JP3313774B2 - Chlorinated ethylene / α-olefin copolymer rubber composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a chlorinated ethylene / α-olefin copolymer rubber composition having excellent rubber elasticity.

[0002]

2. Description of the Related Art Chlorinated ethylene / α-olefin copolymer rubber is a rubber excellent in heat aging resistance, cold resistance and weather resistance. In order to develop such rubber strength and rubber elasticity, an inorganic filler such as carbon black is generally added, but since carbon black is black,
Cannot be used on light rubber products. However, when a white filler such as silica exhibiting a light color is mixed in place of such carbon black, rubber elasticity is reduced, and thus there is a disadvantage that the application is restricted.

Hitherto, as a method for improving the rubber elasticity of a chlorinated ethylene / α-olefin copolymer rubber, a method of increasing the molecular weight of the rubber, a method of increasing the amount of a crosslinking agent and increasing a crosslinking density, and the like have been generally adopted. However, the former has a problem that the processability is deteriorated, and the latter has a problem that the elongation characteristic of rubber is reduced.

[0004] Under such circumstances, in recent rubber products, it is required to use a white filler in terms of color, cost, and the like, and furthermore, rubber seals are required to have improved rubber elasticity in order to improve sealing properties. . Therefore, using a white filler,
In addition, the appearance of a chlorinated ethylene / α-olefin copolymer rubber composition having the same rubber performance and processability as the above and at the same time having excellent rubber elasticity is desired.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and to have a sufficient workability in order to meet the demand for lighter rubber products and improved rubber elasticity. Another object of the present invention is to provide a chlorinated ethylene / α-olefin copolymer rubber composition having excellent rubber elasticity, heat aging resistance, cold resistance and weather resistance.

[0006]

The present invention relates to the following chlorinated ethylene / α-olefin copolymer rubber composition. (1) (A) The ratio of ethylene to α-olefin in the ethylene / α-olefin copolymer before chlorination is ethylene / α-olefin = 80/20 to 92/8 on a molar basis.
100 parts by weight of a chlorinated ethylene / α-olefin copolymer rubber having a chlorine content of 20 to 40% by weight and a Mooney viscosity [ML _{1 + 4} (121 ° C.)] of 10 to 190; General formula [1]

Embedded image (Wherein, R ¹ represents an alkenyl group, a chloroalkenyl group or a chloroalkyl group, and R ² represents a lower alkyl group.) 0.05 to 0.5 parts by weight of a silane compound represented by the following formula: Chlorinated ethylene α-characterized by containing 5 to 200 parts by weight of a white filler.
Olefin copolymer rubber composition. (2) The α-olefin of the ethylene / α-olefin copolymer before chlorination of the chlorinated ethylene / α-olefin copolymer rubber (A) is an α-olefin having 3 to 10 carbon atoms. The chlorinated ethylene / α-olefin copolymer rubber composition according to (1) above.

The chlorinated ethylene α- used in the present invention
The olefin copolymer rubber (A) has a chlorine content of 20-4.
Chlorinated ethylene α having a Mooney viscosity [ML _{1 + 4} (121 ° C.)] of 10 to 190, preferably 20 to 150, and more preferably 30 to 130. -Olefin copolymer rubber (A)
It is. Such chlorine content and Mooney viscosity [M
L _{1 + 4} (121 ° C.)], a rubber composition having excellent physical properties can be obtained and workability during production is good.

[0008] The α-olefin constituting the ethylene / α-olefin copolymer before chlorination of the chlorinated ethylene / α-olefin copolymer rubber (A) has 3 to 10 carbon atoms.
Are preferred, for example, propylene, 1-butene, 1
-Pentene, 1-hexene, 4-methyl-pentene-
1,1-octene, 1-decene, and the like. Among these, propylene, 1-butene, 4-methyl-pentene-1, and 1-hexene are preferred.

The ratio of ethylene to α-olefin is 80 / 20-92 on a molar basis.
/ 8. Ethylene and α-olefin in the above ratio
Ethylene / α-olefin obtained by random polymerization
The copolymer is a rubbery polymer.

[0010] In addition to the above components, other polymerizable components may be copolymerized in the ethylene / α-olefin copolymer. Other polymerizable components include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-
Hexadiene, 6-methyl-1,5-heptadiene, 7
Chain non-conjugated dienes such as -methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2- Norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropylenyl-
Non-conjugated dienes such as cyclic non-conjugated dienes such as 2-norbornene are exemplified. As an ethylene / α-olefin copolymer in which other polymerizable components are copolymerized, in particular, the total weight of ethylene and α-olefin units is 100 g.
On the other hand, those containing at most 30 mmol of 5-vinyl-2-norbornene are preferred. The ethylene / α-olefin copolymer is a rubbery polymer obtained by randomly polymerizing the above components.

The chlorinated ethylene / α-olefin copolymer rubber (A) can be obtained by chlorinating the ethylene / α-olefin copolymer. The chlorination is carried out by, for example, pulverizing an ethylene / α-olefin copolymer into fine granules, bringing the fine granules into an aqueous suspension, and contacting them with molecular chlorine at a temperature of about 70 to 90 ° C. A method in which a copolymer is dissolved in a solvent that is stable against chlorine such as carbon, chloroform and tetrachloroethylene, and brought into contact with molecular chlorine in a uniform solution state, or N-chloroacetamide, N-chlorosuccinimide , 1,3-dichloro-
The method is performed by uniformly kneading a chlorine compound such as 5,5-dimethylhydantoin into the copolymer using a Banbury mixer or a roll, and heating the mixture to a temperature at which chlorine is released. A method of blowing chlorine in a halogen solvent in the presence of a radical initiator is preferred. The degree of chlorination can be adjusted by appropriately selecting the amount of molecular chlorine or other chlorinating agent used, the reaction time, the reaction temperature and the like.

After the chlorination reaction, the treatment is performed as follows. In the case of chlorination in an aqueous suspension state, the chlorinated ethylene / α-olefin copolymer rubber is washed with water to remove molecular chlorine and by-produced hydrogen chloride and dried. In the case of chlorination in a solution state, the reaction solution is poured into a poor solvent of chlorinated ethylene / α-olefin copolymer rubber such as excess methanol, and the precipitate is filtered, washed with this solvent, and dried. Let it.

The silane compound (B) used in the present invention
Is represented by the general formula [1]. Examples of the alkenyl group, chloroalkenyl group or chloroalkyl group represented by R ¹ in the general formula [1] include those having 2 to 6 carbon atoms such as vinyl, allyl, chlorovinyl, chloroallyl, and chloropropyl. Can be exemplified.
Examples of the lower alkyl group represented by R ² include those having 1 to 3 carbon atoms such as a methyl group and an ethyl group.
Specific examples of the silane compound (B) represented by the general formula [1] include chloropropyltrimethoxysilane, chloropropyltriethoxysilane, and vinyltrimethoxysilane.

The white filler (C) containing silicon dioxide used in the present invention is a white filler containing silicon dioxide as a constituent in the molecule, and is specifically a dry silica or a wet silica. , Synthetic silicate-based white carbon, talc, clay, calcined clay, glass fiber and the like. By using such a white filler, a light-colored rubber product can be obtained.

In the chlorinated ethylene / α-olefin copolymer rubber composition of the present invention (hereinafter sometimes simply referred to as a rubber composition), the silane compound (B) with respect to the chlorinated ethylene / α-olefin copolymer rubber (A) The mixing ratio of the white filler (C) and the white filler (C) is 0.05 to 0.5 part by weight, preferably 0.1 part by weight, per 100 parts by weight of the component (A).
1 to 0.5 part by weight, 5 to 200 parts by weight, preferably 10 to 100 parts by weight of the component (C).
Select according to purpose.

By setting the mixing ratio of the above three components in such a range, a rubber composition excellent in processability, rubber elasticity, heat aging resistance, cold resistance and weather resistance can be obtained. Here, chlorinated ethylene / α-olefin copolymer rubber (A)
Exhibits heat aging resistance, cold resistance, and weather resistance by itself, and by blending a white filler (C), improves strength and prevents swell, which is important in processing. Further, rubber elasticity is improved by blending the silane compound (B). Although the reason is not clear, when vulcanizing the rubber composition of the present invention, it is necessary to form a chemical bond between the chlorinated ethylene / α-olefin copolymer rubber (A) and the white filler (C). It is estimated that there is not.

If the amount of the silane compound (B) is small in the above three components, the rubber elasticity of the rubber composition tends to decrease. And the strength characteristics tend to decrease. Also, when the amount of the white filler (C) is reduced, the strength of the rubber composition tends to decrease, and when it is increased, the strength of the rubber composition tends to decrease.

The rubber composition of the present invention can be used in an unvulcanized state, but when used as a vulcanized product, its properties can be exhibited most. The rubber composition of the present invention is a compounding agent known per se, such as a vulcanizing agent, a vulcanizing aid, a rubber reinforcing material, a pigment,
Fillers, softeners, metal activators, scorch inhibitors, hydrochloric acid absorbers, antioxidants, processing aids, and the like can be added.

The total amount of the chlorinated ethylene / α-olefin copolymer rubber (A), the silane compound (B) and the white filler (C) in the rubber composition of the present invention depends on the intended vulcanizate performance, Although it is appropriately selected according to the application, it is usually 40% by weight or more, preferably 50% by weight or more.

In order to vulcanize the rubber composition of the present invention, an unvulcanized rubber compound is first prepared, and then the rubber compound is formed into an intended shape and then vulcanized. Suitable vulcanization methods include triazine vulcanization and organic peroxide vulcanization. When performing triazine vulcanization, a triazine compound such as a triazine thiol represented by the following general formula [2] is used as a vulcanizing agent.

[0021]

Embedded image (Wherein, R ³ represents —NR ⁴ R ⁵ , —OR ^4, or —SR ⁴ , wherein R ⁴ and R ⁵ each represent a hydrogen atom, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted aryl group. Shown.)

Specific examples of the triazine thiols represented by the general formula [2] include triazine-2,4,6
-Trithiol, 2-dibutylaminotriazine-4,
6-dithiol, 2-phenylaminotriazine-4,
6-dithiol, 2-hexylaminotriazine-4,
6-dithiol, 2-diethylaminotriazine-4,
6-dithiol, 2-butoxytriazine-4,6-dithiol and the like can be mentioned.

The vulcanizing agent is chlorinated ethylene / α-olefin
Normally, 1 × 10^-3~
2.5 × 10^-2Mol, preferably 1.5 × 10^-3~ 2x
10 ^-2Mole, more preferably 3 × 10^-3~ 1.3 × 1
0^-2It is desirable to mix them in a molar ratio, and there is one kind alone.
Or a mixture of two or more.

If the amount of the vulcanizing agent is less than the above range, a vulcanizate having a suitable rubber elasticity cannot be obtained. Tends to be difficult.

When a triazine compound is used as a vulcanizing agent, it is preferable to add a vulcanizing aid. The vulcanization aid is added to make the vulcanization speed practical for processing and molding. As the vulcanization aid, an organic base having an acid dissociation constant (pKa) of 7 or more, or a compound capable of generating an organic base is used.

Examples of such vulcanization aids include 1,8-diazabicyclo (5,4,0) undecene-7, laurylamine, benzylamine, dibenzylamine, N-methylmorpholine, dicyclohexylamine, dibutyldithiocarbamic acid. Zinc, pentamethylenedithiocarbamic acid piperidine salt, N-cyclohexyl-2-benzothiazolylsulfenamide, benzoic acid / piperidine salt, benzoic acid / dicyclohexylamine salt, diphenylguanidine, dioltotolylguanidine, dipentamethylenethiuram tetrasulfide, Tetramethylthiuram disulfide, tetramethylsulfonium iodide, tetramethylammonium chloride, tetrabutylphosphonium bromide, tetrabutylammonium bromide, distearyldimethylammonium Including onium salts such as Roraido can be exemplified.

The vulcanization aid is usually 5 × 10 5 per 100 g of the chlorinated ethylene / α-olefin copolymer rubber (A).
^{-4 to} 2 × 10 ^-2 mol, preferably 1 × 10 ^-3 to 1 × 10
^It is desirable to mix them in a proportion of ^-2 mol, and they may be used alone or in combination of two or more.

When organic peroxide vulcanization is carried out, the vulcanizing agent may be dicumyl peroxide or 2,5-dimethyl-2,5.
-Di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane,
Examples include 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, di-tert-butyl peroxide, di-tert-butylperoxy-3,3,5-trimethylcyclohexane, tert-dibutyl hydroperoxide and the like. Among these, dicumyl peroxide, ditertiary butyl peroxide, ditertiary butylperoxy-3,3
5-Trimethylcyclohexane is preferably used.

The amount of the organic peroxide used is based on 100 g of the chlorinated ethylene / α-olefin copolymer rubber (A).
Usually 3 × 10 ^{-4 to} 5 × 10 ^-2 mol, preferably 1 × 10 ^-4 mol
The range of ^{-3 to} 3 × 10 ^-2 mol is desirable, and one kind is used alone or two or more kinds are used in combination.

When an organic peroxide is used as a vulcanizing agent, it is preferable to use a vulcanizing aid in combination. Examples of the vulcanization aid include quinone dioximes such as sulfur and P-quinone dioxime; acrylics such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; allyls such as diallyl phthalate and triallyl isocyanurate;
Other examples include a maleimide type and divinylbenzene. It is desirable that such a vulcanization aid is used in an amount of 0.5 to 2 moles, preferably equal mole, per mole of the organic peroxide used.

When a bright color product is not required, as a reinforcing material for rubber, for example, SRF, GPF, FEF, MAF,
Various carbon blacks such as ISAF, SAF, FT, and MT can be used. As the filler, for example, light calcium carbonate, heavy calcium carbonate, or the like is used.

The amounts of these reinforcing materials and fillers are as follows:
Although it is appropriately selected depending on the desired product, the amount is usually 150 parts by weight or less, preferably 100 parts by weight or less, based on 100 parts by weight of the chlorinated ethylene / α-olefin copolymer rubber (A).

Examples of the softener include petroleum substances such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt and petrolatum; coal tars such as coal tar and coal tar pitch; castor oil, rapeseed oil, and so on. Fatty oils such as bean oil and coconut oil; tall oil; waxes such as beeswax, carnauba wax and lanolin; fatty acids such as ricinoleic acid, palmitic acid, stearic acid, barium stearate and calcium stearate, or metal salts thereof;
Rosin or a derivative thereof; terpene resin; petroleum resin; cumarone indene resin; atactic polypropylene; ester plasticizers such as dioctyl phthalate, dioctyl adipate, dioctyl sebacate; and didodecyl carbonate; Carbonate plasticizers such as ditridecyl carbonate; microcrystalline wax; sub- (factice); liquid polybutadiene; modified liquid polybutadiene; and liquid thiocol.

The amount of these softeners is appropriately selected depending on the desired product.
The amount is usually 100 parts by weight or less, preferably 70 parts by weight or less, based on 100 parts by weight of the olefin copolymer rubber (A).

As the metal activator, magnesium oxide, higher fatty acid zinc, lead red, litharge, calcium oxide, hydrotalcite and the like can be used. It is desirable to use these metal activators in an amount of usually 3 to 15 parts by weight, preferably 5 to 10 parts by weight, based on 100 parts by weight of the chlorinated ethylene / α-olefin copolymer rubber (A).

As the scorch inhibitor, known scorch inhibitors can be used, and examples thereof include maleic anhydride, thioimide compounds, sulfenamide compounds and sulfonamide compounds. These scorch inhibitors are usually 0.2 to 5 parts by weight, based on 100 parts by weight of the chlorinated ethylene / α-olefin copolymer rubber (A).
Preferably, it is used in the range of 0.3 to 3 parts by weight.

As the hydrochloric acid absorbent, an oxide and an organic acid salt of a metal belonging to Group IIA of the periodic table are used. For example, magnesium stearate, magnesia, calcium stearate, manaceite, hydrotalcite, epoxidized soybean oil, epoxy resin A hydrochloric acid absorbent and the like can be exemplified. These hydrochloric acid absorbents can be appropriately blended in an amount of usually 10 parts by weight or less based on 100 parts by weight of the chlorinated ethylene / α-olefin copolymer rubber (A).

The rubber composition of the present invention exhibits excellent heat resistance and durability even without using an anti-aging agent. However, if an anti-aging agent is used, a product using the rubber composition of the present invention can be obtained. The material life can be further extended as in the case of ordinary rubber. Antioxidants used in this case include, for example, phenylbutylamine, N,
Aromatic secondary amines such as N'-di-2-naphthyl-p-phenylenediamine; dibutylhydroxytoluene, tetrakis [methylene (3,5-di-t-butyl-4-hydroxy) hydrocinnamate] methane and the like Phenolic stabilizer; bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl]
And thioether-based stabilizers such as sulfides; dithiocarbamate-based stabilizers such as nickel dibutyldithiocarbamate. These may be used alone or in combination of two or more. The amount of the antioxidant used is usually 0.1 to 5 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the chlorinated ethylene / α-olefin copolymer rubber (A).
It is desirable to use 3 parts by weight.

As processing aids, those used in normal rubber processing can be used. Ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, calcium stearate, zinc stearate, esters of the above acids And higher fatty acids, salts thereof, and esters thereof. These processing aids are usually used in an amount of up to about 10 parts by weight, preferably about 1 to 100 parts by weight, based on 100 parts by weight of the chlorinated ethylene / α-olefin copolymer rubber (A).
It is desirable to use 5 parts by weight.

Further, pigments are used for some products. Known inorganic pigments (for example, titanium white) and organic pigments (for example, naphthol green B) can be used as the pigment. The amount of these pigments varies depending on the product, but it is desirable to use at most 20 parts by weight, preferably at most 10 parts by weight, per 100 parts by weight of the chlorinated ethylene / α-olefin copolymer rubber (A).

The chlorinated ethylene / α-olefin copolymer rubber composition of the present invention can be prepared, for example, by the following method. In addition to the chlorinated ethylene / α-olefin copolymer rubber (A), the silane compound (B), and the white filler (C), which are essential components of the present invention, additives such as a reinforcing material, a filler, a softener, and a pigment. Using a mixer such as a Banbury mixer at a temperature of about 80 to 170 ° C. for about 3 to 1
After kneading for 0 minutes, a vulcanizing agent and a vulcanizing aid are additionally mixed using rolls such as an open roll, and the roll temperature is about 4 ° C.
The mixture is kneaded at 0 to 80 ° C. for about 3 to 30 minutes and parted to prepare a rubber compound in a ribbon or sheet form.

To vulcanize the unvulcanized rubber compound thus prepared, it is molded into a desired shape by, for example, an extruder, a calender roll, a press, etc. In a tank, usually about 150-27
It can be carried out by heating at 0 ° C. for about 1 to 30 minutes. As the vulcanizing tank, a steam vulcan can, a hot air heating tank, a glass bead fluidized bed, a molten salt vulcanizing tank, a microwave vulcanizing tank, or the like can be used alone or in combination.

The vulcanized product itself is useful as an electrical insulating material, an automobile industrial part, an industrial rubber product, a civil engineering building material, a rubber cloth, and the like. Examples of electrical insulating materials include plugs, ignition caps, distributor caps, and other caps around automobile engines, condenser caps, insulating layers that cover the current-carrying parts of electric wires, such as marine electric wires and automobile ignition cables, and cables. It can be used specifically for joint covers. Automotive parts include hoses such as radiator hoses and fuel hoses, and automotive exterior parts such as bumpers, bumper fillers, bumper strips, bumper side guards, overriders, side protection malls, various weather strips, boots, and ball joints. It can be used for seals, various anti-vibration rubbers, etc.

As industrial rubber products, they can be used for rolls, packings, linings, belts and the like. In addition, roofing sheets, heat-resistant belts,
Can be used for gaskets for building materials, highway joint seals, rubber bearings, etc. As the rubberized cloth, it can be used for waterproof cloth, awnings, leisure sheets and the like. Also, natural rubber or existing synthetic rubber such as EPDM, SBR, NBR,
CR and the like are compounded by multi-layer extrusion or the like, and can be suitably used for the above-mentioned applications.

Further, prior to vulcanization, a foaming agent and, if necessary, a foaming aid are blended into the rubber compound, and the foaming agent used for a heat insulating material, a cushion material, a sealing material, a soundproofing material, an electric insulating material, etc. It can also be a sulphate.

Examples of the blowing agent include inorganic blowing agents such as sodium hydrogencarbonate, ammonium carbonate and ammonium nitrite; N, N'-dimethyl-N, N'-dinitrosoterephthalamide, N, N'-dinitrosopentamethylene Nitro compounds such as tetramine; azo compounds such as azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate; benzenesulfonitrile hydrazide, toluenesulfonyl hydrazide, p, p'-oxybis (Benzenesulfonyl hydrazide), sulfonyl hydrazide compounds such as diphenylsulfone-3,3'-disulfonyl hydrazide; calcium azide;
Azide compounds such as 4,4'-diphenyldisulfonyl azide and p-toluenesulfonyl azide are exemplified, and nitro compounds, azo compounds and azide compounds are particularly preferably used.

These blowing agents are chlorinated ethylene α-
It is usually blended at a ratio of 0.3 to 30 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the olefin copolymer rubber (A), and generally has an apparent specific gravity of about 0.03 to 0.1.
Approximately 9 foams are formed.

Examples of the foaming aid include organic acids such as salicylic acid, phthalic acid, and stearic acid, and urea and derivatives thereof. The foaming aid is used for the purpose of lowering the decomposition temperature of the foaming agent, accelerating the decomposition, and homogenizing the bubbles. Use with agents.

[0049]

As described above, according to the present invention, a specific chlorinated ethylene / α-olefin copolymer rubber (A) 100
The specific silane compound (B) 0.05 to 0.5 parts by weight
White filler (C) containing parts by weight and silicon dioxide
5 to 200 parts by weight, so processability,
A chlorinated ethylene / α-olefin copolymer rubber composition having excellent rubber elasticity, heat aging resistance, cold resistance and weather resistance is obtained.

Since the rubber composition of the present invention has such excellent characteristics, it can be used as an electric insulating material, an automobile industrial part, an industrial rubber product, a civil engineering building material article, a rubber cloth cloth, or the like. It can be suitably used.

[0051]

Next, an embodiment of the present invention will be described. Example 1 The compounding ingredients shown in Table 1 were kneaded with a 4.3 liter Banbury mixer (manufactured by Kobe Steel) for 5 minutes and dumped out. Next, the kneaded material dumped out was wound around a 14-inch open roll (manufactured by Nippon Roll Co., Ltd.). At this time, the roll surface temperature was 60 ° C. for the front roll and 70 ° C. for the rear roll. After adding the compounding ingredients shown in Table 2 on this open roll and kneading for 2 minutes, a sheet was formed with a thickness of 3 mm.

The compounded rubber was press-vulcanized at 160 ° C. for 20 minutes, and a 2 mm thick vulcanized rubber sheet was used.
Hardness (Hs), tensile strength (TB), elongation (EB), and permanent elongation (PS) were measured in an atmosphere at 25 ° C. according to the 6301 vulcanized rubber physical test method. Similarly, JIS K63
01, and the compression set (CS) was measured. The test conditions were 135 ° C. for 70 hours. Table 8 shows the results of these measurements.
Shown in

[0053]

[Table 1] 1) Ethylene / 1-butene (molar ratio) = 90/10 ML _{1 + 4} (121 ° C.) = 50 Chlorine content = 27 wt% 2) Trade name: Wacker Silane GF16S, manufactured by Wacker Corporation 3) Trade name: MISTRON Vapor talc, manufactured by Nippon Talc 4) Product name: Kyowa Mag 150, manufactured by Kyowa Chemical Co., Ltd. 5) manufactured by Sanken Kako

[0054]

[Table 2]

Example 2 The procedure of Example 1 was repeated, except that the chlorinated ethylene / α-olefin copolymer rubber used had the following properties. Table 8 shows the results. Ethylene / 1-butene (molar ratio) = 90/10 ML _{1 + 4} (121 ° C.) = 125 Chlorine content = 27 wt%

Example 3 The procedure of Example 1 was repeated, except that the chlorinated ethylene / α-olefin copolymer rubber used had the following properties. Table 8 shows the results. Ethylene / 1-butene (molar ratio) = 90/10 ML _{1 + 4} (121 ° C.) = 50 Chlorine content = 35 wt%

Example 4 The procedure of Example 1 was repeated, except that the chlorinated ethylene / α-olefin copolymer rubber used had the following properties. Table 8 shows the results. Ethylene / 1-butene (molar ratio) = 85/15 ML _{1 + 4} (121 ° C.) = 100 Chlorine content = 23 wt%

Example 5 The procedure of Example 1 was repeated, except that chloropropyltriethoxysilane (trade name: Wackersilane GF18, manufactured by Wacker Inc.) was used instead of chloropropyltrimethoxysilane. . Table 8 shows the results.

Example 6 The procedure of Example 1 was repeated except that the amount of chloropropyltrimethoxysilane was changed to 0.1 part by weight. Table 8 shows the results.

Example 7 The procedure of Example 1 was repeated, except that the amount of chloropropyltrimethoxysilane was changed to 1.0 part by weight. Table 9 shows the results.

Comparative Example 1 The procedure of Example 1 was repeated, except that chloropropyltrimethoxysilane was not used. Table 9 shows the results.

Comparative Example 2 The procedure of Example 1 was repeated, except that 5 parts by weight of chloropropyltrimethoxysilane was added.
However, foaming occurred during vulcanization, and a test sheet was not obtained.

Example 8 The procedure of Example 1 was repeated, except that the formulation in Table 1 was changed as shown in Table 3. Table 9 shows the results.

[Table 3] 1) Ethylene / 1-butene (molar ratio) = 90/10 ML _{1 + 4} (121 ° C.) = 50 Chlorine content = 27 wt% 2) Trade name: Wacker Silane GF16S, manufactured by Wacker Corporation 3) Trade name: Nipsil VN3 4) Product name: Kyowa Mag 150, Kyowa Chemical Co., Ltd. 5) Sanken Kako Co., Ltd.

Comparative Example 3 The procedure of Example 8 was repeated, except that chloropropyltrimethoxysilane was not used. Table 9 shows the results.

Example 9 The procedure of Example 1 was repeated, except that the formulation in Table 1 was changed as shown in Table 4. Table 9 shows the results.

[Table 4] 1) Ethylene / 1-butene (molar ratio) = 90/10 ML _{1 + 4} (121 ° C.) = 50 Chlorine content = 27 wt% 2) Trade name: Wacker Silane GF16S, manufactured by Wacker Corporation 3) Trade name: Aerosil 200 4) Product name: Kyowa Mag 150, manufactured by Kyowa Chemical Co., Ltd. 5) manufactured by Sanken Kako

Comparative Example 4 The procedure of Example 9 was repeated, except that chloropropyltrimethoxysilane was not used. Table 10 shows the results.

Example 10 Example 10 was carried out in the same manner as in Example 1, except that the formulation in Table 1 was changed as shown in Table 5. Table 10 shows the results.

[Table 5] 1) Ethylene / 1-butene (molar ratio) = 90/10 ML _{1 + 4} (121 ° C.) = 50 Chlorine content = 27 wt% 2) Trade name: Wacker Silane GF16S, manufactured by Wacker Corporation 3) Trade name: Satinton No1 4) Product name: Kyowa Mag 150, manufactured by Kyowa Chemical Co., Ltd. 5) manufactured by Sanken Kako

Comparative Example 5 The procedure of Example 10 was repeated, except that chloropropyltrimethoxysilane was not used. Table 10 shows the results.

Example 11 In Example 1, the formulation of Table 1 was changed as shown in Table 6,
The procedure was performed in the same manner as in Example 1 except that the formulation in Table 2 was changed as shown in Table 7. Table 10 shows the results.

[Table 6] 1) Ethylene / 1-butene (molar ratio) = 90/10 ML _{1 + 4} (121 ° C.) = 50 Chlorine content = 27 wt% 2) Trade name: Wacker silane vinyl trimethoxy, manufactured by Wacker 3) Trade name: MISTRON Vapor Talc, manufactured by Nippon Talc 4) Product name: Kyowa Mag 150, manufactured by Kyowa Chemical Co., Ltd. 5) manufactured by Sanken Kako

[0070]

[Table 7] 1) Mitsui Petrochemical Industries 2) Nippon Kasei Co., Ltd.

[0071]

[Table 8]

[0072]

[Table 9]

[0073]

[Table 10]

From the results in Tables 8 to 10, it can be seen that when the silane compound (B) is blended, the rubber elasticity is improved without lowering other physical properties as compared with the case where the silane compound (B) is not blended. Also, it is found that when the amount of the silane compound (B) is large, vulcanization inhibition occurs.

Continuation of the front page (72) Inventor Yoshiaki Kikuchi 3 Chigusa Coast, Ichihara City, Chiba Prefecture Mitsui Oil Chemical Industry Co., Ltd. (56) References JP-A-59-219355 (JP, A) JP-A-2-202935 (JP) (A) JP-A-2-208335 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 23/28 C08K 3/36, 5/54

Claims (2)

(57) [Claims] (A) The proportion of ethylene and α-olefin in the ethylene / α-olefin copolymer before chlorination is (A)
Ethylene / α-olefin = 80 / 20-9 on a molar basis
2/8, the chlorine content is 20-40% by weight,
Chlorinated ethylene / α-olefin copolymer rubber 100 having a Mooney viscosity [ML _{1 + 4} (121 ° C.)] of 10 to 190
Parts by weight, (B) general formula [1] (Wherein, R ¹ represents an alkenyl group, a chloroalkenyl group or a chloroalkyl group, and R ² represents a lower alkyl group.) 0.05 to 0.5 parts by weight of a silane compound represented by the following formula: Chlorinated ethylene α-characterized by containing 5 to 200 parts by weight of a white filler.
Olefin copolymer rubber composition. 2. The chlorinated ethylene / α-olefin copolymer rubber (A), wherein the α-olefin of the ethylene / α-olefin copolymer before chlorination is an α-olefin having 3 to 10 carbon atoms. The chlorinated ethylene / α-olefin copolymer rubber composition according to claim 1, characterized in that: