JP3506551B2 - Seal rubber parts - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealing rubber
For more information on hyper blade rubber, especially
Seal rubber parts and wiper blades with excellent flexibility
About rubber. [0002] TECHNICAL BACKGROUND OF THE INVENTION Ethylene / propylene / non-conjugated di
Ene copolymer rubber (hereinafter sometimes referred to as EPDM)
Is heat aging resistance, weather resistance, water resistance, chemical resistance, low temperature
Due to its excellent properties and flexibility,
Locking, sealing at the junction of glass and sash
Materials and sealing rubber for window frame sealing materials for automobiles
In recent years, in addition to parts applications,
Rake master cylinder cup, brake foil
Hydraulic cylinder seal materials for automobiles, such as cups for cylinders
It is known to be used as [0003] Conventionally, as a sealing material for hydraulic cylinders
Styrene-butadiene rubber is mainly used
It is known. However, in recent years,
Due to the performance improvement, the temperature inside the engine room has increased,
Butadiene rubber undergoes thermal degradation and is no longer the preferred seal.
It is no longer considered to be wood. Therefore, styrene
EPDM has recently become mainstream in place of Tadiene rubber
Have been. [0004] Japanese Unexamined Patent Publication No. Hei 1-268743 discloses this technique.
The composition for sealing rubber parts is one example,
The publication states that (a) the ethylene content is 58 to 72 mol%.
(B) Maximum tensile stress (RS [kgf / cm^Two ] And break
The product of the elongation at break (ε [%]) is 1 × 10^Three ~ 20 × 10
^Three(C) Mooney viscosity [ML_{1 + 4}(100 ° C)]
Is 20 to 50, and (d) the iodine value is 5 to 35.
Peroxidation of ethylene / α-olefin / diene copolymer rubber
A set for sealing rubber parts formed by a vulcanized oxide
The product is described. However, the technique disclosed in this publication is
Seal rubber parts have good low temperature flexibility, but still
Lack of satisfactory low temperature flexibility, still improved
There is room for On the other hand, EPDM utilizes its excellent weather resistance.
It is thus used in automotive parts. Such a car
Among parts applications, wiper blade rubber has a wide temperature range
Required to exhibit good flexibility in the range, especially at low temperatures.
You. To increase productivity, wiper blade rubber
The composition for use is required to have high-speed vulcanizability. However, the conventional EPDM has a third component.
5-ethylidene-2-norbornene (hereinafter referred to as
Below may be referred to as ENB) due to its structure
Adversely affects flexibility at low temperatures
There is a problem of giving. Also improved low temperature flexibility
If the ENB content is reduced to reduce the vulcanization rate,
Therefore, there is a problem that productivity is lowered. [0008] Therefore, the advantages inherent in EPDM are inherent.
Low temperature flexibility without impairing the heat aging resistance, weather resistance, etc.
Rubber parts with significantly improved performance and low temperature flexibility
The emergence of wiper blade rubber with excellent performance and rubber elasticity
It has been desired since now. [0009] SUMMARY OF THE INVENTION The present invention relates to the prior art as described above.
EPDM is intended to solve the problem.
Impair the excellent heat aging resistance, weather resistance, etc.
Without significantly improving low-temperature flexibility
It is intended to provide. The present invention is also excellent in low temperature flexibility and rubber elasticity.
With the aim of providing a customized wiper blade rubber
I have. [0011] SUMMARY OF THE INVENTION A seal rubber part according to the present invention
And an α-olefin having 3 to 20 carbon atoms,
At least one kind of branched-chain polycyclic compound represented by the general formula [I]
Random copolymer rubber (A) comprising an ene compound,
Rubber set containing sulfurizing agent (B) and filler (C)
The random copolymer rubber (A)
(I) ethylene and α-olefin having 3 to 20 carbon atoms
50/50 (ethylene / α-olefin)
(Ii) an iodine value of 5 to 40;
(Iii) measured in decalin at 135 ° C.
Intrinsic viscosity [η] is 1.2 dl / g <[η] <3.5 dl / g
Is characterized by being within the range represented by. [0012] Embedded image [In the formula [I], n is an integer of 1 to 5,¹ Is a carbon source
An alkyl group having 1 to 5 children,^Two And R^Three Is
Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
Is a alkyl group. ] [0013] [0014] [0015] [0016] DETAILED DESCRIPTION OF THE INVENTION A seal rubber portion according to the present invention will be described below.
Product and wiper blade rubber
You. [0017] Seal rubber component and wiper according to the present invention
-Blade rubber is a specific random copolymer rubber (A)
A composition containing a vulcanizing agent (B) and a filler (C)
It is formed with. [0018]Random copolymer rubber (A) The ethylene copolymer rubber (A) used in the present invention is:
Ethylene, 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) has the following composition and characteristics. (I) Random co-weight constituting the composition for seal rubber parts
The united rubber (A) is composed of ethylene and α having 3 to 20 carbon atoms.
-Molar ratio with olefin (ethylene / α-olefin)
Is 50/50 to 75/25, preferably 55/45 to 7
It is in the range of 3/27. Ethylene and α-ole having 3 to 20 carbon atoms
The molar ratio with the fin is random within the above range.
When the copolymer rubber (A) is used, it has excellent mechanical strength.
Both provide seal rubber parts with excellent low-temperature flexibility
A composition that can be obtained is obtained. In addition, a composition for a wiper blade rubber is used.
The resulting random copolymer rubber (A) is composed of ethylene and carbon.
Molar ratio with an α-olefin having 3 to 20 atoms (ethylene
/ Α-olefin) 55 / 45-75 / 25, preferred
In the range of 60/40 to 73/27. Ethylene and α-ole having 3 to 20 carbon atoms
The molar ratio with the fin is random within the above range.
When the copolymer rubber (A) is used, a wax excellent in low-temperature flexibility is obtained.
Along with providing an upper blade rubber,
A composition with excellent crosslinking efficiency with organic peroxides can be obtained.
You. (Ii) Constituting the composition for sealing rubber parts
The random copolymer rubber (A) has an iodine value of 5 to 40,
Preferably it is in the range of 7 to 35. Iodine value is above
Use a random copolymer rubber (A) in the above range
With excellent low temperature flexibility, compression set and pull
We can provide seal rubber parts with small stretch
Thus, a composition having a high vulcanization rate can be obtained. In addition, a composition for a wiper blade rubber is used.
The resulting random copolymer rubber (A) has an iodine value of 5 to 5.
30, preferably in the range of 7 to 25. High iodine value
Using a random copolymer rubber (A) in the range as described above
Provides a wiper blade rubber with excellent low temperature flexibility.
A composition with a high vulcanization rate can be obtained.
You. The polyene component is 4-ethylidene-8-methyl-
1,7-Nonadiene (hereinafter sometimes abbreviated as EMN)
An EPDM (hereinafter sometimes abbreviated as EMN-EPDM)
The polyene component is 5-ethylidene-2-norbornene
(Hereinafter, sometimes abbreviated as ENB)
(Hereinafter sometimes abbreviated as ENB-EPDM).
Comparing with iodine value, EMN-EPDM is more
The sulfur rate is more than twice as fast. It should be noted that ENB-EPDM is a polyene
Even if the content is high, the polyene content exceeds 4 mol%
The effect of improving the vulcanization rate is lost. On the other hand, EMN-E
PDM is used until the polyene content is 7 mol%.
The vulcanization rate can be increased in proportion to the ene content. ENB-EPDM has a high vulcanization rate.
Increase its iodine value to increase
And low-temperature flexibility deteriorates. On the other hand, EMN-EPDM is
It has excellent low-temperature flexibility regardless of its iodine value. (Iii) Constituting the composition for sealing rubber parts
Random copolymer rubber (A) at 135 ° C in decalin
Is less than 1.2 dl / g <[η] <
3.5 dl / g, preferably 1.2 dl / g <[η] <3.
It is in the range represented by 0 dl / g. Intrinsic viscosity [η] is higher
Using a random copolymer rubber (A) in the range as described above
Seal rubber part with excellent mechanical strength and low-temperature flexibility
Excellent roll processability that can provide products
Things are obtained. Further, a composition for a wiper blade rubber is prepared.
The random copolymer (A) to be formed is decalin at 135 ° C.
Is less than 0.5 dl / g <[η] <
5.0 dl / g, preferably 0.8 dl / g <[η] <4.
It is in the range represented by 0 dl / g. Intrinsic viscosity [η] is higher
Using a random copolymer rubber (A) in the range as described above
With excellent mechanical strength and low-temperature flexibility
Thus, a composition capable of providing a raw rubber 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, for example, Vanaji
(V), zirconium (Zr), titanium (T
transition metal compounds such as i) and organoaluminum compounds
(Organoaluminum oxy compound)
-Type catalysts 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], ie,
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 the ionized ionic compound, the 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 is 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, having 3 to 2 carbon atoms
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. The 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. [0063]Vulcanizing agent (B) The vulcanizing agent (B) used in the present invention includes sulfur,
Ow compounds and organic peroxides. 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, sulfur or sulfur
The compound is based on 100 parts by weight of the random copolymer rubber (A).
And 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight
Used in parts by weight. As the vulcanizing agent (B), sulfur or i
When using an au compound, use a vulcanization accelerator in combination.
Is preferred. Specific examples of the vulcanization accelerator include N-silicone.
Clohexyl-2-benzothiazolesulfenamide,
N-oxydiethylene-2-benzothiazolesulfena
Mido, N, N-diisopropyl-2-benzothiazole sulf
Enamide, 2-mercaptobenzothiazole, 2- (2,4-
Dinitrophenyl) mercaptobenzothiazole, 2-
(2,6-diethyl-4-morpholinothio) benzothiazole
And thiazoles such as dibenzothiazyl disulfide
Compound: diphenylguanidine, triphenylguanidine
, Diorsonitrile guanidine, orsonitrile
Guanides, such as guanide and diphenylguanidine phthalate
Niidine compound; acetaldehyde-aniline reactant,
Cyraldehyde-aniline condensate, hexamethylene tet
Aldehydes such as lamin and acetaldehyde ammonia
Min or aldehyde-Ammonia compounds; 2-merca
Imidazoline compounds such as putimidazoline; thiocar
Vanillide, diethylthiourea, dibutylthiourea,
Such as trimethylthiourea and diorthotolylthiourea
Thiourea compound; tetramethylthiuram monosulf
Sulfide, tetramethylthiuram disulfide, tetraethyl
Ruthiuram disulfide, tetrabutyl thiuram disulfide
Sulfide, pentamethylenethiuram tetrasulfide, etc.
Thiuram compounds; zinc dimethyldithiocarbamate;
Zinc diethyldithiocarbamate, di-n-butyldithio
Zinc carbamate, ethylphenyldithiocarbamic acid
Zinc, zinc butylphenyldithiocarbamate, dimethyl
Sodium rudithiocarbamate, dimethyldithiocar
Selenium bamate, tellurium dimethyldithiocarbamate, etc.
Dithionate compounds; zinc dibutylxanthate, etc.
Xanthate compounds; compounds such as zinc white
Can be. In the present invention, the vulcanization accelerator comprises a land
0.1 to 100 parts by weight of the rubber copolymer rubber (A).
20 parts by weight, preferably 0.2 to 10 parts by weight
You can. As the organic peroxide, a rubber peroxide is usually used.
Any compound can be used as long as it is used for vulcanization. For example,
Cumyl peroxide, di-t-butyl peroxide,
Di-t-butylperoxy-3,3,5-trimethylcyclohexyl
Sun, t-butyl hydroperoxide, t-butyl cumyl
Peroxide, benzoyl peroxide, 2,5-dimension
Chill-2,5-di (t-butylperoxin) hexyne-3,2,
5-dimethyl-2,5-di (benzoylperoxy) hexa
2,5-dimethyl-2,5-mono (t-butylperoxy)-
Hexane, α, α'-bis (t-butylperoxy-m-i
(Sopropyl) benzene and the like. Above all,
Cumyl peroxide, di-t-butyl peroxide,
Di-t-butylperoxy-3,3,5-trimethylcyclohexyl
Sun is preferably used. These organic peroxides
One type or a combination of two or more types is used. In the present invention, the organic peroxide is
3 × 1 with respect to 100 parts by weight of the dam copolymer rubber (A)
0^-Four~ 5 × 10^-2Used in mole proportion, but required
It is desirable to determine the optimum amount appropriately according to the physical property values.
No. Use of an organic peroxide as the vulcanizing agent (B)
It is preferable to use a vulcanization aid in combination. Vulcanization aid
As the agent, specifically, sulfur; p-quinonedioxy
Quinone dioxime compounds such as polyethylene glycol
Methacrylate compounds such as coal dimethacrylate
Substances: diallyl phthalate, triallyl cyanurate, etc.
Allyl compounds; other maleimide compounds; divinyl
And benzene. In the present invention, an organic peracid is used as the vulcanizing agent (B).
It is preferable to use a compound. Sulfur as vulcanizing agent (B)
Use organic peroxides rather than sulfur compounds
It is better to use seal rubber parts and
An upper blade rubber is obtained. [0072]Filler (C) The filler (C) used in the present invention includes a filler having a reinforcing property.
There are fillers and fillers that have no reinforcing properties. The filler having a reinforcing property is used for the tensile strength of the 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, a filler having no reinforcing property has 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 (C) is
20 to 100 parts by weight of the dam copolymer rubber (A)
200 parts by weight, preferably 50 to 150 parts by weight
Used. [0076]Other ingredients The composition for sealing rubber parts used in the present invention
In the composition for par blade rubber, the above random copolymerization
In addition to body rubber (A), vulcanizing agent (B) and filler (C)
Therefore, as described above, a vulcanization accelerator and a vulcanization aid are blended.
But also antioxidants, processing aids, heat resistant
Stabilizer, weathering stabilizer, anti-aging agent, antistatic agent, coloring
Agents, lubricants, plasticizers and other rubber compounding agents
It can be blended within a range that does not impair the purpose of light. As the antioxidant, specifically, poly
(2,2,4-trimethyl-1,2-dihydroquinoline, N, N'-di
2-naphthyl-p-phenylenediamine, 2,6-di-t-butyl
4-Methylphenol, 4,4'-thio-bis (6-t-butyl
3-Methylphenol), 2-mercaptobenzimida
Sol, nickel dibutyl-dithiocarbamate
No. [0078] As a processing aid, it is usually used for rubber.
Processing aids are used. Examples of processing aids include Risino
Oleic acid, stearic acid, palmitic acid, lauric acid,
Barium thearate, calcium stearate, steer
Zinc phosphate, esters of the above acids, higher fatty acids and
And their salts and esters. [0079]Preparation of the composition Composition for sealing rubber part used in the present invention and wire
The composition for par blade rubber is prepared, for example, by the following method.
Can be prepared. That is, the seal rubber used in the present invention
The component composition and the wiper blade rubber composition are:
Random with mixers like Banbury mixer
Necessity of copolymer rubber (A), filler (C), plasticizer, etc.
Mixed at a temperature of 80 to 170 ° C for about 3 to 10 minutes.
After kneading, use rolls such as open rolls
And vulcanizing agent (B), if necessary, an antioxidant,
And a vulcanizing aid, and the roll temperature is 40-80.
After kneading at 5 ° C for 5 to 30 minutes,
Can be manufactured. Rubber composition thus obtained
The object is a rubber compound in a ribbon or sheet form. Further, the seal rubber component used in the present invention
Composition for wiper blade rubber
Dam copolymer rubber (A), vulcanizing agent (B), filler (C)
And the above-mentioned additive is heated to about 80 to 100 ° C.
Feed directly to the output machine and set the residence time to about 0.5 to 5 minutes.
Then, it can be granulated and prepared into a pellet form. [0082]Seal rubber parts The seal rubber component according to the present invention is a seal rubber component as described above.
Made of rubber component composition, rubber is usually vulcanized
Have been. The seal rubber part according to the present invention is a conventionally known seal rubber part.
Can be prepared by the method of preparing seal rubber parts
You. [0083]Wiper blade rubber The wiper blade rubber according to the present invention includes the wiper described above.
-Made of a rubber composition, usually vulcanized
Have been. The wiper blade rubber according to the present invention is
It can be prepared by a known preparation method. [0085] The ethylene and carbon atoms used in the present invention
An α-olefin of the formulas 3 to 20 and the above-mentioned branched polyether
Random copolymer rubber (A) consisting of
Molar ratio of i-olefin and iodine value
Excellent in low-temperature flexibility because intrinsic viscosity [η] is in a specific range.
Vulcanized rubber can be provided, and the vulcanization speed
And high speed molding is possible. In addition, this random weight
The combined rubber (A) has weather resistance, ozone resistance and heat aging
Excellent properties such as properties. The seal rubber part according to the present invention is characterized in that
Dam copolymer rubber (A), vulcanizing agent (B), filler
(C) and the composition containing
Excellent heat aging resistance and weather resistance, and low temperature flexibility
Is excellent. In particular, organic peroxides as vulcanizing agents (B)
Seal made of a composition for sealing rubber parts using
Components are resistant to heat aging, weather resistance, water resistance, chemical resistance, etc.
Excellent and low temperature flexibility. According to the present invention, which has the above effects,
Seal rubber parts are specifically used in hydraulic brakes.
Cup for brake master cylinder, brake wheel
Cylinder cup, sealing material for brake fluid pressure control and
O-rings for brakes and clutches in clutches
Can be widely used for applications such as cups for cylinders
You. The wiper blade rubber according to the present invention
Is the above-mentioned random copolymer rubber (A) and a vulcanizing agent (B)
And a filler (C).
It has excellent low temperature flexibility. The wiper excellent in low-temperature flexibility according to the present invention
Even under cold environment of 0 ° C or less due to blade rubber,
Excellent ipper effect. Hereinafter, the present invention by Examples
Although described, the present invention is limited to these examples.
is not. Example, Reference exampleAnd comparative examples
・ Α-olefin ・ polyene copolymer rubber
The evaluation test methods for vulcanized rubber and vulcanized rubber are as follows.
You. [1] Physical property test of unvulcanized rubber Physical property test of unvulcanized rubber
Is performed according to JIS K 6300, and
About Nippon Synthetic Rubber Co., Ltd. Curast Meter
(CURELAST METER) 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
No. 3 dumbbell test piece described in
The test piece was used and specified in JIS K6301 Paragraph 3.
According to the specified method, the measurement temperature is 25 ° C and the tensile speed is 500
Perform a tensile test under the conditions of
T_B And tensile 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)
Was. [4] Compression set test The compression set test is based on JIS K 6301 (1989)
Vulcanized rubber of the composition for sealing rubber parts
For high temperature compression set (CS)
-Low temperature compression for vulcanized rubber of blade rubber composition
The permanent set (CS) was determined. The lower the low temperature compression set,
Low temperature flexibility is good.Test conditions for compositions for seal rubber parts Heating temperature: 150 ° C Time: 22 hours Load: 10.5kgTest conditions for wiper blade rubber composition Cooling temperature: -22 ° C Time: 22 hours Load: 10.5kg [5] Low-temperature torsion test (Gaeman torsion test)
Experiment) The low temperature torsion test is performed according to JIS K6301.
I, T_Two [° C] and freezing temperature [° C] were determined. These warm
The degree is an indicator of the low temperature flexibility of the vulcanized rubber. T_TwoIs low
The lower the flexibility at low temperature. (Test condition) Twist wire twist constant: 0.5 gf · cm / degree Immersion time: 10 minutes Torsion time: 5 seconds The lander used in the examples and comparative examples
The rubber copolymer rubber is as shown in Table 1. [0096] [Table 1][Example of Seal Rubber Parts and
Comparative example] [0098] Example 1 100 parts by weight of copolymer (1) and zinc white 5
Parts by weight, 1 part by weight of stearic acid, and MAF carbon
Rack [filler, manufactured by Tokai Carbon Co., Ltd., Seast 11
6] 50 parts by weight of a Banbury with a capacity of 1.7 liters
The mixture was kneaded with a mixer [manufactured by Kobe Steel Ltd.] for 6 minutes. [0099] The kneaded material obtained in this manner is
Luper oxide [manufactured by NOF Corporation] 3 parts by weight and
Add 0.1 part by weight of sulfur [vulcanization aid] and add roll width 20
8 inch roll (inch roll front and back roll temperature)
At 40 ° C) for 15 minutes, then dispensed into sheets
10 minutes at 170 ° C (for measuring compression set, 170 ° C
20 minutes), 150 kg / cm^Two Press vulcanization under the conditions of
Thus, a vulcanized sheet having a thickness of 2 mm was prepared. The above vulcanized sheet was subjected to the above physical properties test.
And the like were carried out according to the above method. In addition, the above vulcanization is performed.
For the unvulcanized rubber composition before, according to the above method,
t₉₀I asked. The results are shown in Table 2. [0102] Examples 2, 3, 4 In Example 1, the copolymer
Copolymer (2) shown in Table 1 in place of (1),
Except that (3) and (4) were used, the procedure was the same as in Example 1.
Was. The results are shown in Table 2. [0104] Comparative Examples 1 and 2 In Example 1, the copolymer (1)
Instead, copolymers (8) and (9) shown in Table 1 were used.
The procedure was performed in the same manner as in Example 1 except for the above. The results are shown in Table 2. [0106] [Table 2][About the wiper blade rubberReference example
And Comparative Examples] [0108] Reference Example 1 100 weight of copolymer (5) shown in Table 1
Parts, zinc white 5 parts by weight, stearic acid 1 part by weight, F
70 parts by weight of EF carbon black and dioc sebacate
30 parts by weight of chill [plasticizer] and 4.3 liters of
Mix for 5 minutes with a Banbury mixer [manufactured by Kobe Steel Ltd.]
Kneaded. [0109] The kneaded material obtained in this manner is
7.0 parts by weight of luper oxide (content 40%) and g
Limethylolpropane trimethacrylate 1.5 parts by weight
8 inch mixing roll (front roll and rear
After kneading at a roll temperature of 50 ° C), it is dispensed into sheets.
Press vulcanization at 170 ° C for 12 minutes,
A sulfur sheet was prepared. [0110] The obtained vulcanized sheet was subjected to the above physical properties test.
And the like were carried out according to the above method. In addition, the above vulcanization is performed.
For the unvulcanized rubber composition before, according to the above method,
t₉₀I asked. Table 3 shows the results. [0112] [Reference Examples 2 and 3]Reference Example 1In the copolymer (5)
Instead, the copolymers (6) shown in Table 1 respectively,
Except for using (7),Reference Example 1Was performed in the same manner as described above. Table 3 shows the results. [0114] [Comparative Examples 3 and 4]Reference Example 1In the copolymer (5)
Instead, the copolymers (10) and (11) shown in Table 1 were replaced with
Unless used,Reference Example 1Was performed in the same manner as described above. Table 3 shows the results. [0116] [Table 3]

Continuation of front page (56) References JP-A-6-128427 (JP, A) JP-A-8-311267 (JP, A) JP-A-9-3269 (JP, A) JP-A-9-48822 (JP JP-A-7-33921 (JP, A) JP-A-6-192461 (JP, A) JP-A-1-268743 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB Name) C08L 23/16 C08L 23/18

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]. The random copolymer rubber (A) is formed of a rubber composition containing a copolymer rubber (A), a vulcanizing agent (B), and a filler (C). The molar ratio with an α-olefin having 3 to 20 atoms (ethylene / α-olefin) is 50/50.
(Ii) iodine value is in the range of 5 to 40; (iii) intrinsic viscosity [η] measured in decalin at 135 ° C.
Is in a range represented by 1.2 dl / g <[η] <3.5 dl / g; a seal rubber part; [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].