2 EPDM (EP57C made by Japan Synthetic Rubber!) 2
50 U was dissolved in carbon tetrachloride, and chlorine was blown in at 55 to 60 U to obtain chlorination with a chlorine content of 11.5%. jp I)
I got M. The obtained chlorinated IBPDM was finished into a blend in the same manner as in Example-1 using the distribution recipe shown in Table-5.15
The material was press-vulcanized at 0rX for 120 minutes and its physical properties were measured.

The results are shown in Table-6.

Table-5 Compounding recipe Polymer 100 HA F carbon 50 So7 ten oil 10 Zinc white 5 Stearic acid l MgO1504 Vulcanization accelerator OBS 1.5// M
BT” 0.5 I O
2 words 1

] 74th...Made by Kyowa Chemical Industry Co., Ltd. Table-6 Test results Mloo (K91/cm) s ]TB
(Kpf/i) 223EB (φ)3
50 1 (SJ Ding S-A-82 - Adhesive strength K9f layer) 45 Viscoelastic spectrometer Also ゛G tan δ t 5H2'0.114El 7
0H2 ((lyn〆ff1) 2.40X108B
' IH2 (dyn/i) 2.20X1
08 Static dynamic ratio = 1.09 Example - = 8-3 Dissolve gPDM (EP33 manufactured by Japan Synthetic Rubber Co., Ltd.) 250 F in carbon tetrachloride and blow chlorine at 55 to 60'C to chlorinate the chlorine content to 20.0φ Obtained EPDM.

The obtained chlorinated E1)DM was prepared into a compound by the same method as in Example 2, plain vulcanized at 150 UX for 120 minutes, and its physical properties were measured. The results are shown in Table-7.

Table-7 Test results Mloo <wi=> - TB (K9f/CI?L) 180EB
(%) 100 r■ JIS-A 90 adhesive strength K9
f shoulder) 48 Viscoelastic spectrometer 20tZ'tan δ
15H2O, 172 wl701-1z (dynAiL) 3.50X1
08El I Hz (dyn〆ml)
3.05X108 silent ratio = 1.15 Example-4 EPDM (Japan Synthetic Rubber EP33) 250
1i' was dissolved in carbon tetrachloride and chlorine was blown into the solution at 55 to 60C to obtain chlorinated EPT)M with a chlorine content of 28.5%.

The obtained chlorinated EP ]) M was finished into a blend in the same manner as in Example-2, press-vulcanized at 150 rX for 20 minutes, and its physical properties were measured. The results are shown in Table-8.

Table-8 Test results M], OO (K9f/i) -TB (
K9f ~) 202 EB (%) 100 11s JIS-A 9
2 Adhesion strength K9f shoulder) 45 Viscoelastic spectrometer 20Ctan δ
15Hz 0.1901v17o
r-rz(dynlofQ 3.70X108E'
1l-Iz(dyn/ff1) 3.08
X10' quietness ratio==1.20 Comparative Example-3 EPDM (EP33 manufactured by Japan Synthetic Rubber Co., Ltd.) 2509 was dissolved in carbon tetrachloride, and chlorine was blown into the solution at 55 to 60 C to obtain chlorinated FJPDM with a chlorine content of 42%. Obtained 7'1. The chlorinated EPDM was prepared into a mixture in the same manner as in Example-2, and 150 tons of chlorinated EPDM was prepared. Press vulcanization was performed for 240 minutes, and the physical properties were measured. The results are shown in Table-9.

Table-9 Test results Mloo CKql shoulder) - TB (K9Val) 247 B (chi) 30 1-1s JIS-A,
99 adhesive strength K9f/cnf) 32
Viscoelastic spectrometer 20C tan δ 15T-120,210 E' 70H2 (dyn/cIl) 4.20
X108El IHz (dyn/d) 3.
23X108 Static dynamic ratio 130 Example-5 E P ? ) M (Japan Synthetic Rubber gP570) 25
0 P was dissolved in carbon tetrachloride, and a bromine solution in carbon tetrachloride was added dropwise at 70 to 75 tT to obtain brominated E P I) M with a bromine content of 12.5%. The obtained brominated BP J)
M was prepared into a blend in the same manner as in Example-1, and 150
Press vulcanization was performed for 90 minutes, and the physical properties were measured. Display the results -
10.

Table-10 Test results Mloo (Kff/crtt) 85TB
(K9f/i) 230TUB (
350 r-1s JTS-A 83 adhesive strength K
9) 45 Viscoelastic spectrometer λσ゛(ran δ
1 dafu o118E' 70H
z (dYn/i) 2.50X1.08E
IH2 (dyn/cffl) 2.2
3X108 Static dynamic ratio = 1.12 Example-6 EPDM (EP33 manufactured by Japan Synthetic Rubber Co., Ltd.) 250 P was bath-dissolved in n-hexane and 55 to 60 tons? Chlorine was blown in to obtain chlorinated EPDM with a chlorine content of 52%. Using the obtained chlorinated EPT) M, an SB blend formulation was prepared in the same manner as in Example 1 according to the formulation in Table 110, and the mixture was vulcanized at 150C for 30 minutes and its physical properties were measured. The results are shown in Table-12.

Table-1] Mixing recipe A 13 Chlorinated EPDM 30. %50813R
1500''''' 70 50HA F Carbon 5゜Total 172 Month...Made by Japan Synthetic Rubber Co., Ltd. Hakama 2...Made by Kyowa Chemical Industry Co., Ltd. Table-12 Test Results A B TB CK9VCrl) 166 12
7EB (%) 350 2801
-1s JIS-A 70 72
Adhesive strength (K91'/i) 42
45 Viscoelastic Spectrometer 2a'e-tan δ
15H2O, 1700, 160"" 70H2
(dyn, 4w 1.95X], 08 2.45”IO
'El u-1z(dyn/ff1) 1.7
0X1082.17 x+o” static dynamic ratio 1.15
1.13 Application submitted by Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1) A vibration-proof rubber composition characterized in that a halogenated ethylene-α-olefin-nonconjugated diene copolymer rubber containing 1 to 40% by weight of halogen is contained in a proportion by weight of 30% or more in the total amount of rubber components. .