JP3150402B2 - Chlorinated ethylene / α-olefin copolymer rubber composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to chlorinated ethylene α-
The present invention relates to an olefin copolymer rubber composition, and more particularly, to a chlorinated ethylene / α-olefin copolymer rubber composition having excellent plasticity and excellent heat aging resistance, cold resistance and weather resistance.

[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. R & D for manufacturing various rubber products by utilizing its excellent characteristics However, the copolymer rubber itself has low plasticity and thus has a drawback that it is difficult to process. Then, the disadvantage was solved and chlorinated ethylene α-
In order to enhance the plasticity of the olefin copolymer rubber, a softener is used.

[0003] Conventionally, process oils,
Mineral oil softeners such as liquid paraffin, vegetable oil softeners such as castor oil, rapeseed oil and rosin, and alcohol esters such as phthalic acid, adipic acid, sebacic acid, fumaric acid and trimellitic acid have been used.

However, recently, there has been a strong demand for high-performance rubber products having excellent heat resistance and cold resistance mainly in the field of automobiles. There is a current situation that it is no longer possible to respond in terms of properties, weather resistance and the like, and therefore, the appearance of rubber products excellent in the above various properties is expected. In addition, there is a demand for a softening agent which gives a rubber composition having a plasticity to a chlorinated ethylene / α-olefin copolymer rubber and, at the same time, excellent heat aging resistance, cold resistance and weather resistance.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a rubber composition which meets the recent demand for higher performance rubber products. That is, an object of the present invention is to provide a chlorinated ethylene / α-olefin copolymer rubber composition having sufficient processability, heat aging resistance, cold resistance, and weather resistance, and furthermore, its high performance. It is to provide a softening agent which provides a rubber composition.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned chlorinated ethylene.
By blending a specific polyalkylene glycol polycarbonate with the α-olefin copolymer rubber, it imparts excellent processability to the chlorinated ethylene / α-olefin copolymer rubber, and unlike other softeners, heat aging resistance, The inventors have found that they do not adversely affect cold resistance and weather resistance, and have reached the present invention. That is, according to the present invention, 100 parts by weight of a chlorinated ethylene / α-olefin copolymer rubber is represented by the general formula
(I) R ¹ -O-COO-([R ³ -O] m -COO) n -R ² (I) wherein R ¹ and R ² each independently have 1 to 36 carbon atoms It is a linear or branched alkyl group, a cycloalkyl group or an alkyl group containing a cycloalkyl group, and R ³ is an alkylene group having 2 to 20 carbon atoms. M is an integer of 1 to 100;
n represents an integer of 1 to 10], and 5 to 200 parts by weight of a polyalkylene glycol polycarbonate represented by the following formula:

The chlorinated ethylene / α-olefin copolymer rubber, which is one of the essential components of the composition of the present invention, is widely known, and any of the rubbers falling within the category has the above-mentioned results. But especially
The chlorine content is 20 to 40% by weight, preferably 25 to 35% by weight, and the Mooney viscosity [ML _{1 + 4} (121
° C)] is 10 to 190, preferably 20 to 15
Better results are obtained with a chlorinated ethylene / α-olefin copolymer rubber of 0, particularly preferably 30 to 120.

[0008] The chlorinated ethylene α- used in the present invention
The olefin copolymer rubber can be obtained by first preparing an ethylene / α-olefin copolymer and then chlorinating the copolymer.

The α-olefin of the ethylene / α-olefin copolymer before chlorination preferably has 3 to 10 carbon atoms. In particular, propylene, 1-butene,
4-Methyl-pentene-1 and hexene are preferred. When the ratio of ethylene and α-olefin is ethylene /
Preferably, α-olefin is 75/25 to 95/5.

The ethylene / α-olefin copolymer may be copolymerized with other polymerizable components in addition to the above components. It preferably contains at most 30 mmol of vinyl-2-norbornene. In particular, as the ethylene / α-olefin copolymer, a rubber-like polymer obtained by randomly polymerizing the above components is preferable.

For the chlorination of the ethylene / α-olefin copolymer, a known method is used. More specifically, the chlorination of the above-mentioned copolymer is carried out, for example, by pulverizing the copolymer into fine particles, bringing the fine particles into an aqueous suspension, and removing the molecular chlorine at a temperature of about 70 to 90 ° C. A method of contacting, a method of dissolving a copolymer in a solvent stable against chlorine such as carbon tetrachloride, chloroform, and tetrachloroethylene, and contacting it with molecular chlorine in a uniform solution state, or N-chloroacetamide , N-chlorosuccinimide,
It is carried out by a method of uniformly kneading a chlorine compound such as 1,3-dichloro-5,5-dimethylhydantoin into a copolymer with a roll or a Banbury and heating to a temperature at which chlorine is liberated. A preferred method is to blow chlorine into the presence of the radical initiator in a halogen-based solvent such as carbon chloride or chloroform.

After the chlorination reaction, the treatment is performed as follows. In the case of chlorination in aqueous suspension, chlorinated ethylene
The α-olefin copolymer rubber is dried by washing with water to remove molecular chlorine and by-produced hydrogen chloride. 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 and washed with this solvent. dry.

The polyalkylene glycol polycarbonate which is another essential component of the present invention is represented by the general formula (I): R ¹ -O-COO-([R ³ -O] m -COO) n -R ² (I) Wherein R ¹ and R ² are each independently a linear or branched alkyl group having 1 to 36 carbon atoms, a cycloalkyl group or an alkyl group containing a cycloalkyl group, and R ³ is a carbon atom having 1 to 36 carbon atoms. 2 to 20 alkylene groups. M is an integer of 1 to 100;
n represents an integer of 1 to 10].

In the formula, R ¹ and R ² each represent a linear or branched alkyl group having 1 to 36 carbon atoms,
Examples of the cycloalkyl group or an alkyl group containing a cycloalkyl group include the following. The following can be exemplified as the linear or branched alkyl group. Methyl, ethyl, n- and iso-propyl, n-, iso-,
sec-, and tert-butyl, n- and iso-pentyl, n- and iso-hexyl, n- and iso-heptyl, n- and iso-octyl, n- and iso-nonyl,
n- and iso-decyl groups, n- and iso-undecyl groups, n-
And iso-dodecyl, n- and iso-tridecyl, n-
And iso-tetradecyl, n- and iso-pentadecyl, n- and iso-heptadecyl, n- and iso-octadecyl, n- and iso-icosyl, n- and iso-pentacosyl, n- and iso -A triacontyl group.

Examples of the cycloalkyl or an alkyl group containing a cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a dicyclopentyl group and a tricyclotetradecanyl group.

In the formula, the alkylene group having 2 to 20 carbon atoms represented by R ³ includes an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group. , Dodecamethylene, dodecamethylene, propylene, butylene, amylene, hexylene,
-Methyltrimethylene group, 2,2-dimethyltrimethylene group, 3methylpentamethylene group and the like.

These polyalkylene glycol polycarbonates are usually synthesized as follows. The synthesis reactor can be temperature-controlled by an external circulating fluid, and in addition, a distillation apparatus equipped with a reflux device at the top, so that low-boiling fractions generated during the synthesis reaction can be selectively distilled off, A jacketed flask equipped with a stirrer and thermometer is used. This flask is filled with a carbonate ester (for example, dimethyl carbonate) synthesized from a low-boiling alcohol as a raw material, a higher alcohol or a higher alcohol mixture, a desired alkylene glycol, and an organic or inorganic compound-based transesterification catalyst. The reaction mixture is heated with stirring and brought to the boiling temperature, and the reaction proceeds while removing the low-boiling alcohol formed from the top of the distillation column. In some cases, the reaction proceeds in the presence of an inert solvent which forms the lowest azeotrope with the low boiling alcohol by facilitating distillation of the low boiling alcohol. After completion of the reaction, neutralization and washing are performed to remove the catalyst, and then unnecessary reaction products and unreacted raw materials are distilled off, whereby the reaction product is recovered in the flask.

Next, the chlorinated ethylene / α-olefin copolymer rubber composition of the present invention will be described. In the chlorinated ethylene / α-olefin copolymer rubber composition of the present invention (hereinafter simply referred to as rubber composition), the chlorinated ethylene / α-olefin
The mixing ratio of the polyalkylene glycol polycarbonate to the olefin copolymer rubber is selected according to the application and purpose. Usually, it is necessary to blend 5 to 200 parts by weight of the polyalkylene glycol polycarbonate with respect to 100 parts by weight of the chlorinated ethylene / α-olefin copolymer rubber in order to achieve the object of the present invention. To 150 parts by weight.

If the polyalkylene glycol polycarbonate is less than 5 parts by weight in the above ratio, the desired workability cannot be obtained. On the other hand, when it is more than 200 parts by weight, the strength characteristics are remarkably deteriorated, and a desired rubber composition cannot be obtained.

The rubber composition of the present invention may contain known compounding agents such as a vulcanizing agent, a vulcanizing aid, a rubber reinforcing agent, a pigment,
Fillers, softeners, metal activators, scorch inhibitors, hydrochloric acid absorbers, antioxidants, processing aids, foaming agents, foaming aids, and the like can be added.

In the present invention, the total amount of the chlorinated ethylene / α-olefin copolymer rubber and the polyalkylene glycol polycarbonate to be incorporated in the rubber composition is appropriately selected depending on the intended performance and use of the vulcanized product. , Usually 40% by weight or more, preferably 50% by weight or more.

The method for vulcanizing the rubber composition of the present invention includes:
Triazine vulcanization and organic peroxide vulcanization are suitable.

When performing triazine vulcanization, a triazine compound represented by the following general formula is used as a vulcanizing agent.

[0024]

Embedded image (Wherein R ¹ is —NR ² R ³ , —OR ² or —SR ²
Wherein R ² and R ³ represent a hydrogen atom, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted aryl group, respectively. ) Are used.

As the triazine thiols represented by the general formula, specifically, triazine 2,4,6
-Trithiol, 2-dibutylaminotriazine 4,6
-Dithiol, 2-phenylaminotriazine 4,6-
Examples thereof include dithiol, 2-hexylaminotriazine 4,6-dithiol, 2-diethylaminotriazine 4,6-dithiol, and 2-butoxytriazine 4,6-dithiol.

The vulcanizing agent is used in an amount of 1 × 10 ^-3 to 2.5 with respect to 100 g of chlorinated ethylene / α-olefin copolymer rubber.
× 10 ⁻² mol, preferably 1.5 × 10 ⁻³ to 2 × 1
0 ^-2 mol, more preferably 3 × 10 ^-3 to 1.3 ×
It is blended in a proportion of 10 ^-2 mol.

If the amount of the vulcanizing agent is smaller 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, a vulcanizing aid is added. 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.

These vulcanization aids include 1,8-diazabicyclo (5,4,0) undecene-7, laurylamine, benzylamine, dibenzylamine, N-methylmorpholine, dicyclohexylamine, zinc dibutyldithiocarbamate. , Pentamethylenedithiocarbamic acid piperidine salt, N-cyclohexyl-2-benzothiazolylsulfenamide, benzoic acid / piperidine salt, benzoic acid / dicyclohexylamine salt, diphenylguanidine, dioltotolylguanidine, dipentamethylenethiuram tetrasulfide, tetra Methylthiuram disulfide, tetramethylsulfonium iodide, tetramethylammonium chloride, tetrabutylphosphonium bromide,
Examples thereof include onium salts such as tetrabutylammonium bromide and distearyldimethylammonium chloride.

The vulcanization aid is used in an amount of 5 × 10 ^-4 to 2 × per 100 g of chlorinated ethylene / α-olefin copolymer rubber.
10 ⁻² mol, preferably 1 × 10 ⁻³ to 1 × 10 ⁻² mol, used alone or as a mixture of two or more.

When the organic peroxide is vulcanized, the vulcanizing agent may be dicumyl peroxide, 2,5-dimethyl-2,
5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, Tertiary butyl peroxide, ditertiary butylperoxy-3,3,5-trimethylcyclohexane and tertiary dibutylhydroperoxide can be exemplified, and among them, dicumyl peroxide, ditertiary butyl peroxide, ditertiary butylperoxy-3, 3,5-Trimethylcyclohexane is preferably used.

The amount of the organic peroxide to be used is usually 3 to 100 g of chlorinated ethylene / α-olefin copolymer rubber.
× 10 ⁻³ to 5 × 10 ⁻² mol, preferably 1 × 10 ⁻³
Or a range of 3 × 10 ^-2 mol.

When an organic peroxide is used as the vulcanizing agent, it is preferable to use a vulcanizing aid in combination. As the vulcanization aid, sulfur, quinone dioximes such as P-quinone dioxime,
Examples thereof include acrylics such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate, allyls such as diallyl phthalate and triallyl isocyanurate, and maleimides and divinylbenzene.

The vulcanization aid is used in an amount of 0.5 to 2 moles, preferably 1 mole, per mole of the organic peroxide used.

As the rubber reinforcing agent, for example, SRF, G
PF, FEF, MAF, ISAF, SAF, FT, MT
And various types of carbon black, finely divided silica, and the like are appropriately used.

As the filler, for example, light calcium carbonate, heavy calcium carbonate, talc, clay and the like are used.

The amounts of these reinforcing agents and fillers are appropriately selected depending on the desired product, but are usually 200 parts by weight or less based on 100 parts by weight of the chlorinated ethylene / α-olefin copolymer rubber. Preferably, it is used in an amount of 150 parts by weight or less.

As the softener, a specific polyalkylene glycol polycarbonate, which is an essential component in the present invention, is used, but if necessary, a known softener can be used in combination. Examples of such softeners include process oils, lubricating oils, paraffin, liquid paraffin, petroleum-based substances such as petroleum asphalt, petrolatum, coal tars such as coal tar and coal tar pitch, castor oil, rapeseed oil, and soybean oil. , Fatty oils such as coconut oil, tall oil, beeswax, carnauba wax, waxes such as lanolin, ricinoleic acid, palmitic acid, stearic acid, barium stearate, fatty acids such as calcium stearate, or metal salts thereof, naphthenic acid or the like Metal soap, pine oil, rosin or derivatives thereof, terpene resin, petroleum resin, coumarone indene resin, atactic polypropylene, dioctyl phthalate, dioctyl adipate, ester plasticizers such as dioctyl sebacate, and other microcrystalline wax, Bed (factice) include liquid polybutadiene, modified liquid polybutadiene, liquid Thiokol, and the like.

The amount of these softeners to be used in combination is appropriately selected depending on the desired product, but is usually 100 parts by weight or less based on 100 parts by weight of the chlorinated ethylene / α-olefin copolymer rubber. Preferably, it is used in an amount of 70 parts by weight or less.

As the metal activator, magnesium oxide, higher fatty acid zinc, lead red, litharge, calcium oxide, hydrotalcite and the like can be used.

These metal activators are used 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.

As the scorch inhibitor, known scorch inhibitors can be used, and examples thereof include maleic anhydride, thioimide compounds, sulfenamide compounds, and sulfonamide compounds. The above components are used in an amount of usually 0.2 to 5 parts by weight, preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the chlorinated ethylene / α-olefin copolymer rubber.

As the hydrochloric acid absorbent, oxides and organic acid salts of metals of Group IIA of the periodic table are used, for example, magnesium stearate, magnesia, calcium stearate, manaceite, hydrotalcite, epoxidized soybean oil, epoxy-based A hydrochloric acid absorbent and the like can be exemplified. These hydrochloric acid absorbents can be appropriately compounded 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.

The rubber composition of the present invention shows excellent heat resistance and durability even without using an anti-aging agent, but the use of the anti-aging agent makes it possible to use the rubber composition of the present invention. It is possible to further prolong the material life of the product. Antioxidants used in this case include, for example, phenylbutylamine, N, N'di-2-naphthyl-p
-Aromatic secondary amines such as phenylenediamine, dibutylhydroxytoluene, tetrakis [methylene (3,
Phenolic stabilizer such as 5-di-t-butyl-4-hydroxy) hydrocinnamate] methane, bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl] sulfide And a dithiocarbamate-based stabilizer such as nickel dibutyldithiocarbamate alone or in combination of two or more. The amount of the antioxidant used is usually 0.1 to 5 parts by weight per 100 parts by weight of the chlorinated ethylene / α-olefin copolymer rubber.
Parts by weight, preferably 0.5 to 3 parts by weight.

Next, as processing aids, those used in ordinary rubber processing can be used, and ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, calcium stearate, zinc stearate, and the above acid And higher fatty acids, salts thereof, and esters thereof. In general, these processing aids are used up to about 10 parts by weight, preferably about 1 to 5 parts by weight, based on 100 parts by weight of the chlorinated ethylene / α-olefin copolymer rubber.

Further, depending on the product, a known inorganic pigment (for example, titanium white) or an organic pigment (for example, naphthol green B) can be blended. The amount of these pigments varies depending on the product, but is used in a maximum of 20 parts by weight, preferably in a maximum of 10 parts by weight.

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'-dinitrosopentamethylenetetramine Nitro compounds such as; azodicarbonamide,
Azo compounds such as azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate; benzenesulfonitrile hydrazide, toluenesulfonyl hydrazide, p, p'-oxybis (benzenesulfonyl hydrazide), diphenyl sulfone-3 Sulfonyl hydrazide compounds such as 3,3'-disulfonyl hydrazide; calcium azide, 4,4'-diphenyldisulfonyl azide, p-
Azide compounds such as toluenesulfonyl azide can be mentioned. In particular, nitro compounds, azo compounds and azide compounds are preferably used.

The blowing agent is usually added in a proportion of 0.3 to 30 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the chlorinated ethylene / α-olefin copolymer rubber. About 0.03 to 0.9
To form a foam.

As a foaming aid which can be used together with the foaming agent, organic acids such as salicylic acid, phthalic acid and stearic acid, or urea or derivatives thereof are used. It shows the function of equalizing.

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, which is an essential component of the present invention, and a specific polyalkylene glycol polycarbonate, additives such as a reinforcing agent, a filler, a softener, and a pigment are used using mixers such as a Banbury mixer. At about 80-170 ° C.
After kneading for 10 to 10 minutes, a vulcanizing agent and a vulcanization aid are additionally mixed using rolls such as open rolls, and kneaded at a roll temperature of about 40 ° C. to 80 ° C. for about 3 to 30 minutes. A rubber compound in the form of a sheet or a sheet is prepared.

The unvulcanized rubber compound thus prepared is molded into a desired shape by, for example, an extruder, a calender roll, a press or the like, and the molded product is simultaneously or simultaneously molded in a vulcanizing tank. Usually about 150 ° C to 270 ° C
Vulcanization by heating for about 1 to 30 minutes.
As the vulcanizing tank, a steam vulcanizer, a hot air heating tank, a glass bead fluidized bed, a molten salt vulcanizing tank, a microwave vulcanizing tank, or the like is used alone or in combination.

[0052]

As described above, the chlorinated ethylene / α-olefin copolymer rubber composition of the present invention has excellent processability, and exhibits heat aging resistance, cold resistance, and fading resistance.
Therefore, a rubber product having a long product life can be obtained, and it can be widely and effectively used for electrical insulating materials, automobile industrial parts, industrial rubber products, civil engineering building materials, rubber cloth, and the like.

As the electric insulating material, caps around an automobile engine such as a plug cap, an ignition cap, and a distributor cap, and a current-carrying portion of an electric wire such as a condenser cap, a marine electric wire, an automobile ignition cable, etc. are formed in a cylindrical shape. It is specifically used for coated insulation layers, cable joint covers and the like. 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 an industrial rubber product, it can be used for rolls, packings, linings, belts and the like. For civil engineering construction materials, it is used for roofing sheets, heat-resistant belts, gaskets for construction materials, highway joint seals, and the like. As a rubberized cloth, it is used for waterproof cloths, awnings, leisure sheets and the like. Further, a foaming vulcanizate which can be used for heat insulating materials, cushioning materials, sealing materials, soundproofing materials, electric insulating materials, etc. by blending a foaming agent and, if necessary, a foaming aid into the rubber compound prior to vulcanization. It can also be.

[0054]

The present invention will be described below by way of examples. Example 1 First, the compounding ingredients shown in Table 1 were kneaded with a 4.3 l 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 having a thickness of 3 mm was formed. Using this compounded rubber, Mooney viscosity was measured at 125 ° C. in accordance with JIS K 6300 Physical Test for Unvulcanized Rubber. Further, the compounded rubber was press-vulcanized at 160 ° C. for 20 minutes, and a vulcanized rubber sheet having a thickness of 2 mm was used.
According to the vulcanized rubber physical test method, tensile strength, elongation, and low-temperature embrittlement temperature were measured in an atmosphere at 25 ° C. JIS
A heat aging test was performed based on K6301. The aging temperature was 150 ° C., and the aging time was 70 hours. Table 3 shows the measurement results.

Example 2 The procedure of Example 1 was repeated except that the chlorinated ethylene / α-olefin copolymer rubber used had the following properties. Ethylene / 1-butene (molar ratio) 90/10 ML _{1 + 4} (121 ° C.) 125 Chlorine content 27 wt% The results are shown in Table 3.

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

Example 4 The procedure of Example 1 was repeated, except that the chlorinated ethylene / α-olefin copolymer rubber used had the following properties. Ethylene / 1-butene (molar ratio) 85/15 ML _{1 + 4} (121 ° C.) 100 Chlorine content 23 wt% The results are shown in Table 3.

Example 5 Example 5 was carried out in the same manner as in Example 1, except that a softening agent having the following structure and properties was used. Table 3 shows the results.

Example 6 Example 6 was carried out in the same manner as in Example 1, except that a softening agent having the following structure and properties was used. The _{C 9 H 19 OCOO- (CH 2} ) 9 -OOCOC 9 H 19 Table 3 shows the results.

Comparative Example 1 The procedure of Example 1 was repeated, except that the following softening agents were used. Softener Sansen 4240 manufactured by Nippon Sun Oil Co., Ltd. The results are shown in Table 3.

Comparative Example 2 The procedure of Example 1 was repeated, except that the following softening agents were used. Softener di- (2-ethylhexyl) phthalate The product is shown in Table 3 from Daihachi Chemical Co., Ltd.

Example 7 First, the compounding ingredients shown in Table 4 were kneaded with a 4.3 l 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 5 on this open roll and kneading for 2 minutes, a sheet having a thickness of 3 mm was formed. This compounded rubber was press-vulcanized at 160 ° C. for 20 minutes, and a vulcanized rubber sheet having a thickness of 2 mm was used.
A 00 hour weather resistance test was performed to observe changes in the appearance. Table 6 shows the observation results.

Comparative Example 3 The procedure of Example 7 was repeated, except that the following softening agents were used. Softener Sansen 4240 manufactured by Nippon Sun Oil Co., Ltd. Table 6 shows the observation results.

[0064] 1) Ethylene / 1-butene (molar ratio) 90/10 ML1 + 4 (121 ° C) 50 Chlorine content 27 wt% 3) Kyowa Mag 150; Kyowa Chemical Co., Ltd. 4) Asahi 60; Asahi Carbon Co., Ltd.

[0065]

[0066]

[0067] 1) Ethylene / 1-butene (molar ratio) 90/10 ML _{1 + 4} (121 ° C) 50 Chlorine content 27 wt% 3) DHT6; manufactured by Kyowa Chemical Co., Ltd. 4) Talc: manufactured by Nippon Talc

[0068]

[0069]

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazuki Takahata 61-2, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industry Co., Ltd. (56) References JP-A-5-287129 (JP, A (58) Fields surveyed (Int. Cl. ⁷ , DB name) C08L 23/28 C08L 69/00 C08L 71/02-71/03 CA (STN)

Claims (3)

(57) [Claims] 1. 100 parts by weight of a chlorinated ethylene / α-olefin copolymer rubber, and R ¹ —O—COO — ([R ³ —O] m —COO) n —R ² (I) Wherein R ¹ and R ² are each independently a linear or branched alkyl group having 1 to 36 carbon atoms, a cycloalkyl group or an alkyl group containing a cycloalkyl group, and R ³ is a carbon atom It is an alkylene group having a number of 2 to 20. M is an integer of 1 to 100;
n represents an integer of 1 to 10], and the chlorinated ethylene / α-olefin copolymer rubber composition comprises 5 to 200 parts by weight of a polyalkylene glycol polycarbonate represented by the following formula: 2. A chlorinated ethylene / α-olefin copolymer rubber having a chlorine content of 20 to 40% by weight and a Mooney viscosity [ML _{1 + 4} (MLC) (121 ° C.)] of 10 to 190. The chlorinated ethylene / α-olefin copolymer rubber composition according to claim 1, wherein the composition comprises an α-olefin copolymer rubber. 3. The chlorinated ethylene / α-olefin copolymer rubber contains 5 to 10 olefins having 3 to 10 carbon atoms.
The chlorinated ethylene / α-olefin copolymer rubber composition according to claim 1 or 2, which is obtained by chlorinating an ethylene / α-olefin copolymer containing from 25 to 25 mol%.