JPH0768425B2 - Acrylic rubber composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to an acrylic rubber vulcanizable composition containing an active chlorine group. More specifically, active chlorine group-containing acrylic rubber vulcanizates that give vulcanizates that have excellent storage stability, processing stability, rapid vulcanization, and excellent pressure-resistant compression set. It relates to a composition.

[Prior Art] Conventionally, as an acrylic rubber vulcanizable composition, a glycidyl group / polyamine, a diaminecarbamic acid, an organic carboxylic acid ammonium salt, a dithiocarbamic acid metal salt, etc. have been used as a crosslinking site / vulcanization type vulcanization type. Chlorine group / organic carboxylic acid alkali metal salt, diaminecarbamic acid, trithiocyanuric acid, dithiocyanuric acid derivative, etc., carboxyl group / aniline derivative, diaminecarbamic acid, etc., and a system in which the above-mentioned crosslinking sites are combined are known. Has been.

However, this type of known vulcanizable acrylic rubber composition has stability against scorch in the kneading process, long-term storage of the composition, and vulcanization molding process, vulcanization rate, heat resistance of the vulcanizate, and resistance to scorch. There is a drawback in that the balance with thermal stability typified by compression set is not sufficient in practical use.

That is, for example, Japanese Patent Publication No. Sho 49-13215 discloses a vulcanization system using trithiocyanuric acid and dithiocarbamic acid derivatives for an acrylic elastomer having an active halogen atom or an epoxy group. Acrylic elastomers give vulcanizates with high vulcanization speed and excellent compression set resistance, but they are unstable to scorch, while epoxy group-containing acrylic elastomers have good scorch stability. However, it cannot be said that the vulcanization rate and the compression set resistance of the vulcanized product are satisfactory.

Similarly, Japanese Examined Patent Publication (Kokoku) No. 50-15815 discloses an acrylic elastomer having an active halogen atom, an epoxy group or an unsaturated bond in the presence of a triazine compound, and in some cases, an aromatic or aliphatic monobasic acid or polybasic acid. A system in which a basic acid is vulcanized as a vulcanization aid is disclosed. In this case, although the purpose of rapid vulcanization is achieved, it cannot be said that the scorch stability is practically sufficient.

[Problems to be Solved by the Invention] As described above, the problems to be solved by the present invention are well balanced in storage stability, scorch stability, rapid vulcanization and compression set resistance. It is to obtain an acrylic rubber vulcanizable composition.

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies on various acrylic elastomers and vulcanization systems in order to solve the above-mentioned problems, and as a result, have found that a small amount of the activity uniformly distributed in the molecule. A vulcanizable acrylic rubber containing a chlorine group, using a metal salt of trithiocyanuric acid and dithiocarbamic acid as a vulcanizing agent, an imide derivative of a divalent organic carboxylic acid and / or an amide derivative of a monovalent organic sulfonic acid. , And organosilane compounds are used as vulcanization aids, they have excellent storage stability and processing stability against early vulcanization, and also have excellent heat aging resistance and compression set resistance. It was found that a vulcanized product was obtained, and the present invention was completed.

That is, the present invention provides (A) 0.1% active chlorine groups obtained by the seed polymerization method.
To 0.5% (weight%, the same applies hereinafter) 100 parts of vulcanizable acrylic rubber (weight part, the same applies below), (B) trithiocyanuric acid 0.1 to 2.0 parts, (C) dithiocarbamic acid metal salt
0.5-5.0 parts, an imide derivative consisting of (D) N- (cyclohexylthio) phthalimide and / or N-isopropylthio-N-cyclohexyl-benzothiazyl-
0.05-1.5 parts of an amide derivative consisting of 2-sulfonamide, N-cyclohexyl-N-trichloromethylthio-benzyl-2-sulfonamide and (E) β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ
-Epoxy-organofunctional silane consisting of glycidoxypropyltrimethoxysilane and / or mercapto-organofunctional silane consisting of γ-mercaptopropyltrimethoxysilane and / or γ-aminopropyltriethoxysilane, N
-Amino-based organofunctional silane consisting of phenyl-γ-aminopropyltrimethoxysilane 0.05-
It relates to an acrylic rubber composition containing 1.5 parts.

[Example] The vulcanizable acrylic rubber used in the present invention is produced by a seed polymerization method from an active chlorine group-containing monomer and an acrylate ester so that the crosslinking points (active chlorine groups) are uniform in the molecule. It is a distributed elastomer.

The content ratio of active chlorine groups in vulcanizable acrylic rubber is 0.1 ~
It is 0.5%, preferably 0.2 to 0.4%. If the ratio is less than 0.1%, a sufficient crosslink density cannot be obtained, and a vulcanizate having poor compression set resistance will be given.If it exceeds 0.5%, active chlorine groups will remain in the elastomer even after ordinary vulcanization. Remains,
It will adversely affect the heat resistance and compression set resistance of the vulcanizate.

Here, the active chlorine group refers to a chlorine group in which one or more groups of an organic compound are substituted with chlorine and which can be easily thermally dissociated in the presence of a chlorine acceptor.

The vulcanizable acrylic rubber has a Mooney viscosity (ML _{1 + 4} (100
C.)) is 20-60. Mooney viscosity
If it is less than 20, it tends to impair the kneading workability due to stickiness and stickiness of the rubber compound, and if it exceeds 60, the compound has a high Mooney viscosity and lacks fluidity, resulting in impaired molding processability. Tend to

The active chlorine group-containing monomer constituting the vulcanizable acrylic rubber is for introducing an active chlorine group which is a cross-linking point into the acrylic rubber, and is a monomer containing such an active chlorine group. There is no particular limitation as long as it exists.

Specific examples of the active chlorine group-containing monomer include, for example, allyl chloride, 2-chloroethyl vinyl ether,
2-Chloroethyl acrylate, vinyl monochloroacetate, chloromethyl styrene and the like can be mentioned, and among them, monochloro vinyl acetate and chloromethyl styrene are preferable from the viewpoint of rapid crosslinking reactivity. These may be used alone or in combination of two or more.

The acrylic ester is not particularly limited, but specific examples thereof include acrylates having an alkyl group having 1 to 8 carbon atoms such as methyl acrylate, ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and methoxy. Examples thereof include alkoxyalkyl acrylates having an alkoxy group having 1 to 4 carbon atoms such as methyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate and butoxyethyl acrylate, and alkylene groups. These may be used alone or in combination of two or more.

A part of the acrylic acid ester, for example, 5% or less may be replaced with acrylonitrile, vinyl acetate, methacrylic acid ester or the like. If the proportion of acrylonitrile or the like exceeds 5%, the glass transition point of the elastomer becomes high, which tends to impair the rubber elasticity or hinder the mixing and dispersion of the compounding agents.

The ratio of the active chlorine-containing monomer and the acrylic acid ester (including acrylonitrile used if necessary) during the seed polymerization is usually 0.3 to 5.0 parts by weight of the active chlorine group-containing monomer (the same applies hereinafter). ), Preferably 0.5 to 1.5 parts by weight of acrylic acid ester 95 to 99.7 parts, preferably 98.5 to 99.5 parts.
It is a department. If the ratio of the active chlorine group-containing monomer is less than 0.3 part, it is not possible to give a crosslink density that gives good vulcanization resistance to compression set, and if it exceeds 5.0 parts, excess vulcanization after vulcanization will occur. The presence of the group adversely affects the heat resistance and the compression set resistance.

As the polymerization method of the acrylic ester, emulsion polymerization, suspension polymerization, solution polymerization and the like are known, but the vulcanizable acrylic rubber used in the present invention is an active chlorine group-containing monomer that becomes a crosslinking point as described above. In order to uniformly disperse the polymer in the molecule, it is necessary to manufacture by an emulsion polymerization method of a seed polymerization method, that is, a method of continuously adding monomers by initiating seed polymerization.

A redox initiator is used in the seed polymerization, and examples of the redox initiator system include oxidizing agents such as persulfates such as ammonium persulfate and potassium persulfate, hydrogen peroxide, cumene hydroperoxide, diisopropylbenzene hydroheroxide. , Hydroperoxides such as paramenthane hydroperoxide, and divalent iron salts such as ferrous sulfate as a reducing agent,
As a secondary reducing agent, for example, a system using sodium hydrogen sulfite, sodium formaldehyde sulfoxylate, ascorbic acid, its sodium salt, or the like can be mentioned.
Among these, the initiator system of cumene hydroperoxide / ferrous sulfate / sodium formaldehyde sulfoxylate is preferable from the viewpoint of polymerization reactivity in the low temperature range.

The reaction temperature in the polymerization reaction is preferably 0 to 30 ° C., more preferably 0 to 10 ° C. from the viewpoint of adjusting the polymerization degree (Moonie viscosity) of the vulcanizable acrylic rubber, and the monomer continuous addition time is chlorine group-containing. From the viewpoint of making the intramolecular distribution of the monomer uniform, it is preferably 90 to 360 minutes, more preferably 240 to 300 minutes.

The vulcanizable acrylic rubber may be used alone or in combination of two or more kinds.

Trithiocyanuric acid is used as a vulcanizing agent in the composition of the present invention together with a metal salt of dithiocarbamic acid described below.

Trithiocyanuric acid has the formula: Is a compound represented by.

Vulcanization of acrylic rubber is also possible for compounds in which part of the mercapto group (-SH) of trithiocyanuric acid is replaced by secondary or tertiary amines, and compounds in which the hydrogen of the mercapto group is replaced by chain hydrocarbons or cyclic hydrocarbons. Although known as an agent, trithiocyanuric acid is used in the present invention from the viewpoints of rapid vulcanization and crosslink density of the vulcanized product.

The compounding ratio of trithiocyanuric acid is preferably 0.1 to 2.0 parts, and more preferably 0.5 to 1.0 part, relative to 100 parts of the vulcanizable acrylic rubber. If the ratio is less than 0.1 part, a sufficient crosslink density cannot be obtained, which tends to give a vulcanizate with low physical strength.If it exceeds 2.0 parts, excess trithiocyanuric acid bleeds on the vulcanizate surface. And pollute the mold,
Workability tends to be impaired.

The metal salt of dithiocarbamic acid has two hydrocarbon residues, and the hydrocarbon residue is not limited to what is usually called an alkyl group such as a methyl group, an ethyl group and a butyl group. Phenyl group, benzyl group,
Examples include a pentamethylene group.

Specific examples of such metal salt of dithiocarbamic acid include, for example, dimethyldithiocarbamic acid, diethyldithiocarbamic acid, dibutyldithiocarbamic acid, N-
Examples thereof include zinc salts such as ethyl-N-phenyldithiocarbamic acid, dibenzyldithiocarbamic acid and N-pentamethylenedithiocarbamic acid, ferric salts and copper salts. Of these, a zinc salt or ferric salt of diethyldithiocarbamic acid or dibutyldithiocarbamic acid is preferable from the viewpoint of the effect of activating the crosslinking reaction. The metal salt of dithiocarbamic acid may be used alone or in combination of two or more.

The mixing ratio of the metal salt of dithiocarbamic acid is preferably 0.5 to 5.0 parts, more preferably 1.0 to 3.0 parts, based on 100 parts of the vulcanizable acrylic rubber. If the ratio is less than 0.5 part, activation of the crosslinking reaction tends not to be given, and if it exceeds 5.0 parts, the appearance of the vulcanized product tends to be impaired due to bloom.

In the composition of the present invention, as a vulcanization aid, an imide derivative consisting of N- (cyclohexylthio) phthalimide, N-isopropylthio-N-cyclohexyl-benzothiazyl-2-sulfonamide, N-cyclohexyl-N-trichloromethylthio- An amide derivative composed of benzyl-2-sulfonamide (hereinafter, also referred to as imide or amide derivative) is used.

Among these, the point of the effect of suppressing early vulcanization is N-
Isopropyrithio-N-cyclohexyl-benzothiazyl-2-sulfonamide and N-cyclohexyl-N
-Trichloromethylthio-benzyl-2-sulfonamide is preferred. The imide or amide derivative may be used alone or in combination of two or more.

The mixing ratio of the imide or amide derivative is 0.05 to 1.5 parts, and further 0.1 to 100 parts with respect to 100 parts of the vulcanizable acrylic rubber.
It is preferably 0.5 part. If the ratio is less than 0.05 part, there is a tendency that a sufficient effect of suppressing early vulcanization cannot be obtained.
If it exceeds 5 parts, a sufficient crosslink density cannot be obtained, and a vulcanizate having poor compression set resistance tends to be obtained.

The composition of the present invention contains an epoxy system consisting of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane, which are organosilane compounds as a vulcanization aid together with the above derivative. Organofunctional silane, mercapto-based organofunctional silane consisting of γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, amino-based organofunctional silane consisting of N-phenyl-γ-aminopropyltrimethoxysilane is used. To be Of these, γ-aminopropyltriethoxysilane is preferable from the viewpoint of the effect of activating the crosslinking reaction. The organosilane compounds may be used alone or in combination of two or more.

The mixing ratio of the organosilane compound is preferably 0.05 to 1.5 parts, more preferably 0.1 to 0.5 parts, relative to 100 parts of the vulcanizable acrylic rubber. If the ratio is less than 0.05 part, the effect of cross-linking reactivity tends to be unsatisfactory, and if it exceeds 1.5 parts, stability against early vulcanization tends to be impaired.

The acrylic rubber composition of the present invention has resistance to the above-mentioned components,
Ingredients such as reinforcing agents, fillers, plasticizers, stabilizers and processing aids that are generally used in the vulcanization system and rubber industry can be added.

The compounding ratio of the vulcanizable acrylic rubber is preferably 40 to 85%, more preferably 50 to 75% in the composition containing the reinforcing agent and the like. If the ratio is less than 40%, the rubber elasticity of the vulcanized product tends to be impaired, and if it exceeds 85%, a vulcanized product having sufficient physical strength in practical use tends to be unobtainable.

The method for preparing the acrylic rubber composition of the present invention is not particularly limited, and the acrylic rubber composition can be prepared by adding the above-mentioned components and mixing them with a usual kneader such as Banbury or roll.

The thus obtained acrylic rubber composition of the present invention is usually cured at a temperature of about 140 ° C. or higher, preferably about 170 to 200 ° C. for about 1 to 20 minutes so quickly that post-vulcanization is not necessary. Sulfur can be vulcanized, and even when post-vulcanization is performed, vulcanization may be performed at a temperature of about 150 to 180 ° C. for about 1 to 5 hours.

As described above, the acrylic rubber composition of the present invention is excellent in storage and early vulcanization due to the action of the base active chlorine-containing acrylic rubber, the vulcanizing agent, and the vulcanization aid. It gives a vulcanizate that exhibits stability and has good physical properties such as heat aging resistance, compression set resistance, oil resistance, weather resistance, and ozone resistance.

Next, the present invention will be described more specifically based on production examples and examples, but the present invention is not limited to the production examples and examples.

Production Example 1 (seed emulsion polymerization) 40 parts corresponding to 10% of 400 parts of the monomer mixture (A) shown in Table 1, 6 parts of polyoxyethylene dodecyl ether,
2 parts of sodium dodecylsulfate and 600 parts of water were charged into a reaction vessel, and nitrogen substitution was sufficiently carried out while stirring while maintaining the liquid temperature at 2 ° C.

Then, cumene hydroperoxide 0.5 was added to this mixture.
Parts, 0.01 parts of ferrous sulfate and 0.3 parts of sodium formaldehyde sulfoxylate were added in order, and when the polymerization reaction started and the temperature started to rise, 360 parts of the remaining monomer mixture (A) was immediately added in a small amount over about 5 hours. Drop by drop.
At that time, the temperature of the content liquid was kept at 5 ° C., and after completion of the dropping, the mixture was stirred for 90 minutes to complete the copolymerization reaction.

The obtained copolymer emulsion was put into 15% saline solution at about 80 ° C. to coagulate the copolymer to obtain a vulcanizable acrylic rubber.

100 parts of obtained vulcanizable acrylic rubber, 1 stearic acid
Parts, HAF carbon black 50 parts, trithiocyanuric acid
0.5 part and 2 parts of zinc dibutyldithiocarbamate were kneaded with a 6-inch roll for 20 minutes to prepare an acrylic rubber composition (composition
No.1) was obtained.

The obtained composition was subjected to a Mooney scorch test in accordance with JIS K 6300 "Unvulcanized rubber test method".
Further, the properties of the vulcanized product obtained by subjecting the composition to press vulcanization at 180 ° C. for 10 minutes were evaluated according to JIS K 6301 “Vulcanized rubber physical test method”. The obtained results are shown in Table 2 together with the Mooney viscosity of the vulcanizable acrylic rubber. Note that Vm
Indicates the minimum viscosity. Further, a vulcanization curve when the composition was vulcanized and cured at 180 ° C. was prepared based on the result of measurement using an oscillating disc rheometer (manufactured by Toyo Seiki Co., Ltd.). The vulcanization curve is shown in FIG.

Production Examples 2 to 4 (Seed Emulsion Polymerization) Production Example 1 except that the monomer mixture (B), (C) or (D) was used instead of the monomer mixture (A) shown in Table 1. Vulcanized acrylic rubber was produced in the same manner to prepare acrylic rubber compositions (composition Nos. 2 to 4). The characteristics of the obtained composition were evaluated in the same manner as in Production Example 1. The results are shown in Table 2 and FIG.

Production Example 5 (Batch emulsion polymerization) 400 parts of the monomer mixture (A) shown in Table 1, 4 parts of polyoxyethylene dodecyl ether, 1.5 parts of sodium dodecyl sulfate and 200 parts of water were emulsified with stirring using a homomixer. Then, 400 parts of water was charged into a reaction vessel which had been charged in advance, and nitrogen substitution was sufficiently carried out while stirring while maintaining the liquid temperature at 5 ° C.

Then cumene hydroperoxide 0.2 parts, ferrous sulfate
0.01 part, sodium formaldehyde sulfoxylate
When 0.2 parts were sequentially added, the polymerization reaction started and the temperature started to rise. When the temperature of the content liquid reached 30 ° C, stirring was continued for about 3 hours while maintaining the same temperature to complete the copolymerization reaction.

The obtained copolymer emulsion was put into 15% saline solution at about 80 ° C. to coagulate the copolymer to obtain a vulcanizable acrylic rubber.

Production Example 1 except that the obtained vulcanizable acrylic rubber was used.
An acrylic rubber composition (No. 5 in the composition) was prepared in the same manner as above, and the characteristics were evaluated. The results are shown in Table 2 and FIG.

Production Example 6 (batch emulsion polymerization) A vulcanizable acrylic rubber was obtained in the same manner as in Production Example 5 except that the monomer mixture (C) was used instead of the monomer mixture (A) shown in Table 1. .

Production Example 1 except that the obtained vulcanizable acrylic rubber was used.
An acrylic rubber composition (composition No. 6) was prepared in the same manner as in Example 1 and the properties were evaluated. The results are shown in Table 2 and FIG.

Production Example 7 (Suspension Polymerization) 600 parts of monomer mixture (A) shown in Table 1 14 parts of partially saponified polyvinyl alcohol, 1 part of anhydrous neutral sodium sulfate and 1385 parts of water were charged into a reaction vessel. Then, while the temperature of the content liquid was maintained at 30 ° C., nitrogen substitution was performed while stirring at high speed. Then, 6 parts of benzoyl peroxide was added, and the temperature was gradually raised, and the polymerization reaction started at about 60 ° C., and the temperature rose rapidly. When the temperature of the content liquid reached 70 ° C., the copolymerization reaction was completed by stirring at that temperature for about 3 hours.

The obtained copolymer mixture was washed with water as it was and dried to obtain a vulcanizable acrylic rubber.

Production Example 1 except that the obtained vulcanizable acrylic rubber was used.
An acrylic rubber composition (composition No. 7) was prepared in the same manner as in 1. and the properties were evaluated. The results are shown in Table 2 and FIG.

Production Example 8 (Suspension Polymerization) A vulcanizable acrylic rubber was obtained in the same manner as in Production Example 7 except that the monomer mixture (C) shown in Table 1 was used instead of the monomer mixture (A). .

Production Example 1 except that the obtained vulcanizable acrylic rubber was used.
An acrylic rubber composition (composition No. 8) was prepared in the same manner as in 1. and the properties were evaluated. The results are shown in Table 2 and FIG.

As is clear from the results shown in Table 2, FIG. 1 and FIG. 2, when the vulcanizable acrylic rubber obtained by using monochlorovinyl acetate or chloromethylstyrene as the active chlorine group-containing monomer was used, In the _meantime, when an elastomer obtained by a vulcanization-quick composition and obtained by a seed emulsion polymerization formulation is used, a snappy with a large t _{5 and a} small t _{Δ 35-5} in the Mooney scorch test ( snap
It is clear that a composition exhibiting py) vulcanization characteristics can be obtained, and the rapidly vulcanizable acrylic rubber used in the present invention can be obtained only by an emulsion polymerization method by a seed polymerization method.

Examples 1 to 7 and Comparative Examples 1 to 3 100 parts of the vulcanizable acrylic rubber obtained in Production Example 1, 50 parts of HAF carbon black, 0.5 part of N-cyclohexyl-N-trichloromethylthiobenzyl-2-sulfonamide, γ
-Aminopropyltriethoxysilane 0.5 parts and third
A vulcanizing agent shown in the table was kneaded with a 6-inch roll for 20 minutes to prepare an acrylic rubber composition (composition Nos. 9 to 18), which was left for 2 weeks immediately after the preparation and Mooney Scorch The test was conducted. Also, the composition is 180 ℃
The properties of the vulcanizate obtained by vulcanizing for 10 minutes were evaluated. Furthermore, the change in properties after standing at 175 ° C. for 70 hours was examined. Moreover, the compression set was examined under the conditions of 150 ° C., 70 hours, and 25% compression. Furthermore, Examples 1 and 2 and Comparative Examples 1 and 3
For, a vulcanization curve was prepared in the same manner as in Production Example 1. The results are shown in Table 4 and FIG.

From Table 4 and FIG. 3, the acrylic rubber composition of the present invention has an early vulcanization stability (scorch time) as compared with the composition containing a vulcanizing agent which has been conventionally used (composition No. 18). t
₅ ) and rapid vulcanizability (vulcanization time t _{Δ 35-5} ) are well balanced, and even after being left at room temperature for 2 weeks, they show vulcanization characteristics similar to those of the composition immediately after preparation and excellent storage stability. You can see that Further, by appropriately selecting the type and amount of the vulcanizing agent, it is possible to obtain a composition having a good balance between tensile strength and elongation, excellent heat aging resistance, and outstandingly good compression set resistance. You can

Examples 8-12 and Comparative Examples 4-8 100 parts of the vulcanizable acrylic rubber obtained in Production Example 1, 1 part of stearic acid, 50 parts of HAF carbon black, 0.7 part of trithiocyanuric acid, 2.0 parts of zinc dibutyldithiocarbamate.
Part and the vulcanization aid shown in Table 5 with a 6 inch roll.
The composition was prepared by kneading for minutes, and the characteristics were evaluated in the same manner as in Examples 1 to 7. In addition, Examples 8 and 12, Comparative Example 4
For 6 and 6, vulcanization curves were prepared in the same manner as in Production Example 1. The results are shown in Table 6 and FIG.

From the results shown in Table 6 and FIG. 4, when the acrylic rubber composition of the present invention does not contain a sulfonamide or phthalimide derivative (Comparative Example 6), a vulcanization retarder commonly used in the rubber industry is used. When used (Comparative Example 7,
It can be seen that compared with 8), it exhibits excellent stability with respect to early vulcanization. Further, by using the organosilane compound, the value of t _{Δ 35-5} is shortened, the vulcanization is accelerated, the vulcanization starts quickly as shown in FIG. 4, and the vulcanization is flat after a certain time. A vulcanized composition which is practically preferable and has properties can be obtained.

[Advantages of the Invention] The acrylic rubber composition of the present invention improves the delay of vulcanization of an acrylic elastomer, which has been a problem in the past, and makes it possible to shorten or omit post-vulcanization. From the viewpoint of application, it is also effectively improved with respect to compression set resistance, which is a particularly important required characteristic. Moreover, the vulcanizate obtained from the composition of the present invention is very excellent in various properties such as heat aging resistance, compression set resistance, oil resistance, weather resistance, and ozone resistance.
Various types of seals such as gaskets, packing, o-rings, oil seals, etc.
In addition to various hoses and coating materials, it can be widely used for various belts and rolls.

[Brief description of drawings]

1 and 2 are graphs showing vulcanization curves of the compositions obtained in Production Examples 1 to 8, and FIG. 3 is Examples 1 and 2,
FIG. 4 is a graph showing the vulcanization curves of the compositions obtained in Comparative Examples 1 and 3, and FIG. 4 is a graph showing the vulcanization curves of the compositions obtained in Examples 8 and 12 and Comparative Examples 4 and 6.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masayoshi Ichikawa Kasuga-mura, Aichi Prefecture Kasuga-mura, Ochiai, Nagahata No. 1, Toyoda Gosei Co., Ltd.

Claims (1)

[Claims] 1. A vulcanizable acrylic rubber containing (A) 0.1 to 0.5% by weight of an active chlorine group obtained by a seed polymerization method.
0 parts by weight, (B) 0.1 to 2.0 parts by weight of trithiocyanuric acid, (C) 0.5 to 5.0 parts by weight of metal salt of dithiocarbamic acid, (D) imide derivative consisting of N- (cyclohexylthio) phthalimide and / or N- 0.05-1.5 parts by weight of an amide derivative consisting of isopropylthio-N-cyclohexyl-benzothiazyl-2-sulfonamide, N-cyclohexyl-N-trichloromethylthio-benzyl-2-sulfonamide and (E) β- (3,4-epoxy) Cyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane epoxy-based organofunctional silane and / or γ-mercaptopropyltrimethoxysilane mercapto-based organofunctional silane and / or γ-amino Propyltrier Kishishiran, N- phenyl--γ- aminopropyl amino organo functional silanes 0.05-1.5 acrylic rubber composition comprising the parts consisting of trimethoxysilane.