JP3487686B2 - Rubber composition for anti-vibration rubber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] TECHNICAL FIELD The present invention relates to a rubber composition for a vibration-proof rubber.
For more information, see
Insulator, center bearing insulator,
Insulation of rack and pinion type steering device
Suitable for vibration-proof rubber materials that require heat resistance
The present invention relates to a rubber composition for a vibration-proof rubber that can be suitably used. [0002] BACKGROUND OF THE INVENTION In recent years, various types of protection used in automobiles have been developed.
Vibration rubber has very severe heat resistance and vibration proof properties.
I have. That is, in recent years, automobiles
Reduction of heat radiation space and increase in engine output
As a result, the ambient temperature in the engine room rises
And the thermal environment of various rubber is becoming severer.
ing. Examples of various vibration isolating rubbers include engine mats
Und insulator, center bearing insulator
, Rack and pinion steering system
Insulator (hereinafter referred to as rack mount insulator)
Rubber).
It is. Below, these insulators
Each will be described. [0003] First, an engine mount insulator
Now, let's take a look at the functions and
In addition to supporting the torque reaction generated by the engine,
It is required to satisfy good soundproof and anti-vibration characteristics.
You. Conventionally, engine mount insulators
Has excellent vibration damping performance and excellent fatigue resistance (durability)
Natural rubber is used as the main component, and in some cases
Means butadiene rubber, styrene-butadiene rubber, black
Loprene rubber, butyl rubber, etc. alone or in many cases
In some cases, natural rubber is used as a blend
Natural rubber-based material). However, as described above, the engine
Now that the thermal environment in the room is deteriorating, in terms of heat resistance,
Natural rubber-based materials are reaching their limits. On the other hand, butadiengo
Rubber and styrene-butadiene rubber alone have durability.
Inferior to natural rubber, and if heat resistance is not enough
There is a problem. Chloroprene rubber is flexible at low temperatures.
Because of its poor properties, it is unsuitable for use as an anti-vibration rubber. Spot
Ru rubber is excellent in damping performance, but dynamic magnification
Has the fundamental problem of extremely high
Is also inferior to natural rubber. Conventional ethylene
・ Propylene rubber with excellent heat resistance
However, there is a disadvantage that the durability is inferior to natural rubber.
You. [0005] In addition, the center bearing ins
The above-mentioned engine mount-in
As in the case of Schlater, the thermal environment is
With the coming center bearing insulator, heat resistance
Are becoming less satisfied. This Center Bearin
Guinsulator is a propeller for FR and 4WD vehicles.
Located in the center of the shaft, the propeller shaft
Used for the joint with the ring, from the propeller shaft
Vibration transmitted directly to the chassis via the center bearing
The propeller shaft,
It has the role of regulating and supporting movements. Conventionally, center
Bearing insulator has high strength and low settling
Natural rubber-based materials have been used where required.
Was. Conventional center bearing insulators
Naturally, it is a rubber material, so in a thermal environment exceeding 100 ° C
Extremely heat aging, not practical. Also, natural rubber materials
As a method for improving the heat resistance of
Semi-effective vulcanization or vulcanization with less vulcanization
There is a method called effective vulcanization. However, like this
Is to improve the heat resistance of natural rubber-based materials.
The improvement effect is about 10 ° C., and the durability is deteriorated.
To meet the required quality.
won. [0006] Further, heat resistance is superior to natural rubber-based materials.
Chloroprene rubber, ethylene
・ Propylene rubber, butyl rubber, etc. have been known
However, these rubbers have the problems or disadvantages described above.
There is. [0007] Further, a rack mount insulator for an automobile
The engine mount incisor described above
For insulators and center bearing insulators
The thermal environment is deteriorated as in the case of
With heat insulators, heat resistance is no longer satisfactory
coming. [0008] The rack mount insulator is
Used for fastening parts between the ring and the rack.
Vibration is transmitted directly to the steering via the rack
And has a positive effect on steering sensitivity
Has a role to give. Therefore, rackmount
Toinsulator has moderate vibration damping performance and excellent
Fatigue (durability) is required.
Materials for rack mount insulators
Thus, natural rubber-based materials are used. However, as described above, the engine
Due to the deterioration of the thermal environment in the room, natural
System materials are reaching their limits. On the other hand, EP with excellent heat resistance
DM is less durable than natural rubber material
There are drawbacks. [0010] The inventors of the present application disclosed in Japanese Patent Laid-Open No. Hei 6-1893.
Report (Japanese Patent Application No. 4-159696)
It has the same vibration-proof characteristics and durability as vibration-proof rubber
In addition, heat-resistant protection with better heat resistance than natural rubber-based materials
The following rubber compositions are proposed as rubber compositions for vibration rubber.
I thought. [0011] The rubber composition for rubbers for heat and vibration isolation is an
Len / α-olefin / non-conjugated diene copolymer rubber
(A), sulfur (B) and carbon black (C)
A rubber composition containing as a main component ethylene-α-ole
The fin / non-conjugated diene copolymer rubber (A) is (i)
Non-conjugated with Tylene and α-olefin having 3 to 20 carbon atoms
(Ii) ethylene and α-olefin
Has a molar ratio of 65/35 to 73/27, and (iii) 1
The intrinsic viscosity [η] measured in decalin at 35 ° C. is 3.7 to
4.2 dl / g, and (iv) 5 paraffinic oils.
0 phr oil-extended melt flow at 230 ° C
-The index is 0.2-0.5 g / 10 min,
(V) an iodine value of 10 to 25, and (vi) a non-conjugated die
Is 5-ethylidene-2-norbornene (ENB),
In addition, this composition was determined by a dynamic viscoelasticity test after vulcanization.
Loss tangent (tan δ) is 0.03 to 0.15
You. [0012] The rubber composition has an anti-vibration property and a fatigue resistance.
Excellent, but better protection than this rubber composition
Desirable rubber composition for vibration isolating rubber with vibration characteristics and fatigue resistance
Have been. [0013] SUMMARY OF THE INVENTION The present invention relates to the prior art as described above.
In order to solve the problem, natural rubber-based protection
It has the same level of vibration isolation and durability as vibration rubber,
Anti-vibration rubber with better heat resistance than natural rubber-based materials
Provided is a rubber composition for an anti-vibration rubber that can be provided.
It is aimed at. [0014] SUMMARY OF THE INVENTION The rubber composition for rubber vibration insulators according to the present invention comprises:
Ethylene, an α-olefin having 3 to 20 carbon atoms,
At least one kind of branched chain represented by the following general formula [I]
Copolymer rubber composed of glassy polyene compound
(A), a filler (B), and a vulcanizing agent (C).
Wherein the random copolymer rubber (A) comprises:
(I) ethylene and α-olefin having 3 to 20 carbon atoms
50/50 (ethylene / α-olefin)
(Ii) an iodine value of 5 to 30;
(Iii) measured in decalin at 135 ° C.
The intrinsic viscosity [η] is in the range of 1.0 to 6.0 dl / g.
Determined by dynamic viscoelasticity test after vulcanization of the composition.
Loss tangent (tan δ) becomes 0.03 to 0.15
It is characterized by. [0015] Embedded image [In the formula [I], n is an integer of 1 to 5,
R¹ Is an alkyl group having 1 to 5 carbon atoms;^Two And
And R^Three Is independently a hydrogen atom or a carbon atom
It is an alkyl group of Formulas 1 to 5. ] [0017] DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a rubber damper for rubber according to the present invention will be described.
The composition will be described in detail. Anti-vibration according to the present invention
Rubber composition for rubber is a specific random copolymer rubber
(A), a filler (B) and a vulcanizing agent (C).
It is a vulcanizable rubber composition. [0018]Random copolymer rubber (A) The random copolymer rubber (A) used in the present invention is
Tylene, an α-olefin having 3 to 20 carbon atoms,
And a branched polyene compound. Such α-ole having 3 to 20 carbon atoms
As the fin, specifically, propylene, 1-butene,
1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl
1-pentene, 3-ethyl-1-pentene, 4-methyl-1-
Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene
Xen, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene
Sen, 3-ethyl-1-hexene, 1-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecene, 1-oct
Tadecene, 1-eicosene and the like. Among them,
Lopylene, 1-butene, 1-hexene, 1-octene are preferred
Commonly used. These α-olefins may be used alone or
Can be used in combination of two or more. Also branch
The chain polyene compound is represented by the following general formula [I].
You. [0021] Embedded image In the formula [I], n is an integer of 1 to 5;
¹ Is an alkyl group having 1 to 5 carbon atoms;^Two and
R^Three Are each independently a hydrogen atom or a carbon atom number
1 to 5 alkyl groups. As the alkyl group having 1 to 5 carbon atoms,
Specifically, methyl, ethyl, n-propyl, i-pro
Pill, n-butyl, i-butyl, sec-butyl, t-butyl
Tyl group, n-pentyl group, i-pentyl group and the like.
You. Such a branched polyene compound (hereinafter referred to as “polyene compound”)
Below, also referred to as a branched polyene compound [I])
Is a compound as specifically exemplified in the following (1) to (24).
Things. Among them, (5), (6), (9),
(11), (14), (19), (20)
Compounds are preferably used. (1) 4-ethylidene-1,6-octadiene (2) 7-methyl-4-ethylidene-1,6-octadiene (3) 7-methyl-4-ethylidene-1,6-nonadiene (4) 7-ethyl-4-ethylidene-1,6-nonadiene (5) 6,7-dimethyl-4-ethylidene-1,6-octadiene (6) 6,7-dimethyl-4-ethylidene-1,6-nonadiene (7) 4-ethylidene-1,6-decadiene (8) 7-methyl-4-ethylidene-1,6-decadiene (9) 7-methyl-6-propyl-4-ethylidene-1,6-octane
Tadien (10) 4-ethylidene-1,7-nonadiene (11) 8-Methyl-4-ethylidene-1,7-nonadiene (EM
N) (12) 4-ethylidene-1,7-undecadien (13) 8-methyl-4-ethylidene-1,7-undecadiene (14) 7,8-dimethyl-4-ethylidene-1,7-nonadiene (15) 7,8-dimethyl-4-ethylidene-1,7-decadiene (16) 7,8-dimethyl-4-ethylidene-1,7-undecadier
N (17) 8-Methyl-7-ethyl-4-ethylidene-1,7-unde
Kazien (18) 7,8-diethyl-4-ethylidene-1,7-decadiene (19) 9-methyl-4-ethylidene-1,8-decadiene (20) 8,9-dimethyl-4-ethylidene-1,8-decadiene (21) 10-methyl-4-ethylidene-1,9-undecadiene (22) 9,10-dimethyl-4-ethylidene-1,9-undecazi
En (23) 11-methyl-4-ethylidene-1,10-dodecadien (24) 10,11-dimethyl-4-ethylidene-1,10-dodecadie
N These may be used alone or in combination of two or more.
Can be. The above-mentioned branched polyene compound [I] is
It may be a mixture of trans form and cis form,
It may be a single isomer or a single cis isomer. like this
Branched polyene compound according to the applicant's application
By the method described in the specification of Japanese Patent Application No. 6-154952
Can be prepared. That is, a conjugated diamine represented by the following [Ia]
A compound having an ene and ethylene with a transition metal compound and
Reaction in the presence of a catalyst consisting of
Can be produced. [0027] Embedded image (In the formula [Ia], n, R¹, R^TwoAnd R
^ThreeAre n in the general formula [I] described above,
R¹, R^TwoAnd R^ThreeIs the same as ) The random copolymer rubber (A) used in the present invention
Ethylene, α-olefin and branched
Structural unit derived from each monomer of liene compound
Are randomly arranged and linked to form a branched polyene compound.
And the main chain is substantially
It has a linear structure. This copolymer rubber has a substantially linear structure.
And contain substantially no gel-like cross-linked polymer
Is that this copolymer rubber dissolves in organic solvent and
It can be confirmed by not including it qualitatively. And
For example, when measuring intrinsic viscosity [η], this copolymer rubber
Is completely dissolved in decalin at 135 ° C.
Can be recognized. Also, such a random copolymer rubber
In (A), a derivative derived from a branched polyene compound
Has a structure substantially represented by the following formula [II].
Have. [0031] Embedded image In the formula [II], n, R¹ , R^Two And R^Three
Are n and R in the general formula [I] described above, respectively.¹ ,
R^Two And R^Three Is the same as ] Structural units derived from a branched polyene compound
Having the above structure means that this copolymer¹³C-
Confirmation by measuring NMR spectrum
Can be. The random copolymer rubber used in the present invention
(A), for example, ethylene, propylene, 4-ethylidene
-8-methyl-1,7-nonadiene (EMN) copolymer rubber
Anti-vibration rubber made of the rubber composition used is ethylene
Pyrene / 5-ethylidene-2-norbornene (ENB)
Compared to vibration-isolated rubber consisting of a rubber composition using coalesced rubber,
Excellent in anti-vibration characteristics and fatigue resistance. The reason is a minute
EMN, a branched polyene compound, has a cyclic structure
Molecular motion is easier than ENB which is a diene compound
Also, the cross-linking form after vulcanization shows the intermolecular distance effective for fatigue resistance.
This is to take a structure that keeps In addition, ethylene propylene
Len-4-ethylidene-8-methyl-1,7-nonadiene (EM
N) The copolymer rubber has a vulcanization rate of ethylene propylene.
-5-ethylidene-2-norbornene (ENB) copolymer
Very fast compared to rubber, stable physical properties and vibration-proof rubber
Excellent product productivity. The random copolymer rubber used in the present invention
(A) has the following composition and characteristics. (I) This random copolymer rubber is composed of ethylene and carbon
Molar ratio with an α-olefin having 3 to 20 carbon atoms (ethylene /
α-olefin) is preferably 50/50 to 80/20,
Is in the range of 65/35 to 70/30. Ethylene and α-ole having 3 to 20 carbon atoms
The molar ratio with the fin is random within the above range.
Excellent mechanical strength characteristics when copolymer rubber (A) is used
To provide vulcanized rubber products with excellent low-temperature properties.
Thus, a rubber composition is obtained. (Ii) This random copolymer rubber (A)
Has an iodine value of 5 to 30, preferably 10 to 25.
It is in. Random samples with an iodine value in the above range
The use of the polymer rubber (A) has excellent anti-vibration properties
Vulcanized rubber products with excellent heat aging resistance
Thus, a rubber composition having a high vulcanization rate can be obtained. (Iii) This random copolymer rubber (A)
Is the intrinsic viscosity [η] measured in decalin at 135 ° C.
1.0 to 6.0 dl / g, preferably 2.0 to 4.0 d
1 / g. The intrinsic viscosity [η] is in the above range.
The random copolymer rubber (A) is composed of carbon black,
Can be uniformly blended. Also this la
When the copolymer rubber (A) is used, engine and muffle
Supports vibrating supports such as rollers and center bearings.
Anti-vibration rubber with high mechanical strength and excellent fatigue resistance
Is obtained. The above random copolymer rubber (A)
Is ethylene and an α-olefin having 3 to 20 carbon atoms
And a branched polyene represented by the above general formula [I]
Can be obtained by copolymerization with a compound in the presence of a catalyst.
You. As such a catalyst, vanadium
(V), zirconium (Zr), titanium (Ti)
Which transition metal compound and organoaluminum compound (organic aluminum
Luminium oxy compound) and Ziegler-type catalyst
Can be used. In the present invention, [a] a soluble vanadium compound
Catalyst consisting of a product and an organoaluminum compound, or
[B] Metallo of a transition metal selected from Group IVB of the Periodic Table
A cene compound and an organoaluminum oxy compound or a
Particularly preferred is a catalyst comprising an ionized ionic compound.
You can. In the present invention, the above-mentioned catalyst [a] (
From soluble vanadium compounds and organoaluminum compounds
Or a catalyst [b] (selected from Group IV of the periodic table)
Transition metallocene compounds and organoaluminum oxides
Contact with a xy compound or an ionized ionic compound
Medium) in the presence of ethylene and α having 3 to 20 carbon atoms.
-An olefin and a branched polyene compound
Copolymerize in phase. At this time, a hydrocarbon solvent is generally used.
But using an α-olefin such as propylene as a solvent
Is also good. Specific examples of such a hydrocarbon solvent include:
Means pentane, hexane, heptane, octane, deca
, Dodecane, kerosene and other aliphatic hydrocarbons and their halo
Gen derivatives, cyclohexane, methylcyclopentane,
Alicyclic hydrocarbons such as methylcyclohexane and the like
Aromatic derivatives, benzene, toluene, xylene, etc.
Group hydrocarbons and halogen derivatives such as chlorobenzene
Are used. These solvents may be used in combination.
Ethylene and α-olefin having 3 to 20 carbon atoms and branching
The copolymerization with the chain polyene compound is carried out by a batch method or
Any of the continuous methods may be used. Continuous copolymerization
When carrying out the above, the above catalyst is used at the following concentration.
Used. In the present invention, the above-mentioned catalyst [a],
Soluble vanadium compounds and organoaluminum compounds
When a catalyst consisting of
The concentration of the vanadium compound is usually 0.01 to 5 mM.
L / liter (polymerization volume), preferably 0.05 to 3 ml
Remol / liter. This soluble vanadium compound
Is the concentration of the soluble vanadium compound present in the polymerization system.
10 times or less, preferably 1 to 7 times, more preferably
It is desirable to supply at a concentration of 1 to 5 times. Further, the organoaluminum compound is a polymer-based compound.
Ratio of aluminum atoms to vanadium atoms (A
1 / V), 2 or more, preferably 2 to 50, more preferably
Or 3-20. Soluble vanadium compound and organic aluminum
The catalyst [a] composed of a nickel compound is usually
A hydrogen solvent and / or a liquid having 3 to 20 carbon atoms
diluted with α-olefins and branched polyene compounds
Supplied. At this time, the soluble vanadium compound
It is desirable to dilute to the concentration described
The minium compound has a concentration of, for example, 50 in the polymerization system.
Adjusted to any concentration less than 2 times and supplied to the polymerization system
Is desirable. In the present invention, the metallocene compound
And an organic aluminum oxy compound or ionized ion
Compounds (ionic ionized compounds, ionic compounds
Also called. ) When the catalyst [b] consisting of
Means that the concentration of the metallocene compound in the polymerization system is usually 0.1.
0.0005-0.1 mmol / liter (polymerization volume),
Preferably 0.0001-0.05 mmol / l
It is. The organic aluminum oxy compound is
Aluminum atom for metallocene compounds in the polymerization system
In the ratio (Al / transition metal) of 1 to 10,000, preferably
Is supplied in an amount of 10 to 5000. In the case of an ionized ionic compound, a polymerization system
Ionic Compounds for Metallocene Compounds in Water
Molar ratio (ionized ionic compound / metallocene compound
), Supplied in an amount of 0.5-20, preferably 1-10
Is done. Further, an organic aluminum compound is used.
When the polymerization is performed, usually about 0 to 5 mmol / liter (polymerization
Product), preferably about 0 to 2 mmol / l
Used in such amounts. In the present invention, the soluble vanadium compound
Of catalyst [a] consisting of benzene and organoaluminum compound
Below, ethylene and α-olefin having 3 to 20 carbon atoms
When copolymerized with a branched polyene compound,
The copolymerization reaction is usually carried out at a temperature of -50 ° C to 100 ° C, preferably
-30 ° C to 80 ° C, more preferably -20 ° C to
At 60 ° C, the pressure is 50kg / cm^Two Below, preferably 2
0kg / cm^Two It is performed under the following conditions. However, the pressure
Power is not zero. In the present invention, the metallocene compound
Organic aluminum oxy compound or ionized ionic
Ethylene and carbon in the presence of a catalyst [b] comprising
Α-olefins having 3 to 20 atoms and branched polyenes
When copolymerizing with a compound, the copolymerization
Usually, the temperature is -20C to 150C, preferably 0C to 12C.
0 ° C., more preferably 0 ° C. to 100 ° C. and a pressure of 80 ° C.
kg / cm^Two Or less, preferably 50 kg / cm^Two below
It is performed under conditions. However, the pressure is not zero. The reaction time (copolymerization was carried out in a continuous
Average residence time if required), catalyst concentration, polymerization temperature, etc.
It usually varies from 5 minutes to 5 hours, depending on the conditions.
It is 10 minutes to 3 hours. In the present invention, ethylene, C 3 -C 2
The α-olefin of 0 and the branched polyene compound are
A random copolymer rubber having the specific composition described above can be obtained.
Such amount is supplied to the polymerization system. For further copolymerization
Can also use a molecular weight regulator such as hydrogen. As described above, ethylene and carbon atoms 3
.Alpha.-olefins and branched polyene compounds
When copolymerized, random copolymer rubber usually
It is obtained as a polymerization solution containing. This polymerization solution is prepared by a conventional method.
Is processed to obtain a random copolymer rubber. Random copolymer rubber (A) [unsaturated
The method for preparing the above-mentioned [Tylene-based copolymer] is disclosed in the present application.
Details of Japanese Patent Application No. 7-69986 pertaining to the applicant's application
It is described in. [0058]Filler (B) In the present invention, the filler (B) is used.
There are fillers having reinforcing properties and fillers having no reinforcing properties. The filler having a reinforcing property is used for tensile strength of vulcanized rubber.
Enhance mechanical properties such as strength, tear strength and wear resistance
effective. As such a filler, specifically,
Surface treatment with silane coupling agent, etc.
Carbon black, silica, activated calcium carbonate
And fine talc. In the present invention
Is carbon black, which is usually used for rubber.
Any type can be used. In addition, fillers having no reinforcing properties have poor physical properties.
Increase the hardness of rubber products without affecting
Used to reduce costs. this
As such a filler, specifically, talc, clay,
Calcium carbonate and the like. In the present invention, the filler is randomly
Usually, 20 to 1 with respect to 100 parts by weight of the polymer rubber (A)
00 parts by weight, preferably 30 to 80 parts by weight, more preferably
Or 40 to 70 parts by weight. [0062]Vulcanizing agent (C) The vulcanizing agent (C) preferably used in the present invention is a sulfur vulcanizing agent.
Or a sulfur compound. As the sulfur, specifically, powdered sulfur
C, precipitated sulfur, colloidal sulfur, surface-treated sulfur,
Soluble sulfur and the like. As a sulfur compound,
Specifically, sulfur chloride, sulfur dichloride, polymer polysulfide
Things. Also releases active sulfur at the vulcanization temperature.
Sulfur compounds that are released and vulcanized, such as morpholine
Sulfide, alkylphenol disulfide, tetra
Methylthiuram disulfide, dipentamethylenethiura
Muttetrasulfide and the like can also be used. In the present invention, powdered sulfur is preferably used.
It is. In the present invention, the vulcanizing agent (C) is
Usually 0.5 to 100 parts by weight of the polymer rubber (A)
10 parts by weight, preferably 1 to 10 parts by weight, more preferably
Or 1.0 to 5.0 parts by weight. [0065]Other ingredients In the rubber composition for vibration-proof rubber according to the present invention, the above-mentioned lander
Rubber (A), filler (B) and vulcanizing agent
In addition to (C), vulcanization accelerator, vulcanization aid, softener, adhesive
Imparting agent, anti-aging agent, foaming agent, processing aid, heat stabilizer,
Weathering stabilizer, antistatic agent, coloring agent, lubricant, flame retardant, blue
The present invention relates to
Can be blended within a range that does not impair the purpose of the above. The random copolymer rubber used in the present invention
(A) shows the type and group of vulcanization accelerator since the vulcanization rate is high.
Depending on the combination and the selection of the amount added, the vulcanizing agent (B)
The amount of addition can be reduced. Therefore, in the present invention
It is desirable to use a vulcanization accelerator. Specific examples of such a vulcanization accelerator include:
Is N-cyclohexyl-2-benzothiazolesulfene
Amide, N-oxydiethylene-2-benzothiazolsul
Phenamide, N, N-diisopropyl-2-benzothiazo-
Sulfenamide-based compounds such as rusulfenamide;
2-mercaptobenzothiazole, 2- (2,4-dinitrophen
Nyl) mercaptobenzothiazole, 2- (2,6-diethyl)
-4-morpholinothio) benzothiazole, dibenzothia
Thiazole compounds such as zirdisulfide; diphenyl
Luguanidine, triphenylguanidine, diorsonite
Lilguanidine, orthonitrile biguanide, diph
Guanidine compounds such as phenylguanidine phthalate;
Acetaldehyde-aniline reactant, butyraldehyde
-Aniline condensate, hexamethylenetetramine, aceto
Aldehyde amines such as aldehyde ammonia
Aldehyde-ammonia compound; 2-mercaptoimidazo
Imidazoline compounds such as phosphorus; thiocarbanilide;
Diethylthiourea, dibutylthiourea, trimethyl
Thiolia such as thiouria, diorthotrilthiourea
A-based compounds: tetramethylthiuram monosulfide,
Tramethylthiuram disulfide, tetraethylthiura
Mudisulfide, tetrabutylthiuram disulfide,
Thiura, such as pentamethylenethiuram tetrasulfide
Compounds: zinc dimethyldithiocarbamate, diethyl
Zinc rudithiocarbamate, di-n-butyldithiocarba
Zinc mate, zinc ethylphenyldithiocarbamate,
Zinc butylphenyldithiocarbamate, dimethyldithio
Sodium ocarbamate, dimethyldithiocarbamine
Diene such as selenium acid and tellurium dimethyldithiocarbamate
Thioate compounds such as zinc dibutylxanthate
Xanthate compounds; compounds such as zinc white
Can be. Examples of preferred combinations of vulcanization accelerators
As dibenzothiazyl disulfide (MBTS)
And N-cyclohexyl-2-benzothiazolylsulfena
Mido (CBS) and tetramethylthiuram disulfide
(TMTD) and dipentamethylenethiuramtetrasulf
And a combination with a liquid crystal (DPTT). In the present invention, the vulcanization accelerator is a land
1 to 20 parts by weight per 100 parts by weight of the rubber copolymer rubber (A).
Parts by weight, preferably 2 to 10 parts by weight.
You.Rubber composition for anti-vibration rubber The rubber composition for vibration-proof rubber according to the present invention is a random copolymer.
Body rubber (A), filler (B), vulcanizing agent (C) and necessary
Depending on the vulcanization accelerator, vulcanization aid, softener, antioxidant,
From rubber compounding agents such as foaming agents and processing aids to general rubber
It can be prepared by the method of preparing the formulation. For example, a Banbury mixer, a kneader,
Use internal mixers such as Intermix
And a random copolymer rubber (A), a filler (B) and
And other ingredients such as softeners at a temperature of 80-170 ° C.
After kneading for 3 to 10 minutes, if necessary, a vulcanizing agent (C),
Rolls such as open rolls with a vulcanization accelerator
Roll temperature 40-80 ° C using a kind or kneader
After kneading for 5 to 30 minutes, prepare by dispensing
can do. In this way, usually a ribbon or
Gives a sheet-like rubber composition (compounded rubber). The mixing with the internal mixers described above
When the kneading temperature is low, the vulcanizing agent (C), the vulcanization accelerator,
A foaming agent or the like can be kneaded at the same time. According to the present invention
The rubber composition for vibration-proof rubber is determined by a dynamic viscoelasticity test after vulcanization.
Loss tangent (tan δ) to be 0.03-0.15
It has such a composition. In the dynamic viscoelasticity test, a vulcanized rubber sheet having a thickness of 2 mm was used.
About the rheometer, a rheometric viscoelasticity tester (type
Using the formula RDS-2), a measurement temperature of 27 ° C. and a frequency of 10
Hz and a strain rate of 1%, and the dynamic elastic modulus (kg
/ Cm^Two ) And dynamic loss modulus (kg / cm^Two )
The loss tangent tan δ (index of vibration damping) is calculated by the following equation.
I will. G_s = G '+ ιG " (G_s: Static elastic modulus, real part G ': dynamic elastic modulus, imaginary part
G ": dynamic loss elastic modulus) tan δ = G ″ / G ′ Dynamic of rubber vibration can be obtained from dynamic viscoelasticity test.
In the relationship between the elastic modulus (G ′) and the loss tangent (tan δ),
If G 'is the same, the higher the tan δ, the better the vibration isolation of the rubber
Excellent in properties and fatigue resistance. Also, if tan δ is the same,
If there is, the smaller G 'is, the better the anti-vibration characteristics and fatigue resistance of the anti-vibration rubber
Is excellent. [0074]Anti-vibration rubber Vibration-proof rubber (vulcanized rubber) of the rubber composition for vibration-proof rubber according to the present invention
) Usually comprises pressing the unvulcanized rubber composition as described above
Forming machine, calendar roll, press, injection
Various molding methods such as transfer molding machines and transfer molding machines
Pre-molding to the desired shape
Vulcanized by introducing into a vulcanization tank and heating
Can be. The unvulcanized rubber composition is vulcanized by heating.
Hot air, glass bead fluidized bed, UHF
(Ultra-high frequency electromagnetic waves), steam, LCM (hot molten salt tank)
Using a heating tank of a heating form such as
It is preferable to heat at a temperature for 1 to 30 minutes. For molding and vulcanization, a mold may be used.
In addition, it is not necessary to use a mold. When not using a mold
In general, the unvulcanized rubber composition is usually continuously molded and
Vulcanized. Vulcanized rubber molded and vulcanized as described above
Is a weatherstrip, door glass run channel
, Window frame, radiator hose, brake parts, wiper
Automotive industrial parts such as blades, rubber rolls, belts,
Industrial rubber products such as packing and hoses, anode caps
Electrical insulation such as gaskets and grommets,
And civil engineering construction materials such as sheets for civil engineering, rubberized cloth, etc.
Can be used for applications. Further, an unvulcanized rubber compound containing a foaming agent is vulcanized.
Vulcanized foam obtained by thermal foaming is used for insulation, cushioning
It can be used for applications such as sealing materials and sealing materials. [0079] EFFECT OF THE INVENTION The rubber composition for vibration-proof rubber according to the present invention comprises:
Specific ethylene / α-olefin / branched polyene
Comprising a polymer rubber, a filler, and a vulcanizing agent,
The loss tangent (t) determined in the dynamic viscoelasticity test after vulcanization
anδ) is in a specific range, so natural rubber-based
While having excellent vibration isolation characteristics and durability comparable to
Has better heat resistance than natural rubber-based materials
It is possible to provide an anti-vibration rubber having excellent low-temperature flexibility.
it can. Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples. What
Incidentally, random copolymer rubber in Examples and Comparative Examples
(EPT) and test methods performed on vulcanized rubber
Is as follows. [1] Physical properties test of unvulcanized rubber Physical properties of unvulcanized rubber conform to JIS K 6300
And a curast meter manufactured by Nippon Synthetic Rubber Co., Ltd.
(CURELASTMETER) Torque change at 160 ° C using Model 3
And t₉₀[Minute] was determined and the result was taken as the vulcanization rate. t₉₀Is short
The higher the time, the faster the vulcanization rate. [2] Tensile test The vulcanized rubber sheet is punched out and JIS K6301 (198
9 years) prepared dumbbell specimens
Then, using this test piece, the same as JIS K6301 Paragraph 3
According to the prescribed method, the measurement temperature is 25 ° C and the tensile speed is 50
A tensile test was performed under the condition of 0 mm / min, and the elongation was 25%.
% Tensile stress (σ_{twenty five}), 25% modulus
(M_{twenty five}), 50% modulus (M₅₀), 100% module
Lass (M₁₀₀ ), 200% modulus (M₂₀₀ ), 30
0% modulus (M₃₀₀ ), Tensile stress at break T_B and
Elongation at break E_B Was measured. [3] Hardness test Hardness test conforms to JIS K 6301 (1989)
And the spring hardness H_S (JIS A hardness)
It was measured. [4] Endurance test Punched vulcanized rubber sheet and described in JIS K6301
No. 1 dumbbell test piece was prepared and this test piece was prepared.
A 2 mm scratch was made at the center of the. Obtained in this way
Elongation rate of 50% for 20 of 60 test pieces
And expanded at a set temperature of 40 ° C and a rotation speed of 300 rpm.
Long-term fatigue, with the average value of the number of times the dumbbell was cut
As an index of durability. Elongation rate 100%, 150%
A durability test was performed under the same conditions. Monsanto fatigue tester: frequency 5Hz, temperature 27 ℃ [5] Compression set test The compression set test is carried out in accordance with JIS K 6301.
Performed at 0 ° C and 150 ° C respectively for 22 hours
The compression set at each temperature was measured. This
The compression set was used as an index for evaluation of sag resistance. [6] Dynamic viscoelasticity test The dynamic viscoelasticity test is performed according to the method already described above,
Dynamic modulus (G '), dynamic loss modulus (G ") and loss
The loss tangent (tan δ) was determined. [7] Gehman low-temperature torsion test The Gehman low-temperature torsion test was performed according to JIS K 6301 (19
1989) and T_Two [Unit: ° C], T
_Five[Unit: ° C], T_Ten[Unit: ° C] and T₁₀₀[unit:
° C]. Further, the random numbers used in Examples and Comparative Examples were used.
The polymer rubber (EPT) is as shown in Table 1. [0089] [Table 1][0090] [Comparative Examples 1 to 5 and Examples]1-3First, 8 inches
Open roll (surface temperature of front roll 50 ℃, rear roll
Surface temperature 50 ° C, front roll rotation speed 16rpm, rear roll
Weight of EPT kneaded at 18 rpm)
1 part by weight of stearic acid and 5 parts by weight of Zinhua No. 1
And then kneaded, then further FEF-HS carbon black
[Nippon Steel Chemical Co., Ltd., trade name Niteron # 10] 60 layers
Quantity and oil [P-300, manufactured by Fujikosan Co., Ltd.] 60 layers
An amount was added and kneaded. Then obtain as above
The kneaded material is sulfur (trade name, manufactured by Hosoi Chemical Industry Co., Ltd.)
Powder sulfur] 0.75 parts by weight and trade name as vulcanization accelerator
Noxeller PZ [Ouchi Shinko Chemical Industry Co., Ltd.] 1.5
Quantity department, trade name Noxeller TT [Ouchi Shinko Chemical Industry Co., Ltd.
Made) and Noxeller M [made by Ouchi Shinko Chemical Industry Co., Ltd.]
After adding and kneading 0.5 parts by weight, the mixture is separated into sheets.
And press at 160 ° C for 18 minutes to obtain a 2mm thick vulcanized sheet.
The vulcanized sheet is subjected to a tensile test and a hardening test.
Test, durability test, compression set test, dynamic viscoelasticity test
And Gehman low-temperature torsion test. Table 2 shows the results. [0092] [Table 2][0093] [Table 3]FIG. 1 shows a comparative example shown in Table 2 above.
1 to 5 and Examples1-3Dynamic modulus obtained in
(G ′) and the loss tangent (tan δ), G ′ is the vertical axis,
Tan δ was plotted on the horizontal axis. As is clear from FIG. 1, ENB-EP
Comparative Example using T and Example using EMN-EPT
By comparison, when the dynamic elastic modulus is about the same value,
The loss tangent of the example is larger than that of the comparative example,
When the tangents are about the same value, the example is better than the comparative example.
Also, the value of the dynamic elastic modulus is small. Therefore, the rubber of the embodiment
The rubber composition of the rubber composition of the comparative example is better than the rubber composition of the comparative example.
It is most suitable as a rubber composition.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing a relationship between a dynamic elastic modulus (G ′) and a loss tangent (tan δ) obtained in a comparative example and an example.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toshiyuki Tsutsui 1-2-1, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industry Co., Ltd. (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08 F16F 1/36 F16F 15/08

Claims (1)

(57) [Claim 1] A random mixture comprising ethylene, an α-olefin having 3 to 20 carbon atoms, and at least one kind of a branched polyene compound represented by the following general formula [I]. A composition comprising a copolymer rubber (A), a filler (B), and a vulcanizing agent (C), wherein the random copolymer rubber (A) comprises (i) ethylene and carbon The molar ratio (ethylene / α-olefin) to an α-olefin having 3 to 20 atoms is in the range of 50/50 to 80/20, (ii) the iodine value is in the range of 5 to 30, and (ii)
i) The intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 1.0 to 6.0 dl / g, and the loss tangent (tan) determined by a dynamic viscoelasticity test after vulcanization of the composition.
δ) being 0.03 to 0.15; a rubber composition for vibration-proof rubber; [In the formula [I], n is an integer of 1 to 5, R ¹ is an alkyl group having 1 to 5 carbon atoms, and R ² and R ³ are each independently a hydrogen atom or a carbon atom number. 1 to 5 alkyl groups].