JP3193109B2 - Crosslinkable rubber composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crosslinkable rubber composition, and more particularly, to a crosslinkable rubber composition having excellent plasticity, heat aging resistance, cold resistance and weather resistance.

[0002]

2. Description of the Related Art Rubber products have a unique property called rubber elasticity, which is not found in products obtained from other materials, and are suitably used in tires, hoses, sealing materials, etc. by making use of such properties. . In order to fully exhibit this property, it is necessary to increase the molecular weight as much as possible.
As is already widely known, when the molecular weight is increased, a problem arises that the viscosity increases and it becomes difficult to process into a desired shape. Then, in order to solve the problem, it has been conventionally attempted to add a softening agent to the vulcanizable rubber.

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

However, recently, mainly in the field of automobiles,
There is a strong demand for rubber products with higher performance, and products using conventional softeners cannot meet these requirements in terms of heat aging resistance, cold resistance, weather resistance, and the like. Therefore, there has been a demand for a new softening agent which provides plasticity to various crosslinkable rubbers and at the same time provides a rubber composition excellent in 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 of rubber products. Specifically, the present invention provides a rubber composition having sufficient processability and heat aging resistance. Another object of the present invention is to provide a crosslinkable rubber composition having cold resistance and cold resistance.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, added a specific alkyl carbonate to a crosslinkable rubber and compounded the rubber product obtained from the compound. Were found to be excellent in properties, and the present invention was completed. That is, according to the present invention, a crosslinkable rubber (however, chlorinated
Excluding len-α-olefin copolymer rubber. The present invention provides a crosslinkable rubber composition, which must contain 100 parts by weight and 5 to 200 parts by weight of a polyalkylene glycol polycarbonate 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 straight-chain having 1 to 36 carbon atoms. A chain or branched alkyl group, a cycloalkyl group or an alkyl group containing a cycloalkyl group, wherein R ₃ is an alkylene group having 2 to 20 carbon atoms. M represents an integer of 1 to 100, and n represents an integer of 1 to 10.]

[0007]

DETAILED DESCRIPTION OF THE INVENTION The crosslinkable rubber itself is
Shows rubber elasticity and strength properties required for rubber products.Polyalkylene glycol polycarbonate is added to crosslinkable rubber to give excellent workability to crosslinkable rubber composition and to soften other Unlike agents, it does not adversely affect heat aging resistance, cold resistance, and weather resistance.

As the crosslinkable rubber, any known crosslinkable rubber can be used.
Among them, chloroprene rubber, chlorinated polyethylene, epichlorohydrin rubber, acrylic rubber, nitrile rubber, and hydrogenated nitrile rubber are particularly preferably used.

As the chloroprene rubber, one having a Mooney viscosity [ML _{1 + 4} (100 ° C.)] of 30 to 150 is particularly preferably used. Either a sulfur-modified product or a non-sulfur-modified product can be used.

As the chlorinated polyethylene, those having a chlorine content of 20 to 50% by weight and a specific gravity in the range of 1.05 to 1.30 can be suitably used. Further, those having a Mooney viscosity [ML _{1 + 4} (100 ° C.)] in the range of 10 to 150 are preferable. This chlorinated polyethylene contains 1.5 as sulfur as a chlorosulfonyl group.
What contained in the ratio within the weight% may be used.
Further, the polyethylene before chlorination may be a copolymer of ethylene and an α-olefin, and in this case, the α-olefin may contain up to 5 mol%.

Examples of the epichlorohydrin rubber include not only homopolymers of epichlorohydrin but also epichlorohydrin / ethylene oxide copolymers, epichlorohydrin / propylene oxide copolymers, epichlorohydrin / ethylene oxide / propylene oxide copolymers, and homopolymers or homopolymers thereof. A copolymer obtained by copolymerizing an allyl glycidyl ether with a copolymer can be used. The chlorine content of such epichlorohydrin rubber is usually preferably in the range of 15 to 40% by weight,
Those having a Mooney viscosity [ML _{1 + 4} (100 ° C.)] in the range of 20 to 150 can be suitably used.

As the acrylic rubber, those obtained from a copolymer of alkyl acrylate are preferably used. As the alkyl ester of the copolymer, those having an alkyl group having 2 to 8 carbon atoms can be used alone or in combination. Further, the copolymer,
2-chloroethyl vinyl ether as a crosslinking site,
Monochlorovinyl acetate, acryl chloroacetate, glycidyl methacrylate, allyl glycidyl ether,
It is preferable that a small amount of a comonomer such as ethylidene norbornene or dicyclopentadiene is contained as a copolymer component. The Mooney viscosity of these acrylic rubbers [ML
_{1 + 4} (100 ° C.)] in the range of 20 to 100 can be suitably used.

As the nitrile rubber, one obtained by copolymerizing acrylonitrile and butadiene is used, and those having an acrylonitrile content in the range of 15 to 50% by weight are preferably used. The nitrile rubber having a Mooney viscosity [ML _{1 + 4} (100 ° C.)] in the range of 20 to 100 can be suitably used.

The hydrogenated nitrile rubber of the present invention refers to a rubber obtained by hydrogenating the above nitrile rubber so that the content of conjugated diene units in the polymer chain becomes 25% by weight or less. Mooney viscosity of hydrogenated nitrile rubber [ML _{1 + 4} (100
° C)] is in the range of 50 to 150.

The polyalkylene glycol carbonate which is another component constituting the rubber composition of the present invention is:
It 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 straight-chain having 1 to 36 carbon atoms. Or a branched alkyl group, a cycloalkyl group or an alkyl group containing a cycloalkyl group, wherein R ₃ is an alkylene group having 2 to 20 carbon atoms. M represents an integer of 1 to 100, and 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.

The following can be exemplified as the cycloalkyl or the alkyl group containing the cycloalkyl group. Cyclopentyl, cyclohexyl, dicyclopentyl, tricyclotetradecanyl and the like.

Examples of the alkylene group having 2 to 20 carbon atoms represented by R ₃ include the following.
Ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group,
Nonamethylene group, decamethylene group, dodecamethylene group,
Dodecamethylene group, propylene group, butylene group, amylene group, hexylene group, 2-methyltrimethylene group, 2,
2-dimethyltrimethylene group, 3-methylpentamethylene 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 charged 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 a transesterification catalyst based on an organic or inorganic compound. 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 by facilitating the distillation of the low boiling alcohol in the presence of an inert solvent that forms the lowest azeotrope with the low boiling alcohol. After the completion of the reaction, neutralization and washing are performed to remove the catalyst, and thereafter, unnecessary by-products and unreacted raw materials are distilled off, thereby collecting the reaction product in the flask.

Next, the crosslinkable rubber composition of the present invention will be described. <Crosslinkable Rubber Composition> In the crosslinkable rubber composition of the present invention (hereinafter simply referred to as a rubber composition), the mixing ratio of the polyalkylene glycol polycarbonate to the rubber is selected according to the use and purpose. Usually, 5 to 200 parts by weight of polyalkylene glycol polycarbonate is blended with respect to 100 parts by weight of rubber.
It is necessary to achieve the object of the present invention, and more preferably 10 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 a compounding agent known per se, for example, a vulcanizing agent, a vulcanization aid, a rubber reinforcing agent, a pigment, depending on the intended use of the vulcanizate and the performance based on the vulcanizate.
Fillers, softeners, metal activators, scorch inhibitors, hydrochloric acid absorbers, antioxidants, processing aids, and the like can be added.

In the present invention, the total amount of rubber and polyalkylene glycol polycarbonate in the rubber composition is
It is appropriately selected depending on the intended performance and use of the vulcanized product, but is usually at least 40% by weight, preferably at least 50% by weight.

The vulcanization of the rubber composition of the present invention can be carried out by a method known per se. Specifically, it is selectively used depending on the characteristics of the rubber. Examples thereof include vulcanization, quinoid vulcanization, triazine vulcanization, and organic peroxide vulcanization.

The vulcanizing agent is 1 × 10
^-3 to 7.0 × 10 ^-2 mol, preferably 1.5 × 10
^-3 to 5.0 × 10 ^-2 mol, more preferably 3 × 10
^-3 to 4.0 × 10 ^-2 mol.

When 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.

Adjustment of the vulcanization rate is extremely important for practical use in order to cope with various rubber processing steps. For this purpose, a vulcanization aid is added. In the present rubber composition, these vulcanization aids may be added as needed.

As the rubber reinforcing agent, for example, SRF, G
PF, FEF, MAF, ISAF, SAF, FT, MT
Various carbon blacks, finely divided silicic acid, 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.
200 parts by weight or less, preferably 1 part by weight,
50 parts by weight or less is used.

As the softening agent, a specific polyalkylene glycol polycarbonate which is a basic requirement in the present invention is used, but an existing softening agent may be used if necessary. Examples of such softeners include process oils, lubricating oils, paraffin, liquid paraffin, petroleum-based substances such as petroleum asphalt and petrolatum, coal tars such as coal tar and coal tar pitch, castor oil, rapeseed oil, and soybean oil. , Palm oil and other fatty oils, tall oil, beeswax, carnauba wax, lanolin and other waxes,
Fatty acids such as ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate,
Or its metal salt, naphthenic acid or its metal soap, pine oil, rosin or its derivative, terpene resin, petroleum resin, coumarone indene resin, atactic polypropylene, dioctyl phthalate, dioctyl adipate,
Ester plasticizers such as dioctyl sebacate, other microcrystalline wax, sub (factice),
Examples thereof include liquid polybutadiene, modified liquid polybutadiene, and liquid thiocol.

The mixing amount of these softeners is appropriately selected depending on the desired product, but is usually 100 parts by weight or less, preferably 70 parts by weight or less based on 100 parts by weight of rubber.

As the metal activator, magnesium oxide, zinc white, higher fatty acid zinc, leadtan, 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 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 component is rubber 10
It is used in an amount of usually 0.2 to 5 parts by weight, preferably 0.3 to 3 parts by weight with respect to 0 parts by weight.

The hydrochloric acid absorbent is added as needed, and generally an oxide or an organic acid salt of a metal of Group IIA of the periodic table is used, and examples thereof include magnesium stearate, magnesia, calcium stearate, manaceite, hydrotalcite, Examples include epoxidized soybean oil and epoxy-based hydrochloric acid absorbent. These hydrochloric acid absorbents are rubber 100
Usually, it can be appropriately added in an amount of 10 parts by weight or less based on parts by weight.

The rubber composition of the present invention can also use an antioxidant to improve durability, as in the case of ordinary rubber. As the antioxidant used in this case, known ones can be used. For example, phenylbutylamine, aromatic secondary amines such as N, N′di-2-naphthyl-p-phenylenediamine, dibutylhydroxytoluene, Tetrakis [methylene (3,5-di-t-
Butyl-4-hydroxy) hydrocinnamate] a phenolic stabilizer such as methane, bis [2-methyl-4-
(3-n-alkylthiopropionyloxy) -5-t
-Butylphenyl] sulfide; dithiocarbamate stabilizers such as nickel dibutyldithiocarbamate;
It is blended in combination of more than one species. The amount of such an antioxidant to be used is usually 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, per 100 parts by weight of rubber.

Next, as processing aids, those used in usual rubber processing can be used, and ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, calcium stearate, zinc stearate, and the above-mentioned acids can be used. And higher fatty acids, salts thereof, and esters thereof. These processing aids are usually used up to about 10 parts by weight, preferably about 1 to 5 parts by weight, based on 100 parts by weight of rubber.

Further, depending on the product, a pigment is used. Known inorganic pigments (for example, titanium white) and organic pigments (for example, naphthol green B) are used as the pigment. The amount of these pigments varies depending on the product, but an amount of up to 20 parts by weight, preferably 10 parts by weight or less is used.

Examples of the blowing agent include inorganic blowing agents such as sodium hydrogen carbonate, 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.

These foaming agents are usually used in an amount of 0.3 to 30 parts by weight, preferably 0.5 to 100 parts by weight of rubber.
To 20 parts by weight to form a foam having an apparent specific gravity of about 0.03 to 0.9.

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

The rubber composition of the present invention can be prepared, for example, by the following method. In addition to the crosslinkable rubber and the specific polyalkylene glycol polycarbonate, which are essential components of the present invention, additives such as a reinforcing agent, a filler, a softening agent, and a pigment are added at about 80 ° C. to 170 ° C. using a mixer such as a Banbury mixer. After kneading at a temperature of about 3 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 to 80 ° C. for about 3 to 30 minutes. To prepare a rubber compound in the form of a ribbon or sheet.

The unvulcanized rubber compound thus prepared is formed into a desired shape by, for example, an extruder, a calender roll, a press, etc., and the molded product is formed simultaneously with or 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.

Examples of suitable uses of the rubber composition of the present invention include electrical insulating materials, automotive parts, industrial rubber products, civil engineering materials, and rubberized fabrics.

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, and the like 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, packing, 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 agent and, if necessary, a foaming aid are compounded in the rubber compound prior to vulcanization,
It can also be a foamed vulcanizate that can be used as a heat insulating material, a cushion material, a sealing material, a soundproofing material, an electric insulating material and the like.

[0048]

As described above, the crosslinkable rubber composition of the present invention comprises, as essential components, a commercially available rubber and a polyalkylene glycol polycarbonate having a specific structure, and the polyalkylene glycol is used per 100 parts by weight of the rubber. It is characterized by containing 5 to 200 parts by weight of polycarbonate. The crosslinkable rubber itself has rubber elasticity, a characteristic not found in other products, heat aging resistance, cold resistance, weather resistance, and polyalkylene glycol polycarbonate is blended with the crosslinkable rubber to form a crosslinkable rubber composition It imparts excellent workability to the product and, unlike other softeners, does not adversely affect heat aging resistance, cold resistance, and fading resistance. Therefore, a rubber product having a long product life can be obtained. Since the rubber composition of the present invention has such excellent physical properties, as described above, it can be effectively used for electric insulating materials, automobile industrial parts, industrial rubber products, civil engineering building materials, rubber cloth, and the like. .

[0049]

Example 1 The ingredients shown in Table 1 were first 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 40 ° C. for the front roll and 50 ° 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 120 ° C., and the aging time was 70 hours. Table 13 shows the results of these measurements.

[0050] *** Nocrack PA; manufactured by Ouchi Shinko

[0051] ** Noxeller EUR; manufactured by Ouchi Shinkosha

Example 2 The procedure of Example 1 was repeated, except that the following softening agent was used. The results are shown in Table 13.

Example 3 The procedure of Example 1 was repeated, except that the following softening agent was used. _{C 9 H 19 OCOO- (CH 2} ) 9 -OOCOC 9 H 19 The results are shown in Table 13.

Comparative Example 1 The procedure of Example 1 was repeated, except that a commercially available aromatic process oil shown below was used as a softening agent. Diana Process Oil AH-10S: Idemitsu Kosan Co., Ltd. The results are shown in Table 13.

Comparative Example 2 The procedure of Example 1 was repeated, except that a commercially available ester plasticizer shown below was used as the softener. DOP (Dioctyl phthalate): manufactured by Daihachi Chemical Co., Ltd. The results are shown in Table 13.

Example 4 In Example 1, the formulation of Table 1 was changed as shown in Table 3, and
As shown in Table 4, the vulcanization conditions were 160 ° C. for 30 minutes, and the aging temperature in the heat aging test was 150 ° C. at 70 ° C.
Except for the time, the procedure was the same as in Example 1. The results are shown in Table 1.
3 is shown.

[0057]

[0058]

Comparative Example 3 The procedure of Example 4 was repeated except that a commercially available aromatic process oil shown below was used as a softening agent. Diana Process Oil AH-10S: manufactured by Idemitsu Kosan Co., Ltd. This was press-vulcanized, but the vulcanization was too sweet to measure the vulcanization properties.

Comparative Example 4 The procedure of Example 4 was repeated, except that a commercially available ester plasticizer shown below was used as a softening agent. DOP (Dioctyl phthalate): manufactured by Daihachi Chemical Co., Ltd. The results are shown in Table 13.

Example 5 In Example 1, the composition shown in Table 1 was changed to that shown in Table 5, and
As shown in Table 6, the vulcanization conditions were 150 ° C. for 30 minutes, and the aging temperature in the heat aging test was 135 ° C. at 70 ° C.
Except for the time, the procedure was the same as in Example 1. The results are shown in Table 1.
3 is shown.

[0062] *** Nocrack 224; Ouchi Shinkosha

[0063] The results are shown in Table 13.

Comparative Example 5 The procedure of Example 5 was repeated except that a commercially available aromatic process oil shown below was used as a softening agent. Diana Process Oil AH-10S: Idemitsu Kosan Co., Ltd. The results are shown in Table 13.

Comparative Example 6 The procedure of Example 5 was repeated except that a commercially available ester plasticizer shown below was used as the softener. DOP (Dioctyl phthalate): manufactured by Daihachi Chemical Co., Ltd. The results are shown in Table 13.

Example 6 In Example 1, the composition of Table 1 was used as shown in Table 7, and
The vulcanization conditions were as follows: primary vulcanization 150 ° C
Press vulcanization for 10 minutes at 150 ° C
The procedure was the same as that of Example 1 except that the oven vulcanization was carried out for an hour and the aging temperature in the heat aging test was 150 ° C. for 70 hours. The results are shown in Table 13.

[0067] *** Nocrack NBC; Ouchi Shinkosha

[0068]

Comparative Example 7 The procedure of Example 6 was repeated, except that the following commercially available aromatic process oil was used as a softening agent. Diana Process Oil AH-10S: Idemitsu Kosan Co., Ltd. The results are shown in Table 13.

Comparative Example 8 The procedure of Example 6 was repeated, except that a commercially available ester plasticizer shown below was used as the softener. DOP (Dioctyl phthalate): manufactured by Daihachi Chemical Co., Ltd. The results are shown in Table 13.

Example 7 In Example 1, the formulation in Table 1 was changed as shown in Table 9, and
Of the composition as shown in Table 10, and vulcanization conditions were 155 ° C. and 30
The procedure was the same as in Example 1 except that the amount was changed to minutes. The results are shown in Table 13
It was shown to.

[0072] *** Nocrack NBC; Ouchi Shinko Co., Ltd.

[0073]

Comparative Example 9 The procedure of Example 7 was repeated, except that the following commercially available aromatic process oil was used as a softening agent. Diana Process Oil AH-10S: Idemitsu Kosan Co., Ltd. The results are shown in Table 13.

Comparative Example 10 The procedure of Example 7 was repeated, except that a commercially available ester plasticizer shown below was used as the softener. DOP (Dioctyl phthalate): manufactured by Daihachi Chemical Co., Ltd. The results are shown in Table 13.

Example 8 In Example 1, the formulations in Table 1 were as shown in Table 11, the formulations in Table 2 were as shown in Table 12, and the vulcanization conditions were 160 ° C. and 1
Example 5 was carried out in the same manner as in Example 1, except that the aging condition in the heat aging test was 150 ° C. for 70 hours. Result is,
The results are shown in Table 13.

[0077] *** Nocrack NBC; Ouchi Shinkosha
***** Nocrack ODA; Ouchi Shinkosha

[0078]

Comparative Example 11 Example 8 was carried out in the same manner as in Example 8, except that a commercially available aromatic process oil shown below was used as a softening agent. Diana Process Oil AH-10S: Idemitsu Kosan Co., Ltd. The results are shown in Table 13.

Comparative Example 12 The procedure of Example 8 was repeated, except that a commercially available ester plasticizer shown below was used as a softening agent. DOP (Dioctyl phthalate): manufactured by Daihachi Chemical Co., Ltd. The results are shown in Table 13.

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C08L 69/00 C08L 69/00 71/03 71/03 (72) Inventor Kazuki Takahata 6-1-2, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture (56) References JP-A-5-247291 (JP, A) JP-A-52-120734 (JP, A) JP-A-62-290740 (JP, A) JP-A-3-3 59045 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 21/00 C08L 11/00 C08L 23/28 C08L 33/08 C08L 9/02 C08L 69/00 C08L 71/03

Claims (2)

(57) [Claims] 1. A crosslinkable rubber (provided that chlorinated ethylene-
Excluding α-olefin copolymer rubber. ) 5 a polyalkylene glycol polycarbonate represented by 100 parts by weight of general formula (I) to the crosslinkable rubber composition characterized in that it comprises 200 parts by _{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, cycloalkyl group or cycloalkyl group having 1 to 36 carbon atoms. Wherein R ₃ is an alkylene group having 2 to 20 carbon atoms. M represents an integer of 1 to 100, and n represents an integer of 1 to 10.] 2. The crosslinkable rubber is at least one selected from the group consisting of chloroprene rubber, chlorinated polyethylene, epichlorohydrin rubber, acrylic rubber, nitrile rubber, and hydrogenated nitrile rubber. 2. The crosslinkable rubber composition according to item 1.