WO2002102892A1

WO2002102892A1 - Ethylene/hexafluoropropylene elastomer composition

Info

Publication number: WO2002102892A1
Application number: PCT/JP2002/005577
Authority: WO
Inventors: Hideya Saito; Masao Otsuka; Tatsuya Morikawa; Mitsuhiro Otani
Original assignee: Daikin Industries, Ltd.
Priority date: 2001-06-15
Filing date: 2002-06-06
Publication date: 2002-12-27
Also published as: JPWO2002102892A1

Abstract

An ethylene/hexafluoropropylene elastomer composition which comprises an ethylene/hexafluoropropylene elastomer, a peroxide vulcanizing agent, and a vulcanization aid capable of generating an (un)saturated benzoyloxy radical. The vulcanization aid is, for example, p,p'-benzoylquinone dioxime. In the composition, the ethylene/hexafluoropropylene elastomer shows significantly improved suitability for vulcanization with the peroxide. Even when the composition contains a lowly reinforcing filler, no foaming is observed therein.

Description

Akira Itoda Ethylene-hexafluoropropylene-based elastomer composition Technical field

The present invention relates to a method for vulcanization and processability when vulcanizing an E-HFP-based elastomer containing ethylene (E) and hexafluoropropylene (HFP) as essential constitutional units in a peroxide vulcanization system. In particular, it relates to a composition having improved antifoaming properties.

The vulcanizates obtained by peroxide vulcanization of this E-HFP elastomer composition are excellent in amine resistance, and are used in automotive oils, especially engine oils, transmission oils and differential oils. It is suitable as a material for oil seals. Background art

Copolymers of ethylene (E) and hexafluoropropylene (HFP) exhibit elastomeric properties and, like other fluoroplastics and elastomers, have heat resistance, oil resistance, and chemical resistance (particularly, (Such as alkalinity). In particular, it is expected to be used as a material for oil seals for automobiles because of its excellent amine resistance and oil resistance. In addition, it has properties that are electrically advantageous, such as high electrical insulation, low dielectric loss tangent and dielectric constant, and low frequency dependence, and can be expected to be used in the field of electric and electronic components.

As a vulcanization method for such E-HFP elastomers, a so-called peroxide vulcanization method using an organic peroxide as a vulcanizing agent is most frequently used. In the case of vulcanization of peroxide, a vulcanization aid such as triaryl isocyanurate (TAIC) is commonly used for the purpose of improving vulcanizability. The vulcanization is usually carried out in the presence (for example, pamphlet of W094 / 24 175). In addition, in order to meet the required characteristics in various applications, it is sometimes required to mix fillers such as carbon black, silica, and calcium metasilicate in practical compounding designs.

However, compounding formulations that use TA IC as a vulcanization aid do not necessarily exhibit sufficient vulcanizability, and such phenomena are caused by the use of fillers with small reinforcing properties, such as calcium metasilicate and barium sulfate. The vulcanized product after press vulcanization has foaming marks and is not usable as a sealing material, because it is remarkably recognized in the prescribed formulation and the degree of vulcanization does not increase. Disclosure of the invention

The present invention provides a composition in which when vulcanizing an E-HFP-based elastomer with peroxide, the vulcanizability is remarkably improved, and no foaming phenomenon is observed even with a formulation containing a filler having a small reinforcing property. The purpose is to do. That is, the present invention relates to an E-HFP-based elastomer composition comprising an E-HFP-based elastomer, a peroxide vulcanizing agent, and a vulcanization aid capable of generating a substituted or unsubstituted benzoyloxy radical.

As the vulcanization aid, the following formula (I), (II) or (III):

(Unlike wherein, R, R \ R ² and R ³ are the same or an alkyl group containing 1 to 4 carbon atoms, an alkoxyl group or a halogen atom; n and m are the same or different and each is 0-5 And p and Q are the same or different, each of which is an integer of 0 to 4), and at least one of substituted or unsubstituted dibenzoylquinonedioxime compounds, particularly p, p'dibenzoylquinonedioxane. Kissim is preferably used.

The composition of the present invention may further contain other vulcanization aids such as triaryl isocyanurate.

The composition of the present invention is particularly remarkable in a formulation containing a filler having a small reinforcing property such as at least one selected from the group consisting of calcium metasilicate, barium sulfate, magnesium gayate and aluminum silicate. The effect, especially the effect of suppressing foaming is achieved.

As the E-HFP-based elastomer, a copolymer of ethylene and hexafluoropropylene or a copolymer of ethylene, hexafluoropropylene and another fluorinated olefin is preferable. With other fluorine-containing olefins At least one selected from the group consisting of monomers of tetrafluoroethylene, vinylidene fluoride, trifluoroethylene, trifluoroethylene, pentafluoropropylene and perfluoro (alkylbierether). One type is suitably mentioned. BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the E-HFP-based elastomer used can be produced by various polymerization methods, but a radical polymerization method is generally used.

For example, the monomer composition in the elastomer is such that the molar ratio of E / HFP is 90/10 to 50Z50, preferably 7030 to 5050. These may be copolymerized with another copolymerizable fluorine-containing olefin so that the content thereof is 0 to 15 mol%, preferably 0 to 10 mol%.

Examples of fluorinated olefins that can be copolymerized with ethylene and HFP include tetrafluoroethylene (TFE), vinylidene fluoride (VdF), trifluoroethylene (CTFE), trifluoroethylene, and pentafluoroethylene. Preference is given to at least one selected from the group consisting of fluoropropylene and perfluoro (alkyl vinyl ether) (PAVE) monomers, and TFE and CTFE are particularly preferred in that productivity can be improved. However, the resulting copolymer must exhibit elastomeric properties.

As the radical polymerization initiator, an organic peroxide or a persulfate, or a redox initiator obtained by combining these with a reducing agent is preferable.

As the polymerization method, an emulsion polymerization method is preferable, and a low-temperature polymerization method in which a polymerization reaction is performed at a polymerization temperature of up to 40 is particularly preferable. E-HFP-based elastomers obtained by this low-temperature polymerization method have few branches and are therefore excellent in processability. The present invention relates to an elastomer composition containing such an E-HFP-based elastomer, a peroxide vulcanizing agent and a specific vulcanization aid.

As the peroxide which is a vulcanizing agent used for peroxide vulcanization, an organic peroxide which easily generates a peroxide radical in the presence of heat or a redox agent is preferably used. Specific examples include, for example, 1,1-bis (t-butyl carboxy) -1,3,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, DG t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butyl peroxide) hexane,, α-bis (t-butyl oxide) 1-)-p-diisopropylbenzene, 2,5-dimethyl-2,5-di- (t-butylperoxy) -hexine-3, benzoylperoxide, t-butylperoxybenzene, t-butylperoxybenzoate, 2,5-Dimethyl-2,5-di (benzoylperoxy) 1-hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, 1,1- 2- (t-butyloxy) 2-methylcyclohexane, 1,1-bis (t-hexyloxy) cyclohexane, 1,1-bis (t-butylbaroxy) 3,3, 5-triethylcyclohexane, 1,1-bis (t-butylvinyl) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxybenzoate, t-petit Ruperoxyacetate, 2,2-bis (t-butylperoxy) butane, n-butyl-4,4-bis (t-butylperoxy) pentanoic acid, di-t-butylperoxysophthalate, 2,5 —Jetyl-2,5-di (benzoylperoxy) hexane. Among these, dialkyl-based, peroxyster-based, and particularly t-butyl benzoic benzoate and dicumyl peroxide are preferable in that the foaming of the vulcanized product is easily prevented. The amount of the vulcanizing agent may be appropriately determined in consideration of the amount of active -o-o-bonds in the organic peroxide, the decomposition temperature, and the like. Usually, 100 parts by weight of the copolymer (hereinafter, "parts") In the peroxide vulcanization, which is 0.5 to 10 parts, preferably 1.0 to 5 parts per vulcanization, vulcanization is remarkably accelerated by using a vulcanization aid. In the present invention, a compound capable of generating a substituted or unsubstituted benzoyloxy radical is used as such a vulcanization aid. As the vulcanization aid, the following formula (I), (II) or (II):

(Wherein, R, RR ² and R ³ are the same or different, and are all alkyl groups, alkoxyl groups or halogen atoms having 1 to 4 carbon atoms; n and m are the same or different, and are all integers of 0 to 5) P and q are the same or Differently, each of which is an integer of 0 to 4), and at least one kind of a substituted or unsubstituted dibenzoylquinonedioxime compound. Specifically, for example, p, p 'dibenzoylquinone dioxime, dibenzoyl_1,4_naphthyl quinone dioxime, etc. can be exemplified, and in particular, it is easy to obtain and the price is low. Jopenzilquinone dioxime is preferred.

It is known that the degree of vulcanization increases when quinone dioxime compounds are used for peroxide vulcanization of ethylene-propylene (II) elastomer. The mechanism of action is as follows: (1) Radicals generated from peroxide, which is a vulcanizing agent, react with tertiary radicals generated by extracting hydrogen from the propylene unit of the elastomer, and the quinonedioxime compound reacts to decompose the main chain. (2) An action mechanism that forms a crosslinked structure by crosslinking reaction via oxime is claimed (Journal of the Rubber Society of Japan, Vol. 41, No. 5, p. 435-441, p. 442- 450 pages (1968)). In this document, it is also reported that the degree of vulcanization is reduced when peroxidic crosslinking of polyethylene or the like containing no propylene unit is attempted.

Also, as an example where a quinonedioxime compound is added in a peroxide vulcanization system of fluororubber, an example of addition to a TF-propylene copolymer is known (Japanese Patent Publication No. 49-7058).

However, there is no known example of adding a quinonedioxime compound in a peroxide vulcanization system of a fluoroelastomer-based copolymer containing no propylene unit as a main component.

It is unknown why compounds that can generate substituted or unsubstituted benzoyl radicals can specifically improve the vulcanizability in the peroxide vulcanization system of E-HFP elastomers. In particular, in the case of a formulation containing a filler with low reinforcing properties, it is conventionally used for peroxide vulcanization of E-HFP elastomers. The foaming phenomenon that occurred with other vulcanization aids such as TA IC used does not appear only when a compound that can generate substituted or unsubstituted benzoyl radicals is used as the vulcanization aid. .

The amount of the specific vulcanization aid used in the present invention is 0.2 to 10 parts, preferably 0.5 to 5 parts, per 100 parts of E-HFP-based elastomer. If the amount is too large, the coloring becomes large, and if the amount is too small, the effect of suppressing foaming cannot be expected.

In the present invention, in addition to the specific vulcanization aid, other conventionally known vulcanization aids may be used. Specific examples include TAIC, triaryl cyanurate, triallyl formal, triaryl trimellitate, N, N'-m-phenylenebismaleimide, dipropargyl terephthalate, diaryl phthalate, tetraaryl terephthalate amide And triaryl phosphate, and in particular, triallyl isocyanurate is preferred because the vulcanizate has high heat resistance. The combined amount may be selected within a range that does not impair the effects of the present invention.

Peroxide vulcanization can be carried out in the same manner as before. For example, an E-HFP-based elastomer and a vulcanizing agent, a vulcanizing aid, and other additives that can be mixed as appropriate are kneaded in a roll, put into a mold, pressurized, and subjected to primary vulcanization (press vulcanization). Then, there is a method of secondary vulcanization (oven vulcanization). Generally, the primary vulcanization conditions are a temperature of 100 to 200, a time of 5 to 60 minutes, and a pressure of about 2 to 1 OMPa.The secondary vulcanization conditions are a temperature of 150 It is adopted from the range of about 30 minutes to 30 hours.

In the composition of the present invention, a filler, a processing aid, an antioxidant, and the like can be further added as necessary.

Examples of the filler include metal oxides such as magnesium oxide, calcium oxide, zinc oxide, lead oxide, titanium oxide, iron oxide, silver oxide, chromium oxide, bismuth oxide, silicon oxide, aluminum oxide, and copper oxide; and water. Magnesium oxide Metal hydroxides such as shim, aluminum hydroxide and calcium hydroxide; carbonates such as magnesium carbonate, aluminum carbonate, calcium carbonate and barium carbonate; metal sulfides such as molybdenum disulfide, iron sulfide and copper sulfide; sulfuric acid Sulfates such as rusium, aluminum sulphate and barium sulphate; silicates such as magnesium manganate, calcium metasilicate, sodium silicate and aluminum silicate; other talcite, lytbon (a mixture of zinc sulphide and barium sulphate) ), Diatomaceous earth, graphite, power pump rack, lamp black, MT carbon black, fluorinated carbon, calcium fluoride, coke, fluororesin powder or fiber, carbon fiber, etc. Points that contribute to improving metal adhesion and lubricity Chromium oxide, silicon oxide, and iron oxide powder which are inorganic powders having a Mohs hardness of 6 or more described in JP-A-8-27343 and JP-A-8-151565; Polytetrafluoroethylene powder impregnated with carbon described in Japanese Patent Application Laid-Open No. Hei 7-188500; a fluororesin filled with a filler described in Japanese Patent Application Laid-Open No. 56-151 739 as a main component Fibers made of a material which is made of carbon fiber; a fiber of a material mainly composed of carbon fiber and fluororesin; calcium metasilicate or graphite described in Japanese Patent Publication No. 5-64177 is preferable; Carbon black and silicon oxide are preferred from the standpoint of remarkable improvements in strength and compression set.

Further, as a formulation in which the present invention exhibits a surprising effect specifically, a formulation using a filler having a small reinforcing strength as a filler is given. The foaming phenomenon can be suppressed by using the above-mentioned specific vulcanization aid. Here, a small reinforcing property means that the ability to increase the strength of the vulcanizate is low.

Fillers with small reinforcing properties include calcium metasilicate and barium sulfate And at least one selected from the group consisting of magnesium silicate and aluminum silicate.

The compounding amount of the filler can be appropriately selected depending on the kind and the purpose of the compounding, and is usually 0 to 100 parts, preferably 10 to 60 parts per 100 parts of the elastomer. Higher fatty acids such as stearic acid, oleic acid, palmitic acid and lauric acid; higher fatty acid salts such as sodium stearate and zinc stearate; higher fatty acid amides such as stearic acid amide and oleic acid amide; edil stearate, butyl stearate; Higher fatty acid esters such as ethyl oleate and butyl oleate; higher fatty acid amines such as stearic acid; polyols such as ethylene glycol, glycerin, and methyl alcohol; aliphatic hydrocarbons such as petrolatum and paraffin; Wax, silicone oil, low molecular weight polyethylene Emissions, such as low molecular weight polypropylene.

Antioxidants include 4,4-bis (α, dimethylpentyl) diphenylamine, phenyl-1-naphthylamine, alkylated diphenylamine, octylated diphenylamine, ρ- (ρ-toluenesulfonylamide) diphene Nilamine, Ν, Ν '—-2-naphthyl- ρ-phenylenediamine, N, N'-diphenyl ρ-phenylenediamine, Ν-phenyl-Ν '1 ^ Γsopropyl _ ρ-phenylenediamine , Ν—phenyl N '— (1,3-dimethylbutyl) —ρ-phenylenediamine, Ν-phenyl N' one (3-methacryloyloxy-1-hydroxypropyl) ρ-phenylenediamine, Examples include 2,2,4-trimethyl-11,2-dihydroquinoline polymer and tris (noelphenyl) phosphite. The composition of the present invention can be obtained by a continuous molding process such as extrusion, transfer, calender, roll coating, brush coating, impregnation, etc., in addition to ordinary mold molding. It can be formed into molded products such as sheets, pipes, rods, tubes, angles, channels, drawn cloths, and coated boards. It can be formed into a deformed product, a special molded product, for example, a sponge-like rubber, etc. by various other known molding methods. It is also possible to perform primary processing on a film- or tape-shaped molded product, and to further process this by secondary processing such as lamination, pasting, and winding. The composition formed in this manner is vulcanized by the vulcanizing means as described above. In addition, the composition is applied to the surface of the substrate by application, impregnation, spraying, etc. in a solution form and then vulcanized, or vulcanized and bonded in a film or sheet form by laminating and vulcanizing. A vulcanized film can also be formed by bonding and laminating a vulcanized film or sheet on the surface of a substrate, and various vulcanized rubber products can be provided.

As described above, the vulcanizates thus obtained have excellent heat resistance, oil resistance, amine resistance, and chemical resistance, and are used in various parts in the automotive, aircraft, semiconductor, food, and chemical industries. Can be used for In particular, it is suitable for parts for oil seals, such as hoses and oil seals for engine oils of automobiles, utilizing heat resistance, oil resistance, and amine resistance. Other suitable molded articles are listed below.

General applicable molded products:

Packing, o-rings, hoses, and other sealing materials, diaphragms, valves, wire coatings, and chemical plants for transportation of automobiles, ships, aircraft, etc. Similar packing in O-rings, seals, diaphragms, valves, hoses, rolls, tubes, and similar packing in food plant equipment and food equipment (including household goods), O-rings, hoses, seals, belts , Diaphragms, valves, rolls, tubes, similar packing in nuclear plant equipment, O-rings, hoses, seals, diaphragms Similar packing, o-rings, hoses, sealing materials, diaphragms, valves, rolls, tubes, mandrels, wire coatings, flexible joints, belts, rubber plates for general industrial parts for frames, valves and tubes

It is suitable for applications such as weather strips and roll blades of PPC copiers.

More specifically, the following uses can be indicated.

(B) Automotive related

The elastomer obtained by the present invention has high heat resistance and excellent resistance to mainly amine-based additives (specifically, succinimides and metal dialkyl dicarbamates) added to automotive oils. In addition, since the volume change is small with respect to the oil itself, it is suitable as a molded product of various members for automobile oil, for example, automatic transmission fluid (ATF), engine oil, and differential gear oil. In particular, gasoline and diesel engine oil seals and hoses; various transmission oil seals and hoses; various gear oil seals and hoses; sensors for sensing the environment of these oils It is suitable as a material for an elastomer molded article that can come into contact with oil, such as a wire covering material.

More specifically,

① Seal application:

• Crankshaft seal,

• 0-ring, gasket of engine cylinder and sleeve

• Wet cylinder sleeve sealing and gasket

• Power piston packing,

• Seal of cylinder liner,

• Valve stem seal, Front pump seal for automatic transmission,

Rear axle binion seal,

Universal joint gasket,

Speedometer pinion seal,

Foot brake piston cup,

O-ring and oil seal for torque transmission

Exhaust gas reburning device seal,

Bearing seal,

Differential seal (drive pinion seal, side seal

)

Gasket for differential, 〇 ring,

Oil seal for manual transmission, gasket, o_ring, packing, oil seal for automatic transmission, gasket, o-ring, packing, oil seal for continuously variable transmission (belt type or toroidal type), gasket, o— Ring, packing,

Wheel bearing seal,

Laje overnight seal, gasket, o-ring,

Oil cooler seals, gaskets, pneumatic rings,

Power steering seals, gaskets, wheel rings

②Hose application:

Oil hose for manual transmission,

ATF hose for automatic transmission,

CVTF hose, EGR tube, for continuous transmission (belt or toroidal)

Twin cab tubes,

Laje night hose, • Hose for oil cooler,

• Power steering hose

③ Diaphragm application:

• Carburetor sensor diaphragm

④Electric components use:

• Wire sheathing materials,

•Insulating material,

-Sheath,

• cooler hose,

• tubes,

• Rings,

⑤Other uses:

'' Vibration isolation rubber (engine mount, exhaust, etc.)

• Hose for reburning equipment

(Mouth) Chemical industry related

① Seal application:

• Chemical pumps, rheometers, pipe seals, • Heat exchanger seals,

• Glass cooler packing for sulfuric acid production equipment,

• Pesticide sprayer, Pesticide transfer pump seal,

• gas pipe seals,

• Seal for plating liquid,

• High temperature vacuum dryer packing,

• Roller seals for papermaking belts,

• fuel cell seals, • Wind tunnel joint seal

② For roll:

-Roll for tricline (for fiber dyeing)

③Other uses:

• Acid resistant hose (for concentrated sulfuric acid),

• Gas chromatography, packing at the tube connection of the pH meter, • Chlorine gas transfer hose,

• Rainwater drain hose for benzene and toluene storage tanks,

• Seals, tubes, diaphragms, valve parts for analytical instruments and physics and chemistry instruments • Steam hoses

(C) General equipment and machinery-related

① Seal application:

• Hydraulic and lubricating machine seals,

• Bearing seal,

• Dry copier seals,

• Dry cleaning equipment windows, other seals,

• Seals for uranium hexafluoride enrichment equipment,

• Cyclotron seal (vacuum) valves, etc.

• Automatic packaging machine seal

②Other uses:

'' Printing equipment printing rolls, scrapers, tubes, valve parts,

• Coating, coating equipment coating rolls, scrapers, tubes, valve parts, • Pudding ink tubes, rolls, belts,

'' Dry copier belts, rolls,

• Sulfuric acid gas in air, chlorine diaphragm pump diaphragm (pollution measuring device), • rolls, belts,

• squeezing roll for pickling,

• Pipes, hoses and flexible joints for dry cleaning equipment (2) Aircraft related

• Fuel supply hoses, gaskets and rings,

• Rotating tink shaft series,

• Hydraulic equipment gaskets,

• Firewall seal

(E) Ship-related

• Screw propeller shaft stern seal,

• Valve stem seal for intake and exhaust of diesel engines,

• Butterfly valve valve seal,

• Butterfly valve shaft seal

(F) Food and pharmaceutical related

• Plate heat exchanger seals,

• Vending machine solenoid valve seals,

• stoppers,

• Rubber materials for food processing equipment (for example, heat exchanger gaskets, diaphragms, various seals such as O-rings, pipes, hoses, sanitary packing, valve packing, joints between mouths such as filling bottles and fillers) Packing used for filling),

• Products such as alcoholic beverages and soft drinks, packing equipment, food sterilizing equipment, brewing equipment, water heaters, packing for various automatic food vending machines, gaskets, tubes, diaphragms, hoses, joint sleeves

(G) Electric related • Shinkansen insulation oil cap,

• Ventilator seal of liquid ring type transformer,

• oil well cable jacket,

• Electrical insulation materials (for example, insulation spacers for various electrical equipment, insulation tape used for the joint end of cables, materials used for heat-shrinkable tubes, etc.),

• Electrical and electronic equipment materials used in high-temperature atmospheres (for example, materials for power outlets for electric motors, materials for electric wires around high-temperature furnaces)

In addition, the molded body obtained above can be used for manufacturing equipment such as semiconductors, liquid crystal panels, plasma display panels, plasma addressed liquid crystal panels, field emission display panels, and solar cell substrates, such as CVD equipment, etching equipment, and oxidation equipment. O-rings, seals, hoses, tubes, diaphragms, rolls, linings, coatings for parts requiring plasma resistance, such as diffusion equipment, sputtering equipment, asshing equipment, ion implantation equipment, and exhaust equipment; In addition, wet etching, cleaning equipment, chemical liquid piping, gas piping, and other parts requiring chemical resistance, rings, sealing materials, hoses, tubes, diaphragms, and rolls; O-rings and seas where free is required Wood, hoses, Ji Yubu, diaphragm, may also be used as a roll.

Specific examples of other parts requiring chemical resistance include: O-rings for resist developing solution, stripping solution, wafer cleaning solution, and sealing materials in manufacturing equipment such as semiconductors, liquid crystal valves, and plasma display panels. Examples include hoses, tubes, diaphragms for pumps, rolls for transporting wafers, and the like. Further, there are other uses in which the above-described vulcanized film is formed and used. Specifically, the following uses can be shown. ， Non-adhesive oil-resistant roll for copier,

• weatherstrips to prevent weather icing,

• Rubber stopper for infusion,

• vial rubber stopper,

•Release agent,

• Non-adhesive light conveyor belt,

• Anti-adhesive coating on play gaskets of automobile engine mounts • Coating of synthetic fibers,

• Bolt members or joints with a thin packing layer

Next, the present invention will be described more specifically based on Production Examples and Examples, but the present invention is not limited only to these.

Production example (Production of E-HFP elastomer)

In a 200 liter stainless steel autoclave, 100 liters of ion-exchanged water, 5 kg of perfluorooctanoic acid ammonium, 80 g of sodium hydroxide, 780 g of disodium hydrogen phosphate dodecahydrate 780 g, t-butyl alcohol 3.64 kg, perbutyl PV (containing 70% by weight of t-butyl valoxypivalate, manufactured by NOF CORPORATION), 243 g, and sufficiently purged with nitrogen; 54.6 kg of propylene (HFP) was charged, the temperature was adjusted to 15, and 1760 g of a premixed ethylene / TFE (87.7 / 12.3, mol%) mixed monomer was charged in the autoclave at an internal pressure of 1760 g. Until it reaches 0.85MPa · G. The autoclave was left at a temperature of 15 with stirring until the pressure became constant (0.85 MPa · G). When the temperature and pressure became constant, 3.17 g of iron sulfate (II) heptahydrate, 1.17 g of ethylenediaminetetraacetic acid disodium salt dihydrate 1.37 g and hydroxymethane were added to 3300 g of ion-exchanged water. An aqueous solution containing 194 g of sodium sulfinic acid dihydrate dissolved in nitrogen gas After bubbling with, the charging reaction was started with a plunger pump. As the pressure decreases as the reaction proceeds, the pressure drop is compensated for by adding a monomer mixed with ethylene ZTFE (91.7 / 8.3.3, mol%). , 0.85 MPa-G) for 42 hours.

After the completion of the reaction, the remaining monomer is released into the atmosphere, the obtained emulsified dispersion is pulverized with hydrochloric acid, washed with ion-exchanged water, dried at 120 ° C. until a constant weight is reached, and then subjected to elastomeric property. 23.1 kg of E—HFP—TFE copolymer was obtained. The average polymerization rate was 5.5 gZhrZl liter / water.

The copolymer composition of this E-HFP-TFE elastomer was analyzed by ¹ H-NMR, GPC, and other analytical methods, and the copolymer weight of ethylene was 53.9 mol%, HFP4 was 1.0 mol%, and TFE was 5.1 mol%. It was united. The glass transition temperature was +2, and the Mooney viscosities were ML (1 +4, lO Ot :) 143 and ML (1 +10, lO Ot) 132.

Example 1

100 parts of E-HFP-TFE elastomer obtained in the production example, t-butyl peroxybenzoate (Perbutyl Z, Nihon Yushi Co., Ltd.) as a peroxide curing agent 3.7 parts, vulcanization aid P, p '— dibenzoylquinone dioxime (Barnock DGM, manufactured by Ouchi Shinko Chemical Co., Ltd.) 3.4 6 parts and calcium metasilicate (NYAD # 400, manufactured by NYCO) as a small reinforcing filler 40 Parts were mixed and kneaded at room temperature using an open mouth to prepare a composition of the present invention. This composition had good adhesion to rolls and was easy to knead. The resulting composition is placed in a mold, subjected to primary vulcanization by press vulcanization (150 ° C x 15 minutes), and then to secondary vulcanization by oven vulcanization (180 ° C x 4 hours) to produce a vulcanized product. did. In addition, the vulcanization characteristics at 150 were examined. Table 1 shows the results. The physical properties of the vulcanizate obtained, the presence or absence of foaming, and the heat resistance were measured by the following methods. Table 1 shows the results.

(Vulcanization properties)

Seeking vulcanization curve at 150 using a J SR type Kyurasutome Isseki type II in primary press vulcanization, the minimum viscosity (ML), vulcanization degree (MH), induction time (T ₁₀₎ and between optimum vulcanization time ( Τ ₉ )).

(Normal physical properties)

100% modulus (Ml 00), tensile strength at break (TB) and tensile elongation at break (EB) are in accordance with JIS K6251 (1993), and hardness (Hs) is in accordance with JIS K6253 (1997) Durome overnight type A Measure.

(With or without foam)

The surface of the obtained primary vulcanizate is visually observed.

(Heat-resistant)

Measurement of change in tensile strength at break (ΔΤΒ), change in tensile elongation at break (ΔΕΒ) and change in hardness (AHs) after exposure to 230t: x for 72 hours in air Comparative Example 1

A composition was prepared in the same manner as in Example 1 except that 2.5 parts of TAIC was blended in place of p, '-dibenzoylquinonedioxime as a vulcanization aid. The vulcanization characteristics were examined in the same manner as described above. Table 1 shows the results.

Then, primary vulcanization and secondary vulcanization were carried out in the same manner as in Example 1 to produce a vulcanizate for comparison. In the same manner as in Example 1, the vulcanizate was examined for physical properties in a normal state, presence or absence of foaming, and heat resistance. Table 1 shows the results. Example 1 Comparative Example 1 Composition (parts by weight)

t.—i 'P yarn L fusomer 100 100 Vulcanizing agent 3.7 3.7 Vulcanizing aid

3.46

T A I C 2.5 Filler

Ν YAD # 400 40 40

ΜΤCarphone

Carosulfur te

ML 0.35 0.20

ΜΗ 3.30 1.60 丄 1 u 0.9 0.8

T 9 0 6.0 5.0 Foaming C, A Dodo / J'I Sat

M 丄 U U 49

TB 133 foamed

EB 360 not measured

H s (Shore A) 72

Heat-resistant

ΔΤΒ (%) -16.7

ΔΕΒ ()

5.6

Without measuring

ΔΗ s 1 Example 2

To 100 parts of E-HFP-TFE elastomer obtained in the preparation example, 3.7 parts of perbutyl Z as a peroxide curing agent, and ρ, ρ 'dibenzoylquinone dithio as a vulcanization aid Kissim (Barnock DGM, manufactured by Ouchi Shinko Chemical Co., Ltd.) 3. Mix 46 parts and 30 parts of MT carbon black (N-990, manufactured by Cancarb) as a filler, and use an open mouth. Mix at room temperature By kneading, the composition of the present invention was prepared. This composition had good adhesion to rolls and was easy to knead. The resulting composition was placed in a mold, primary vulcanized by press vulcanization (150 at XI for 5 minutes), and then secondary vulcanized by oven vulcanization (180 t: x 4 hours). To produce a vulcanizate. In addition, the vulcanization characteristics of 15 were examined. Table 2 shows the results.

The obtained vulcanized product was examined for physical properties in the normal state, presence or absence of foaming, and heat resistance in the same manner as in Example 1. Table 2 shows the results.

Example 3

A composition was prepared in the same manner as in Example 2, except that 3.46 parts of p, ρ'-dibenzoylquinonedioxime was used as a vulcanization aid and 1.0 part of TAIC was used in combination. The vulcanization characteristics of the product were examined in the same manner as in Example 1. Table 2 shows the results.

Then, primary vulcanization and secondary vulcanization were carried out in the same manner as in Example 1 to produce a vulcanized product. In the same manner as in Example 1, the vulcanizate was examined for physical properties in a normal state, presence or absence of foaming, and heat resistance. Table 2 shows the results.

Comparative Example 2

A composition was prepared in the same manner as in Example 2 except that 2.5 parts of TAIC was used in place of ρ, ρ′-dibenzoylquinonedioxime as a vulcanization aid. The vulcanization characteristics were examined in the same manner as in 1. Table 2 shows the results.

Then, primary vulcanization and secondary vulcanization were carried out in the same manner as in Example 1 to produce a vulcanizate for comparison. In the same manner as in Example 1, the vulcanizate was examined for physical properties in a normal state, presence or absence of foaming, and heat resistance. Table 2 shows the results. Table 2

Industrial applicability

According to the present invention, it is possible to provide a composition in which the vulcanizability at the time of peroxide vulcanization of an E-HFP-based elastomer is remarkably improved. In addition, a foaming phenomenon during vulcanization can be suppressed even with a formulation containing a filler having a small reinforcing property.

Claims

The scope of the claims

1. Ethylenehexafluoropropylene comprising an ethylene-hexafluoropropylene-based elastomer, a peroxyside vulcanizing agent, and a vulcanization aid capable of generating a substituted or unsubstituted benzoyloxy radical. Elastomer composition.

2. The vulcanization aid has the following formula (I), (II) or (Π Ι):

(Wherein, R, RR ² and R ³ are the same or different, and are all alkyl groups, alkoxyl groups or halogen atoms having 1 to 4 carbon atoms; n and m are the same or different, and are all integers of 0 to 5) P and Q are the same or different, and each is an integer of 0 to 4) 2. The composition according to claim 1, wherein the composition is at least one dibenzoylquinonedioxime compound.

3. The composition according to claim 2, wherein said vulcanization aid is p, p'dibenzoylquinonedioxime.

4. The composition according to claim 1, further comprising another vulcanization aid.

5. The composition according to claim 4, wherein the other vulcanization aid is triallyl isocyanurate.

6. The composition according to claim 1, further comprising a filler having a small reinforcing property.

7. The composition according to claim 6, wherein the filler having a small reinforcing property is at least one selected from the group consisting of calcium metasilicate, barium sulfate, magnesium silicate and aluminum silicate.

8. The ethylene-hexafluoropropylene-based elastomer is a copolymer of ethylene and hexafluoropropylene or a copolymer of ethylene, hexafluoropropylene and another fluorinated olefin. A composition according to claim 1.

9. The above-mentioned other fluorine-containing olefins are obtained from monomers of tetrafluoroethylene, vinylidene fluoride, trifluoroethylene, trifluoroethylene, pen fluorfluoropropylene and perfluoro (alkyl vinyl ether). 9. The composition according to claim 8, wherein the composition is at least one selected from the group consisting of: